SONOCHEMISTRY

An Emerging Green Technology

SONOCHEMISTRY
An Emerging Green Technology

Edited by
Suresh C. Ameta, PhD
Rakshit Ameta, PhD
Garima Ameta, PhD
Apple Academic Press Inc. Apple Academic Press Inc.
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Library and Archives Canada Cataloguing in Publication

Sonochemistry : an emerging green technology / edited by

Suresh C. Ameta, PhD, Rakshit Ameta, PhD, Garima Ameta, PhD.
Includes bibliographical references and index.
Issued in print and electronic formats.
ISBN 978-1-77188-629-1 (hardcover).--ISBN 978-1-315-10274-0 (PDF)
1. Sonochemistry. I. Ameta, Suresh C., editor II. Ameta, Rakshit, editor III. Ameta, Garima, editor
QD801.S66 2018 541'.3 C2018-900505-X C2018-900506-8
Library of Congress Cataloging-in-Publication Data

Names: Ameta, Suresh C., editor. | Ameta, Rakshit, editor. | Ameta, Garima, editor.
Title: Sonochemistry : an emerging green technology / editors, Suresh C. Ameta, PhD,
Rakshit Ameta, PhD, Garima Ameta, PhD.
Description: Toronto : Apple Academic Press, 2018. | Includes bibliographical references and index.
Identifiers: LCCN 2018002163 (print) | LCCN 2018004391 (ebook) | ISBN 9781315102740
(ebook) | ISBN 9781771886291 (hardcover : alk. paper)
Subjects: LCSH: Sonochemistry. | Chemistry, Physical and theoretical. | Ultrasonic waves--
Physiological effect. | Ultrasonic waves--Industrial applications.
Classification: LCC QD801 (ebook) | LCC QD801 .S65 2018 (print) | DDC 541/.3--dc23
LC record available at https://lccn.loc.gov/2018002163

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CONTENTS

List of Contributors  �������������������������������������������������������������������������     vii

Preface  ���������������������������������������������������������������������������������������������     ix
About the Editors   ����������������������������������������������������������������������������    xi
About the Book  �������������������������������������������������������������������������������     xiii

1. Introduction ����������������������������������������������������������������������������    1
Suresh C. Ameta
2. Basic Concepts  �����������������������������������������������������������������������    9
Garima Ameta
�������������������������������������������������������������������    23
3. Instrumentation 
Garima Ameta
4. Organic Synthesis  ����������������������������������������������������������������    45
Chetna Ameta, Arpit Kumar Pathak, P. B. Punjabi
5. Inorganic, Coordination and Organometallic
Compounds  ��������������������������������������������������������������������������   115
Kiran Meghwal, Sharoni Gupta, Chetna Gomber
6. Nanomaterials  ��������������������������������������������������������������������    159
Meenakshi Singh Solanki, Surbhi Benjamin, Suresh C. Ameta
7. Polymers �����������������������������������������������������������������������������    197
Kiran Meghwal, Gunjan Kashyap, Rakshit Ameta
8. Wastewater Treatment  ������������������������������������������������������    225
Arpita Pandey, Arpita Paliwal, Rakshit Ameta
9. Food Technology  ����������������������������������������������������������������    271
Sanyogita Sharma, Neetu Shorgar
10. Anaerobic Digestion  �����������������������������������������������������������    295
Sangeeta Kalal, Satish Kumar Ameta, Abhilasha Jain
viContents

11. Medical Applications  ���������������������������������������������������������    323

Dipti Soni, Surbhi Benjamin
12. Industrial Applications  ������������������������������������������������������    341
Anil Kumar Chohadia, Yasmin, Neelam Kunwar
13. Sonochemistry: A Versatile Approach  �����������������������������    371
Rakshit Ameta
Index  ���������������������������������������������������������������������������������������������    375
LIST OF CONTRIBUTORS

Chetna Ameta
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Garima Ameta
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Rakshit Ameta
Department of Chemistry, J.R.N. Rajasthan Vidyapeeth (Deemed to be University), Udaipur, India
E-mail: [email protected]
Satish K. Ameta
Department of Environmental Science, Mewar University, Chittorgarh, India
E-mail: [email protected]
Suresh C. Ameta
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

Surbhi Benjamin
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

Anil Kumar Chohadia

Department of Chemistry, M. P.Govt PG College, Chitttorgarh, India
E-mail:[email protected]

Chetna Gomber
Department of Chemistry, JIET Group of Institutions, Jodhpur, India
E-mail:[email protected]

Abhilasha Jain
Department of Chemistry, St. Xavier’s College, Mumbai, India
E-mail: [email protected]

Sangeeta Kalal
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Gunjan Kashyap
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Neelam Kunwar
Department of Chemistry, PAHER University, Udaipur, India,
E-mail: [email protected]
viii List of Contributors

Kiran Meghwal
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Arpita Paliwal
Department of Chemistry, Sangam University, Bhilwara, India
E-mail:[email protected]

Arpita Pandey
Department of Chemistry, Sangam University, Bhilwara
E-mail:[email protected]
Arpit Kumar Pathak
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]
P. B. Punjabi
Department of Chemistry, M. L. Sukhadia University, Udaipur, India,
E-mail: [email protected]

Sanyogita Sharma
Department of Chemistry, PAHER University, Udaipur, India,
E-mail: [email protected]

Gupta Sharoni
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail:[email protected]

Neetu Shorgar
Department of Chemistry, PAHER University, Udaipur, India,
E-mail:[email protected]
Meenakshi Singh Solanki
Department of Chemistry, B. N. University, Udaipur, India,
E-mail : [email protected]
Dipti Soni
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

Yasmin
Department of Chemistry, Techno India NJR Institute of Technology, Udaipur, India
E-mail: [email protected]
PREFACE

Nature needs protection from the fast growing chemical pollution. The
primary challenge for chemists is to make chemical processes more envi-
ronmentally benign and sustainable. World has witnessed a tremendous
outburst in modifying chemical processes to make them sustainable for
making our environment clean and green. One such environmental friendly
technique is the use of ultrasound.
Sonochemistry deals with the effect of ultrasonic waves on chemical
systems. It has green value because of nonhazardous acoustic radia-
tion and therefore, it is duly recognized as a part of Green Chemistry by
synthetic chemists as well as environmentalists. There is no direct interac-
tion of ultrasound with molecular species, but the observed chemical and
physical effects of ultrasound are due to the cavitational collapse, which
produces drastic conditions of temperature and pressure locally. It induces
the formation of various chemical species, which cannot be easily attained
under conventional conditions. Sometimes, these species are responsible
for driving towards an unusual reactivity in molecular entities.
Exposure to ultrasonic radiation and the resultant sonochemical and/or
sonophysical effects have established this technique for driving a particular
chemical reaction more efficiently and that too with high yields and selec-
tivity. Sonochemistry utilizes less hazardous starting materials, reagents
and solvents. In this process, product selectivity and product yields are
increased; in addition, energy consumption is also reduced. This book
provides the complete development of sonochemistry starting from intro-
duction, basic concepts of sonochemistry, different types of sonochemical
reactions, instrumentation, use of ultrasound in driving particular chemical
reactions and its applications in various fields such as polymer synthesis,
decontamination of water and waste water, preparation of nanomaterials,
food technology, pharmaceutical sciences and so forth.
Apart from this, some fields are also discussed in brief, which do not
fall in the actual arena of sonochemistry, but utilize ultrasounds of different
frequencies. These are food products and their processing, anaerobic diges-
tion of waste, medical applications such as ultrasonography, sonodynamic
xPreface

therapy, drug delivery and so on. Sonochemistry will be successfully used

on industrial scale in pharmaceutical drugs, polymers, nanomaterials, food
technology, material science, biogas production, etc. in years to come and
will be an established as green chemical technology of the future.
ABOUT THE EDITORS

Suresh C. Ameta, PhD, is currently Dean of Faculty of Science at PAHER

University, Udaipur. He has served as professor and head of the depart-
ment of chemistry at North Gujarat University Patan (1994) and at M. L.
Sukhadia University, Udaipur (2002–2005), and as head of the department
of polymer science (2005–2008). He also served as Dean of Postgrad-
uate Studies (2004–2008). Prof. Ameta has held the position of President,
Indian Chemical Society, Kotkata, and is now a life-long advisor. He was
awarded a number of prestigious awards during his career, such as national
prizes twice for writing chemistry books in Hindi; the Prof. M. N. Desai
Award (2004), the Prof. W. U. Malik Award (2008), the National Teacher
Award (2011), the Prof. G. V. Bakore Award (2007), Life Time Achieve-
ment Awards by Indian Chemical Society (2011) as well as Indian Council
of Chemist (2015), etc. He has successfully guided 81 PhD students and
having more than 350 research publications to his credit in journals of
national and international repute. He is also the author of many undergrad-
uate- and postgraduate-level books. He has published three books with
Apple Academic Press, Microwave-Assisted Organic Synthesis, Green
Chemistry, and Chemical Applications of Symmetry and Group Theory,
and two with Taylor and Francis: Solar Energy Conversion and Storage
and Photocatalysis. He has also written chapters in books published by
several international publishers. Prof. Ameta has delivered lectures and
chaired sessions at national conferences and is a reviewer of number of
international journals. In addition, he has completed five major research
projects from different funding agencies, such as DST, UGC, CSIR and
Ministry of Energy, Government of India.

Rakshit Ameta, PhD, is Associate Professor of Chemistry, J.R.N.

Rajasthan Vidyapeeth (Deemed to be University), Udaipur, India. He
has several years of experience in teaching and research in chemistry
as well as industrial chemistry and polymer science. He is presently
guiding six research students for their PhD theses, and eight students have
already obtained their PhDs under his supervision in green chemistry.
xii About the Editors

Dr. Rakshit Ameta has received various awards and recognition in his
career, including being awarded first position and the gold medal for his
MSc and receiving the Fateh Singh Award from the Maharana Mewar
Foundation, Udaipur, for his meritorious performance. He has served at
M. L. Sukhadia University, Udaipur; the University of Kota, Kota, and
PAHER University, Udaipur. He has over 100 research publications to
his credit in journals of national and international repute. He holds one
patent, and two more are under way. Dr. Rakshit has organized several
national conferences as Organizing Secretary at the University of Kota
and PAHER University. He has delivered invited lectures and has chaired
sessions in conferences held by the Indian Chemical Society and the
Indian Council of Chemists. Dr. Rakshit was elected as council member
of the Indian Chemical Society, Kolkata (2011–2013) and council
member (2012–2014) and zonal secretary (2016–2018), Indian Council
of Chemists, Agra as well as associate editor, Physical Chemistry Section
(2014–2016) of Indian Chemical Society. Dr. Rakshit has also worked
as Scientist-in-Charge in the Industrial and Applied Chemistry Section
of Indian Chemical Society (2014–2016). He has written five degree-
level books and has contributed chapters to books published by several
international publishers. He has published three previous books with Apple
Academic Press: Green Chemistry (2014), Microwave-Assisted Organic
Synthesis (2015), Chemical Applications of Symmetry and Group Theory
(2016) and two books Solar Energy Conversion and Storage (2016) and
Photocatalysis (2017) with Taylor and Francis. His research areas focus
on wastewater treatment, photochemistry, green chemistry, microwave-
assisted reactions, environmental chemistry, nanochemistry, solar cells
and bioactive and conducting polymers.

Garima Ameta, PhD, is working as a post-doctoral fellow at M. L.

Sukhadia University, Udaipur, India. She has 13 publications including
chapters in the fields related to sonochemistry. She has received Young
Scientist Award (2016) for best presentation in a National Conference. Her
research interests are in the field of use of ultrasound in wastewater treat-
ment and synthesis of ionic liquids.
ABOUT THE BOOK

Normally, heat and light are thought as energy sources to drive a particular
chemical reaction, but now, ultrasound can also be used as a promising
energy source for this purpose. Collapse of a bubble generates a wide range
of high temperatures and pressures and, therefore, use of ultrasound has a
considerable potential in chemical and allied sciences. This book presents
a complete picture of ultrasound-assisted reactions and technologies such
as organic synthesis, polymer synthesis and degradation, nanomaterials,
waste water treatment, food ingredients, and products, pharmaceutical,
bioenergy applications, and so forth. Ultrasound-assisted reactions are
green and economically viable alternatives to conventional techniques.
This book is aimed to throw light on the diversified applications of ultra-
sound and its significant role as a green chemical pathway.
CHAPTER 1

INTRODUCTION
SURESH C. AMETA1
1
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

CONTENTS

1.1 Introduction  ��������������������������������������������������������������������������������  1

1.2 Homogeneous Sonochemistry  ����������������������������������������������������  3
1.3 Heterogeneous Sonochemistry  ���������������������������������������������������  4
References  ���������������������������������������������������������������������������������������������  6

1.1 INTRODUCTION

The concept of the present-day generation of ultrasound was estab-

lished and it dates back to the early 1880s, with the discovery of the
piezoelectric effect by the Curies (1880a, 1880b). The first commer-
cial application of ultrasonics came into existence in the form of echo-
sounder (Chilowsky and Langévin, 1917). This original echo-sounder
eventually became underwater sound navigation and ranging (SONAR)
for submarine detection during World War 2. The transducer used was
simply a mosaic of thin quartz crystals glued between two steel plates
(the composite having a resonant frequency of about 50 kHz), which was
mounted in a housing so that it can work under water (submersion). The
echo-sounder simply sent a pulse of ultrasound from the keel of a boat to
the bottom of the sea wherein it was reflected back to a detector available
on the keel.
Wood and Loomis (1927) were the first to note the advantages of using
ultrasound in chemistry. They observed that chemical reactions were
2Sonochemistry

not a consequence of the heat but a consequence of sonic energy. There

was a very slow growth in the field of sonochemistry even though it was
known for the last five decades. Significantly, an interest in ultrasonics
was renewed only in the 1980s. Initially, sonochemistry was used only
for chemical effects induced by ultrasound but now this field has been
extended to other applications too. Currently, the term “sonochemistry”
is used to describe the applications of ultrasound in diverse fields such
as food processing, stabilization of oil emulsions, particle size reduction,
filtering systems for suspended particles, homogenization, atomization,
environmental protection, and so forth.
Ultrasound finds its application in animal communications (e.g. bat
navigation and dog whistles). It is also used in the medical field for fetal
imaging, in underwater range finding (SONAR), or in the nondestructive
testing of metals for flaws, etc. A few decades back, a chemist would prob-
ably not consider sound as the type of energy that could be used for the
enhancement of a chemical reaction and the use of ultrasound in chemistry
was something of a curiosity. One would probably turn towards heat, pres-
sure, light, or the use of any catalysts, etc., instead of choosing ultrasound
to increase chemical reactivity. It is perhaps surprising that for several years
sound was not considered as a potential source of increasing chemical reac-
tivity. The only exception to this being the green-fingered chemists, who
in the privacy of their own laboratories, talk, sing or even shout at their
sonochemical reactions. In fact, sound is transmitted through a medium as
a pressure wave and only this act of transmission must cause some excita-
tion in the medium in the form of enhanced molecular motion. However, in
order to produce real effects, the sound energy must be transmitted within
the liquid itself. This is attributed due to the fact that transfer of sound
energy from the air into a liquid is not an effective process.
Sonochemistry is still considered a strange word by most of the chem-
ists till date. The term sonochemistry comprises two terms: the prefix sono
means sound and the suffix chemistry has its own meaning. The combi-
nation of these two terms could lead to an understanding that this is a
kind of chemistry in the presence of sound. Thus, sonochemistry is the
use of sound waves of high frequency and power to input energy into
a liquid reaction mixture. When high-frequency sound waves are passed
through a liquid medium, compression and rarefaction zones are formed.
The liquid molecules are pulled apart, when the power exceeds a certain
minimum value in the rarefaction zone, thereby creating voids, bubbles,
Introduction3

or cavitations filled with gas or liquid vapours. These bubbles suddenly

collapse after several acoustic cycles and release a large temperature
(nearly 5000°C) and very high pressure (1000 bar or 14,000 psi into the
liquids). During this process, the mechanical energy of ultrasound is trans-
formed and transferred through bubbles into renewable energy through a
chemical reaction. Thus, cavitational phenomenon is the essence of sono-
chemistry and sonochemical effects.
These cavitations can create extreme conditions in liquids of both the
types: physical and chemical. Similar phenomena can be also observed in
liquids containing solid, when these are exposed to ultrasound. However,
in this case, cavitation occurs near an extended solid surface. Near this
surface, the cavity collapse is nonspherical and drives high-speed jets of
liquid to the surface. These jets and associated shock waves can damage
the highly heated surface. Liquid power suspensions produce high-
velocity interparticle collisions. Such interparticle collisions can change
the surface morphology, composition and reactivity.
As these bubbles are very small and are found to collapse rapidly,
these can act as microreactors offering an opportunity of enhancing rates
of reactions and also permitting some novel reactions to proceed in an
absolutely controlled safe manner.

1.2  HOMOGENEOUS SONOCHEMISTRY

Chemical reactions in homogeneous systems proceed via radical inter-

mediates. It means that sonication is able to affect reactions proceeding
via radical formations and it does not affect ionic reactions. The bubbles
or cavities act as microreactors in the case of volatile molecules as these
molecules enter the microbubbles. High temperature and pressure is
generated during cavitation which eventually breaks the chemical bonds.
The short-lived chemical species are returned to the bulk liquid at room
temperature and they can react with other species. Compounds of low
volatility do not enter bubbles and therefore, these will be directly exposed
to these extreme conditions of temperature and pressure. Thus, they expe-
rience a high-energy environment, which is due to the pressure changes.
These pressure changes are associated with the propagation of the acoustic
wave or with bubble collapse (shock waves).
4Sonochemistry

1.3  HETEROGENEOUS SONOCHEMISTRY

The chemical reactions in a heterogeneous system are basically through the

mechanical effects of cavitations. These effects include surface cleaning,
particle size reduction, and improved mass transfer. If cavitation occurs
in a liquid near a solid surface, then there is a significant change in the
dynamics of cavity collapse.
The cavity remains in a spherical shape in a homogeneous system
during cavity collapse because its surroundings are uniform. Cavity
collapse is mostly asymmetric in proximity to a solid boundary in hetero-
geneous systems with generation of high-speed jets of liquid. These jets
hit the surface with tremendous force and this process can cause a lot of
change at the point of impact and produce newly exposed highly reactive
surfaces.
Enhancement of chemical reactions by ultrasound has been widely
studied. It has found some beneficial applications in mixed-phase synthesis,
materials chemistry, biomedical uses, etc. As cavitation can only occur in
liquids, such chemical reactions are not observed in the ultrasonic irradia-
tion of solids or solid–gas systems.
Most of the modern ultrasonic devices rely on transducers (energy
converters), which are composed of piezoelectric materials. Such mate-
rials respond to the application of an electrical potential across opposite
faces with a small change in dimension. This is the inverse of the piezo-
electric effect. If the potential is alternated at high frequencies, the crystal
converts the electrical energy to mechanical vibration (sound) energy. At
sufficiently high alternating potential, high-frequency sound (ultrasound)
will be generated.
A bath or ultrasonic horn (a high-power probe) is used to carry out
sonochemical reactions. Various reactions are conducted using a simple
ultrasonic cleaning bath and in that case, the amount of energy released
during the reaction varies only between 1 and 5 W cm−2, but the tempera-
ture control is normally poor. Large-scale sonochemical reactions can be
performed using immersible ultrasonic probes that circumvent the transfer
of energy through water and the reaction vessel. In such cases, applied
energies can be higher in the order of several hundred times. Ordinary
laboratory equipment uses frequency range between 20 and 40 kHz, but
cavitation can be generated well above these frequencies. At present, much
broader range of frequencies is used.
Introduction5

Ultrasound finds its application in manufacturing of some chalcogen-

ides, coordination polymers, and organometallic compounds. It has wide
applications in synthesizing various organic moieties including hetro-
cycles such as oxazoles, thiazoles, pyrazoles, benzimidazoles, triazoles
and tetrazoles. These hetrocycles have proved their importance in phar-
maceutical chemistry. The rates of various name reactions have also been
found to be enhanced in the presence of ultrasound; some of these reac-
tions worth mentioning are Knoevenagel condensation, Pinacol coupling
reaction, Biginelli reaction, Suzuki reaction, Wittig reaction others.
Particles of nanosize have gained an increasing attention of all the
scientists worldwide due to their unique properties. This is all due to their
high surface-to-volume ratios. These may be also used as efficient cata-
lysts in various reactions. Nanomaterials of different morphologies can be
synthesized using ultrasonic irradiation. Variety of nanostructures can be
accomplished using ultrasound such as nanoflowers, nanobelts, nanorings,
nanonails, nanoribbons, nanosheets and so on. Even metal loading can be
conveniently accomplished using this technique.
Now, polymers have almost replaced all of the traditional materials of
construction, furniture, textile, etc., such as metals, wood, cotton, and there-
fore, the present era is perfectly named as Polymer Era. The society has to
contribute a lot to this and is facing problems for this replacement, because
polymers are not biodegradable and their disposal after use is becoming
a challenge for all of us. Ultrasound comes to our rescue at this stage for
the degradation of some polymers or at least convert these polymers to a
biodegradable component so that this can be used in further applications.
This source of energy is also used in the synthesis of some polymers.
Ultrasound plays a vital role in the treatment of waste water-containing
phenols, dyes, chloro compounds, surfactants, thio compounds, nitrogen-
containing compounds, etc. to decrease the organic load making aquatic
life easier by increasing the sustainability of aquatic organism and also
to increase the recyclability of water. Ultrasound irradiation is not only
utilized in the treatment of sludge, sewage and solid wastes, can be also
utilized in the conversion of such materials into some useful compounds
such as biogas through anaerobic digestion.
Food technology also finds a number of applications of ultrasound, for
example, in the extraction of some natural products from bioresources,
homogenization, emulsification, food preservation and so on. Various other
industries such as textile, pharma, sugar, are also benefited by ultrasound
6Sonochemistry

in the processes of dyeing, washing, finishing, cleaning, etc. Many indus-

tries that use boilers are affected by the problem of scaling, because these
require the removal of scales, which is a difficult task, because it is hard
enough. The use of ultrasound makes this scale relatively soft so that it can
be easily removed, thus improving the life of boilers.
Ultrasound is commonly used in the form of ultrasonography and
drug delivery. Therapeutic ultrasound is basically used for sonodynamic
therapy. It has also been used for the treatment of cancer. Normally, high-
intensity-focused ultrasound is medically used in killing tumor cells.
Ultrasonic imaging is another aspect of sonochemistry in medical field.
The use of sound waves leads to nondestructive testing of ailments.
The subject of sonochemistry has been excellently reviewed from time
to time by various workers (Mason, 1999; Thompson and Doraiswamy,
1999; Ameta et al., 2001; Mason and Peters, 2002; Mason and Lorimer,
2002; Gedanken, 2004; Mousavi and Ghasemi, 2012; Xu et al., 2013;
Grieser et al., 2015; Asgarzadehahmadi et al., 2016; Ashokkumar, 2016;
Panda and Manickam, 2017; Chatel, 2017).
However, some of the applications required different frequencies,
which do not fall under the range of sonochemical reactions, but a brief
description of such applications has also been provided and discussed in
this book. Currently, sonochemistry is considered a green chemical tech-
nology as it has many advantages such as reduction in the reaction time,
increasing the product yields, eco-friendly in nature and so on.

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78, 627–633.
Asgharzadehahmadi, S.; Raman, A. A. A.; Parthasarathy, R.; Sajjadi, B. Renewable Sustain-
able Energy Rev. 2016, 63, 302–314.
Ashokkumar, M. Ed. Handbook of Ultrasonics and Sonochemistry; Springer: Singapore,
2016.
Chatel, G. Sonochemisrty: New Opportunities for Green Chemistry; World Scientific: Singa-
pore, 2017.
Chilowsky, C.; Langevin, P. Production of Submarine Signals and the Location of Subma-
rine Objects. U.S. Patent 1,471,547, 1917.
Curie, J.; Curie, P. Bulletin de la Société Minérologique de France 1880a, 3, 90–93.
Curie, J.; Curie, P. Comptes Rendus 1880b, 91, 294–295.
Gedanken, A. Ultrason. Sonochem. 2004, 11(2), 47–55.
Introduction7

Grieser, F.; Choi, P.-K.; Enomoto, N.; Harada, H.; Okitsu, K.; Yasui, K. Eds. Sonochemistry
and the Acoustic Bubble; Elsevier: Amsterdam, 2015.
Mason, T. J. Sonochemistry; Oxford University Press: Oxford, 1999.
Mason, T. J.; Lorimer, J. P. Applied Sonochemistry: The Uses of Power Ultrasound in Chem-
istry and Processing; Wiley-VCH: Weinheim, 2002.
Mason, T. J.; Peters, D. Practical Sonochemistry: Power Ultrasound Uses and Applications,
2nd ed.; Woodhead Publishing: Sawston, 2002.
Mousavi, M. F.; Ghasemi, S. Eds. Sonochemistry: A Suitable Method for Synthesis of
Nano-Structured Materials; Nova Science: New York, 2012.
Panda, D.; Manickam, S. Ultrason. Sonochem. 2017, 36, 481–496.
Thompson, L. H.; Doraiswamy, L. K. Ind. Eng. Chem. Res. 1999, 38(4), 1215–1249.
Wood, R. W.; Loomis, A. L. Philos. Mag. 1927, 4, 414–436.
Xu, H.; Zeiger, B. W.; Suslick, K. S. Chem. Soc. Rev. 2013, 42, 2555–2567.
CHAPTER 2

BASIC CONCEPTS
GARIMA AMETA1
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]

CONTENTS

2.1 Introduction  ������������������������������������������������������������������������������  9

2.2 Cavitation  ����������������������������������������������������������������������������������  18
References  �������������������������������������������������������������������������������������������  20

2.1 INTRODUCTION

Chemistry is the interaction of energy with matter. Different forms

of energy such as heat (thermo), light (photo), and so on can drive any
chemical reaction in a particular direction. But in the last few decades,
ultrasound has also emerged as a potential source of energy that can
enhance chemical reactivity apart from its use in other applications, which
are nonchemical such as material testing, medical diagnosis, navigation
systems of bats, sound navigation and ranging (SONAR), and cleaning or
drilling of teeth. We have found that the chemical reactivity of a chemical
system is affected by ultrasound in low-frequency range passed through
that system. The effect of ultrasound on chemical reactivity forms a basis
of sonochemistry. The degradation of some compounds in the presence of
ultrasound is known as sonolysis. Ultrasound can also be used to synthe-
size compounds in reduced reaction time, increase in yield or sometimes
with diversion from the main route (chemical switching).
Scientifically, sound may be defined as the transmission of energy
through the generation of acoustic pressure waves in the medium. As these
pressure waves are mechanical in nature, a medium is required and the
10Sonochemistry

particles in the medium vibrate to transfer sound waves. The frequency of

the wave determines its regime. The medium may be air, water, solid, or
human soft tissue.
Sound is classified into four different categories depending on its
frequency range, and these are given as:

• Infrasound—Sound waves having frequency less than 20 Hz

• Audible sound—Sound waves having frequency between 20 and
20 kHz
• Ultrasound—Sound waves with frequency more than 20 kHz to
10 GHz
• Hypersound—Sound waves with frequency higher than 10 GHz.

There are two types of ultrasonic waves: (i) bulk (fundamental) waves
that can propagate inside an object, and (ii) guided waves that propa-
gate near the surface or along the interface of an object (Brekhovskikh,
1980; Auld, 1990; Achenbach, 1990; Rose, 1999). Waves propagating
completely inside an object are called bulk waves and these are inde-
pendent of its boundary and shape. Bulk waves exist in two types in an
isotropic medium. These are:

1. Longitudinal (dilatational, compression, or primary) waves and

2. Shear (distortional, transverse, or secondary) waves.

Distortion is effected on ultrasound irradiation and it depends on the

condition of application, whether this force is applied normal or parallel to
the surface at one end of the solid and whether it will produce compression
or shear vibrations, respectively. Thus, two types of ultrasonic waves, that
is longitudinal waves or transverse waves propagate through the solid and
energy of the wave is also carried with it (Figs. 2.1 and 2.2).
Propagation of ultrasonic wave is commonly described in terms of
the direction of motion of particles in relation to the direction, in which
wave propagates. The longitudinal waves are defined as waves where the
motion of particle is parallel to the direction of the wave propagation. On
the other hand, shear waves are defined as waves where the motion of
particle is perpendicular to the direction of the wave propagation. Both
these waves can exist in solids because solids have rigidity to offer resis-
tance to shear as well as compressive loads, unlike liquids and gases. But
Basic Concepts11

FIGURE 2.1  Longitudinal waves.

FIGURE 2.2  Transverse waves.

the shear waves cannot exist in liquid and gaseous medium as they offer
no resistance to shear loads in such media.
Other type of waves includes the guided waves. These are propagated
by considering the influences of the boundaries or the shape of an object.
Such guided waves are of three types depending on the geometry of an
object and these are:

1. Surface acoustic waves (SAWs)

1. Plate waves
2. Rod waves

Surface acoustic waves are defined as waves that propagate along a

free surface with disturbance amplitude, which decays exponentially with
depth into the object. Wave propagation characteristics of SAWs strongly
depend on the properties of that material, surface structure, and nature at
the interface of the object. Different kinds of SAWs such as Love, Scholte,
Stoneley, and Rayleigh waves exist. When a SAW propagates along
12Sonochemistry

a boundary between a semi-infinite solid and air, the wave is normally

called a Rayleigh wave. Here, particle motion is elliptical, and the effec-
tive penetration depth is of the order of one wavelength. Rayleigh wave is
the most common and well-known SAW and therefore, any SAW is often
called Rayleigh wave.
If ultrasonic wave propagates in a finite medium (like a plate), it is
bounded within the medium and may resonate. Such waves in an object
(with multilayered structure) of finite size are called plate waves, but these
are called Lamb waves, if the object has a single layer. If the force is
applied to the end of a slender rod, then an ultrasonic wave propagates
axially along the rod. Wave propagations in structures such as thin rod and
hollow cylinders have also been studied.
The propagation characteristics of guided waves depend strongly
not only on the properties of a material but also on the thickness of the
plate, the diameter of rod, and the frequency. The dependence of the wave
velocity of guided waves on frequency is called frequency dispersion. This
dispersion not only makes wave propagation behaviour much complicated
but also provides unique material evaluations using these guided waves.
Similar types of bulk and guided waves can exist for anisotropic mate-
rials but their behaviours become much more complicated than those for
isotropic materials (Auld, 1990; Achenbach, 1990; Rose, 1999).
Two types of cavitation are distinguished. These are stable and tran-
sient. Stable cavitation usually takes place when microbubbles mainly
contain a gas (e.g. air) and their mean life is relatively longer than a
cycle of the ultrasound. As long as their resonance frequency is higher
than that of the ultrasound during their growth, they are driven into pres-
sure antinodes, where they may induce some chemical reactions. On the
contrary, transient cavitation is a phenomenon of quite shorter duration.
Here, a cavity is rapidly formed containing mainly vapor of the liquid
and it vigorously collapses after a few cycles. Both these cavitations take
place at ultrasound intensities of a few W·cm−2. Transient cavitation is
quite often considered the most efficient way of driving different chem-
ical reactions, but it is true with high ultrasound intensities, so that the
formation of standing waves is avoided. At low ultrasound intensities,
standing waves are there to achieve high bubble numbers and significant
yields. In such a case, chemical reactions are induced through stable
cavitation.
Basic Concepts13

The cavitational bubbles increase in size in the positive cycle of the

wave due to the positive acoustic pressure. Then these bubbles finally
collapse, which leads to the formation of new nuclei for the next cavita-
tion. Each one of the bubble would collapse and it acts as a hot spot. The
process of collapse generates energy and, as a result, the temperature and
pressure rises up to 5000 K and 1000 atm., respectively, and cooling rate
as fast as 109 K·s−1. The process of formation, growth, and collapse of the
cavitation bubbles is shown in Figures 2.3 and 2.4.

FIGURE 2.3  Growth and implosion of a bubble.

FIGURE 2.4  Formation, growth and collapse of a bubble.

Such collapsing bubbles create an unusual mechanism for high-energy

chemical reactions due to abnormal increase in local temperatures and
pressure.
This can be divided into three regions (Fig. 2.5):

• First one is the thermolytic center (hot spot). This is the core of the
bubbles with localized hot temperature (5000 K) and high pres-
sure (500 atm) during final collapse of cavitation. Bubble water
molecules are pyrolyzed in this region forming •OH and •H in the
14Sonochemistry

gaseous phase. Then the substrate will either react with the •OH or
it will undergo pyrolysis.
• Second one is an interfacial region between the cavitational bubble
and bulk liquid. Here, similar reaction as hot spot occurs, but in the
aqueous phase. However, some additional reactions may occur in this
region, where •OH dimerize to form H2O2. Hydrophobic compounds
are more concentrated in the interfacial region than in the bulk solution.
• Third one is the bulk region. In this region, the temperature remains
almost similar to the room temperature because the process of cavi-
tation is adiabatic in nature. The chemical reactions occurring in
this region are basically between the substrate and the •OH or H2O2.
The effects of ultrasound in homogeneous and heterogeneous
media are clearly distinct. Sonochemical reactions are related to
some new chemical species produced during cavitation in homoge-
neous media, whereas for the latter, enhancement of the reactions
in heterogeneous media could also be related to mechanical effects
induced in liquid system under sonication (Destaillats et al., 2003).

FIGURE 2.5  Reaction zone in cavitation process

Source: P. Chowdhury and Viraraghavan, 2009, with permission.
Basic Concepts15

The study of sonochemistry is concerned with understanding the effect

of ultrasound in forming acoustic cavitation in liquids, which is respon-
sible for the initiation or enhancement of the chemical activity in the solu-
tion. The chemical effects of ultrasound are not due to a direct interaction
of the ultrasonic sound wave with the molecules present in the solution.
Sound waves propagating through a liquid at ultrasonic frequencies do
these changes with a wavelength that is significantly longer than the bond
length between atoms of the molecule. Therefore, the sound waves cannot
affect vibrational energy of the bond, and therefore, it cannot increase the
internal energy of a molecule directly (Suslick, 1990; Suslick and Flan-
nigan, 2008). Sonochemistry arises from acoustic cavitation, that is, the
formation, growth, and implosive collapse of bubbles in a liquid (Suslick
and Kenneth, 1989).
The collapse of these bubbles is an almost adiabatic process and it
results in the massive buildup of energy inside the bubble. This results
in very high temperatures and pressures in a microscopic region of the
sonicated liquid. Such extreme conditions of temperatures and pressures
result in the chemical excitation of any matter that is either present inside
the bubble, or in the close vicinity of the imploding bubble. A number of
processes result from acoustic cavitation, an increase in chemical activity
in the solution either due to the formation of primary and secondary
radical reactions, and or through the formation of some new, relatively
stable chemical species that can diffuse further into the solution to show
chemical effects, etc. Hydrogen peroxide (H2O2) may be formed from the
combination of two hydroxyl radicals generated in dissociation of water
vapor inside the collapsing bubbles on exposed of water to ultrasound.
Wood and Loomis (1927) were the first to report the effect of sonic
waves traveling through liquids. They have conducted experiments on the
frequency of the energy that it took from sonic waves to penetrate the
barrier of water. They concluded that sound does travel faster in water,
but because of the density of water compared to our earth’s atmosphere,
it was very difficult to get the sonic waves into the water. They decided
that sound can be dispersed into water by making loud noises into water
by creating bubbles. They put sound into water by simply yelling. But
another disadvantage of this was the ratio of the amount of time it took for
the lower frequency waves to penetrate the bubble walls and access water
around the bubble, and then the time from that point to a point on the other
end of the body of water. But this exciting idea remained mostly ignored
16Sonochemistry

for a few decades till the 1980s, when some of inexpensive and reliable
generators of high-intensity ultrasound were developed.
Acoustic cavitation usually occurs upon irradiation with high-inten-
sity sound or ultrasound. Cavitation is the formation, growth, and implo-
sive collapse of bubbles on exposure to ultrasound. It gave impetus to
sonochemistry and sonoluminescence (Leighton, 1994). Bubble collapse
in liquids produces large amounts of energy. It comes from the conver-
sion of kinetic energy of the liquid motion into heating the contents of the
bubble. The compression of the bubbles during cavitation is quite rapid
than thermal transport, and it generates a short-lived localized hot spot.
These bubbles have temperatures around 5000 K, pressures of roughly
1000 atm, and heating and cooling rates above 1010 K·s−1 (Suslick et al.,
1986; Flint and Suslick, 1991). These cavitations can create extreme phys-
ical and chemical conditions in otherwise cold liquids.
Similar phenomena may occur with exposure to ultrasound within
liquids containing solids. If this cavitation occurs near an extended solid
surface, the cavity collapses in a nonspherical way and it drives high-
speed jets of liquid to the surface (Leighton, 1994). These jets and asso-
ciated shock waves can damage the highly heated surface. Suspensions
of liquid powder produce high-velocity interparticle collisions, which can
change the surface morphology, composition, and reactivity (Suslick and
Docktyez, 1990).
Basically, sonochemical reactions can be classified into three classes.
These are:

• Homogeneous sonochemistry of liquids

• Heterogeneous sonochemistry of liquid–liquid or solid–liquid
systems, and, overlapping
• Sonocatalysis (Einhorn et al., 1989; Luche, 1996; Pestman et al., 1994)

Sonoluminescence is taken as a special case of homogeneous sono-

chemistry (Crum, 1994; Putterman, 1995). The enhancement of chemical
reactions by ultrasound has found applications in mixed-phase synthesis,
materials chemistry, and biomedical uses. Chemical reactions have not
been studied in the solids or solid–gas systems in the presence of ultra-
sonic radiation as cavitation can occur only in liquids.
It has been observed that ultrasound greatly enhances chemical reac-
tivity in the order of million-folds in a number of systems (Suslick and
Basic Concepts 17

Casadonte, 1987), acting as an effective catalyst by exciting the atomic

and molecular modes of the system such as the vibrational, rotational,
and translational modes. This is due to the fact that ultrasound breaks
up the solid pieces from the energy released from the bubbles created
by cavitation collapsing through them. This gives larger surface area to
the solid reactant for the reaction to proceed, thus increasing the rate of
reaction.
The intensity of sound decreases with distance on traveling through a
medium. The amplitude of signal is reduced by the spreading of the wave
in case of idealized materials, but in natural materials, further weakening
is there from scattering and absorption of sound. Scattering is the process
of reflection of the sound in different directions than its original direction
of propagation whereas absorption is the conversion of the sound energy
in other forms of energy. The combined effect of both these processes,
scattering and absorption, is called attenuation. Attenuation is the decay
rate of the wave as it propagates through some materials.
Attenuation can be used a tool for measurement to decide the factors
decreasing the ultrasonic intensity. The change in the amplitude of a
decaying plane wave can be expressed by the following expression:

A  A0 e  z

where A0 is the original (unattenuated) amplitude of a propagating sound

wave at some location, A is the reduced amplitude, when the wave has
traveled a distance z from the starting point, α is the attenuation coefficient
of the wave traveling in the direction of propagation, α is expressed in
Nepers/length (Np/m), and a Neper is a dimensionless quantity. The term
e is the exponential (or Napier’s constant) and it is equal to approximately
2.71828.
It can be converted to other unit, that is decibels/length by dividing it
by 0.1151, as decibel is a widely used unit.
The attenuation is generally proportional to the square of frequency of
sound. The values of attenuation are normally given for a single frequency,
or it is averaged over many frequencies. Actual value of the attenuation
coefficient for a material depends on the process of manufacturing of that
material.
Attenuation can be determined by evaluating the multiple backwall
reflections seen in a typical A-scan display. The number of decibels between
18 Sonochemistry

two adjacent signals is measured and this value is divided by the time
interval between these two signals. This provides an attenuation coefficient
in decibels per unit time Ut. This can be converted to Nepers/length as:

0.1151
 Ut
v
where v is the velocity of sound in m·s−1 and Ut is in decibels·s−1.

2.2 CAVITATION

Collapse of a transient bubble is the main source of some chemical and

mechanical effects of ultrasound. The collapsing bubble may act as a micro-
reactor, where drastic conditions are created instantaneously (Suslick et
al., 1986). This cavitation causes thermolysis of solute molecules to form
highly reactive radicals such as hydroxyl radicals and others. This active
species provides vigorous reaction conditions for the substrate in the reac-
tion media. If some solid is also present in the solution, ultrasonic radia-
tions causes solid disruption and, as a result, particle size of the solid is
reduced. This results in the increase of the total solid surface giving higher
rate of the reaction or greater yield of the products. No method other than
ultrasonic irradiation provides such an effect and therefore, ultrasonication
becomes a unique technique.

2.2.1 FACTORS AFFECTING CAVITATION

Cavitation under ultrasonic irradiation is a physical phenomenon, and

different factors are affecting cavitation. Some of the major factors that
affect cavitation are:

• Intensity of sonication
• Frequency of ultrasound
• Temperature
• Solvent
• Pressure and bubbled gas
Basic Concepts19

2.2.1.1  INTENSITY OF SONICATION

Intensity of sonication is directly proportional to the amplitude of ultra-

sonic source and, therefore, any increase in amplitude of vibration will
also increase the intensity of sonication. This will give an increased sono-
chemical effect. A minimum intensity of sonication is required for any
reaction so that the cavitation threshold can be accomplished. It only
means that it is always not necessary to use higher amplitudes. Higher
amplitudes of vibration should be avoided, unless necessary as it will lead
to deterioration of the source. It may also result in the agitation of liquid
rather than cavitation and also a poor transmission of the ultrasound in
liquid media.

2.2.1.2  FREQUENCY OF ULTRASOUND

The cavitation bubbles are easily produced at low ultrasonic frequen-

cies, but at higher ultrasonic frequencies, it is very difficult to produce
cavitation bubbles. Cavitation can be accomplished at higher frequency
by increasing the intensity of applied ultrasound so that voids are
formed by overcoming cohesive forces of liquid. Normally, more power
is required to induce cavitation at higher frequencies, because the cycle
of compression and rarefaction becomes too short that liquid molecules
cannot be separated. As a consequence, void is not formed and no cavi-
tation is there.

2.2.1.3 TEMPERATURE

It was observed that better cavitation is there at lower temperatures. The

use of higher temperatures of the solvent assists in disrupting some strong
solute–matrix interaction involving hydrogen bonding, dipole interac-
tion, and Van der Waal forces. It is also accompanied by faster diffusion
rates. The vapour pressure of the solvent increases with the increasing
temperature and these solvent vapours fill the cavitation bubbles. Here,
the effect of sonication is less intense, because the bubbles will collapse
less violently and therefore, one has to make a compromise between
cavitation and the temperature of the solvent to achieve better sono-
chemical reactions.
20Sonochemistry

2.2.1.4 SOLVENT

The selection of the solvent should be made with utmost care. Normally
water is used as a solvent, but sometimes less polar liquids (polar organic
solvents or a mixture of solvents) are also used. Two physical properties
of the solvent inhibit cavitation. These are surface tension and viscosity.
These two natural cohesive forces of liquids are acting within a liquid
(solvent) acting against the formation of voids to attain cavitation.

2.2.1.5  PRESSURE AND BUBBLED GAS

As the cavitation is produced by breaking the molecular forces, this is not

supported by high external pressure. In such cases, more ultrasonic energy
is required to induce cavitation. An enhanced sonochemical reaction will
be achieved at a particular external pressure with a specific reference.
Ultrasonication processes are favored by dissolved gas bubbles as they
can act a nucleus for cavitation. The gas should be continuously bubbled
into the solvent to obtain more cavitation. Generally inert monoatomic
gases such as helium, argon, neon and so forth are used for this purpose.
Cavitation is the basic mechanism involved in sonochemistry. The high
temperature and pressure generated during cavitation results in sonochem-
ical reactions and sometimes, even sonochemical switching. Some reac-
tions, which are difficult to be performed under normal conditions, can
be carried out under ultrasound exposure. An enhancement in the rate of
certain reactions is also observed along with improvement in yields, when
performed using sound waves.

REFERENCES

Achenbach, J. D. Wave Propagation in Elastic Solids; Elsevier: Amsterdam, 1990.

Auld, B. A. Acoustic Fields and Waves in Solids, 2nd ed.; Krieger Publishing: Florida, 1990.
Brekhovskikh, L. M. Waves in Layered Media, 2nd ed.; Academic Press: New York, 1980;
Vol. 1 & 2.
Chowdhury, P: Viraraghavan, T. Sci. Total Environ. 2009, 407, 2474-2492.
Crum, L. A. Phys. Today 1994, 47, 22–30.
Destaillats, H.; Hoffmann, M. R.; Wallace, H. C. Sonochemical degradation of Pollutants. In
Chemical Degradation Methods for Wastes and Pollutants: Environmental and Industrial
Applications; Tarr, M. A., Ed.; Marcel Dekker: New York, USA, 2003.
Einhorn, C.; Einhorn, J.; Luche, J. L. Synthesis 1989, 787–813.
Basic Concepts21

Flint, E. B.; Suslick, K. S. Science 1991, 253, 1397–1399.

Leighton, T. G. The Acoustic Bubble; Academic Press: London, 1994.
Luche, J. L. Comptes Rendus Series IIB 1996, 323, 203 and 307.
Pestman, J. M.; Engberts, J. B. F. N.; de Jong, F. Recueil des Travaux Chimiques des PaysBas
1994, 113, 533–542.
Putterman, S. J. Sci. Am. 1995, 272, 46–51.
Rose, J. L. Ultrasonic Waves in Solid Media; Cambridge University Press: Cambridge, 1999.
Suslick, K. S. Sci. Am. 1989, 260, 80–86.
Suslick, K. S. Science 1990, 247, 1439–1445.
Suslick, K. S.; Casadonte, D. J. J. Am. Chem. Soc. 1987, 109, 3459–3461.
Suslick, K. S.; Doktycz, S. J. Science 1990a, 247, 1067–1069.
Suslick, K. S.; Doktycz, S. J. Adv. Sonochem. 1990b, 1, 197–230.
Suslick, K. S.; Flannigan, D. J. Ann. Rev. Phys. Chem. 2008, 59, 659–683.
Suslick, K. S.; Hammerton, D. A.; Cline, Jr. R. E. J. Am. Chem. Soc. 1986, 108, 5641–5642.
Wood, R. W.; Loomis, A. L. Philos. Mag. 1927, 4, 414–436
CHAPTER 3

INSTRUMENTATION
GARIMA AMETA1
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]

CONTENTS

3.1 Introduction  ������������������������������������������������������������������������������  23

3.2 Ultrasonic Transducers  �������������������������������������������������������������  24
3.3 Gas-Driven Transducers  �����������������������������������������������������������  24
3.4 Liquid-Driven Transducers  �������������������������������������������������������  26
3.5 Electromechanical Transducers  ������������������������������������������������  27
3.6 Single-Crystal Ultrasonic Transducer  ���������������������������������������  35
3.7 Ultrasonic Cleaning Bath  ����������������������������������������������������������  39
3.8 Ultrasonic Probe  �����������������������������������������������������������������������  40
3.9 Flow Cell  ����������������������������������������������������������������������������������  41
3.10 Tube Reactor  �����������������������������������������������������������������������������  44
References  �������������������������������������������������������������������������������������������  44

3.1 INTRODUCTION

Richards and Loomis (1927) were the first to report chemical effects of
ultrasound. The concept of the present-day generation of ultrasound was
established and it dates back to the early 1880s, with the discovery of piezo-
electric effect by the Curies (Jacques Curie and Pierre Curie) (1880, 1881).
Crystalline materials showing this effect are known as piezoelectric mate-
rials. Ultrasonic devices consist of transducers (energy converters) which
are composed of these piezoelectric materials. An inverse piezoelectric
24Sonochemistry

effect is used in transducers, that is a rapidly alternating potential is passed

across the faces of piezoelectric crystal, which generates dimensional
changes and thus, converts electrical energy into sound energy.
The first ultrasonic transducer was a whistle developed by Galton (1883),
who was then investigating the threshold frequency of human hearing.

3.2  ULTRASONIC TRANSDUCERS

Ultrasonic sound can be produced by transducers which operate either by the

piezoelectric effector themagnetostrictive effect. The magnetostrictive trans-
ducers can be used to produce high-intensity ultrasonic sound in the range of
20–40 kHz for ultrasonic cleaning and other mechanical applications.
Ultrasonic medical imaging typically uses relatively higher ultrasound
frequencies in the range of 1–20 MHz. Such ultrasound is produced by
applying the output of an electronic oscillator to a thin wafer of piezoelec-
tric material.
Transducer is a device capable of converting one form of energy into
another. Ultrasonic transducers are designed to convert either mechanical
or electrical energy into high-frequency sound. These transducers are of
three types:

• Gas-driven
• Liquid-driven
• Electromechanical

3.3  GAS-DRIVEN TRANSDUCERS

These are, quite simple, in the form of whistles with high-frequency output.
The generation of ultrasound via whistles is more than a century old, when
a whistle-generating sound of known frequencies was produced. Galton
was able to determine that the normal limit of human hearing is around
18 kHz. This whistle was constructed from a brass tube with an internal
diameter of about 2 mm. It is operated by passing a jet of gas through
an orifice into a resonating cavity. On moving the plunger, the size of
the cavity could be changed to alter the pitch or frequency of the emitted
sound (Fig. 3.1).
Instrumentation25

FIGURE 3.1  Galton’s whistle.

When a solid object is passed rapidly back and forth across a jet of
high-pressure gas, it interferes with the gas flow. As a result, a sound is
produced having the same frequency at which the flow was disturbed. A
siren can be designed in such a way that the nozzle of a gas jet impinges
on the inner surface of a cylinder and as a result, there are a series of
regularly spaced perforations. When the cylinder is rotated, the jet of gas
emerging from the nozzle will rapidly alternate between facing a hole and
the solid surface. The pitch of the sound generated by this device depends
on the speed of rotation of the cylinder. Neither type of transducer has
any significant chemical application since the efficient transfer of acoustic
energy from a gas to a liquid is not possible. However, whistles are used
for the atomization of liquids.
An atomized spray from a liquid is produced by forcing it at a high
velocity through a small aperture. The disadvantage is blockage at the
orifice of low-viscosity liquids.
A gas-driven atomizer comprises an air or a gas jet, which is forced into
an orifice, where a shock wave is produced, on expansion (Fig. 3.2). As a
result, an intense field of sonic energy is focused between the nozzle body

FIGURE 3.2  Gas-driven atomizer.

26Sonochemistry

and the resonator gap. When any liquid is introduced into this region, it is
vigorously sheared into droplets by the acoustic field. Very small droplets
are produced having a low velocity.

3.4  LIQUID-DRIVEN TRANSDUCERS

This type of transducer is a liquid whistle. It generates cavitation via the

motion of a liquid rather than a gas. The material is forced at high velocity
by the homogenizer pump through an orifice (Fig. 3.3). It emerges as a jet
which impacts upon a steel blade. There are two ways in which cavita-
tional mixing can occur at this point and these are:

• Through the Venturi effect as the liquid expands rapidly into a

larger volume on coming out of the orifice
• Via the blade which is caused to vibrate by the process material
flowing over it

The activity of the blade can be optimized by controlling the relationship

between orifice and blade. The required operating pressure and throughput
are determined by using the orifices of different sizes and shapes. Velocity
can also be changed to achieve the necessary particle size or the degree
of dispersion. With no movement, only a pump is the moving part, none
others and therefore, such a system is rugged and durable. When a mixture
of immiscible liquids was forced through the orifice and across the blade,
extremely efficient homogenization is produced by cavitational mixing.

FIGURE 3.3  Liquid whistle.

Instrumentation27

3.5  ELECTROMECHANICAL TRANSDUCERS

Electromechanical transducers are of two types. These are either based

on the piezoelectric or the magnetostrictive effect. The most commonly
used transducers are piezoelectric transducers. These are generally used
to power the bath- and probe-type sonicator systems. Electromechanical
transducers are more commonly used as compared to mechanical trans-
ducers, in spite of the fact that these are relatively more expensive.

3.5.1  MAGNETOSTRICTIVE TRANSDUCERS

Magnetostriction can be explained as the corresponding change in length

per unit length produced as a result of magnetization. Any material exhib-
iting this phenomenon is magnetostrictive in nature and this effect is known
as magnetostrictive effect. The same effect can be reversed in the sense
that, if an external force is applied on a magnetostrictive material, there
will be a proportionate change in the magnetic state of the material. This
property was first discovered by Joule (1842) by noticing the change in
length of the material according to the change in magnetization. He called
this phenomenon as Joule’s effect. The reverse process is called Villari
effect or magnetostrictive effect. This effect explains the change in magne-
tization of a material due to the force applied. Joule effect is commonly
applied in magnetostrictive actuators whereas Villari effect is applied in
magnetostrictive sensors. This process is highly applicable as a transducer
as the magnetostriction property of a material does not degrade with time.
First is the case when no magnetic field is applied to the material under
this condition, there will be no change in the length along with the magnetic
induction produced. In the second case, the amount of the magnetic field
(H) is increased or decreased to its saturation limits (±Hs). This causes
an increase or decrease in the axial strain, respectively. The maximum
strain saturation and magnetic induction are obtained at the point when
the value of Hs is at its maximum. Beyond this limit, if the value of the
field increases, it does not bring any change in the value of magnetization
or field to the device. Thus, when the field value hits the saturation limit,
the values of strain and magnetic induction will increase moving from the
center outward.
28Sonochemistry

FIGURE 3.4  Magnetostrictive transducers (www.instrumentationtoday.com).

On the other hand, it the value of Hs is kept fixed and the magnitude of
force on the magnetostrictive material is increased, then the compressive
stress in the material will also increase on to the opposite side along with a
reduction in the values of axial strain and axial magnetization.
There are no flux lines present due to null magnetization. Figures 3.4(b)
and (d) have magnetic flux lines in a lesser magnitude, according to the
alignment of the magnetic domains in the magnetostrictive driver. Figures
3.4(a) and 3(e) also have flux lines in the same design, but its flow will
be in the opposite direction. The flux lines according to the applied field
Hs and the placing of the magnetic domains are shown in Figure 3.4(f).
These flux fields are measured using the principle of Hall effect or by
calculating the voltage produced in a conductor kept in right angle to the
flux produced. This value will be proportional to the input strain or force.
Such magnetostrictive materials transduce or convert magnetic energy
to mechanical energy and vice versa. Bidirectional coupling between the
magnetic and mechanical states of a magnetostrictive material provides a
transduction capability, which is used for both actuation and sensing devices.
Magnetostrictive transducers consist of a large number of nickel (or
some other magnetostrictive material) plates or laminations. These are
arranged in parallel with one edge of each laminate attached to the bottom
of a process tank or other surface undergoing vibration. A coil of wire is
placed around this magnetostrictive material. A magnetic field is produced
when a flow of electrical current is supplied through the coil of wire. This
Instrumentation29

magnetic field causes the distortion in length of the magnetostrictive mate-

rial, either it contracts or elongates; thus, a sound wave is introduced into the
fluid. Of course, it is the oldest ultrasonic transducer technology, and was
commonly used before the development of efficient and powerful piezoelec-
tric transducers. Magetostrictive transducers have low electrical efficiency
(50–60 %) as compared to the 95 % + electrical efficiency, offered by piezo-
electric transducers. This efficiency difference is still retained and there-
fore, most of the ultrasonic equipment used are piezoelectric transducers.
With the discovery of giant magnetostrictive alloys, interest in magne-
tostrictive transducer technologies has been renewed. Ultrasonic magne-
tostrictive transducers have been developed for surgical tools, underwater
sonar, chemical and material processing, magnetostrictive actuators, sensors,
dampers, and so on. With more reliable and larger strain and force, magne-
tostrictive materials have become commercially available such as Terfenol-
D Metglass. Wide range of applications for magnetostrictive devices can
be found in ultrasonic cleaners, active vibration, or noise control systems,
high-force linear motors, medical and industrial ultrasonics, positioners for
adaptive optics, pumps, and sonar. Apart from these, magnetostrictive trans-
ducers find some applications in hearing aids, high-cycle accelerated fatigue
test stands, razor blade sharpeners, mine detection, and seismic sources.
Magnetostrictive transducers were used to generate high-power ultra-
sound on an industrial scale. These are based on an effect, normally found
in some materials. It was observed that a metal like nickel reduces in size,
when it is placed in a magnetic field, but it returns back to its normal
dimensions on removal of the field. This property is known as magneto-
striction. When the magnetic field is applied as a series of short pulses to
a magnetostrictive material, then it starts vibrating at the same frequency.
Such transducers can be considered like a solenoid, where magnetostric-
tive material forms the core with copper wire winding.
The major advantages of these magnetostrictive systems are their dura-
bility, robustness, and very large driving forces, but these are also associ-
ated with some disadvantages. These are:

• There is an upper limit to the frequency range (~ 100 kHz), and

above this range, the metal cannot respond fast enough to the
magnetostrictive effect, and
• Its electrical efficiency is also less than 60 %, as there are signifi-
cant losses in the form of heat.
30Sonochemistry

Due to heat, normally magnetostrictive transducers have to be liquid

cooled. On the contrary, piezoelectric transducers are more efficient and
they operate over a relatively wider frequency range and therefore, these
are considered more suited for sonochemical studies, particularly under
laboratory conditions. Industries require heavy duty and continuous use of
transducers and that too at high operating temperatures, the magnetostric-
tive transducers are gaining their importance in large-scale operations.
Presently, nickel-based alloys (which were used previously) have almost
been replaced by more electrically efficient systems such as cobalt/iron
combinations, aluminum/iron with a small amount of chromium. An alloy
of the rare earths metals such as terbium and dysprosium with iron being
used these days, which can be produced in different forms such as rods,
laminates, tubes. A magnetostrictive transducer based on these materials can
generate relatively more power than a conventional piezoelectric transducer.

3.5.2  PIEZOELECTRIC TRANSDUCERS

The term piezoelectricity means electricity resulting from pressure. It is

derived from the Greek term piezō, which means to squeeze or press,
and electron, which means amber, an ancient source of electric charge.
The piezoelectricity effect was discovered by Curie brothers, Pierre and
Jacques Curie (1880; 1881). They observed that a quartz sample becomes
electrically charged, when subjected to compressive stress. Reverse is also
true, when an electrical voltage is applied to the quartz crystal, it causes a
deformation in the crystal.
When crystals of piezoelectric materials are deformed, compressed,
twisted or distorted by applying mechanical stress upon them, an electrical
charge will appear on their surfaces as a consequence. Here, mechanical
energy is converted into electrical energy. This process of transformation
of energy from one form to other is called the piezoelectric effect. This
provides a convenient transducer effect between electrical and mechanical
oscillations on the contrary, if an electrical oscillation is applied to these
materials, then they will respond in such mechanical vibrations which
produces ultrasound. This is the reverse piezoelectric effect.
Instrumentation31

3.5.2.1  PIEZOELECTRIC MATERIALS

There are many materials, both natural and man-made, that exhibit a range
of piezoelectric effects. Some of the naturally occurring piezoelectric
materials are:

• Berlinite (structurally identical to quartz)

• Quartz
• Cane sugar
• Rochelle salt
• Topaz
• Tourmaline
• Bone
• Silk
• Wood due to piezoelectric texture.

Examples of synthetic (man-made) piezoelectric materials including

ceramic are:

• Titanates of lithium, barium, bismuth, and lead

• Langasite
• Gallium orthophosphate
• Niobates of lithium, sodium, and potassium
• Bismuth ferrite
• Lithium tantalate
• Lead zirconate titanate[Pb(ZrxTi1−x)O3], with 0 ≤ x ≤ 1 more
commonly known as PZT
• Ba2NaNb5O5
• Pb2KNb5O15

Piezoelectric ceramic materials are ionically bonded and these consist

of atoms with positive and negative charges, called ions. These ions occupy
positions in specific repeating units (called unit cells). If a unit cell is
noncentro symmetric (means it lacks a center of symmetry), then the appli-
cation of a stress produces a net movement of the positive and negative ions
with respect to each other and this results in an electric dipole or polarization.
Polymers such as polyvinylidene fluoride and self-assembled diphe-
nylalanine peptide nanotubes are also good examples of piezoelectric
32Sonochemistry

FIGURE 3.5  Piezoelectric transducer.

materials. Piezoelectric polymers exhibiting piezoelectric effect have

some advantages like low acoustic impedance and softness.
Piezoelectric transducers are commonly used for the generation and
detection of ultrasound (Fig. 3.5). It utilizes materials exhibiting the piezo-
electric effect. Such materials show two effects. These are:
Direct Effect—When pressure is applied across the large surfaces of
the section, then a charge is generated on each face, which is equal in size
but have opposite signs. This polarity is reversed, if tension is applied
across the surfaces.
The Inverse Effect—If a charge is applied to one face of the section
and an equal but opposite charge is applied to the other face, then the
whole section of crystal will either expand or contract and it depends upon
the polarity of the applied charges. When rapidly reversing charges are
applied to a piezoelectric material, then some fluctuations in dimensions
will be produced. Such an effect can be harnessed to transmit ultrasonic
vibrations from the crystal section through the medium.
Quartz was a piezoelectric material used earlier in devices such as
underwater ranging equipment. It is not a good material for this purpose
because it is somewhat fragile and difficult to machine. Instead, modern
transducers are based on ceramics containing piezoelectric materials. As
these materials cannot be obtained as large single crystals and, therefore,
they are ground with binders and sintered under pressure at above 1000 °C
Instrumentation33

so as to form a ceramic. When these are cooled above their ferroelec-

tric transition temperature in a magnetic field, then the crystallites of the
ceramic are aligned. These transducers can be produced in different shapes
and sizes. At present, the most frequently employed piezoceramic mate-
rials contain PZT (P for plumbum, Z for zirconate and T for titanate).
The most common form of transducers is a disk with a central hole.
Normally, two such piezoelectric disks are clamped between metal blocks
in a power transducer. It serves both purposes: protecting the delicate crys-
talline material and also preventing it from overheating by acting as a heat
sink. The resulting sandwich provides a durable unit with doubled mechan-
ical effect. This unit is generally one half-wavelength long. (However,
multiples of this can also be used.) The peak-to-peak amplitudes generated
by such systems are of the order of l0–20 μ in general and they are elec-
trically efficient. Piezoelectric devices cannot be used for long periods at
high temperatures as the ceramic material will degrade under these condi-
tions and therefore, under these conditions, these devices must be cooled.
Such piezoelectric transducers are highly efficient (> 95 %) and can be
used almost over a range of ultrasonic frequencies from 20 kHz to some
MHz depending on the dimensions. These are good choice in medical
scanning, which requires frequencies above 5 MHz.
The degree of polarization depends upon the stress and tensile or
compressive stresses affecting the charge produced. Dipoles, present due
to the noncentro symmetric structure, form regions having a same align-
ment of neighbouring dipoles.
Initially, these domains are randomly oriented and there is no overall
polarization of the ceramic and therefore, no piezoelectric effect were
exhibited. These domains are subjected to poling, when heat and strong
DC field are applied causing the domains nearly aligned to the field to
grow at the expense of those at differing alignments. When these are
cooled to room temperature and DC field is removed, the domains are
locked resulting in an overall alignment. As a result, the material shows
piezoelectric behaviour.The piezoelectric materials used at present are
based mostly on sintered materials. These materials are beneficial because
they have high performance and are readily available in a large variety
of shapes. They most often occur as a disc or ring with metal electrodes
attached to their surfaces.
The thickness of the ceramic disc is e and it is subjected to a compres-
sive force F. The voltage that appears at the electrode terminals is:
34 Sonochemistry

V  g33  e  F / S

where g33 is the characteristic of the materials and S is the section of the
disc.
If thickness of the ceramic disc e is subjected to a continuous electrical
voltage V, the thickness of disc increases to e +Δe. The voltage and move-
ment of the disc are related by the following expression:

ee  d33V

where Δe = 0.5 μ per 1000 V of excitation and d33 = 500 10 – 12 m/V.

This effect is used particularly for thin ceramic multilayer stacks to
produce stacks, which create movement of several tens of microns under a
voltage of a few hundred volts up to 1000 V.
The relationships used to determine the thickness corresponding to a
particular frequency are:

Velocity of ultrasound
trasound in crys
cr tal material
Frequency =
Wavelengt
ngth

wavelength = 2 × thickness (t)

city (v)
Velocity
cit
Therefore, Frequency (f ) =
2t

v
or t=
2f

It means that thinner is the crystal, the higher will be the frequency.
A variety of ultrasonic transducers are manufactured depending on
its different applications. A proper attention has to be paid in selecting a
transducer based on the field of application. It is quite desirable to select
transducers that have the desired frequency, bandwidth and focusing to
optimize its capability for a particular application. Transducer is chosen so
as to either enhance the sensitivity or resolution of the system.
Instrumentation35

3.6  SINGLE-CRYSTAL ULTRASONIC TRANSDUCER

A piezoelectric transducer consists of:

• Piezoelectric crystal
• Electrical connections
• Backing materials
• Front layers
• Casing and so forth

The typical construction of a single-crystal transducer is shown in

Figure 3.6.

FIGURE 3.6  Components of the single-crystal transducer.

3.6.1  PIEZOELECTRIC CRYSTAL

A single-crystal ultrasonic transducer consists of a thin layer of piezo-

electric material sandwiched between epoxy, a glue-like backing material,
and a number of layers of facing. The active element is a piezoelectric- or
single-crystal material. This crystal converts electrical energy into ultra-
sonic energy. It also then receives back the ultrasonic energy and converts
it into electrical energy. The electrical energy pulse is generated from a
device such as a flaw detector.
36Sonochemistry

3.6.2  BACKING BLOCK

The backing material functions as a damping block. It is usually made

of an epoxy-like material, and is glued to the inner surface of the crystal.
It absorbs the reversed ultrasound waves that are transmitted to the back
of the crystal. The material must have the same acoustic impedance as
that of the crystal, in order to prevent an echo from a crystal/damping
interface from returning the energy back to the crystal and creating rever-
beration noise. This damping block is also known as the mechanical pulse
damper as it serves to limit the spatial pulse length by mechanically stop-
ping the ringing of the crystal. This helps in optimizing axial resolution.
Pulse damping also reduces the amplitude of ultrasound and, as a result, it
reduces the sensitivity of the transducer. Excessive pulse damping gives a
very wide frequency bandwidth. The backing is most commonly a highly
attenuative and very dense material. It is used to control the vibration of
the transducer crystal by absorbing the energy that is radiated from the
back face of the piezoelectric element. When the acoustic impedance
of the backing material matches with that of the piezoelectric crystal, it
resulted in a highly damped transducer with high-quality resolution. By
varying the backing material and in turn varying the difference in imped-
ance between the backing and the piezoelectric crystal, a transducer is
affected in a way that resolution may be relatively higher in signal ampli-
tude or sensitivity.

3.6.3  INSULATION RING

It is also known as a sidewall acoustic insulator. This part of a transducer is

made of the same material as that of the damping block. It serves primarily
to absorb energy generated from the sides of the crystal.

3.6.4  TUNING COIL

The crystal is a capacitative device forming part of the pulser and receiver
circuits. The tuning coil serves to offset the capacitative effect of the
crystal by removing residual electrical charges. The tuning coil, by dusting
off the excess electrical charges, improves the transmitting and receiving
functions of the transducer.
Instrumentation37

3.6.5  ELECTRICAL SHIELD

The electrical shield is an isolation barrier that serves to eliminate

unwanted, stray signals, also known as noise. It accomplishes this task
by detecting, isolating, and sending the stray signals to ground. Noise is
any unwanted vibration that interferes with the efficient production of a
sonographic image. All electrical outlets that are isolated carry spurious
vibrations and radiofrequency (RF) signals from respirators, eleva-
tors, typewriters, coffee grinders, etc., which are also connected to the
same circuit. Shields built into the imaging system can eliminate most
of this unwanted, low-level, electronic noise from being detected by the
very sensitive receiver. Any vibratory or RF noise that is detected by the
receiver will be displayed on the image and will degrade the overall image
quality. During the operation of the imaging system outside the ultrasound
department, external noise is most appreciable in a clinical environment,
such as in the intensive or critical-care units, where multiple electronic and
mechanical devices are operating in close proximity.

3.6.6  ELECTRIC CONNECTORS

These connectors serve to link the transducer electrically to the ultrasound

instrument. It is through these connectors that the electrical impulse ringing
the crystal is delivered, and the returning echoes are received. Generally,
these are a pair of very thin wires attached to each crystal. Highly sophisti-
cated ultrasound imaging probes may have more than 1000 crystals, each
one of which is attached to a separate pair of electrical connectors. These
wires are housed in the transducer cable that is attached to the probe port
on the imaging system.

3.6.7  MATCHING LAYERS

The primary objective in designing transducers for diagnostic ultrasound

imaging systems is to have highest sensitivity, penetration, optimal focal
characteristics, and best possible resolution all at low acoustic power
levels. It is made more difficult by the physical reality that the differ-
ence in acoustic impedance between the transducer crystal (PZT) and the
surface of the patient’s skin is significant. The magnitude of this difference
38Sonochemistry

in acoustic impedance effectively prohibits the adequate transmission of

ultrasound energy into a patient’s body so that an engineering solution has
been devised to overcome this obstacle to imaging.
A layer of material is placed that possesses an intermediate acoustic
impedance between the crystal surface and skin. Thus, a type of mechan-
ical transformer has been created, which steps down the impedance change
more gradually. Engineers have created a shoehorn that helps sound waves
slip into the body more easily by placing multiple layers of “transforming”
material in the probe face, thereby saving majority of the energies for
imaging deeper inside. These layers of transforming material are called
multiple matching layers.
The optimum thickness of this layer is one quarter of a wavelength.
Since a broad spectrum of frequencies exists in any given ultrasound
beam, the natural frequency is used to determine the appropriate wave-
length. Basically, a phase reversal occurs by using one-quarter wavelength
thickness, which increases signal performance and strengthens the wave-
front entering the body. The quarter wavelength matching layer design
provides increased sound transmission and reception.

3.6.8  ACOUSTIC COUPLANT

In addition to such matching layers, an acoustic gel is applied as a sonic

couplant to the patient’s skin. It also aids in reducing the large acoustic
mismatch between the transducer and the patient. The transducer face is
normally designed to have an impedance value midway between that of
the crystal and that of the patient’s skin, so that the gel is chemically engi-
neered to have impedance value halfway between that of the transducer
face and the skin. Both matching layers and acoustic couplant address the
physical challenges of insonating the human body.

3.6.9  WEAR PLATE

The main purpose of the wear plate is to simply protect piezoelectric trans-
ducer element from the environment. Wear plates are selected to generally
protect against wear and corrosion. In an immersion-type transducer, the
wear plate also serves as an acoustic transformer between the piezoelectric
transducer element and water, wedge, or delay line.
Instrumentation39

The front layer protects the piezoelectric element against external

stresses and other influences of the environment. It also functions as an
impedance matching layer with which the transfer of ultrasonic energy
to the target medium is optimized whereas the backing material functions
as a damping block to alter the resonance frequency of the piezoelectric
element. In addition to this, the unwanted ultrasonic waves reflected from
the back wall are also deleted. The electrical line is used to connect AC
or DC voltage supplies that are operated at the resonant frequency of the
piezoelectric element. Depending on the type of applications, other types
of transducers are also available.

3.7  ULTRASONIC CLEANING BATH

The simple ultrasonic cleaning bath is the most widely available and low-cost
source of ultrasonic irradiation in the chemical laboratory. It is possible to
use the cleaning bath itself as a reaction vessel, but it is not used commonly,
because of the problems associated with corrosion of the bath walls and
containment of any evolved vapours and gases. Therefore, normal use
involves the immersion of standard glass reaction vessels into the cleaning
bath, which provides a fairly even distribution of energy into the reaction
medium (Fig. 3.7). The reaction vessel does not need any special adaptation,

FIGURE 3.7  Ultrasonic cleaning bath.

40Sonochemistry

since it can be placed into the bath. An inert atmosphere or pressure can be
readily maintained during a sonochemical reaction. The amount of energy
reaching the reaction through the vessel walls is low, normally between 1
and 5 W·cm−2. Temperature control in commercial cleaning baths is gener-
ally poor and so the system may require additional thermostatic control.

3.8  ULTRASONIC PROBE

This allows acoustic energy to be introduced directly into the system rather
than relying on its transfer through the water of a tank and the reaction
vessel walls as done in the case of ultrasonic cleaning bath. The power of
such systems can be easily controlled and the maximum power ranges in
the order of several hundreds of W·cm−2. Ultrasonic probe system is more
expensive than the cleaning bath and it is slightly less convenient to use also
as special seals will be needed, if the horn is to be used in reactions requiring
reflux, inert atmospheres or pressures more or less than ambient conditions.
Ultrasonic probe is classified into two types:

1. Direct sonication
2. Indirect sonication

3.8.1  DIRECT SONICATION

It is the most common way to process a sample by inserting a probe

directly into a sample vessel. In this case, energy is transmitted from the
probe directly into the sample with high intensity and, as a result, sample
is processed quickly. The diameter of the probe’s tip decides the volume
of the liquid that can be effectively processed (Fig. 3.8). Smaller tip diam-
eters (microtip probes) deliver high-intensity sonication and the energy is
focused within a small, but concentrated area. On the contrary, larger tip
diameters can process larger volumes of liquids. Probes are offered with
either replaceable or solid tips. These tips are made of titanium.

3.8.2  INDIRECT SONICATION

It eliminates the need for a probe to come in contact with sample. This
technique is commonly described as a high-intensity ultrasonic bath. Here,
Instrumentation41

FIGURE 3.8  Probe system.

Note: WE is working electrode (platinum wire), RE is reference electrode (silver wire) and CE
is counter electrode (platinum flag).

the ultrasonic energy is transmitted from the horn, through the water, and
finally transmitted into a vessel or multiple sample tubes. Indirect sonica-
tion is most effective for small samples because most of the damages to
the sample such as loss, over temperature, etc. are eliminated. Pathogenic
or sterile samples are ideal for this method because aerosols and cross-
contamination are prevented. The cup horns deliver indirect sonication
and these are ideal for many applications, where the liquid sample is more
in volume (Fig. 3.9).

3.9  FLOW CELL

There are basically two systems. These are (i) continuous stirred tank reac-
tors (CSTRs) and (ii) continuous plug-flow reactors (CPFRs).
CSTRs are in principle equipped in the same way as batch systems
while in ultrasonic plug flow reactors, the reaction mixture flows through
one or more tubes. The setup is often designed as a loop in a mixed-flow
system (mixed-flow reactor with recirculation), that is, the sonoreactor is
placed in the loop linked to a conventional reactor containing the reac-
tion mixture. It allows for a repeated flow and the coupling of several
42Sonochemistry

FIGURE 3.9  Cup horn.

modules, which may be used for pre-reactions or secondary processes.

Several different types of plug-flow reactors are commercially available
for their use in laboratory.

• Flow-cell attachment for the probe system

• Liquid whistle homogenizer
• Tube with transducers bonded around the outside so that the metal-
forming tube becomes the ultrasonically vibrating source
• Bar arranged so that the vibrations are emitted radially from the
cylindrical face rather than the end. This bar is placed concentri-
cally in the center of a tube through which the medium flows.

Flow systems are best suited for processes requiring only a short soni-
cation time since the residence duration is short in this case (Fig. 3.10).
Instrumentation43

FIGURE 3.10  Flow cell.

They allow a high-processing throughput. It is known that the penetra-

tion depth of ultrasound decreases strongly with increasing frequency and,
therefore, batch reactors are not suitable at high frequency. In such cases,
a flow loop with or without recirculation can be used.
Immersible (submersible) transducers are designed for use in a heavy,
industrial environment. These transducers are enclosed in a water-proof
casing so that it can be immersed into a cleaning tank, used as part of
an online cleaning process, or used to trouble shoot, where cleaning of
hot spots is required. The hermetically sealed welded housings are manu-
factured from stainless steel. Plastic tanks are not suitable for ultrasonic
applications because they dampen the ultrasonic waves and reduce the
available ultrasonic cleaning power from anything between 60 and 90 %.
Submersible cleaning systems are powered by ultrasonic generators
that are housed in transducer packs, which are made of stainless steel.
These packs contain a double stack of individual high-efficiency ultra-
sonic transducers. They are ordinarily mounted to the bottom or the side
walls of an existing tank so that ultrasonic cleaning is better in the tank
in which these transducers are submerged. The transducer packs have
special mounting tabs with holes and these are so designed that they can
be attached permanently/temporary to the tank. Submersible systems are
available with single- or multiple-frequency ultrasonic systems.
44Sonochemistry

3.10  TUBE REACTOR

It is a modern method of continuous or intermittent inline ultrasonic

processing for any liquid material or food requiring ultrasonic treatment.
Single or multiple transducers are connected to custom clamps. These
clamps are designed in such a way that they fit into tubes or pipes of any
size, constructed of aluminum, stainless steel, or titanium. Unique multi-
frequency, multimode, and modulated (MMM) technology offers a highly
efficient transfer of ultrasonic energy to this metal pipe or tube. This pipe
or tube becomes a radiating element allowing internal or external material
treatment. Such assemblies will turn nearly any suitable pipe or tube into a
highly efficient ultrasonic reactor. Longer pipe sections may be used with
multiple clamps powered by one or more MMM generators.
Ultrasonic transducers are manufactured for a variety of applications.
These can be fabricated depending on the type of applications. However, a
proper transducer should be carefully selected for a particular application.
It is quite important to select transducers that have the desired frequency,
bandwidth, and focus to optimize inspection capability for an application.
Most often, the transducer is chosen to enhance the sensitivity or the reso-
lution of system.
Various instruments have been designed to carry out different sono-
chemical reactions. If such reactions are to be performed on industrial
scales, then these instruments need to be robust and more stable for a
longer period of time. Another aspect, which could be improved for sono-
chemical instrumentation, is their ease of use and handiness. It will make
sonochemistry a more developed branch of chemistry and gain a higher
status as a green chemical technology.

REFERENCES

Curie, J.; Curie, P. Comptes Rendus 1880, 91, 294–295.

Curie, J.; Curie, P. Comptes Rendus1881, 93, 1137–1140.
Galton, F. Inquiries into Human Faculty and Development; McMillan: London, 1883.
Joule, J. P. Ann. Electr. Magn. Chem. 1842, 8, 219–224.
Richards, W. T.; Loomis, A. L. J. Am. Chem. Soc. 1927, 49, 3086–3100.
www.instrumentationtoday.com.
CHAPTER 4

ORGANIC SYNTHESIS
CHETNA AMETA1, ARPIT KUMAR PATHAK2, P. B. PUNJABI3
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
3
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]

CONTENTS

4.1 Introduction  ������������������������������������������������������������������������������  45

4.2 Name Reactions  ������������������������������������������������������������������������  46
4.3 Phase-Transfer Catalysis  ����������������������������������������������������������  92
4.4 Sugars  ���������������������������������������������������������������������������������������  93
4.5 Ionic Liquids  �����������������������������������������������������������������������������  94
4.6 Heterocycles  �����������������������������������������������������������������������������  96
4.7 Sonochemical Switching  ��������������������������������������������������������  103
4.8 Miscellaneous  �������������������������������������������������������������������������  105
References  �����������������������������������������������������������������������������������������  108

4.1 INTRODUCTION

The application of ultrasound in organic synthesis has gained consider-

able momentum in recent years and as a consequence, several organic
transformations were effected using ultrasound. It has been observed that
46Sonochemistry

ultrasound reduces the requirement of higher reaction temperature, and

higher reaction rates can be achieved even under ambient conditions.
Two types of effects are mediated by ultrasound. These are chemical
and physical effects. Mainly physical rate acceleration plays a vital role,
when the quantity of bubbles is low. A specific effect is the asymmetric
collapse near a solid surface, forming microjets. Basically, this effect is
the major reason for using ultrasound effectively in cleaning, but it is
also responsible for rate enhancement in multiphasic reactions as surface
cleaning and erosion lead to improved mass transport.
Water is a desirable solvent for synthesis because water is low cost,
safe, and nontoxic. As the use of water as a solvent is limited to water-
soluble compounds, it excludes most of the organic, lipophilic substances.
A solution to this issue is to increase the solubility of organic compounds
by using a surfactant to form micelles, thus increasing contacts with the
reagent.
A number of name reactions have been carried out under sonochemical
conditions, but only some of these name reactions have been discussed in
this chapter. It does not mean that other reactions cannot be carried out
with ultrasound.

4.2  NAME REACTIONS

There are several name reactions that have been carried out under sono-
chemical conditions, and we have restricted our discussion only to some
of these name reactions in this chapter.

4.2.1  ALDOL CONDENSATION

An aldol condensation is a condensation reaction in organic chemistry

in which an enol or an enolate ion reacts with a carbonyl compound to
form a β-hydroxyaldehyde or β-hydroxyketone, followed by dehydration
to give a conjugated enone. Aldol condensations are important in organic
synthesis, because they provide a smooth way to form carbon–carbon
bonds (Carey and Sundberg, 1993). These reactions are usually catalysed
by strong acids or bases, and a variety of different Lewis acids have been
evaluated in this reaction (Reeves, 1966). Unfortunately, the presence of
a strong acid or base promotes the reverse reaction (Hathaway, 1987) and
Organic Synthesis47

this leads to the self‐condensation of the reacting materials to give the

corresponding byproducts in low yields (Nakano et al., 1987).
Based on the importance of the methylene moiety found in many natu-
rally occurring compounds and antibiotics and the use of aldols as precur-
sors for the synthesis of bioactive compounds, Khaligh and Mihankhah
(2013) proposed ultrasound‐assisted aldol condensation reaction for a wide
range of ketones with a variety of aromatic aldehydes using poly(N‐vinyl-
imidazole) as a solid base catalyst in a liquid–solid system. The catalyst
can be recovered by simple filtration and reused at least 10 times without
any significant reduction in its activity. The reaction is also amenable
to the large scale, making the procedure potentially useful for industrial
applications.

There are several advantages to the current methodology such as:

• Simple procedure as the use of poly(N‐vinylimidazole) as a solid

base catalyst does not require any inert or anhydrous conditions
• A green process because PVIm is environmentally benign
• Atom economical
• Avoids the occurrence of adverse-side reactions because PVIm can
facilitate the aldol condensation under mild and neutral conditions
and therefore eliminate any side‐reactions resulting from strong
basic conditions
48Sonochemistry

• Catalyst can be conveniently recovered and reused without any

significant impact on its activity

The current method represents an attractive alternative for the prepara-

tion of chalcones.
Cravotto et al. (2003) studied the aldol reaction under high-intensity
ultrasound (HIU). HIU was employed to reinvestigate the aldol reaction
in water. A number of aldols that would eliminate or form side products
under conventional conditions were isolated in good yields within minutes
under ultrasonics (Table 4.1).
According to Table 4.1, we can see that the results are highly reproduc-
ible because the sonochemical parameters were rigorously controlled.
TABLE 4.1  Aldol Condensation under Ultrasonics.

4.2.2  BAYLIS–HILLMAN REACTION

The Baylis–Hillman reaction is a carbon–carbon bond-forming reaction

between the α-position of an activated alkene and an aldehyde, or gener-
ally a carbon electrophile. This reaction provides a densely functional-
ized product (e.g. functionalized allyl alcohol in the case of aldehyde as
the electrophile) employing a nucleophilic catalyst, such as tertiary amine
and phosphine (Baylis and Hillman, 1972). Roos and Rampersadh (1993)
observed that the rate of reaction of 1,4-diazabicyclo [2. 2. 2] octane
(DABCO) catalysed coupling of aldehydes with methyl acrylate increases
by the application of ultrasound.
Organic Synthesis49

In Baylis–Hillman reaction, several aldehydes (aromatics as well as

aliphatics) react with different α,β-unsaturated reactants. The effect of
ultrasound radiation on the Baylis–Hillman reaction has been studied by
Fernando et al. (2002).

where R = H, 4–OCH3, 3,4–OCH2O, 4–Cl.

The utilization of ultrasound radiation in the reaction with several alde-
hydes (aromatics and aliphatics) and different α,β-unsaturated reactants
has also been described by Coelho et al. (2002). The utilization of ultra-
sound sources augmented the reaction rate and the chemical yields for
all aldehydes. The use of ultrasound with two different catalysts (tri-n-
butylphosphine and DABCO) was also investigated. It was demonstrated
that DABCO is relatively effective for catalyzing a Baylis–Hillman reac-
tion under the influence of ultrasound than tri-n-butylphosphine.

where R = CO2CH2, COCH2, CN.

A convenient protocol was developed for the synthesis of the Baylis–
Hillman adducts in the presence of weak lewis base and l-proline at room
temperature under ultrasound irradiation (Mamaghani and Dastmard,
2009). This method provides products in good to high yields (65–90 %)
and that too in reasonable reaction times.
A catalyst-free one-pot four-component methodology for the synthesis of
2H-indazolo[2,1-b]phthalazine-triones under ultrasonic irradiation at room
temperature has been described by Shekouhy and Hasaninejad (2012). They
50Sonochemistry

used 1-butyl-3-methylimidazolium bromide [BMIM]Br, as a neutral reac-

tion medium. A broad range of structurally diverse aldehydes (aromatic alde-
hydes bearing electron-withdrawing and/or e­ lectron-releasing groups as well
as heteroaromatic aldehydes) were used successfully, and the corresponding
products were obtained in good to excellent yields without any byproduct.
Pourabdi et al. (2016) synthesized various derivatives of thiopyrano[4,3-
b]pyran structure via a multicomponent procedure starting from tetra-
hydro-4H-thiopyran-4-one, aromatic aldehydes and malononitrile. This
reaction takes place using catalytic quantities of LiOH·H2O in one pot
under ultrasonic conditions and in an ethanolic medium.

4.2.3  BENZOIN CONDENSATION

The benzoin condensation is a reaction between two aromatic aldehydes,

particularly benzaldehyde. The reaction is catalysed by a nucleophile such
as cyanide anion or an N-heterocyclic carbene. The reaction product is
an aromatic acyloin with benzoin as the parent compound (Adams and
Marvel, 1941).
Benzoin condensation is an important method for the formation of
carbon–carbon bonds starting from aldehydes giving α-hydroxycarbonyl
compounds, which are important building blocks for the synthesis of
natural and pharmaceutical compounds (Iwamato et al., 2006). After the
first report by Wohler and Liebig, who used cyanide as a precatalyst in
1832 (Wohler and Liebig, 1832), various other catalysts have been used to
promote the benzoin condensation reaction effectively.
There is still a need to introduce novel methods to permit better selec-
tivity under milder conditions and with easy work-up procedures. Ultra-
sonic irradiation has been considered as a clean and useful protocol in
organic synthesis during the last few decades, as the procedure is more
convenient compared with conventional methods.
Organic Synthesis51

Kinetics of the benzoin condensation of benzaldehyde in the pres-

ence of KCN as the catalyst in water and in ethanol–water binary solu-
tions was investigated without sonication and under ultrasound at 22 kHz
(Hagu et al., 2007). A statistically significant 20 % decrease in the rate was
observed in water. The retardation effect of ultrasound gradually decreases
up to 45 wt.% ethanol content. It is an evidence of ultrasonic retardation
of reactions. Ultrasound can disturb solvation of the species in the solu-
tion. Sonication hinders the reaction whereas perturbation of the solvent
stabilization of the reagents accelerates the reaction.
A new method for the benzoin condensation has been proposed
by Estager et al. (2007) with imidazolium-based ionic liquids (ILs) as
solvents/catalysts. The use of a 30-kHz ultrasonic irradiation as activa-
tion method provided a quantitative yield of benzoin in 1-octyl-3-methyl-
imidazolium bromide without degrading the ionic medium, which can be
reused at least three times with no loss of activity.
Safari et al. (2015) developed a rapid, highly efficient and mild green
synthesis of benzoin using substituted benzaldehyde catalysed by KCN
and imidazolium salts in EtOH/H2O under ultrasonic activation.

The products were obtained in good yields and high purity within short
reaction times with N,N-dialkylimidazolium salts, which were found to be
more effective precatalysts at room temperature for benzoin condensation
in comparison to corresponding cyanide ion in heating method. This is a
simple method affording benzoin derivatives at room temperature.
The imidazolium salts efficiently catalyse the benzoin condensation
of aldehydes in the presence of a base. These tricationic and dicationic
imidazolium salts show considerable catalytic potential, when compared
with monocationic imidazolium salts and toxic cyanide anions. Safari
et al. (2015) also made use of tricationic imidazolium salts in the acyloin
condensation under ultrasound. This afforded benzoin derivatives at room
temperature in short reaction times with high yield and purity. It can be
52Sonochemistry

used as a replacement for conventional thermal synthetic methodology,

allowing rapid access for the synthesis of natural and pharmaceutical
compounds.

4.2.4  BIGINELLI REACTION

Due to increasing environmental consciousness, a challenge exists for a

sustainable clean procedure avoiding the use of harmful organic solvents,
or it will be still better, if no solvent is used at all. Sonochemistry has
offered such a versatile and environmentally benign condition for a large
variety of syntheses and emerged as a new trend in organic chemistry.
This has led to multistep synthetic strategies that can produce better
yields; however, it lacks the simplicity of the original one-pot Biginelli
protocol.
The Biginelli reaction is a multicomponent reaction that gives
3,4-dihydropyrimidin-2(1H)-ones from ethyl acetoacetate, an aryl alde-
hyde (such as benzaldehyde) and urea. This reaction was developed by
Biginelli (1893). The reaction can be catalysed by Bronsted acids and/
or by Lewis acids such as copper(II) trifluoroacetate hydrate and boron
trifluoride (Kappe, 1993).
Li et al. (2003) reported that the condensation of aldehydes, β-keto
esters and urea catalysed by NH2SO3H in ethanol results in the formation
of dihydropyrimidinones with high yields under ultrasound irradiation.
Liu and Wang (2010) reported an efficient synthesis of novel
4-(2-phenyl-1,2,3-triazol-4-yl)-3,4-dihydropyrimidin-2(1H)-(thio)ones
from 1,3-dicarbonyl compounds, 2-phenyl-1,2,3-triazole-4-carbaldehyde
and urea or thiourea using samarium perchlorate [Sm(ClO4)3] as a catalyst
in water bath of the ultrasonic cleaner at 75–80 °C. The main advantages
of this method are milder conditions, shorter reaction times, and higher
yields than that of conventional methods.
Singhal et al. (2010) reported an efficient, simple, and environmen-
tally clean synthesis of 3,4-dihydropyrimidinones in excellent yields
in the presence of water without additional solvent/acid catalyst under
conventional heating, and microwave irradiation/ultrasound. In this
reaction, a small flask containing aldehyde (2 mmol), urea (2 mmol),
β-dicarbonyl compound (2 mmol), and water (3–4 drops) was sonicated
at 25 kHz.
Organic Synthesis53

where Ar = Ph, 4–CH3C6H4, CH3OC6H4, NO2C6H4, ClC6H4; 2–ClC6H4,

Pyridyl, Furyl; C6H5CH=CH, C6H5; R = OEt, OMe, Me.
Mandhane et al. (2010) reported an environmentally benign aqueous
Biginelli protocol for the synthesis of substituted 3,4-dihydropyrim-
idin-2(1H)-ones using thiamine hydrochloride as a catalyst under ultra-
sound. These reactions proceed efficiently in water in the absence of an
organic solvent. Utilization of ultrasound irradiation, simple reaction
conditions, isolation, and purification makes this manipulation very inter-
esting from an economic and environmental perspective.

Biginelli reaction is carried out by simply heating a mixture of all

the three components (aldehyde, urea or thiourea and ethyl acetoacetate)
dissolved in ethanol with a catalytic amount of HCl at reflux temperature.
This method has some drawbacks such as low yields (20–40 %), particu-
larly, when substituted aldehydes are used. It is also accompanied by the
loss of acid-sensitive functional groups during this reaction. Kakaei et al.
(2015) reported an ecofriendly method for the synthesis of dihydropyrim-
idinones under ultrasonic irradiation in the presence of holmium chloride
hexahydrate as a catalyst under solvent-free conditions. The reactions
were completed within 2–4 h with 87–96 % yields.

Dhawanpalli et al. (2015) described the Biginelli reaction for

the synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives under
54Sonochemistry

solvent-free conditions (involving cyclocondensation) with ultrasound

irradiation as the energy source. This synthesis was performed in the pres-
ence of polymer nanocomposite polyindole-Fe as the catalyst. The reac-
tions were compared with the classical Biginelli reaction conditions. This
method has the advantage of excellent yields (82–92 %).

Girase et al. (2016) reported an efficient ultrasound promoted synthesis

of 3,4-dihydropyrimidin-2(1H)-one/thione by using aluminium sulphate as
a catalyst for aromatic aldehydes, 1,3-dicarbonyl compounds, and urea or
thiourea in PEG as a reaction solvent. It was compared with the classical
Biginelli reaction conditions. This new procedure is simple, rapid and high
yielding. The catalyst also exhibited a remarkable reactivity and is reusable.

4.2.5  BLAISE REACTION

Blaise reaction is an organic reaction that forms a β-ketoester from the

reaction of zinc metal with α-bromoester and a nitrile (Rao et al., 2008).
The reaction was first reported by Edmond Blaise in 1901 (Blaise, 1901).
The final intermediate is a metaloimine, which is then hydrolysed to give
the desired β-ketoester (Cason et al., 1953).
Organic Synthesis55

Sonication is a very important tool for the formation of β-amino-α,β-

unsaturated esters. These are produced by Blaise reaction of nitriles, zinc
powder, zinc oxide, and ethyl bromoacetate in THF in the presence of
ultrasound (Lee and Chang, 1997).

Where R = Alkyl, Ar, Bn.

2,3-o-Isopropylidene-d-glyceraldehyde was selected as the initial
compound, which is a chiral material. Naturally occurring (s)-(+)-­
dihydrokavain was synthesized by a procedure that involves a sonochem-
ical blaise reaction as the key step (Wang and Yue, 2005). The absolute
configuration of (s)-(+)-dihydrokavain was demonstrated for the first time
by total synthesis from a chiral source. Its opposite enantiomer, (r)-(–)-
dihydrokavain, was also synthesized after the inversion of the chiral center
in a Mitsunobu reaction.

4.2.6  CANNIZZARO REACTION

Cannizzaro reaction was named after its discoverer Stanislao C ­ annizzaro.

It is a chemical reaction that involves the base-induced disproportion-
ation of an aldehyde lacking a hydrogen atom in the alpha position
(Cannizzaro, 1853).
Ultrasound accelerates the Cannizzaro reaction of p-chlorobenzaldehyde
under phase-transfer conditions. Three phase-transfer catalysts (PTCs),
benzyltriethylammonium chloride (TEBA), aliquat, and 18-crown-6, were
tested by Polackova et al. (1996), out of which benzyltriethylammonium
56Sonochemistry

chloride (TEBA) was found to be the most effective. Ferrocene carbal-

dehyde and p-dimethylaminobenzaldehyde gave 1,5-diaryl-1,4-pentadien-
3-ones as the main product under similar conditions (TEBA as the catalyst).
Entezari and Shameli (2000) reported their observations on the
­Cannizzaro reaction under ultrasonic waves. The reaction of benzalde-
hyde with potassium hydroxide was chosen as the reference reaction.
The kinetics of the reaction was followed by the amount of benzoic acid.
They also discussed the effect of parameters such as temperature, PTC,
aldehyde, frequency and other possible variables. As the PTC depends
strongly on mass transfer between two phases, ultrasonic waves do have
a greater efficiency of interface mixing than conventional agitation. The
results showed that an ultrasonic wave of 20 kHz dramatically accelerates
the reaction (Table 4.2).
Thus, there is a high potential for increasing the efficiency of this
kind of heterogeneous reaction using high-power ultrasonic waves. By

TABLE 4.2  Cannizzaro Reaction with and without Sonication.

Aldehyde Product yield (%)
Conventional 900 kHz 20 kHz
Benzaldehyde 33.3 36.2 62.9
p-Chlorobenzaldehyde 47.5 70.4 94.6

optimizing the conditions, it is possible to use ultrasonic waves instead

of PTC. A combination of the PTC and ultrasonic waves could be more
favorable for the reaction.
Abimannan and Rajendran (2016) synthesized 1-(isopentyloxy)-4-nitro-
benzene under ultrasound-assisted liquid–liquid PTC. The reaction rate of
1-chloro-4-nitrobenzene with isoamyl alcohol catalysed by PTC combined
with ultrasonic irradiation was investigated. Various process parameters
(stirring speed, catalyst concentration, base concentration, different cata-
lysts, and solvents, volume of isoamyl alcohol, inorganic salts and temper-
ature) have been optimized. Apparent reaction rates were observed to obey
the pseudo-first-order kinetics with respect to the 1-chloro-4-nitrobenzene.
The reaction rate was found to increase with increase in temperature, cata-
lyst amount, base concentration, and inorganic salts.
Chen et al. (2016) reported a novel three-component coupling
reaction of substituted 2-aminobenzimidazoles, aromatic aldehydes,
Organic Synthesis57

and 1,3-­
cyclohexadiones under ultrasonic irradiation to synthesize
benzimidazo[2,1-b]quinazolin-1(1H)-ones.

Ultrasound wave causes acoustic cavitations to trounce molecular

attractive forces and to promote molecular mixing, which increases the
intimate contact between different molecules to form highly reactive
species. They studied a mild reaction condition to provide a simple access
toward functionalized benzimidazo-quinazolinones by one-pot multicom-
ponent reaction. Substituted 2-aminobenzimidazoles were synthesized
via aromatic nucleophilic substitution of o-nitrofluoroarenes with various
amines, followed by nitro reduction to furnish diamines. The diamines
on cyclization with cyanogen bromide gave 2-aminobenzimidazoles. All
these transformations were performed under ultrasound to give better
yields in shorter reaction time compared to those under conventional
heating conditions.

4.2.7  CLAISEN–SCHMIDT CONDENSATION

The α, β−unsaturated ketones are very common in natural product chem-

istry, which are usually synthesized via Claisen–Schmidt condensation
of aromatic aldehydes with ketone using reagents (such as NaOH, KOH,
Ba(OH)2) as catalyst by heating method. However, there were always
some problems due to long reaction time, or difficult workup. Fuentes
et al. (1987) have reported that the sonochemical synthesis of chalcones
catalysed by an activated Ba(OH)2 catalyst can be carried out with very
good yields. This sonochemical process took place at room temperature
58Sonochemistry

and with a lower catalyst weight and reaction time than the thermal
process.
To test the selectivity of the reaction, Li et al. (1999) carried out the
reaction in the ratio (furfural/cyclohexanone) of 2:1 and 1:1.1. Both the
reactions provided the same product, α,α′-bisfurfurylidene cyclohexa-
none, and no α-furfurylidene cyclohexanone was obtained. Claisen–
Schmidt condensation of furfural with acetophenones at room temperature
results in 78–96 % yields of chalcones within 4–12 min under ultrasound.
The synthesis of α,α′-bisfurfurylidene cycloalkanones was carried out in
68–96 % yields for Claisen–Schmidt condensation of furfural with cycloal-
kanones catalysed by KOH under ultrasound irradiation for 30–50 min in
anhydrous ethanol at 20–50 oC.

It involves condensation of an aromatic aldehyde with an aliphatic alde-

hyde or ketone in the presence of a base or an acid to form α,β-unsaturated
aldehyde or ketone. Here, activated barium hydroxide is used as a catalyst.
It is nontoxic, easy to handle, low cost, and high catalytic activity (Pinto
et al., 2000).
Li et al. (2002) reported pulverized KOH-catalysed condensation of
aromatic aldehydes with acetophenone to afford the corresponding chal-
cones under sonication. This synthesis of chalcones was carried out in
good yields (52–97 %).
Organic Synthesis59

In the absence of ultrasound, the mixture of acetophenone and KOH

has to be stirred at 26–30 °C for 5 h to produce 1,3-diphenylpropenone
in 79 % yield, while the reaction was carried out with 80 % yield at room
temperature for 25 min under ultrasonication. In the classical reaction
catalysed by NaOH in 50 % aq. EtOH, 59 % yield was obtained, while the
ultrasound procedure gave 91 % yield.
It is worth noting that the size of cycloalkanones and the electronic
effect of substituents in benzene ring of aceophenones seems to have no
effect on the yield of the products.
The condensation of cyclopentanone or cyclohexanone with a variety
of aromatic aldehydes was improved using ultrasound. Catalysed by
KF-Al2O3 in MeOH at 30–40 °C for 0.5–2.5 h, α,α′-bis(substituted benzyl-
idene), cycloalkanones were prepared in good yields (Mahata et al., 2002).

In the classical condensation of aromatic aldehydes with cycloalka-

nones catalysed by NaOH(aq.) in 95 % EtOH, products were obtained in
moderate yields (40–50 %), whereas ultrasound method gave 80 % to 90 %
yield. KF-Al2O3-catalysed condensation of cyclopentanone with furfural
gave higher yield (96 %) than that of the procedure catalysed by KOH
(85 %).
Meciarova et al. (2002) reported that Al2O−3, Ba(OH)−2, and K2CO3− cata-
lysed condensation of aromatic aldehydes with vinyl acetate yielded inter-
esting substituted cinnamic aldehydes, but the results were not found to be
60Sonochemistry

reproducible and even with application of ultrasound, only 10–23 % yields

of the product were isolated.
Calvino et al. (2005) synthesized chalcones under sonochemical irra-
diation by Claisen–Schmidt condensation between benzaldehyde and
acetophenone. Two basic activated carbons (Na and Cs-Norit) have been
used as catalysts. A significant enhancement in the yield was observed,
when the carbon catalyst was activated under ultrasonic waves. This green
method (combination of alkaline-doped carbon catalyst and ultrasound
waves) has been applied for the synthesis of several chalcones with excel-
lent activities and selectivity.
A comparative study under nonsonic activation showed that the yields
are lower in silent conditions, which confirms that the sonication exerts a
positive effect on the activity of the catalyst. Cs-doped carbon gives excel-
lent activity for this type of condensation. Cs-Norit carbon catalyst can
compete with the traditional NaOH/EtOH, when the reaction was carried
out under ultrasounds.
1,5-Diarylpenta-2,4-dien-1-ones were also synthesized with ultrasound
irradiation in the presence of activated barium hydroxide as the catalyst.

Activated barium hydroxide has also been used as a catalyst for the
synthesis of 1,5-diarylpenta-2,4-dien-1-ones under ultrasound exposure
(Zhang et al., 2007). This methodology offers several advantages over
other conventional methods like simple procedure with excellent yields,
shorter reaction time, and milder conditions. 1,5-Diarylpenta-2,4-dien-
1-ones are important intermediates and raw materials, which are widely
used as precursors to different drugs, nonlinear optical materials, and also
for their biological activities. Conventional synthesis of 1,5-diarylpenta-
2,4-dien-1-ones takes a longer time (20 h) and that too with poor yields
(15–81 %) via Claisen–Schmidt condensation. The time of this condensa-
tion reaction was reduced to 180–420 min, in the presence of ultrasound
(Batovska et al., 2007).
Organic Synthesis61

Ramesh et al. (2016) reported a methane sulphonic acid-catalysed

efficient protocol for the synthesis of 2-hydroxy chalcones. Methane
sulphonic acid was found to be an efficient catalyst for the synthesis
of 2′-hydroxy chalcone via aldol condensation of 2-hydroxy acetophe-
none and substituted benzaldehyde. This catalyst also worked well with
electron-donating as well as electron-withdrawing group present in the
aromatic ring.

4.2.8  CURTIUS REARRANGEMENT

The Curtius rearrangement is the thermal decomposition of an acyl azide to

an isocyanate with loss of nitrogen gas (Curtius, 1890 and 1894). ­Isocyanate
then undergoes attack by a variety of nucleophiles, to yield a primary
amine, carbamate, or urea derivative (Kaiser and Weinstock, 1988).
An efficient conversion of Nα-[(9–fluorenylmethyl)oxy]carbonyl
(FMOC) amino acid azides to the corresponding isocyanates was
carried out using ultrasound (Babukantharaju and Tantry, 2005). The
Curtius rearrangement was observed using acid azides in toluene solu-
tion as well as solid powder at room temperature. All the synthesized
isocyanates have been obtained as crystalline solids. Coupling of isocy-
anates with amino acid methyl ester hydrochloride salts in the presence
of N-methylmorpholine (NMM) resulted in FMOC-protected dipeptidyl
urea esters.
Hemantha et al. (2009) reported a facile one-pot procedure for the
synthesizing urea-linked peptidomimetics and neoglycopeptides via
Curtius rearrangement. They employed Deoxo-Fluor and TMSN3 as
efficient catalysts, which avoid the isolation of acyl azide and isocy-
anate intermediates. This reaction was carried out under ultrasound
irradiation.
62Sonochemistry

4.2.9  DIELS–ALDER REACTION

The Diels–Alder reaction is a reaction (specifically, a [4 + 2] cycload-

dition) between a conjugated diene and a substituted alkene, to form a
substituted cyclohexene system. It was first described by Diels and Alder
(1928; 1929). Ultrasonic irradiation provides efficient promotion of the
reaction between substituted buta-1,3-dienes with substituted 2,3-dime-
thoxycyclohexadiene-1,4-diones in a Diels–Alder cycloaddition, which
affords a variety of bicyclo[4.4.0] fused-ring systems just in one step with
high yields. Sonochemistry provides an increase in yield over a much
shorter period than the conventional methodology for reactions performed
in benzene, toluene, and methylene chloride. It provides a convenient
route to naphthaquinols and lonapalene, a 5-lipooxygenase inhibitor in the
treatment of psoriasis (Javed et al., 1995).
Ultrasound acts either by mechanical effects (as a very efficient stir-
ring), by the generation of radicals acting as catalysts or via the in situ
formation of molecules, which themselves act as catalysts. Ultrasound
does not affect a cycloaddition reaction itself but it promotes in situ gener-
ation of a hydrogen halide acting as the catalyst. Thus, sonochemical effect
is indirect in this case.
The yield of a silent (conventional) reaction is n% in a specific period
of time, while the yield of this reaction is m% in the presence of ultrasound
and m/n ratio is > 1, then this is considered as a sonochemical effect. Inter-
estingly, this m/n ratio depends on n. It only means that if a silent reaction
(especially a heterogeneous reaction) is performed without stirring or an
inefficient stirring or if this reaction is carried out in the absence of a cata-
lyst (which can be generated by ultrasound), it is expected that there will
be some sonochemical effect.
Such a sonochemical effect has been observed on Diels–Alder reac-
tion by Caulier and Reisse (1996). They demonstrated a clear-cut effect
of ultrasound on a Diels–Alder reaction in various halogenated solvents.
Reactions were performed in strictly homogeneous solutions, and
Caulier and Reisse observed such sonochemical effects in CHCl3, CH2Cl2,
and CH2Br2. The occurrence of these effects in halogenated solvents only
suggests that solvent molecules take a predominant part in the sonochem-
ical pathway. Additional experiments have been performed in dichloro-
methane to confirm this assumption. A possible explanation could be that
direct sonication of halogenated molecules by a titanium horn leads to
Organic Synthesis63

the formation of Lewis acids (TiCl4, TiBr4) known to catalyze this Diels–
Alder reaction.
A sealed tube was immersed in a thermostated cleaning bath in order
to avoid direct contact between the solution and the ultrasonic transducer
in a control experiment. In these conditions, increases of rate and stereose-
lectivity were still observed, precluding the hypothesis of an artifact due to
an in situ generation of a Lewis acid derived from the titanium horn. Then,
a set of experiments was performed in the presence of radical scavenger
such as 2,2-diphenyl-1-picrylhydrazyl.
A hetero Diels–Alder reaction between 1-dimethylamino-1-azadienes
and electron-deficient dienophiles under ultrasound irradiation has been
described by Villacampa et al. (1994). Other advantages of these sonicated
reactions are lower reactions times, increased yields and in some cases,
even a decrease in some side reactions.

The Yb(OTf)3 catalysed formal aza-Diels–Alder (or Povarov) reaction of

cyclopentadiene and 1,3-cyclohexadiene with in situ generated N-arylimines
under conventional/ultrasonic techniques (Pelit and Turgut, 2014).
64Sonochemistry

4.2.10  HECK REACTION

Heck reaction (also called the Mizoroki–Heck reaction) is the chemical

reaction of an unsaturated halide (or triflate) with an alkene in the presence
of a base and a palladium catalyst (or palladium nanomaterial-based cata-
lyst) to form a substituted alkene (Mizoroki et al., 1971; Heck and Nolley,
1972; Drahl, 2010).
Heck reaction involves palladium-catalysed coupling of alkenes/
alkynes with aryl and vinyl halides. Deshmukh et al. (2001) reported Heck
reaction at an ambient temperature (30 °C) with enhanced reaction rate
(1.5–3 h) via the formation of Pd–biscarbene complexes and stabilized
clusters of zero-valent Pd nanoparticles in ILs under ultrasonic irradiation.
Generally, such reactions are carried out in polar solvents such as dimeth-
ylformamide (DMF) and required longer reaction times (8–72 h) and that
too at higher temperatures (80–140 °C).

Where R = H, 4-OMe, 4-Cl; R1 = COOMe, COOEt, Ph.

It was found that the formation of Pd–biscarbene complex and its
subsequent sonolytic conversion to a highly stabilized cluster of zero-
valent Pd nanoparticles increased the rate of reactions.
Heck reaction of iodobenzene with methyl acrylate was initially
studied in the presence of PdCl2 in water. A reaction mixture containing
iodobenzene, methyl acrylate, PdCl2, Na2CO3 (as base), and tetrabutylam-
monium bromide (TBAB) was stirred in 3 mL of water at 25 °C for 4.5 h.
(E)-Methyl cinnamate was obtained with a very low yield of only about
10 %. Observing the fact that ultrasonic irradiation may promote organic
Organic Synthesis65

reactions, Zhang et al. (2006) carried out the Heck reaction in water under
ultrasonic irradiation but without heating. They observed that this reac-
tion can be carried out in aqueous solution at ambient temperature with
good yields (86 %). This was attributed to in situ formation of palladium
nanoparticles, which can be recycled again.

Where R = H, OMe, Cl, Br, OMOM, NHCOMe or NO2; R1 = I, CHO, or

H; R2 = I or H; X = COOMe, COOEt, COOH, CN or Ph.
The ultrasound-promoted Heck reaction was also carried out under
mild and environmental-friendly conditions by An et al. (2011). It gave
significantly high yield (96 %) and products with high regioselectivities
and stereoselectivities (E/Z > 99:1). They used acrylamide and acrylic acid
for the first time as substrates in the ultrasound-promoted Heck reaction.
This reaction was conducted and completed within 20 min.

Where R2 = CONH2, COOMe, COOH.

Heck reaction of aryl bromide with styrene in N,N-DMF/water (solvent)
has been studied using different catalysts under ultrasonic irradiation at
room temperature by Said et al. (2011). The coupling reaction of aryl
halides (10 mmol) and styrene (9 mmol) were carried out in DMF/water
(4 mL/4 mL) with catalyst (1 % mol), K2CO3 (15 mmol), and aliquat-336
(5 mmol) for 2 h at 95 °C. The reaction mixture was subjected to ultrasonic
irradiation during 5 min at room temperature. The results show that ultra-
sonic irradiation increases the yield of Heck reaction and becomes faster
with the amount of aliquat-336.
66Sonochemistry

Ghotbinejad et al. (2014) synthesized a novel and highly stable

[Pd(EDTA)]2− salt as a catalyst, using a counter-cation of N-methylimid-
azolium bonded to 1,3,5-triazine-tethered superparamagnetic iron oxide
nanoparticles. This complex catalysed the Mizoroki–Heck and Suzuki–
Miyaura cross-coupling reactions quite efficiently. The cross-coupled prod-
ucts were produced under conventional heating and ultrasound irradiation
at an extremely low-­catalyst loading (as low as 0.032 mol% Pd). It was
indicated that conventional synthesis took relatively a longer and gave only
moderate yields, while in the presence of ultrasound irradiation, the reaction
was very fast with high to excellent yields. It was found that catalyst can
be quickly recovered by an external magnetic field and could be reused for
several reaction cycles without any significant change in catalytic activity.
Mizoroki–Heck coupling afforded a number of 3-vinylindole deriva-
tives in good to acceptable yields under ultrasound irradiation. Recently,
it was revealed that Pd/C–PPh3 catalyst system facilitated the C–C bond
forming reaction between 3-iodo-1-methyl-1H-indole and various terminal
alkenes under ultrasound irradiation (Bhavani et al., 2016).

4.2.11  HENRY REACTION

In this reaction, the addition of bromonitroalkanes to aldehydes afforded

the corresponding nitroalkanols in good yields on using zinc in the pres-
ence of a catalytic amount of indium under sonication (Soengas and
Silva, 2012) (Table 4.3).

where R = Ar, Alkyl; R′ = Me, H; R′′ = H, Me.

Indium-catalysed ultrasound-assisted Henry reaction is better than
the classical base-catalysed reaction in terms of yields and selection of
Organic Synthesis67

TABLE 4.3  Henry Reaction Under Ultrasound.

Product Yield (%) Product Yield (%)
94 87

34 90

substrate. It avoids the use of larger amounts of the expensive indium

powder as only catalytic amount is required here and it can also be scaled
up easily.
Rodriguez and Dolors (2011) reported the Henry condensation reac-
tion under microwave irradiation or ultrasound as the energy source.
β-Nitroalcohol or nitroethylene derivatives can be obtained from aryl
aldehydes and nitromethane with Henry condensation by the modification
that microwave irradiation or ultrasound can be used as the energy source.
Microwave irradiation allowed a novel one-pot synthesis of nitroolefins
from aryl aldehydes using ammonium acetate as a catalyst without solvent.
Different reaction conditions, such as base, solvent, and reaction time, were
also studied by them. Only small amounts of β-hydroxyl nitro compounds
were isolated, using microwave irradiation for less than 25 min, but on
the contrary, the use of ultrasound increased the yield of the nitroalcohols.

4.2.12  KNOEVENAGEL CONDENSATION

The Knoevenagel condensation reaction is an organic reaction named

after Emil Knoevenagel. It is a modification of the aldol condensation
68Sonochemistry

(­Knoevenagel, 1898). A Knoevenagel condensation is a nucleophilic

addition of an active hydrogen compound to a carbonyl group followed
by a dehydration reaction, where a molecule of water is eliminated. The
product is often an α,β-unsaturated ketone (a conjugated enone).
Li et al. (1999) reported an ultrasound-assisted and pyridine-catalysed
Knoevenagel condensation of ethyl cyanoacetate with a variety of aromatic
aldehydes afforded ethyl α-cyanocinnamates in a good to excellent yield
(80–96 %), whereas the conventional methods gave relatively lower yields
(47–92 %) (Popp, 1960).

Ultrasound technique represented a better procedure in terms of milder

conditions and easier work-up. The product was prepared in a moderate
yield (58 %) in dry dioxane after withstanding overnight at room tempera-
ture, whereas the ultrasonic method without other solvent at 20 °C in only
3 h provided the same product in 94 % yield. Electron-donating groups
such as Me2N, H2N, MeO, HO, and Me in the aromatic ring did not retard
the condensation under these conditions.

Li et al. (2001) studied ultrasound irradiation-accelerated condensation

of ketones with ethyl cyanoacetate catalysed by NH4OAc-AcOH, giving
ethyl alkylidene α-cyanoacetates in 31–89 % yields. The synthesis of ethyl
cycloalkylidene cyanoacetate was carried out in good yields (55–89 %)
under ultrasound irradiation at 41–50 oC for 2.5–9 h, without any extra
solvent than with that of conventional methods.
Organic Synthesis69

Application of ultrasound has been found to greatly assist the

­ noevenagel condensation reaction of activated methylenes with aromatic
K
aldehydes under mild conditions. The outcome of the ultrasound-promoted
reaction depends upon the electronic nature of the aromatic aldehyde, the
solvent employed, and the addition of acids, bases, or ammonium salts.
Ultrasound efficiently promotes the condensation of aromatic aldehydes
with active methylenes under mild conditions.
McNulty et al. (1998) reported that ultrasound promoted the conden-
sation of nitromethane with a variety of aromatic aldehydes with elec-
tron-donating groups catalysed by NH4OAc-HOAc to give nitroalkenes
in good to excellent yields. Typical conditions to affect the condensation
are heating HOAc solution of the aldehyde with appropriate nitromethane
with NH4OAc at 100 °C for a few hours.

However, benzaldehyde reacted with same reagents at room tempera-

ture by the application of ultrasound to give nitroalkene in 99 % yield. It was
observed that the ultrasound failed to promote the condensation without
HOAc or NH4OAc. However, on using diisopropylethylamine in place of
HOAc, aromatic aldehydes with electron-deficient groups condensed with
nitromethane to give nitroaldols in good yields under ultrasound.
Keipour et al. (2015) prepared potassium fluoride–clinoptilolite from
commercially available and low-cost starting materials, which was used
as an efficient and recyclable catalyst for Knoevenagel condensation of
aromatic aldehydes with active methylene compounds under ultrasound
irradiation. Short reaction times, high yields of products, ease of recovery,
and catalyst reusability make this new method quite economic and efficient.
70Sonochemistry

De-la-Torre et al. (2014) made a comparative study of the effects

on three techniques in the reactions between heterocyclic aldehydes
and 2-(benzo[d]thiazol-2-yl)acetonitrile, that is, stirring, ultrasound
coupled to PTC conditions (US-PTC), and MW irradiation (MWI)
under solvent and catalyst-free conditions. The effects of conditions on
reaction parameters were evaluated and compared in terms of reaction
time, yield, purity, and outcomes. The US-PTC method was found to be
more efficient than the MWI and conventional methods. The reaction
times were considerably shorter, with high yields (> 90 %), and good
levels of purity.
Martín-Aranda et al. (1997) studied ultrasound-activated Knoevenagel
condensation of malononitrile with carbonylic compounds catalysed by
alkaline-doped saponites and β-unsaturated nitriles have been synthesized.
Two alkaline promoted clays (Li+- and Cs+-exchanged saponites) have
been employed as catalysts. The influence of the carbonylic compound
(benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic
activity have been studied. A remarkable increase in the conversion values
has been found, when the reaction is activated by ultrasound, as compared
to thermal activation. In this green, solvent-free procedure, β-unsaturated
nitriles have been produced in very high yields (97 %), particularly, when
the Cs+-saponite was used as a catalyst.
Suresh and Sandhu (2013) reported ultrasound-assisted synthesis
of 2,4-thiazolidinedione and rhodanine derivatives catalysed by task-
specific ILs. Some 1,1,3,3-tetramethylguanidine-based task-specific
ionic liquids (TSILs) were prepared and employed to catalysed
solvent-free K ­ noevenagel condensation of 2,4-thiazolidinedione and
rhodanine with a variety of aldehydes. Best results were obtained with
1,1,3,3-tetramethylguanidine lactate ([TMG][Lac]). The TSIL can be
easily recovered and recycled, yielding products in excellent yields
under ultrasonic environment without the formation of any side prod-
ucts or toxic waste.

4.2.13  LOSSEN REARRANGEMENT

Lossen rearrangement is the conversion of a hydroxamic acid to an isocya-

nate via the formation of an o-acyl, sulphonyl, or phosphoryl intermediate
hydroxamic acid O-derivative and then conversion to its conjugate base
(Lossen, 1872; Lossen, 1875).
Organic Synthesis71

Carboxylic acids are converted into hydroxamic acids in conventional

Lossen rearrangement. Vasantha et al. (2010) used 1-propanephosphonic
acid cyclic anhydride (T3P) to promote this reaction. They reported that
the application of ultrasound accelerates this conversion, whereas T3P has
also been employed to activate the hydroxamates, thus leading to isocya-
nates via Lossen rearrangement.

where T3P is

4.2.14  MANNICH REACTION

Mannich reaction involves amino alkylation of acidic proton placed next to

a carbonyl functional group by formaldehyde and a primary or secondary
amine or ammonia. The final product is a β-amino-carbonyl compound,
which is also known as Mannich base. Reactions between aldimines and
α-methylene carbonyls are also considered as Mannich reactions because
these imines are formed between amines and aldehydes (Mannich and
Krosche, 1912).
Zhang et al. (2009) reported the Ga(OTf)3-catalysed three-component
Mannich reaction of aromatic aldehydes, aromatic amines, and cyclok-
etones in water promoted by ultrasound gave the corresponding β-amino
cycloketones in good to excellent yields and good anti selectivities.
Sulphamic acid (NH2SO3H, SA) was used as an efficient, inexpensive,
nontoxic, and recyclable green catalyst for the ultrasound-assisted one-pot
Mannich reaction of aldehydes with ketones and amines.
72Sonochemistry

Li et al. (2011) reported that the synthesis of Mannich bases related

to gramine via Mannich reaction of secondary amine, formaldehyde, and
indole or N-methylindole can be carried out in 69–98 % yields in acetic
acid aqueous solution at 35 °C under ultrasound irradiation.

Magnetite nanoparticles (Fe3O4) (MNPs) were introduced as a heteroge-

neous novel catalyst for ultrasound-assisted stereoselective synthesis of
β-aminocarbonyl using Mannich reaction. These MNPs with particle size
< 40 nm were synthesized via a simple chemical precipitation method. A
mixture of benzaldehyde, aniline, cyclohexanone or acetophenone, and
MNPs was sonicated in ethanol at room temperature for 30–75 min to
afford β-aminocarbonyl compounds (Saadatjoo et al., 2012). The reaction
product was eluted from the MNPs with hot ethanol, and the catalyst was
removed by using a permanent magnet.

where Ar1 = C6H5, 2NO2-C6H4, 2-Naphtyl, 4-Br-C6H4; Ar = C6H5,

4-Br-C6H4.
Organic Synthesis73

The use of MNPs and ultrasonic-assisted method as an alternative to

other synthesis methods involving Mannich reaction offers several advan-
tages, such as high yield, reaction rate, short reaction times, low costs, and
a recyclable catalyst with a very simplified procedure. As the catalyst can
be magnetically separated, it improved the separation rate of product as
the time-consuming column passing or filtration operation is avoided in
this case.
A green, rapid, and highly efficient method was developed for the
synthesis of β-aminoketone derivatives by Ozturkcan et al. (2012). The
coupling reactions of cyclohexanone, various substituted aromatic amines,
and aromatic or heteroaromatic aldehydes were successfully carried out under
ultrasonic irradiation with bismuth(III) triflate in water at room temperature.
It can be considered the first report of three-component Mannich-type reac-
tion in water catalysed by bismuth(III) triflate under ultrasonic irradiation.
The higher yields and anti-selectivity, versatility, convenient operation, low
cost, and ecofriendly nature of the reaction support this as a practical and
rapid method for the preparation of β-aminoketone derivatives.

Direct-type three-component Mannich reaction of aromatic or heteroaro-

matic aldehydes with substituted aromatic amines and cyclohexanone
proceeded smoothly and yielded products in moderate to good yields
(38–79 %). This three-component reaction using 4-bromobenzaldehyde
was performed under the same conditions, but in the presence of ultra-
sonic irradiation at room temperature. It was found that this reaction
was completed within 1 h and the product was obtained in reasonably
good 89 % yield. Some other aldehydes and amines were also tested for
Mannich reactions with cyclohexanone in water under ultrasonic irradia-
tion at room temperature. The three-component direct-type Mannich reac-
tions proceeded very smoothly in a short time (1–2 h) in the presence of
5 mole% of Bi(OTf)3·4H2O in the presence of ultrasound irradiation with
corresponding β-aminoketone with high yields.
74Sonochemistry

Ghadami and Jafari (2015) carried out an efficient synthesis of

Mannich bases by sonication in sodium dodecyl sulphate micellar media
by Mannich reaction of aldehydes, aromatic amines, and acetophenone
derivatives or cyclohexanone. The sonication of biphasic systems was
performed at 37 kHz, 300 W, under neutral conditions. It was observed
that the reaction can be carried out readily under milder conditions. The
precipitated solid Mannich product was recovered by simple filtration
without using any organic solvent.

TABLE 4.4  A Comparative study of Mannich Reaction.

Reaction conditions Time (h) Yield (%)
Conventional 12–24 < 2
With 0.2 mol% acidic IL under ultrasonic irradiation 2–6 64–97

Qian et al. (2016) reported an efficient and facile process for the prepa-
ration of a series of β-amino carbonyl compounds via Mannich reactions
catalysed by caprolactam-based Brønsted acidic ILs under ultrasonic irra-
diation. [Capl][BF4] was the most effective catalyst in the Mannich reac-
tion, and good yields were obtained within 2–6 h (Table 4.4). The activity
and stability of the catalyst were maintained even after using it for five
times. The use of ultrasound can effectively shorten the reaction time and
enhance the yields at ambient conditions.

A novel series of 5-(4-(benzyloxy)-substituted phenyl)-3-((phenyl amino)

methyl)-1,3,4-oxadiazole-2(3H)-thione Mannich bases were synthesized
in good yields from the key compound 5-(4-(benzyloxy)phenyl)-1,3,4-­
oxadiazole-2(3H)-thione by aminomethylation with paraformaldehyde
and substituted amines using molecular sieves and sonication (Nimbalkar
et al., 2016).
Organic Synthesis75

4.2.15  MICHAEL ADDITION REACTION

Michael reaction is the nucleophilic addition of a carbanion or another

nucleophile to α,β-unsaturated carbonyl compounds. This is one of the
most useful methods for the mild formation of C–C bonds (Little et al.,
1995; Mather et al., 2006).
The use of ultrasound has found to be very effective for the Michael
addition of indole to α,β-unsaturated carbonyl ketones. Ceric ammonium
nitrate (CAN) is used as a catalyst in this reaction. The corresponding
adducts were obtained in excellent yields with selectivity of substitution
on the indole ring only at the 3-position without any N-alkylation products
(Ji and Wang, 2003).
76Sonochemistry

where CAN = Ceric ammonium nitrate.

Ultrasound-assisted hetero-Michael reaction has been studied by
Arcadi et al. (2009). They described an alternative protocol for the Michael
addition of thiols to 4-hydroxy-2-alkynoates. The reaction proceeds at
room temperature in water under ultrasound irradiation. A sequential
conjugate addition/lactonization reaction leads to important 4-amino-
furan-2-one derivatives, when amines were used instead of thiols. An
efficient protocol for the highly regioselective Michael addition of thiols
to 4-hydroxy-2-alkynoates in water under ultrasound irradiation has also
been reported. These reactions proceeded without the addition of any acid
or base. Significant rate acceleration was observed in water as compared
to organic solvents. A sequential conjugate addition/lactonization reaction
leads to important 4-amino-furan-2-one derivatives on using amines in
place of thiols. Ultrasound irradiation has shown significant advantages
compared to the traditional stirring.
Long-chain dicationic ammonium salts were successfully used as effi-
cient PTCs in the Michael addition reaction of various active methylene
compounds to 2-cyclohexenone without solvent under ultrasonic irra-
diation (Oge et al., 2012). Sodium hydroxide (0.05 mmol) and a PTC
(0.05 mmol) were added to a mixture of 2-cyclohexenone (1 mmol) and
Michael donor (2 mmol). This reaction mixture was sonicated at 25 °C.

where X = Y = COOEt; X = Ph, Y = CN.

Imanzadeh et al. (2013) described an efficient, mild, nonexpensive,
and eco-friendly protocol for the synthesis of p-toluenesulphonamide
Organic Synthesis77

derivatives by aza-Michael addition reaction of p-toluenesulphonamide to

fumaric esters using potassium carbonate under ultrasound irradiation. This
method is simple, convenient, and products are also obtained in excellent
yields.

Imanzadeh and Gatar (2015) described solvent-free highly regiose-

lective Michael addition of phenytoin to α,β-unsaturated esters in the
presence of TBAB under ultrasound irradiation. α,β-unsaturated ester (2
mmol) was added to a well-ground mixture of DPH (5,5-diphenylhydan-
toin 2 mmol), (TBAB 2 mmol), and K2CO3 (2 mmol). Then these were
mixed thoroughly with a glass rod, and this mixture was irradiated in the
water bath of an ultrasonic cleaner at 25–70 °C.
78Sonochemistry

2-Pyrrolidinon-3-olates were synthesized via one-pot four-component

reaction of 2-aminobenzothiazole, aromatic aldehydes, dimethyl acetyl-
enedicarboxylate and morpholine/piperidine in the presence of Co3O4@
SiO2 core–shell nanocomposite as a catalyst under ultrasound irradiation.
Apart from other advantages this protocol provides advantage like reus-
ability of the catalyst. The core-shell nanocomposite was also prepared
using ultrasound irradiation (Ghasemzadeh and Abdollahi-Basir, 2016).

A simple, efficient, and green chemical ultrasound-assisted thio-Michael

addition reaction between thiols and (Z)-azolactones was reported by
Rocha et al. (2016), aiming to produce nonnatural amino acid derivatives
by using chiral Zn[(L)-Pro]2 as a heterogeneous catalyst. The product was
obtained in good to excellent yields presenting high diastereoselectivity.

4.2.16  PINACOL COUPLING REACTION

A pinacol coupling reaction is an organic reaction in which a carbon–

carbon covalent bond is formed between the carbonyl groups of an alde-
hyde or a ketone in the presence of an electron donor in a free radical
process (Fittig, 1859).
The corresponding products of this reaction can be used as intermedi-
ates for the preparation of ketones and alkenes. Generally, the reaction is
effected by treatment of carbonyl compounds with an appropriate metal
reagent and/ or metal complex to give rise to the corresponding coupled
product. The coupling products can have two newly formed stereocenters.
As a consequence, efficient reaction conditions are required to control the
stereochemistry of the 1,2-diols.
Organic Synthesis79

Anhydrous conditions and long reaction time are necessary to achieve

high yield of the products. Apart from these, some of the reductants are
expensive or toxic, the reduction conditions are critical, as well as an
excess amount of metal is needed. The ultrasound irradiation was found
effective in enhancing the reactivity of metal and is favorable for single-
electron transfer reaction of the aldehydes resulting in diols.
The effect of ultrasound on pinacol coupling of benzaldehyde was
studied by Meciarova et al. (2001) in aqueous medium mediated by
magnesium, zinc, iron, nickel, and tin. It was observed that pinacol
coupling of various aromatic carbonyl compounds yielded very good
results in magnesium-mediated reaction. The use of ultrasonic irradiation
reduces the reaction time and lower mole excess of the metal is required.
Pinacol coupling proceeded well with zinc also, too, but no such reac-
tion was observed with iron, however, some unexpected reaction (oxida-
tion of benzaldehyde) was observed on using nickel and tin as metals.
The conversion of starting material as well as the proportion of pinacol to
corresponding benzyl alcohol was found to be strongly dependent on the
steric environment surrounding the carbonyl group.
Zang et al. (2002) reported coupling reaction of aromatic aldehydes
and ketones using Zn–ZnCl2 in 50 % aq. THF under ultrasound to afford
pinacols in 5–77.5 % yields.

The Zn–ZnCl2 reagent is not sensitive to oxygen. The coupling reaction

of aromatic aldehydes afforded pinacols in 23.3–87.1 % yields under ultra-
sound, by using ZnCl2/Montmorillonite K10-Zn in 50 % aqueous THF. But
no pinacols were obtained from aromatic ketones such as acetophenone and
4-chloroacetophenone. No coupling reaction had occurred from benzaldehyde
and 2, 4-dichlorobenzaldehyde without ZnCl2 even for 8 h. The K10-ZnCl2
could be recycled for three times without any significant loss in activity.
When the catalyst is recycled first, second, and third time, and used again,
the products were obtained in 87.1 %, 86 %, and 85 % yield, respectively. No
pinacol was obtained from benzaldehyde in the absence of ultrasound.
80Sonochemistry

Zhang and Li (1999) reported pinacol coupling reaction of various

aromatic aldehydes and ketones in aqueous NH4Cl mediated by Mg.
They could obtain pinacols in 40–90 % yields. The reaction time was
about 12–24 h and the molar ratio of ArCHO:Mg turning as high as
1:20. Toma and Mecarova (1999) employed Mg powder instead of
Mg turning, which decreased the molar ratio of PhCHO:Mg to 1:10,
shortened the reaction time to 10 min under ultrasound. They proved
that reaction could be carried out in pure water (without the addition of
ammonium chloride) in very good yields. Very good yields of pinacols
are formed with zinc powder in aqueous NH4Cl, but no reaction was
observed with iron, nickel, and tin powders, even under sonication
(Meciarová et al., 2002). Under ultrasound irradiation, complexes of
TiCl4–THF in CH2Cl2 could be reduced by Zn or Al to corresponding
low-valent titanium complexes, which can reduce some aromatic alde-
hydes to corresponding pinacols in 33–98 % yields within 4–25 min, but
without ultrasound, the pinacols were obtained in lower yield. Pinacols
were obtained in 57 % yield using TiCl4–THF–Zn under Ar stirring for
30 min (Li et al., 2000), and in 50 % yield using TiCl4–Et2O–Al and
stirring for 38 h (Li et al., 2003), but in the presence of TiCl4–THF–
Zn, and replacement of Ar by N2, pinacols were obtained in 96 % yield
under ultrasonication for only 5 min. Under ultrasound, TiCl4–THF–Al
system provided pinacols in 90 % yield for 20 min. Al was proved to be
more diastereoselective (dl/meso) than Zn.

4.2.17  REFORMATSKY REACTION

Reformatsky reaction is a zinc-catalysed reaction between α-haloesters

and aldehydes or ketones resulting in the formation of β-hydroxyesters.
Disadvantages of this reaction include the use of zinc dust, which has
low reactivity and also control of the resulting exothermic reaction. In
that case, one has to activate the zinc dust to initiate the reaction. Yields
of the Reformatsky reaction were found to be improved on using freshly
prepared zinc powder, a heated column of zinc dust, copper–zinc couple,
acid-washed zinc, and trimethylchlorosilane (Reformatsky, 1887).
The Reformatsky reaction is an organic reaction, which condenses
aldehydes or ketones, with α-halo esters, using a metallic zinc to form
β-hydroxy-esters (Reformatsky, 1887).
Organic Synthesis81

Han and Boudjouk (1982) found that there was a significant increase
in the yield and rate of Reformatsky reaction under ultrasound. The best
solvent was found to be dioxane. Neither ether nor benzene, the common
Reformatsky solvents, produced good yields even after several hours of
sonication.
Bang et al. (2002) reported Reformatsky reaction of indium, benzal-
dehyde with ethyl bromoacetate in various solvents. Among the several
solvents tested, THF gave the best results in terms of conversion and reac-
tion time. The reaction of benzaldehyde with ethyl bromoacetate resulted
in ethyl 3-hydroxy-3-phenylpropanoate with 97 % yield in the presence of
indium within 2 h; however, the yields were decreased in other solvents
despite prolonged reaction time.

In the absence of ultrasonic waves, the reaction occurred much more

slowly (17 h), and the yield of the β-hydroxyester was only 70 %. Ethyl
iodoacetate gave similar results to that of ethyl bromoacetate. The reac-
tion afforded the desired compounds in excellent yields (89–95 %) in case
of aliphatic aldehydes, while aromatic aldehydes with the substituents,
for example, methyl, chloro, bromo, monomethoxy, dimethoxy, nitro, or
hydroxy showed little effects on the efficiency of the reactions. The desired
products were also obtained in good to excellent yields in alkyl-substituted
ethyl bromoacetate. Benzaldehyde reacted with ethyl 2-bromopropanoate
and ethyl 2-bromo-2-methylpropanoate in the presence of indium to give
β-hydroxyesters in 76 % and 82 % yields, respectively.
Reactions of sym-(keto)dibenzo-16-crown-5 with ethyl α-bromoesters,
zinc dust, and iodine in dioxane and/or tetrahydrofuran under irradiation
by HIU provided β-hydroxy lariat ether esters in 79–91 % yields (Ross
and Bartsch, 2001). HIU-promoted Reformatsky reactions offer several
advantages over conventional thermal reaction conditions.
Ross and Bartsch (2003) have reported the synthesis of
β-hydroxyesters via the ultrasound-promoted Reformatsky reaction.
They used nonactivated zinc dust and a catalytic amount of iodine.
There are two methods for the improvement of the rate and yield of the
82Sonochemistry

Reformatsky reactions. One is the use of low-intensity ultrasound (LIU)

and another is using HIU.

The use of a LIU using laboratory-cleaning bath can also improve the rates
and yields of simple aldehydes and ketones with ethyl bromoacetate to a
greater extent (Han and Boudjouk, 1982). However, in this case also, zinc
dust has to be activated by washing with nitric acid.
Nathan and Richard (2003) reported Reformatsky reactions of a phenyl
ketone, an α-bromoester, zinc dust, and a catalytic amount of iodine in
dioxane under HIU irradiation from an ultrasonic probe. It gave high
yields of β-hydroxyesters in shorter reaction times.

where R = Me, Et, i-Pr, t-Bu, Tr, Ph; R1, R2 = H, ME.

Reformatsky reactions of an imine, α-bromoester, zinc dust, and a
catalytic amount of iodine in dioxane under HIU irradiation have been
explored by Ross et al. (2004). They used direct immersion horn as the
ultrasonic source.
Organic Synthesis83

where R = OMe, Cl, CF3, NMe2; R1 = Ph, p-MeOC6H4, p-ClC6H4.

A series of aldimines with a variety of sustituents were evaluated as
potential electrophiles for this reaction with three α-bromoesters with
differing steric demands. This method is quite successful for both enolizable
and nonenolizable types of imines affording β-lactam in very good yields.
Raquel and Amalia (2012) reported the indium-mediated Reformatsky
addition of bromoesters to glyoxylic oxime. Sonication of mixtures of oxime,
indium powder, and ethyl 2-bromopropionate in tetrahydrofuran (THF) at
room temperature for 6 h afforded 81 % yield of products as a 3:2 mixture
of syn/anti-isomers. Similarly, reaction of oxime and ethyl 2-bromophen-
ylacetate provided the adduct in 88 % yield, but as a 2:1 mixture of syn/
anti-isomers. Interestingly, no reaction had occurred in the absence of soni-
cation. Thus, ultrasonic irradiation was necessary to complete this reaction.

4.2.18  SONOGASHIRA COUPLING

Sonogashira reaction is a cross-coupling reaction used in organic

synthesis to form carbon–carbon bonds. It employs a palladium catalyst
to form a carbon–carbon bond between a terminal alkyne and an aryl or
84Sonochemistry

vinyl halide (Sonogashira, 2002). The Sonogashira cross-coupling reac-

tion has been employed in a wide variety of areas, due to its usefulness
in the formation of carbon–carbon bonds. The reaction can be carried out
under mild conditions, such as room temperature in aqueous media and
with a mild base. These conditions are favorable for extending the use
of the Sonogashira cross-coupling reaction in the synthesis of complex
molecules.
A copper-ligand free one-pot synthesis of benzo[b]furans via palladium
acetate- catalysed tandem Sonogashira coupling and 5-endo-dig cycliza-
tion (inside the ring diagonal sp-hybridized carbon) was carried out under
ultrasonic irradiation at ambient temperature (Palimkar et al., 2006). They
applied the same method for synthesizing 2-substituted indoles via Sono-
gashira coupling and 5-endo-dig cyclization (Palimkar et al., 2008).
Li et al. (2009) synthesized 4,5-disubstituted-1,2,3-(NH)-triazoles in
excellent yields by palladium- catalysed and ultrasonic-promoted Sono-
gashira coupling/1,3-dipolar cycloaddition of acid chlorides, terminal
acetylenes, and sodium azide in one pot.

The ultrasound-mediated Pd nanoparticle- catalysed cross-coupling reac-

tion was carried out between aryl iodides or bromides and terminal acety-
lenes in acetone as well as in IL [bbim]BF4, under normal conditions of
temperature and pressure (Gholap et al., 2005). It was interesting to observe
that this reaction had worked well with a large number of substrates in the
absence of any phosphine ligand or copper co-catalyst. However, the use
of acetone as solvent furnished the desired coupled products in a shorter
time. The yield was less in these conditions as compared to ILs, but it
requires relatively more time to complete the reaction. It was observed that
a catalyst can be recycled and reused with little loss of activity even after
five runs. A control experiment was carried out under conventional condi-
tions, and it was observed that no reaction took place even after several
hours of stirring without ultrasound.
Organic Synthesis85

where R1 = H, CH3, NO2, CHO; R2 = Aryl, Cyclohexyl; X = I, Br.

This method was also carried out by Fu et al. (2008) for the Sono-
gashira coupling of ethynylferrocene with aryl iodides.

4.2.19  STRECKER SYNTHESIS

This is one of the important methods for the synthesis of amino acids via
an aminonitrile intermediate. The Strecker synthesis is used for a series of
chemical reactions for synthesizing an amino acid from an aldehyde and
ketone (Strecker, 1850; 1854). The aldehyde is condensed with ammonium
chloride in the presence of potassium cyanide to form an α-aminonitrile,
which is subsequently hydrolyzed to give the desired amino acid.
Hanafusa et al. (1987) reported a direct reaction between an aldehyde,
KCN, and NH4Cl in acetonitrile in the presence of alumina under ultra-
sound exposure. Conventionally, this protocol normally leads to a mixture
of products, but this can be made more specific under sonication.
The yield of the aminonitrile (the desired intermediate) is very poor
on using benzaldehyde under stirring. The benzoin and hydroxynitrile
were obtained as major products. They observed that alumina suspended
in acetonitrile coupled with sonication improved the yield of target amino-
nitrile to about 90 %.

4.2.20  SUZUKI REACTION

Suzuki reaction is an organic coupling reaction catalysed by a palladium(0)

complex, where the coupling partners are boronic acid and organohalide
(Miyaura et al., 1979; Miyaura and Suzuki, 1979). Suzuki reaction was first
investigated employing Pd(OAc)2 as a catalyst in the absence of phosphine
ligands. The ultrasound-assisted cross-coupling reaction between potas-
sium trifluoroborate salts and aryl- or vinyltellurides for the preparation of
86Sonochemistry

Z- or E-stilbenes has been reported by Cella and Stefani (2006). A series of

alkenes with defined stereochemistry were obtained in good yields within
40 min under comparative conditions. It was observed that most of the
starting material remained unchanged even after 24 h of magnetic stirring.
However, the same reaction gives a yield of 63 % in 18 h under reflux
conditions. An important feature of this reaction is that it can even tolerate
ester groups, which are sensitive to normal conditions.

Guadagnin et al. (2008) have used this procedure with some modifications
for the synthesis of 1,3-dienes, 1,3-enynes, and (Z)-(2-chlorovinyl)- alkenes.
Rajagopal et al. (2002) carried out Pd-catalysed Suzuki cross-coupling
reactions of halobenzenes with phenylboronic acid in ILs under ultrasound
irradiation. They used tetrafluoroborate bis-butylimidazol-2-ylidene-
palladium(II) carbene complex instead of Pd(OAc)2 and [bbim]+[BF4]–/
MeOH as a solvent system.

where X = I, Br, Cl; R = H, OCH3, CH3, Cl, NO2.

Under these conditions, a series of biaryls were synthesized in good
yields in shorter reaction times. This methodology is considered very
important as aryl halides containing both the groups, electron-donating
as well as electron-withdrawing groups, react readily. Even chloroben-
zene undergoes the Suzuki reaction and afforded biaryls with 42–65 %
yields. The yield was moderate on using Pd(OAc)2 as a catalyst. Chlo-
robenzenes are known to have poor reactivity under Suzuki conditions.
Organic Synthesis87

The modification allowed for recycling and using the palladium cata-
lyst without any appreciable loss in its activity as a catalyst. A simple
ultrasound-assisted procedure was reported by Martina et al. (2011)
to synthesize solid-supported Cu(I) and Pd(II) catalysts. Cross-linked
chitosan derivatives (CS-Cu, CS-Pd) were obtained by reacting hexa-
methylene isocyanate and chitosan in the presence of the corresponding
metal salt. The in situ polymerization in water under sonochemical expo-
sure was extremely fast and efficient. The Cu(I)-loaded polyurethane/
urea-bridged chitosan was used for the azide/alkyne [3 + 2] cycloaddi-
tion, while those bearing Pd(II) complexes were used for Suzuki cross-
couplings. In both these reactions, these novel catalysts can be reused
several times with a little low activity.
Kulkarni et al. (2014) showed the use of an energy-efficient surface
acoustic wave (SAW) device for driving closed-vessel SAW-assisted
(CVSAW), ligand-free Suzuki couplings in aqueous media. The reactions
were carried out on an mM scale with low- to ultra-low catalyst loadings,
which were found to be driven by heating, resulting from the penetration
of acoustic energy. The yields were uniformly high, and the reactions can
be carried out without added ligand and in water.
The coupling reaction of aryl bromide and aryl boronic acid in water/
DMF as solvent was studied using a palladium complex as a catalyst in
the presence of ultrasound at room temperature by Said and Salem (2016).
The effect on the reaction of a base and a solvent was also studied with
and without ultrasound, and it was found that the rate of the reaction had
increased.

4.2.21  ULLMANN REACTION

Ullmann reaction normally requires a 10-fold excess of copper and a

longer reaction time of 48 h, but this amount can be reduced to only a
4-fold excess of copper and a reaction time of 10 h on the application of
ultrasound (Lindley et al., 1986; 1987). The particle size of the copper was
found to reduce from 87 to 25 μm. Only an increase in the surface area
cannot explain the observed increase in reactivity and, therefore, it was
suggested that the process of sonication also assists in the breakdown of
intermediates and desorption of the products from the surface.
88Sonochemistry

They revealed that the sonication is responsible for breaking down

of intermediates or desorption of products from the surface as it also
prevented the adsorption of copper on the walls of reaction vessels,
which is quite a common problem encountered in conventional
Ullmann reaction (Table 4.5). Such ionic reactions are accelerated by
better mass transport and physical effects. They also called it false
sonochemistry. It occurs, when the cavitation effects produce purely
mechanical effects and this is most often in heterogeneous system

TABLE 4.5  Ullmann Reaction in the Presence of Ultrasound.

Product Yield (%)
95

92

90

90

84
Organic Synthesis89

where rate enhancement derive from surface cleaning in heteroge-

neous catalysis, the enhancement of mass transfer and in liquid–liquid
or solid–solid phase transfer reactions. On the other hand, true sono-
chemistry is the result of effects directly derived from the hotspots of
cavitational collapse energy.
Smith and Dennis (1992) described the use of ultrasound in the reac-
tions of phenols with bromoarenes in the presence of potassium carbonate
and copper(I) iodide without an added solvent. It gave better yields of
diaryl ethers (typically 70–90 %), at lower temperature (140 °C) than the
traditional Ullmann reactions. The role of ultrasound here is primarily to
break up the particles of the inorganic solids.
Docampo and Pellon (2003) studied Ullmann condensation between
2-chlorobenzoic acid and 2-aminopyridine derivatives using ultrasound.
This reaction was conducted in the presence of anhydrous potassium
carbonate and copper powder using DMF as a solvent. The ultrasound-
assisted reaction required a shorter reaction time (20 min) with better
yields as compared to conventional heating, that is, stirring for 6 h at reflux
temperature.
Nelson and Horst (1991) reported that ultrasonic irradiation was found
to promote the Ullmann coupling of picryl bromide at or below room
temperature. In the presence of excess copper, a long-lived intermediate is
formed that is quenched upon the work-up affording variable mixtures of
trinitrobenzene and picric acid.
One‐pot syntheses of 5H‐[1,3]thiazolo[2,3‐b] quinazolin‐5‐one, 12H‐
[1,3]benzothiazolo [2,3‐b]quinazolin‐12‐one, and corresponding deriva-
tives were developed using the copper‐catalysed Ullmann condensation
(Rolando et al., 2007). The use of ultrasonic irradiation enhanced yields
and reduced the reaction time to minutes.
90Sonochemistry

Michael et al. (2012) described the ultrasound-assisted Ullmann

N-coupling of 2-halobenzoic acid with complex aryl- and alkylamines to
give the corresponding products in good to excellent yields.

where R1 = Aryl, Alkyl.

4.2.22  VILSMEIER–HAACK REACTION

The Vilsmeier–Haack reaction (also called the Vilsmeier reaction) is

the reaction of a substituted amide with phosphorus oxychloride and an
­electron-rich arene to produce an aryl aldehyde or ketone. The reaction is
named after Anton Vilsmeier and Albrecht Haack (Vilsmeier and Haack,
1927).
Ali et al. (2002) studied the Vilsmeier cyclization of acetanilides with
Vilsmeier–Haack reagent under ultrasound irradiation. A solution of acet-
anilides was treated with Vilsmeier–Haack reagent (formed from POCl3/
DMF) in CH2Cl2 under ultrasound at 40 °C for 60 min to give corre-
sponding 2-chloro-3-formylquinolines in good yields (65–85 %). On the
other hand, the reaction under thermal condition resulted in the forma-
tion of the products with relatively lower yields (0–68 %). The desired
formylated products were formed in 75–90 % yields under ultrasonic
irradiation (Table 4.6). The acetophenone gave β-chlorocinnamaldehyde
in 85 % yield, whereas 2-hydroxyacetophenone and 2,4-dihydroxyaceto-
phenone provided corresponding 3-formylchromones in 82 % and 74 %
yields, respectively.
Organic Synthesis91

TABLE 4.6  A Comparison Between Ultrasound and Thermal methods.

Substrate Product Yield (%)
USa Thermalb
Acetanilide 2-Chloro-3-formyl quinoline 84 68
4-Methylacetanilide 6-Methyl-2-choro-3-formyl quinoline 85 50
4-Methoxyacetanilide 6-Methoxy-2-choro-3-formyl quinoline 82 58
3-Nitroacetanilide 7-Nitro-2-choro-3-formyl quinoline 65 0
4-Bromoacetanilide 6-Bromo-2-choro-3-formyl quinoline 68 35
a
Ultrasound irradiation at 40 °C for 1 h.bThermal reaction at 75 °C for 6 h.

4.2.23  WITTIG REACTION

Wittig reaction or Wittig olefination is a chemical reaction of an alde-
hyde or ketone with a triphenyl phosphonium to give an alkene and triphe-
nylphosphine oxide. This reaction was discovered by Georg Wittig (Wittig
and Schollkopf, 1954). These reactions are most commonly used to couple
aldehydes and ketones to singly substituted phosphine ylides with unsta-
bilized ylides. This results in almost exclusively the Z-alkene product
(Wittig and Haag, 1955).
Wittig reaction results in a novel type of annulation of an aromatic
ring, when applied to o-quinones. Such reaction is called as Double-Wittig
reaction. Yang et al. (1992) have reported that this process may be simpli-
fied by using ultrasound irradiation, which allowed the use of bases insen-
sitive to moisture and air.
A comparison of solventless Wittig reactions to Wittig reactions under
ultrasonication has been studied by Watanabe et al. (2005). Simple heating
of a mixture of added components at 100 °C in an electric oven gives the
corresponding olefins in good yields. Wittig reactions can be carried out in
a biphasic medium under ultrasonication. In this case, the Wittig products
92Sonochemistry

can be isolated by simple evaporation of the organic phase without addi-

tional work-up.
Ramazani et al. (2015) reported ultrasound-promoted three-component
reaction of n-isocyaniminotriphenyl-phosphorane, (E)-cinnamic acids,
and biacetyl.

Fully substituted 1,3,4-oxadiazole derivatives were obtained in a one-pot

three-component reaction of n-isocyaniminotriphenylphosphorane, biacetyl,
and (E)-cinnamic acids in dichloromethane under ultrasound irradiation.
This method produced the products in short reaction times (16–27 min)
with excellent yields (91–97 %).

4.3  PHASE-TRANSFER CATALYSIS

A PTC transfers an active species from one phase to the other, when
two reactants are immiscible. Sometimes, a particular reaction is quite
slow because of poor mass transfer. Thus, vigorous stirring is necessary
for increasing the reaction rate. The presence of a PTC is also helpful in
such reactions. Sonication either produces an extremely fine emulsion of
immiscible liquids or assists in mass transfer and surface activation (in
a solid/liquid system). These factors helped in enhancing PTC-catalysed
heterogeneous reactions.
Regen and Singh (1982) cyclopropanated styrene in 96 % yield in 1 h
using a combination of both sonication and mechanical stirring. It was
observed that the yield is reduced to 38 % in 20 h with sonication alone
because the power of the bath was not sufficient enough to disperse the
solid reagent into the dense chloroform.
Organic Synthesis93

Davidson et al. (1987) observed only 19 % yield of N-alkylated product of

indole in 3 h using tert-butylammonium nitrate in toluene at 25 °C in the
presence of solid KOH. This yield can be significantly improved by using
ultrasound from 19 % to 90 % within 80 min.

4.4 SUGARS

Deng et al. (2006) established that it is feasible to carry out a large number
of conventional reactions in the synthesis and fictionalization of carbohy-
drates under ultrasound irradiation with better yields and reduced reaction
times. It is very significant to note that the hindered disaccharide treha-
lose undergoes the reaction to afford the desired acetylated sugar in good
yields. Tosylation and diol protection were also carried out successfully
under sonochemical conditions.
94Sonochemistry

It was reported that the acyl group migrates within the carbohydrate scaf-
fold in a few minutes (Deng and Chang, 2006). Otherwise, it takes hours
or sometimes even days for the completion of this reaction under conven-
tional conditions.

Tanifum and Chang (2008) have developed a new method for the synthesis
of oligomannosides in good yields, in short reaction times and high stere-
oselectivity under ultrasound.

where X = SPh and OAc.

4.5  IONIC LIQUIDS

The increasing importance of sonochemistry as a green process and

ILs as green solvents materials has resulted in their wide applications.
The ILs find mild applications such as storage media for toxic gases,
­catalysts/solvents in organic syntheses, electrolytes, performance addi-
tives in pigments, and matrices because of their tailor-made nature. The
existing conventional preparation of ILs requires excess solvents and
hours or even days for completion in some cases. Microwaves were used
for solving these problems. Although the reaction time was reduced from
Organic Synthesis95

several hours to a few minutes and a large excess of alkyl halides and
organic solvents was also avoided, the reaction is exothermic in nature
and due to this, continuous microwave heating takes place leading to
the formation of colored products. Ultrasound-assisted method was used
to avoid this problem in dealing with these highly viscous materials,
where efficient mixing is a challenge. Ultrasound-accelerated chemical
reactions are well known and they proceed via the formation and adia-
batic collapse of the transient cavitation bubbles. An efficient method for
the preparation of ILs has been reported using ultrasound as the energy
source by the simple exposure of neat reactants in a closed container to
ultrasonic irradiation using a sonication bath. The current solvent-free
approach requires shorter reaction time and lower reaction temperature
in contrast to several hours needed under conventional heating conditions
using an excess of reactants.
Namboodiri and Varma (2002) developed ultrasonic-assisted efficient
method for the preparation of ILs using ultrasound as the energy source.
In this process, they exposed neat reactants in a closed container using
a sonication bath. One of the main advantages of this method is that the
formation of the IL could be visibly monitored as the reaction contents
turned from a clear solution to opaque and finally a clear viscous phase
of solids.

where n = 2, 4, or 6; X = Cl, Br, I; R = nPr, n Bu, i-Bu, etc.

Imidazolium-based IL derivatives were synthesized using a facile and
green ultrasound-assisted procedure (Ameta et al., 2015). A large number
of ILs can be synthesized by a simple combination of different cations
and anions. Ultrasound-assisted synthesis of ILs has an edge over clas-
sical conventional methods, that is, ecofriendly nature, simple product
isolation, higher yield, shorter reaction times. The main advantages of
this procedure as compared with conventional method were its milder
conditions, shorter reaction time, higher yields and selectivity without the
need for a transition metal or base catalyst. Introducing such an efficient
96Sonochemistry

synthetic protocol will reduce the cost of ILs, thus encouraging a wider
use of these neoteric solvents.
Step I

Step II

4.6 HETEROCYCLES

Some of the heterocycles are discussed in the following sections.

4.6.1  IMIDAZOLE DERIVATIVES

2-Arylbenzimidazole was synthesized by the reaction of substituted

aldehydes with o-phenylenediamine catalysed by tetrabutylammonium
fluoride (TBAF) in water under ultrasonic irradiation at room tempera-
ture (Joshi et al., 2010). It is a mild and chemoselective method for
preparing such heterocycles. The use of quaternary ammonium fluoride
salts is economical and these are relatively nontoxic reagents. Water
is used as it is commonly accepted to be a green solvent in organic
synthesis.
Organic Synthesis97

Arani and Safari (2011) reported a rapid and efficient synthesis of

5,5-diphenylhydantoin and 5,5-diphenyl-2-thiohydantoin derivatives with
high yield (96–98 %) under mild conditions. These reactions were performed
in DMSO/H2O with ultrasonic irradiation and catalysed by KOH.

4.6.2  PYRAZOLE DERIVATIVES

A comparative study was made by Pathak et al. (2009) between four activating
methods to obtain N-acetyl-pyrazolines. These include reflux, solvent-free
conditions, microwave irradiation, and ultrasonic irradiation. Out of these
four methods, microwave irradiation method was found to be the most effec-
tive, followed by ultrasound-assisted method. The reaction of 1,4-pentadien-
3-ones with hydrazine and acetic acid in ethanol was completed within
10–25 min and afforded the products in good yields (79–95 %).
98Sonochemistry

An efficient and highly regioselective synthesis of ethyl

1-(2,4-dichlorophenyl)-1H pyrazole-3-carboxylates was reported under
ultrasound irradiation (Machado et al., 2011). This reaction is completed in
10–12 min whereas it requires 2.5–3 h under conventional thermal condi-
tions. An ultrasound-assisted and bismuth nitrate- catalysed eco-friendly
route has been designed to synthesize a series of novel N-­substituted
pyrrole derivatives. (Bandyopadhyay et al., 2012) This is a simple method
to prepare a series of N-substituted pyrroles with less nucleophilic polyaro-
matic amines.

4.6.3  ISOXAZOLE DERIVATIVES

Ultrasound-promoted synthesis of substituted pyrazoles and isoxazoles

containing sulphone moiety has been investigated via the one-pot reaction
of the carbanions of 1-aryl-2-(phenylsulphonyl)-ethanone with several
different hydrazonyl halides in ethanol (Saleh and El-Rahman, 2009).
These reactions were enhanced by ultrasonic irradiation, and the products
were isolated in high yields (90–97 %).
Organic Synthesis99

A benign and improved synthesis of 5-(2-chloroquinolin-3-yl)-

3-phenyl-4,5-dihydroisoxazoline using acetic acid aqueous solution under
ultrasound irradiation has been carried out by Tiwari et al. (2011). It was
observed that sonochemical method gave better yields (87–90 %) of the
products in shorter times of 90–120 min than the corresponding thermal
reactions (72–78 %) and that too in 6–7 h.

4.6.4  OXAZOLE DERIVATIVES

Mirkhani et al. (2009) developed an improved sulphonated carbon-based

solid acid as a novel, efficient, and reusable catalyst for chemoselective
synthesis of 2-oxazolines and bis-oxazoline. It was found that reactions
performed with a combination of the new catalyst and sonication was
more efficient than those without ultrasonic irradiation.

4.6.5  THIAZOLE DERIVATIVES

Spiro[indole-thiazolidinones] were prepared sonochemically via a three-

component reaction in aqueous medium in the presence of cetyltrimeth-
ylammonium bromide as a PTC (Dandia et al., 2011). This reaction was
completed in 40–50 min under ultrasound with the desired product in good
to excellent yields (80–98 %).
100Sonochemistry

Ultrasound-promoted greener synthesis of 2-(3,5-diaryl-4,5-dihydro-

1H-pyrazol-1-yl)-4-phenylthiazoles was reported by Venzke et al. (2011).
This synthesis was completed in only 15 min in ethanol at room tempera-
ture and afforded the pure products in 47–93 % yields by simple filtration
of the reaction mixture.

Thiazolidinones from piperonilamine were also obtained in good yields

under sonication for 5 min. The corresponding conventional thermal reac-
tions without ultrasound also furnished similar yields, but it required much
longer times of 16 h (Neuenfeldt et al., 2011).

4.6.6  SELENAZOLE DERIVATIVES

An ultrasound-mediated preparation of 1,3-selenazoles was reported by

Lalithamb et al. (2010). They reported an efficient preparation of desired
products by the treatment of bromomethyl ketones with selenourea in
acetone under ultrasonic irradiation for 5–10 min.
Organic Synthesis101

4.6.7  TRIAZOLE DERIVATIVES

Cravotto et al. (2010) used ultrasound with/without microwave for

producing 1,2,3-triazole derivatives via copper- catalysed azide-alkyne
cycloaddition reaction. It was reported that the best results were obtained,
when azides and terminal alkynes were sonicated in the presence of Cu
turnings in dioxane/H2O at 70 °C or DMF at 100 °C. Substitution of water
by DMF was required to prevent the formation of copper complexes so
that the purification of the products is made simpler.

4.6.8  OXADIAZOLE DERIVATIVES

A comparison between conventional heating with microwave and ultra-

sound as ecofriendly energy sources for the synthesis of 2-substituted
1,2,3-triazoles and 4-amino-5-cyanopyrazole derivatives has been made
by Al-Zaydi (2009). The products were obtained with excellent yields in
this green chemical approach.
Ultrasound-promoted synthesis of 3-trichloromethyl-5-alkyl(aryl)-
1,2,4-oxadiazoles was carried out by Bretanha et al. (2011), with excellent
yields (84–98 %) and shorter reaction times of 15 min as compared to
silent conditions.
102Sonochemistry

4.6.9  THIADIAZOLE DERIVATIVES

Some new 1,3,4-thiadiazole and bi(1,3,4-thiadiazole) derivatives incorpo-

rating pyrazolone moiety were synthesized by reacting 1-methyl-5-oxo-
3-phenyl-2-pyrazolin-4-thiocarboxanilide with a series of hydrazonyl
halides or N,N′-diphenyl-oxalodihydrazonoyl dichloride in the presence
of triethylamine (TEA) (El-Rahman et al., 2009).

The reactions were carried out under both conventional and ultrasonic
irradiation conditions. Improvement in rates and yields was observed,
when reactions were carried out under sonication compared to classical
condition.

4.6.10  TETRAZOLE DERIVATIVES

The reaction of a series of aromatic nitriles with sodium azide was cata-
lysed by montmorillonite K-10 or kaolin clays in water or DMF as solvent,
under ultrasound (Chermahini et al., 2010). The use of ultrasonic irradia-
tion reduced the reaction times and increased the activity of a catalyst.
Organic Synthesis103

The amount of nitrile to sodium azide mole ratio, amount of catalyst,

reaction time, and solvent type were also optimized. The versatility of
this method was checked by using various nitriles, which showed reason-
able yields of tetrazoles formation compared to conventional heating. It
was found that using nitriles with electron-withdrawing groups result in
both higher yields and lower reaction times. The catalysts could also be
reused several times without significant loss of their catalytic activity.
This methodology finds widespread use in organic synthesis for the
preparation of tetrazoles. The advantages of this catalytic system are as
follows: mild reaction condition, high product yields, easy preparation of
the catalysts, nontoxicity of the catalysts, and simple and clean work-up
of the desired products.

4.7  SONOCHEMICAL SWITCHING

Sonochemical switching is a unique feature of sonochemistry, which

differentiates this technique from other methods enhancing chemical
reactions. The extreme conditions within the bubble may lead to
totally new reaction pathways, that is, via radicals generated in the
vapor phase that would only have a transient existence in the bulk
liquid. Such a switching has been observed in case of Kornblum–
Russell reaction, where sonication favors a single-electron transfer
pathway.
Dickens and Luche (1991) reported that 4-nitrobenzyl bromide reacts
with 2-lithio-2-nitro-propane via a polar mechanism to give 4-nitroben-
zaldehyde as a final product. When this reaction was carried out under
sonication, it leads to the formation of a dinitro compound depending on
the irradiation conditions and intensity of ultrasound.
104Sonochemistry

Ando and Kimura (1991) demonstrated a reaction between benzyl

bromide and alumina-supported potassium cyanide in toluene. Benzyl
cyanide was produced by nucleophilic displacement of the bromine by
supported cyanide, but substituted toluene was obtained without sonication.

This reaction afforded diphenylmethane products via a Friedel–Crafts

reaction between the bromo compound and the solvent, catalysed by
Lewis acid sites on the surface of the solid phase reagent under stirring
alone. On the contrary, sonication of the same reaction produced only the
substitution product, that is, benzyl cyanide. It may be due to cavitations,
which produce a structural change to the catalytic sites of the solid support,
may be through masking them via cavitationally induced cyanide absorp-
tion. When nitric acid reacts with alcohol under ultrasound, the product
obtained is acid. This reaction proceeds through radical cation. On the
other hand, the product is nitrate ester under silent conditions.
Organic Synthesis105

The reaction of o-allyl benzamides with Li/THF results in the forma-

tion of indanone in two steps (Einhom et al., 1988). The first step is accel-
erated by ultrasound which involves the ketyl radical anion. This anion
cyclizes to 2-methylindanone and liberates an amide ion, which deproton-
ates the allyl moiety. Due to sonication, the ketyl is generated much more
rapidly so that only the cyclization to 2-methylindanone occurs and other
side reactions are omitted.

4.8 MISCELLANEOUS

It is necessary to develop some alternative methods for desulphurization

of fossil fuel-derived oil, due to the requirement of stringent rules for ultra-
low sulphur content of diesel fuels. Dibenzothiophene can be quantitatively
oxidized by using appropriate oxidants and catalysts with the assistance of
ultrasound irradiation within a few minutes. The removal efficiency of
sulphur-bearing compounds in diesel fuels can reach or exceed 99 % in a
short contact time at ambient conditions (temperature and pressure) by the
use of catalytic oxidation and ultrasound followed by solvent extraction.
This approach is known as ultrasound-assisted oxidative desulphurization
and it can be the basis for obtaining ultra-low sulphur-containing diesel oil
(Mei et al., 2003).
Another application of ultrasound is allylation of carbonyl groups.
Homoallylic alcohols can be obtained by sonicating a mixture of allylic
halides, zinc, and aldehydes or ketones in aqueous THF (Petrier and Luche,
1985; Einhorn and Luche, 1987). However, the yields are not always satis-
factory, but the replacement of the THF-water solvent by THF-aqueous
NH4Cl greatly improves this method. In this condition, stirring at room
temperature is sufficient to provide activation.
106Sonochemistry

One more application of ultrasound is alkylation. Bogolubsky et al.

(2008) studied structurally and functionally diverse N-carbamoylamino
acids, which were obtained through the alkylation of monosubstituted
parabanic acids followed by hydrolysis of the intermediate products in
very good yields and excellent purity.

where R= Alkyl, Bn, Ph; R′= Benzyl, CHR′′CO2H.

Ultrasound has also been used for oxidation and reduction reactions.
The use of ultrasonic irradiation accelerated the oxidation reaction of
aromatic and heteroaromatic compounds. Ruthenium-catalysed oxidation
of aromatic and heteroaromatic compounds has been reported. It was found
that ultrasonic irradiation in a biphasic system consisting of substrate,
CH2Cl2, H2O, CH3CN, NaIO4 and catalytic amounts of RuCl3·nH2O,
accelerates the oxidation reaction to afford the desired products in good
yields (Tabatabaein et al., 2007).
Various mono-, di- and α,β-unsaturated cyanides were reduced with
a Cu–Al alloy in NaOD–D2O and THF to the corresponding deuterated
aliphatic amines, such as nonylamines, putrescine, and 1,6-hexanedi-
amine, with high deuterium content in the presence of ultrasound (Tsuzuki
et al., 1996).
Salvador et al. (1993) studied the zinc-mediated reduction of
α,β-unsaturated ketones in acetic acid. They reported that this reac-
tion proceeds very efficiently under sonochemical conditions. Different
α-enone systems gave two kinds of products: olefins and allylic alcohols.
The steroids with the common 4-en-3-one system are efficiently reduced
to D3-steroids whereas 16-ene-20-one gave the corresponding allylic
alcohol systems under similar conditions.
Organic Synthesis107

A convenient one-pot cyclocondensation method for benzothiazole

and benzimidazole syntheses was reported by Yuan and Guo (2011).
Some benzothiazoles and benzimidazoles were prepared from aromatic
o-diamines or o-aminothiophenol and aldehydes using chlorotrimethylsi-
lane in DMF as promoter and water scavenger under ultrasonic irradiation
in good yields (84–97 %).

where X = S, NH.
Xiong et al. (2013) reported a simple and an efficient method for the
selective cleavage of terminal acetonides. When terminal acetonides in
the presence of wide range of functional group are treated with silica-
supported boron trifluoride as a catalyst under ultrasound irradiation, it
furnished the corresponding diols in reasonable good yields (82–95 %). It
was interesting to note that acid labile p-methoxybenzyl group (protecting
group) remained as such under these conditions of deprotection.
Sonochemistry is gaining significant importance in organic synthesis
based on laboratory results and the availability of scale-up systems. Ultra-
sound is an efficient and practically benign means of activation in synthetic
108Sonochemistry

chemistry and it has been employed for decades with varied success. This
high-energy input not only enhances mechanical effects in heterogeneous
processes but also induces new reactivity thereby leading to the forma-
tion of unexpected chemical species. It has made sonochemistry a unique
technique supported by the remarkable phenomenon of cavitation, which
is currently the subject of intense research and it has already yielded some
thought-provoking results. Although applications for sonochemistry can be
found in many areas, sonochemical processes are most widely developed
for heterogeneous reactions. It is a multidisciplinary field where chem-
ists, physicists, chemical engineers, and mathematicians must cooperate
to develop a better understanding of the processes taking place within the
collapsing bubbles to develop some newer dimensions in its applications.
The challenges of scale-up still represent a current concern of noncon-
ventional technologies. A series of commercially available ultrasonic
reactors can be readily adapted for scaling up a particular process, even
operating below the ultrasonic threshold.
Because organics are invariably linked to biomaterials and pharmaceu-
ticals, sonochemical reactions conducted on larger scales in these areas will
have a wide and long-term impact without any debate. Besides improving
numerous organic reactions, sonication can also initiate crystal nucleation,
switching a chemical reaction, etc. Both sonosynthesis and sonocrystalli-
zation are likely to be very useful in drug discovery. Chemists, in general,
but organic synthetic chemists, in particular, must explore their researches
further using this harmless and greener sound energy. The usefulness of
sonochemistry has now no limitations and it will continue to expand its
arena encompassing, Green chemistry, photochemistry, electrochemistry,
bio-imaging, biosensors, industrial chemistry, biotechnology, etc.

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CHAPTER 5

INORGANIC, COORDINATION AND

ORGANOMETALLIC COMPOUNDS
KIRAN MEGHWAL1, SHARONI GUPTA2, CHETNA GOMBER3
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
3
Department of Chemistry, JIET Group of Institutions, Jodhpur, India
E-mail: [email protected]

CONTENTS

5.1 Introduction  ����������������������������������������������������������������������������� 115

5.2 Oxides  �������������������������������������������������������������������������������������� 118
5.3 Sulphides  ��������������������������������������������������������������������������������  125
5.4 Coordination Compounds  �������������������������������������������������������  131
5.5 Organometallic Compounds  ���������������������������������������������������  138
References  �����������������������������������������������������������������������������������������  154

5.1 INTRODUCTION

One of the potential and widely studied areas in the field of sonochem-
istry is the synthesis of inorganic compounds. The physical and chem-
ical effects generated after collapse of the bubbles are responsible for
the formation of these materials and in some of the cases these may also
result in the generation of some unusual materials with novel properties.
Normally, preparation of inorganic materials is carried out in liquid phase
116Sonochemistry

using 20–40 kHz ultrasound irradiation. Here, either a horn- or bath-type

transducer is used with/without the presence of Ar or some other inert
gases. Smaller-sized particles could be formed under ultrasonic conditions
as compared to traditional chemical processes. This process assists in the
generation of inorganic materials without using any toxic precursors and
common additives as required in case of conventional methods. Thus,
sonochemical process could be considered as an eco-friendly or green
chemical-processing technique.
It is an established fact that the processing techniques and the experi-
mental parameters are deciding factors for the size and morphology of
the materials generated. Many conventional methods are known including
co-precipitation, hydrothermal, sol-gel, combustion, microemulsion,
microwave assisted, photochemical, mechanochemical, solid state, elec-
trochemical, gas reaction, pyrolysis and so on. Most of these methods
require high temperature, air, or use temperature-sensitive organome-
tallic precursors/environmental pollutants. Sonochemical- or ultrasound-
assisted synthesis seems to be an alternative and effective mean as
compared to these techniques. The use of ultrasound promotes a reaction
in a liquid medium due to the dynamics of bubbles that involves its forma-
tion, growth, and implosive collapse. Such an implosive collapse gener-
ates drastic intensity for a short time that is sufficient to induce either
chemical or physical transformations. Sonochemical processes are gener-
ally environmentally benign in nature and applicable to synthesis of inor-
ganic compounds, which are selective in achieving amorphous/crystalline
products with uniform size distribution of particles.
The reactivity of a number of inorganic solids is affected on exposure
to ultrasonic irradiation. A large increase in the rates of intercalation of a
wide range of compounds into various layered inorganic solids has been
observed by Suslick and Grinstaff (1990). It has been revealed that ultra-
sound has multiple effects on the morphology and surface characteristics
of inorganic solids. It creates substantial surface damage resulting into
increased surface area and causes increased particle aggregation (Green
and Thompson, 1987).
Roger et al. (1989) investigated ultrasound-assisted alkyl-metal
synthesis and found that sonochemically activated potassium metal is a
powerful and stoichiometric-reducing reagent. The corresponding metal-
lates [M(C5Me5)(CO)n]− K+ quickly form the dimers M(C5Me5)(CO)n]2
(M = Fe, Ru, n = 2; M = Mo, n = 3). They carried out reduction on a small
Inorganic, Coordination and Organometallic Compounds117

scale (1–20 mmol) with a 100- or 600-W acoustic power generator and a

titanium horn directly immersed in the solution. These reduction reactions
were completed within 15–20 min. In situ alkylation of these metallates
was done with one equivalent of an electrophile RX (where R = CH3,
CH3CH2, CH3OCH2, CH3OCH2), which provided a facile synthesis of
metal alkyl M(C5Me5)(CO)nR.
Nagarjun and Tomar (2009) applied ultrasound for the synthesis
of ternary oxide AgMO2 (M = Fe, Ga). They observed that crystalline
α-AgFeO2 can be obtained from the alkaline solutions of silver and iron
hydroxides by sonication for 40 min. When β-NaFeO2 was sonicated with
aqueous silver nitrate solution for 60 min, β-AgFeO2 (orthorhombic) was
ion-exchanged product. Similarly, sonication of β-NaGaO2 with aqueous
silver nitrate solution for 60 min resulted in the formation of olive green-
coloured α-AgGaO2. It was confirmed that the ion exchange was complete
through sonication.
A rapid ultrasound-assisted extraction procedure for the determina-
tion of total mercury, inorganic mercury (IM), and methyl mercury (MM)
was reported by Krishna et al. (2005) in various environmental matrices
such as animal tissues, samples of plant origin, and coal-fly ash. The
mercury contents were estimated by cold vapor atomic absorption spec-
trometry. SnCl2 was used as reducing agent in estimation of IM whereas
total mercury was determined after the oxidation of MM through UV irra-
diation. Various operational parameters such as composition of extractant
(HNO3 and thiourea), time, and amplitude of sonication were found to
be different for different matrices. Quantitative recovery of total mercury
was achieved using mixtures of nitric acid and urea. These were opti-
mized at 5 % HNO3 and 0.02 % thiourea, 10 % HNO3 and 0.02 % thio-
urea, 20 % HNO3 and 0.2 % thiourea for fish tissues, plant matrices, and
coal-fly ash samples, respectively. This ultrasound-assisted extraction
procedure reduces the time required for sample treatment significantly for
the extraction of mercury species. It was observed that extracted mercury
species were quite stable even after 24 h of sonication. This method can
be successfully applied for the determination of Hg in samples of lichens,
mosses, coal-fly ash, and coal samples.
Olivine-structured LiFePO4/C composite powder was synthesized by
Jugovic et al. (2008) via ultrasound-assisted method. Lithium iron phos-
phate is of utmost importance as it is used as storage cathode for the next
generation of rechargeable lithium batteries. Polyvinyl alcohol (PVA)
118Sonochemistry

solution was used as the source of in situ-formed carbon. Electrochemical

characteristic of this composite was also evaluated by using galvanostatic
charge/discharge tests. Carbon film with a thickness of several nanometers
can be observed on the thin particle edges as well as small carbon agglom-
erates (typical size < 6 nm) at certain spots on the substrate surface.

5.2 OXIDES

Antonelli and Ying (1995) synthesized hexagonally packed mesoporous

TiO2 via a modified sol-gel synthesis. Mesoporous TiO2 has been widely
known because of its high surface area and large uniform pores, as these
properties have vital importance in catalysis and solar cell applications.
A variety of mesoporous TiO2 have been synthesized using surfactants as
templates through conventional methods (Kluson et al., 2000), but conven-
tional synthesis of mesoporous TiO2 takes longer times, sometimes even
several days for completion. Wang et al. (2000) reported a sonochemical
synthesis of mesoporous TiO2 with wormhole-like framework structures.
Long-chain amine and titanium isopropoxide (TIP) were used as the struc-
ture-directing agent and precursor. This has shortened the synthesis time to
a considerable extent. Mesoporous anatase with a broad pore size distribu-
tion was obtained on injecting TIP directly into deionized water in a cell
under continuous sonication without using any surfactants (Huang et al.,
2000).
Yu et al. (2002) also synthesized three-dimensional and thermally
stable mesoporous TiO2 without using any surfactants via treatment with
high-intensity ultrasound irradiation for a short period of time. These
monodispersed TiO2 sol particles were generated initially by ultrasound-
assisted hydrolysis of acetic acid-modified TIP. Then, the mesoporous
spherical or globular particles were produced by controlled condensation
and agglomeration of these sol nanoparticles under high-intensity ultra-
sound irradiation. It was indicated that these mesoporous TiO2 particles
retain mesoporosity with a narrow pore size distribution and high surface
area up to 673 K. It was found thermally stable, may be due to its thick
inorganic walls, consisting of TiO2 nanoparticles. This synthetic method is
environmentally benign. The photocatalytic activity of mesoporous TiO2
for the oxidation of acetone in air was also observed. Negligible activity
of as-prepared mesoporous TiO2 was attributed to its amorphous structure;
Inorganic, Coordination and Organometallic Compounds119

however, calcined mesoporous TiO2 shows better activity than commer-

cial photocatalyst P25.
Nano-sized noble metal particles show high activity because of their
unique optical, magnetic, and electric properties. These particles have
high catalytic activities for the degradation of some contaminants because
of their very large surface-to-volume ratios. Zhang et al. (2010) devel-
oped a simple, facile, and rapid sonochemical method to synthesize Fe3O4/
Ag composites. These composites can be recycled six times by magnetic
separation without any major loss of activity. The catalytic activity of this
as-prepared composite was also investigated for rhodamine B degradation.
Fe3O4 nanoparticles were also prepared by Li and Gaillard (2009)
using the conventional chemical co-precipitation of Fe(II) and Fe(III)
chlorides (Fe(II)/Fe(III) ratio = 0.5) with 1.5 M NaOH. The black precipi-
tate was magnetically separated and washed. These Fe3O4 microspheres
were modified with (3-aminopropyl)triethyoxysilane (APTES) and soni-
cated for 30 min. Fe3O4/APTES composite (0.05 g) microspheres were
dispersed in 100 mL of 2.9 mM Ag(NH3)2+ solution. After the adsorption
of Ag(NH3)2+, the reaction mixture was irradiated with a high-intensity
ultrasonic probe (20 kHz) in ambient air for 1 h. The resulting dark mate-
rial was separated by a magnet. It was indicated that Fe3O4 and Ag were
present mainly as separated phases in Fe3O4/Ag composites. The catalytic
activity of as-prepared composite catalysts was found to decrease during
the degradation reaction in the recyclable experiments. This may be due to
the fact that a small portion of crystal is lost during the process of catalytic
reaction. It was found that only 0.033 µg mL-1 Ag was in the processed
water indicating that Ag was stable enough to remain attached to the
Fe3O4/APTES. Therefore, it was concluded that this catalyst is stable.
ZnO has been considered as the reference standard among various
semiconducting metallic oxides used for photocatalysis, due to its high
photocatalytic activity, excellent chemical and mechanical stability, lack
of toxicity, and low cost (Miquel et al., 2010). The photocatalytic activity
of ZnO can be improved by changing its size and morphology (Bokhimi et
al., 2008), doping (Kang et al., 1996), use of composite materials (Omidi
et al., 2013), and so forth. ZnO doped with transition metals such as Co,
Ni, Cu, Mn, and Fe has been used to improve photocatalytic activity.
Doping of the ZnO matrix is possible by using various methods (Suwan-
boon et al., 2014). Cd-doped ZnO was synthesized with different amounts
of Cd dopant using sonochemical method. The photocatalytic activity of
120Sonochemistry

as-prepared ZnO was evaluated by the degradation of methylene blue and

methyl orange in solution as model systems. It was interesting to note that
all the as-synthesized Cd-doped ZnO samples were more active photo-
catalytically than pure ZnO for degrading these dyes.
Both 0.005 mol Zn(NO3)2·6H2O and 0–3 % mol Cd(NO3)2·4H2O
were dissolved separately in 100 mL deionized water with vigorous stir-
ring until complete dissolution. Then it is followed by drop-wise addition
of NaOH solution (3 M) until pH becomes 10. The solutions were then
mixed and the mixtures were sonicated for 5 h at 120/480 W, 35 kHz. The
precipitates obtained were isolated by filtration, and washed with water
and ethanol several times. All samples were dried and collected. X-ray
powder diffraction (XRD) patterns of Cd-doped ZnO were found very
similar to those of pure ZnO, indicating that Cd doping did not change the
crystalline structure of ZnO. A slight increase in the lattice constant may
due to the stress developed on the substitution of Zn atoms (0.074 nm) by
Cd atoms (0.092 nm) (Lupan et al., 2011).
Titanium dioxide is a commonly used photocatalyst because of its
unique properties of high optical activity, low cost, nontoxicity, and chem-
ical stability and, therefore, semiconducting titanium dioxide is widely
used in the purification of air and water. Composites of TiO2 and SiO2
were used as they have high photocatalytic and thermal photocatalysts
(Mohseni et al., 2013). As titanium is nontoxic, it is combined with mate-
rials such as ZnO and Ag, and used to eliminate harmful bacteria (Lo and
Huang, 2010). The absorption of visible light is very important for photo-
catalysts. So these days, a combination of two photocatalytic nanocom-
posite components is used to overcome this problem (Chong et al., 2010).
The nontoxic titanium produced nano composites as triplet photocatalysts,
TiO2/SiO2/Ag by sonochemical method, and these composites were used
for removing paint and controlling water pollution.
Copper oxide nanoparticles were synthesized by Reza et al. (2010)
via a sonochemical process using copper nitrate and sodium hydroxide in
the presence of PVA as a starting precursor. The product was calcined at
various temperatures ranging between 400 and 700 °C. High-purity CuO
nanoparticles were obtained by this process. It was also reported that crys-
tallization and particle size of CuO were strongly dependent on the reac-
tion time and calcination temperature.
Thermogravimetric (TG) and differential-thermal analyses of copper
oxide nanoparticles (sonicated for 30 min) were performed. There are two
Inorganic, Coordination and Organometallic Compounds121

weight losses in the temperature ranges of 180–250 °C and 500–700 °C.

The first weight loss is originated from evaporation of PVA and deionized
water in mixed solution. The second weight loss is due to the oxidation
of metal copper in air resulting to the crystallization of CuO. XRD data
indicated that good powder of CuO particles can be obtained by sono-
chemical process only. The time of sonication and calcination tempera-
ture were the major factors that decide the formation and crystallization of
CuO nanoparticles (Wongpisutpaisana et al., 2011).
Liu et al. (2009) successfully synthesized porous Cu2O microcubes via
in situ sonochemical route at an ultrasound power of 90 % for 3 h in the
presence of polyvinylpyrrolidone. They used CuCl2·2H2O, C6H12O6·H2O,
trisodium citrate, and NaOH as precursor materials. They showed that
the as-prepared porous Cu2O microcubes possessed good electrochem-
ical and photocatalytic properties. It can degrade organic dye pyronin
B and restrain the propagation of Escherichia coli. It was indicated that
the as-obtained Cu2O crystals have good crystallinity and large size. The
degradation effect was much better as porous Cu2O microcubes have a
bigger surface area in comparison with smooth Cu2O microcubes. It was
observed that the solution was opaque due to the rapid propagation of E.
coli in the absence of porous Cu2O microcubes but the cultivating liquid
containing porous Cu2O microcubes was still transparent, which indicates
that the propagation of E. coli has been restrained. The concentration of
E. coli gradually reduced with the increase in the amount of porous Cu2O
mirocubes from 0 to 200 mgl−1.
A single-step sonochemical synthesis of hybrid vanadium oxide/poly-
aniline nanowires has been carried out by Malta et al. (2008) starting from
crystalline V2O5 and aniline in aqueous medium. This method of synthesis
provides high-power ultrasounds on heterogeneous solid–aqueous phases,
ultimately leading to nanowires with the dimension 5–10 mm length. The
oxidative polymerization within the inorganic matrix goes along with
morphological changes and monomer intercalation. The electronic conduc-
tivity of these hybrid nanowires reaches 0.8 S·cm−1 at room temperature.
Zhang et al. (2007) synthesized polycrystalline CeO2 nanorods
(5–10 nm diameter and 50–150 nm length) via ultrasonication using poly-
ethylene glycol (PEG) as a structure-directing agent at room temperature.
The effect of various operation reaction parameters was investigated such
as content and molecular weight of PEG, KOH concentration, pH, and
the time of sonication. They also observed that the content and molecular
122Sonochemistry

FIGURE 5.1  TEM images of CeO2 nanorods. (a and b) HRTEM image of the single
nanorod (c)
Source: Zhang et al., 2007, with permission.

weight of PEG as well as sonication time played a crucial role in the

formation of one-dimensional CeO2 nanorods. High-resolution transmis-
sion electron microscopy (HRTEM) revealed that the CeO2 nanorods
were composed of many tiny interconnected grains at various orientations
(Fig. 5.1).
Activated barium hydroxide is used as a catalyst as it is nontoxic, easy
to handle, low cost, and has a high catalytic activity (Pinto et al., 2000).
Activated barium hydroxide has been used as a catalyst for the synthesis
of 1,5-diarylpenta-2,4-dien-1-ones under ultrasound exposure (Xin et al.,
2009). This methodology offers several advantages over other conven-
tional methods with simple procedure such as excellent yields, shorter
reaction times, and milder conditions. 1,5-Diarylpenta-2,4-dien-1-ones
are important intermediates and raw materials widely used as precursors
to different drugs, nonlinear optical materials, and biological activities.
Inorganic, Coordination and Organometallic Compounds123

Conventional synthesis of 1,5-diarylpenta-2,4-dien-1-ones takes a longer

time (20 h) via Claisen–Schmidt condensation and poor product yields
(55–81 %) (Batovska et al., 2007).
Patil and Gogate (2016) synthesized vanadium pentoxide supported on
alumina as a heterogeneous catalyst. They used two different approaches:

1. Conventional synthesis which is based on ozonation

2. Combination of ultrasound with ozonation

In both these cases, commercially available vanadium sulfate hydrate

was used as a precursor. It was observed that nanoparticles of synthe-
sized catalyst with ultrasound resulted in reduced particle size and higher
stability. As-obtained catalyst was used in the reaction for synthesis of
n-hexyl acetate.
LiCoO2 compound exhibits two different phases. These are:

• Low-temperature phase (LT-LiCoO2 and pseudo-spinel structure)

• High-temperature phase (HT-LiCoO2 and a-NaFeO2-type structure)

Nanosized HT-LiCoO2 powders were synthesized sonochemically in

an aqueous solution of lithium hydroxide containing cobalt hydroxide at
∼ 80 °C without high-temperature treatment (Kim and Kim, 2008). The
effects of various parameters such as LiOH concentration, oxidation
conditions, time of ultrasound irradiation, and temperature on the forma-
tion of the nano-sized HT-LiCoO2 phase were observed. The HT-LiCoO2
aggregates have a mean particle diameter of ∼ 20  nm.
A facile and surfactant-free method was reported by Xie et al. (2012)
for synthesizing double-pyramid-like ZnO architectures via an ultrasound-
assisted route. On ultrasound irradiation, uniform octahedral ZnC2O4
precursors were first formed, which were then transformed to macro-/
mesoporous ZnO with the original shape after calcination at 350 °C.
As-obtained hierarchical ZnO double-pyramids were having ZnO nanopar-
ticles (∼ 35 nm size and pores of 20–100 nm). It was revealed that the
presence of intrinsic defects in the porous ZnO accounts for the narrowed
band gap (3.16 eV). This ZnO has large specific surface area and therefore,
exhibits extraordinary photocatalytic activity to degrade organic pollutants.
Nano-sized CoAl2O4 pigments are important as a colouring agent in
glaze and bulk tile compositions. These were successfully synthesized by
124Sonochemistry

avoiding mechanical stirring via hydrothermal process with ultrasonic irra-

diation (Kim et al., 2012). A difference was also observed by Kim et al. in
physicochemical and optical properties of the CoAl2O4 pigments prepared
by an ultrasonic-assisted-hydrothermal method. It was reported that ultra-
sonic-assisted CoAl2O4 pigments presented a narrow particle size distribu-
tion with vivid blue colour, and better thermal stability so as to allow their
use for ceramic inks processed at high temperature. Nanosized powders
with better physicochemical and optical properties were achieved by the
application of ultrasonic irradiation during the hydrothermal process.
Yahyavi et al. (2015) synthesized Ni–Co/Al2O3–MgO nanocatalysts
by taking different ratios of Al/Mg ratios via sonochemical method.
These catalysts were used in CH4/CO2 reforming. Ni–Co/Al2O3–MgO
nanocatalyst with Al2O3/MgO = 1.5 was also prepared via impregnation
method to know the effect of ultrasonic irradiation. It was observed that
the sonochemical method gives better dispersion, smaller particle size,
higher specific area, uniform morphology and higher catalytic efficiency
in comparison with the sample obtained by impregnation. Among all the
prepared samples via sonochemistry with different ratios, the Ni–Co/
Al2O3–MgO nanocatalyst with Al2O3/MgO = 5 showed good catalytic
performance.
Manganese dioxide was obtained via an ultrasound–microwave-inten-
sified precipitation reaction with the soft template of triblock polymer P123
(Wang et al., 2014). By combining these methods, microwave heating and
ultrasonic dispersion, MnO2 particles were obtained with loose sphere-
network structure with tiny pores of 4–5 nm diameter inside the spheres
along architectural mesopores and macropores among the secondary parti-
cles. This loose network became more solid with bigger particles and less
surface area on replacing microwave heating or ultrasonic dispersing with
conventional hot-plate heating or magnetic stirring. It was reported that
MnO2 prepared with intensified precipitation had the highest discharge
specific capacitance of ∼ 214  Fg−1 and it showed almost no capacitance
decline even after 1000 cycles but some acceptable decline after 5000
cycles. The MnO2 sample had a spherical morphology and the diameter
was ∼ 200 nm. These spheres had a loose network structure and were
composed of nanorods (∼ 5 nm in diameter and 100 nm length) (Fig. 5.2).
X-ray diffraction patterns of sample indicated that the sample of MnO2
was in a partially crystalline state and it is in α-MnO2 form; however, this
sample changed to Mn2O3 with high crystallinity on calcining at 520 °C.
Inorganic, Coordination and Organometallic Compounds125

FIGURE 5.2  SEM (a, b) and TEM images of MnO2 sample (c, d)
Source: Wang et al., 2014, with permission.

Ultrafine powders of chromium oxide (Cr2O3) and manganese oxide

(Mn2O3) have been prepared at room temperature by the sonochemical reduc-
tion of an aqueous solution containing ammonium dichromate [(NH4)2Cr2O7]
and potassium permanganate (KMnO4), respectively (Dhas et al., 1997). The
yield of the sonochemical reduction has been enhanced by raising the reaction
temperature or by using an aqueous solution of ethanol (0.1 M). As-obtained
powders are nano-sized (50−200 nm), and the surface area varies from 35 to
48 m2·g−1. Amorphous Mn2O3 and Cr2O3 powders were converted into crys-
talline form by heating them at 600 and 900 K, for 4 h, respectively.

5.3 SULPHIDES

Dhas and Suslick (2005) first reported the sonochemical preparation of bulk
MoS2 using Mo(CO)6 and elemental sulfur in 1,2,3,5-tetramethylbenzene.
126Sonochemistry

Later, mixed Co–Mo and Ni–Mo sulfides supported on Al2O3 were also
prepared using a similar approach (Dhas et al., 2001). Catalytic activity
of these materials was found to be three to five times higher than that of
the conventional catalysts. Thus, there is a good potential in sonochemical
method for improving the performance of hydrodesulfurization catalysts.
Uzcanga et al. (2005) developed a sonochemical reaction between
(NH4)6Mo7O24 and CH3COSH in aqueous solution that leads to the forma-
tion of hollow MoS2 microspheres. It was observed that the walls of these
hollow spheres have short- and low-stacked MoS2 fringes. These fringes
provide this material a very high intrinsic catalytic activity in the thio-
phene hydrodesulfurization reaction. The sonochemically prepared MoS2
consists of open spherical aggregates of 0.2–2 μm in diameter with walls
composed of smaller size particles (fig. 5.3a), while it was clearly shown
by transmission electron microscopy (TEM) (fig. 5.3b) that the large
aggregates as well as surrounding smaller particles are hollow. Such a
morphology is like the shape of the cavitation bubbles in the sonicated
solution. It seems to be first report of ultrasound-assisted formation of
inorganic hollow-based spheres.

FIGURE 5.3 Sonochemically prepared MoS2 microspheres: Scanning electron

micrograph (a) and Low-magnification transmission electron micrograph (b)
Source: Uzcanga et al., 2005, with permission.
Inorganic, Coordination and Organometallic Compounds127

FIGURE 5.4  High-resolution electron microscopy images of MoS2 (Sonochemically

prepared (left) and MoS2 ex-ATM (right).
Source: Weber et al., 1995, with permission.

It was found that sonochemical preparation of MoS2 in aqueous solu-

tion affects not only the shape of agglomerates but also the properties of
MoS2 crystallites. The XRD pattern of this MoS2 indicates that there is
lower stacking of the slabs than the sample obtained by thermal decom-
position. This fact is further supported by high-resolution electron micro-
graphs (fig. 5.4). It was also noticed that the slabs are much shorter in
the sonochemically prepared sample and less ordered as compared to
ex-ATM sample. In spite of this difference in sonochemically and ther-
mally decomposed ATM, molybdenum is present in fully sulfidized form,
with Mo 3d3/2˗5/2 doublet with the respective binding energies 229.2 and
232.6 eV corresponding to the Mo(IV) species in the MoS2 sulfide (Weber
et al., 1995).
Wang et al. (2006) synthesized PbS hollow nanospheres of diameter
80–250 nm using surfactant-assisted sonochemical route. The structural
characterization of PbS nanoparticles indicates that these particles have
diameters of about 12 nm and the shells are hollow spheres. The formation
of the hollow nanostructure was explained by a vesicle-template mecha-
nism, where sonication and surfactant play important roles. Uniform silica
layers were successfully coated onto the hollow spheres via a modified
Stober method to enhance their performance for some promising applica-
tions. The morphology and microstructure of PbS hollow nanospheres are
128Sonochemistry

FIGURE 5.5  TEM, HRTEM and SEM images of the PbS hollow spheres (a–e)
Source: Wang et al., 2006, with permission.

clearly demonstrated by TEM and scanning electron microscopy (SEM)

images (Fig. 5.5), where the strong contrast between the dark edge and
the relatively bright center is due to their hollow nature. The diameter
of the hollow sphere is in the range of 80–200 nm and the wall thick-
ness was around 20 nm (approximately) from the enlarged TEM image
of a single hollow sphere. Spherical nanostructures with a smooth exte-
rior are clear from the SEM image. The diameter of the sphere is about
80–250 nm, which was comparable to the TEM results. SEM indicates
that the spheres are not very compact and some of them may be destroyed
by intensive post sonication. PbS nanocrystals with diameters of about
12 nm were observed, indicating that the walls of the PbS nanospheres are
really constructed by small particles.
The synthesis of single-crystalline Sb2S3 nanorods by the ionic liquid-
assisted sonochemical method (ILASM) was carried out by Salinas-
Estevan et al. (2010) (Fig. 5.6). Antimony(III) chloride, thioacetamide,
and absolute ethanol were used as starting materials and 1-butyl-3-methy-
limidazolium tetrafluoroborate ([BMIM][BF4]) was used as ionic liquid.

FIGURE 5.6  Synthesis of Sb2S3 nanorods

Source: Wang et al., 2003, with permission).
Inorganic, Coordination and Organometallic Compounds129

It was reported that the ionic liquid played an important role in the final
morphology of Sb2S3. Single-crystalline Sb2S3 nanorods were prepared in
the presence of [BMIM][BF4], whereas round Sb2S3 structures were formed
in the absence of [BMIM][BF4], under otherwise identical conditions.
CuInS2 (CIS) nanoparticles were synthesized successfully via a new
copper precursor [bis(acetylacetonato)copper(II)], [Cu(acac)2], at room
temperature by ultrasonic method (Amiri et al., 2014). The effect of sulfur
source, solvent, and reaction time was investigated on product morphology
and particle size. CuInS2 nanoparticles were prepared and coated on FTO.
Later, the coated FTO was sintered so that a compact and dense CuInS2
film was produced and photovoltaic characteristics were measured.
Wang et al. (2002) prepared bismuth sulfide nanorods by sonochem-
ical method from an aqueous solution of bismuth nitrate and sodium thio-
sulfate in the presence of complexing agents. Bismuth sulfide nanorods
with different diameters and lengths could be obtained by using different
complexing agents, including ethylenediaminetetraacetic acid, triethanol-
amine and sodium tartrate. Bi2S3 nanorods have also been successfully
prepared by using thioacetamide as the sulphur source. When 20 % N,N-
dimethylformamide was used as the solvent, higher yield was observed and
smaller sizes of Bi2S3 nanorods were obtained. The TEM image revealed
that the product consists of needle-shaped nanorods. The diameter of the
nanorods ranges from 20 to 30 nm, and the length is about 200–250 nm.
This rod-type morphology of the product was possibly due to the inherent
chain-type structure of bismuth sulfide.
It is known that Bi2S3 crystallizes with a lamellar structure with linked
Bi2S3 units forming infinite bands, which in turn are connected via weaker
Van der Waals interactions. It seems that the formation of Bi2S3 may have
been originated from the preferential directional growth of Bi2S3 crystallites.
The sonication of InCl3 with thioacetamide in an aqueous solution has
led to different products, depending on the sonication temperature (Avivi
et al., 2001). On one hand, sonication at 0 °C yielded In2O3 as the major
product and In2S3 as a minor component. On the other hand, when the
reaction was carried out at room temperature, nanocrystalline In2S3 was
obtained as the sole product. The products of sonication at 0 °C were
obtained in the amorphous form.
Amorphous WS2 has been prepared by ultrasound irradiation of
W(CO)6 solution in diphenylmethane (DPhM) in the presence of a slight
excess of sulfur at 90 °C under argon (Nikitenko et al., 2002). On heating,
130Sonochemistry

the amorphous powder at 800 °C under argon yields WS2 nanorods and
their packings. The average size of WS2 nanorods was found to be 3–10 nm
and 1–5 mm thickness and length, respectively.
Yin et al. (2003) obtained ZnS/PS microspheres through sonochemical
treatment containing zinc acetate and thioacetamide in an ethanol solution.
It was observed that the composite particles were optically hollow due to
the large refractive index contrast between the core and shell materials.
Hollow ZnS spheres were formed by annealing the core-shell spheres in a
muffle oven under the stream of 3:1 nitrogen and hydrogen gas at 600 °C.
PS microspheres obtained by emulsion polymerization were smooth, and
monodisperse with diameter was about 265 nm. TEM image showed that
ZnS shell appears as a dark ring around the PS core. It was found that the
particles slightly agglomerated.
However, it was found that the coating on the PS microspheres was
smooth and uniform after the microspheres were treated in the ethanol
solution of zinc acetate and thioacetamide by sonochemical treatment. The
thickness of ZnS shells was about 67.5 nm. When the PS microspheres
were treated in ethanol solution for 3 h, smooth and integral coating on PS
beads was obtained. If the treatment time was carried out < 3 h, only part
of PS microspheres was covered with ZnS and nonintegral coating was
formed. They indicated that ZnS nanoparticles were formed first and then
adsorbed onto the surface of PS microspheres. The diameter of hollow
ZnS spheres was about 220 nm. In order to protect the ZnS from oxida-
tion, the composite was calcined in a muffle oven under the stream of 3:1
nitrogen gas and hydrogen gas.
Slurry of amorphous silica microspheres, zinc acetate, and thioacet-
amide in an aqueous medium for 3 h under ambient air and ultrasonic irra-
diation yields zinc sulphide coated on silica (Dhas et al., 1999). XRD of
the initial zinc sulfide–silica (ZSS) powder yields diffraction peaks corre-
sponding to the ZnS phase. TEM image of ZSS showed that the porous
ZnS nanoparticles (diameter 1–5 nm) coated the silica (SiO2) surface as
thin layers or nanoclusters, depending on the reactant concentration. Some
structural changes occurred in the siloxane network and surface silanol
groups of SiO2 on ultrasonic deposition of ZnS as evident from IR. The
optical absorption of porous ZnS shows a broad band at around 610 nm,
which was attributed to the unusual surface-state transition.
The absorption energy of the surface state transition was lower than
the band gap of the ZnS particles and probably, it stems from the dangling
Inorganic, Coordination and Organometallic Compounds131

surface bonds or defects. On the other hand, ZSS does not show the
surface-state transition of ZnS, may be due to the strong surface interac-
tion with SiO2. It was proposed that the coating process takes place via
ultrasonic-cavitation-induced initial grafting of zinc acetate onto the silica
surface, followed by the displacement of acetate ion by in situ-generated
S2− species.
Regular stibnite (Sb2S3) nanorods with diameters of 20–40 nm and
lengths of 220–350 nm have been successfully synthesized by Wang et  al.
(2003), using a sonochemical method under ambient air from an etha-
nolic solution containing antimony trichloride and thioacetamide. It was
revealed that the Sb2S3 nanorods crystallize in an orthorhombic structure
and predominantly increase in size along the (001) crystalline plane. High-
intensity ultrasound irradiation plays an important role in the formation of
these Sb2S3 nanorods. The sonochemical formation of stibnite nanorods
can be divided into four steps. These are:

• Ultrasound-induced decomposition of the precursor, which leads to

the formation of amorphous Sb2S3 nanospheres
• Ultrasound-induced crystallization of these amorphous nano-
spheres and generation of nanocrystalline irregular short rods
• A crystal growth process, giving rise to the formation of regular
needle-shaped nanowhiskers
• Surface corrosion and fragmentation of the nanowhiskers by ultra-
sound irradiation, resulting in the formation of regular nanorods

The optical properties of the Sb2S3 amorphous nanospheres, irregular

short nanorods, needle-shaped nanowhiskers, and regular nanorods were
investigated by diffuse reflection spectroscopic measurements, and the
band gaps were measured to be 2.45, 1.99, 1.85 and 1.94 eV, respectively.

5.4  COORDINATION COMPOUNDS

Reversible coordination networks were prepared by Paulusse et al.

(2007) combining diphenylphosphinite telechelic polytetrahydrofuran
with [RhCl(COD)]2 or [IrCl(COD)]2 in chloroform. Both these systems
resulted in stable gel formation at concentrations above 50 and 30 g·L−1
for the rhodium(I) and iridium(I) networks, respectively. It was reported
132Sonochemistry

FIGURE 5.7  Effects of sonication on the coordination networks, resulting in loss of the
gel fraction.
Source: Paulusse et al., 2007, with permission.

that ultrasonication of the rhodium(I) gel caused liquefaction after 3 min

followed by regelation, just after 1 min of stopping sonication. On the
contrary, iridium(I) gel was also liquefied after 3 min of sonication, but its
regelation took about 1.5 h at room temperature and required more than 10
days at − 20 °C (fig. 5.7).
It was proposed that sonication of the gels resulted in ligand exchange,
which changes the network topology keeping the coordination chemistry
intact. The fraction of metal centers in active cross-links decreases on
sonication and, as a result, the gel fraction is reduced to zero. Such an
effect offers opportunities to use ultrasound in the activation of dormant
transition metal catalysts.
There is the transient formation of coordinatively unsaturated metal
complexes during reversibly breaking coordinative bonds in the rhodium(I)
and iridium(I) coordination networks. These species are known to be
excellent catalysts in a number of reactions and therefore, this coordina-
tion networks will prove to be promising systems to probe the effect of
mechanical forces on catalytic activity and selectivity.
Co-B catalysts show good practice for hydrogen evolution via hydro-
lysis of alkaline sodium borohydride solutions and, therefore, Cogkuner
et al. (2014) investigated this and proposed a sonochemical approach for
synthesis of Co-B catalysts and hydrolysis of alkaline NaBH4 solutions.
Application of ultrasound on synthesizing process improved both the prop-
erties intrinsic and extrinsic properties of Co-B catalysts such as surface
area, particle size, pore volume, spectral, crystal, and pore diameter. It
was observed that Co-B catalysts prepared by this sonochemical approach
have smaller particle size, higher surface area, and higher pore volume
as compared to the Co-B catalysts prepared by routine co-precipitation
synthesis. It was also indicated that the advantages of alkaline NaBH4
Inorganic, Coordination and Organometallic Compounds133

solution sonohydrolysis provide superficial effects on hydrogen evolution,

that is, maximum hydrogen generation rate with minimizing activation
energy (Fuentes et al., 1987).
Liu et al. (2011) employed ultrasonic irradiation to modify activated
carbon (AC) by sodium hypochlorite, and tested its ability to remove
cobalt(II) from aqueous solutions. Modified AC show enhanced adsorp-
tion capacity for Co(II) and it increases with the increasing NaOCl
impregnating concentration. A combination of adsorption and chemical
precipitation was considered responsible for Co(II) removal. Liu et al.
(2011) reported that enhanced Co(II) removal by the ultrasonic-assisted
NaOCl modified carbons was due to improved cation exchange capacity
and higher content of adjacent aliphatic functional groups providing more
complexation sites for cobalt.
Dharmarathna et al. (2012) developed a rapid and direct sonochemical
method to synthesize cryptomelane-type manganese octahedral molec-
ular sieve (OMS-2) materials. Such materials have very high surface area
of 288 ± 1  m2g−1 and small particle sizes in the range of 1–7 nm under
nonthermal conditions. Reaction time was reduced by 50 % using a cosolvent
system such as water/acetone apart from achieving higher surface area. The
following factors were identified as most important in the formation of the
pure cryptomelane phase: (i) reaction time, (ii) temperature, and (iii) acetone
concentration. They reported that OMS-2 materials synthesized using sono-
chemical methods were having greater amounts of defects and, as a result,
show excellent catalytic performances for oxidation of benzyl alcohol than
to OMS-2 synthesized using reflux methods and commercial MnO2.
Li et al. (2013) investigated the adsorption of chromium(VI) and
uranium(VI) nitrate on Ca–Al hydrotalcite (Ca–Al LDHs) compounds.
These materials were synthesized in a modified co-precipitation method
under ultrasonic irradiation. Different factors affecting synthesis of
compounds were also investigated such as temperature, reaction time,
calcination and aging conditions. It was reported that Ca–Al LDHs has
the highest capacity absorption for both Cr(VI) and U(VI), 104.82 ± 0.02
and 54.79 ± 0.02 mg g−1 for rate of adsorption up to 98.78  ±  0.02 % and
90.28 ± 0.02 %, respectively. It suggests that Ca–Al LDHs are efficient in
removing these U(VI) ions; however, they show fast adsorption and slow
release as compared to Cr(VI).
The sonochemical synthesis of Mn–ferrite nanoparticles was reported
by Goswami et al. (2013) using acetates as precursors. Mn–ferrite oxide
134Sonochemistry

FIGURE 5.8  Field-emission scanning electron microscopy (FE-SEM) images of Mn–

ferrite formed with external calcination.
Source: Goswami et al., 2013, with permission.

precursors were formed by sonication followed by their external calci-

nation. It was observed that pH does not play any dominant role in this
synthesis. Collisions between metal oxide particles induced by shock
waves generated by transient cavitation were not sufficient to cross the
activation energy barrier so as to form ferrite. Calcination temperature is
an important parameter that influences the magnetic properties of ferrites.
It was observed that calcination at 950 °C leads to the formation of rods
with grain growth that introduces large shape anisotropy. Ferrite particles
have a spherical shape, more or less, with a narrow size distribution as
evident from FE-SEM images. The particle size was found to increase
with calcination temperature (fig. 5.8). High surface activity at the nano-
meter size range may be due to some agglomeration.
The preparation of micro-hexagonal rods of a new 1D polymeric
lead(II) complex containing the Pb2-(μ-N3)2 motif, [Pb(dmp)(N3)2]n
Inorganic, Coordination and Organometallic Compounds135

(where dmp = 2,9-dimethyl-1,10-phenanthroline) by the sonochemical

method has been reported by Hanifehpour et al. (2012). A single-crys-
talline material was obtained by applying a heat gradient applied to a
solution of the reagents. The single-crystal XRD analyses show that
the coordination number for the Pb(II) ions is six, PbN6, with stereo-­
chemically active electron lone pairs and that the coordination sphere
being hemidirected. It also show that the chains of [Pb(dmp)(N3)2]n
interact with each other through the π–π stacking interactions creating
a 3D framework.
Mizukoshi et al. (1999) prepared platinum nanoparticles in an aqueous
system using high-intensity ultrasound (200 kHz, 6 W·cm−2). The particles
formed in the presence of a surfactant (sodium dodecyl sulfate, SDS) were
stable, homogeneously spherical, and relatively monodispersed with an
average 2.6 nm diameter. The rate of formation of the platinum nanopar-
ticles was 26.7  μM min−1 in the Pt(II)–SDS system. Reducing species
generated near and/or in the hot bubbles, which were sonochemically
induced in the media, would react with the [PtCl4]2− complexes to form
the platinum nanoparticles.
Three kinds of the reducing species were proposed to be formed in the
sonicated system and these are:

• Radicals formed from the thermal decomposition of SDS at the

interfacial region between the cavitation bubbles and bulk solution
• Radicals formed via reactions of the hydroxyl radicals or hydrogen
atoms with SDS
• Hydrogen atoms

During the reduction of the Pt(II) ion, the effectiveness of while first
these processes are in the order: Second is more effective and then third
is only slightly effective, whereas in the cases of gold and palladium
nanoparticles, the hydrogen atoms were the main reductive species.
A nano-sized mixed ligand Cd(II) coordination polymer, {[Cd(bpa)
(4,4′-bipy)2(H2O)2](ClO4)2}n (where bpa = trans-1,2-bis(4-pyridyl)ethane
and 4,4′-bipy = 4,4′-bipyridine, has been synthesized by a sonochemical
method (Ranjbar and Morsali, 2011). This grows in one dimension by
two different bridging ligands, 4,4′-bipy and bpa. CdO nanoparticles were
obtained by direct calcination at 500 °C and decomposition in oleic acid at
200 °C of this nano-sized coordination polymer.
136Sonochemistry

Moosavi et al. (2012) investigated the growth of silver bromide

nanoparticles on polyester fiber by sequential dipping steps in alternating
bath of potassium bromide and silver nitrate under ultrasound irradia-
tion. They studied the effects of ultrasound irradiation, concentration, and
sequential dipping steps in growth of the AgBr nanoparticles. Particle sizes
and morphology of nanoparticle were found to depend on power of ultra-
sound irradiation, sequential dipping steps, and concentration. Moosavi
et al. (2012) reported a decrease in the particles size in these systems, on
increasing the sonication power. An increase in sequential dipping steps
and concentration also led to an increase in particle size.
A new methodology for the synthesis of pillared clays with the Al13–Fe
and Al13–Fe–Ce polymers in solid state was adapted by using microwaves
and ultrasound in the aging of the olygomeric solution, in the precipitation
of the corresponding sulfates, and in the intercalation of the polymer with
the powdered clay (Olaya et al., 2009). This methodology reduces signifi-
cantly the water consumption in the intercalation process, and the time for
the synthesis of both the polymer in the solid state, and the pillared clay.
A higher percentage of Fe and Ce, associated with Al13–Fe and Al13–Fe–
Ce sulphates, was dissociated during the exchange process with nitrate. A
monoclinical structure of Al13 and Al13–Fe sulfates was observed, whereas
the Al13–Fe–Ce sulfates present two crystalline phases, monoclinical and
cubical. It was shown that the pillared clays, synthesized with this meth-
odology, have more intense and remarkably homogenous pillaring signals,
and better textural properties also than the clays pillared by other conven-
tional method of synthesis. The catalytic activity was assessed for the
phenol oxidation in dilute aqueous medium at 25 °C and at atmospheric
pressure. As-synthesized solids showed similar catalytic properties than
those prepared by the conventional method.
Arenas et al. (2013) obtained hybrid nanocomposites based on anatase
titania:polypyrrole (TiO2:PPy) from a simple, one-step, ultrasonic (UT)-
assisted synthesis. The properties of these crystalline nanocompos-
ites were compared with those of others fabricated using cold-assisted
synthesis without any UT assistance, which required a hydrothermal
treatment to yield crystalline anatase titania in the nanocomposite at low
temperature (130 °C) and that too in a short time (3 h). The SEM results
demonstrated that the UT-assisted synthesis is an easy method to obtain
anatase TiO2:PPy nanocomposites with controlled morphology using low
Inorganic, Coordination and Organometallic Compounds137

energy. As absorption in the visible region was observed (λmax = 670  nm),

which indicates that these nanocomposites are promising candidates for
harvesting energy in solar cells. Devices based on these nanocomposites
were also evaluated for their electrical properties, where an increase in the
photocurrent was observed with the nanocomposites obtained a from the
UT-assisted synthesis.
A new nanostructured Bi(III) supramolecular compound, {[Bi2(4,4′-
Hbipy)1.678(4,4′-H bipy)0.322(μ-I)2I5.678] (4,4′-bipy)}, (where 4,4′-
bipy = 4,4′-bipyridine}, was synthesized by a sonochemical method
(Soltanzadeh & Morsali, 2010). Its nanostructure and crystal structure were
investigated using SEM, powder XRD, IR spectroscopy, and elemental
analysis. The thermal stability of bulk compound and nano-sized particles
was studied by TG and differential thermal analyses. Bi2O3 and BiI3 nano-
structures were obtained by calcinations of these nanostructures at 400 °C
under air and nitrogen atmospheres, respectively.
Fard-Jahromi and Morsali (2010) synthesized nanostructures of two
new Pb(II) two-dimensional coordination polymers, [Pb(μ-4-pyc)(μ-NCS)
(μ-H2O)]n and [Pb(μ-4-pyc)(μ-N3)(μ-H2O)]n, where (4-Hpyc = 4-pyridin-
ecarboxylic acid), via the sonochemical method. These compounds were
structurally characterized and consisted of two-dimensional polymeric
units. Pb2(SO4)O and PbO nanoparticles were obtained by calcination of
the nanostructures at 600 °C. This method of preparation of coordination
polymers may have some advantages such as it takes place in shorter reac-
tion times, produces better yields, and also coordination polymers of nano-
size. Reduction of the particle size of the coordination polymers to a few
dozen nanometers results in lower thermal stability as compared to the
single crystalline samples.
A new nano-sized lead(II) coordination polymer of maleic acid
(H2Mal), [Pb(μ7-Mal)]n has been synthesized by Aboutorabi and Morsali
(2010) via sonochemical method. The compound was structurally char-
acterized by single-crystal XRD. Thermal stability of nano and bulk
samples of compound was compared with each other. Pure-phase micro-
sized lead (II) oxide was produced after the calcination of nano-sized
compound at 600 °C. The morphology of compound is also quite inter-
esting. It is a nano flower-like structure formed by nano-plates with sizes
of about 40–70 nm. XRD shows that the complex in the solid state is a
2D polymeric network.
138Sonochemistry

Okitsu et al. (2005) investigated the rate of sonochemical reduction

of Au(III) to produce Au nanoparticles in aqueous solutions containing
1-propanol. This reaction was found to be strongly dependent on the ultra-
sound frequency. The size and distribution of the Au nanoparticles can
also be correlated with the rate of Au(III) reduction, which in turn is influ-
enced by the applied frequency. They suggested that the rate of Au(III)
reduction as well as the size distribution of Au particles was governed
by the chemical effects of cavitation and therefore, the rate is not signifi-
cantly affected by the physical effects accompanying ultrasound-induced
cavitation.
Straw-like nanostructure of a new mixed-ligand Zn(II) two-
dimensional coordination polymer, {[Zn(μ-4,4′-bipy)(μ-3-bpdb)(H2O)2]
(ClO4)2·4,4′-bipy·3-bpdb·H2O}n, (where 4,4′-bipy = 4,4′ bipyridine and
3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene), was synthesized by
a sonochemical method (Khanpour et al., 2010). This compound consisted
of two-dimensional polymeric units. ZnO nanoparticles were obtained by
calcination of this compound at 500 °C under atmospheric air.

5.5  ORGANOMETALLIC COMPOUNDS

The field of organometallic sonochemistry was pioneered by Renaud

(1950), who reported the preparation of organolithium, organomer-
cury, and organomagnesium compounds in undried solvents in simple
cleaning bath. Based on the formation or reaction step, organometallic
sonochemistry is divided into two categories: homogeneous and hetero-
geneous processes. Homogeneous process requires a high-intensity
ultrasound to alter chemical reactions in a single liquid, whereas hetero-
geneous process uses ultrasound to alter chemical reactions in two-phase
system, where the mass transfer takes place from the bulk solution to
metal surface.

5.5.1  HOMOGENEOUS SONOCHEMISTRY

5.5.1.1 CLUSTRIFICATION

The clustrification of Fe(CO)5 to Fe3(CO)12 in alkane solvents during

sonolysis was observed, together with the formation of finely divided iron
Inorganic, Coordination and Organometallic Compounds139

(Suslick et al., 1981; 1983). The proposed mechanism during sonolysis of

Fe(CO)5 has been proposed as:

During cavitation, the initial multiple dissociative loss of CO from

Fe(CO)3 takes place.

Fe(CO)3 + Fe(CO)5   Fe2(CO)8

Formation of Fe(CO)8 was confirmed by ligand-trapping studies.

2Fe(CO)4   Fe2(CO)8

Dimerization of Fe(CO)4 takes place in the localized cavitation site.

The reaction of putative Fe2(CO)8 with Fe(CO)5 proceeds through
initial dissociation in analogy to the matrix isolation following first-order
kinetics.

Fe2(CO)8 + Fe(CO)5   Fe3(CO)12 + CO

Sonolysis of Fe2(CO)9 yields Fe(CO)5 and finely divided iron; on the

contrary, Fe2(CO)9 is not generated during the sonolysis of Fe(CO)5 to
Fe3(CO)12. These reactions are summarized in Table 5.1.

TABLE 5.1  Some Clustrifications.

Reactant Product References
Fe(CO)5 Fe3(CO)12, Fe Suslick et al. (1981)
Fe2(CO)9 Fe, Fe(CO)5 Suslick et al. (1983)

5.5.1.2  LIGAND SUBSTITUTION

Sonication of Fe(CO)5 in the presence of phosphines or phosphites yields:

Fe(CO)5−n Ln  (n = 1, 2, and 3).

140Sonochemistry

Fe(CO)4 + L   Fe(CO)4L

Fe(CO)4L does not sonochemically convert to Fe(CO)3L2.

Fe(CO)3 + L   Fe(CO)3L

Fe(CO)3 + CO   Fe(CO)4

Fe(CO)3L + L   Fe(CO)3L2

Sonochemical ligand substitution has been observed to occur with a

variety of metal carbonyls. Ligand substitution (L)* reaction in homoge-
neous organometallic sonochemistry is represented in Table 5.2.

TABLE 5.2  Some of the Ligand Substitution Reactions.

Reactants Products References
Fe(CO)5 + L Fe(CO)4L, Fe(CO)3L2, Fe(CO)2L3 Suslick et al. (1981, 1983)
FeCp(CO)2I + L FeCp(CO)(L)I Suslick and Wang
Cr(CO)6 + L Cr(CO)5L, Cr(CO)4L2, Cr(CO)3L3 Suslick et al. (1981, 1983)
Mo(CO)6 + L Mo(CO)5L, Mo(CO)4L2 Suslick et al. (1981, 1983)
W(CO)6 + L W(CO)5L, W(CO)4L2 Suslick et al. (1981, 1983)
Mn2(CO)10 + L Mn2(CO)8L2 Suslick et al. (1981, 1983)
L: Phosphines and phosphites

π-Allyl lactone (tricarbonyl) iron complexes are useful intermediates

to synthesize lactones and lactam (Geoffroy and Wrighton, 1979).
Similar reaction is observed thermally with Fe(CO)4 (Tetrahydrofuran)-
Fe(CO)5 and Fe3(CO)12 do not undergo this type of reaction.

5.5.1.3  SECONDARY SONOCHEMICAL REACTIONS

Metal carbonyls in halocarbon solvents undergo halogenation. The rate of

this reaction is solvent independent.

))))
R3CX   R3C• + X•

2R3C•   R3CCR3
Inorganic, Coordination and Organometallic Compounds141

2X•   X2

M2(CO)10 + 2X•   2 M(CO)5X

M2(CO)10 + X2   2 M(CO)5X

Secondary sonochemical reaction of Co2(CO)8 in n-alkanes (C5H12

through C10H22) yields Co2(CO)6(H2C2) and Co2(CO)10(H2C2) with a small
amount of Co4(CO)12, as it is formed due to pyrolysis of Co2(CO)8. The
presence of (H2C2) is confirmed by isotopic labeling.

5.5.1.4  SONOCATALYTIC REACTIONS

Isomerization of 1- pentene to cis- and trans-2-pentene can be catalysed

by metal carbonyls upon sonication.

M(CO)n   M(CO)m + (n − m)CO

M(CO)n + 1-alkene   M(CO)x  (1-alkene) + (m − x)CO

M(CO)x (1-alkene)   M(CO)x(H) (π-allyl)

M(CO)x(H) (π-allyl)   M(CO)x(2-alkene)

M(CO)x (2-alkene) + 1-alkene   M(CO)x(1-alkene) + 2-alkene

These reactions give the formation of a hydrido-π-allyl intermediate

and alkene rearrangement through hydride migration, which forms more
stable 2-alkene complex. Some of the sonocatalytic reactions are shown
in Table 5.3.

TABLE 5.3  Some of the Sonocatalytic Reactions.

Reactant Product References
Fex(CO)y + 1-alkene cis-, trans-2-alkene Suslick et al. (1981, 1983)
Rux(CO)y + 1-alkene cis-, trans-2-alkene Suslick et al. (1983)
Mox(CO)y + 1-alkene cis-, trans-2-alkene Suslick et al. (1983)
Cox(CO)y + 1-alkene cis-, trans-2-alkene Suslick et al. (1983)
142Sonochemistry

5.5.2  HETEROGENEOUS SONOCHEMISTRY

Sonochemistry has been utilized to accelerate reaction rates involving

metals through surface activation, which is accomplished in the following
three different ways:

• Sonication during the reaction

• Pretreatment of the metal before using it in a conventional reaction
• Conversion of a metal to a different and more reactive form

5.5.2.1 MERCURY

Organomercury refers to the group of organometallic compounds

containing mercury. The Hg–C bond exhibits stability towards air and
moisture, but it is sensitive to light.
The use of ultrasound in liquid–liquid heterogeneous system was
limited to mercury at initial level. Fry and Bujanauskas (1978) observed
that the reduction of 2,4-dibromo-2-4-dimethylpentan-3-one by finely
dispersed mercury in ketonic solvents provides a method to synthesize
4-isopropylidene-5,5-dimethyl-1,3-dioxolan ring system. Here, first
oxyallyl cation is formed.
Inorganic, Coordination and Organometallic Compounds143

 
Oxyallyl cation

This oxyallyl cation reacts with some alcohol or carboxylic acid to

yield the final product.

These reactions represent synthesis of 1,3-dioxolan, which involves

nucleophilic attack on the mercurial oxyallyl cation. The use of ultrasound
results in rate enhancement (Fry and Ginsburg, 1979) in this system. Electro-
chemical reduction by dispersed mercury is explained by the given reaction:

Thiobenzaldehyde or 1,2-diphenylthiirane is not reported to be formed

during the reaction.
Sonochemical reactions of nucleophiles with α,α′-dibromoketones and
mercury have been reported by Fry et al. (Fry and Hen, 1979; Fry and
Lefor, 1979; Fry et al., 1979).
144Sonochemistry

Al-Juaid et al. (1996) studied the preparation and thermal stabili-

ties of organomercury compounds containing the bulky ligands such as
(Me3Si)3C or (PhMe2Si)3C.

where R = Me, iPr, Bu, t-Bu or Ph.

where R2 = C(SiMe2Ph)3; R = Me, Bu or Ph.

where R2 = C(SiMe2Ph)3; R = CH2Ph

It was observed that the replacement of one R group in HgR′′Cl by
some bulky R′ or R′′ group leads to a significant increase in thermal
stability. The compound HgR′′Cl does not react further with LiR′′ in tetra-
hydrofuran, but with LiR′, it gives HgR′R′′.
Hashemi et al. (2012) synthesized a new nano-sized mercury(II) coor-
dination polymers [Hg(4-bpdb)(SCN)2n]; (4-bpdb = 1,4-bis(4-pyridyl)-
3,4-diaza-1,3-butadiene) by a sonochemical method. Such coordination
polymers are suitable precursors for the preparation of nanoscale materials
without the need conditions such as high temperature, longer time, and
control of pressure.

))))
Hg(NO3)2 + 2-bpdh[L]* +  Hg(SCN)2 Hg(4-bpdb)(SCN)2]n

Ranjbar et al. (2013) carried out reaction between 2,9-dimethyl-

1.10-phenanthroline and Hg(CH3COO)2 in the presence of halide ions
(KX, where X = I, Br) under ultrasonic irradiations. This reaction leads to
the formation of HgI2(C14H12N2) and HgBr2(C14H12N2), respectively.
The positive charge on Hg(II) is neutralized by the halide ions serving
as ligands.
Inorganic, Coordination and Organometallic Compounds145

5.5.2.2 ZINC

Kitazume and Ishikawa (1981) synthesized triflurotrimethyl carboninols

from trifluoromethylation of carbonyl compounds with trifluoromethyl
zinc iodide under sonication using 35 W (32 kHz) for irradiation 30 min.

TABLE 5.4  Organometallic Sonochemistry of Mercury.

Reactant Product References
(R2BrC)2CO+(H3C)2CO Fry et al. (1978)

C6H5(H)(Br)CSC(Br)(H)C6H5 t- C6H5(H)C=C(H)C6H5 Fry et al. (1981)

(R2BrC)2CO+ROH (HR2C)CO[C(OR′)R2] Fry et al. (1981)
Hg(NO3)2 + 2-bpdh+Hg(SCN)2 Hg(4-bpdb)(SCN)2]n Al-Juaid et al.
(1996)
Hashemi et al.
(2012)
146Sonochemistry

It was one of the pioneer works in sonication, which formed, when the
reaction was carried out with Zn powder, CF3I dimethylformamide solu-
tions of ketones, and aldehydes alcohols in good yields.
Low-intensity ultrasound was used in this closely related Reformatsky
reaction.

Ultrasonically generated organozinc complexes for perfluoroalkylation

of allyl, vinyl, and aryl halides with Palladium-catalysed cross-coupling
reactions between allyl, vinyl, or aryl halide and perfluoroalkyl iodide
with zinc were also carried out by Kitazume and Ishikawa (1982) using
ultrasonic irradiation catalyst Pd(0).

Han and Boudjouk (1982) by ultrasonic irradiation of zinc with α,α′-

dibromo-o-xylene-generated o-xylene-like species. This σ-xylene species
was reported to be trapped by dienophiles.

It was reported that o-xylylenes derived from 2-bis(bromomethyl)

benzene and 2,3-bis(bromomethyl)naphthalene on reaction with so a
Inorganic, Coordination and Organometallic Compounds147

carbohydrate enone with zinc powder under ultrasound irradiation gave some
tri- and tetra-cyclic products (Chew and Ferrier, 1984), which were finally
converted into the hexahydro-anthracene and –naphthacene derivatives.

Ultrasonic irradiation of the organic halides with Li in the presence

of zinc bromide results in the formation of organozinc reagents. An effi-
cient preparation of various organozinc reagents was reported on sonica-
tion, which adds an α-enones in a conjugate fashion in the presence of
Ni(acac)2. These reagents undergo conjugate addition (Luche et al., 1983).

Repic and Vogt (1982) reported that Simmons–Smith reaction was

facilitated by the activation of zinc with ultrasonic irradiation.

where R = Alkyl, Ar, Bn.

β-Amino-α, β-unsaturated esters were obtained by a sonochemical
Blaise reaction of nitriles, zinc powder, zinc oxide, and ethyl bromoacetate
in THF (Lee and Cheng, 1997). This type of sonication allows for a more
convenient and one-step synthesis using zinc powders, which does not
require any specific activation. This reaction also lowered the amount of
self-condensation side product using only a slight excess of bromoacetate.
148Sonochemistry

It has been reported by Atobe et al. (1998) that the stereoselectivity in the
debromination of dl-stilbenedibromide with zinc powder depended remark-
ably on the frequency of ultrasounds, while this was not true for meso-form.
Ultrasonic radiation increased the rates and the yields of the reactions
of some α-dicarbonyls towards zinc and trimethylchlorosilane (Boudjouk
and So, 1986). It gave bis(trimethylsiloxy)alkenes as the product.

It was observed that zinc powder reduces titanium tetrachloride to

its corresponding low-valent titanium complexes, which can promote
coupling of some aromatic aldehydes and ketones to pinacols. These
corresponding pinacols were obtained with 35–99 % yield in ethyl acetate
at 20–25 °C in 20–45 min under ultrasonic radiation (Li et al., 2007).

5.5.2.3 LITHIUM

It was observed that the preparation of organometallic compounds of

lithium and with various halide derivatives can be improved with ultra-
sonic waves.

R-Br + Li R-Li + Br

where R = n-Pr, n-Bu, Ph.

Excellent yields of organolithium compounds were reported for
n-propyl-, n-butyl-, and phenyl lithium even at room temperature in wet
solvents.
A facile sonochemical preparation of organolithiums and their Barbier-
type coupling with carbonyls has been observed.

R-Li + R′R″CO RR′R″COCOH

The coupling of organic halides (bromides including t-butyl and benzyl)

with carbonyl compounds (aldehydes and ketones) through lithium inter-
mediates occurs in one step in Barbier reaction (Luche & Damiano, 1980).
Such reactions are fast and also provide excellent yields (76–100 %). Trost
Inorganic, Coordination and Organometallic Compounds149

and Coppola (1982) used intramolecular Barbier reaction to synthesize

complex cyclopentanones.
S(+)2-octyl halides react spontaneously or under sonication with
lithium and cyclohexanone to give an optically active alcohol (Souza-
Barboza, Luche, & Petrier, 1987). Its enantiomeric excess and absolute
configuration, strongly suggest the existence of two reactive intermediates
following different stereochemical pathways to the condensation alcohol.
Danhui et al. (1994) reported that sonication of a n-butyl halide,
lithium benzoate, and lithium metal in THF at room temperature provides
the expected ketone and/or benzil in good yields; however, it depends on
the nature of the halogen.

Alkyl and aryl halides were used by Luche et al. (1982) to form
organocopper reagents in the presence of lithium under ultrasonic irradia-
tion, when these were treated in situ with enones to give high yields of
β-alkylated ketones.

This reaction represents organocopper conjugate alkylations of oxones

(Luche et al., 1982).
In a cleaning bath, Petrier et al. (1982) observed that sonication of the
mixture of organic halide, dimethyl formamide and lithium sand in tetra-
hydrofuran provides good yields of aldehydes.

R-Li + (H3C)2NCHO RCH(OLi)(NCH3)2 RCHO + (CH3)2NH

150Sonochemistry

Wurtz-type coupling reactions have been reported of lithium or lithium

borohydride in the presence of organic halides and chlorosilanes/chlo-
rostannanes under sonication.

where M = C, Si, Sn and R = alkyl or aryl.

where M = Si, Ge, Sn; X = Cl, NR2, OR.

The preparation of some main group hydrides from corresponding
chlorides and lithium aluminum hydride using low-intensity ultrasound
has also been reported (Lukevics et al., 1984).

Synthesis of West’s novel disiline (West et al., 1981) upon sonication of

Li with bis(mesityl)dichlorosilane was reported by Boudjouk (Boudjouk
et al., 1982).

…(x)
Inorganic, Coordination and Organometallic Compounds151

Hexamesityl-cyclotrisilane has also been observed in this type of

reaction.

5.5.2.4  OTHER METALS

5.5.2.4.1 Sodium

Ultrasound was used to produce colloidal Na, which produces radical anion
salt of 5,6-benzo-quinoline (Slough & Ubbelohde, 1957). Ultrasound also
facilitates the synthesis of phenylsodium (Pratt & Helsby, 1959).

Aromatic compounds such as naphthalene and biphenyl are also reduced

by alkali metals, giving aromatic anion radicals which are useful as strong
bases in organic synthesis. The use of ultrasound to form such aromatic radical
anions from Na in solvents has also been reported by Azuma et al. (1982).

5.5.2.4.2 Potassium

Colloidal potassium can be easily obtained by ultrasonic irradiation solu-

tion alkyl of dihalides (α, ω) in toluene (Luche et al., 1984). The ultrasonic
dispersion of potassium in toluene or xylene was reported and has been
used for the cyclization of α,ω-difunctionalized alkanes and other reactions.

5.5.2.4.3 Magnesium

Ultrasound has been used in initiating and enhancing synthetic reactions

involving metals as a reagent or catalyst, for example, in the prepara-
tion of Grignard reagent. In the synthesis of Grignard reagent, oxide-free
magnesium and periodic crushing of metal are essential in conventional
methods. To overcome this problem, Yamaguchi et al. (1982) developed
152Sonochemistry

a ultrasound-assisted method for the synthesis of Grignard reagent, where

any grade of magnesium can be used, and no crushing is required.
Ultrasound-accelerated coupling reaction of Grignard reagents with
1,3-dioxolanes of α, β-unsaturated aldehydes has been studied by Lu et al.
(1998).

where R1 = C6H5, C3H7, CH3; R2 = CH3, C2H5, n-C4H9, CH2CH = CH2.

Tuulmets et al. (1995) observed the effect of ultrasonic irradiation on
the kinetics of the reaction of alkyl bromides with magnesium in toluene
in the presence of catalytic amounts of organic bases such as diethyl ether,
tetrahydrofuran. It was observed that sonication exerts an accelerating
effect on all the steps of this reaction.
It has been reported that the pinacol coupling of aromatic aldehydes
and ketones by Mg powder in ammonium bromide aqueous solution
(0.1 mol·L−1) leads to the corresponding pinacols in 22–90 % yields within
1–3 h at room temperature, but under ultrasound irradiation (Li et al., 2005).
They also conducted pinacol coupling reaction of aromatic aldehydes and
ketones with 8–95 % yield, when magnesium in 0.1 M aqueous NH4Cl was
used under ultrasound irradiation at room temperature for 3 h (Li et al., 2006).
Sano et al. (2015) reported a magnesium (II)-mediated Horner–
Wadsworth–Emmons reaction of bis(2,2,2-trifluoroethyl) phosphonoace-
tate derivatives with disubstituted ketenes. Tri- and tetra-substituted allenes
including α-fluorinated allenylcarboxamides were observed as products.

However, the sonochemistry of other alkali metals is less explored.

Inorganic, Coordination and Organometallic Compounds153

5.5.2.5  TRANSITION METALS

Transition metals salts have also been used in sonochemical reactions such
as Fe, Mn, Ni, Cr, V, Ta, Mo, and W. Some of these reactions are reported
in the following section.
A direct immersion ultrasonic horn was used for the reduction of tran-
sition metal (V, Nb, Ta, Cr, Mo, W, Mn, Fe, and Ni) halides soluble in
THF or diglyme with Na to produce carbonyl anions under 1–4 atm. CO at
10 °C (Suslick and Johnson, 1984).

Bonnemann et al. (1983) reported the activation of transition metals,

where Mg species was used to reduce metal salts in the presence of cyclopen-
tadiene, 1,5-cyclooctadiene, and other ligands to form their metal complexes.

2Co(acac)3 + 3Mg(THF)3(η2 – C14H10) 2Co* + 3Mg2+

2Co* + 2C5H6 + 31,5-C8H12 2Co(Cp)(COD) + C8H14

The use of ultrasound in the heterogeneous reactions of some metals of
high reactivity has also been reported.
154Sonochemistry

Wang et al. (2006) carried out pinacol coupling of aromatic aldehydes

by aqueous vanadium(II) solution under ultrasound irradiation at room
temperature, which leads to the corresponding pinacols in 54–93 % yields
within 15–30 min.
It was been observed that titanium tetrachloride is reduced by
lanthanum filings to the corresponding low-valent titanium complex,
which can induce some aromatic aldehydes to the corresponding pinacols
in 28–97 % yields within 10–50 min in ethyl acetate at room temperature
under ultrasound irradiation (Li et al., 2006).

Ultrasound plays a significant role in the synthesis of metal chalcogen-

ides. Sonication is used in the synthesis of oxides and sulfides followed
by calcinations. It has also proved its worth in the preparation of some
coordination polymers. Synthesis of organometallic chemical with Zn,
Hg, Li and Mg like metals was also performed using sound waves and it
has proved to be beneficial. Both the rate of synthesis and the amount of
product were found to increase by the use of sound waves. Ultrasound is
a better option to carry out such processes due to its time-saving and easy
mode of operation.

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CHAPTER 6

NANOMATERIALS
MEENAKSHI SINGH SOLANKI1, SURBHI BENJAMIN2, SURESH C.
AMETA3
1
Department of Chemistry, B. N. University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]
3
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

CONTENTS

6.1 Introduction   ���������������������������������������������������������������������������  160

6.2 Nanoflowers  ����������������������������������������������������������������������������  164
6.3 Nanorods  ���������������������������������������������������������������������������������  167
6.4 Nanocubes  ������������������������������������������������������������������������������  171
6.5 Nanotubes  �������������������������������������������������������������������������������  172
6.6 Nanoribbons  ����������������������������������������������������������������������������  175
6.7 Nanosheets  ������������������������������������������������������������������������������  177
6.8 Nanospheres  ����������������������������������������������������������������������������  179
6.9 Nanoflakes  ������������������������������������������������������������������������������  180
6.10 Nanowires �������������������������������������������������������������������������������  181
6.11 Nanoporous Materials  �������������������������������������������������������������  182
6.12 Graphene and Related Materials  ���������������������������������������������  183
6.13 Miscellaneous �������������������������������������������������������������������������  189
References  �����������������������������������������������������������������������������������������  192
160Sonochemistry

6.1 INTRODUCTION

For many ears, scientists are trying to settle on a precise definition of nano-
materials. In all these attempts, they came to a conclusion that nanoparticles
can be partially characterized by their tiny size, measured in nanometers. A
nanometer is one-millionth of a millimeter—approximately 100,000 times
smaller than the diameter of a human hair. More precisely, nanomaterials
can be defined as a physical substance with size less than approximately
100 nm. Thus, synthesis of nanomaterials is a kind of approach that is
being widely followed in the field of miniaturization of materials.
Some nanomaterials are already present in nature such as blood-borne
proteins essential for life and lipids found in the blood and body fat or
carbon. Nanomaterials could be synthesized from different materials.
But researchers are particularly interested in engineered nanomaterials
(ENMs), which are designed for use in many commercial materials, elec-
tronic device manufacture, chemistry, engineering, environmental reme-
diation or clean-up to bind with and neutralize toxins. Already, thousands
of common products manufactured using ENMs are as follows:

• Day-to-day products: Sunscreens, cosmetics, sporting goods,

stain-resistant clothing, tires, and electronics.
• Medical applications: Diagnosis, imaging and drug delivery
and also in environmental remediation. Nanomaterials can target
specific organs or cells in the body such as cancer cells, and enhance
the effectiveness of any therapy.
• Others: Nanomaterials can also be added to cement, cloth, and
other materials to make them stronger and yet lighter.

Ultrasound provides a new method for the synthesis of nanomaterials

or nanoparticles as it helps us in controlling the size and morphology
of nanoparticles. The formation of nanoparticles (Fig. 6.1) includes the
following steps:

• Acoustic cavitation, which involves the formation, growth, and

implosive collapse of bubbles in a liquid creating extreme condi-
tions inside the collapsing bubble, which serves as the origin of
most of the sonochemical phenomena in liquids or liquid–solid
slurries.
Nanomaterials161

FIGURE 6.1  Formation of nanoparticles.

Source: Wang et al., 2013, with permission.

• Nebulization, which is the creation of mist from ultrasound passing

through a liquid and impinging on a liquid–gas interface and it
forms the basis for ultrasonic spray pyrolysis (USP) with subse-
quent reactions occurring in the heated droplets of the mist.

Cavitation-induced sonochemistry provides a unique interaction between

energy and matter, with hot spots inside the bubbles with tempera-
ture ~ 5000 K, pressures ~ 1000 bar, and heating and cooling rates of
> 1010 K·s−1. Such extraordinary conditions allow a wide range of chem-
ical reactions possible, which is normally impossible otherwise under
ordinary conditions. Thus, it permits the synthesis of different types of
unusual nanostructured materials. In addition to cavitational chemistry,
the microdroplet reactors created by USP also facilitate the formation of a
wide range of nanocomposites (Bang and Suslick, 2010).
Sonication treatment also improves the effectiveness of nanoparticles.
It increases the capability of same photoactive nanoparticles, which can
be widely used in photoelectrochemical (PEC), water splitting, dye-sensi-
tized solar cells, and photocatalysis (Wang et al., 2013).
Ultrasound has various applications in the preparation of nanocom-
posites such as elemental metals, alloys, salts, metal oxides, carbon nano-
forms, coordination compounds, macrocycles, and polymers, as well as
nanoemulsions and nanogels. Not only nanocatalysts can be synthesized
by ultrasound but also can function more actively in its presence. Nano-
catalysts prepared by sonication could also be used in the degradation of
162Sonochemistry

organic pollutants, treatments of tumor, and drug delivery (Kharissova et

al., 2011).
Pokhrel et al. (2016) opined that ultrasound technique provides a simple
pathway for the synthesis of nanomaterials. The high-energy ultrasound
creates tiny acoustic bubbles and within each period—formation, growth
and collapse of bubbles, a coherent phase of material formation is there.
Sonochemical method was proved to be highly localized and effective
method for the synthesis of various chemical and biological compounds
featuring unique morphology and intrinsic property.
Xu et al. (2013) reported that high-intensity ultrasound not only helps
in the synthesis of nanomaterials but also can modify them. As sonochem-
istry caused acoustic cavitation, that is the formation, growth, and implo-
sive collapse of bubbles and therefore, the effect of sonochemistry could
be basically categorized into three effects. These are:

• Primary sonochemistry: It involves gas-phase chemistry occur-

ring inside collapsing bubbles.
• Secondary sonochemistry: It involves solution-phase chemistry
occurring outside the bubbles.
• Physical modifications: These are caused by high-speed jets or
shock waves derived from bubble collapse.

Various physical, chemical, biological, and hybrid processes have been

used for the synthesis of nanomaterials in different forms such as nanopow-
ders, nanoclusters, nanocollides, nanotubes, nanorods, nanowires, nano-
films, nanoplatelets, nanopins, nanoneedles, nanopillars, nanoflowers,
nanocones, nanopencils, nanoflakes, nanosheets, nanoribbons, nanobelts,
nanoplates, nanodots, nanoalloys, nanodiscs, nanorings, nanotripods,

Nanoflower Nanotube Nanowire

FIGURE 6.2  Nanomaterials in different shapes.

Nanomaterials163

Nanorod Nanodisk Nanocubes

Nanocore shell Nanobowl Nanocapsule

Encapsulated nanoparticles Nanodumb bell Nanorice

Nanocone Nanonail Nanoflake

Nanoplatelet Nanopillar Nanoneedle

FIGURE 6.2  (Continued)

164Sonochemistry

nanobricks, nanonails, nanoarrows, nanodumb-bells, nanospheres, and so

on (Fig. 6.2).
Preparation methods depend on the material of interest, type of nano-
materials (zero dimension, 1D or 2D), their size and quantity (Kulkarni,
2014). Some of the methods of synthesis are vacuum synthesis, gas-phase
synthesis, condensed-phase synthesis, high-speed deposition, deposition
method, sol-gel method, high-energy milling, chemical vapour synthesis,
precipitation method, sonochemical method, and so on (Gleiter, 1989;
Solanki et al., 2015).
Among these methods, sonochemical method is the most effective
technique to fabricate nanomaterial as it involves nonhazardous acoustic
radiation. Ultrasound does not directly interact with molecular species
but affects the physical and chemical properties because of cavitational
collapse. It generates drastic conditions of temperature and pressure
locally. Ultrasound irradiation helps to carry out chemical reaction effec-
tively along with high yield and selectivity. This method is beneficial than
other methods as it involves less hazardous starting material, reagent, and
solvent (Gedanken, 2004).

6.2 NANOFLOWERS

Tai and Guo (2008) used ultrasound and microwave simultaneously for the
preparation of single crystalline CdS nanoflowers. The synergistic effect
of both these processes was responsible for formation of well-defined
flower-like CdS nanostructures. It consists of hexagonal nanopyramids
and/or nanoplates depending on different sources of sulphur. CdS nano-
flowers exhibited large blue-shift up to 100 nm as compared to simple
low-dimensional CdS nanostructures. Such nanostructure could be widely
used in optoelectronics devices, catalysis, and solar cells, because of this
shift in optical properties.
Flower-shaped ZnO nanostructures were also synthesized by Singh et al.
(2008) by sol-gel method under exposure to ultrasound. The root size of ZnO
nanoflower structure was 1 µ with a tip of 150 nm solvent. They observed that
the morphology of nanoparticles changes depends on the nature of solvent. It
means that the shape and size of a sample changes on changing the solvent.
ZnO nanorods with diameter < 60  nm and length > 1  μ were synthesized
using methanol as solvent. As-prepared ZnO were highly pure and crystalline
Nanomaterials165

in nature. They also studied the effect of vapour pressure of solvent on this
sonication process. The presence of vapours affected the intensity of sonica-
tion, which affects various chemical reactions taking place during the forma-
tion of ZnO. They also analysed effect of ethylenediamine on the chemical
reactions leading to the formation of these ZnO nanostructures.
8-Hydroxyquinoline aluminum nanoflowers were prepared via sono-
chemical method (Mao et al., 2011). It was made up of nanobelts with
thickness about 50 nm, average width of 200 nm, and length up to 10 μm.
As-prepared sample nanoflowers showed good electro-generated chemi-
luminescence behaviour.
Nanoflower Pb(II) coordinated compound, [Pb(phen)2(4-abs)2]n, was
prepared with the ligands 1,10-phenanthroline (phen) and 4-aminobenzene
sulphonic acid (4-abs) in the presence of ultrasound (Mirtamizdoust et al.
2012). In this coordinated nanoflower compound, metal ion has six coor-
dination numbers, that is, (PbN4O2) and it has a stereochemically active
lone pair of electrons and a hemi-directed coordination sphere. The chains
interact with each other through π–π stacking to create a 3D framework.
Zak et al. (2013) used Zn salt, sodium hydroxide, and ammonia solu-
tion as precursors without any other structure directing agent or surfactant
for preparation of different-shaped ZnO nanostructures (ZnO–NS). They
used a simple, feasible, and green sonochemical method for this purpose
as it does not require high temperature and/or highly toxic chemicals. They
observed that the shape of the ZnO–NS can be changed by adjusting the
ultrasound energy dissipated via variation of the exposure time of ultra-
sound from 5 to 60 min. Following different shapes were observed on
varying the ultrasonication time.

• Plate-like, irregular-shaped nanoparticles were observed on 5 min

ultrasonication.
• Uniform ZnO nanorods with diameter around 50 nm were formed
on 15 min of ultrasonication.
• Flower-like ZnO–NS was formed, when time was increased to
30 min ultrasonication.
• Well-defined and magnified flower-shaped ZnO–NS was observed
after 60 min ultrasonication.

Thus, this method provided high-quality ZnO–NS with controllable

shapes, uniformity, and purity.
166Sonochemistry

Flower-like-shaped nanostructures (nanoflowers) of a protein-inor-

ganic hybrid consisting of laccase as a model protein and copper phos-
phate were synthesized by Batule et al. (2015). It was synthesized within
5 min in the presence of ultrasound. This sample exhibited interesting
good features such as:

• Increased activity
• Enhanced stability
• Reusability

These properties were demonstrated by its application in the colo-

rimetric detection of epinephrine. They also found application of this
sample in biosensor and enzyme catalysis indicating further utilization of
nanoflowers in diverse fields of biotechnology.
Hanifehpour et al. (2015) synthesized two neutral nanoflower poly-
meric Pb(II) coordination compounds under sonication. These are
[Pb(tmph)(l-SCN)2]n, [Pb(tmph)(l-NO3)2]n, [where, tmph = 3,4,7,8-tetra-
methyl-1,10-phenanthroline]. Flower-shaped nanostructures of both these
complexes were observed by SEM. Single-crystal X-ray data indicated 1D
double-chain net-like coordination polymers.
Qi et al. (2016) reported synthesis of hydroxyapatite nanoflowers
(HAFs) by using creatine phosphate disodium salt as an organic phos-
phorus source in single step via a sonochemical method. It was observed
that the HAFs (diameters 300 nm) are formed by self-assembly of hydroxy-
apatite nanosheets with thicknesses of < 10 nm. As-prepared sample
showed excellent cytocompability, which was proved by its essentially
inappreciable toxicity to MC-3T3 osteoblast cells. Not only this but these
HAFs also exhibited good protein adsorption ability on using hemoglobin
(Hb) as a model protein, which suggests that HAFs may have some prom-
ising applications in different biomedical fields such as protein and drug
delivery (Fig. 6.3).
Shahverdizadeh and Hossein (2016) prepared 3D Cd(II) coordination
polymer nanoflowers, [Cd2(pcih)(N3)3(CH3OH)]n, (where pcih = 2-pyri-
dinecarbaldehyde isonicotinoylhydrazonate), under ultrasonic irradia-
tion. These individual particles were assembled by strong π–π-staking
interaction to form a compressed supramolecular 3D network. Later on,
pure CdO nanoparticles were also prepared by thermolysis of [Cd2(pcih)
(N3)3(CH3OH)]n precursor in oleic acid at 180 °C in the presence of air.
Nanomaterials167

Ultrasound Ultrasound

HA Hollow
Microsphere
HA Nanoflower
FIGURE 6.3  Synthesis of hydroxyapatite nanoflowers (HAFs).
Source: Qi et al., 2016, with permission.

Chung et al. (2014) reported sonochemical synthesis of discrete Pb(II)

coordination compound. The lead ion was coordinated by six ligands, that is,
four nitrogen and two oxygen atoms from two pcih ligands. It was observed
that the overall structure of 1D supramolecular chain and with other direc-
tional intermolecular interactions, it is further extended into a 3D supramo-
lecular structure via a strong π–π interaction. This complex was used to obtain
PbO nanoparticles by thermolysis at 180 °C with oleic acid as a surfactant.

6.3 NANORODS

Single-crystalline needle-shaped ZnO nanorods were prepared using zinc

acetate dihydrate and sodium hydroxide as starting materials at room
temperature in the presence of high-energy sound (Wahab et al., 2007).
The needle-shaped sample was made up of hexagonal surfaces along
the length with typical diameter and length in the range of 120–160 nm
and 3–5 μm, respectively. The nanorods were found to be single crystal-
line with wurtzite hexagonal phase. They also found that the sonication
exposure time affects the shape of nanoparticles. As-synthesized material
has good optical properties as evident from ultraviolet-visible and room
temperature photoluminescence spectroscopy.
Zhu et al. (2007) synthesized CeVO4 nanorods using Ce(NO3)3 and
NH4VO3 in aqueous solution without any surfactant or template under
ultrasound irradiation. They also prepared high specific surface area
168Sonochemistry

FIGURE 6.4  SEM image of plate-like hydroxyapatite (HAp) nanoparticles.

Source: Jevtic et al., 2008, with permission.

mesoporous CeVO4 by the same method by using Ce(NO3)3, V2O5, and

NaOH. Mesoporous CeVO4 has a specific surface area of 122 m2·g−1 and
an average pore size of 5.2 nm, while CeVO4 nanorods have a diameter
and a length of 5 nm and 100–150 nm, respectively. The rod-like shape
formation takes place due to two key factors and these are ultrasound irra-
diation and the presence of ammonia in the reactive solution.
Plate-like hydroxyapatite (HAp) nanoparticles were synthesized in
an ultrasound field by homogeneous precipitation method (Jevtic et al.,
2008). This plate-like structure consists of specifically oriented and later-
ally connected nanorods with a length of about 500 nm and a diameter of
100 nm (Fig. 6.4). A single nanorod showed a highly regular and defect-
free lattice with unique crystallographic plane orientations. They also
noticed the influence of the ultrasound on the growth mechanism.
Warule et al. (2009) prepared various morphologies of the ZnO nano-
structures such as nanoneedles, tetrapods, nanowires, nanopetals, self-
assembled hexagonal rods, and nanocups (Fig. 6.5). All these shapes were
achieved by varying some parameters such as:

• Concentration of the precursors

• Ultrasonic irradiation period
• Duty cycle

The samples were prepared by a sonochemical as well as a sonochem-

ical-assisted hydrothermal method. The physicochemical properties were
determined by different methods.
Nanomaterials169

FIGURE 6.5  SEM image ZnO nanostructures.

Source: Warule et al., 2009, with permission.

• SEM showed the surface morphology of the ZnO nanostructures.

The nanoneedles originate from the hexagonal tube.
• TEM analysis demonstrated the nanocrystalline nature of the ZnO
structures with unique morphologies like hexagonal nanocups.

These ZnO nanostructures (nanocups and nanoneedles) had an excellent

photocatalytic activity. These unique nanostructures can find application
in ZnO-based dye-sensitized solar cells as a prospective semiconductor,
because they have a wide band gap.
Li et al. (2009) used a mixture of ZnO nanorods, [Ag(NH3)2]+, and
formaldehyde in an aqueous medium to form Ag nanoparticles on ZnO
nanorods sonochemically. X-ray diffraction of the ZnO/Ag composites
showed that this sample has the face-center-cubic-structured crystalline
Ag. ZnO nanorods were coated with Ag nanoparticles with a mean size of
several tens of nanometer in ZnO/Ag composites. The absorption band of
these composite is distinctly broadened and red-shifted, which indicates
a strong interfacial interaction between ZnO nanorods and Ag nanoparti-
cles. This sonochemical method is simple, mild, and can be readily scaled
up, affording a simple way for the synthesis of other composites also.
Ultrasound-assisted synthesis of two coordination polymers of
Hg(II) was reported by Yaser et al. (2010) with polyimine ligands,
that is, 4-bpdh and 3-bpdh, as [Hg(4-bpdh)Br2]n and [Hg(3-bpdh)
Br2]n (where 4-bpdh  = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and
170Sonochemistry

3-bpdh = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene). Thermal gravi-

metric and differential thermal analyses revealed that these nanostructures
were relatively thermally less stable than their bulk materials.
Jung et al. (2010) synthesized zinc oxide nanorod arrays on a quartz
wafer without using any metal catalysts via a sonochemical route. The
average diameter of ZnO nanorods was 156 nm and length was 933 nm.
This sonication method constitutes a practical technique for the design
of state-of-the-art nanodevices (based on laterally grown ZnO nanorod
arrays on planar substrates) as compared to conventional standard semi-
conductor microfabrication technologies.
Cho et al. (2012) also fabricated ZnO nanorods by a sonochemical
method using zinc acetate dihydrate as a precursor. A thin film of ZnO
was formed on fluorine-doped tin oxide (FTO) glass by decomposition
of zinc acetate dehydrate. It was deposited on FTO glass by sputtering
method. They could achieve different thicknesses (20, 40, and 60 nm) by
adjusting the sputtering time. This was observed that the ZnO nanorods
grown on the catalytic layer of 40 nm thickness represented the best
crystal and spatial orientation leading to the appreciable optical proper-
ties. As-prepared ZnO thin film (40 nm thickness) yields well aligned and
high-quality ZnO nanorods, due to small surface roughness and struc-
tural strain.
Kianpour et al. (2013) prepared NiMoO4 nanorods by a reaction
between Ni(CH3COO)2·4H2O and (NH4)6Mo7O24·4H2O under ultrasound
irradiation. They also studied the effect of various parameters such as ultra-
sonic power, ultrasonic irradiation time, stirring, solvent, and surfactant.
This method provides a general, simple, and an effective way to control
the composition and morphology of NiMoO4 in aqueous solution, which
can prove to be important for inorganic synthesis methodology.
Zhang et al. (2005) synthesized ZnO nanorods and trigonal-shaped
ZnO ultrafine particles by decomposition of zinc acetate dihydrate in
paraffin oil on irrradating with ultrasound. As-prepared were character-
ized by different techniques such as XRD, TEM, selected area electron
diffraction (SAED), SEM, and UV-visible techniques.
Single-phase antlerite, Cu3(OH)4SO4, nanorods were synthesized by
the sonochemical method from an aqueous solution of CuSO4, without
any additives (Segal et al., 2015). This reaction is a single-step reac-
tion process with short irradiation time of < 30 min. Here, protonation of
sulphate ions resulted in bisulphate and hydroxyl ions. The extreme local
Nanomaterials171

conditions developed inside the cavity during the collapse of bubble, that
is, higher pressure and temperature, lead to the formation of the crystal-
line mineral. On implosive collapse of the bubbles, the distances between
the oppositely charged cupper and sulphate ions were decreased and as a
result, the crystallization process was initiated.

6.4 NANOCUBES

Wu et al. (2006) dissociated K4Fe(CN)6 in acidic media under ultrasonic

condition to obtain Fe4[Fe(CN)6]3 nanocubic particles. These nanocubic
particles were found to be regular, single-crystalline, and Prussian blue
in colour. They observed that the size and size distribution of particles
depend on reaction temperature, the concentration of K4Fe(CN)6, and
ultrasonic condition.
Chen et al. (2012) prepared plasmonic photocatalyst AgCl with a small
amount of Ag metal species. These nanocubes of Ag/AgCl hybrid were
formed by sonication method. It was observed that the concentration of Ag
ions and polyvinylpyrrolidone molecules in precursor solutions affects the
size of Ag/AgCl photocatalysts. The compositions, microstructures, influ-
encing factors, and possible growth mechanism of the Ag/AgCl hybrid
nanocubes were also studied. They also used this hybrid for degradation
of various dye molecules under visible light.
Abbas et al. (2013) carried out sonochemical reaction using inexpen-
sive and nontoxic metal salt (FeSO4·7H2O) as reactant for the preparation
of monodisperse magnetite nanocubes in aqueous medium. The nanopar-
ticles were found to be of uniform size of approximately 80 nm. These
particles showed enhancement in their crystallinity by annealing treatment
up to 600 °C with uniform shape and size distribution. When annealing
temperature was 700 °C, then a distortion in shape and a broad size distri-
bution was observed.
CoSn(OH)6 nanocubes were synthesized using CoCl2, SnCl4, and
NaOH as precursors without any surfactant or template by a simple sono-
chemical route at room temperature for 30 min (Cheng et al., 2013). It
was further calcined at 500 °C for 120 min in air to obtain SnO2–Co3O4
hybrids. The SnO2–Co3O4 hybrids also had cubic morphology. They
observed that SnO2–Co3O4 hybrids exhibited more photocatalytic activity
than CoSn(OH)6 nanocubes for the degradation of methylene blue.
172Sonochemistry

FIGURE 6.6  SEM image of SnO2–Co3O4 hybrid nanocubes.

Source: Raj et al., 2016, with permission.

Raj et al. (2016) also prepared SnO2–Co3O4 hybrid nanocubes from

CoSn(OH)6 nanocubes using sonication method. They avoided the use of
any surfactant or template in this reaction. The sample was prepared at room
temperature in the presence of stannous and cobalt precursors. The elec-
trochemical performance of the hybrid SnO2–Co3O4 nanocubes exhibited
enhanced supercapacitor performance (Fig. 6.6). This enhanced electro-
chemical property of the electrode material was due to the synergetic effect
between nanostructured SnO2 and Co3O4. It was observed that about 77 % of
its initial capacitance was retained even after 1000 cycles. It showed its high-
capacitance retention and electrochemical stability. These results confirmed
that this material is a promising candidate for supercapacitor applications.
Cu2O nanocubes were synthesized in a single step by reacting copper
sulphate in the presence of polyvinylpyrrolidone and ascorbic acid at pH 11
under ultrasound irradiation (Kaviyarasan et al., 2016). Ultrasound acoustic
cavitation-generated radicals reacted with CuSO4 and resulted in Cu(OH)2
intermediate, which finally reacts with ascorbic acid to generate Cu2O nano-
cubes. As-synthesized Cu2O nanocubes were found to be very effective for
enhancing chemiluminescence in the presence of luminol-H2O2 system.

6.5 NANOTUBES

Katoh et al. (1999) applied high-intensity sound in homogeneous liquid

consisting of chlorobenzene with ZnCl2 particles and o-dichlorobenzene
Nanomaterials173

FIGURE 6.7  TEM image of tin nanoparticle-coated MWCNTs.

Source: Qui et al., 2004, with permission.

with ZnCl2 and Zn particles to form carbon nanotubes (CNTs). This high-
intensity sound helps in the formation of polymer and the disordered carbon
by cavitational collapse in homogeneous liquid. These were annealed by
the interparticle collision induced by the turbulent flow and shockwaves.
Sonication time has a major influence on reduction in amorphous
carbon. Raja and Ryu (2009) prepared single and multiwalled carbon
nanotubes (MWCNTs) using dichlorobenzene and ZnCl2 and character-
ized it. The electronic band structural characterization confirmed the exis-
tence of metallic and semiconducting CNTs.
MWCNTs surface was also uniformly decorated with crystalline tin
nanoparticles (< 5 nm) via a sonication route (Qui et al., 2004). MWCNTs
were coated by time on treating it in a solution of SnCl2 in ethylene glycol
under an N2 atmosphere and ultrasound irradiation (Fig. 6.7). Formation
of as-prepared sample supported that this technique can also be used for
coating different metals on CNTs.
The oxidation of CNTs in the presence of ultrasound helps in increasing
the density of surface functional group. Xing et al. (2005) reported that
functionalization of CNTs enhanced deposition of metal nanoparticles
in the preparation of supported catalyst. Thus, sonication method is very
effective in functionalization of CNTs. Most of the CNT surface oxidation
takes place between one to two hours.
Sonication method promotes the deposition of metal nanoparticles on
the surface of carboxylate functionalized MWCNTs. Pan and Wai (2009)
deposited rhodium nanoparticles with an average diameter of 2.5 ± 0.7 nm
174Sonochemistry

on the surface of carboxylate functionalized MWCNTs. The sample was

prepared in ethanol solution containing RhCl3 and an organic-reducing
agent, borane morpholine complex (C4H12BNO). CNT-supported Rh
nanoparticles showed highly active and reusable catalytic activity for
hydrogenation of benzene and its derivatives at room temperature. It was
found that complete ring saturation of polycyclic aromatic hydrocarbons
(PAHs) can be obtained by mild hydrogenation conditions using the Rh/
MWCNT catalyst, which is not possible by commercially available Rh
nanocatalysts otherwise. This one-pot synthesis technique gave a simple
and rapid way of preparing highly active and recyclable CNT-supported
nanocatalysts for hydrogenation reactions at low temperatures.
Later, they also studied the effect of deposition of bimetallic nanopar-
ticles (Pt-Rh) on the surface of carboxylate functionalized MWCNTs (Pan
and Wai, 2011). These metals show a synergistic effect and enhance cata-
lytic hydrogenation of PAHs, neat benzene and alkyl benzenes. Bime-
tallic nanoparticles-coated MWCNTs promote complete ring saturation
of PAHs even at room temperature. CNT-supported monometallic and
bimetallic nanocatalysts were prepared in single step and these could be
recycled or reused for further hydrogenation reaction and that too at low
temperatures.
Chuong et al. (2011) fabricated TiO2 and TiO2-ZrO2 composite nano-
tubes using ultrasound. These nanomaterials were used for synthesis of
lead zirconate titanate (PZT) ceramic, (Pb[Zr(x)Ti(1−x)]O3), at low sintering
temperature. It is one of the widely used piezoelectric ceramic materials.
PZT has a perovskite crystal structure, each unit of which consists of a
small tetravalent metal ion in a lattice of large divalent metal ions.
The surface modification of amine-grafted or epoxy-grafted MWCNTs
composites in polyethylene polyamine or in liquid epoxy resin, respec-
tively, was done by Kotsilkova et al. (2014). The amine epoxy grafted
MWCNT composites produced an extra phase on the CNT walls, which
was confirmed by the presence of a thick polymer layer. It positively
affects the electrical conductivity and radiofrequency response properties.
The epoxy-grafted composites could be applied for producing effective
antistatic and electrostatic dissipation coatings.
Colloidal silver nanoparticles were prepared using starch by sono-
chemical reduction process (Kumar et al., 2014). Starch was used as a
reducing as well as stabilizing agent. As-prepared silver nanoparticles
were spherical, polydispersed, and amorphous with diameter ranging from
Nanomaterials175

23 to 97 nm with mean particle size of 45.6 nm. These nanoparticles could

be used for efficient catalyst in the synthesis of 2-aryl substituted benz-
imidazoles, which have numerous biomedical applications. The optimized
conditions for this reaction are 10 mL of 1 mM AgNO3, 25 mg starch, pH
11, and sonication for 20 min at room temperature.
Zhang et al. (2007) decomposed iron pentacarbonyl in cis-trans decalin
by irradiating it with ultrasound for very short time. The high-energy ultra-
sonic irradiation promoted the process of crystallization, which further
extended to monodisperse iron oxide nanoparticles at low temperature.
They also studied the effect of concentration of the surfactant and the
refluxing time on the size as well as the size distribution of iron oxide
nanoparticles.
Hassanjani-Roshan et al. (2011) prepared iron oxide (α-Fe2O3)
nanoparticles (smaller than 19 nm) via a sonochemical method. They also
noticed that temperature, power of ultrasonication, and sonication time
had a major effect on size and morphology of the iron oxide.
The sensing properties of FeSbO4 nanoparticles were tested toward
1000 ppm and 1, 2, 4, and 8 % hydrogen at 300 °C and 450 °C. It was
observed that sample prepared at 300 °C exhibited a response of 76 %
toward 4 % H2 gas, whereas sample calcined at 450 °C showed a higher
response of 91 %.
Safaei-Ghomi et al. (2016) prepared benzo[g]chromenes using Fe3O4/
polyethylene glycol (PEG) core/shell nanoparticle via ultrasonic irradia-
tion. These nanoparticles have advantages such as mild reaction conditions,
high-yield products, short reaction times, reusability of the catalyst and
requirement of little catalyst loading as compared to conventional method.

6.6 NANORIBBONS

Wu et al. (2010) used sonochemical method for preparation of narrow

and long graphene nanoribbons (GNRs) by chemically derived graphene
sheets (GSs). The yield of GNRs was approximately 5 wt.% of the starting
GSs (Fig. 6.8). The final GNRs have several micrometers in length, with
∼ 75 % being single-layer, and ∼ 40 % being narrower than 20 nm in width.
Graphene nanoribbons have properties of electronic and spin transport
and if it has width < 10 nm, then it has a band gap that can be utilized to
fabricate field effect transition. But today also, preparing nanoribbons of
176Sonochemistry

Sonochemical

Cutting

100nm 200nm
FIGURE 6.8  SEM image of GNRs.
Source: Wu et al., 2010, with permission.

excellent quality and of high volume is a major challenge. Jiao et al. (2010)
made pristine few-layer nanoribbons from unzipping mildly gas-phase-
oxidized MWCNTs using mechanical sonication in an organic solvent.
As-prepared nanoribbons had some novel properties such as:

• High quality
• Smooth edge
• Low ratios of disorder to graphitic Raman bands
• The highest electrical conductance and mobility up to 5 e2/h and
1500 cm2·V−1·s−1, respectively, for ribbons 10–20 nm in width.

Temperature also affects types of nanoribbons. At low temperatures,

the nanoribbons exhibited phase-coherent transport and Fabry–Perot
interference. It shows minimal defects and edge roughness. The yield of
nanoribbons was approximately 2 % of the starting raw nanotube soot
material. It had even higher quality and narrow ribbons than nanoribbons
prepared from the earlier methods. The relatively high-yield synthesis of
pristine GNRs will make these materials easily accessible for a wide range
of fundamental and practical applications.
Nanomaterials177

Nanoribbons graphene of narrow, straight-edged striped and single-

layer graphite proved to be useful in electronic devices. Nanrorib-
bons graphene (less than 10 nm) prepared from 2-D starting material
graphene showed semimetallic behavior, quantum confinement, and
edge effects. As stated earlier, preparation of GNRs of smaller size
than 10 nm with chemical precision remains still a significant chal-
lenge, whether it is synthesized by chemical, sonochemical, and litho-
graphic methods as well as through the unzipping of CNTs (Cai et al.,
2010).
Xie et al. (2011) prepared GNRs of widths ∼ 10–30 nm from sono-
chemical unzipping of MWCNTs. The layer–layer stacking angles ranged
from 0° to 30°. It includes average chiral angles near 30° of armchair
orientation or 0° of zigzag orientation. A large fraction of GNRs is with
bent and smooth edges, whereas the rest portion exhibited flat and less
smooth edges with roughness of ≤ 1 nm.
When the width of a graphene nanoribbon is only a few nanometers,
it possesses semiconducting properties that enable various high-end elec-
tronic applications. Yoon et al. (2015) used the dense and stable disper-
sion of a natural graphite made up of flavin mononucleotide (FMN) as
a surfactant to form GNRs as small as 10 nm in width. In this sono-
chemical method, they unzipped graphene with a template of 1-D FMN
supramolecular to form nanoribbon structure. Thermal annealing showed
increase in the optical contrast and van der Waals interactions of the
graphene film, which led to the enhancement of conductivity compared
to the as-prepared graphene film, which is also better than that of reduced
graphene oxide (rGO).

6.7 NANOSHEETS

By the reduction of Rh3+ salt on poly(ethylene oxide)/poly(propylene

oxide)/poly(ethylene oxide) (PEO/PPO/PEO) triblock copolymer or
pluronic-stabilized graphene oxide (GO) nanosheets with borohydride,
highly water-dispersible rhodium–graphene nanocomposite was prepared
by sonochemical process (Chandra et al., 2011). Rhodium nanoparticles
of size 1–3 nm were homogeneously distributed throughout the GSs.
They also observed some porous structures of GSs after the reduction of
pluronic-stabilized GO in the presence of metal ions. This material has
178Sonochemistry

proved to be very effective for hydrogenation of arenes, especially for

benzene as the substrate material at room temperature and 5 atm. pressure
of hydrogen.
Iqbal et al. (2016) prepared gallium oxynitride (GaON) nanosheets at
a reaction time of 24 h at 180 °C via direct sono-assisted solvothermal
approach. Its band gap energy was observed to be ~ 1.9 eV. It was calcu-
lated from both absorption and diffused reflectance spectroscopy, which
indicated stronger p-d repulsions in the Ga (3d) and N (2p) orbitals. This
effect and chemical nitridation led to an upward shift of valence band and
band gap reduction. The GaON nanosheets were found to have application
in the field of photoelectrochemical cells (PECs) (Fig. 6.9). It was studied
with a standard three-electrode system under 1 Sun irradiation in 0.5 M
Na2SO4. These GaON nanosheets can be used as potential photocatalysts
for solar water splitting also.

FIGURE 6.9  SEM images of GaON nanosheets (a, b) low-resolution micrographs at 2

and 1 μm showing growth patterns of nanosheets (c, d) higher-magnification micrographs
show internal texture and defects attributing toward availability of high surface area.
Source: Iqbal et al., 2016, with permission.
Nanomaterials179

6.8 NANOSPHERES

Qi et al. (2015) used the adenosine-5′-triphosphate (ATP) disodium salt

for the preparation of amorphous calcium phosphate (ACP) vesicle-like
nanospheres by sonochemical method (Fig. 6.10). Here, ATP disodium
salt was used as a biocompatible phosphorus source and stabilizer. The
sample was prepared in mixed solvents of water and ethylene glycol. The
ACP vesicle-like nanospheres showed essentially inappreciable toxicity
to the cells in vitro. These could be used as anticancer drug nanocarriers.
It exhibited a pH-responsive drug-release behaviour using doxorubicin
(Dox) as a model drug. The ACP vesicle-like nanosphere drug delivery
system showed a high ability to damage cancer cells. It shows that it has
promising application in pH-responsive drug delivery.
d
un
so
tra

PO43- Ca2+
Ul

ATP molecule ACP cluster

ACP vesicle-like
nanosphere

FIGURE 6.10  Sonochemical synthesis of ACP.

Source: Qi et al., 2015, with permission.

Dhas and Suslick (2005) prepared ceramic hollow spheres of MoS2

and MoO3. These ceramic samples were synthesized using MoS2 and
MoO3 template on silica nanoparticles (diameters 50 to 500 nm), which
were prepared under irradiation of ultrasound. MoS2 and MoO3 template
on silica nanoparticles was further treated with acid to remove the silica
core. These hollow sphere nanoparticles were found to be active catalysts
for the hydrodesulphurization (HDS) of thiophene.
PbS hollow nanospheres were synthesized by a surfactant-assisted
sonochemical pathway (Wang et al., 2006). The nanospheres were of
80–250 nm. Structural study showed that shells of the hollow spheres
180Sonochemistry

were made up of PbS nanoparticles with diameters of about 12 nm.

This formation of the hollow nanostructure was explained by a vesicle-
template mechanism, in which sonication and surfactant played important
roles. They also coated uniform silica layers onto the hollow spheres via a
modified Stöber method to enhance their performance for some promising
applications.
Magnetic fluorescent nanospheres (MFNs) were prepared by Wu et al.
(2011). MNFs were synthesized by sonochemical method in the pres-
ence of hydrophobic Fe3O4 nanopaticles. Further, the nanospheres were
modified with rhodamine B through an electrostatic interaction. These
nanosphere had 160 nm particle size and showed supermagnetic property.
MNFs have their wide applications in medical imaging, drug targeting,
and catalysis.
Zhu et al. (2007) doped 5.0 mol.% of Eu3+ dopant in BaF2 nanocrystals
via ultrasonic solution route. In this method, reactions between Ba(NO3)2,
Eu(NO3)3 and KBF4 under ambient conditions was carried out under ultra-
sound. They observed the effect of sonication time on the morphology of
the FBaF2:Eu3+ particles. The caddice-sphere-like particles with an average
diameter of 250 nm were obtained with ultrasonic irradiation, whereas only
olive-like particles were produced without ultrasonic irradiation. It was
found that BaF2:Eu3+ nanospheres crystallized well with a cubic structure.
Dai et al. (2013) synthesized pectin-coated Fe3O4 magnetic nanospheres
(PCMNs) by sonochemical method. The pectin-coated nanosphere had
magnetite content up to 63 %, with the saturation magnetization of about
32.69 emu/g. PCMNs could be applied in some biomedical applications.

6.9 NANOFLAKES

Ghosh et al. (2014) prepared ZnO nanoflakes via sonochemical method

by using cetyltrimethylammonium bromide (a cationic surfactant) as a
structure-directing agent. It was observed that surfactant concentration
modified the morphology of ZnO from starlet-like 3D structures to 2D
flakes. As-prepared sample of ZnO flakes was 200–400 nm wide and a
few nanometres thick. Its band gap was found to be 3.37 eV.
Vabbina et al. (2015) prepared 2D ZnO nanoflakes in one step under ultra-
sound irradiation. It was fabricated on Au-coated substrates. As-prepared
sample was label-free, highly sensitive and selective electrochemical
Nanomaterials181

immunosensors and it was used in the detection of cortisol. It was also

found useful in sensing advantages as compared to bulk materials. Nano-
flakes possess large surface area. ZnO-NSs also exhibited higher chemical
stability, high catalytic activity, and biocompatibility. ZnO nanoflakes were
having the lowest detection limit of 1 pM, which was almost 100 times
better than conventional enzyme-linked immunosorbant assay (ELISA).
It was also used to examine human saliva samples, and the results were
compared with the performance of conventional (ELISA) method. Sensors
could be integrated with microfluidic system and miniaturized potentiostat
for point-of-care cortisol detection and such developed protocol can be
used in personalized health monitoring/diagnostics.
Liu et al. (2012) prepared CdWO4 nanoflakes without using mild
template or any surfactant through ultrasonication method. Ultrasound
plays a major role in the formation of nanocrystals. First nanoflakes are
formed, which further change to nanorods on increasing ultrasonic period
from 0.5 to 1.5 h. Zhou et al. (2007) also prepared Bi2Te3 hexagonal nano-
flakes by an ultrasonic-assisted disproportionation route. It edge length was
in the range of 150 nm to as small as 10 nm. The mechanochemical effects
of the ultrasonic irradiation increased the rate of reaction and were also
helpful in obtaining relatively small and uniform nanocrystals. They also
studied electro-generated chemiluminescence of the as-prepared sample.

6.10 NANOWIRES

Chiniforoshan and Tabrizi (2015) synthesized Au nanowires of gold-

containing polymers of the formula [(Au(I)-NCN-R-NCN-Au(III)-NCN-R-
NCN-)]n; (where R = biphenyl or NCN-R-NCN, 4,4′-dicyanamidobiphenyl,
bpH2). Au nanowires were of 20–100 nm, length up to several microns and
showed thermal stability. As-prepared sample was used as gas sensor. It
was highly sensitive toward CO with the detection limit (1 ppm) at room
temperature.
β-AgVO3 nanowires of 30–60 nm diameter and length 1.5–3 μ were
synthesized by sonochemical reaction (Mao et al., 2008). As-prepared
sample has electrochemical properties and was used as cathode materials
for lithium-ion batteries. In the initial discharge and charge process, the
as-prepared β-AgVO3 nanowires showed the initial charge and discharge
capacities of 69 and 102 (mAh)·g−1, respectively.
182Sonochemistry

Chen et al. (2006) synthesized ceria (CeO2) nanowires in ambient

air and alkali aqueous solution from CeO2 nanoparticles without using
any templates in the presence of ultrasound irradiation. In this reaction
involving the fabrication of nanowires, alkali concentration and ultrasonic
irradiation both played a critical role. The catalytic activity of Au/CeO2
using CeO2 nanowires as support for CO conversion showed better perfor-
mance than bulk CeO2.
Ultrasound was used as a driving force for both nucleation and disper-
sion for the preparation of selenium nanowires (Mayers et al., 2003). They
observed that the trigonal Se seeds were formed during sonication and
grew in hours at the expense of the amorphous Se colloids in a process
very similar to Ostwald ripening. As-prepared nanowires were typically
single crystals of trigonal Se. The morphology of these wires could be
tuned by adjusting the reaction conditions.

6.11  NANOPOROUS MATERIALS

Talebi et al. (2010) studied addition of silver ions into the nanoporous
(1.2 nm) zeolite lattice by ion-exchange route. Silver ions were introduced
by 24 kHz ultrasonic waves. This range of ultrasound reduced silver ions
to silver nanoparticles. After the reduction process, silver nanoparticles
were placed in the cavities having size about 1 nm and also on the external
surfaces of the zeolite, with sizes about less than 10 nm. Many methods
have been used for the reduction of silver ions but the use of ultrasonic
waves was found to be a new, simple, and size-controllable method with a
high practical value, which does not need any complicated facilities. As a
huge amount of energy is provided by the collapse of bubbles, this released
energy causes the formation of reducing radicals that consequently reduce
the silver ions. It was also observed that increasing the irradiation time
and ultrasonic power do not affect the silver crystal growth significantly,
but the extent of silver ion reduction was found to increase as the power of
ultrasonic waves was increased.
Nanoporous amorphous-MnO2 was fabricated by Hasan et al. (2015) by
using solid manganese (II) acetate tetrahydrate in 0.1 M KMnO4. Absorp-
tion study of as-prepared sample was done by remazol reactive dye or red
3BS dyes. In batch experiment, 10 ppm of remazol reactive dye was used,
and the experiment was carried out at room temperature. Adsorption of
Nanomaterials183

remazol dye on 0.2 g synthesized nanoporous amorphous-MnO2 showed

almost 100 % decolorization.
Zhan et al. (2014) prepared solid-state dodecyl perylene diimide
(DDPDI) fluorescent materials (DDPDI/MCM-41) by introducing the
DDPDI molecules into the nanopores of MCM-41 in toluene solution
under ultrasonic irradiation. The DDPDI molecules were incorporated into
the mesopores of MCM-41 in the monomeric or dimeric state after being
treated with ultrasound (Fig. 6.11).

Ultrasonic treatment Monomeric

Liquid assembling composite

Emission
Exciting light light

FIGURE 6.11  Incorporation of DDPDI into nanopores of HCM-41.

Source: Zhan et al., 2014, with permission.

6.12  GRAPHENE AND RELATED MATERIALS

6.12.1 GRAPHENE

Graphene consists of an atomic-scale honeycomb crystal lattice with

sp2-hybridized carbon. It possesses unique mechanical, electrical,
chemical, and physical properties. But its zero band gap puts hurdle on
its utilization in field-effect transistors (Fig. 6.12). Graphite is 2D sheet
of sp2-hybridized six-member carbon atoms ring (the graphene), which
are regularly arranged. Graphene has excellent strength and firmness
along its basal levels that reaches with approximately 1020 GPa. This
is almost close to the strength value of diamond. It has varied methods
of its synthesis and finds numerous applications as its electrical, phys-
ical and mechanical properties are increasing dramatically. Even the
barrier properties of its polymer composites change a lot at extremely
low loadings. Due to these characteristics, it is considered a material of
interest and, therefore, it is a promising material for various industries
184Sonochemistry

FIGURE 6.12  Graphene sheet.

producing composites, coatings, biosensors, drug delivery, microelec-

tronics and so on.
Widenkvist et al. (2009) prepared suspensions of GSs by a combina-
tion of solution-based bromine intercalation with mild sonochemical exfo-
liation. Graphite formed suspensions of graphite flakes in water through
ultrasound treatment. The delamination showed improvement by inter-
calation of bromine into the graphite before sonication. SEM and TEM
showed a significant content of few-layer graphene with sizes up to 30 µm,
corresponding to the grain size of the starting material.
Chia et al. (2014) prepared graphene (1 mg·ML−1) by exfoliating raw
graphite sonochemistry in ethanol–water mixtures. The effective surface
area of the graphene was found around 1000 m2·g−1 and the average thick-
ness of GSs was < 2 nm. The cyclic voltammetry test was used to study the
electrochemical characteristics of the graphene and amperometric detec-
tions of hydrogen peroxide (H2O2), a by-product of most oxidase based
enzymatic reactions. The graphene was deposited onto the surface of
screen-printed carbon electrodes (SPCEs). This modified electrode showed
increased electrocatalytic response of more than two-fold as compared
to unmodified electrodes. The detection of hydrogen peroxide exhibited
good stability with a more than 20 times improvement in sensitivity by
optimizing the number of deposition layers on the electrode surface.
Yang et al. (2014) studied that graphene nanomesh (a new graphene
nanostructure) with tunable band gap has outstanding performance. It can
be used in electronic or photonic devices such as highly sensitive biosensors,
new generation of spintronics and energy materials. The use of graphene
nanomesh will add a step further in nanoscience and technology (Fig. 6.13).
Nanomaterials185

FIGURE 6.13  Graphene nanomesh.

Source: Yang et al., 2014, with permission.

FIGURE 6.14  Mechanochemical effect.

Source: Xu and Suslick, 2011, with permission.

The reaction of graphite with styrene was studied under ultrasonic irra-
diation by Xu and Suslick (2011), which resulted in the mechanochemical
exfoliation of graphite flakes to single-layer and few-layer GSs (Fig. 6.14).
These sheets were combined with functionalization of the graphene with
polystyrene chains. The polystyrene chain was formed by the radical
polymerization of styrene initiated by this sonochemical process. The
functionalized graphene was formed up to 18 % weight. Such a one-step
protocol can be used for preparation of graphene-based composite mate-
rials by using functionalization of graphenes with other vinyl monomers.
186Sonochemistry

Sahoo et al. (2013) modified graphene as graphene/polypyrrole and

graphene/polyaniline. They also observed the effect of this modification
on thermal and electrical properties of nanocomposites. It was prepared
by in situ-oxidative polymerization method using ammonium persulphate
as an oxidant. The modified graphene was responsible for enhanced elec-
trical conductivity of the as-prepared nanocomposites.
Graphitic precursors in the presence of chloroform under ultrasound
resulted in the formation of exfoliated graphitic materials as mesographite
and mesographene. The properties of material depend on the number
of layers and exfoliation conditions. Mesographene was made up to
nanoscaled two-dimensional graphene layers, and three-dimensional
carbon nanostructures sandwiched between these layers, similar to those
found in ball-milled and intercalated graphites. Mesographite exhib-
ited higher conductivity than mesographene despite the flake damage as
2700 and 2000 Sm−1, respectively. Optical absorption measurements of
mesographite sonicated in different solvents exhibited significant changes
in dispersion characteristics, and also indicated significant changes to
mesoscopic colloidal behaviour (Srivastava et al., 2014).
Geetha et al. (2016) carried out sonochemical synthesis of highly crystal-
line graphene-gold (G-Au) nanocomposite. Ultrasound was used for exfoli-
ation of graphite as well as the reduction of gold chloride to give the desired
product. In situ growth of gold nanoparticles occurred on the surface of
exfoliated few layer GSs. This nanocomposite was used to fabricate glassy
carbon electrode (GCE) for an electrochemical sensor in the selective detec-
tion of nitric oxide (NO), which is prominently a cancer biomarker. G-Au
modified GCE presented an enhanced electrocatalytic response for the
oxidation of NO compared to other control electrodes. The combination
of graphene and Au NPs provided exceptional electron transfer processes
between the electrolyte and the GCE. It provides excellent sensing perfor-
mance of the fabricated G-Au-modified electrode with stable and repro-
ducible responses. They found that this nanocomposite will prove to be an
electrode material in the sensitive and selective detection of NO.

6.12.2  GRAPHENE OXIDE

Park et al. (2012) used potassium permanganate to oxidize the carbon

atoms in the graphene oxide (GO) support. Reduced manganese oxide and
Nanomaterials187

Ultrasound
irradiation

KMnO4

GO Redox reaction MnO2 precipitation

Ultrasound
irradiation

Reduction

GO/Mn3O4 Nanocomposite MnO2 Migration

FIGURE 6.15  Graphene oxide–manganese oxide nanocomposite.

Source: Park et al., 2012, with permission.

graphene oxide (GO) have formed graphene oxide–manganese oxide nano-

composite (GO–Mn3O4) under ultrasound irradiation (Fig. 6.15). This ultra-
sound-assisted synthesis is a green chemical pathway as the number of steps
is reduced along with temperature, and the rate of reaction is enhanced. It
also helped in obtaining Mn3O4 phase. The effect of change in the ratio of
permanganate to GO dispersion on coverage and crystallinity of Mn3O4 was
also studied. It was used as a catalyst for poly(ethylene terephthalate) (PET)
depolymerization into its monomer, bis(2-hydroxylethyl) terephthalate
(BHET). The highest monomer yield was more than 95 % with the nano-
composite containing the lowest amount of Mn3O4. On the other hand, PET
glycolysis with the Mn3O4 without GO yielded 82.7 % BHET.
Sonochemical approach was used for in situ reduction and direct func-
tionalization of graphene oxide by Maktedar et al. (2016). They function-
alized graphene oxide directly with tryptamine (TA) within 20 min. This
was a rapid, robust, scalable, and nonhazardous sonochemical approach
without using any hazardous acylating and coupling reagents. The direct
covalent functionalization and formation of f-(TA) GO was observed.
An enhanced thermal stability of f-(TA) GO was also observed. It was
suggested that f-(TA) GO is emerging as an advanced functional biomate-
rial for thermal and biomedical applications.
The graphene oxide nanosheets (GOS) and hydrazine hydrate were
used as template and reductant, respectively, to form highly dispersed 2D
copper/rGO nanosheets (Cu/RGOS) nanocomposites under ultrasound
irradiation. Here, uniform layers of Cu of 60 nm thickness have single-
crystalline with (111) preferred crystalline direction and have tight binding
with RGOS. In this electroless Cu plating, ultrasound helps in promoting
188Sonochemistry

interfacial bonding and avoids the chance of aggregation of 2D Cu/RGOS

nanocomposing (Peng et al. 2014).
One-pot sonochemical synthesis of graphene oxide-wrapped gold
nanoparticles (Au NPs) hybrid materials was carried out by Cui et al.
(2015) using ethylene glycol as the reducing agent. This reaction took
nearly 60 min to complete. The hybrid materials exist as spheres wrapped
with gauze-like GO sheets via ionic interaction-based self-assembly.
Graphene oxide sheet helped in the dispersion of the Au NPs. As-prepared
sample showed enhanced photocatalytic activity under visible light irra-
diation due to synergistic effect of these two components in the hybrid
materials.

6.12.3  REDUCED GRAPHENE OXIDE

Pt and Sn precursors were used for simultaneous loading of Pt and Sn

(monometallic) and Pt–Sn (bimetallic) nanoparticles on the surface of
reduced GO (rGO) (Anandan et al., 2012). They used low-frequency ultra-
sound of 20 kHz for this purpose. These reduced monometallic and bime-
tallic nanoparticles were spherical in shape with diameters of about 2–6 nm
and also uniformly embedded on rGO sheets of few layers thickness. The
electrocatalytic performance of the prepared nanomaterials was tested.
Shi et al. (2014) used sonochemical method for fabricating CuS
nanoparticle-decorated rGO (CuS/rGO) composites. CuS nanoparti-
cles were of 10–25 nm size and these were well distributed on the rGO
nanosheets. Its efficiency was evaluated for photocatalytic degradation of
methylene blue solution under natural light. As-prepared nanocomposites
showed enhanced photocatalytic activity compared with pure CuS. This
enhancement may be due to the enhanced light adsorption, strong absorp-
tion of the dye, and efficient charge transport after the introduction of rGO.
An aqueous solution containing a silver ammonia complex,
[Ag(NH3)2OH], and graphene oxide was used to prepare rGO uniformly
decorated with silver nanoparticles (Ag NPs) via ultrasonic method. This
involves simultaneous formation of cubic-phase AgNPs and the reduc-
tion of GO. The proportion of the precursors and the ultrasonic irradiation
period were the deciding factors for the size of nanoparticles. A uniform
distribution of ultrafine spherical Ag NPs with a narrow size distribution
on the rGO sheets was obtained by silver ammonia complex and not by
Nanomaterials189

silver nitrate precursor. The average particle size of the silver with the
narrowest size distribution was 4.57 nm. As-prepared modified GCE was
found to have electrocatalytic activity toward the non-enzymatic detection
of H2O2 with a wide linear range of 0.1–70 mM and a detection limit of
4.3 μM (Golsheikh et al., 2014).
TEM images and size distribution diagrams of AgNPs–rGO prepared
by using solution with GO (1.0 mg·mL−1) to Ag(NH3)2OH (0.04 M)
volume ratio of 4 at different ultrasonic irradiation times of 15 min (a
and b) and 30 min (c and d), and HRTEM image of AgNPs anchored on
surface of GS (e).
rGO decorated with zinc sulphide nanospheres (ZnS NSs) was also
fabricated under ultrasound by Golsheikh et al. (2015). Here, aqueous
solution containing zinc acetate dehydrate, thioacetamide, and graphene
oxide was irradiated with ultrasound. They reported that this involves
simultaneous formation of cubic-phase ZnS NSs along with reduction of
GO. Incorporation of rGO sheets with ZnS NSs reduced the electron-hole
recombination and increased the surface area of the composite. Therefore,
a significant enhancement in the photocatalytic degradation of methylene
blue was observed with the ZnS NSs–rGO nanocomposite, as compared
to the bare ZnS particles.
Fe3O4 nanoparticles were prepared by sonochemical method, where
these nanoparticles were uniformly dispersed on the rGO sheets (Fe3O4/
rGO) (Zhu et al., 2013). Hemoglobin, a biosensor, was prepared using
modified GCE with the combination of Fe3O4/rGO. This biosensor showed
an excellent electrocatalytic reduction toward H2O2 at a wide, linear range
from 4 × 10−6 to 1 × 10−3 M, and with a detection limit of 2 × 10−6 M. The
high performance of H2O2 detection was attributed to the synergistic effect
of the combination of Fe3O4 nanoparticles and rGO, promoting the elec-
tron transfer between the peroxide and electrode surface.

6.13 MISCELLANEOUS

Dharmarathna et al. (2012) used water/acetone co-solvent for the synthesis

of cryptomelane-type manganese octahedral molecular sieve (OMS-2)
materials under nonthermal condition on ultrasonic irradiation. Co-solvent
was used to decrease the reaction time and it was observed that it reduced
reaction time by 50 %. Calcination was not needed in this process to obtain
190Sonochemistry

the pure cryptomelane phase. OMS-2 material possesses greater amount

of defect, surface area of 288 ± 1 m2g−1 and small particle sizes in the range
of 1–7 nm. Because of greater amounts of such defects, OMS-2 showed
excellent catalytic efficiency for the oxidation of benzyl alcohol as
compared to OMS-2 prepared by reflux methods and commercial MnO2.
Yayapao et al. (2013) synthesized hexagonal wurtzite ZnO nanonee-
dles via ultrasonic solution method. It was doped with 0–3 % Ce, which
resulted into a direct energy gap (3.00 eV). As-prepared nanoneedles were
used for photocatalytic degradation of methylene blue.
Khanjani and Morsali (2013) carried out consecutive dipping of silk
yarn in alternating bath of magnesium nitrate and potassium hydroxide to
develop magnesium hydroxide nanostructures under ultrasound irradia-
tion. It was observed that different factors such as ultrasound irradiation,
concentration, pH, and sequential dipping steps affect the growth of the
Mg(OH)2 nanostructures. These nanoparticles were transformed to nanon-
eedles on decreasing pH from 13 to 8.
Sonochemical reaction of iron pentacarbonyl in water with protein
bovine serum albumen (BSA) was carried out to prepared nanofiber
and nanoneedle. These nanomaterials consisted of mixtures of goethite
(α-FeOOH), lepidocrocite (γ-FeOOH), and hematite (α-Fe2O3). The reac-
tion proceeds with thermal decomposition mechanism for iron pentacar-
bonyl with BSA acting as a templating agent (Bunker et al. 2007).
Water-dispersed two-dimensional materials in the form of platelets
have wide applications in the field of inkjet printing on hard and flex-
ible substrates. Water is an ideal dispersion medium as it is readily avail-
able in abundance and it is also of low cost. But, the hydrophobicity of
platelet surfaces restricts its widespread use. Kim et al. (2015) reported
that these 2D materials could be exfoliated and dispersed in water by
increasing the temperature of the sonication bath. They also investigated
inkjet printing on hard and flexible substrates as a potential application
of water-dispersed 2D materials. Palanisamy et al. (2015) prepared meta-
stable cadmium sulphide nanoplatelets (10 nm thickness) in a continuous
flow sonochemical reactor. This reactor helps in micromixing of reagents.
The unique shape and crystal structure of the obtained nanoplatelets were
due to high localized temperatures within the sonochemical process.
The particle size was more uniform in case of continuous sonochemical
process in comparison to the batch sonochemical process and conven-
tional synthesis processes.
Nanomaterials191

In situ template approach for the synthesis of metal chalcogenides

in the hollow form of spherical assemblies was also carried out in the
presence of ultrasound (Xu et al., 2004). They observed self-assembly of
metallic hydroxide particles into spherical templates generated in situ and
subsequent surface crystal growth resulting in hollow spherical structures.
In addition, ultrasound played a major role in the formation of the interme-
diate templates and also crystal growth process. This approach provides a
simple and an efficient one-step procedure to the large-scale synthesis of
hollow spherical nanostructures. Zhu et al. (2003) prepared CdSe hollow
spherical assemblies by sonochemical method. In situ template amorphous
Cd(OH)2 helps in the development of primary CdSe nanoparticles on its
surface and their assembly into hollow spherical structures.
One-pot synthesis of water-soluble Ag nanoclusters (NCs) was carried
out by Liu et al. (2013) by using bovine serum albumin as a stabilizing
agent and reducing agent in aqueous solution via a sonication process.
This sample showed intensive electrogenerated chemiluminescence
(ECL). It was used for ECL detection of dopamine with high sensitivity
and a wide detection range. Dopamine concentration was found in the
range of 8.3 × 10–9 to 8.3 × 10–7 mol·L−1 without the obvious interference
of uric acid, ascorbic acid, and some other neurotransmitters, such as
serotonin, epinephrine, and norepinephrine, and the detection limit was
9.2 × 10–10 mol·L−1 at a signal/noise ratio of 3. Xu and Suslick (2010) used
polyelectrolyte, polymethylacrylic acid, as a capping agent for synthesis
of highly fluorescent, stable, water-soluble Ag nanoclusters via sonochem-
ical method. Sonication period, stoichiometry of the carboxylate groups to
Ag+, and polymer molecular weight were found to control the optical and
fluorescence properties of the Ag nanoclusters.
PbS nanobelt was fabricated via a sonochemical method by using a
solution of PbCl2 and Na2S2O3. As-prepared nanobelt possesses a width
of 80 nm, length up to several millimeters, and width-to-thickness ratio of
nearly 5 (Zhou et al., 2005).
Nanomaterials have a wide range of applications in widely different
areas such as electronic device manufacture, catalyst, chemical sensors,
hydrogen production, environmental remediation, or clean-up to bind
with and neutralize toxins due to their optical, magnetic, electrical, and
other properties, and so on like degradation of organic dye (Chen et al.
2012, Cheng et al. 2013, Hasan et al. 2015, Guo et al., 2016), solar-driven
photoelectrochemical water-splitting (Iqbal et al. 2016), hydrogenation
192Sonochemistry

of arenes (Chandra et al. 2011), pH-responsive drug delivery (Qui et al.

(2015), supercapacitor (Raj et al. 2016), photoelectrochemical devices and
sensing (Tan et al. 2013), better chemiluminescence (Kaviyarasan et al.
2016), chemical and biological assay (Ruan et al. 2007), and so on. Nano-
materials have been also used as electrode-building material in recharge-
able Li batteries, and also in the preparation of rare-earth-doped optical
fibers (Gedanken, 2003).

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CHAPTER 7

POLYMERS
KIRAN MEGHWAL1, GUNJAN KASHYAP2, RAKSHIT AMETA3
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
3
Department of Chemistry, J.R.N. Rajasthan Vidyapeeth (Deemed to
be University), Udaipur, India, E-mail: [email protected]

CONTENTS

7.1 Introduction  ����������������������������������������������������������������������������  198

7.2 Polyaniline  ������������������������������������������������������������������������������  200
7.3 Polypyrrole  �����������������������������������������������������������������������������  204
7.4 Polythiophene  �������������������������������������������������������������������������  206
7.5 Poly (Methyl Methacrylate)  ����������������������������������������������������  207
7.6 Polyurethane  ���������������������������������������������������������������������������  209
7.7 Polyvinyl Alcohol  �������������������������������������������������������������������  210
7.8 Composites of Carbon Nanotubes  ������������������������������������������� 211
7.9 Coordination Polymers  ������������������������������������������������������������ 211
7.10 Others ��������������������������������������������������������������������������������������  212
7.11 Polymer Degradation  ��������������������������������������������������������������  215
References  �����������������������������������������������������������������������������������������  220
198Sonochemistry

7.1 INTRODUCTION

Polymer is a large molecule or macromolecule, composed of many

repeating subunits. Because of their broad range of properties, both
synthetic and natural polymers play an essential and ubiquitous role in
day-to-day life. Polymers range from familiar synthetic plastics to natural
biopolymers (DNA and proteins) that are fundamental to the biological
structure and function. Polymers (natural and synthetic) are formed via
polymerization of many small molecules, known as monomers. Their
consequently large molecular mass relative to small molecules produces
unique physical properties, including toughness, viscoelasticity and a
tendency to form glasses and semicrystalline structures rather than crys-
tals. Polymerization is the process of combining many small molecules
(monomers) into a covalently bonded chain or network. During the polym-
erization process, some chemical groups may be lost from each monomer.
Synthetic methods are generally divided into two categories: step-growth
polymerization and chain-growth polymerization. The essential differ-
ence between the two is that in chain-growth polymerization, monomers
are added to the chain one at a time only, as in polyethylene, whereas in
step-growth polymerization chains of monomers may combine with one
another directly, such as in polyester. Synthetic polymerization reactions
may be carried out with or without a catalyst.
Polymers are among the most important materials produced commer-
cially and these are used in a wide range of applications. Their synthetic
methods are generally straightforward, but there are often several
processing steps and these steps depend critically on the bulk properties
such as melting temperature and viscosity. At this point, there is an extra
consideration of the molecular weight also. Any polymer will contain a
distribution of chain lengths and this plays an important role in deter-
mining the properties of that material.
Most effects in sonochemistry arise from cavitation. As a result of
cavitation radicals are produced, which are used in making polymers.
However, the exact origin of cavitation effects is relatively unimportant
to a polymer chemist, whether from thermal “hot spots” or electrical or
corona discharges. Most of the effects involved in controlling molecular
weight can be attributed to the large shear gradients and shock waves
generated around collapsing cavitation bubbles (Basedow and Ebert,
1977; Price et al., 1990).
Polymers199

Organic polymers are prepared under ultrasound exposure. These are

polymerized by a variety of mechanisms, but the most widely used method
is initiation by radicals undergoing chain growth or addition reactions. A
majority of organic polymers are prepared from monomers containing a
reactive double bond (e.g. α-olefins and vinyl monomers).
The mechanistic work of Price et al. (1992) suggested high-molecular
weight polymers are formed under sonochemical polymerization early in
the reaction, but the average chain length shortens at longer times. This is
caused by the onset of the degradation process, once sufficient long chains
are formed. Miyata and Nakashio (1975) and Price et al. (1990) found that
ultrasound affects the propagation, and hence, differences in the sequences
of the two monomers along the chain were observed.
Ultrasound irradiation is used in polymer chemistry to initiate radical-
mediated polymerizations and also to cleave polymer chains. Ultrasound
(high-intensity energy) provides a facile and multipurpose synthetic tool
to generate novel materials with unusual properties. Ultrasound irradia-
tion has been utilized in the synthesis of polymers and composites. As
compared to traditional energy sources, ultrasonic irradiation offers rather
some uncommon reaction conditions (mainly enormously high tempera-
tures and pressures in liquids, but for short periods) that cannot be reached
at, otherwise using other methods. It also provides some control over the
molecular weight, tacticity and polydispersity (Bhavase et al., 2012).
Polymerization can be enhanced by the extreme conditions produced by
ultrasound and these are known to act as a special initiator to allow chem-
ical bonds to break.
Ultrasound, the high-intensity energy provides a facile and multipur-
pose synthetic tool to generate some novel materials with unusual proper-
ties. Ultrasound irradiation has been proved to be an effective method for
the synthesis of polymers and composites (Bradley and Griser, 2002; Xia
and Wang, 2002). Polymerization of styrene has been proposed by Kojima
et al. (2001), Kobayashi et al. (2008), acrylonitrile, acrylamide, and acrylic
acid by (Xiuyuan et al. (2001). Ultrasound polymerization of methyl meth-
acrylate (MMA) (Price et al., 1992), styrene (Biggs and Griaser, 1995),
and n-butyl acrylate (Xia et al., 2002) was also studied. Ultrasonic irradia-
tion in copolymerization has also been widely studied since it does not
only allow shorter reaction times, but it is also easy to handle. Particularly,
this method is very useful for those copolymers, which are difficult to
prepare by conventional methods (Fujiwara et al., 1992, 1999).
200Sonochemistry

The susceptibility of a polymer to degradation depends on its struc-

ture. Polymer degradation means a change in the properties, that is, tensile
strength, colour, shape or molecular weight of a polymer or polymer-based
product under the influence of one or more environmental factors such
as heat, light, chemicals and, in some cases, galvanic action. It is due to
the scission of polymer chain bonds via hydrolysis, thereby leading to a
decrease in the molecular mass of the polymer. The degradation of poly-
mers via ultrasound is best known in solutions.
Sonochemistry opens up a new frontier of chemistry as ultrasound
leads to some new chemical reactions as well as the enhanced rate of a
chemical reaction (Xu et al., 2013). The ultrasound is high-intensity radia-
tion, which can accelerate and break the aggregation of the heterogeneous
liquid–liquid chemical reactions. The particle size can be reduced by using
the techniques such as dispersion, crushing, emulsifying and activation
effect, and, thus, it has a better control on the morphology of particles,
especially on the hard solid particles.

7.2 POLYANILINE

Polyaniline (PANI) is a polymer of aniline. Electrical properties of PANI

are reversibly controlled by charge-transfer doping and protonation. It is
environmentally stable and inert and has electrical, electrochemical, and
optical applications. It finds use in cell phones, calculators, LCD tech-
nology, and so on.
Advanced conducting polymeric materials can be prepared by ultra-
sonic-assisted polymerization. PANI is an easily aggregated substance and,
therefore, this method is especially useful for the preparation of PANI–EB
because in strong acidic medium, conductive PANI can be easily prepared.
Many researchers have adopted the strategy to co-dope PANI with both
inorganic and organic acids so as to synthesize semiconducting PANI-EB
so as to accomplish good conductivity and thermal stability (Bhadra et al.,
2007; Trovati et al., 2010) efficiently.
Xia and Wang (2003) prepared PANI/nano–SiO2 particle composites
through polymerization of aniline by ultrasonic irradiation in the presence
of two types of nano–SiO2 (porous nanosilica and spherical nanosilica).
A sonochemical synthesis of PANI nanotubes containing Fe3O4
nanoparticles has been carried out by Lu et al. (2006), starting from
Polymers201

aqueous solutions of aniline, ammonium peroxydisulphate (APS), phos-

phoric acid (H3PO4), and 10 or 20 wt.% of Fe3O4. It was shown that Fe3O4
nanoparticles were embedded in PANI nanotubes. The mechanism of
the formation of PANI/Fe3O4 nanotubes could be attributed to the ultra-
sonic irradiation and the H3PO4–aniline salt template. On polymerizing
the solution of aniline, APS, phosphoric acid, and 10 or 20 wt. % Fe3O4
nanoparticles under magnetic stirring, no PANI/Fe3O4 nanotubes could be
obtained, but only PANI/Fe3O4 powder was produced. However, PANI/
Fe3O4 composite nanotubes were obtained under the ultrasonic irradiation.
Ho et al. (2009) synthesized nanotubular, nanofibrouspolyaniline
(PANINT). These were prepared by an emulsion polymerization in the
presence of n-dodecylbenzene sulphonic (DBSA) and hydrochloric acids.
The building of the tubular structure was based on the tubular micelles from
the accumulation of micelles at high surfactant concentration. It leads to
early stage of centipede-like and eventual tubular morphologies. The solid
rods were filled with helical emeradine base (nano-EB) molecules associ-
ated with intermolecular H-bonding. These solid rods of nano-EB went on
cross-linking and carbonization after 200–300 °C by opening the quinoid
rings and the inter-molecular H-bondings were destroyed with nano-EB
molecules cross-linking into ladder-like structure.
Kowsari and Faraghi (2010) applied ultrasound for the synthesis of
PANI–Y2O3 nanocomposites. These nanocomposites were prepared under
controlled conductivity with the assistance of an ionic liquid (IL). Ultra-
sound energy and the IL replace conventional oxidants and metal complexes
in promoting the polymerization of aniline monomer, respectively. This
nanocomposite consists of regular solid microspheres of average diameter
3–5 nm, which were covered with some 40 nm nanoparticles. Under certain
different polymerization conditions, PANI nanofibres and nanosheet were
also obtained. This method opens a new pathway for the preparation of
nanoscale-conducting polymer nanocomposites with the help of ILs. It was
observed that the conductivity of the product varied with the mass ratio
of aniline monomer to Y2O3 and IL. This composite was more thermally
stable than pure PANI. The reaction conditions have been optimized by
varying parameters such as the aniline/Y2O3 ratio and also the type and
amount of IL used. The effect of the ultrasonic irritation time and frequency
on the morphology, conductivity, and yield was also observed.
Silver wire/PANI composites were synthesized by De Barros and
Azevedo (2010) via a sonochemical process using aniline monomer, silver
202Sonochemistry

nitrate, and anilinium nitrate aqueous solution in the presence of isopropyl

alcohol. Isopropyl alcohol has a remarkable effect on the growth and the
morphological structure of reduced silver. The reaction time is also an
important parameter, which allowed to obtain silver wires with a mean
diameter of 120 nm and a medium length of 4 µm instead of the spherical
particles obtained by its synthesis without alcohol. Bigger silver wires
with a mean diameter of 1.5 µm and length of 85 µm were obtained on
keeping reaction medium in a dark place after the completion of sonica-
tion process. The reduced silver was highly crystalline, and the polymer
obtained was PANI in the emeraldine salt form.
Ai and Jiang (2011) applied ultrasound for the synthesis of PANI
nanosticks. They successfully synthesized PANI nanosticks by a facile
template-free method in aqueous solution using ultrasonic irradiation.
These synthesized PANI nanosticks found potential application in water
treatment for the removal of Cu(II) ions by adsorption. In the beginning,
the adsorption rate is relatively fast as the Cu(II) is adsorbed on the exterior
surface of PANI nanosticks, but after some time, the adsorption capacity
becomes constant because the free exterior surface of adsorption sites of
the adsorbent gets diminished.
Barkade et al. (2011) also synthesized PANI–Ag (polyaniline/Ag)
nanocomposite using ultrasound radiation. These nanocomposites were
prepared under in situ miniemulsion polymerization of aniline along with
different loading of silver nanoparticles. PANI–silver nanocomposites
have potential application as sensor for ethanol vapour. Colloidal silver
nanoparticles were synthesized by reduction of silver nitrate with sodium
borohydride using sodium dodecyl sulfate. The sonochemically prepared
PANI–silver (PANI/Ag) nanocomposites and the average particle size
of Ag nanoparticles consists of open spherical aggregates of 50 nm and
~ 5–10 nm in diameter, respectively.
Manuel et al. (2014) used ultrasonic irradiation for synthesis of PANI
nanofibres involving oxidative polymerization of aniline monomer, dilute
hydrochloric acid, and doping with ammonium persulphate. As-prepared
PANI was evaluated for its suitability in lithium cells after doping with
lithium perchlorate salt. DC conductivity of doped PANI nanofibres was
measured at different temperatures and compared with the conductivity of
emeraldine base form of PANI, which was found to be 5.0 × 10−11 S·cm−1
after doping with ammonium persulphate, but it was dramatically
improved to 1.0 × 10−2  S·cm−1 at room temperature after doping with
Polymers203

lithium salt. Electrochemical properties of nanofibres were evaluated,

where a remarkable increase in cycle stability was achieved on comparing
with that to PANI prepared by simple oxidative polymerization of aniline.
This cell delivers a stable and higher discharge capacity even at 2 C—rate
compared to the cell prepared with bulk PANI doped with LiClO4.
PANI nanocomposites (PANI/NiCoFe2O4) were synthesized with
and without ultrasonic irradiation (Chitra et al., 2014). They observed
that PANI nanocomposites (PANI/NiCoFe2O4) were obtained by in
situ chemical polymerization of aniline in the presence of NiCoFe2O4
nanoparticles (20 %, 10 % w/w of fine powders). Ferromagnetic nature
of PANI/NiCoFe2O4 nanocomposites was confirmed by vibrating sample
magnetometer.
Jangid et al. (2014) reported ultrasound-assisted synthesis of conducting
functional polymers such as PANI and ring-substituted PANIs, which was
conventionally prepared by the stoichiometric oxidative polymerization
of aniline (ANI) and its derivatives with ammonium persulphate. Here,
PANIs were synthesized by oxidative polymerization of aniline in the
presence of different dopants such as inorganic (orthophosphoric acid,
PA) and organic acids (hippuric, HA and tosic acids, TA). It was observed
that the synthesized PANIs form of emeraldine base show reasonably
good room temperature conductivity and better thermal stability. N,N′-
Dimethylformamide (DMF)was used as a solvent in the UV-Visible
spectra of the PANI-PA, PANI-TA and PANI-HA in UV-vis absorption
spectroscopy.
Bhanvase et al. (2015) synthesized PANI and PANI/ZnMoO4 nano-
composite with different loading of ZnMoO4 (ZM) nanoparticles using
ultrasound-assisted in situ semibatch emulsion. ZM nanoparticles were
functionalized for better compatibility with PANI by using myristic
acid (MA). During this process, the cavitational effects induced due to
ultrasonic irradiations show significant enhancement in the dispersion
of functionalized ZM nanoparticles into the PANI. The presence of ZM
nanoparticles in PANI/ZM nanocomposite showed significant improve-
ment in the different types of physical properties like mechanical (cross-
cut adhesion), thermal, anticorrosion and sensing properties of PANI/
ZM nanocomposite/alkyd coatings over PANI/alkyd and neat alkyd resin
coating. PANI (p-type)/ZM (n-type) heterojunction has the improved LPG
sensing ability with minimized response time to sense LPG significantly
as compared to neat PANI.
204Sonochemistry

7.3 POLYPYRROLE

Polypyrrole (PPy) is a type of organic polymer formed by the polymeriza-

tion of pyrrole. These conductive polymers are used in electronic devices
and chemical sensors. It is a potential vehicle for drug delivery. Together
with other conjugated polymers such as PANI, poly (ethylenedioxythio-
phene) and so forth, polypyrrole may also find its use as a material for
artificial muscles.
Very fine and stable uniform monomer droplets were created in the
nanometer range in the ultrasound-assisted miniemulsion process, due
to the cavitational activity quite close to the interface of the immiscible
organic liquid phase. This emulsion polymerization has improved polym-
erization rate, narrow molecular weight, and particle size distribution, as
well as higher monomer conversion and several other advantages are these
over the conventional emulsion polymerization process (Hu et al., 2011;
Teo et al., 2008). There is a rapid dissociation of the initiator, which gener-
ates an enhanced quantum of radicals during the miniemulsion polymer-
ization process. It is all due to the mechanical effects of ultrasound (intense
turbulence associated with shear and liquid circulation) (Bang and Suslick,
2010; Sivakumar and Gedanken, 2005; Bhanvase et al., 2011).
Qiu et al. (2006) prepared polypyrrole (PPy)/Fe3O4 magnetic nanocom-
posites using ultrasonic irradiation. These nanocomposites were prepared
by chemical oxidative polymerization of pyrrole in the presence of Fe3O4
nanoparticles. PPy was found deposited on the surface of Fe3O4 nanopar-
ticles whereas Fe3O4 nanoparticles were dispersed at the nanoscale, which
leads to the formation of polypyrrole-encapsulated Fe3O4 composite parti-
cles. The doping level of PPy in PPy/Fe3O4nanocomposite was found to
be higher than that of neat PPy. These composites possess good electrical
and magnetic properties. It was observed that the magnetization increases
and the conductivity first increases and then decreases with an increase in
the Fe3O4 content. The conductivity reached its maximum value of 11.26 S
cm−1 with Fe3O4 content 40 wt. %, which is about nine times higher than
that of neat PPy. The introduction of Fe3O4 nanoparticles enhanced the
thermal stability of PPy/Fe3O4 composite.
Deshpande et al. (2009) synthesized core/shell structure containing
organic–inorganic phases using ultrasound-assisted in situ miniemul-
sion polymerization process, but they obtained a range of grain sizes
rather than monodispersed particles. The sensing performance of
Polymers205

polypyrrole was improved by incorporating, zinc oxide nanoparticles

into polypyrrole.
Ansari and Mohammad (2011) synthesized (pTSA/Pani:TiO2) an
electrically conductive polymer, p-toluene sulphonic acid-doped PANI/
titanium dioxide nanocomposites using in situ polymerization of aniline
along with TiO2 nanoparticles. It was observed that this polymer showed
superior ammonia-sensing capacity as compared to the pure PANI. Tang
et al. (2012) synthesized PANI/ZnO organic−inorganic hybrids by chem-
ical oxidative polymerization, and used these for detecting VOCs at low
temperature.
Roy et al. (2012) developed a rapid and direct sonochemical method
to synthesize polypyrrole salt. As-synthesized particles were found to be
irregular in shape and the particle morphology with diameter in the range
200–500 nm was observed. It was found that polyprrole salt has effective
chromium(VI) sorption–desorption properties and the sorption of chro-
mate did not change the morphology significantly.
The sonochemical synthesis of hybrid nanocomposites titania
(anatase):polypyrrole (TiO2:PPy) wasreported by Arenas et al. (2013).
Theses hybrid nanocomposites were prepared from a simple, one-step,
ultrasonic-assisted synthesis. The properties of these crystalline nanocom-
posites were compared with others, which were prepared under without
any ultrasound assistance, but it required a hydrothermal treatment to
yield crystalline titania(anatase) in the nanocomposite (TiO2:PPy) at low
temperature (130 °C) and in a short time (3 h). Strong interaction between
the secondary amine groups (N-H) of PPy and the oxygen from TiO2is
detected in crystalline nanocomposites. Absorption in the visible region
(λmax = 670 nm) by this composite indicates that these are good candidates
for harvesting energy in solar cells. An increase in the photocurrent was
observed for the devices with such nanocomposites prepared from the
ultrasound-assisted synthesis.
An ultrasound-assisted in situ miniemulsion polymerization of pyrrole
in the presence of ZnO nanoparticles was reported (Barkade et al., 2013).
Synthesized polypyrrole–zinc oxide (PPy/ZnO) hybrid nanocomposites
were of uniform size around 100 nm and these can be used as a sensor for
the detection of liquefied petroleum gas (LPG). (Fig. 7.1).
ZnO nanoparticles were encapsulated by the polymerized polypyr-
role as evident for Fourier Transform Infrared Spectroscopy (FTIR). They
indicated that the PPy/ZnO composite particles were of the crystalline
206Sonochemistry

FIGURE 7.1  Mechanism of functionalization of ZnO nanoparticles using polypyrrole in

the presence of ultrasound during miniemulsion polymerization.
Source: Barkade et al., 2013, with permission.

nature of ZnO (Wurtzite) giving a well-defined hybrid nanocomposite

structure suitable as an LPG sensor. The controlled size of the hybrid
particles obtained using this ultrasound synthesis strategy minimizes its
response time to sense the LPG significantly (2.2 min for PPy/ZnO). A
LPG sensing mechanism for the PPy(ptype)/ZnO(n-type) heterojunction
has been presented through a change in the height of the barrier potential.

7.4 POLYTHIOPHENE
Polythiophenes (PTP) are polymerized thiophenes, which is a sulphur
heterocycle. These polymers can become conducting on oxidation. Optical
properties (colour changes) and conductivity of polythiophenes change, by
Polymers207

twisting the polymer backbone, disrupting conjugation making conjugated

polymers, and so on. Polythiophenes have found their wide applications in
field-effect transistors, solar cells, batteries, chemical sensors, and so on.
Barkade et al. (2013) synthesized polythiophene (PTP)-coated SnO2
nano-hybrid particles using an ultrasound assisted-in situ oxidative
polymerization of thiophene monomers. Control experiments have also
been performed in the absence of ultrasound to know the effect of ultra-
sonic irradiation. Conjugation and chemical interactions between PTP and
SnO2 particles have been studied using FTIR spectroscopy. This hybrid
nanocomposite has the potential application as chemical sensors due to the
strong synergetic interaction between the SnO2 nanoparticles and polythio-
phene. LPG having high sensitivity at room temperature could be detected
by PTP/SnO2 hybrid sensors. Hybrid composite containing 20 wt. % SnO2
showed the maximum sensitivity at room temperature. The sensing mech-
anism of PTP/SnO2 hybrid nanocomposites to LPG was mainly attributed
to the effects of p–n heterojunction between PTP and SnO2.

7.5  POLY (METHYL METHACRYLATE)

Poly (methyl methacrylate) (PMMA) is also known as acrylic or acrylic

glass. It is a transparent thermoplastic, which is often used in sheet form as
a strong and lightweight material. PMMA has been used in a wide variety
of fields as rear lights, instrument clusters for vehicles, appliances and
lenses for glasses, LCD screens, medical, dental, and so on.
Choi et al. (2007) polymerized MMA in the presence of polycarbonate
by ultrasonic irradiation. The homopolymerization of MMA formed
PMMA, while copolymerization with macroradicals of PC formed PC
and PC-PMMA copolymer; thereby the resulting products consisted of a
mixture of homopolymers of PMMA, PC and PC-PMMA copolymer.
The PMMA synthesis by emulsion polymerization under ultrasonic
radiation was also carried out by Albano et al. (2010). These products
were obtained by varying the concentration of the anionic surfactant and
monomer concentration. At low concentrations of the surfactant (0.5 % p/v),
the latex particles presented a rough surface but at high surfactant concen-
tration, nanometric spherical particles were obtained with a smooth surface.
Patra et al. (2012) studied ultrasound-assisted emulsifier-free emul-
sion polymerization and synthesized PMMA/clay nanocomposites. The
dispersion of the clay layers with polymer matrix can be enhanced by
208Sonochemistry

using different power and frequencies of ultrasound waves. The struc-

tural information of the PMMA/clay nanocomposites by XRD revealed
that the interlayer spacing increased with clay loading. The magnitude of
dispersion of the clay in the polymer matrix was detected by transmission
electron microscopy (TEM). Various physical properties such as Young’s
modulus, breaking stress, elongation at break, toughness, yield stress and
yield strain of the nanocomposites as a function of different clay concen-
trations and ultrasonic power were also measured. Oxygen permeability
of the samples was studied, and the oxygen flow rate was found to be
reduced by the combined effect of clay loading and ultrasound. The flame-
retardant property of the nanocomposites due to clay dispersion was also
investigated by measuring limiting oxygen index.
Prasad et al. (2013) observed polymerization of MMA and MMA–
CaCO3 systems that possessed the combined effects of sonochemical
and conventional chemical initiation. Ultrasound and conventional initia-
tion by potassium persulphate (KPS) were combined to increase the final
conversion for the MMA and MMA–CaCO3 systems. An increase of 15 %
for the MMA only system (from 72 to 87 %) and of 10 % for the MMA–
CaCO3 system (from 76 to 86 %) was observed as compared to the initia-
tion by KPS alone. Also, an increase of 18 % (from 69 to 87 %) and 20 %
(from 66 to 86 %) for the MMA only and MMA–CaCO3 systems, respec-
tively, was observed for the combined initiation as compared to that of
ultrasound alone. Although the size of all particles synthesized varied in
between 60 and 130 nm, for both PMMA and PMMA–CaCO3 systems, an
excellent dispersion ability of ultrasound helped us to obtain narrow size
distribution and smaller average sizes.
Vargas-Salazar et al. (2015) synthesized polymer of MMA with the
reactive surfactant polyoxyethylene (10) alkylphenyl ether ammonium
sulphate (HBC10) in the presence of ultrasound at 50 °C by using semi-
continuous heterophase polymerization technique. The effects of HBC10
concentrations and the monomer addition rate (Ra) on kinetics, colloidal
behaviour and molar masses were studied. Polymer content between 20
and 24 % was obtained by latexes.
When HBC10 concentration was increased, it was observed to decrease
very high-average molecular weights (1.63 × 106 ≤ Mw  ≤ 2.34 × 106 g/mol),
while it increases with increased Ra. The corresponding polydispersity

indexes M w M n  were in the range of 1.55–2.30, showing relatively
Polymers209

wide molar masses distributions. Polymers with HBC10 showed two Tgs
(123 and 178 °C).
The influence of ultrasound and cavitation in the synthesis of PMMA
and its nanocomposite using the organo-modified Cloisite 30B clay was
observed by Poddar et al. (2016). The nanocomposites revealed better
thermal properties (maximum degradation temperature of 277 °C at
T5 % and glass-transition temperature of 120 °C at 2 % clay loading) as
compared to neat PMMA. The physical effect of ultrasound and cavitation
on generation of intense microturbulence in the system played a major
role in the process rather than the chemical effect of generation of radicals.
MMA–HNT nanocomposites (Halloysite nanotubes) were synthesized
(Kumar et al., 2016). These nanocomposites were synthesized by a solu-
tion-casting method using ultrasound irradiation. The use of ultrasound
energy provides is a greener, safer, faster, and facile way of synthesizing
PMMA–HNT nanocomposites. HNTs are naturally occurring hollow
nanotubes. The effect of clay loading and ultrasound energy on the struc-
ture, morphology, and thermal properties of nanocomposites were also
investigated. As-synthesized nanocomposites utilizing ultrasound revealed
complete exfoliation of filler into the polymer matrix. Sonication time of
60 min resulted in uniform distribution of particles. Increase in sonication
time resulted in a decrease in glass transition temperature (Tg) of nano-
composites due to breaking of polymer chains, because of an excessive
temperature and pressure generated during sonication. Successful incor-
poration of HNTs in the polymer matrix was confirmed by FTIR.

7.6 POLYURETHANE

Polyurethane (PU) is a polymer composed of organic units joined by

carbamate (urethane) links. PUs are thermosetting polymers but now ther-
moplastic PUs are also available. PU products are available in the form
of foams. Materials made of PUs have wide range of stiffness, hardness,
and densities and find their application in bedding, automotive, seating,
thermal insulation, gel pads, print rollers, footwear, and so on.
Polymerization of PU proceeds through two commonly used synthetic
strategies: one- and two-shot methods. The first method, one-shot method
requires the addition of all the components simultaneously (Rogers and
Long, 2003). The second method is as two-shot method. It requires the
210Sonochemistry

synthesis of oligomer with isocyanate functionality (end-capping) first,

and then adding the chain extender in a following step (Nelson and Long,
2014). Ion-containing PUs represent an industrially established class of
waterborne polyurethanes (WPUs), or waterborne PU dispersions (Lee
and Kim, 2009; Lee et al., 2012).
Chen et al. (2007) prepared PU/titania (PU/TiO2) nanocomposites
viaan ultrasonic process. These PU/titania nanocomposites were dispersed
homogeneously in PU matrix on nanoscale as supported by TEM and SEM.
It was observed that the heat stability of the composite was also improved.
Tarek et al. (2016) synthesized waterborne PU copolymer by ultrasonic
irradiation via acoustic cavitation, which allows the synthesis of such new
materials with unusual properties. It was observed that the acoustic power,
type of solvent, catalyst, and monomers molar ratio affect the polymerization
of urethane. As-prepared waterborne polyurethanes were duly characterized
by FTIR and GPC. The molecular weight of ultrasonically obtained poly-
urethane was found to be large in magnitude as compared to that of poly-
urethane which is prepared thermally. The increase in ultrasonic irradiation
power also had noticeable increases in the molecular weight of a polymer.

7.7  POLYVINYL ALCOHOL

Polyvinyl alcohol (PVA) is a water soluble synthetic polymer, which

is commonly used in paper making, textiles, and so on. It has certain
biomedical application also of contact lenses, artificial heart surgery, drug
delivery system, wound dressings, and so on. PVA has properties like
nontoxicity, noncarcinogenic, swelling properties, bioadhesive character-
istics, and so on.
Uniformly dispersed amorphous nanoparticles of magnetite in PVA
have been obtained by Kumar et al. (2000) using ultrasound radiation. The
size of magnetite particles was 12 ± 20 nm in diameter, and these particles
were very well dispersed in the PVA. Such a composite material was found
to be superparamagnetic in nature.
Kumar et al. (2002) synthesized nanospherical Ag2S/PVA (PVA)
and nanoneedles of CuS/PVA composite. These have been prepared by
10 % ethylenediamine–water solution of elemental sulfur, silver nitrate,
or copper acetate in the presence of polyvinyl under using sonochemical
irradiation. The resulting nanocomposites particle sizes were 25 and
Polymers211

225 nm for Ag2S/PVA and CuS/PVA, respectively. A band gap of 1.05

and 2.08 eV was estimated for Ag2S/PVA and CuS/PVA nanocomposites,
respectively. Micro scale zinc oxide-PVA (ZnO–PVA) composite has also
been prepared by ultrasound irradiation (Kumar et al., 2003). The proper-
ties of the as-prepared ZnO–PVA composite material were characterized
by different techniques such as XRD, TGA, TEM and DRS. A band gap of
3.25 eV was estimated for this composite.

7.8  COMPOSITES OF CARBON NANOTUBES

Ultrasonication has been used for functionalization of CNTs (Xing et al.,

2005; Chakraborty and Raj, 2005) and fabrication of polymer/CNTs nano-
composites (Xia et al., 2003; Park et al., 2002). Park et al. (2003) studied
different multiwalled carbon nanotube (MWCNTs) contents of PMMA/
MWCNT nanocomposites prepared by in situ bulk polymerization under
ultrasonication (frequency of 28 kHz, power of 600 W). Initially, the
acid-treated MWCNT was dispersed in a liquid MMA monomer state.
Then, the presence of 2,2-azoisobutyronitrile (AIBN) initiator polymer-
ized MMA and MWCNT-MMA suspension. Molecular weight of PMMA
was found to increase as the MWCNT contents wereincreased due to the
involvement of MWCNTs in polymer reaction and the consumption of
AIBN (Jia et al., 1999).
MWCNT and polysytrene (PS) composites were synthesized via
an in situ bulk polymerization under the application of ultrasonication
without any added initiator (Kim et al., 2007). Polymerization was initi-
ated by ultrasound and the radicals generated by decomposition of styrene
monomer. The acid-treated MWCNTs were dispersed in such a monomer.
The role of nanocomposites as an initiator was observed during polymer-
ization in comparison with AIBN.
The nanocomposite MWCNTs are almost completely embedded in the
PS matrix. The diameter of MWCNTs becomes larger than the pristine one
after removing the ungrafted PS with excess chloroform, which indicates
that the PS was successfully adhered to the MWCNTs surface making this
combination quite strong. The wrapped MWNT plays an important role in
dispersing the MWNTs.
212Sonochemistry

7.9  COORDINATION POLYMERS

New synthetic methods such as sonochemical synthesis can provide

control over size, morphology, and nano/microstructure. The utilization
of high-intensity ultrasound offers a facile, environmental-friendly, and
versatile synthetic tool for these nanostructured materials that are often not
obtained by conventional methods.
Silicon-based inorganic polymer, poly (organosilanes) was prepared
by a Wurtz-type coupling of dichlorodiorganosilanes using molten sodium
in refluxing toluene to remove the halogens (Miller and Michl, 1989). Han
and Boudjouk (1981) synthesized R3SiR3 in the presence of ultrasound
using lithium to couple organochlorosilanes. It is highly desirable that
such polymers should be prepared under more environmentally acceptable
conditions with a controlled structure and preferably monomodal distribu-
tion. Kim and Matyjaszewski (1989) also reported sonochemical synthesis
of such polymers.
Miller et al. (1991) reported some conflicting results because only
sonication did not yield polymers with a monomodal distribution unless
diglyme or 15-crown-5 was added to the solvent. Price (1992) and Price
and Patel (1997) have reported that a number of polysilanes with diverse
substituents can be prepared under a wide range of conditions, and all these
reactions gave higher yields and faster reactions under ultrasound. The
effect of ultrasonic intensity on polymer molecular weights and distribu-
tions established that higher intensities lead to narrower distributions and
smaller amounts of low-molar-mass material. A similar reaction was used
by Bianconi et al. (1989) to prepare polysilynes, (RSi)n, with sonochem-
ical activation of Na–K alloy. Here also, the use of ultrasound removed the
very high-molecular-weight fractions and allowed the synthesis of poly-
mers with molecular weights in the range of 10,000–100,000 and mono-
modal distributions.
A new nanosized lead(II) coordination polymer, {[Pb2(μ-3-bpdh)
(μ-NO3)3(NO3)]n; (3-bpdh = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene)},
was synthesized sonochemically by Hashemi and Ali (2010). This coor-
dination polymer of lead(II) consists of metallocyclic chains formed by
bridging NO3−and 3-bpdh ligands, thus, making a 2D array of Pb(NO3)2 and
3-bpdh. Thermal stability of this compound was also studied. The particle
size of coordination polymerprepared by the sonochemical method was
about 95 nm. The PbO nanoparticles were obtained by its thermolysis at
Polymers213

180 °C with oleic acid as a surfactant. Scanning electron microscopy study

showed that the size of such PbO particles is ~ 60 nm.
Hojaghani et al. (2013) synthesizednano-sized cobalt(II) coordination
polymer has been prepared by a sonochemical method using ligand, 5-(4-
carboxy phenyl azo) salicylic acid. These synthesized nanosized polymer
have thermal stability. Nanoparticles of Co3O4 were obtained by calcina-
tion of these nano-sized polymer at 550 °C.
Yawer et al. (2014) synthesized nanoparticles of coordination polymer
[Co2(pydc)2(H2O)6]n·2n H2O[H2pydc = pyridine-2,5-dicarboxylic acid]
by sonochemical method. The structure of single-crystalline coordination
polymer was determined by X-ray crystallography, which revealed that
nanoparticles of coordination polymer have the same structure as that of
a bulk single crystalline polymer. This coordination polymer possesses a
1-D chain-like extended structure with binuclear cobalt(II) nodal unit. The
average particle size of nanoparticles calculated was found to be ~ 27 nm.
The nanoparticles are composed of polyhedral blocks with definite edges.
These nanoparticles are thermally stable up to 352 K and thereafter decom-
pose in well-defined steps.
Safarifard and Morsal (2015) reported the sonochemical synthesis of
crystalline metal–organic coordination polymers. They discussed sono-
chemical synthesis of nanostructured metal complexes, including mono-
nuclear complexes, one-, two-, and three-dimensional coordination/
supramolecular polymers (CPs), and metal–organic frameworks (MOFs).
Ranjbar and Yousefi (2016) prepared nanosized Pb(II) coordination
polymer, {[Pb(pydc)(pydc.H2)(H2O)2]2}n, (where pydc.H2 = 2,6-pyri-
dinedicarboxylic acid) by sonochemical method. The sizes of the nano-
structures were ~ 90 nm. Pure phase PbO nanoparticles were obtained by
calcination of nanosized compound at 600 °C under argon atmosphere,
and the particles size of the PbO were approximately 26 nm. The coor-
dination polymers are suitable precursors for the simple one-pot prepa-
ration of nanoscale metal oxide materials with different and interesting
morphologies.

7.10 OTHERS

Polymer surface are modified also by ultrasound and this was first reported
by Urban and Salazar-Rojas (1988), who worked on a piezoelectric
214Sonochemistry

material, that is poly(vinylidene difluoride). It is normally an insulator, but

after dehydrofluorination produced a surface with carbon–carbon double
bonds (C=C). This process can be accelerated by ultrasound. Ultrasound
helps in enhancing contact between the solid surface and the solution,
which in turn provided excellent wetting of the surface and also better
mass transport of reagents.
The conversion of solar energy into electrical energy requires semi-
conductor materials such as photo anodes in photoeletrochemical cells
(Hillhouse and Beard, 2009; Kalambhe and Kharat, 2002). Polymer–semi-
conductor devices based on metal oxide materials offer cost effectiveness
for the energy conversion process (Xiong et al., 2008). Two approaches
were used in the preparation of thin film-based photo anodes and these are:

• Metal or semiconductor metal oxides are deposited onto a conduc-

tive glass (ITO) at higher temperature using chemical vapour depo-
sition or electrochemical deposition and
• Semiconductors incorporating conducting polymers, such as PANI/
polypyrrole/porphyrin (Wang and Jing, 2007; Brune et al., 2004;
Du Pasquier et al., 2009; Claudia et al., 2002) are coated onto the
nonconducting transparent matrix such as poly(methyl methacry-
alate) and polyethylene terphthalate.

Gumel et al. (2012) reported enzymatic synthesis of poly-E-caprolactone

using ultrasound. The rate constant for chain propagation was only slightly
enhanced. The acoustic effects allowed this reaction to continue longer and
the viscosity remains under control as compared to the nonsonicated process,
where it became almost impossible to operate due to the highly elevated
viscosity (> 2000 times increase from initial viscosity) of reaction mixture.
Zhao et al. (2016) investigated the ultrasound-assisted enzymatic
synthesis of poly(ethylene glutarate). Diethyl glutarate and ethylene
glycol diacetate were used as start-up materials, without the need of
addition of any extra solvent. Lipase B catalysed the reactions by from
Candida antarctica immobilized on glycidyl methacrylate-ter-divinylben-
zene-ter-ethylene glycol dimethacrylate at 40 °C during 1 h in ultrasonic
bath followed by 6 h in vacuum in both the cases for evaporation of ethyl
acetate. The same degree of polymerization was obtained for the same
enzyme loading in reaction but on using the ultrasound treatment required
for lesser time. The ultrasound treatment enhanced initial kinetics with
high degree of polymerization and it is considered demonstrated to be an
Polymers215

effective green approach to intensify the polyesterification reaction. The

effect of reaction operating parameters on the time of reaction, degree of
polymerization, and monomer conversion rate were also observed.
Sonawane et al. (2010) prepared metal oxide-loaded poly(butyl meth-
acrylate) films sonochemically. These films were used as photo anodes in
photoelectrochemical cells. A small quantity of PANI was added during the
latex synthesis to facilitate the transport of charge carriers. The semicon-
ductor metal oxides used were ZnO, TiO2 and Bi2O3/ZrTiO4. It was found
that there was a decrease in photocurrent with an increase in the thickness
of the latex film, but photocurrents generated were directly proportional
to the amount of metal oxide loading. Bi2O3/ZrTiO4 latex at 0.4 g loading,
showed the highest photocurrent of 0.9 μA·cm−2 in aqueous formic acid
solution. The reaction of the three different oxide films was found as:

Bi2O3/ZrTiO4  > ZnO > TiO2

7.11  POLYMER DEGRADATION

The polymer chain degradation (an irreversible lowering of the chain

length caused by cleavage, and not necessarily any chemical change) in
solution was one of the first reported effects of high-intensity ultrasound
on polymers (Flosdorf and Chambers, 1933). This common behaviour is
a result of a physical process that is independent of the chemical nature
of the polymer, but rather it depends on the polymer chain dimensions in
solution. Several studies have demonstrated that when sonicated under the
same conditions, the rate of degradation and Mlim are not sensitive to the
nature of the polymer.
The degradation proceeds faster and to lower molecular weights at
lower temperatures in more dilute solutions, and in solvents with low
volatility. This pattern follows the effect of the parameters on cavitational
bubble collapse. At higher temperatures or in volatile solvents, sonica-
tion results in more vapours entering the bubble and so cushioning the
collapse, making it less violent. The polymer chains are not entangled in
dilute solutions and are free to move in the flow fields around the bubbles.
The degradation is more efficient at high ultrasonic intensities, owing
to the greater number of bubbles with larger radii. Many other factors
have been quantified including the nature of any dissolved gases, and the
conformation that the polymer adopts in solution.
216Sonochemistry

Hence, one can exert a great deal of control over the degradation process
by suitable variation of the experimental conditions. It has been observed
that degradation does not occur under conditions, which suppress cavita-
tion. The polymer chains are subjected to extremely large forces in the
rapid liquid flows near collapsing cavitation bubbles and in the shock after
bubble implosion. The polymer chains have negligible vapour pressure
and are unlikely to be found at the bubble interface that is why there is no
evidence that in nonaqueous liquids, the extreme conditions of tempera-
ture found in cavitation bubbles contribute to polymer degradation.
The molecular weight dependence of the degradation indicates that
longer chains are preferentially removed from a sample and the polydis-
persity of the polymer is also changed. Thus, degradation can be used as
an additional processing parameter to control the molecular weight distri-
bution. A commercial process uses a sonochemical treatment during the
final processing stage to control the molecular weight distribution to give
the desired processing properties of the polymer (Price, 1996).
Ultrasonic degradation is better than the thermal degradation, which
produces cleavage along the chain at random points and in ultrasonic
degradation, cleavage occurred preferentially near the middle of the chain
(Van der Hoff and Glynn, 1974). Van der Hoff and Gall (1977) also inves-
tigated the degradation of polystyrene in tetrahydrofuran. They found
that the degradation could be best modeled, when it was assumed that
the probability of chain breakage was distributed in a Gaussian manner
within ~ 15 % of the center of the chain. This center cleavage model is also
consistent with the stretching and breakage mechanism.
Degradation of poly(vinyl acetate) was carried out in the presence of
an oxidizing agent, benzoyl peroxide, using ultrasonic irradiation. It was
reported that degradation rate coefficient of the polymer decreased with
increasing benzoyl peroxide concentration (Madras and Chattopadhyay,
2001a). Daraboina and Madras (2009) observed that the ultrasonic degra-
dation of different polymers is also influenced by the alkyl group substitu-
ents present in it.
The primary products of the degradation are radical species arising
from homolytic bond breakage along the chain in all the carbon backbone
polymers. Evidence for macromolecular radicals may be obtained from
radical trapping experiments as well as using electron-spin resonance
spectroscopy (Tabata et al., 1980). One of the applications of degradation
is that it provides those macromolecular radicals, which can be used as
Polymers217

initiating species in the preparation of copolymers. When mixture of two

polymers dissolved in a common solvent was sonicated, then combina-
tion of the two different macromolecule fragments leads to the formation
of a block co-polymer. However, it is slightly difficult to separate these
copolymers from the starting materials, and there are also some problems
in controlling the block structure. An alternative approach is also there,
which involves sonicating a polymer dissolved in a solution containing
the second monomer. The macromolecular radical generated initiates the
polymerization of the second monomer.
Encina et al. (1980) reported that the peroxide linkages in the backbone
increased rate of degradation of poly(vinyl pyrrolidone) about 10-folds,
when the polymer was prepared with a small number, suggesting that
chain cleavage can occur preferentially at weak spots in the chain.
Although heat, light, chemical reagents, or ultrasonic radiation can
be used for the degradation of polymers, but in ultrasonic degradation,
the chain cleavage is preferentially near the middle of the chain whereas
thermal degradation occurs principally at the chain end and/or there is a
random chain scission. There are several unique features of ultrasound that
make it a viable option from practical viewpoints. The limiting molecular
weight polymer degradation by ultrasound is unique. The rapid growth
and violent collapse of bubbles is responsible for their degradation. Rela-
tive motion of the polymer segments and solvents produces stresses in
polymer chains leading to scission of chain (Madras et al., 2000; Madras
and Chattopadhyay, 2001a, 2001b). Passage of ultrasonic waves through
the solution creates the localized shear gradient, which is responsible for
tearing off the molecules leading to chain scission and also for a decrease
in molecular weight (Singh and Sharma, 2008). Concentration, initial
molecular weight, temperature, frequency, and intensity of ultrasound are
the major factors that affect the degradation rates of polymers (Vijayalak-
shmi and Madras, 2004).
The application of ultrasonic energy for polymer degradation dates
back to the 1930s. When natural polymers were subjected to sonication,
it resulted in a reduction in viscosity (Price et al., 1994). Suslick (1988)
reported in the late 1930s, that ultrasonic irradiation depolymerized starch,
gum arabic, gelatine and polystyrene.
Ultrasonic degradation of PVA was carried out by Taghizadeh and
Mehrdad (2003) in aqueous solution at 25 °C. The effect of solution
concentration on the rate of degradation was investigated. Kinetics of
218Sonochemistry

degradation was studied using viscometry method. They indicated that

degradation rate of PVA solutions decreases with increasing solution
concentration. This behaviour in the rate of degradation was interpreted in
terms of viscosity and concentration of polymer solution. With increasing
solution concentration, viscosity was found to increase and it causes a
reduction in the cavitation efficiency and, as a result, the rate of degrada-
tion also decreased.
Ultrasonic degradation of polybutadiene and isotactic polypropylene
(PP) was studied by Chakraborty et al. (2004). Degradation of these poly-
mers was studied at different temperatures and in different solvents. The
variation of rate coefficients with vapour pressure and kinematic viscosity
was also investigated.
A new method using high-intensity ultrasonic wave has been devel-
oped for the degradation of polymer melt using an intensive mixer (Kim
and Lee, 2002). They observed that a significant degradation of PP melt
in a mixer occurred due to the action of ultrasonic wave without any addi-
tives or solvents. The degradation efficiency of ultrasonic irradiation was
compared with that of peroxide, dicumyl peroxide. They also found that
the direct sonication of polymer mixture in melt state reduces the domain
sizes and stabilizes the phase morphology of the blend. Ultrasound-
assisted melt mixing can lead to in situ copolymer formation between the
components and consequently provide an effective route to compatibilize
immiscible polymer blends.
Konaganti and Madras(2010) synthesized and characterized the
copolymers, PMMAMA, poly(methyl methacrylate-co-ethyl acry-
late) (PMMAEA), and poly(methyl methacrylate-co-butyl acrylate)
(PMMABA), of different compositions. The effect of alkyl acrylate
content, alkyl group substituents, and solvents on the ultrasonic degra-
dation of these copolymers was studied. A model based on continuous
distribution kinetics was used to study the kinetics of degradation. The rate
coefficients depend linearly on the logarithm of the vapour pressure of the
solvent, which indicated that vapour pressure is on important parameter
controlling the degradation process. The rate of degradation was found to
increase with an increasing alkyl acrylate content. At a particular copo-
lymer composition, the rate of degradation follows the order:

PMMAMA > PMMAEA > PMMABA

Polymers219

It was observed that the degradation rate coefficient varies linearly with
the mole percentage of the alkyl acrylate in the copolymer.
Koda et al. (2011) utilized ultrasonic irradiation for the degradation of
methyl cellulose, pullulan, dextran, and poly(ethylene oxide) in aqueous
solutions. They investigated these degradations at the frequencies of 20
and 500 kHz. The average molecular mass and the polydispersity were
observed as a function of sonication time. It was observed that the degra-
dation under sonication at the 500 kHz frequency proceeded faster in
comparison with the 20 kHz sonication for all the four polymers. The addi-
tion of a radical scavenger, t-BuOH, resulted in the suppression of degra-
dation of water-soluble polymers. The degradation rate of methyl cellulose
was the largest one among these polymers. They discussed differences in
the degradation rates in terms of flexibility and the hydrodynamic radius
of polymer chains in aqueous solutions.
Mohod and Gogate (2011) also used ultrasound for the polymer degra-
dation. The ultrasonic degradation of two water-soluble polymers such as
carboxy methyl cellulose (CMC) and PVA has been studied. The effect of
different operating parameters such as time of irradiation, immersion depth
of horn and solution concentration has been investigated with different
additives such as air, sodium chloride, and surfactant. They showed that
the viscosity of polymer solution decreased with an increase in the ultra-
sonic irradiation time and it approached a limiting value and the use of
additives such as air, sodium chloride, and surfactant helps in increasing
the extent of viscosity reduction.
Wang et al. (2015) studied that the sonocatalytic degradation of methyl
orange (MO) with Fe3O4/polyaniline (Fe3O4/PANI) microspheres in near
neutral solution (pH ~ 6) using ultrasound-assisted advanced oxidation
process (AOP) (Fig. 7.2).These Fe3O4/PANI microspheres were character-
ized and tested for adsorption and sonocatalytic decolourization of MO
in solution. The isotherms and kinetics of MO adsorption with Fe3O4/
PANI followed Langmuir model and the pseudo-second-order model,
respectively, as Fe3O4/PANI has a high capacity to adsorb MO in solu-
tion. The percentage of room temperature sonocatalytic degradation of
MO with Fe3O4/PANI is about 4.8, 8.8, and 5.7 times that with Fe3O4,
dedoped Fe3O4/PANI, and ultrasonication alone, respectively. The eco-
friendly Fe3O4/PANI added with superparamagnetism and excellent reus-
ability offers to be a promising sonocatalyst for rapid decolourization and
enhanced degradation of azo dyes in effluents.
220Sonochemistry

FIGURE 7.2  Proposed sonocatalytic degradation mechanism of MO upon Fe3O4/PANI.

Source: Wang et al., 2015, with permission.

The use of polymer in day-to-day life has proved to be a boon for

humans as it has almost replaced traditional materials such as iron,
wood, paper, cloth, and so on. Polymers have been used in many things
such as furniture, vehicle bodies, wrapping materials, nonstick coating
of utensils, textile, and so on. The synthesis of these polymers using
ultrasound has been a great development. In this polymer era, the most
developed countries are extensively using polymers in different kinds
for one purpose or the other and are therefore facing a new emerging face
of pollution, that is, polymer pollution. The degradation and disposal of
polymers is posing a serious problem nowadays. In this aspect, ultra-
sonic treatment of polymers for their degradation and disposal will play
an important role and prove to be a technology involving green chem-
ical routes.

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CHAPTER 8

WASTEWATER TREATMENT
ARPITA PANDEY1, ARPITA PALIWAL2, RAKSHIT AMETA3
1
Department of Chemistry, Sangam University, Bhilwara, India
E-mail: [email protected]
2
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
3
Department of Chemistry, J.R.N. Rajasthan Vidyapeeth (Deemed to
be University), Udaipur, India E-mail: [email protected]

CONTENTS

8.1. Introduction  ����������������������������������������������������������������������������  225

8.2. Methods of Wastewater Treatment  �����������������������������������������  226
8.3. Sonochemical Wastewater Treatment  �������������������������������������  232
References  �����������������������������������������������������������������������������������������  263

8.1 INTRODUCTION

The development of industrial sector has played a major role in the

economic growth of several countries on one land, but various industrial
processes generating wastewater have also caused so many environmental
problems on the other. Among all the other pollutants, the pollution caused
by dyestuff is considered as the main source of water contamination
because synthetic dyestuffs are extensively used by several industries and
these are not biodegradable.
Many dyeing, printing and textile industries dispose their wastewater
directly to the stream without any proper treatment or with only some
preliminary treatments. This negligence on the part of industries has
226Sonochemistry

caused harmful effects for the ecosystem. Such water pollution causes
aesthetic problems and disrupts the incident sun rays to reach under
water and as a consequence the process of photosynthesis is disturbed.
Water pollution also causes lack of dissolved oxygen in water stream and,
as a consequence, degradation of water quality is observed ultimately
resulting in the death of various species in stream. Many of the pollut-
ants are higher toxic and sometimes even carcinogenic in nature. These
are harmful and because of bioaccumulation, they can also influence the
whole food chain.

8.2  METHODS OF WASTEWATER TREATMENT

Various methodologies have been adopted for treating wastewater and

these include biological treatment, oxidation, membrane filtration, sorp-
tion, coagulation/flocculation, and so on, which are discussed in detail in
the following sections.

8.2.1  BIOLOGICAL TREATMENT

Biological treatment is the secondary treatment of water, where a wide

variety of microorganisms, primarily bacteria, are used. These microorgan-
isms convert biodegradable organic matter contained in wastewater into
simple substances and additional biomass. Successful biological treatment
depends on the development and maintenance of an appropriate, active,
and mixed microbial population in the system. Biological treatments are
those, which use organisms to break down organic substances in waste-
water, and these are widely used worldwide. Biological treatments rely
on bacteria, nematodes, or other small organisms to break down organic
wastes using normal cellular processes.
The effect of salinity in the decolourization of azo dye by Shewanella
sp. was investigated by Khalid et al. (2008). They reported that bacterium
decolourized 100.0 mg·L−1 dye under static and low-oxygen conditions
in presence of NaCl (60.0 g·L−1). The addition of glucose or ammonium
nitrate inhibited the decolourization process, whereas the presence of yeast
extract and Ca(H2PO4)2·H2O were found to enhance the decolourization
rate. Dawkar et al. (2008) reported 100 % degradation of dye brown 3REL
Wastewater Treatment227

by Bacillus sp. VUS within 8 h at static anoxic condition. This bacterium
was also able to degrade 80 % of dye in textile effluent.
The simultaneous removal of Cr(VI) and azo dye acid orange 7 has
been observed by Ng et al. (2010) using Brevibacterium casei under
nutrient-limiting conditions, whereas Ghasemi et al. (2010) studied the
decolourization of different azo dyes by Phanerochaete chrysosporium
RP 78 under optimized conditions. They showed that the decolouriza-
tion of azo dyes was due to an enzymatic degradation and almost 100 %
decolourization was acquired after 24 h. The potential of Lemna minor for
the treatment of reactive dye polluted wastewater was also investigated
by Kilic et al. (2010). Nearly 59.6 % brilliant blue removal was found
in samples containing 2.5 mg·L−1 dye and 1.0 mg·L−1 of triacontanol
hormone concentration.

8.2.2 OXIDATION

Chemical oxidation oxidizes organic pollutants to less toxic or harmless

substances. Complete oxidation or mineralization of organic substances
will give CO2 and H2O. Oxidation can be used to remove some inor-
ganic components such as cyanide. It can also be used in combination
with biological purification and this process is known as partial oxida-
tion. Chemical oxidation is used as a pretreatment technique, that is,
either to break down recalcitrant components or to make them suitable for
biological degradation and also for limiting sludge production by partly
oxidizing the sludge.
Such an oxidation requires addition or generation of oxidants in waste-
water. Most commonly used oxidants are oxygen, hydrogen peroxide,
ozone, bleaching liquor or sodium hypochlorite, chlorine dioxide, chlo-
rine gas, peroxy acetic acid, and so on. However, different combinations
of oxidants are also possible.
The heterogeneous catalytic ozonation of methylene blue (MB) using
volcanic sand showed a higher removal efficiency of MB as compared to
homogenous system. One et al. (2000) studied the use of V2O5 catalyst in the
oxidative dehydrogenation of propane. Hofmann et al. (2005) reported the
degradation of chlorobenzene (CB), 4-chlorophenol, 4-chloroaniline and
1-nitro-4-CB using catalytic oxidation with hydrogen peroxide. The conver-
sion of a wide spectrum of components including aliphatic and aromatic
228Sonochemistry

hydrocarbons as well as halogenated organic compounds into nontoxic or

minor-toxic substances and finally into carbon dioxide and water can be
obtained. It was demonstrated that the type of catalyst and oxidation agent
as well as the reaction parameters influence the degradation rate.
Enhanced dye wastewater degradation efficiency was studied by Xu
et al. (2008) using a flowing aqueous film photoelectrocatalytic reactor.
It was observed that higher treatment efficiency can be achieved for the
degradation of reactive brilliant blue X-BR by this process. An indirect
electrochemical oxidation method for the decolourization of textile waste-
water was explored by Maljaei et al. (2009). Here, graphite and sodium
chloride were used as an electrode and electrolyte, respectively. Various
variables affecting the efficiency of the decolourization and degradation
process of reactive yellow 3 were studied.
Catalytic oxidation of simulated wastewater containing acid chrome
blue K was investigated by Yu and Shi (2010) using chlorine dioxide as an
oxidant. The activated carbon–MnO2 catalyst was used for this catalytic
oxidation and the removal efficiency of acid chrome blue K was observed
to be 87.8 %. Photocatalytic degradation of rhodamine B using thiocya-
nate complex of iron and H2O2 was reported by Lodha et al. (2011).
Wang et al. (2012) reported the use of amorphous Fe78Si9B13 alloy
as a heterogeneous Fenton catalyst in the degradation of phenol. The
Fe78Si9B13 showed better catalytic activity than iron powder and Fe2+.
Addition of n-butanol (hydroxyl radical scavenger) decreased the degrada-
tion rate of phenol, which demonstrates that hydroxyl radicals were mainly
responsible for the removal of phenol. They observed that phenol may be
degraded by hydroxyl radicals on the surface of Fe78Si9B13. This amor-
phous alloy exhibited high stability in recycling experiments and showed
excellent reuse performance even after continuous operations of 8 cycles.
Thermal catalytic oxidation of octachloronaphthalene (CN-75) using
anatase TiO2 nanomaterials was investigated at 300°C. Oxidation interme-
diates is classified into the following three types:

• naphthalene ring
• Single-benzene ring
• Completely ring-opened products

Reactive oxygen species on anatase TiO2 surface, such as O2−•and

O , contributed to oxidative degradation. The naphthalene ring oxidative
2−
Wastewater Treatment229

products with chloronaphthols and hydroxyl-pentachloronaphthalene-

dione could be formed via attacking the carbon of naphthalene ring at one
or more positions by nucleophilic O2−. Lateral cleavage of the naphtha-
lene ring at different carbon–carbon bonds by electrophilic O2−• may also
occur. This will lead to the formation of tetrachlorophenol, tetrachloroben-
zoic acid, tetrachlorophthalaldehyde, and tetrachloroacrolein benzoic acid,
partially with further transformation into tetrachlorobenzene-­dihydrodiol
and tetrachloro-salicylic acid. Complete cleavage of naphthalene ring
could produce the ring-opened products such as formic and acetic acids
(Su et al., 2015).

8.2.3  MEMBRANE FILTRATION

Membranes are thin and porous sheets, which are able to separate contam-
inants from water on the application of a driving force. It was considered
a viable technology for a long time for desalination, but these membrane
processes are increasingly employed in both drinking water and wastewater
treatment. It is useful in the removal of bacteria and other microorgan-
isms, particulate material, micropollutants, and natural organic materials,
which is responsible for imparting colour, taste and odour to water and
can also react with disinfectants to form disinfection by-­products (DBPs).
As advancements are being made in membrane production, module
design, capital and operating costs are continuing to decline. Membranes
are becoming increasingly more popular for the production of potable
drinking water from ground, surface and seawater sources, as well as for
the advanced treatment of wastewater and desalination.
Many types of membranes are used for the treatment of water in the
processes such as reverse osmosis (RO), nanofiltration (NF), dialysis and
electrodialysis, ultrafiltration (UF) and microfiltration (MF), and so on.
Reverse osmosis is primarily used to remove salts from salty water and it
is capable for very high rejection of synthetic organic compounds. Nano-
filtration is used to soften fresh waters and remove DBPs whereas UF
and MF are used to remove turbidity, pathogens, and particles from fresh
water.
Ultrafiltration, which typically operates pressures of between 5 and
15 bars, is widely used in chemical separation processes, because it can
separate species according to molecular size. However, MF separates
230Sonochemistry

according to particle size. It is a process that can take place at low temper-
atures. This is mainly important because it enables the treatment of heat
sensitive matter. It is a process with low-energy cost. Most of the energy
that is required is used to pump liquids through the membrane.
The total amount of energy that is used is minor, compared to alterna-
tive techniques, such as evaporation. The membrane separation process
is based on the presence of semipermeable membranes. The principle
is quite simple. The membrane acts as a very specific filter that will let
water flow through, but it catches suspended solids and other substances.
The advantage of membrane technology is the fact that it works without
the addition of chemicals, with a relatively low-energy use and easy- and
well-arranged process conductions.
Novel asymmetric aromatic polyamide NF membrane has been used
by Ren et al. (2010) for the treatment of dye aqueous solutions. This NF
membrane was prepared using a phase inversion method. The copoly
phthalazinone biphenyl ether sulphone UF membrane with low-molecular
weight cut-off possesses excellent thermal resistance, and it is suitable
for being used in dye wastewater treatment at high temperatures (Han et
al., 2010). It showed 100 % rejection for Congo red, sulphur black B, and
gentian violet.
A new plate MF membrane was fabricated using low-cost cement and
quartz to catalyse dissolved ozone. The membrane-catalysed ozonation
process successfully increased the degradation efficiency of p-chloronitro-
benzene (p-CNB) compared with the ozone-alone process in aqueous condi-
tions under continuous flow. The ozone-membrane process decomposed
1.5 mg·L−1 of dissolved ozone and increased the p-CNB removal by 50 %
with little adsorption. It was confirmed that p-CNB degradation followed
the mechanism of hydroxyl radical oxidation during the ozone-membrane
process. The hybrid process was observed to maintain the ability of removal
of p-CNB efficiently in different water sources, and it also had the stability
of long-time operation. The cementitious membrane was an efficacious
catalyser for p-CNB degradation by ozonation (Wang et al., 2015a).
Naidu et al. (2016) reported the removal of phenol from wastewa-
ters using a novel nanoparticle adsorption and NF technique named as
nanoparticle-assisted nanofiltration. Tri and di particle studies showed
more phenol removal than that of their individual particles, particularly
for using small particles on large membrane pore size and large particles
at low concentrations.
Wastewater Treatment231

8.2.4  SORPTION PROCESS

Sorption (adsorption and absorption) is a physical and chemical process by

which one substance becomes attached to another substance. Absorption
is the incorporation of a substance in one state into another of a different
state (e.g. liquids being absorbed by a solid or gases being absorbed by
a liquid). Adsorption is the physical adherence or bonding of ions and
molecules onto the surface of another phase (e.g. reagents adsorbed to a
solid catalyst surface).
Active manganese oxide was used for the treatment of wastewater
containing dye Congo red (Chakrabarti et al., 2009). It was reported
that the removal of Congo red by active manganese oxide is a revers-
ible adsorption process. Asuha et al. (2010) carried out adsorption study
using mesoporous TiO2 (prepared by hydrothermal method) and showed
that the maximum adsorption capacity for methyl orange (MO) and Cr(VI)
were 454.5 and 33.9 mg·g−1, respectively. Here, cetyltrimethylammonium
bromide (CTAB) was used as a structure-directing agent.
A study on the porous magnetic microspheres prepared with sulpho-
nated macroporous polydivinylbenzene as a template and its ability
to remove cationic dyes was conducted by Liu et al. (2010). It was
interesting to note that basic fuchsin and methyl violet can be removed
with high efficiency using these porous magnetic microspheres. These
can be easily regenerated and used for wastewater treatment. Hollow
Fe3O4 and magnetic nanospheres were used as an adsorbent for the
removal of neutral red dye from aqueous solutions by Iram et al.
(2010). Nanoscale particle size, magnetic property and hollow porous
nature of Fe3O4 were influencing factors for better adsorption behav-
iour of neutral red.
Bottom ash and deoiled soya can also be used as adsorbents for the
removal of Congo red (Mittal et al., 2009). The effects of pH, dye concen-
tration and amount of adsorbents were studied for the degradation of Congo
red on these adsorbents. Appreciably adsorptive tendencies for Congo red
with 96.95 % and 97.14 % saturation were reported on bottom ash and
deoiled soya, respectively. The possibility of producing an adsorbent for
dye removal by calcinating waste drilling fluids was also explored by
Song et al. (2009). Other low-cost adsorbents such as coconut and coffee
husks were identified as potential biosorbents for hazardous dye quinoline
yellow (Mittal et al., 2010).
232Sonochemistry

8.2.5 COAGULATION/FLOCCULATION

Coagulation is the destabilization of colloidal particles brought about

by the addition of a chemical reagent called as coagulant. Flocculation
is the agglomeration of destabilized particles into microfloc and later on
into bulky floccules, which can be settled as floc. The addition of another
reagent called flocculant and flocculant aid may promote the formation of
the floc. The factors which can promote the coagulation–flocculation are
the velocity gradient, time, and pH. The time and the velocity gradient are
important to increase the probability of particles to come together.
Decolourization of effluent-containing dye produced electrocoagu-
lation, when mineral coagulant was used by Zidane et al. (2008). The
inorganic coagulants used in this study were labelled as C1 (from the
electrolysis of NaOH, 7.5 × 10−3 M), C2 (from the electrolysis of NaCl,
1.0 × 10−2 M), and C3 (from the electrolysis of NaOH, 7.5 × 10−3 M + NaCl,
10−2 M). Results showed that the best performance of reactive red 141
removals was obtained with coagulant C2.
Red mud is a by-product of bauxite processing during Bayer process
and its role in gas cleaning and wastewater treatment has been explored
by Wang et al. (2008). They revealed some promising results of using this
red mud as a coagulant, an adsorbent and a catalyst for some industrial
processes. It was indicated by leaching and eco-toxicological tests that red
mud is not toxic in nature to the environment before and after reuse.

8.3  SONOCHEMICAL WASTEWATER TREATMENT

Several technologies have already been used for wastewater treatment.

These are physical, chemical, biological or a combination of these tech-
niques. Advanced oxidation processes have been found to be suitable
methods for the degradation of various organic compounds. AOPs are
characterized by production of •OH (hydroxyl) radical as the primary
oxidant. The •OH radicals are extremely reactive species, nonselective and
powerful oxidizing agent.
Sonochemistry is one of AOPs that utilizes the potential of ultrasound
(US) in degrading dissolved organics in aqueous solution. Sonication is a
relatively novel AOP and it is based on the application of low to medium
frequency (20–1000 kHz) and high-energy US to catalyse the destruction
Wastewater Treatment233

of organic pollutants in aqueous solutions (Mahvi et al., 2009). Sono-

chemical treatment typically operates at ambient conditions and does not
require the addition of extra chemicals or catalysts.
In the present era, US has been considered as a model process, which
has the potential for being used in the treatment of water, wastewater and
sludge. Ultrasonic sound irradiation can effectively degrade different
contaminants present in water because of the presence of localized high
concentrations of oxidizing species. Ultrasound enhances the degradation
of various chemical pollutants such as herbicides, pesticides, dyes, chloro-
aromatics, nitro compounds, phenols, and so on from the industrial efflu-
ents. The US technique is a feasible means of disintegrating sewage sludge
and degrading or transforming wastewater pollutants. This technique has
also been used for anaerobic sludge degradation of aerobic or anaerobic
wastewater.
The advantage of US is the use of ambient temperatures to preserve
thermally sensitive substrates and to enhance the selectivity. Sonochem-
ical process affects the reaction rate, activate metals and solids by US.
Ultrasound can enhance or promote chemical reactions and mass
transfer and offer the potential for shorter reaction cycles, cheaper reagents,
and less extreme physical conditions (Goel et al., 2004). Ultrasound has
been applied in studies of cleaning, organic synthesis, catalysis, extrac-
tion, emulsification, material processing, food processing, and wastewater
treatment (Saleh and Gupta, 2012).
The use of US has some advantages over other conventional methods.
These are:

• Ultrasound technique has a good potential to enhance the rate of

many reactions.
• It has also the ability to be used with not very pure solvent and
reagents.
• Sonochemical reactions can be conducted at relatively milder
conditions.
• It helps in improving conversion and yield of reactions and some-
times, it may also change reaction pathway.
• It can be applied for the preparation of emulsions, leaching,
grinding, and so on and
• It has proved to be effective in the treatment of effluent containing
highly toxic organic pollutants.
234Sonochemistry

8.3.1 DYES

Several industries used dyestuff because these are low-cost, have long-
term stability, and easy to use. But wastewater generated by textile dyeing
and printing industries is colourful and hard to degrade. Azo dyes (–N=N–)
are the major contributors and accountable for 60–70 % of all dyestuffs.
This is the most common chromophore in reactive textile dyes. Reactive
dyes have high solubility in water and, therefore, their loss to wastewater
is also in significant amount. An estimate indicates about 15–20 % of the
synthetic textile dyes used are lost in wastewater streams during manufac-
turing or processing operations.
Moholkar et al. (2003) studied the effect of application of US on the
intensification of mass transfer in wet textile processes. It was noted that
the formation of standing waves assists ultrasonic wet textile processing
by raising the power consumption of the system. Industrial textile pretreat-
ment and finishing process require a relatively long residence time, large
amounts of water and chemicals, and these are also energy-consuming.
EMPA 101-test fabric was selected as a model for the cleaning process. It
focuses on two aspects: first is the mechanism of the US-assisted cleaning
process, and second is effect of the presence of the cloth on the US wave
field generated in a bath. It was found that the dissolved gas content in
the system plays an important role in the cleaning process. The cleaning
effects thus observed are explained by two different mechanisms:

• Small-amplitude acoustic bubble oscillations

• Microjets resulting from the collapse of acoustic bubbles in the
boundary layer between the fabric and the bulk fluid giving rise to
convective mass transfer in the intra-yarn pores.

Ince and Tezcanli (2001) studied the degradation of reactive dye using
US. They observed that the rate of degradation increases by a combined
process involving sonolysis (520 kHz) and ozonation. Rehorek et al.
(2004) reported the use of US for the degradation of various industrial
azo dyes such as acid orange 5 and 52, direct blue 71, reactive black 5
and reactive orange 16 and 107. Ultrasound was able to mineralize these
azo dyes to same nontoxic and final products. All these dyes were deco-
lourized and degraded within 3–15 h at 90 W and within 1–4 h at 120 W,
respectively. It was shown that hydroxyl radicals degraded these azo dyes
Wastewater Treatment235

by the simultaneous process of azo bond scission, oxidation of nitrogen

atoms and hydroxylation of aromatic ring structures.
Vajnhandl and Marechal (2007) reported the decolourization and miner-
alization of reactive dye, reactive black 5 at three different frequencies of
ultrasonic irradiation, that is, 20, 279 and 817 kHz. It was observed that
the decolourization increased with increasing frequency, acoustic power
and irradiation time; however, an increase in dye concentrations resulted
in a decrease of decolourization rates. Bejarano and Suarez (2007) studied
the degradation of malachite green by sonolytic, photocatalytic and sono-
photocatalytic methods.
Basic violet 16 (BV 16) is a cationic dye which is highly water-
soluble and nonvolatile. It is widely used in textile, leather industries, in
preparing carbon paper, bull pen, stamp-pad inks and paints. This dye is
also a well-known water tracer fluorescent. BV 16 directly harms skin,
eyes and gastrointestinal and respiratory tract. It provokes phototoxic and
photo allergic reactions also. Its carcinogenicity, reproductive and devel-
opmental toxicity, neurotoxicity and chronic toxicity towards humans and
animals have already been established. Rahmani et al. (2012) reported the
degradation of BV 16 by ultraviolet radiation, ultrasonic irradiation (US),
UV/H2O2, and US/H2O2 processes in a laboratory-scale batch photore-
actor. This reactor was equipped with a 55 W immersed-type low-pressure
mercury vapour lamp and a sonoreactor with high-frequency (130 kHz)
plate-type transducer at 100 W of acoustic power. Basic violet 16 was
almost degraded 99 %, with UV/H2O2 within 8 min, whereas relatively
low decolourization efficiency was observed using UV (23 %), US (< 6 %)
and US/H2O2 (< 15 %) processes.
Mishra and Gogate (2011) studied the degradation of rhodamine B
using sonochemical reactors in combination with UV irradiations at oper-
ating capacity of 7 l. The degradation of naphthol blue black (NBB), a
diazo dye widely used in the textile and soap industries, was carried out
using US at 278 kHz. Sonochemical decolourization was enhanced by
bicarbonate ions at low concentration of NBB, due to the formation of
carbonate radicals, which are likely to migrate in the bulk of liquid and
attack the substrate (Dalhatou et al., 2015).
Guzman-Duque et al. (2011) reported the ultrasonic degradation
(800 kHz) of crystal violet (CV) under the effects of saturating gas (argon,
carbon dioxide and air), concentration of CV 2.45–1225 μmol·L−1, pH (3–9)
and power (20–80 W). The best performance was achieved at 80 W with argon
236Sonochemistry

as a saturating gas. Analyses of intermediates by gas chromatography–mass

spectrometry (GC–MS) indicated several sonochemical by-products: N,N-
dimethylaminobenzene, 4-(N,N-dimethylamino)-4′-(N′,N′-dimethylamino)
benzophenone, and N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane.
The presence of these aromatic structures showed that the main ultra-
sonic CV degradation pathway was due to oxidation by •OH radicals. At
the completion of the treatment, these intermediate products were finally
converted into biodegradable organic by-products, which could be easily
treated in a subsequent biological treatment.
The degradation of eosin Y and rhodamine B dyes was carried out
using iron oxide nanoparticles under simultaneous irradiation with light
and US (Gobouri, 2016). He et al. (2011) also carried out the degradation
of MO using light and US. Similarly, Sandhyaa et al. (2013) reported the
use of titania, titania-polyaniline and clay-titania-polyaniline composites
for the degradation of acid blue 25, acid orange 7 and MB under visible
light and US.
Wang et al. (2015b) carried out the degradation of MO with Fe3O4/
polyaniline (Fe3O4/PANI) microspheres in near neutral solution (pH ~ 6)
using US. The percentage of sonocatalytic degradation of MO with Fe3O4/
PANI is about 4.8, 8.8 and 5.7 times that with Fe3O4, dedoped Fe3O4/PANI
and ultrasonication (US) alone, respectively. Cui et al. (2011) also reported
the degradation of MO using ultrasonic-enhanced ceramic membrane MF
and TiO2. Ceramic membrane MF could efficiently recover TiO2 photo-
catalyst with a mean granular size of 0.33 μm from slurry reactor, thus,
achieving 99.9 % recovery rate.
Alahiane et al. (2014) reported the photocatalytic degradation of the
synthetic textile dye reactive yellow 145 (RY 145) in aqueous solution,
using TiO2 coated nonwoven fibres as photocatalyst, under UV-lamp
irradiation and US. The removal of reactive yellow 145 on TiO2-coated
nonwoven fibres followed Langmuir–Hinshelwood model. Degradation
of MO was also carried out using CNT/TiO2 composites and US (Wang
et al., 2009). The polyaniline/zinc oxide (PANI/ZnO) nanocomposites
were used for the degradation of MB dye. The PANI/ZnO nanocomposites
showed three times higher photocatalytic activity to MB dye degradation
as compared to pristine PANI, which may be attributed to high photogen-
erated electron–hole pair separation (Ameen et al., 2011).
Gemeay et al. (2012) also reported the degradation of acid blue 25
dye (AB-25) by hydrogen peroxide using polyaniline/manganese dioxide
Wastewater Treatment237

(PANI/MnO2) composites and US. The decomposition of unhydrolysed

and hydrolysed forms of reactive blue 19 dye (RB 19) was carried out
using the US-assisted electrochemical process (Siddique et al., 2011).
A new hybrid material composed of BiVO4 and HKUST-1 MOF (a
metal organic framework made up of copper nodes with 1,3,5-benzen-
etricarboxylic acid struts between them, that is, HKUST-1-MOF–BiVO4)
was synthesized (Mosleh et al., 2016). It was found active under blue light
irradiation. This sonophotocatalyst was used for the degradation of disul-
phine blue and rose bengal (RB) in the presence of light and US. FeS/ZnO
nanoarrays also have high sonophotocatalytic activity for degrading MB
in water under ultrasonic and solar irradiation (Guo et al., 2016).
Panneerselvam et al. (2014) reported the degradation of acid blue 113
in the presence of visible light-driven rare-earth nanoclusters loaded TiO2
nanophotocatalysts. Gd3+, Nd3+ and Y3+ were used for leading 1 wt.  %
using a low-frequency sonicator of rare earth nanoclusters (42 kHz).
Khan et al. (2015) carried out the degradation of reactive blue 19 (RB 19)
dye successfully using sulphur-doped TiO2 (S-TiO2) nanoparticles under
visible light and US.
ZnO nanoparticles decorated on multiwalled carbon nanotubes (ZnO/
MWCNTs composites) were used for the degradation of rhodamine B
using US (Ahmad et al., 2014). The sonocatalytic degradation of some
textile dyes such as MB, texbrite BAC-L, texbrite BBU-L, and texbrite
NFW-L was carried out under ultrasonic irradiation, and compared with
ZnO/graphene (ZG), graphene, ZnO and TiO2, respectively. The results
indicated that ZnO/graphene/TiO2 (ZGT) displayed higher US-activated
sonocatalytic activity than the other catalysts (Nuengmatcha et al., 2016).
Tang et al. (2012) reported the use of TiO2-coated activated carbon (TiO2/
AC) for the sonocatalytic degradation of rhodamine B dye.

8.3.2 HYDROCARBONS

Hydrocarbons are a class of compounds, which are primarily composed of

carbon and hydrogen only. These are major components of oil, natural gas
and pesticides. These hydrocarbons contribute not only to the greenhouse
effect and global warming, and depleting the ozone but also increase in
the occurrence of cancer and respiratory disorders along with reducing the
photosynthetic ability of plants.
238Sonochemistry

Aromatic hydrocarbons are produced from the combustion of coal,

oil, tar and plant materials. Benzene is used as a solvent and in fuels. It
depletes red blood cells, causes cancer in mammals and damages bone
marrows. Marine oil pollution is becoming a major problem today. Oil
and oil products spill, cause severe damages to the ecosystems in marine
system and the amount of this pollution is expected to increase further in
the future due to:

• An increase in number of ships

• The use of shelf zones for oil drilling
• Poor control to prevent oil pollution in the seas

Visscher et al. (1996) reported the degradation of benzene, ethylben-

zene, styrene and o-chlorotoluene in aqueous solution using ultrasonic
waves. The basic assumptions of the model are first-order pyrolysis in the
cavitations yielding both reactive/volatile and inert/nonvolatile products,
and lowering of the maximum cavitation temperature due to the presence
of the organic compounds in the bubble phase.
Wu et al. (2004) reported the sonolytic degradation of cyclic hydrocar-
bons such as benzene, 1,3-cyclohexadiene, 1,4-cyclohexadiene and cyclo-
hexene. Sonolysis was found to follow first-order kinetics and depends
on the solubility of the substrates in water. The rate of degradation was
inversely proportional to the concentration of substrate. Benzene showed
more resistance against degradation as compared to cyclohexene.
Hydrocarbons in the middle distillate range (C8–C26) have been treated
with US at 20 kHz, a frequency sufficient to drive acoustic cavitation. The
high temperatures experienced as a result of the implosion of fuel vapour
bubbles are sufficient to produce pyrolytic degradation and dehydrogenation.
During this process, formation of small particles takes place that have similar-
ities with the primary soot particles produced during diesel combustion. The
particles are carbonaceous in character as it is a mixture of amorphous and
graphitic-like carbon. The mass of material produced increases with the C/H
atomic ratio of the hydrocarbon undergoing cavitation (Price et al., 2015).
Psillakis (2004) reported the degradation of naphthalene, acenaph-
thylene and phenanthrene in water using US. A horn-type sonicator was
used to deliver the US energy, whereas immersion sampling solid-phase
microextraction coupled with GC–MS was employed to follow concentra-
tion–time profiles of the selected polyaromatic hydrocarbons (PAHs).
Wastewater Treatment239

Littl et al. (2002) also carried out the degradation of naphthalene,

acenaphthylene and phenanthrene in water using US. The effects of
increasing sonication time (60–150 min), calcium chloride (1–10 g·L−1),
ferrous oxide (2·10 mg·L−1), aluminium oxide (2–10 mg·L−1) and sodium
carbonate (2–12 mg·L−1), on the destruction of six polycyclic aromatic
hydrocarbons and acute toxicity in a petrochemical industry waste-
water, were investigated at a sonication intensity and a frequency of
251.48 W·cm−2 and 35 kHz, respectively. The contribution of 4–6 mg·L−1
CaCl2 to the yields in more hydrophobic PAHs (benz[a]pyrene (BaP)
and indeno[1,2,3-cd]pyrene (IcdP) was low (6–8 %), whereas it was high
(21–26 %) in less hydrophobic PAHs such as acenaphthene, fluoranthene,
benz[a]anthracene, benz[k]fluoranthene at 30°C after 150 min sonication
(Sponza and Oztekin, 2010).
Okuno et al. (2000) reported the degradation of benzene and biphenyl in
aqueous solutions using 200 kHz US at an intensity of 6 W·cm−2 under an
argon atmosphere. Nearly 80–90 % of initial amount of these compounds
was degraded in 30–60 min of sonication, when the initial concentra-
tions were 10–100  μmol·L−1. The degradation rate of these compounds
increased with increase in their vapour pressures.

8.3.3  CHLORO COMPOUNDS

Chlorinated compounds are one of the most widespread pollutants in our

environment (Vogel et al., 1987) and, because of this, a large number
of techniques, including traditional techniques (Hitchman et al., 1995),
sequential combinations of techniques (Entezari et al., 2005), hybrid
(Adewuyi, 2005) and new technologies (Shannon et al., 2008) are continu-
ously being developed to provide an efficient solution to this problem.
Among these methods, sonochemical treatment has received a lot of atten-
tion due to its special features. Ultrasound is a unique means of interacting
energy and matter, and it differs from traditional energy sources such as
light, heat or ionizing radiation in duration, pressure and energy per mole-
cule (Suslick, 1990).
Drijvers et al. (1996) reported that the degradation of trichloroeth-
ylene (TCE) was the fastest in basic solutions saturated with argon. TCE
was not degraded in the bulk solution. Some volatile and nonvolatile
organic degradation products were formed during sonication. The most
240Sonochemistry

important volatile compounds were identified as C2HCl, C2Cl2, C4Cl2,

C2Cl4, C4HCl3, C4Cl4, C4HCl5 and C4Cl6. Those products are typical in
the pyrolysis of TCE. These intermediates are formed in single cavitation
events and disappeared from the aqueous solution as well.
Degradation of CB in aqueous solution was carried out using US (Drijvers
et al., 1998). The addition of the radical scavenger, benzoate, demonstrated
that no significant degradation took place in the bulk solution. Different
degradation products were identified as methane, acetylene, butenyne,
butadiyne, benzene, chlorophenols, phenylacetylene and other chlorinated
and nonchlorinated monocyclic and dicyclic hydrocarbons in air-saturated
solutions, whereas same products were found, except for the chlorophenols
in case of argon-saturated solutions. The presence of the chlorophenols in
the case of air-saturated solutions only supported the interaction between
the radicals formed and oxygen, and not direct degradation by •OH radicals.
The kinetics of several organic degradation products and chloride were also
studied for the sonolysis of air- and argon-saturated solutions.
Griffing (2004) reported that the rate of the hydrolysis of CCl4 is strongly
dependent on the dissolved gas. Weissler et al. (1950) confirmed the effect
of dissolved gases (O2, N2, He, CO2) on the yields of iodine during the
ultrasonic irradiation of KI solutions in the absence of CCl4 and with a large
excess of CCl4. Ultrasonic degradation of carbon tetrachloride leads to chlo-
rine formation. Carbon tetrachloride was used as an additive in this sono-
chemical degradation. It was shown that carbon tetrachloride was found to
improve the degradation efficiency of the sonochemical process. Bhatnagar
and Cheung (1994) reported that the degradation of TCE and carbon tetra-
chloride remained constant between −7 and 20 and 20–60°C, respectively.
Destaillats et al. (2000) indicated that the sonochemical degradation of
CB and TCE, increased with increasing temperature. Degradation of dilute
aqueous solutions of 2-, 3- and 4-chlorophenols and pentachlorophenol
was carried out under air or argon atmosphere using US. This degrada-
tion follows first-order kinetics in the initial state with rates in the range
of 4.5–6.6 mM·min−1 under air and 6.0–7.2 µM·min−1 under argon at a
concentration of 100 µM of chlorophenols. The rate of •OH radical forma-
tion from water is 19.8 µM·min−1 under argon and 14.7 µM·min−1 under
air in the same sonolysis conditions (Nagata et al., 2000).
Pandit et al. (2001) carried out degradation of 2,4,6-trichlorophenol
at 20 kHz using US in the presence of TiO2. Cresol and 2-chloro-5-meth-
ylphenol (2C5MP) are used in the manufacture of resins, herbicides,
Wastewater Treatment241

pharmaceuticals and surfactants. Degradation of an aqueous solution of

2C5MP in the presence of TiO2 and H2O2 in combination with US (33 kHz)
was reported by Laxmi et al. (2009). The order of the effect of inorganic
ions on degradation rate of 2C5MP was found as:

Cl− > SO42− > HPO42− > HCO3−

Perchloroethylene is used as a solvent and degreaser. The degrada-

tion of perchloroethylene (PCE) in aqueous solution was carried out using
ultrasonic irradiation and photochemical oxidation by ultraviolet rays and
hydrogen peroxide (Kargar et al., 2012). Saez et al. (2010) also carried
out the degradation of PCE using US. The combination of US and elec-
trical fields provides a favourable reaction environment for PCE aqueous
solution treatment, which significantly improves on the sonochemical and
electrochemical treatments.
Barik and Gogate (2016) reported the degradation of 4-chloro-2-ami-
nophenol (4C2AP) using ultrasonic reactors and combination of US with
photolysis and ozonation. Sivasankar and Moholkar (2010) reported about
the degradation of 2,4-dichlorophenol (2,4-DCP) using US. The degra-
dation of 4-chlorophenol (4-CP) in aqueous media was carried out by
516-kHz ultrasonic irradiation. The degradation of concentrated 4-CP
solution by means of US, UV irradiation, and their combination was also
studied (Hamdaoui and Naffrechoux, 2008).
The use of US was made in the degradation of polychlorinated
biphenyl (PCB)-contaminated sediments by Lu and Weavers (2002). Li
and Zhu (2015) reported the degradation of 1,1,1-trichloroethane (TCA)
using US. The degradation of 2-chloro-5-methyl phenol (2C5MP) was
carried out in aqueous solution by US in the presence of TiO2 and H2O2.
Maximum degradation rate of 2.66 × 10−2 was accomplished by US/TiO2/
H2O2 process, when compared to US/TiO2 (1.01 × 10−2) and US/H2O2
(5.5 × 10−3) systems. The impact of synthetic additives such as CCl4 as
hydrogen radical scavenger and CH3OH as hydroxyl radical scavenger
was studied, which confirmed the involvement of hydroxyl radicals in the
degradation of 2C5MP (Laxmi et al., 2010).
Ultrasonic degradation of 2,4-dichlorophenol (2,4-DCP) was carried
out under oxygen, air, argon, and nitrogen atmosphere in aqueous solu-
tions for a liquid temperature of 20°C at 489 kHz. The degradation rate
was found to increase in the presence of O2 and argon, whereas it remains
242Sonochemistry

the lowest under nitrogen (Uddin and Hayashi, 2009). Experiments have
also been performed at three different pH, 11.0, 6.3 and 2.0. A significant
degradation was achieved at pH 6.3 under O2 (0.86 × 10−3 s−1), which is 1.9
and 4 times higher than the acidic (pH 2.0) and basic (pH 11.0) conditions,
respectively. The degradation rates have decreased in the order:

O2 > Ar > air > N2 irrespective of pH.

Chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, and PCBs such as

2-,4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions were
subjected to sonolysis with 200 kHz US at an intensity of 6 W·cm−2 under
an argon atmosphere. Nearly 80–90 % of initial amount of these compounds
were degraded by 30–60 min of sonication when the initial concentrations
were 10–100 μmol·l−1. The degradation rate of these compounds increased
with increase in their vapour pressures. In all the cases of sonolysis of
chlorinated organic compounds, an appreciable amount of liberated chlo-
ride ion was observed (Okuno et al., 2000).
Jiang et al. (2002) reported the ultrasonic degradation of chloroben-
zene (ClBz), 1,4-dichlorobenzene and 1-chloronaphthalene at 500 kHz.
The disappearance of ClBz on sonication is almost simultaneously accom-
panied by the release of chloride ions as a result of the rapid cleavage of
carbon–chlorine bonds with a release of CO, C2H2, CH4 and CO2. The
intermediates resulting from the attack of •OH radicals were detected but
in a quite low yield (<2 μM). The generation of H2O2 on sonolysis was not
significantly affected by the presence of aqueous ClBz, whereas the gener-
ation of NO2−and NO3− is inhibited initially. The degradation of p-chloro-
phenol in water using high-frequency US (1.7 MHz) was carried out. The
p-chlorophenol was degraded successfully in the high-frequency ultra-
sonic device with low consumption of energy. No products or intermediate
products were detected in the reaction mixture by MS and 1H-NMR after
ultrasonic irradiation (Hao et al., 2004).
Neppolian et al. (2004) studied the degradation of p-chlorobenzoic
acid (a model compound for free radical-mediated reactions) using US
and Fenton-like oxidation (FeOOH–H2O2). The oxidation rate of p-CBA
was measured at various concentrations of H2O2 and FeOOH particles
and pH conditions at pH values < 3.98, which is pKa of p-CBA, showed
significantly better degradation of p-CBA than at higher pH values from 5
to 9. The rates of degradation of p-CBA by FeOOH–H2O2 were enhanced
Wastewater Treatment243

in the presence of US. This rate enhancement for the degradation of

p-CBA may be due to the continuous cleaning and chemical activation
of the FeOOH surfaces by acoustic cavitation and the accelerated mass
transport rates of reactants and products between the solution phase and
the FeOOH surface.
Lin and Ma (2000) studied the use of US (20 kHz) for the degradation
of 2-chlorophenol in the presence of Fe2+ and H2O2. This degradation reac-
tion was monitored by measuring its redox potential that increases slightly
with increasing amounts of Fe2+. The main intermediate formed during the
decomposition was identified as 2-chloro-p-benzoquinone, which readily
decomposed during further treatment.
Goskonda et al. (2002) have reported the degradation of chlorophe-
nols with US (920 kHz). It was found that the rate of mineralization was
dependent on various factors such as the structure and concentration of
substrate, temperature, pH and the presence of other solutes (detergents
and humic acids).
Aqueous solutions of CB and PCBs have been degraded under
200 kHz sonication under an atmosphere of argon. More than 80 % of
the initial amounts of substrates degraded after 30 min sonication, and it
was found that degradation rates increased with their increasing vapour
pressure. The effect of US on CB in water containing iron and palladium
sulphates was observed by Stavarache et al. (2002). The degradation of
CB begins with pyrolysis inside the cavitation bubble giving, initially,
benzene radicals, which migrate outside the bubble and are converted
into benzene.
Pentachlorophenol (PCP) has been used for a long period as an
important component of biocides, pesticides, insecticides and wood
preservatives, but now it has become a source of priority pollutant.
Weavers et al. (2000) reported the degradation of aqueous solutions of
PCP using 20 and 500 kHz US as well as in the presence of ozone. Here,
pyrolysis and oxidation by hydroxyl radical both processes occur. It
was reported that the addition of ozone did not affect the degradation
constant of PCP.
Peters (2001) studied remediation of ground water contaminated
with some simpler, but more volatile chlorinated alkanes and alkenes.
They concluded that chlorinated hydrocarbon (1, 2-dichloroethane) was
completely decomposed in 60–120 min in pure and natural water using US
at frequencies of 20, 206, 361, 620, and 1086 kHz. The destruction rate
244Sonochemistry

in deionized water and in ground water was found to depend only on the
dose rate and not on the frequency of US. However, the energy efficiency
decreases with higher frequency.

8.3.4  SULPHUR-CONTAINING COMPOUNDS

Crude oil contains numerous aromatic sulphur-containing compounds

such as sulphides, thiophenes, benzothiophene, dibenzothiophene (DBT),
and their substituted derivatives. During distillation and refining of crude
oil, these compounds end up in the gasoline and diesel fractions. Combus-
tion of these compounds in vehicle engines results in the generation of
SO2 and particulate matter emission. Growing concerns over air pollution
created by these emissions have led to stringent restrictions on the sulphur
content of the liquid fuels (Bolla et al., 2014).
Sulphur compounds in transportation fuels are converted to SOx by
combustion, leading to acid rain and air pollution. In many countries,
the average sulphur content in diesel has been restricted to 10  μg·ml−1,
and it may be reduced even to zero level in the near future. Hydrode-
sulphurization process is a very efficient technique for removing simple
sulphur compounds, but it is not effective for DBT and its derivatives.
This method is not suitable for deep desulphurization of diesel, because it
requires severe operation conditions, high-energy and hydrogen consump-
tion (Faghihian and Sadeghinia, 2014).
Chemical warfare agent (CWA) is a chemical substance, which has
toxic properties to kill, injure, or incapacitate human beings. Decontami-
nation of CWA involves the conversion of toxic chemicals into harmless
products by degradation. Solvent extraction process is considered one of
the best methods for decontamination of sensitive CWAs. This is a type of
physical decontamination, which is relatively fast and nondestructive. The
efficiency increases on combining its ultrasonics with higher temperature.
Dimethyl methylphosphonate (DMMP) is a simulant for nerve CWAs.
The role of 20 kHz US in photocatalytic oxidation of DMMP was studied
in a batch reactor by Chen et al. (2003). It was observed that DMMP did
not undergo mineralization under low-frequency (20 kHz) ultrasonic irra-
diation. An increase in the rate of DMMP photocatalytic mineralization
in the presence of US was achieved. It was not due to deagglomeration of
titania, but it was associated with an enhanced mass transport of reagents.
Wastewater Treatment245

Similar intermediate products were detected in both photocatalytic and

sonophotocatalytic degradations. Apparent rate constants of DMMP
mineralization increase under sonication in all stages. A reaction route for
DMMP mineralization under US was found to be without intermediate
products. Such a behaviour was attributed to enabling mass transport of
DMMP into micropores and to the surface of TiO2.

An effort was made to develop some novel photocatalysts for the

destruction of some CWAs such as HD, G-type (GA, GB, GD) and VX
to harmless products in gas and liquid phases (Smirniotis, 2002). Some
visible light/solar active photocatalysts were synthesized, characterized
and finally used for the degradation of CWA. Ultrasound was found to
enhance the photochemical transformation and sidewise, it also avoids the
formation of any toxic intermediates. Photodegradation of diethylsulphide
(DES) in gas phase as a simulant of mustard gas (HD) over various titanias
was carried out utilizing UV light. It was revealed that main routes of DES
degradation are C–S cleavage, S oxidation and α-C and β-C oxidation.
Vorontsov et al. (2002) carried out photocatalytic and sonophotocata-
lytic treatment of some CWAs such as DMMP, diethyl phosphoramidate
(DEPA), pinacolyl methylphosphonate (PMP), butylaminoethanethiol
(BAET) in aqueous suspensions of TiO2. It was observed that complete
conversion of these imitants to inorganic products was obtained within
600 min for DMMP, DEPA, PMP, but it required a longer time to degrade
BAET. Ultrasound was found to enhance photodegradation of DMMP.
Decontamination of CWAs is usually carried out either by oxidation or
by basic hydrolysis (Koskela et al., 2007). Most decontaminants such as
hypochlorite bleach and super tropical bleach solutions have limited ability
to solve organic CWAs and remove them from contaminated surfaces, as
well as they are mostly corrosive in nature (Kim et al., 2011). Decontami-
nation solution 2 (DS2) is an organic medium, but it has certain unwanted
effects on other organic parts of contaminated objects such as its paints,
and so on (Fallis et al., 2009).
246Sonochemistry

Wagner et al. (2008) reported hydrolysed reactions of o-ethyl S-[2-

(diisopropylamino)ethyl] methylphosphonothioate) (VX), pinacolyl
methylphosphonofluoridate (GD), and bis(2-chloroethyl) sulphide (HD)
on nanotubular titania and anatase TiO2 as a reactive sorbent. The result is
significant so that VX is typically the least reactive, most persistent, and
most toxic CWA. The use of semiconductors photocatalysis for the degra-
dation of CWAs and corresponding simulants was reported by Vorontsov
et al. (2003). Prasad et al. (2011) reported the decontamination of HD on
ZnO nanoparticles by US whereas decontamination of sulphur mustard
was carried out using titania nanoparticles (Ramacharyulu et al., 2012).
Decomposition of 2-chloroethyl ethyl sulphide was carried out using TiO2
and US by Thompson et al. (2004).
Ultrasound-assisted oxidative desulphurization process (UAOD) was
used to reduce sulphur compounds of gas oil containing various types of
sulphur contents. UAOD is a promising technology with lower operating
cost and higher safety and environmental protection. The typical phase-
transfer agent (tetraoctyl-ammonium-bromide) was replaced for the first
time with isobutanol as it is much more economical than TOAB, and
imposing no contamination (Shayegan et al., 2013).
Margeta et al. (2016) reported the degradation of hydrocarbon fuels,
diesel fuels and produced wastewater using US. The US-assisted oxidative
desulphurization (UAOD) process of diesel fuel has gained an increasing
attention due to the regulation of sulphur content in the fuel. The conver-
sions of DBT ODS and UAOD tests were 36 and 87 %, respectively in
30 min. Subsequent extraction with acetonitrile resulted in the sulphur
removal of 96.5 %.
The impact of US application for oxidative desulphurization (ODS) of
hydrocarbon fuels was investigated by Margeta et al. (2016). The model
diesel fuel with initial sulphur concentration of 1220–3976 mgL−1 was
used for ODS and UAOD tests, and hydrogen peroxide/acetic acid was
applied as the oxidant/catalyst system, respectively.

8.3.5  NITROGEN-CONTAINING COMPOUNDS

Pyridine and its derivatives are of major concern as environmental pollut-

ants due to their recalcitrant, toxic, and teratogenic nature (Stapleton et al.,
2007). Pyridine is produced from coal tar and as a by-product of the coal
Wastewater Treatment247

gasification. Increased demand for pyridine resulted in the development of

more economical methods of synthesis from acetaldehyde and ammonia,
and more than 20,000 tons per year are manufactured worldwide. Thus,
researchers have long sought to develop effective, economically feasible
techniques for cleaning the atmosphere of wastes such as pyridine (Mittal
et al., 2008). Ultrasonication not only promotes oxidative degradation of
pyridine by hydroxyl radicals but also provides a possible route for its
thermal decomposition in the gas phase (Naffrechoux et al., 2000).
Kotronarou et al. (1991) investigated the influence of the changes in
the initial pH of the p-nitrophenol (PNP) solutions on the decay of PNP
under US. PNP decayed exponentially with time at all pH values. The
pseudo-first-order rate constant decreased with the increase of pH (pH 5
to 8), and remained constant up to pH 10.
A simple and an efficient sonochemical method was developed for the
degradation of organic matter and ammonia nitrogen in azodicarbonamide
(ADC) wastewater. The removal of organic matter and ammonia nitrogen
in ADC wastewater by a combination of power US radiation and hydrogen
peroxide was investigated by Wenjun et al. (2012). The effects of reaction
time, initial pH, ultrasonic format and peripheral water level on the chem-
ical oxygen demand (COD) reduction and ammonia removal efficiency
were studied. Higher initial pH was found favourable to the sonolysis of
hydrazine, but this effect on the degradation of urea is relatively small.
Song et al. (2007) reported the degradation of aniline using US in
the presence of ozone. It was found that only a little decomposition was
observed with US only, whereas using a combination of US and ozone
gives complete removal after 25 min. By-products such as nitrobenzene
(NB), p-benzoquinone, p-aminophenol and low-molecular weight carbox-
ylic acids were observed during this degradation.
Mishra and Gogate (2012) carried out the degradation of PNP using
ultrasonic reactors at pilot-scale operation. The effect of air sparging, addi-
tion of CCl4, solid particles such as TiO2 and CuO, and ozone on the extent
of degradation of PNP was studied. The sonochemical reactor used was an
ultrasonic longitudinal horn-type reactor operating at 25 kHz frequency,
power output of 1 kW, and capacity of 7 l. It was observed that the extent of
degradation increased for all the additives used due to enhanced cavitational
activity and generation of additional free radicals or oxidizing species.
Morteza and Tabatabae (2011) reported the degradation of 2-butyl-
4,6-dinitrophenol in aqueous solution using titanium dioxide nanoparticles
248Sonochemistry

and US. Oxidative degradation of dinitrotoluene and 2,4,6-trinitrotoluene

in wastewater was carried out using electrochemical and electro-Fenton
processes, respectively, combined with ultrasonic irradiation. The influ-
ence of various operating variables on the sonoelectrolytic behaviour, such
as electrode potential, sonoelectrolytic temperature, acidity of wastewater,
oxygen dosage, and dosage of ferrous ions, was also observed. The nitro-
toluene contaminants could be completely decomposed by sonoelectro-
Fenton method, where hydrogen peroxide was in situ generated from
cathodic reduction of oxygen and was also supplied partially by the anodic
oxidation of water (Chen and Huang, 2014).
Verma et al. (2013) reported the degradation of 4-chloro-2-nitrophenol
(4C2NP) using heterogeneous TiO2 and US. Experiments were performed
in slurry mode with artificial UV-125 W medium-pressure mercury lamp
coupled with US (100 W, 33 + 3 kHz) for sonication of the slurry. The
degradation follows the trend:

Sonophotocatalysis > Photocatalysis > Sonocatalytic > Sonolysis.

The sonocatalytic degradation of NB in aqueous solution was carried

out using H2O2 oxidant and nanostructured metal oxide catalysts. Nano-
structured metal oxide catalysts was prepared in the absence of CTAB
(series I), (Fe2O3-I, CuO-I, NiO-I, and Co3O4-I) and nanostructured metal
oxide catalysts prepared in the presence of CTAB (series II), (Fe2O3-II,
CuO-II, NiO-II, and Co3O4-II). The potential degradation feasibility for
NB in US/nano-metal oxide (series I and/or series II)/H2O2 systems was
measured. The effect of various operational parameters such as ultra-
sonic irradiation time, solution pH value, H2O2 concentration, different
weights of the nanosized catalysts, NB concentration, leaching of the
nanosized catalysts, and reaction kinetics was examined. H2O2 oxidant
can effectively assist the sonocatalytic degradation of NB in the presence
of nanosized oxides (series I) and with more efficiency in the presence of
nanosized oxides (series II) (Yehia et al., 2015a). The effect of efficiency
in degradation was in the order of:

Fe2O3 > CuO > NiO > Co3O4

The influence of surface modification of some metal oxides (Fe2O3,

CuO, NiO, and Co3O4) with amino acids was investigated in the sono-
catalytic degradation of NB (Yehia et al., 2015b). Glycine, arginine and
Wastewater Treatment249

glutamic acid were used as surface modifiers. This modification resulted in

a considerable enhancement of sonochemical degradation of NB at pH > 7,
with respect to the pristine catalysts before modification. Catalysts modi-
fied with arginine exhibited the highest degradation of NB. The enhanced
degradation efficiency was attributed to the promoted coupling via elec-
trostatic attraction between the negatively charged NB molecules and the
positively charged arginine layer on the surface of Fe2O3, CuO, NiO and
Co3O4. The attraction capability at all modified metal oxides increased
via secondary forces such as hydrogen bonding, n–π and π–π interactions.
Nakui et al. (2007) studied the sonolysis of 4-nitrophenol in argon-
saturated water using frequency of 321 kHz. 4-Nitrophenol was fully
deprotonated at pH 10 and therefore, it was concluded that the degradation
proceeded by hydroxyl radical action.

8.3.6 PHENOLS

Phenol is released to the environment from effluents discharge by industries

such as petroleum refining, coal tar, steel, dyestuff, synthetic resins, coal
gasification and liquefaction, surface runoff from coal mines, by-products
of agricultural chemicals, paper and pulp mills, tanning, fibreboard produc-
tion, paint stripping operations, pesticides, medications, pharmaceuticals,
and even from food-processing industries (Lathasreea et al., 2004).
Phenol has to be handled with utmost care because it causes imme-
diate white blistering on the skin. The major hazard of phenol is its ability
to penetrate through the skin rapidly, particularly when in liquid state,
causing severe injury, which can also be fatal sometimes. Phenol also has
a strong corrosive effect on body tissue causing severe chemical burns.
Phenols have attracted public attention because their exposure can result
in acute and chronic effects to human health. Due to its toxicity, hazardous
character and increasing social concern on the environment, the discharge
of such compounds in the environment has been restricted. Therefore,
there is more demand for some improved methods of treatment containing
phenol (Beltran et al., 2005).
The rates of ultrasonic degradation of phenol can be increased by
using simple sodium chloride addition to its aqueous phenol (Seymore
and Gupta, 1997). They also reported that pyrolytic destruction of phenol
in the gas phase is negligible, and the degradation occurs mainly in the
250Sonochemistry

bulk solution, which is accelerated with the addition of Fenton’s reagent.

The most effective ultrasonic frequency for destroying phenol in solution
was found to be 200 kHz, which has been explained by a larger potential
for the ejection of radical species to the bulk solution at this frequency
(Petrier and Francony, 1997).
The rate of degradation by the 487 kHz was 10 times more due to the
much faster hydroxyl radical transfer from the gas phase to the aqueous
solution at this frequency as compared to 20 kHz (Petrier et al., 1994).
They reported that the larger efficiency observed at 487 kHz is due to
the fact that radicals are concentrated at the surface of the solution at
these higher-frequency conditions, whereas at 20 kHz frequency, they are
located intensely around the tip of the transducer.
Wu et al. (2001) have studied the effect of UV irradiation on sono-
chemical degradation of phenol. They reported that total phenol destruc-
tion was possible, the degree of mineralization was not more than 20.6 %;
however, this could be effectively improved by the addition of Fenton’s
reagent to the solution.
Singh et al. (2016) carried out the degradation of phenol using ultrason-
ically dispersed nano-metallic particles (NMPs). The probable mechanism
of phenol degradation by ultrasonically dispersed NMPs was the oxidation
of phenol caused by the hydroxyl radicals. These radicals are produced by
the reaction between H2O2 and the NMPs during the US process.
Some phenolic compounds, such as model pollutants in aqueous solu-
tion using ZnO-immobilized horseradish peroxidase (HRP), were studied
(Zhang et al., 2016). The ZnO-immobilized HRP exhibited higher removal
efficiencies for these phenolic compounds. The irradiation of microwaves
and US can further promote the oxidation of primary intermediates in the
conversion experiment, whereas the immobilization showed an obvious
protective effect on HRP against the inactivation/inhibition effects.
Yehia et al. (2016) reported the degradation of phenol using nano-
sized zero-valent copper or nanosized zero-valent nickel in combina-
tion with H2O2 and 20 kHz US irradiation. Catalytic wet air oxidation of
phenol over copper catalysts supported by CeO2-ZrO2 under atmospheric
pressure of oxygen at 160oC in a stirred batch reactor using US was
carried out (Parvas et al., 2014a). They also reported the degradation
of phenol using nonnoble metal Ni with different loadings coated on
precipitated CeO2–ZrO2 using US and catalytic wet air oxidation Parvas
et al. (2014b).
Wastewater Treatment251

The combination of peracetic acid and heterogeneous catalyst (MnO2)

was used for the degradation of phenol in an aqueous solution in the pres-
ence of US irradiation (Rokhina et al., 2013). Ren et al. (2014) carried
out the degradation of triclosan in aqueous solutions with high-frequency
US (850 kHz) and various electrodes. Diamond-coated niobium electrode
showed the best results as an electrode, leading to effective degradation
and positive synergistic effect.
The combination of 50 kHz US and ozone was used for the degradation
of phenol (Yang et al., 2010). The effect and different conditions of degra-
dation of phenol in wastewater samples was studied using US and H2O2
(Wu et al., 2015). Anju et al. (2012) reported the sonocatalytic activity of
ZnO, TiO2 and ZnO-TiO2 for the degradation of phenol pollutant in water.
The efficiency of the catalysts for the degradation was found to be in the
following order:

ZnO-TiO2 > ZnO > TiO2

At lower concentrations of ZnO, the percentage degradation in the

presence of coupled ZnO-TiO2 was more than the sum of the degrada-
tion achieved in the presence of these individual oxides under identical
conditions, implying that there is a synergistic effect. Mahvi and Maleki
(2010) reported the degradation of phenol in water using light and US.
Identification of the first intermediates of the reaction (hydroquinone,
catechol, benzoquinone, and resorcinol) indicated that hydroxyl radicals
are involved in the photosonochemical degradation mechanisms.
Entezari et al. (2003) reported the degradation of phenol using hydrogen
peroxide, US and copper sulphate (Fenton-like conditions). The degrada-
tion of phenol was higher at 500 kHz than at 35 or 20 kHz, when water
alone was used. When hydrogen peroxide and copper sulphate (Fenton-
like conditions) were used, the most efficient system was at 35 kHz
frequency. Thus, additives like hydrogen peroxide and copper sulphate
can be used to enhance the sonodegradation of phenol. The degradation of
2-butyl-4,6-dinitrophenol in aqueous solution was carried out using tita-
nium dioxide nanoparticles and US (Morteza and Tabatabaei, 2011).
Cravotto et al. (2008) have studied an integrated system by using a
combination of sonochemical and microbial treatment for the removal
of nonylphenols from water. Polluted water containing 1000 ppm of
nonylphenol was subjected to the sono-Fenton process and then it was
252Sonochemistry

followed by biosorption by the fungus Paecilomyces lilacinus. A decrease

in nonphenol content of 90 % was achieved by treating the sample with
300 kHz US in the presence of Fe3O4/H2O2 for 1 h and then inoculating the
fungus and culturing it for 7 days.

8.3.7 PESTICIDES

Fresh water pollution with insecticides, pesticides, herbicides, weedi-

cides, and so on is an environmental problem due to the high toxicity and
nonbiodegradability of these compounds.
Diazinon and malathion are highly effective pesticides, which are
extensively applied in agriculture (Liu et al., 2008). However, their residues
have negative effects on the environment, even on human health because
of their toxicity and stability (Fadaei et al., 2012). If the organophospho-
rous pesticides are released in the suitable environmental conditions, it is
possible for them to persist in many environmental compartments for a
long period of time (Evgenidou et al., 2005). These pollutants are usually
poorly biodegradable or persistent to environmental conditions.
Different types of synthetic pesticides are mostly used worldwide
for the agricultural activities and increasing the yield. These pesticides
are categorized into various groups such as insecticides, micro-biocides,
fungicides, herbicides and so on. Nearly 98 % of sprayed insecticides
and 95 % of herbicides reach a destination other than their target species
including nontarget species, air, water, bottom sediments, and food
(Miller, 2004). The most shocking and dangerous effects of exposure to
pesticide, that is, mutated DNA, have been found in blood samples of
farmers in some areas.
Many organophosphate insecticides (esters of phosphoric acid) such
as monocrotophos (MCP), parathion, malathion and methylparathion are
well known for their bioaccumulation and neurotoxic properties, because
they act on the enzyme acetyl cholinesterase. Organophosphate pesticides
inactivate acetylcholinesterase irreversibly, which is essential for nerve
function in insects, humans, and many other animals. Therefore, they have
full potential for neurotoxicity (Randhawa and Kullar, 2011).
MCP is one of the highly hazardous organophosphate insecticides that
is widely used and easily available. It is acutely toxic to birds and humans,
and kills bird like Swainson’s Hawks (Bai and Reddy, 1977). It can be
Wastewater Treatment253

absorbed through injection, inhalation and skin contact. When inhaled, it

also affects the respiratory system. Many organophosphate pesticides are
not completely degraded during conventional treatment technology due
to their low biodegradability. It has been shown that due to incomplete
mineralization, some amount of pesticides are released in aquatic environ-
ment and mix up into ground water and become a part of drinking water.
Degradation of pesticides was also carried out using US (Chowdhury
and Viraraghavan, 2009). Degradation of MCP was carried out using US,
TiO2 and Fe3+ ions (Madhavan et al., 2010A) whereas degradation of
MCP pesticides was carried out in the presence of TiO2 and US (Agarwal
and Das, 2014). Degradation of diazinon pesticide was carried out using
high-frequency US wave. It was observed that as the concentration of
diazinon increases, the degradation also increases, but when the volume
of solution was increased, the ability to degrade pesticides decreases
(Matouq et al., 2008).
Alachlor is an acetanilide herbicide which is widely used to control
most annual grasses and many broad leaf weeds. It has been classified
as carcinogen of B2 group due to its strong carcinogenic effects on the
animals. The degradation of alachlor was carried out using sonolysis
(US), photocatalysis (UV) and sonophotocatalysis (US/UV) using three
different photocatalysts, namely TiO2 (mixture of anatase and rutile), TiO2
(anatase) and ZnO. TiO2 (a mixture of anatase and rutile) showed highest
photocatalytic activity as compared to TiO2 (anatase) and ZnO due to the
enhanced generation of hydroxyl radicals and slow electron hole recombi-
nation (Bagal et al., 2013).
Azinphos-methyl and chlorpyrifos are the organophosphorous pesti-
cides, which pose serious threats to the environment including their
detrimental effect on humans and, therefore, their removal from the envi-
ronment is a must. Ultrasonic irradiation is a promising process for the
removal of azinphos-methyl and chlorpyrifos from aqueous solutions
(Agarwal et al., 2016).
Shayeghi et al. (2010) studied the degradation of diazinon using
US and acoustical processor reactor. Acoustical processor reactor with
130 kHz was used to study the degradation of pesticide solution. Samples
were analysed using high-performance liquid chromatography (HPLC) at
different time intervals. Khan et al. (2015) reported the use of zinc oxide
nanoparticles for the degradation of pesticide chlorpyrifos by sonochem-
ical method. ZnO exhibits good photocatalytic efficiency under UV light
254Sonochemistry

irradiation but when combined with membrane filtration, degradation rate

increases several times as compared to ZnO-mediated photocatalysis.
Dehghani and Fadaei (2013) studied the degradation of organophos-
phorus pesticides, diazinon, and malathion in aqueous solution by ultra-
sonic irradiation. The degradation of diazinon and malathion by US
followed first- and second-order model. Formetanate hydrochloride (FMT)
is an insecticide–acaricide, quite widely used in agriculture. The degrada-
tion of FMT in the presence of homogeneous (Fe3+) and heterogeneous
photocatalysts (TiO2) was carried out using US (Madhavan et al., 2010b).
Carbaryl (1-naphthyl-N-methyl carbamate) is a chemical of the carba-
mate family used as an insecticide. It is a cholinesterase inhibitor and is
also toxic to humans. It is classified as a likely human carcinogen. The
degradation of the carbaryl pesticide was carried out using US. A combi-
nation of high-frequency US wavelength and UV irradiation was consider-
ably more effective than US or ultraviolet irradiation alone for degradation
of carbaryl in water (Khoobdel et al., 2010).
Shayeghi et al. (2011) reported the sonochemical degradation of
malathion using acoustic wave technology (AWT). AWT can be used to
reduce the concentration of dissolved insecticide using high frequency.
MCP, present as a severe contaminant in surface water, was studied in
slurry batch photoreactor by using aeroxide P-25 and laboratory reagent
(LR)-grade TiO2 as catalysts. Aeroxide P25 showed better degradation
efficiency than LR grade TiO2 in both UV and sunlight conditions under
optimized parameters. The degradation of MCP was carried out using US
(Sraw et al., 2014).
The insecticide dichlorodiphenyltrichloroethane (DDT) is widely used
in indoor residual spraying for malaria control owing to its longer residual
efficacy in the field compared to other World Health Organization (WHO)
alternatives. The degradation of DDT was carried out using US (Sibanda
et al., 2011). Norflurazon (4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)
phenyl]pyridazin-3(2H)-one) is an excellent weed-controlling agent used in
the agricultural lands. The excessive addition or the undissolved norflurazon
enters into the aquatic environment and causes the adverse effects associated
with its high concentration. To avoid such problem, visible light-assisted
photocatalysis setup coupled with the 42 kHz US producing bath type soni-
cator was used to degrade the norflurazon (Panneerselvam et al., 2016).
The herbicide (4-chloro-2-methylphenoxy) acetic acid (MCPA)
is normally used in paddy fields and, therefore, wastewater may be
Wastewater Treatment255

contaminated. Ultrasonic degradation of aqueous solutions of MCPA was

investigated with 500 kHz under argon atmosphere by monitoring libera-
tion of chloride ion, total organic carbon (TOC) and by-product production.
Kojima et al. (2005) reported the degradation of MCPA under sonication in
the presence of nitrogen, air, oxygen, argon, and argon/air (60/40 %v/v). The
4-chloro-2-methylphenoxy acetic acid was fully decomposed after 180 min
sonication with a power of 21 W, but 60 % of the TOC remained in solution
even after 6 h. The rate of decomposition of MCPA was found to be greater
in oxygen-enriched atmospheres as radical production was more there, but
dechlorination and TOC removal rates were relatively higher with argon.
Diuron, (N-(3,4-dichlorophenyl)-N,N-dimethyl-urea), is a water-
soluble herbicide belonging to the phenylamide and the subclass of
phenylurea. It is used to control a wide variety of annual and perennial
broadleaf and grassy weeds, as well as mosses. Diuron can contaminate
the surface and ground water by agricultural runoffs and also by waste-
waters generated from diuron manufacturing plants. The degradation of
(N-(3,4-dichlorophenyl)-N,N-dimethyl-urea) by electrochemical oxida-
tion at a boron-doped diamond anode was enhanced by low-frequency
(20 kHz) US (Bringas et al., 2011).

8.3.8  PHARMACOLOGICAL DRUGS

Pharmaceutical manufacturers are under strict regulations by the food and

drug agencies in different countries so as to maintain acceptable water
quality standards for use, discharge, or reuse in the plant. These pharma-
ceuticals reach the environment through usage and inappropriate disposal
from the manufacturing units as such plants generate a large amount of
waste during manufacturing, purification, cleaning, washing, and mainte-
nance (Gadipelly et al., 2014).
Madhavan et al. (2010c) have studied US-assisted photocatalytic degra-
dation of diclofenac (DCF) in an aqueous environment and reported that
the degradation of dichlofenac using a sonophotocatalytic process showed
a slight synergy, when TiO2 was present as a photocatalyst under UV light
irradiation and in the presence of Fe-ZnO also, degradation showed an
additive effect.
Safari et al. (2015) reported the sonochemical degradation of tetracy-
cline (TC) in aqueous solution in the presence of S2O82−. The activation
256Sonochemistry

energy value of this reaction was 31.71 kJ·mol−1, which means that this
degradation process is thermodynamically feasible. Ultraviolet-visible
spectra before and after US irradiation in the presence of S2O82− indicated
that the proposed degradation pathway for TC involves loses of N-methyl,
hydroxyl, and amino groups.
The degradation of 17β-estradiol (E2) and 17α-ethinylestradiol
(EE2) in water and wastewater was carried out at ultrasonic frequency
of 850 kHz. The degradation process followed the pseudo-second-order
kinetic model and the rate constant was 1.719 × 10−2 min−1 at 25°C. The
value for activation energy was found to be 15.21 kJ·mol−1, indicating
that the ultrasonic degradation of steroid hormones is thermodynamically
feasible, and does not progress only on radical reactions but other interme-
diate reaction processes. The higher dissolved organic carbon reduces the
effectiveness of degradation of the E2 and EE2 in wastewater and, there-
fore, US treatment may be more effective as a tertiary treatment option in
wastewater applications (Ifelebuegu et al., 2014).
Atenolol is a β-blocker drug and it is an identified emerging pollutant.
The degradation of atenolol was carried out using US with frequencies
ranging from 200 kHz to 1 MHz. The degradation was monitored by TOC
and COD reduction. It was observed that the degradation depends on the
frequency and power of the US. Studies were carried out in the presence
of various additives generally present in contaminated water (Nejumal et
al., 2014).
The degradation of seven estrogen hormones (17α-estradiol,
17β-estradiol, estriol, 17α-ethinylestradiol, 17α-dihydroequilin, estrone
and equilin) was carried out using US (Andaluri et al., 2012). They used
artificial neural networks (ANNs) as a tool to identify the correlations
between process parameters. ANN enabled the establishment of relation-
ship between sonication parameters such as power density, power intensity,
US amplitude, as well as the reactor design parameters. The antiepileptic
drug “carbamazepine (CBZ)” is one of the most abundant pharmaceuticals
in the aquatic environment. The degradation of CBZ was also carried out
using US (Braeutigam et al., 2012).
The degradation of aqueous solutions of antipyrine was carried out
using homogeneous sonophotocatalytic oxidation process (H2O2/UV/Fe/
Ultrasound) with an artificial UV lamp. Photodegradation of antipyirine
proceeds mainly through a radical mechanism. Probably, it begins with
cleavage of the N–N bond of penta heterocycle leading to the formation
Wastewater Treatment257

of aromatic acids (anthranilic and 1,4-benzenedicarboxylic acids), which

is then followed by the opening of phenyl ring to form small molecular
organic acids (mainly 2-butenedioic, 4-oxo-pentanoic and butanedioic
acids). These acids may be decomposed further into CO2 (Duran et al.,
2013).
Guo et al. (2010) carried out the degradation of cephalexin in aqueous
solution under US irradiation. Biodegradability of the solution was evalu-
ated by the BOD5/COD ratio, which was increased from 0 to 0.36 after
US treatment. It indicates that the US irradiation process is a successful
pretreatment step to improve the biodegradability of cephalexin solution.
The degradation of cephalexin follows a pseudo-first-order kinetics.
Guyer and Ince (2011) also reported the degradation of a widely used
anti-inflammatory drug, DCF, using high-frequency US and iron species.
Occurrence and fate of pharmaceutically active compounds (PhACs) in
the aquatic environment has been recognized as one of the emerging issues
in environmental chemistry and has become a matter of public concern.
Residues of PhACs have been found as contaminants in sewage, surface,
ground and drinking water samples (Heberer et al., 2002).
Hirsch et al. (1999) reported the degradation of various water samples
for 18 antibiotic substances, from the classes of macrolid antibiotics,
sulphonamides, penicillins and TCs. Samples were preconcentrated via
lyophilization and quantified using HPLC-electrospray-tandem-mass
spectrometry. The investigated sewage treatment plant effluents and
surface water samples showed frequent appearance of an erythromycin
degradation product, roxithromycin and sulphamethoxazole with concen-
trations up to 6 mg·L−1.
Acetaminophen (AAP) and naproxen (NPX) are used as analgesics.
The degradation of a pharmaceutical (PhAC) mixture of acetaminophen
and naproxen was carried out using US and single-walled carbon nano-
tube (SWNT)-catalysed ultrasonic (US/SWNT) in water. In the absence
of SWNTs, maximum degradation of AAP and NPX was found to occur
at a high-frequency (1000 kHz), acidic conditions (pH = 3) and different
solution temperatures (25°C at 28 kHz and 35°C at 1000 kHz) during US
reactions (Im et al., 2013).
Paracetamol is a widely used nonsteroidal anti-inflammatory recalci-
trant drug found in water and levodopa, the most frequently used drug
for the treatment of Parkinson disease. The degradation of paracetamol
(PARA) and levodopa was carried out using US (Isariebel et al., 2009).
258Sonochemistry

Jelic et al. (2013) carried out the degradation of the antiepileptic CBZ
by sonolysis, TiO2-based heterogeneous photocatalysis under UV-A and
simulated solar irradiation, and also by the combined use of UV-A and US
irradiation (sonophotocatalysis) in demineralized water, ground water and
effluent wastewater.
Ibuprofen is ordinarily and widely used as a pain reliever, but it is
a persistent organic pollutant it is not biodegradable and passes through
normal sewage treatment process. Mendez-Arriya et al. (2008) made use
of 300 kHz US to increase the extent of degradation from 30 % to 98 %
in 30 min by keeping initial concentration low. The rate of degradation of
ibuprofen was found to increase under air or oxygen and it was highest in
acidic pH. Although, complete removal of IBP was accomplished in this
case, but the presence of intractable degradation products was observed,
which means that there was still residual TOC.
Langenhoff et al. (2013) reported the degradation of ibuprofen and
DCF using US. Ibuprofen was completely removed, whereas DCF yielded
a residual concentration, showing a necessity of post-treatment to remove
DCF using activated carbon.
The combination of US and heat was used for the oxidation of some
ethyl 3,4-dihydropyrimidin-2(1H)-one-5-carboxylates to their corre-
sponding ethyl pyrimidin-2(1H)-one-5-carboxylates by using potas-
sium peroxydisulphate in aqueous acetonitrile. The degradation of
dihydropyrimidinone was carried out by Memarian and Farhadi (2008).
Rahmani et al. (2014) reported the degradation of aqueous solutions
of the tinidazole (TNZ) using the combination of US irradiation and
H2O2. It was observed that the degradation of TNZ was enhanced with
decreasing both TNZ the initial concentrations and pH. Furthermore,
TNZ removal efficiency in the case of actual wastewater was less than
of synthetic wastewater (75 and 68 % of synthetic and actual wastewa-
ters, respectively).
Fluoxetine (FLX) is one of the most widely used antidepressants in
the world. It is an emergent pollutant found in natural waters that causes
disrupting effects on the endocrine systems of some aquatic species. The
total elimination of FLX was carried out using sonochemical treatment
coupled with a biological system. The biological process alone was shown
to be unable to remove the pollutant, even under favourable conditions
of pH and temperature. Sonochemical treatment (600 kHz) was able to
remove this pharmaceutical (Serna-Galvis et al., 2015).
Wastewater Treatment259

Suri et al. (2007) reported the use of US to destroy many estrogen

compounds in water including 17α-estradiol, 17β-estradiol, estrone,
estriol, equilin, 17α-dihydroequilin, 17α-ethinyl estradiol and norgestrel.
Cetirizine dihydrochloride is a pharmaceutical drug of the class antihista-
mines and it is frequently detected in wastewater samples. The degrada-
tion of cetirizine dihydrochloride was carried out using a novel technique
of laccase enzyme as a catalyst under the influence of US irradiation (Sutar
and Rathod, 2015).
A hybrid advanced oxidation process combining sonochemistry (US)
was developed and electrochemistry (EC) for the batch-scale degradation of
ibuprofen (Thokchom et al., 2015). The performance of this hybrid reactor
system was evaluated by quantifying the degradation of ibuprofen under
the variation in electrolytes, frequency, applied voltage, ultrasonic power
density and temperature in aqueous solutions with a platinum electrode.
The degradation of CBZ in synthetic solution and in municipal effluent
was carried out using a sonoelectrochemical reactor. Sonoelectrolysis was
conducted using two concentrical electrodes installed in a cylindrical
reactor containing a ceramic transducer (Tran et al., 2015). The N-doped
TiO2 was used for the photocatalytic degradation (PCD) of pharmaceutical
micropollutants, namely ciprofloxacin HCl (CFX), NPX and PARA and it
was found that the rate of degradation of CFX and NPX is higher than that
of PARA (Shetty et al., 2016).
Bis(indol-3-yl) methane (BIM) derivative is a potential drug in curing
cancerous cells and disorders in the nervous system, and the degradation
of BIM derivative by US was carried out by Li et al. (2010).

8.3.9 SURFACTANTS

Surfactant is a group of chemicals widely used as detergents and other

cleaning products. The residual surfactants are discharged into sewage
systems or directly into surface waters after use. As a result, most of them
end up via dispersion creating different kinds of environmental pollution
such as water, soil, sediment, and so on. The toxic effects of these surfac-
tants on various aquatic organisms are well established. Although most of
surfactants are readily biodegradable in nature and their amount is signifi-
cantly reduced with secondary treatment in wastewater treatment plants,
but more concern arises about the release of untreated wastewater or
260Sonochemistry

wastewater that has undergone only primary treatment. Such a discharge

of wastewater polluted with large quantities of surfactants could have
deleterious effects on our ecosystem. Therefore, it is a demand of the day
to replace them with some more environmental-friendly surfactants or to
search for some alternate technologies to degrade them, where sonochem-
istry can play an important role.
The degradation of sodium dodecylbenzene sulphonate from aqueous
solutions was carried out by Manousaki et al. (2004) using ultrasonic irra-
diation. Ultrasound was used for the degradation of nonvolatile surfactants,
sodium 4-octylbenzene sulphonate (OBS) and dodecylbenzenesulphonate
(DBS) and a nonvolatile nonsurfactant 4-ethylbenzene sulphonic acid
(EBS), as single components and binary mixtures by (Yang et al., 2006).
OBS exhibited a faster degradation rate than DBS at shorter pulse inter-
vals as it has faster rate of transfer to the cavitation bubble interfaces, but
at longer pulse intervals, DBS (which is more surface active) degrades
faster than OBS due to the increased amounts of DBS accumulation on the
bubble surfaces.
The application of pulsed US for the degradation of the nonvolatile
surfactants, OBS and DBS was investigated at a frequency of 354 kHz
(Yang et al., 2005). The enhanced degradation of surfactants by pulsed US
was due to the accumulation of surfactants on cavitation bubble surfaces.
As compared to shorter pulse intervals, longer pulse intervals enhanced
DBS degradation, indicating that DBS, a more surface-active compound,
accumulated and equilibrated with the bubble interface more slowly.
Perfluorosulphonates and carboxylates, C4 to C8 surfactants, were
sonolytically degraded primarily at the vapour–water interface of cavi-
tation bubbles (Campbell and Hoffmann, 2015). Pseudo-first-order rate
constants for the elimination of the perfluorosurfactants indicated that
the rates should be proportional to the degree of interfacial bubble–water
partitioning. Sonochemical degradation rates of the more soluble and less
hydrophobic perfluorobutane sulphonate, PFBS, and perfluorobutanoate,
PFBA, were found to be slower than longer chain analogs as they have
greater water solubility as compared to their C8 counterparts. It was
observed that the degradation rate constants were found to increase with
increasing power density. Enhanced degradation rates were observed for
the C8 surfactants, PFOS (12 %), and perfluorooctanoic acid (PFOA; 23 %)
under simultaneous irradiation at 20 and 202 kHz at a power-combined
power density of 250 W L−1.
Wastewater Treatment261

Singla et al. (2010) reported sonochemical degradation of the cationic

surfactant, laurylpyridinium chloride (LPC), in water at concentrations
of 0.1–0.6 mM, much below its critical micelle concentration (15 mM).
It has been found that the initial step in the degradation of LPC occurs
primarily by a pyrolysis pathway. Propionamide and acetamide were iden-
tified as two of the degradation intermediates. These are formed due to
opening of the pyridinium ring following addition of •OH radicals. Most
of the LPC is eventually converted into carboxylic acids. The complete
mineralization of these carboxylic acids by sonolysis is comparatively a
slow process due to the hydrophilic nature of these low molecular weight
products.
PFOA is an aqueous anionic surfactant, which is a persistent organic
pollutant. It can be easily adsorbed onto the bubble–water interface and
both mineralized and degraded by US cavitation at room temperature. The
effect of US on the degradation of PFOA in solution can be enhanced by
the addition of surfactant like cationic (hexadecyl trimethyl ammonium
bromide, CTAB), a nonionic (octyl phenol ethoxylate, Triton-X-100), and
an anionic (sodium dodecyl sulphate, SDS) surfactant. It was found that
the addition of CTAB increased the degradation rate followed by Triton
X-100 whereas SDS inhibited the degradation rate. The removal effi-
ciency of PFOA increased with increasing CTAB concentration, with the
efficiency reaching 79 % after 120 min at 25°C with 0.12 mM CTAB dose
(Lin et al., 2015).

8.3.10 MISCELLANEOUS

Beckett and Hua (2003) investigated the degradation of 1,4-dioxane using

Fe(II) and US. Sodium bicarbonate is a hydroxyl radical scavenger and
its addition reduced the rate of decomposition; however, it could not stop
the degradation completely. Son et al. (2006) studied the effect of adding
Fe(0), Fe (II) and S2O82− during the sonication of aqueous 1,4-dioxane.
Nakajima et al. (2007) reported the sonochemical oxidation of 1,4-dioxane
by a combination of TiO2 and SiO2. TiO2 proved to be more effective as
compared to SiO2 but the photocatalytic destruction through sonolumines-
cence was not the main mechanism. It seems that the process of sonication
produced thermally excited holes in the TiO2 and oxygen vacancies in the
TiO2 surface help in the decomposition by enhancing cavitation.
262Sonochemistry

Wen et al. (2011) reported the use of noble metal nanoparticles such as
Au/TiO2, Au/ZrO2, Ag/AgCl as efficient sonocatalysts for the degradation
of environmental pollutants including aldehydes, alcohols, and acids using
US. Nowadays, ultrasonic irradiation has received a considerable interest
as an advanced oxidation process.
Liu et al. (2005) studied the application of US for enhancing organic
pollutant biodegradation in biological-activated carbon membrane reactor.
Ultrasonic treatment at 10 W for 24 h could increase organic load of the
bioreactor and the removal efficiency of organic substances. The ultra-
sonic effect on biodegradation was studied through the organic load of
the bioreactor, 2,3,5-triphenyl tetrazoliumchloride-dehydrogenase activity
(TTC-DHA) of biological-activated carbon and the apparent molecular
size distribution of the organic compounds in influent and effluent water.
The ultrasonic field in the reactor was analysed, and the mechanism of
biological activity enhancement by ultrasonics was investigated.
The decomposition of com­plex organic compounds to much simpler
compounds during cavitation proc­ess was reported by Mahvi (2009). Doosti
et al. (2012) reported the degradation of halomethanes, total suspended
solid, algae and [(1,1,1,-trichloro-2,2-bis(p-chlorophenyl)ethane] DDT
using US. The results show that this technique could improve the water
treatment process environmentally. Various parameters could affect the
efficiency of US technique such as power density, frequency and irradia-
tion time. So, it becomes necessary to obtain the optimum power density,
frequency and irradiation time to be cost-effective.
Yaqub et al. (2012) observed that the concentration of lead (Pb)
decreased from 11.5 to 0.6 ppm at 80 kHz from battery industries, 95 %
chromium (Cr) was removed from tannery industry using lead cathode,
and high COD removal was observed using steel anode at 80 kHz. Thus,
use of US is quite effective in the removal of heavy metals and organic
pollutants from industrial wastewater. Karaboga et al. (2007) observed the
effect of application of US in enzymatic pretreatment processes of cotton
fabrics. It was reported that the use of US during enzymatic treatment of
cotton fabrics significantly improved the efficiency of enzymes without
affecting the strength of the fabric as well as it increases mass transfer
toward the textile material.
Water is the basic need for all plants, animals and human beings,
but its quality and quantity is degrading day by day. There is an urgent
need to improve the quality of water as it is required for survival of
Wastewater Treatment263

life in enormous amount for human beings, animals and plant king-
doms. Various methods have been employed for wastewater remedia-
tion. Ultrasound is one such advanced oxidation technique, which can be
used in wastewater treatment and that too without many complications.
Sonochemistry finds great potential in degradation of several pollutants
like dyes, pesticides, phenols, chloro compounds, surfactants, and so
on under ambient conditions and can be carried out without adding any
chemical. It can be thus considered as a green chemical pathway for
wastewater treatment.

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CHAPTER 9

FOOD TECHNOLOGY
SANYOGITA SHARMA1, NEETU SHORGAR2
1
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

CONTENTS

9.1 Introduction  ����������������������������������������������������������������������������  271

9.2 Materials  ���������������������������������������������������������������������������������  273
9.3 Processes  ���������������������������������������������������������������������������������  278
9.4 Product Identification  �������������������������������������������������������������  282
9.5 Inactivation  �����������������������������������������������������������������������������  283
9.6 Other Applications  ������������������������������������������������������������������  288
References  �����������������������������������������������������������������������������������������  291

9.1 INTRODUCTION

Nowadays food scientists are focused on the development of products that

have long storage life and are not only microbiologically safe but at the
same time, these products must also have fresh-like characteristics and
high quality in taste, flavour and texture. This is the requirement of the
consumers, and it has become one of the major areas of research in the
so-called emerging technologies for food science. Traditionally, thermal
treatments have been used for a long time to produce safe food prod-
ucts. Pasteurization of juice, milk, beer and wine is a common process,
where the final product can gain a long storage life of some weeks under
272Sonochemistry

refrigeration. Although it is known that vitamins, taste, colour, and other

sensorial characteristics are decreased with such treatment. High tempera-
ture is responsible for causing these effects. It is observed that in the loss
of nutritional components and changes in flavour, taste and texture, it often
creates the need for additives to improve the quality of a product. Thus,
one of the main challenges in food science today is to develop new tech-
nologies that can ensure high-quality properties and long storage life of
food simultaneously.
In recent years, the most popular emerging technologies being tested in
food science laboratories have been high pressure, electric-pulsed fields,
ultraviolet light, irradiation, light pulses and ultrasound, and some of these
technologies are already being used in the food industry. The use of ultra-
sonics has a wide scope in the food industry for the analysis and amend-
ment of food products. The possibility of using low-intensity ultrasound to
characterize foods was first realized almost six decades ago; however, the
full potential of this technique has been realized by Povey and ­McClements
(1988). The food industry is becoming increasingly more aware of the
importance of developing new analytical techniques such as ultrasonic
techniques to study complex food materials and to monitor properties of
foods during processing. McClements (1995) suggested that sonication
is a nondestructive and noninvasive method which can easily be adapted
for online applications and is used to analyse systems particularly that
are optically opaque. The use of ultrasound in processing develops some
novel and interesting methodologies which are often balancing to conven-
tional techniques.
Various areas have been identified with immense potential for future
progress such as freezing, extraction, drying, crystallization, homog-
enization, filtration, meat tenderization, degassing, sterilization and so
forth. There is a wide-growing area of research into the use of ultrasound
in food processing both from an industrial and academic perspective.
Ultrasound technology has not only been applied in the food industry
mostly as a processing aid but also for the cleaning or disinfecting of
factory surfaces. Kentish and Feng (2014) discussed the physical and
chemical effects of power ultrasound treatments, which are based on the
actions of aural cavitation and also the biological effects of ultrasonica-
tion biological systems present in food such as microorganisms and food
enzymes. Carcel et al. (2012) also reported the ultrasonic applications
in various media such as liquid, gas and supercritical fluid. These are
Food Technology273

dependent on the travelling medium of ultrasound and also on the mate-

rial to be used.
In various areas of science, high-frequency ultrasound has more
applications as compared to power ultrasound. Low-intensity ultra-
sound has been used more in the food industry than power ultrasound
due to it is nondestructive, rapid and traditional technique. Ultrasound
is a novel technology adapted in many countries. Chemat and Hoarau
(2004) proposed that ultrasound operations in food engineering require
the establishment of a hazard analysis and critical control point. McCle-
ments (1995) has reviewed the role of low-intensity ultrasound technique
in food processing for providing information about physicochemical
properties such as composition, structure, physical state and flow rate
whereas high-intensity ultrasound is used to modify physically or chemi-
cally, the properties of foods for the generation of emulsions, cell disrup-
tion, chemical reaction, enzyme inhibition, tenderize meat and modify
crystallization processes. Rastogi (2011) found thermosonication, mano-
sonication and manothermosonication more relevant energy-efficient
process for alternative in the food industry and concluded role of ultra-
sound in the inactivation of microorganisms and enzymes, crystallization,
drying, degassing, extraction, filtration, homogenization, meat tender-
ization, oxidation, sterilization and so forth. Simal et al. (1998) observed
the use of ultrasound to increase mass transport rates during osmotic
dehydration. Osmotic dehydration of 1-cm apple cubes in sucrose solu-
tion carried out using ultrasound treatment at various temperatures mass
transfer was described by Fick’s unsteady-state diffusion equation,
and measured water diffusivity coefficients (Dw) ranged from 2.6 to
6.8 × 10−10 m2·s−1 at 40–70 °C and found a significant decrease in water
and solute transport rate.

9.2 MATERIALS

Quality assurance is an area that is important for food technologists

because it deals with the consumer’s desire for quality foods. Longer treat-
ment times are required, and destructive techniques are used in some tests.
Here, ultrasound appears to be quite helpful in some of these tests. Low-
intensity ultrasound has been used to assess the quality of some fruits such
as mangoes, avocados and melons according to their ripeness by various
274Sonochemistry

ultrasonic parameters such as velocity and reduction in relation to the

physical characteristics of the medium. Benedito et al. (2002) observed the
quality of beef, chicken, cod, pork meat, milk, wine, sugar solutions and
oils with ultrasonic parameters while textures of products such as cheese
and cooked vegetables and the ripeness of fruits have also been deter-
mined by Coupland (2004) using ultrasonic waves.

9.2.1 BEVERAGES

Although power ultrasound has been capable to achieve pasteurization

standards for some beverages such as fruit juices, milk and ciders, low-
intensity ultrasound can also be useful for quality evaluation purposes.
Ultrasound has been used for removing oxygen from orange juice. The
final vitamin A content in product was higher during storage in ultrasoni-
cated juice than in conventionally heat-treated juice. Lemonin content,
brown pigments and colour were evaluated in orange juice after sonica-
tion at 500 kHz, 240 W; low temperature, 5 and 14 °C, where only minor
changes were formed in these characteristics in the product (Valero et al.,
2007). Ultrasound has been successfully used to process strawberry and
blackberry juice and apple cider as well. It was observed that enzymes
such as pectin methylesterase and polyphenoloxidase were inactivated
along with pathogenic bacteria. Minor changes in ascorbic acid and antho-
cyanins were also detected in sonicated juice by Valdramidis et al. (2010).
Beer yield was also improved by using ultrasound at the beginning of the
mashing process (Knorr et al., 2004).
This improvement in yield, occur with beer as well as cheese produc-
tion. The yield increases after the milk is pasteurized with power ultra-
sound. It shows economic benefits for the dairy and beer industries.
Ultrasound can develop various characteristics of products such as colour,
texture and storage life, as well as maintain some of the same nutritional
values in fresh products.
Oxidation process is widely used in the alcoholic beverage industry.
This process is assisted by ultrasound as it enhances oxidation in fermented
products, which leads to characteristic flavour and early maturation. Mason
(1996) stated that ultrasound of 1 MHz alters the alcohol/ester balance
producing an apparent aging in the product which has been used for wines,
whiskeys and spirits.
Food Technology275

9.2.2 BREAD

There are always some innovation and improvement in bread quality by

food scientists. The texture of the bread is an important parameter. Soni-
cation offers the benefit of being a nondestructive method that enables to
know the texture of breads through acoustic parameters. Physical structure
of foods is quite tough to study due to the nonhomogeneity of foods, as in
case of breads, but sound waves can give intensity information about the
structure of bread crumbs. Velocity and reduction of ultrasonic waves have
been used to explain certain quality factors of bread such as changes in
the microstructure of freeze-dried bread crumbs due to changes in density
(Elmehdi et al., 2003). They showed that the size and shape of the gas cells
in bread are susceptible to ultrasound measurements, whereas the signal
amplitude increases linearly with density. This nondestructive system is a
very helpful tool in the cereal industry.

9.2.3  CHEESE AND TOFU

Cheese industry is one of the most important food industries in most of

the countries as evident from their sales reports of cheese products and
high consumer demand. Production of cheese can take several hours or
several years and it depends on the place of manufacture and the type of
cheese. The desirable characteristics in cheese depend on its variety or
type. Cheese manufacturing consists of various stages such as coagula-
tion, drainage, salting and ripening. The low-intensity ultrasound has been
used to monitor these different stages of the process, particularly in the
evaluation of internal cracks due to bad fermentation and the determina-
tion of the optimum rennet cut time. This nondestructive technique also
helped in improving packaging and storage of check. Ultrasound has been
directly involved in the production of soft cheese by promoting the coag-
ulation of proteins and oils (Mason, 1996). High-frequency ultrasound
has also been used to assess the quality of tofu during its manufacture.
It is a water-based gel composed mainly of soy protein and its quality is
based a lot on the final texture of product. Ting et al. (2009) observed the
ultrasound can be used to monitor the development of texture during the
gelation process of tofu. The propagation of ultrasonic waves through the
structure of the tofu gel provides information regarding the whole process
276Sonochemistry

in relating the ultrasound parameters to the enzyme activity in milk during

the coagulation process. Ultrasonic characteristics of Torta del Casar-type
cheese have been investigated by Jiménez et al. (2010). This method was
used to assess the quality of many foods in a nondestructive manner. This
noninvasive ultrasonic method also controls the change in physical prop-
erties of organic cheese made from the sheep milk.
Vilkhu et al. (2008) reviewed the use of ultrasound in the extraction
process in food industries. They concluded worthwhile gain can be accom-
plished in extraction efficiency and extraction rate. In addition, it also
provides an opportunity for enhanced extraction of heat-sensitive bioac-
tive and food component at lower processing temperatures. There is also
a potential for achieving simultaneous extraction and encapsulation of
extracted components to provide protection using ultrasound.

9.2.4 MEAT

The use of ultrasound for envisaging fat and muscle content in live cattle
has been investigated by Wild (1950).Wilson (1992) reported that the
ultrasound technology can be used in the beef industry for evaluating seed
stock, palatability and cutability in carcasses, identifying dates to slaughter
cattle, and also predicting quality. One of the most important quality
aspects of beef considered by the consumer is its tenderness. Koohma-
raie (1994) evaluated that inconsistency in beef softness has been one of
the major problems faced by the meat industry. Jayasooriya et al. (2004)
reported that the tenderness is influenced by composition, structural orga-
nization and the integrity of skeletal muscle.
Jayasooriya et al. (2007) determined the tenderness of meat by two
major components of the skeletal muscle that are contractile tissue, which
is largely the myofibrillar fraction, and connective tissue fraction. Tradi-
tional ageing relies on endogenous proteases (Koohmaraie 1994), though
it is timeconsuming and its effectiveness differs between animals. Meat
tenderness can be controlled by manipulating pre- and post-slaughter
situations through the use of physical methods, such as electrical stimu-
lation (Hwang and Thompson, 2001) and tender stretch of the pre-rigor
carcass. Post-rigor meat tenderness can also be improved by mechanical
techniques such as blade tenderization (Hayward et al., 1980) and high-
pressure technology (Cheftel and Culioli, 1997). The use of ultrasound
Food Technology277

can cause physical disruption of materials through cavitation-related

mechanisms such as high shear, pressure and temperature, and forma-
tion of free radicals. Ultrasound was also tested for its ability to induce
membrane cell disruption that could increase meat tenderness either
directly, through the physical weakening of muscle structure, or indi-
rectly by the activation of proteolysis either by the discharge of cathep-
sins from lysosomes or of Ca2+ ions from intracellular stores so that it
may activate the calpains.
Jayasooriya et al. (2004) reported that the sonication treatment of
meat has produced incompatible effects on meat tenderness. The use
of high-power ultrasound to disrupt muscle structure may prove effec-
tive for reducing both myofibrillar and collagenous toughness. The
experiment was carried out with longissimus lumborum etthoracis and
semitendinosus muscles from 3–4-year-old steers. Alterations in muscle
structure, particularly the loss of the typical myofibrillar structure, were
observed for sonicated horse semimembranosus muscle pumped with
brine. Dolatowski (1988) also observed that the ultrasound treatment
caused fragmentation of myofibrils and disintegration of other cellular
components. Dolatowski and Stasiak (1995) reported that the ultra-
sound-assisted process of meat tumbling caused the major improvement
in the yield, tenderness and juiciness of the end product. Sonication
resulted in decreased drip loss and sheer force of pale, soft and exuda-
tive (PSE) meat.
Got et al. (1999) evaluated the effect of high-frequency ultrasound on
meat texture, pre- and post-rigor meat on treatment with high frequency.
Ultrasound-treated meat was having a slightly softer raw meat texture
after 3–6 days of ageing. The difference between control and ultrasound
treated sample texture had disappeared after 14 days of ageing.
Alarcon-Rojo et al. (2015) studied the application of ultrasound in
meat processing. The effects on quality and technological properties
such as texture, water retention, colour, curing, marinating, cooking
yield, freezing, thawing and microbial inhibition were observed. They
concluded that ultrasound is a useful tool for the meat industry as it
helps in tenderization, accelerates maturation and mass transfer, reduces
cooking energy and increases shelf life of meat without affecting other
quality properties. It also improves functional properties of emulsified
products, eases mould cleaning and improves the sterilization of equip-
ment surfaces.
278Sonochemistry

9.3 PROCESSES

9.3.1 DRYING

Garcia-Perez et al. (2006) reported that the application of high-power

ultrasound for dehydration of porous materials may be very effective in
processes, when heat-sensitive materials such as foodstuffs have to be
treated. Ultrasound helps in reducing temperature as well as treatment
time. The effect of air flow rate, ultrasonic power and mass loading on
hot air drying assisted by a new power ultrasonic system was studied.
An aluminium-vibrating cylinder was used as the drying chamber, which
is able to create a high-intensity ultrasonic field in the gas medium.
Drying of carrot cubes and lemon peel cylinders was carried out at 40 °C
for different air velocities, with and without ultrasound. It was observed
that the effect of ultrasound on drying rate is affected by air flow rate,
ultrasonic power and mass loading. The acoustic field inside the chamber
is disturbed and at high air velocities the effect of ultrasound on drying
kinetics diminishes.
The effect of osmotic dehydration and ultrasound pretreatment on
melon tissue structure at atmospheric pressure for different time was
evaluated by Fernandes et al. (2008a). It was observed that the ultrasound
induced the formation of microscopic channels in the fruit structure but
it did not induce breakdown of the tissue. The changes observed on the
structure of the fruit show the effects of these two pretreatments on the
water diffusivity of the subsequent air-drying step. Ultrasound treatment
enhances water diffusivity due to the formation of microscopic channels,
which also offers lower resistance to water diffusion.
Fernandes et al. (2008b) investigated the effect of ultrasonic pretreat-
ment and ultrasound-supported osmotic dehydration on the dehydration
of pineapple (Ananascomosus) before air drying. They concluded that the
water diffusivity increased after the application of ultrasound and that the
overall drying time was reduced by 8 % over 1 h of air-drying time. They
showed that the water loss increased with increasing soluble solids content
of the osmotic solution and that the ultrasound-assisted osmotic dehydra-
tion incorporated more sugar than the conventional osmotic dehydration.
The water-effective diffusivity of the pineapples during the air-drying
process was influenced by the pretreatment, increasing the water-effective
diffusivity application of ultrasound.
Food Technology279

Azoubel et al. (2010) studied the drying kinetics of fresh and ultra-
sonic-pretreated banana cv Pacovan using the diffusional model. These
diffusivities increased with increasing temperature and with the appli-
cation of ultrasound, but the process time reduced which represents an
economy of energy, as air drying is cost intensive.
The potential nonthermal technique of power ultrasound is also appli-
cable to inactivate the microorganism relevant to fruit juices. Adekunte
et al. (2010) observed the modeling of yeast inactivation in tomato juice.
Tomato juice samples were sonicated at amplitude level. The sonication
is an effective process to achieve the desired level of yeast inactivation in
tomato juice.
Oliveira et al. (2011) studied the dehydration of Malay apple
(­Syzygiummalaccense L.). Using ultrasound as pretreatment, they exam-
ined drying of a large variety of tropical and subtropical fruits (also called
exotic fruits), diverse drying techniques, drying kinetics and key quality
parameters of dried fruits.

9.3.2  FREEZING AND CRYSTALLIZATION

Every day newer and newer applications of ultrasound are being reported
and tested in the food industry. High-power ultrasound is used in thawing
processes for the thawing of beef, pork and fish, with frequencies and
intensities around 500 kHz and 0.5 W·cm−2 (Miles et al., 1999). Zheng
and Sun (2006) have reported that cavitation process can not only lead to
the production of gas bubbles but also is responsible of microstreaming.
The use of ultrasound for freeze preservation of fresh food stuffs results
in the improvement of quality of product. The ultrasound is beneficial to
control crystal size distribution in the frozen product and reducing crystal
size, which prevents incrustation on freezing surface.
Power ultrasound is also useful in the formation of ice crystals during
the freezing of water. The mechanism involved in this process is acoustic
cavitation, where the acoustically generated bubbles act as nuclei for
crystal growth (Sun and Li, 2003). Sonication is a helpful tool in the
control of crystallization processes. It increases the nucleation rate and
crystal growth rate, and, therefore, generates new and fresh nucleation
sites. They observed that the freezing rate of potato assisted by ultra-
sound was very fast, with an output power of 15.85 W and a treatment
280Sonochemistry

time of 2 min, and a better microstructure was attained under these

freezing conditions.
Ultrasound plays a very important role in some crystallization methods
in the initial stage of freezing. As a result, the size of crystal is smaller than
conventional freezing for products such as strawberries. Therefore, there is
reduction in damage to the microstructure of product. Mason (1996) studied
the use of ultrasound on ice lollipops. A better adherence of the lollipop to
the wooden stick was observed, and the lollipop became harder than the
common product. Sonication has also been used to monitor the cooling
processes of gelatin, chicken, salmon, beef and yogurt by measuring the
ultrasonic pulse time-of-travel to the cool surface. Sigfusson et al. (2004)
measured the movement of the ice front by the time-of-flight of an ultra-
sonic pulse by recording echoes as a function of time, and it was correlated
with the percentage of frozen food.

9.3.3 EXTRACTION

The use of ultrasound in extraction processes has certain benefits. There is

greater diffusion of the solvent into cellular materials, upgrading in mass
transfer, which improves discharge of contents due to the disruption of cell
walls. Extraction of sugar from sugar beets, medicinal compounds such
as helicid, berberine hydrochloride and protein from defatted soybeans
and tea are some good examples of extraction using sonication. Extraction
of the enzyme rennin by ultrasound for cheese-making achieved a higher
yield of the enzyme as compared to normal extraction. The other advan-
tages of ultrasound in extraction methods include the decrease of tempera-
tures and the shortening of treatment times consequential in a pure extract.
One specific advantage of ultrasound is in the extraction of tea solids
from water and that too with increased yield. Compounds from Salvia
officinalis were also extracted. The extraction of antioxidant carnosic acid
from the culinary herb Rosmarinus officinalis was found to be increased
and extraction times were reduced. A reduction in maceration time was
also achieved with ultrasound in the extraction of alkaloid reserpine from
Rauwolfia serpentina. Albu et al. (2004) observed the extraction using
ultrasound combined with temperature from 47 to 53 °C and at different
time intervals. Only 15 min were sufficient to extract most of the mate-
rials. Karki et al. (2010) extracted sugar and protein from soy flakes and
Food Technology281

obtained excellent results after a few seconds of sonication only. The

total sugar and protein release was up to 50 and 46 %, respectively, as
compared to untreated samples. Vilkhu et al. (2008) reported the extrac-
tion of almond oils, herbal extracts (marigold, fennel, hops mint), ginseng
saponins, ginger, rutin, carnosic acid from rosemary, polyphenols, amino
acid and caffeine from green tea and pyrethrins from flowers. In general,
all these processes using ultrasound show higher extraction yields and
rates, shorter processing times and, on the whole, very efficient processing.
Sonochemical reactions could be an important tool for food extraction, if
these reactions are successfully controlled. Muthupandian et al. (2008)
reported some promising effects of ultrasound in the extraction of gingerol
from ginger, homogenization of milk and generation of high-quality emul-
sions from food ingredients at laboratory-scale trials. They concluded that
undesired reactions between radicals generated by ultrasonication and
food ingredients could be neglected by using lower ultrasonic frequencies,
while high-frequency ultrasound is used for the identification of the poten-
tial of sonochemical hydroxylation of phenolic compounds to enhance the
antioxidant properties of certain food materials.
The quality and the efficiency of specific products in food and chemical
industries can be improved by the use of ultrasonication. Easy formulation
and lower energy requirement are other additional advantages. Rastango
et al. (2003) compared the mix-stirring extraction with ultrasound extrac-
tion of daidzin, glycitin, genistin and malonylgenistin from freeze-dried
ground soybeans by the variation of solvents and extraction temperatures.
They found that ultrasound improved the extraction, but was dependent on
the solvent used.

9.3.4 CLEANING

Ultrasound is also a proficient method for cleaning apart from other uses.
It can also remove dirt and bacteria from surfaces and reach crevices that
are difficult to find using conventional methods. Medical, surgical, dental
and food-processing instruments and surfaces can be cleaned with ultra-
sound. Ultrasound has also been applied in combination with a bacteri-
cide to clean the surfaces of hatchery eggs. Mason (1996) observed that
the activities of chemical biocides are also enhanced with ultrasound. A
number of studies have revealed that ultrasound can be used to remove
282Sonochemistry

biofilm, which causes sometime fouling in some food industry equip-

ment. Fouling of tubes used to pasteurize and process certain products is
the main cause for the contamination of milk in dairy industry, because
some microorganisms can be added to the walls of these tubes. Oulahal-
Lagsir et al. (2000) showed that the ultrasound was twice as effective in
removing such biofilm from some of the evaluated surfaces compared to
the common process of swabbing to clean the equipment. Ultrasound is
very useful for cleaning in dairy membrane processes during ultrafiltration
activities, when applied at a constant low frequency (Muthukumaran et al.,
2007). It is also being studied as an alternative to chlorination for disin-
fection of water. Some studies carried out in water have focused on the
emergent pathogen Cryptosporidium parvum due to the generation of free
radicals in aqueous solutions during the ultrasound treatment. The use of
ultrasound as a disinfectant technique could avoid some of the troubles
associated with carcinogenic products formed in chlorination processes.
Tsukamoto et al. (2004a, 2004b) reported that Saccharomyces cerevisiae
has a structure similar to the pathogenic microorganisms and ultrasound
treatment at 27.5 MHz for longer treatment times with a sodium hypochlo-
rite solution, yielded a better effect against the cells.

9.4  PRODUCT IDENTIFICATION

Food quality assurance refers to the detection of foreign bodies in the final
product so as to ensure the safety of foods. All food industries have specific
detectors for glass, bones, metals and other materials. Haeggström and
Luukkala (2001) observed the presence of animal bones in meat products,
fragments of glass in glass jars and metal in the products as manufacturing
practices were poor. Knorr et al. (2004) showed that foreign bodies such as
glass and plastic pieces and other raw materials can be detected in yogurt,
fruit juices and tomato ketchup by ultrasonic signals in a time–frequency
analysis. Strange bodies of materials such as stone, wood, plastic, glass
and steel spheres were detected in cheese and marmalade using ultrasound.
Ultrasound technique is nondestructive and highly sensitive method and
it is viable for use in a homogeneous product with 20–75 mm of probing
depth. Ultrasonic pulse compression is used to detect variations in the
uniformity of several liquids, liquid leveling in polymer-based soft drink
bottles and foreign objects present in containers.
Food Technology283

The air-coupled ultrasonics is a new method to be used to estimate the

level of water within a polymer drink bottle (Gan et al., 2002). The volume
fractions of some components in foods such as fruit juices, syrups and
alcoholic beverages were also determined using ultrasonic waves. Sonica-
tion technique was also used by Saggin and Coupland (2001) to detect the
thickness of some foods, including cheddar cheese, luncheon meat and
cranberry sauce. Bamberger and Greenwood (2004) also demonstrated
that ultrasound affects product quality. The concentration of solids is an
important parameter in slurries processing industry, where the parameters
density and attenuation of ultrasonic waves have proved to be useful tools
for quality assurance and process control of the thick slurry suspensions,
because both these parameters are related to concentration of the medium.
Schöck and Becker (2010) used ultrasound in fermentation as the concen-
tration of sugars changes with the production of ethanol because of the
yeast activity. The concentrations of ethanol and sugar were estimated
based on the sound wave velocity travelling through the medium. Gestre-
lius et al. (1993) tested the use of ultrasound in microbial control such as
packaged milk. They showed that the acoustic streaming induced by ultra-
sound in a liquid is affected by the microbial activity. Therefore, bacteria
affecting physicochemical parameters can be easily detected using ultra-
sonic waves.

9.5 INACTIVATION

Some of the inactivation studies are discussed in the following sections.

9.5.1 MICROORGANISMS

Ultrasound was studied as a microbial inactivation technique about six

decades back (Piyasena et al., 2003). This killing effect was first observed
when ultrasonic waves were applied in a US army experiment to investi-
gate their use in antisubmarine warfare, but fishes died in large numbers.
The goal of such emerging technologies in food processing is to inactivate
the initial population of microorganisms to a safe level so as to mini-
mize damage to the product’s quality features. However, microorganisms
become more resistant over time to the action of a specific factor such as
284Sonochemistry

sound waves, pressure or electricity. Rodríguez et al. (2003) reported that

the ultrasound treatments can have deleterious effects on microorganisms,
when applied with sufficiently high frequencies above 18 kHz. Raso and
Barbosa-Cánovas (2003) reported that the use of ultrasound, along with
pressure, heat and low water activity isa good combination for reducing
microbial populations in foods. Guerrero et al. (2001) reported no change
in the sensitivity of S. cerevisiae, when ultrasound and heat were applied
with different pH values, but in Sabouraud broth at pH 5.6, the addition
of chitosan enhanced the inactivation of yeast under thermosonication
(Guerrero et al., 2005).
Knorr et al. (2004) reported that inactivation of Bacillus stearother-
mophilus and Escherichia coli K12DH5α was improved with the use of
direct steam injected into the ultrasound treatment, which leads to reduc-
tion in temperature and process time. On the other hand, a different type of
microorganism Lactobacillus acidophilus was more resistant to the ultra-
sound-assisted thermal combination process. In ultrasound technology, a
new area called manosonication is being tested, where the use of moderate
and high pressures along with ultrasound reduces the initial level of micro-
bial population effectively. Manosonication and heat action have also been
reported to have an additive effect in achieving the inactivation of Listeria
monocytogenes. It was observed that on subjecting the microorganisms to
ultrasound energy at 20 kHz and 117 μm at ambient conditions, no reduc-
tions were found; however, when pressure was added as an obstacle, the
microbial inactivation was observed to be quite high (Piyasena et al., 2003).
Raso and Barbosa-Cánovas (2003) developed a mathematical model
to describe the resistance of various bacteria to manosonication treat-
ments. They came to a conclusion that with the combination of heat and
ultrasound, substantial reductions in D values are obtained for Listeria
innocua and Salmonella. The studies on Zygosaccharomyces bailii have
shown that thermosonication is independent of the treatment medium
and good reductions in D values were observed with the combination of
temperature and sonication. Pagán et al. (1999) showed the combination
of ultrasound with pressure clearly improves the inactivation of microor-
ganisms as for L. innocua. Raso et al. (1998) also showed that the use of
pressure in combination with thermosonication enhanced the inactivation
of Bacillus subtilis spores compared to thermal treatment. Various results
of thermoultrasonic treatments on moulds such as Aspergillus flavus and
Penicillium digitatum also showed the effect of adding antimicrobials on
Food Technology285

increasing the inactivation. An interesting study was made on the use of

ultrasound to delay fruit decay and to maintain fruit quality. Ultrasound
was used at different frequencies at maximum 59 kHz and temperature
20 °C to process strawberries immersed in water. Decay was delayed and
the number of microorganisms also decreased. Cao et al. (2010) observed
that the firmness of the fruit and the levels of total soluble solids, titratable
acidity and vitamin C were also retained after processing.
The most common techniques currently used to inactivate microorgan-
isms in food products are conventional thermal pasteurization and ster-
ilization. Thermal processing does kill vegetative microorganisms and
some spores; however, its effectiveness is dependent on the treatment
temperature and time. However, the magnitude of treatment, time and
process temperature is also proportional to the amount of nutrient loss,
development of undesirable flavours and deterioration of functional prop-
erties of food products. High-power ultrasound is known to damage or
disrupt biological cell walls, which will result in the destruction of living
cells. Unfortunately, very high intensities are needed if ultrasound alone
is to be used for permanent sterilization. However, the use of ultrasound
coupled with other decontamination techniques, such as pressure, heat or
extremes of pH looks quite promising technology. Thermosonic (heat plus
sonication), manosonic (pressure plus sonication) and manothermosonic
(heat plus pressure plus sonication) treatments are likely to be the best
methods to inactivate microbes, as these are more energy-efficient and
effective in killing microorganisms.
The advantages of ultrasound over heat pasteurization are minimiza-
tion of flavour loss, greater homogeneity and significant energy savings
(Mason et al., 1996; Piyasena et al., 2003). A considerable amount of
data is available regarding the impact of ultrasound on the inactivation of
microorganisms. The effectiveness of an ultrasound treatment is depen-
dent on the type of bacteria being tested. Other factors include amplitude
of the ultrasonic waves, exposure time, volume of food being processed,
the composition of food and the treatment temperature. Bactericidal
effects of ultrasound were observed while suspended in culture medium
(Davies 1959). Salmonellae attached to broiler skin were reduced upon
sonication in peptone at 20 kHz for 30 min (Lillard, 1993). Dolatowski
and Stasiak (2002) proved that ultrasound processing do have a signifi-
cant influence on microbiological contamination of meat. There are a large
number of potential applications of high-intensity ultrasound in the food
286Sonochemistry

industry. Applications of both high- and low-frequency ultrasound in the

food industry have considerable potential for either modifying or char-
acterizing the properties of foods. At many places, techniques based on
ultrasound have considerable advantages over the existing technologies.

9.5.2 ENZYMES

High-intensity ultrasound is used for the degassing of liquid foods, the

extraction of enzymes and proteins, the induction of oxidation/reduction
reactions, the inactivation of enzymes and the induction of crystallization
processes. Ultrasound is also combined with other treatments to enhance
the efficiency of these treatments. Enzymatic inactivation using different
technologies is widely studied to attain low residual enzymatic activities
in several products. Earlier studies in enzyme inactivation were carried
out almost 60 years ago, when pure pepsin was inactivated by ultrasound
possibly due to cavitation. Inhibition of sucrose inversion can also be
achieved by cavitation. Vercet et al. (2002) observed the use of ultrasound
in combination with heat and pressure and proved its effectiveness in the
inactivation of enzymes such as soybean lipoxygenase, horseradish perox-
idase, tomato pectic enzymes, orange pectin methyl esterase and water
cressperoxidase. Some of these enzymes have been tested in a number of
different food products and it was observed that the medium is a signifi-
cant factor affecting the intensity of inactivation of enzymes. One of the
big challenges of using ultrasound is the heterogeneity of the food matrix,
because it showed assist in enzyme inactivation not only after processing
but also during storage of food as well.
They observed that the manothermosonication is responsible for
particle size decrease and molecular breakage. It induces the breakage of
pectin molecules in a purified pectin solution. Ultrasound can also lead
to denaturation of proteins, maybe due to changes in pressures producing
stretching and compression effects in the cells and tissues. It is known
that the free radical production is promoted by ultrasound and such free
radicals as ·H+ and ·OH− could recombine with amino acid residues of the
enzymes. These residues are associated with structure stability, substrate
binding, and catalytic functions. In the case of enzymes, the main mecha-
nism is free radical formation, which allows changing some characteristics
of the enzymes. Disorder of tissue is much important because it generates
Food Technology287

improved surface contact between the enzymes and free radicals. Mason
(1996) observed that the oxidases are usually inactivated by sonication,
while catalases are affected at low concentrations and reductases and
amylases are highly resistant to sonication. Manothermosonication has
inactivated several enzymes at lower temperatures and/or in a shorter time
than thermal treatments. Sensitivity of the enzymes to manothermosonica-
tion treatment is independent of the medium of treatment. The substrates,
small co-solutes and other proteins are unable to shield the enzymes during
treatments (Vercet et al., 2001).
Food is one of the most basic needs of mankind. Till date, many methods
have been used for preparing, sterilizing, dehydrating, freezing and tender-
izing food products. Scientists have found ultrasound to be versatile in
applications; it has also played significant role in the field of food tech-
nology. One of the most important advantages of ultrasound is its property
of nondestructiveness even at high frequencies. Nowadays, ultrasound is
substituting some of the traditional methods of food processing for moni-
toring the quality of food. Inactivation of microbes and enzymes using
sound waves, integrated with parameters like temperature, pressure, and so
on is proving to be of great significance. The other advantages of food prod-
ucts processed by ultrasound also include improvement in yield, texture
and colour along with reduced process time. Thus, it can be concluded that
ultrasound proves to be a boon for the development of food technology.
Nowacka et al. (2012) investigated the utilization of ultrasound as a
mass transfer enhancing method prior to drying of apples tissue. Apple
cubes were dried using traditional technology at 70 °C and at air velocity
of 1.5 m s−1. The ultrasound treatment caused reduction in the drying time
by 31 % as compared to untreated tissue. The ultrasound-treated apples
showed around 9–11 % higher shrinkage, and porosity of 9–14 % higher
than untreated samples. Ultrasound application caused modification of
rehydration properties in comparison to untreated sample.
Lida et al. (2008) developed a method for controlling the viscosity
of starch (polysaccharide) solutions and it is one of the most prom-
ising processes. Power ultrasound can effectively decrease the viscosity
of starch solutions after gelatinization. At high starch concentrations
(20–30 %), starch gel can be liquidized by sonication. The viscosity of the
starch solution of moderate concentration (5–10 %) can be reduced by two
orders of magnitude to 100 mPa·s by the ultrasonic irradiation for 30 min.
The treated solution can be efficiently powdered by a spray-dryer after the
288Sonochemistry

sonication. The ultrasonic process is applicable for many kinds of starches

(corn, potato, tapioca and sweet potato) and polysaccharides.
There has been a growing interest in the development of processes using
waste or residual biomass as source of cellulose nanocrystals (CNCs).Tang
et al. (2015) extracted the CNCs from old corrugated container fibre using
phosphoric acid and enzymatic hydrolysis using ultrasound treatment. The
effect of enzymatic hydrolysis on the yield and microstructure of resulting
CNC has been reported. The enzymatic hydrolysis was found effective
in increasing CNC yield after phosphoric acid hydrolysis. The presence
of enzymatic hydrolysis gave CNC with improved dispersion, increased
crystallinity and thermal stability.
The combination of sonication and dispersive liquid–liquid microex-
traction based on the solidification of floating organic drop (SDLLME–
SFO) has been developed by Pirsaheb et al. (2015) for the extraction and
determination of imidacloprid and diazinon from apple and pear samples.
Target pesticides were determined by high-performance liquid–liquid
chromatography–ultraviolet detector. Extraction recoveries for different
fruits are in the range of 58–67 % under optimum conditions. This method
was applied with satisfactory results to the analysis of these pesticides in
apple and pear samples. They showed that DLLME–SFO is a very simple,
rapid, sensitive and efficient analytical method for the determination of
trace amount of pesticides in fruit samples.
Saeeduddin et al. (2016) investigated the effect of sonication on physi-
cochemical parameters and microorganisms of pear juice. Ultrasound
processing of fresh pear juice was done at fixed amplitude and frequency
for different time intervals at room temperature. pH, titratable acidity total
soluble solids and Ca and Mn remained stable, whereas the total flavo-
noids, total antioxidant capacity, cloud value, ascorbic acid, total phenols,
sugar contents and Na, K, Fe and Mg showed a considerable increase
during this process. Decreases in microbial population and P and Cu
were also observed. Ultrasound processing for 60 min exhibited optimum
results in terms of physicochemical and microbial quality.

9.6  OTHER APPLICATIONS

Variation in ultrasonic parameters is often coupled with the changes in

the different food products during processing. Hæggström and Luukkala
Food Technology289

(2000) examined the transmission of ultrasound in crushed beef during

simulated automated roasting, which gave good results. Here, tempera-
tures ranged from 45 to 74 °C, with ultrasonic wave (300 kHz), and
only small pieces of crushed beef were used with thicknesses between
7.15 and 15 mm. Sonication has also been used to study changes in
flow actions and thermophysical properties of whey protein isolate
(WPI) and whey protein concentrate (WPC). Water solubility of both
WPI and WPC was significantly increased after sonication as compared
to control samples. The apparent viscosity, flow behaviour index and
consistency coefficient of WPI and WPC were significantly changed
after sonication.
Kresic et al. (2008) reported also that thermophysical properties, such
as initial freezing and initial thawing temperatures, were changed on soni-
cation. The effects of ultrasound on the solubility and foaming properties
of whey proteins were studied by Jambrak et al. (2008). Some important
effects on these properties were observed, on exposing whey proteins at
low frequency (20 kHz) compared to high frequency (40 kHz); however,
higher frequencies (500  kHz) did not show any significant effect. An
important effect with increase in temperature was observed in sonicated
sample at low frequency. Mason (1996) stated that the stable emulsions
were generated by the use of ultrasound requiring little if any surfactant,
which include tomato ketchup and mayonnaise. Ultrasonic velocity and
attenuation spectra were also measured as a function of frequency in emul-
sions treated with ultrasound at 1–5 MHz.
The emulsions were made of corn oil in water and the velocity and
attenuation was found to increase with frequency in all emulsions having
different particle sizes (Coupland and McClements, 2001). Ultrasound
is also being tested to inactivate microorganisms in combination with
heat and pressure. Wu et al. (2001) suggested that the ultrasound can
also stimulate living cells and it is very useful in the production of
yogurt, where up to 40 % of production time is reduced by using ultra-
sound. Milk is homogenized better using ultrasound than by traditional
methods. Additional positive effects in yogurt due to ultrasound are
improvements in uniformity and texture with added sweetening effects.
Mason (1996) also observed faster germination of agricultural crops as
well, when seeds are subjected to ultrasound treatment. Moreover, ultra-
sound can be used in some wastewater treatment plants within the food
industry.
290Sonochemistry

The use of sonic waves has assisted the bioprocess and an improved
biological activity has been observed by Schläfer et al. (2002). The rate of
drying was increased in drying processes, and the final moisture content
was reduced by ultrasonic treatments carried out at lower temperatures.
Jambrak et al. (2007) have shown that ultrasound pretreatment of vege-
tables for drying decreases the drying time significantly, because of the
increased water loss. The rehydration properties of some vegetables such
as mushrooms, sprouts, cauliflower and so on are better than others. Similar
results were achieved during the drying of bananas. A sonication pretreat-
ment to air drying had significant effect on the banana tissue. Fernandes
and Rodrigues (2007) also reported that the drying time of banana was
reduced by up to 11 %, due to ultrasound, which allowed the elimination
of larger amounts of water from the fruit. Ultrasound has been shown to
be effective during osmotic dehydration processes in speeding up and
enhancing the diffusivity of water and solids.
Cárcel et al. (2007) observed that sonication was able to increase the
water diffusivity up to 117 % and dry matter diffusivity up to 137 % in
apple–sucrose solution. The application of ultrasound was found effective
in removing the water from the cell structure of the apple tissue, as well
as in taking solids from the sucrose solution. Garcia-Perez et al.(2012)
reported the feasibility of power ultrasound at low-temperature drying
processes for kinetics of carrot, eggplant and apple cubes in the presence
and absence of ultrasound. Similar effects have been observed for all prod-
ucts such as reduction in drying time (between 65 % and 70 %). Further
ultrasonication results into the increase in mass transfer coefficient and
effective moisture coefficient and effective moisture diffusivity increased
by 96–170 % and 407–428 %, respectively.
Jambrak et al. (2007) used ultrasound treatment for drying of mush-
rooms, Brussels sprouts and cauliflower and found reduction in drying time.
The effect of the ultrasound in mass transfer process was also observed.
They investigated the effect of ultrasound and blanching pretreatments on
weight and moisture loss/gain, upon drying and rehydration. The drying
time after ultrasound treatment was shortened for all samples, as compared
to untreated one. The rehydration properties (weight gain, %) were found
to be the best for freeze-dried samples, which showed weight gains for
mushrooms, Brussels sprouts and cauliflower. It was observed the rehy-
dration properties for ultrasound-treated samples were higher than those
for untreated samples.
Food Technology291

Deng and Zhao (2008) studied the effect of pulsed vacuum and ultra-
sound pretreatments on glass transition, texture, rehydration, microstruc-
ture, and other selected properties of air- and freeze-dried apples were
investigated. Apple cylinders (15 mm height × 15 mm diameter) were
first osmo concentrated in a 60 g/100 g high-fructose corn syrup solution
containing 7.5 g/100 g Gluconal Cal combined with agitation, under ultra-
sound for 3 h. It is followed by hot-air or freeze drying. Ultrasound led to a
higher glass transition temperature, lower water activity, moisture content
and rehydration rate.
Food is one of the most basic needs of mankind. Till date, many
methods have been used for preparing, sterilizing, dehydrating, freezing
and tenderizing food products. Ultrasound is a versatile energy source and
it has played a significant role in the field of food technology. One of the
most important advantages of ultrasound is its property of nondestructive-
ness even at high frequencies. Nowadays, ultrasound is substituting some
of the traditional methods of food processing for monitoring the quality of
food. Inactivation of microbes and enzymes using sound waves, integrated
with parameters such as temperature, pressure and so on is proving to be
of great importance. The other advantages of food products processed by
ultrasound also include improvement in yield, texture and colour along
with reduced processing time. Thus, it can be concluded that ultrasound
proves to be a boon for the development of food technology.

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CHAPTER 10

ANAEROBIC DIGESTION
SANGEETA KALAL1, SATISH KUMAR AMETA2, ABHILASHA JAIN3
1
Department of Chemistry, M. L. Sukhadia University, Udaipur, India
E-mail: [email protected]
2
Department of Environmental Science, PAHER University, Udaipur,
India, E-mail: [email protected]
3
Department of Chemistry, St. Xavier’s College, Mumbai, India
E-mail: [email protected]

CONTENTS

10.1 Introduction ����������������������������������������������������������������������������  295

10.2 Anaerobic Digestion  ���������������������������������������������������������������  296
10.3 Anaerobic Digesters  ���������������������������������������������������������������  298
10.4 Ultrasonic Pretreatment  ����������������������������������������������������������  302
10.5 Mechanisms of Anaerobic Digestion  ��������������������������������������  305
10.6 Factors Affecting Ultrasonic Treatment  ���������������������������������  307
10.7 Applications of Ultrasound  �����������������������������������������������������  312
References  �����������������������������������������������������������������������������������������  319

10.1 INTRODUCTION

Wastewater treatment has become a necessity of the day as the world is in

cancerous grip of water pollution and is facing a scarcity of potable water
in many developing and undeveloped countries. Many techniques are used
for the treatment of wastewater, and biological treatment of wastewater
is one of these widely used techniques. Excess sludge production is one
296Sonochemistry

of the most serious challenges in biological wastewater treatment plants.

Biodegradation of excess sludge is a commonly used method in biological
treatment by anaerobic digestion. Anaerobic digestion is quite attractive
waste treatment practice, where two objectives can be accomplished and
these are pollution control and energy recovery. It is a suitable technology
to treat not only solid waste but wastewater also.
Major progress has been made in all areas of waste management but
the use of anaerobic digestion has emerged as one of the most successful
and newer technology developments in the field of waste management in
the past few decades (De Baere, 2000). Anaerobic digestion offers distinct
advantages in the production of biogas compared to some other forms of
bioenergy production. As carbon dioxide and some other emissions are
placed under limitation by emission regulations and the carbon taxes,
anaerobic digestion has become relatively a more attractive and competi-
tive technology for the management of waste.
Formation of methane in anaerobic digestion involves basically four
different steps and these are:

• Hydrolysis
• Acidogenesis
• Acetogenesis
• Methanogenesis

In the near future, bioenergy will be the most significant renewable

energy source because it is economical and is an alternative to fossil fuels.
Thus, anaerobic digestion has various advantages that are as follows:

• Less consumption of energy

• Low sludge production
• Requirements of smaller space
• Reduction in the volume of waste
• Production of biofertiliser and valuable soil conditioners

10.2  ANAEROBIC DIGESTION

Anaerobic digestion is a series of biological processes, where microorgan-

isms break down biodegradable material in the absence of oxygen. One of
Anaerobic Digestion297

Sun

Live stock
Vegetation

Fertilizer
Vegetable waste
Manure
Electrical

Organic waste Biogas

Thermal energy
Anacrobic treatment

Fuel

FIGURE 10.1  The process of anaerobic digestion.

the final products of this process is biogas which is composed of methane

as a major component and carbon dioxide. This biogas may be utilized to
generate electricity and heat through combustion or it can be processed
into some other renewable natural gas and transportation fuels (Fig. 10.1).
Traditional anaerobic digesters have a residence time of about 20 days
and they also require large digesters. The rate-limiting step can be defined
as the step that causes process failure in an anaerobic digestion process
under imposed kinetic stress. Sludge hydrolysis is the rate-limiting step of
anaerobic digestion (Eastman and Ferguson, 1981; Malina and Pohland,
1992), and it is all due to the low biodegradability of the cell walls and the
presence of extracellular biopolymers (Tiehm et al., 2001).
There are various already known pretreatments for waste treatment
such as mechanical, thermal, chemical and biological interventions
(Dewil et al., 2007; Climent et al., 2007) and all these pretreatments
298Sonochemistry

result in a certain degree of lysis or disintegration of sludge cells. These

processes release and solubilize intracellular material into the water
phase and transform refractory nonbiodegradable organic compounds
into biodegradable material. Dewil et al. (2006a) have demonstrated
that ultrasound (US) causes disruption of sludge flocs, thus changing
the structure of its constituent and solubilizing the organics. Any
improvement method in the biodegradability of a particular substrate
is mainly based on the fact that the substrate is better accessible to
microorganisms.
Therefore, interest of researchers, technology designers and manufac-
turers of relevant equipment was focused on using US for disintegration
(Tiehm et al., 2001). Such ultrasonic disintegration of waste-activated
sludge (WAS) was examined to improve the anaerobic stabilization
process. It was observed that:

• Ultrasonic pretreatment enhances the subsequent anaerobic diges-

tion resulting in a better degradation of volatile solids (VSs) and
increased production of biogas.
• VSs concentration in the effluent of the digester fed with disinte-
grated sludge was 31 % less than in the conventional process.
• Total biogas production was almost two times higher for disinte-
grated WAS.

10.3  ANAEROBIC DIGESTERS

Anaerobic digester is an air-tight, oxygen-free container, where anaerobic

bacteria digest sewage producing methane and CO2. Anaerobic digesters
have been used around the world for decades for utilizing organic waste
and its products, that is, biogas to increase self-sufficiency. It may be of the
following types.

10.3.1  STANDARD-RATE (COLD) DIGESTER

This type of anaerobic digester is simple digester, but it requires a long

digestion period of 30–60 days. This type of digester is schematically
represented in Figure 10.2. Normally, the sludge content is neither heated
Anaerobic Digestion299

FIGURE 10.2  Standard-rate sludge digester.

nor mixed in this digester. However, the biogas generated provides some
form of mixing. Stratification occurs in four zones and these are:

• Scum layer
• Liquid layer (or supernatant)
• Layer of digesting solids
• Layer of digested solids

10.3.2  HIGH-RATE DIGESTER

This digester was designed with major improvement in standard-rate

digester (Fig. 10.3). In this case, the sludge is heated and completely
mixed. The raw sludge is thickened and there is a uniform feeding. All
these elements combined create a uniform environment and as a conse-
quence, the tank volume is reduced and the process stability and effi-
ciency are improved (Turovskiy and Mathai, 2006). The sludge is mixed
by gas recirculation, pumping or draft-tube mixers and it is mostly heated
by external heat exchangers because of their flexibility and ease of
300Sonochemistry

FIGURE 10.3  High-rate sludge digester.

maintenance. Other ways of heating include internal heat exchangers and

steam injection (Metcalf & Eddy, 2004).
These are of three types:

• Anaerobic Fluidized-Bed Reactor: In anaerobic fluidized-bed

reactor systems, the medium adhered with microbes is fluidized
within the reactor. This results in the conversion of organic mate-
rials to CH4 and CO2. Anaerobic microbes grow on the surface of
the medium, expanding the apparent volume of the medium and
hence, this reactor is also known as an expanded-bed reactor. Media
such as sand, quartzite, alumina, anthracite, granular-activated
carbon or cristobalite are usually employed with a particle size of
approximately 0.5 mm.
• Upflow Anaerobic Sludge Blanket Reactor: An upflow anaer-
obic sludge blanket (UASB) process capable of affording self-
granulation (flocculation) of anaerobic microbes was first reported
by Lettinga et al. (1980). In this type of reactor, wastewater enters
from the bottom of the reactor and passes through a sludge bed and
sludge blanket where organic materials are anaerobically decom-
posed. The gas produced is then separated by a gas–solid separator
and the liquid is discharged over a weir, while the granular sludge
naturally settles at the bottom. Granules range in size from 0.5
Anaerobic Digestion301

to 2.5 mm and are in different concentrations, that is 50–100 kg

VSS·m−3 at the bottom to 5–40 kg·VSS·m−3 in the upper part of the
reactor. Such UASB systems are primarily used in the treatment
of wastewater derived from the food-processing industry. Major
parameters in the UASB operation are flow diameter, microbial
density and the structure of the gas–solid separator, which effec-
tively retains the microbial granules within the reactor. Granule
formation in a UASB system is influenced by the growth of rod-
type Methanothrix spp. which produces spherical granules.
• Fixed-Film Digester: In this type of digester, methane-forming
microorganisms grow on supporting media such as wood chips
or small plastic rings filling a digestion column. These digesters
are also called attached growth digesters or anaerobic filters. The
slimy growth coating the media is called a biofilm. Hydraulic
retention times of such fixed-film reactors can be shorter than 5
days. Usually, effluent is recycled to maintain a constant upward
flow. One of the drawbacks of fixed-film digesters is that manure
solids can plug the voids between the supporting media. A solid
separator is thus needed to remove particles from the manure
before feeding it to the digester. Some potential biogas is also
lost due to removal of manure solids.

10.3.3  TWO-STAGE DIGESTER

A high-rate digester is coupled with a second tank in two-stage digestion,

and sometimes, it is called a secondary digester (Fig. 10.4). It is merely
used to store the digested solids and decant the supernatant. It is neither
heated nor mixed.

10.3.4  MESOPHILIC AND THERMOPHILIC DIGESTION

Most of the high-rate digesters are operated in the mesophilic range, with a
temperature between 30 and 38 °C (Climent et al., 2007). Anaerobic diges-
tion can also take place at higher temperatures, that is in the thermophilic
region where digestion occurs at temperatures between 50 and 57 °C suitable
for thermophilic bacteria. Thermophilic digestion is faster than mesophilic
302Sonochemistry

FIGURE 10.4  Two-stage sludge digester.

digestion since the biochemical reaction rates increase with increasing

temperature. Thermophilic bacteria are far more sensitive to temperature
fluctuations than their mesophilic counterparts (Qasim et al., 1999).

10.4  ULTRASONIC PRETREATMENT

Ultrasound is a sound wave at a frequency above the normal hearing range

of human beings (> 20 kHz). The rarefactions are the regions of low pres-
sure (excessively large negative pressure), where liquid or slurry is torn
apart. Microbubbles are formed in these rarefaction regions, when pressure
is reduced. These microbubbles are also known as cavitation bubbles, essen-
tially containing vapourized liquid and gas that was previously dissolved in
the liquid. Cavitation occurs above a certain intensity (threshold intensity)
when gas bubbles are created. These bubbles increase in size and collapse
violently within a few microseconds. The radius of the bubble is inversely
proportional to the frequency of the generating US (Tiehm et al., 2001;
Young, 1989). The collapse of the bubbles often results in localized temper-
atures up to 5000 K and pressures up to 180 MPa (Flint and Suslick, 1991).
The sudden and violent collapse of a huge number of these micro-
bubbles generates powerful hydromechanical shear forces in the bulk
liquid surrounding the bubbles (Kuttruff, 1991). The collapsing bubbles
disrupt the nearby (adjacent) bacterial cells by extreme shear forces, thus
Anaerobic Digestion303

rupturing the cell wall and membranes. The localized high temperature and
pressure could also assist in the disintegration of sludge at high tempera-
tures. Lipids in the cytoplasmic membrane are also decomposed. It results
in holes within the membrane through which intracellular materials are
released into the aqueous phase (Wang et al., 2005).
Some additional effects are observed on quality and properties of the
sludge when it is treated with US. These are disruption of the extracellular
polymeric substances (EPS) and the cell walls of the microorganisms in the
sludge (Onyeche et al., 2002), a reduction of the floc size (Dewil et al., 2006a)
and a reduced dewaterability (unless extra polyelectrolyte is used), and incon-
clusive effects on the filamentous WAS components (Neis and Tiehm, 1999).
Sonication was also used as an extraction method to characterize the
mineral fraction in extracellular matrix biofilm from activated sludge
(Bourven et al., 2011). Sonication disturbs and dissolves the extracellular
matrix and increases the accessibility of various inorganic cations, such
as Ca2+, Mg2+, Fe3+, Al3+, K+ and so forth, trapped in the organic matrix of
flocs (Jorand et al., 1995). Li et al. (2010) studied the effect of ultrasoni-
cally enhanced two-stage acid-leaching method on the extraction of heavy
metals from electroplating sludge. The overall recovery rate of Cu, Ni, Zn,
Cr and Fe from electroplating sludge ranged between 97.42 and 100 %.
Moreover, they were successful in the scale-up of lab-scale results to a
pilot-scale industrial test. Deng et al. (2009) showed the mechanism of
release of heavy metals from sludge flocs by ultrasonication (Fig. 10.5).
Hristozov et al. (2004) compared the two techniques, that is ultrasonica-
tion and microwave-assisted methods for the extraction of eight metals,
that is Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn from sewage sludge. Both these
methods achieved higher rate of metal recovery (75–84 %) within similar
treatment time. However, ultrasonication method offers several advantages
such as it can operate under atmospheric pressure with no acid requirement
and cost-effectiveness over the microwave-assisted extraction method.
Sonochemical reactions resulting in the formation of highly reac-
tive radicals (e.g. •OH, HO2•, H•) and hydrogen peroxide have also been
reported to contribute to the ultrasonic disintegration of sludge. This is
most likely due to the strong hydrodynamic shear resulting from cavita-
tion effects at low frequency. Wang et al. (2005) explored the mechanism
of ultrasonic disintegration of WAS at a frequency of 20 kHz. They added
NaHCO3 as a masking agent to eliminate the oxidizing effect of hydroxyl
radicals during ultrasonic treatment.
304Sonochemistry

FIGURE 10.5  Regions of acoustic streaming.

Another mechanism operative during sonication of sludge is acoustic

streaming. Acoustic streaming has been studied since the early 1930s
(Faraday, 1831). It occurs at the solid/liquid (sludge) interface. The major
benefit of streaming in sludge processing is mixing. This mixing facilitates
uniform distribution of US energy within the sludge mass, convection of
the liquid and distribution of heating. Acoustic streaming has three regions
(Fig. 10.5). These regions are:

• Eckart streaming (Region I): This is the largest region and furthest
from the vibrating tool. It has circulating currents that are defined
by the shape of the container and the wavelength of the acoustic
wave in the liquid.
• Rayleigh streaming (Region II): The region near the tooling is
called region II. It is located around the horn and has circulating
currents. Its size and shape are primarily defined by acoustic tooling.
These circulations are typical with much longer wavelengths than
that of the acoustic wave in liquid.
• Schlichting streaming (Region III): This region is closest to the
vibrating tool. It is adjacent to the fluid acoustic boundary layer.
In this region, tangential fluid velocity is near the velocity of the
horn face. This layer is relatively thin, for example, the acoustic
Anaerobic Digestion305

boundary layer for water at 20°C is < 4 μm at 20 kHz (Graff, 1988).

All these three regions play a critical role in mixing of the fluid.

10.5  MECHANISMS OF ANAEROBIC DIGESTION

The digestion process begins with hydrolysis of bacteria present in input

materials so as to break down insoluble organic polymers such as carbo-
hydrates and make them available for other bacteria. Thereafter acidogenic
bacteria convert the sugars and amino acids into carbon dioxide, hydrogen,
ammonia and organic acids and it is followed by conversion of these resulting
organic acids into acetic acid by acetogenic bacteria, along with additional
ammonia, hydrogen and carbon dioxide. Finally, methanogens convert these
products to methane and carbon dioxide (Metcalf & Eddy, 2004).
Formation of methane in anaerobic digestion proceeds in four
different steps and these are hydrolysis, acidogenesis, acetogenesis and
methanogenesis.
Most of the researchers have reported that the rate-limiting step for
complex organic substrate is hydrolysis (Fernandes et al., 2009; Heo et al.,
2003; Izumi et al., 2010; Duong et al., 2011; Miah et al., 2005; Rafique et
al., 2010; Valo et al., 2004) due to the formation of toxic by-products (here,
complex heterocyclic compounds) or nondesirable volatile fatty acids
(VFAs) formed (Lu et al., 2008; Nevers et al., 2006), whereas methano-
genesis is the rate-limiting step for easy biodegradable substrates (Gavala
et al., 2003; Rozzi and Remigi, 2004; Skiadas et al., 2005). The anaerobic
digestion process can be divided into two phases (Fig. 10.6).
This process involves four basic stages. These are hydrolysis, acido-
genesis, acetogenesis and methanogenesis stages.

FIGURE 10.6  Phase separation of the anaerobic digestion system.

306Sonochemistry

10.5.1  HYDROLYSIS STAGE

Most of the waste compounds have nonbiodegradable nature and, there-

fore, it is not possible to treat them directly by microorganisms. Due
to this fact, hydrolysis of these complex and insoluble organics is very
important so that these can be used by bacteria as an energy and nutrient
source. Stabilization of the organic material is not possible during the
process of hydrolysis. In this stage, only transformation of the organic
materials to another structure is there and therefore, these can be used
by microorganisms. This hydrolysis stage is carried out by enzymes
produced and given to the environment by bacteria (Filibeli et al., 2000).
Hydrolysed complex organic materials, carbohydrates, fats and proteins
are fermented to fatty acids, alcohol, carbon dioxide, ammonium, formic
acid and hydrogen.

10.5.2 ACIDOGENESIS

The monomers produced in the hydrolytic phase are then taken up by

different facultative and obligatory an aerobic bacteria and are further
degraded into short-chain organic acids such as acetic acid, butyric acid,
propanoic acid, alcohols, hydrogen and carbon dioxide. In general, simple
sugars, fatty acids and amino acids are converted into organic acids and
alcohols during this phase (Gerardi, 2003).

10.5.3 ACETOGENESIS

The products produced in the acidogenic phase are then consumed as

substrates by the other microorganisms which are active in the third phase,
which is also called the acetogenic phase. Anaerobic oxidation occurs in
this third phase (Aslanzadeh, 2014). Products which cannot be directly
converted to methane by methanogenic bacteria are first converted into
methanogenic substrates, VFAs and alcohols, which in turn are further
oxidized into methanogenic substrates such as acetate, hydrogen and
carbon dioxide. VFAs with carbon chains longer than one unit are oxidized
into acetate and hydrogen(Al Seadi et al., 2008).
Anaerobic Digestion307

10.5.4 METHANOGENESIS

In the methanogenic phase, the production of methane and carbon dioxide

from intermediate products by methanogenic bacteria under strict anaer-
obic conditions occurs. The complete biochemical processes are shown in
Figure 10.7.

FIGURE 10.7  The key process stages of anaerobic digestion

10.6  FACTORS AFFECTING ULTRASONIC TREATMENT

Sludge pretreatment with US causes a bypass of the rate-limiting hydro-

lysis step, which leads to either an increased biogas production with a
reduced sludge quantity or reduced retention times (Onyeche et al., 2002;
Show et al., 2010).There are several factors that influence the effect of
US on anaerobic digestion, including organic loading rate (OLR), sludge
(solid) characteristics, particle size, sonication time, temperature, pH,
specific energy input, operating frequency, sludge retention time, the frac-
tion of the stream and so forth.

10.6.1  ORGANIC LOADING RATE

This factor plays an important role in anaerobic wastewater treatment.

Overloading results in biomass washout in the case of nonattached biomass
reactors, when the hydraulic retention time is relatively long. This, in turn,
308Sonochemistry

leads to process failure. Braguglia et al. (2011) examined the effect of

OLR and the degree of disintegration on anaerobic digestion efficiency
of ultrasonic-treated sludge. They reported that despite low sonication
inputs (5000 kJ·kg−1 total solid [TS]), the digestion process (in a semicon-
tinuous reactor) improved in terms of solid degradation (+ 20.6 %), soluble
chemical oxygen demand (SCOD) removal (90 %) and biogas production
(+ 30 %) depending on the soluble organic load.

10.6.2  SLUDGE (SOLID) CHARACTERISTICS

The sludge characteristics such as type of sludge (primary solids, WAS,

animal manure, etc.) and TS content, have significant effects on ultra-
sonic disintegration. The effect of US pretreatment on pulp and paper mill
sludge solubilization and subsequent anaerobic digestion was investigated
by Saha et al. (2011). Gronroos et al. (2005) reported the maximum SCOD
concentration at the highest dry solid (DS) content. However, they did not
present the data in terms of mg·SCOD·g−1 DS, which made it difficult
to understand whether sludge disintegration was efficient at higher solids
content. Khanal et al. (2006c) conducted an extensive study to evaluate
the effect of TS content on SCOD release at different specific energy
inputs. SCOD release showed an increasing trend with increase in both TS
content and energy input. However, the release in SCOD slowed down at
an energy input of over 35 kW·s·g−1 TS for all TS contents. SCOD releases
were 1.6, 2.2, 2.5 and 3.2 mg·kW·s−1 at TS contents of 1.5, 2.0, 2.5 and
3.0 %, respectively. This corresponds to 38, 59 and 98 % increase in SCOD
release at TS contents of 2.0, 2.5 and 3.0 %, respectively, as compared to
1.5 %. Wang et al. (2005) also reported a significant effect of TS content
on SCOD release. The SCOD release increased from 3966 to 9019 mgL−1,
when the TS content was increased from 0.5 to 1.0 % during 30 min of
sonication at an ultrasonic density of 1.44 W·ml−1. These findings appar-
ently show that a higher TS content is more energy-efficient for ultrasonic
disintegration than the lower one.
The ease of ultrasonic disintegration is also governed by the compo-
sition of the sludge matrix. It is believed that nonbiological solids, for
example, primary sludge and animal manure, are relatively easy to disin-
tegrate as compared to biological sludge such as WAS. The DS content of
the sludge is an important parameter for the disintegration with increased
Anaerobic Digestion309

effectiveness at increased concentration of DS in the WAS (Dewil et al.,

2006a). More DS creates more nuclei for cavitation and, as a result, more
particles were exposed to the resulting shear forces (Lehne et al., 2001).

10.6.3  PARTICLE SIZE

Particle size can affect the rate of anaerobic digestion as it affects the
availability of a substrate (i.e. the surface area) to hydrolyzing enzymes,
and this is particularly true with plant fibres. Fibre degradation and
methane yield improved with decreasing particle size from 100 to 2 mm
(Mshandete et al., 2006). Maceration of manure to reduce the size of
recalcitrant fibres was found to increase the biogas potential by 16 %
as compared with a fibre size of 2 mm, and a 20 % increase in biogas
potential was observed with a fibre size of 0.35 mm; however, no signifi-
cant difference was found with fibre sizes of 5–20 mm (Angelidaki and
Ahring, 2000).

10.6.4  SONICATION TIME

The sonication time has a significant effect on the biogas production and
solids reduction. Wang et al. (1999) observed a significant improvement of
11, 20, 38 and 46 % in VS removal and 12, 31, 64 and 69 % improvement
in methane generation during the anaerobic digestion with 11 days solids
retention time (SRT) of sludge sonicated (200 W, 9 kHz) for 10, 20, 30 and
40 min, respectively. Tiehm et al. (2001) reported a notable enhancement
in VS reduction by 5.6, 27, 46 and 56.7 % during the anaerobic digestion
of sludge sonicated at 41 kHz for 7.5, 30, 60 and 150 min, respectively.

10.6.5 TEMPERATURE

Anaerobic digestion is strongly influenced by temperature and it can

be grouped under one of the following categories (Pol, 1995): psychro-
philic or cryophilic (0–20 °C), mesophilic (20–42 °C) and thermophilic
(42–75 °C). Although a large section of the work deals with mesophilic
operation only. In the mesophilic range, the bacterial activity and growth
310Sonochemistry

decrease by one-half for each 108 °C drop below 358 °C. Thus, for a given
degree of digestion to be attained, lower is the temperature, the longer will
be the digestion time.

10.6.6  pH

Anaerobic reactions are highly pH dependent. The optimal pH range for

methane-producing bacteria is 6.8 ± 7.2 while for acid-forming bacteria,
a more acidic pH is desirable (Mudrak and Kunst, 1986). The pH of an
anaerobic system is typically maintained between methanogenic limits to
prevent the predominance of the acid-forming bacteria, which may cause
accumulation of VFA. It is essential that the reactor contents provide
enough buffer capacity to neutralize any eventual VFA accumulation, thus
preventing build-up of localized acid zones in the digester. In general,
sodium bicarbonate is used for supplementing the alkalinity, since it is the
only chemical, which gently shifts the equilibrium to the desired value
without disturbing the physical and chemical balance of the fragile micro-
bial population.
The SCOD release was found to increase when the sludge was sonicated
at a higher pH (Wang et al., 2005). It is likely that addition of alkali to raise
the pH may have weakened the bacterial cell wall that facilitated better
destruction during ultrasonic treatment. Therefore, alkaline treatment of
sludge followed by ultrasonic application could lower the energy cost of
ultrasonic systems to achieve a desired degree of sludge disintegration.

10.6.7  SPECIFIC ENERGY INPUT

The effect of specific energy input on the sludge solubilization and subse-
quent anaerobic digestion was also examined by several researchers.
Bougrier et al. (2005) observed that biogas generation was 1.48, 1.75,
1.88 and 1.84 times higher during anaerobic digestion (16 days SRT)
of the sludge (2 % TS) sonicated (225 W, 20 kHz) at specific energy of
1355, 2707, 6951 and 14,547 kJ·kg−1 TS, respectively. Donoso-Bravo et
al. (2010) reported a significant improvement of 40 % in biogas genera-
tion at specific energy input of 12,400 kJ·kg−1 TS. However, the specific
energy of up to 2754 kJ·kg−1 did not cause any noteworthy improvement
Anaerobic Digestion311

in sludge disintegration and subsequent biogas production during anaer-

obic digestion. Khanal et al. (2006a) observed that 11.3 % more SCOD
was removed during anaerobic digestion as compared to the untreated
sludge. The ultrasonically pretreated and digested sludge was more stable
biologically. Salsabil et al. (2010) observed a 20 % improvement in total
suspended solids (TSS) removal efficiency for sludge sonicated with a
specific energy input of 200,000 kJ·kg−1 TS. The TSS removal increased
with increasing sludge solubilization.

10.6.8  OPERATING FREQUENCY

Operating frequency is another important parameter that controls the effi-

cacy of ultrasonic systems. This is because operating frequency governs
the critical size of cavitational bubbles (Hua and Hoffmann, 2004). The
cavitational effect is greatly reduced at high frequency range, whereas
lower frequency range generates extremely violent cavitation. Tiehm et al.
(2001) reported that hydrodynamic shear forces produced by ultrasonic
cavitation are primarily responsible for particle disruption. They found
the degree of disintegration based on COD (DDCOD) to be 13.9, 3.6, 3.1
and 1.0 %, respectively, at frequencies of 41, 207, 360 and 1068 kHz and
concluded that a frequency lower than 41 kHz would yield better sludge
disintegration. Sonochemical reactions are particularly predominant at a
higher ultrasonic frequency of 200–1000 kHz (Mark et al., 1998).Thus,
nearly all sludge disintegration tests are conducted at the lower frequency
range of 20 kHz (Khanal et al., 2006a, 2006b).
Several researchers investigated and compared the anaerobic diges-
tion efficiency of the sonicated sludge and control (untreated) sludge at
different SRT. Neis (2000) observed a 30 % higher VS removal in shorter
digestion period of 4 days as compared to the control reactor. The effect
of part stream and full stream sonication on the methane generation and
COD removal efficiency of anaerobic digester was examined by Perez-
Elvira et al. (2010). Pretreating the full stream with US resulted in a higher
biogas generation (+ 41 %) in comparison to pretreatment of a part of the
stream. On the other hand, Kim and Lee (2012) observed a maximum
methane yield, when only 30 and 16 % of the sludge was disintegrated.
They suggested that excess ultrasonic irradiation transforms VSs into inert
312Sonochemistry

or inhibitory compounds, which hamper the methanogenic activity during

anaerobic digestion.
The ultrasonic treatment has been successfully applied to enhance
the anaerobic digestibility of sludge. Laboratory- and pilot-scale studies
showed that the application of sonication with low frequency (20 kHz
waves) and limited specific energy (1000–3000 kJ·kg−1 TS equal to
approximately 20–60 kJ·L−1 of sludge) led to a significant increase in
biogas generation (Dewil et al., 2006b). Thus, higher sludge solubilization
by US pretreatment led to a significant improvement in biogas generation
and solids reduction during the biological digestion of sonicated sludge.
A remarkable improvement in biogas generation (from 24 to 84 %),
solids reduction (from 21 to 57 % as VS) and specific methane genera-
tion (32–104 %) was observed in batch, continuous and semicontinuous
systems. Moreover, higher F/M (food to microorganisms) ratio (10) and
higher percentage of sonicated sludge (full stream sonication) have a posi-
tive effect on biodegradability, biogas generation and solid-removal effi-
ciency of biological digesters.

10.7  APPLICATIONS OF ULTRASOUND

Various applications of US are discussed in the following sections.

10.7.1  TREATMENT OF SEWAGE SLUDGE

Tiehm et al. (1997) reported that US treatment is a suitable method to disin-

tegrate sewage sludge. Due to sludge disintegration, organic compounds
are transferred from the sludge solids into the aqueous phase resulting
in an enhanced biodegradability. In semicontinuously operated fermen-
ters with identical residence times of 22 days, a reduction of VSs (45.8 %
for untreated sludge and 50.3 % for disintegrated sludge) was observed.
Reduction of VSs was about 44.3 % in the fermenter operated with disin-
tegrated sludge and 8 days residence time. In this fermenter, the produc-
tion of biogas was significantly enhanced due to the increased throughput.
According to the concentration of fatty acids, the biogas production and
its composition in the anaerobic systems receiving US treated raw sludge
were stable even at reduced digestion times. Therefore, US pretreatment
Anaerobic Digestion313

of sewage sludge is a promising method to enhance fermentation rates and

to reduce the volume of sludge digesters.
The effect of low-power ultrasonic radiation on anaerobic biodegrad-
ability of sewage sludge was investigated by Liu et al. (2009). Soluble
substances and variation of microbial system of sewage sludge were
subjected to low-power ultrasonic radiation. The well-known hydrome-
chanical shear forces and heating effect of low-frequency US play a major
role in the sludge pretreatment process. It was found that the increase
insoluble substance may partly result from the destruction of microbial
cell by excess ultrasonic pretreatment, but it will inhibit the anaerobic
process. By orthogonal tests, the optimal parameters were found as expo-
sure time 15 min, ultrasonic intensity 0.35 W·cm−2 and ultrasonic power
density of 0.25 W·ml−1. Under these conditions, anaerobic biodegrad-
ability of sewage sludge was increased by 67.6 % and, therefore, it was
concluded that low-power ultrasonic pretreatment is a valid method for
improving anaerobic biodegradability of sewage sludge.
Alkaline and ultrasonic sludge disintegration can be used as the
pretreatment of WAS to promote the subsequent anaerobic or aerobic
digestion. Different combinations of these two methods were investigated
by Jin et al. (2009). The evaluation was done on the basis of the quantity
of SCOD in the pretreated sludge as well as the degradation of organic
matter in the subsequent aerobic digestion. The released COD levels were
higher than those with ultrasonic or alkaline pretreatment alone in case of
WAS samples. NaOH treatment was more efficient than Ca(OH)2 with the
ultrasonic treatment for WAS solubilization. The COD levels released in
various sequential options of combined NaOH and ultrasonic treatments
were in the following order:
Simultaneous treatment >NaOH treatment > ultrasonic treatment
>ultrasonic treatment followed by NaOH treatment.
Low NaOH dosage (100 g·kg−1 DS) for a short duration (30 min) of
NaOH treatment and low ultrasonic specific energy (7500 kJ·kg−1 DS)
were found suitable in simultaneous treatment for sludge disintegration.
The degradation efficiency of organic matter was increased from 38.0 to
50.7 % with combined NaOH and ultrasonic pretreatment with optimal
parameters, which is much higher than that of ultrasonic (42.5 %) or that
of NaOH pretreatment (43.5 %) in the subsequent aerobic digestion at the
same retention time.
314Sonochemistry

Ultrasonication encompasses a comprehensive range of applicability in

sludge treatment via enhancement in sludge solubilization and subsequent
biodegradability, effective degradation of hazardous compounds such as
endocrine-disrupting compounds (EDCs), polycyclic aromatic hydro-
carbons (PAHs), heavy metals, apart from resource recovery (bio-fuels,
enzymes, metals) and stimulating enzymatic activity, thus enhancing the
biodigestion efficiency, sludge minimization by ultrasonication-assisted
lysis–cryptic growth and the extraction of chemical compounds, that is,
organotin compounds (OTC), enzymes, deoxyribonucleic acid (DNA),
PAHs, EDCs, linear alkylbenzenesulphonates (LAS) and EPSs. The higher
specific energy input (> 5000  kJ·kg−1 TS), high-power density/intensity
and longer sonication time were found suitable for sludge disintegration
as evident from particle size reduction, COD solubilization, supernatant
turbidity and morphological changes in the sludge. The quantitative and
qualitative enhancements in products, saving in time, space and equipment
are the paramount reasons for preferring ultrasonication technique over
other conventional methods for sludge disintegration (Tyagi et al., 2014).
Slow degradation of WAS is a disadvantage of anaerobic digestion
leading to high sludge retention time in conventional digesters and, there-
fore, Wonglertarak and Wichitsathian (2014) have investigated the effect
of pretreatment on the performance of anaerobic digestion. Treatment
efficiency was evaluated under both ambient and thermophilic conditions.
They concluded that the biodegradability of WAS was increased by alka-
line pretreatment. The SCOD and biochemical oxygen demand (BOD)
fractions also increased when pH values were increased.
Two cases of anaerobic digestion of sludge were assessed, that is
(i) with pretreatment and (ii) without pretreatment, using mass–energy
balance and the corresponding greenhouse gas (GHG) emissions. VS
degradation of the control sludge and the ultrasonicated secondary sludge
were 51.4 and 60.1 %, respectively, for a digestion period of 30 days (Pilli
et al., 2016). It was observed that the quantity of digestate required for
dewatering, transport and land application was the lowest (20.2 × 106g dry
sludge day−1) for ultrasonicated secondary sludge at 31.4 g TS·L−1 and the
maximum net energy (energy output − energy input) of total dry solids
was 7.89 × 10−6 kW·h·g−1 with energy ratio (output/input) 1.0. As the
sludge solids concentration was increased, GHG emissions were reduced.
Ultrasonication pretreatment has proved to be efficient and beneficial
Anaerobic Digestion315

for enhancing anaerobic digestion efficiency of the secondary sludge as

compared to the primary and mixed sludge.
The effect of combined microwave-ultrasonic pretreatment on the
anaerobic biodegradability of primary, excess activated and mixed sludge
was observed (Yeneneh et al., 2013). All sludge samples were subjected
to microwave treatment at 2450 MHz, 800 W for 3 min followed by
ultrasonic treatment at a density of 0.4 W·ml−1, amplitude 90 %, inten-
sity 150 W and pulse 55/5 for 6 min. Methane production in microwave-
ultrasonic pretreated primary sludge was found to be significantly greater
(11.9 ml·g−1 TCOD) than the methane yield of the untreated primary
sludge (7.9 ml·g−1 TCOD).
Tian et al. (2015) observed the sequential combination of ultrasonica-
tion and ozonation as sewage sludge treatment prior to anaerobic digestion.
They observed synergistic volatile suspended solids (VSS) solubilization
when low-energy ultrasonication (≤ 12 kJ·g−1 TS) was followed by ozona-
tion. Nearly 0.048 g O3g−1 TS ozonation induced the maximum VSS solu-
bilization of 41.3 %, when the sludge was preultrasonicated at 9 kJ·g−1
TS, but the application of same ozone dosage without prior ultrasoni-
cation induced only 21.1 % VSS solubilization. High molecular weight
(MW) components (MW > 500 kDa) were found to be the main solubi-
lization products when sludge was only ozonated. However, solubiliza-
tion products by ozone were mainly in the form of low-MW components
(MW < 27 kDa) on preultrasonication of sludge. The high-MW products
generated by US were effectively degraded in the subsequent ozonation.
Anaerobic biodegradability was found to increase by 34.7 % when ultra-
sonication (9 kJ·g−1 TS) and ozonation (0.036 g O3 g−1 TS) were combined
sequentially. The maximum methane production rate increased from 3.53
to 4.32, 4.21 and 4.54 ml after ultrasonication, ozonation and ultrasonica-
tion–ozonation pretreatments, respectively.
An enhancement in the degradation of micropollutants (pesticides)
absorbed in agro-food industrial sewage sludge was reported during its
disintegration with US treatment (Ibáñez et al., 2015). The US treatment
resulted in a significant reduction in the sludge pesticide content, which
means that about 90 % of the total pesticide mass was removed and, there-
fore, pollutant accumulation in the sludge was prevented. Sono-degra-
dation of three characteristic pesticides (thiabendazole, acetamiprid and
imazalil) revealed the formation of transformation products (TPs). Such
TPs were already reported in earlier studies on the degradation of these
316Sonochemistry

compounds by advanced oxidation processes, which confirmed the partic-

ipation of hydroxyl radical reactions during ultrasonication. Thus, this US
treatment for the excess sludge reduction is efficient for pesticides and the
removal of their TPs.

10.7.2  INDUSTRIAL WASTEWATER

Rajeshwari et al. (2000) reviewed anaerobic digestion for industrial waste-

water treatment (effluents from sugar and distillery, pulp and paper, slaugh-
terhouse and dairy units) and the suitability and the status of development
of anaerobic reactors for the digestion of selected organic effluents. The
presence of biodegradable components in the effluents coupled with the
advantages of anaerobic process over other treatment methods makes it an
attractive option. In the case of slaughterhouse wastewater, an anaerobic
contact reactor can be used without pretreatment whereas for the usage
of high-rate digester such as UASB, a pretreatment step for the removal
of the suspended solids (SSs) and fats is essential just before anaerobic
treatment. Two-phase digestion with pH and temperature control results
in a higher biogas production rate with cheese whey waste water diges-
tion. UASB and fixed-film reactors are more commonly used for distillery
effluent due to their ability to withstand high OLR. An aerobic posttreat-
ment is necessary to attain the permissible COD and BOD level before
discharge. Due to the generation of waste water from various sections of
pulp and paper industry, there are variations in the composition and the
treatability of effluents. Hence, it is preferable to treat the effluents from
each section separately depending on their biodegradability and suitability
to the digestion process rather than treating the combined effluent.
Pulp and paper mill effluent (PPME) is a rich cellulosic material which
was found to have great potential for biohydrogen production through
a photo fermentation process. However, pretreatments were needed for
degrading the complex structure of PPME before biohydrogen production.
The effect of ultrasonication process on PPME was studied as a pretreat-
ment method and on photo fermentative biohydrogen production using
Rhodobacter sphaeroides NCIMB (Hay et al., 2015). They demonstrated
the potential of using ultrasonication as a pretreatment for PPME as the
yield and rate of biohydrogen production were highly enhanced compared
to the raw PPME.
Anaerobic Digestion317

Oz and Uzun (2015) investigated the applicability of low-frequency US

technology to olive mill wastewaters (OMWs) as a pretreatment step prior
to anaerobic batch reactors to improve biogas production and methane
yield. OMWs originating from three phase processes were characterized
to have high organic content and complex in nature. Thus, the treatment of
the wastewater is problematic and alternative treatment options should be
searched. For this, first OMW samples were subjected to US at a frequency
of 20 kHz with applied powers (50–100 W) under temperature-controlled
conditions for different time periods to find out the most effective sonica-
tion conditions. The level of organic matter solubilization at US experi-
ments was calculated as the ratio of SCOD and TCOD.
They revealed that the optimum ultrasonic condition for diluted OMW
is 20 kHz, 0.4 W·m·L−1 for 10 min and its application increased SCOD/
TCOD ratio from 0.59 to 0.79. The US was significantly effective on
diluted OMW (p < 0.05) in terms of SCOD parameters, but not for raw
OMW (p > 0.05). This increase has been found to be limited due to the
high concentration of SSs for raw OMW. Biogas and methane produc-
tion rates of anaerobic batch reactor fed with the US pretreated OMW
samples were compared with the rates obtained with control reactor fed in
case of untreated OMW. The application of low-frequency US to OMW
significantly improved both biogas and methane production in anaerobic
batch reactor fed with the wastewater (p < 0.05). Anaerobic batch reactor
fed with US pretreated diluted OMW produced approximately 20 % more
biogas and methane as compared with the untreated one (control reactor).
They indicated that low-frequency US pretreatment increased soluble
COD in OMW and subsequently biogas production.

10.7.3  ANAEROBIC DIGESTION OF ORGANIC SOLID

WASTES

Nickel (2002) reported that biosolids from agriculture, food production

and wastewater treatment show a great potential as a source of renewable
energy to be transformed by anaerobic processes. Anaerobic degradation
is a slow process and therefore, large fermenters are necessary. The rate-
limiting hydrolysis of VSs is substituted by ultrasonic disintegration so
that a considerable intensification of the anaerobic biogas process takes
place. In case of sewage sludge, the anaerobic digestion time could be
318Sonochemistry

reduced to one-fourth without any noticeable losses in the yield of biogas.

Fermentation times are reduced under US irradiation on one hand and the
anaerobic degradation was enhanced on the other. Thus, US disintegra-
tion has a strong potential to reduce fermentation times and as a result the
volume of anaerobic digesters is minimized.
Fruit and vegetable wastes have low TSs and high VSs and are easily
degraded in an anaerobic digester. The rapid hydrolysis of these feed
stocks leads to acidification of a digester and the consequent inhibition
of methanogenesis. Two-stage reactors effectively use the first stage as a
buffer against the high OLR, which offers some protection to the methano-
gens. Separation of the acidification process from methanogenesis by the
use of sequencing batch reactors has been shown to give higher stability,
a significant increase in biogas production and an improvement in the
effluent quality, when used with fruit and vegetable waste (Bouallagui
et al., 2004).
Biomass is a promising feedstock for anaerobic digestion. Grasses,
including straws from wheat, rice and sorghum, may provide an adequate
supply of biomass, much of which is a waste product of food production.
Harvesting time can also significantly affect the biogas yield of plants, as
demonstrated by Amon et al. (2007a, 2007b). Maize crops were harvested
after 97 days of vegetation at milk ripeness, 122 days of vegetation at wax
ripeness and 151 days of vegetation at full ripeness. The maize varieties
produced 9-37 % more methane at 97 days of vegetation as compared to
151 days.
Bohdziewicz et al.(2005) reported the influence of ultrasonic field on
biodegradation of refractory compounds in leachate and enhancement of
treatment efficiency during anaerobic digestion process. They found that
in the case of leachate ultrasonication for 300 s at the amplitude of 14 m,
the COD removal efficiency was 7 % higher as compared to that in fermen-
tation of nonconditioned wastewater. An increase in a biogas production
was also noted, where a son the 8th day of the process, a specific methane
yield was 22 % higher in comparison to that of nonconditioned leachate.
To enhance the anaerobic digestion of municipal WAS, US, thermal
and US + thermal (combined) pretreatments were conducted using three
US-specific energy inputs (1000, 5000 and 10,000 kJ·kg−1 TSS) and
three thermal pretreatment temperatures (50, 70 and 90 °C) (Dhar et al.,
2012). Combined pretreatments significantly improved VSS reduction by
29–38 %. The largest increase in methane production (30 %) was observed
Anaerobic Digestion319

after 30 min of 90 °C pretreatment followed by 10,000 kJ·kg−1 TSSUS

pretreatment. Combined pretreatments improved the dimethyl sulphide
removal efficiency by 42–72 %. Such a treatment did not show any
improvement in hydrogen sulphide removal, when compared with US and
thermal pretreatments alone. It was also reported that combined pretreat-
ments can reduce operating costs as compared to conventional anaerobic
digestion without pretreatments.
Although anaerobic fermentation is the most applied process for the
stabilization of sewage sludge because of its ability in mass reduction,
methane production and improved dewatering properties of the fermented
sludge, a disadvantage associated with it is the limitation in hydrolysis phase.
As a consequence, it is a slow process. This reduced efficiency of anaerobic
digestion can be significantly enhanced by using US. US pretreatment aims
to convert recalcitrant particulate organics into a soluble, more biodegrad-
able form maximizing anaerobic stabilization and biogas recovery. Some
advantages of US pretreatment of sludge can be summarized as below:

• Low cost and efficient operation compared to other pretreatment

processes
• Complete process automation
• Potential to control filamentous bulking and foaming in the digester
• Better digester stability
• Improved VS destruction
• Better sludge dewatering ability and improved sludge quality

By applying pretreatments, it is possible to accelerate the hydrolysis of

organic matter, thus increasing SCOD and, in many cases, also increasing
methane yield. Thus, the use of ultrasonic process for pollutant degradation
from wastewater and WAS is a promising method to enhance fermentation
rates and to reduce the volume of sludge digesters in order to protect the
environment from pollutants as a key technology for future in the world.

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CHAPTER 11

MEDICAL APPLICATIONS
DIPTI SONI1, SURBHI BENJAMIN2
1
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]
2
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

CONTENTS

11.1 Introduction ����������������������������������������������������������������������������  323

11.2 Applications ����������������������������������������������������������������������������  324
References  �����������������������������������������������������������������������������������������  337

11.1 INTRODUCTION

One of the most significant features of ultrasound is its ability to pene-

trate the human body. Ultrasound finds therapeutic uses, when its high
frequency (~ 5 MHz) is properly employed at low powers.
Basically, therapeutic ultrasound has two major applications; first one
is sonodynamic therapy (SDT). In this medical treatment, a chemotherapy
drug is given to a patient, which first gets accumulated in the cancerous
tissue and is then targeted by the focused ultrasound so that it is activated
inside the affected cells only. In this procedure, sonochemical formation of
activated radicals occurs, which play an important role in initiating chain
peroxidation of lipids present in cell membranes. This ultimately weakens
the cell membrane and helps in cancer treatment.
The second application of therapeutic ultrasound is the high-intensity-
focussed ultrasound (HIFU) which generates a very high concentration of
energy that can be used to kill the tumour cells with sound. This treatment
324Sonochemistry

is mainly used in curing patients suffering from prostrate and soft-tissue

cancers.
Another very common and widely used application of ultrasound is
the ultrasonography (ultrasonic imaging). For this, frequency of 2 MHz
and higher is used. This frequency range with shorter wavelength permits
easy resolution of details of internal structures and cells. The power is kept
less than 1 W cm−2 to prevent cavitation effects and heating in the target
object. This technique of ultrasonic imaging is effective in non-destruc-
tive testing. It is a medical imaging technique employed to study the size
and structure of internal organs, and to obtain tomographic images of the
same. The medical sonography using ultrasound has been widely used as
a diagnostic tool as it is not very expensive and is very easy in application.
While using this technique, care should be taken to use lower powers and
to avoid ionizing radiations so as to protect the tissue against any adverse
heating or pressure effects.
Ultrasound diagnosis is also observed in veterinary medicine. The
ultrasound radiations with desirable frequency are externally and inter-
nally used for evaluation of soft tissue and pregnancy detection in animals.
This technology also finds use in improving animal health, breeding, and
to study the characteristics of unborn calves.
Ultrasound can be used for detection and treatment of pelvic abnor-
malities, muscle and ligament sprains, joint inflammation, rheumatoid
arthritis, osteoarthritis trauma and many more applications.

11.2 APPLICATIONS

Ferrara et al. (2007) reviewed the medical microbubbles and their use
in therapeutic delivery and control. The ultrasonic pulse oscillates these
minute gas bubbles with a wall velocity of the order of tens to hundreds
of metres per second and these can be deflected back to the container wall
or broken into nanoparticles. In the same way, targeted ultrasound can be
used to disrupt blood vessel walls, thus helping in focussed delivery of
drug or gene.
Ishtiaq et al. (2009) reviewed different applications of ultrasound in
pharmaceutics, such as drug dispensation, formulation, drug delivery, and
so forth and its use. They have also discussed the process such as sonopho-
resis, ultrasonic microfeeding and pharmaceutical dosing.
Medical Applications325

Microbubbles have great potential as carriers for different drugs, tiny

molecules, nucleic acids and polypeptides. Tinkov et al. (2009) reviewed
new frontiers of the pharmaceutical science using ultrasound.. The
approach of ultrasound-targeted microbubble destruction for drug delivery
was discussed. Manufacturing and drug-loading microbubbles were also
presented.
Fyfe and Bullock (1985) reviewed the scientific approach for the thera-
peutic use of ultrasound in soft-tissue lesions. Yu et al. (2004) reviewed
the effects of low-power ultrasound on the biological changes induced in
the morphology and functioning of tissues.
Hitchcock and Holland (2010) reviewed ultrasound-activated throm-
bolysis and its use in the treatment of ischemic stroke. In this review, stable
cavitation and clot lysis were analysed. It was concluded that ultrasound-
enhanced stable cavitation helped in recombinant tissue plasminogen acti-
vator thrombolysis. This effect had the potential to lower the morbidity
and death rate of victims of ischemic stroke.
Kremkau (1979) gave a historical review of cancer therapy using ultra-
sound. He presented that there can be three approaches to this aspect and
these are:

• Only ultrasound
• Ultrasound integrated combination with radiotherapy
• Ultrasound in addition to chemotherapy

The mechanism in most cases is absorption heating. The potential of

ultrasound to treat tumours has helped to better understand its actions on
different kinds of malignancies.
Kennedy et al. (2003) reviewed the recent developments made in the
field of HIFU applications. They have discussed the potential of HIFU as
a noninvasive surgical technique in the treatment of tumours of various
internal organs such as liver, kidney, breast, bone, uterus and pancreas and
different other ailments. They suggested that high intensity focussed ultra-
sound (HIFU) is likely to play a major role as surgery of future.
Rosenthal et al. (2004) reviewed sonodynamic therapy (SDT) which
deals with the enhancement of cytotoxic activities of sonosensitizers in the
studies of cells in tumour-bearing animals, as the ultrasound energy can be
directly focussed on malignancy sites present deep in tissues and can be
used to activate a preloaded sonosensitizer. Probable mechanism of SDT
326Sonochemistry

include the formation of radicals derived by sonosensitizer, making the

cell more susceptible to ultrasound-assisted drug transport across the cell
membrane. This is also termed as sonoporation.
Bai et al. (2012) also reviewed the induction of apoptosis of cancer cell
using SDT. They discussed that ultrasound could prevent the prolifera-
tion or initiate the apoptosis of the malignant cells in vitro or in vivo. It
was concluded that low-frequency and low-intensity ultrasound induced
apoptosis.
Naor et al. (2016) reviewed scientific aspects of ultrasonic fields,
with respect to both space and time, and their impact on neuronal
activity. SDT can be defined as the experimental cancer therapy which
employs ultrasound to increase the cytotoxic effects of drugs known as
sonosensitizers.
Haar (1995) reviewed the ultrasound focal beam surgery. In this
surgery, high-intensity beams of ultrasound are focussed at depth within
the body, thereby producing selective damage within the focal volume,
with no harm to overlying or surrounding tissues. This surgery is used in
ophthalmology, urology and oncology.
Harris (2005) discussed instrumentation and techniques, process of
calibration, standardization, rate and the effects of nonlinear propagation
related to use of ultrasound in medicine and biology.
Mason (2011) has reviewed the use of ultrasound in physiotherapy,
surgical instruments, chemotherapy and drug delivery. Certain historical
perspectives of clinical use of ultrasound have been presented in this
chapter.
Pahk et al. (2015) used ultrasonic histotripsy for tissue therapy. Histo-
tripsy is an extracorporeal noninvasive technique. HIFU has been used
for inducing tissue fractionation without causing coagulative necrosis.
The proposed mechanisms for this fractionation are combined effect of
nonlinear wave propagation, explosive bubble generation and ultrasonic
atomization. This work focusses on different types of cavitation activity
for both thermally and mechanically induced lesions. Numerical studies
were also carried out on the bubble dynamics; both ex and in vivo liver
experiments were performed with histological analysis (haematoxylin
and eosin stain). It was concluded that the acoustic emissions produced
during the thermal ablation and the histotripsy exposure could be distin-
guished easily and the suggested cell therapy was a potential replacement
for disordered hepatocytes.
Medical Applications327

Ultrasonic waves have been found to be effective in focussing into

milimetre-scale regions across the human body and brain, and therefore,
have a potential in producing controlled artificial modulation of neuronal
activity.
Ultrasound plays an important role in the delivery of genetic, protein-
aceous and chemotherapeutic drugs. Cavitating microbubbles act as the
mediators by which the energy of pressure waves makes cell membranes
permeable to drug carriers and disrupts the vesicles that carry drugs.
The presence of microbubbles enhances ultrasonic delivery of smaller
chemical agents. Attaching the DNA to the microbubbles or to liposomes
increases the gene uptake. Ultrasonic gene delivery has been investigated
in different tissues such as cardiac, vascular, skeletal muscle, tumour and
fetal tissue. Ultrasonic-enhanced delivery of proteins and hormones helps
in transdermal transport of insulin (Pitt et al., 2004).
Mitragotri (2005) observed that ultrasound facilitates the delivery of
drugs across the skin, enhances gene therapy to focussed tissues, trans-
ports chemotherapeutic drugs into malignant cells and transfers thrombo-
lytic drugs into blood clots in the healing of wounds and fractured bones.
Chemotherapy plays a crucial role in cancer treatment. The main draw-
back of chemotherapy is the adverse side effects of the anticancer agents
and the development of chemoresistance. Yu et al. (2006) discussed that
ultrasound assists chemotherapy by overcoming drug resistance. The
efficiency of various anticancer agents could be enhanced by ultrasonic
exposure either in vitro or in vivo. Ultrasound-assisted chemosensitiza-
tion could be attained by increasing intracellular drug accumulation.
Ultrasound also helps in targeted chemotherapy by transporting anticancer
chemicals directly into the lesions.
Taradaj et al. (2007) observed the effect of the sonotherapy and
compression therapy on the enhancement of healing ulcers after surgical
treatment. They concluded that both these therapies helped in decontami-
nation of the affected area.
Regar et al. (2003) investigated the intracoronary sonotherapy (IST)
and its effect on the coronary vessel. After undergoing angioplasty, IST
was performed using a 5-French catheter with three serial ultrasound
transducers working at 1 MHz. IST was successfully carried on in 36
lesions with success rate of 90 %. IST exposure time per lesion was keptas
718 ± 127 s. It was concluded that IST could be used safely and with acute
procedural success.
328Sonochemistry

The major limitation of stent implantation is intimal hyperplasia and

in-stent restenosis. Fitzgerald et al. (2001) studied the efficiency of intra-
vascular sonotherapy treatment on intimal hyperplasia in a swine stent
model. A total of 48 stented sites underwent sonotherapy using a custom-
built, 8-French catheter intravascular sonotherapy system. Ultrasound
energy of 700 kHz was used for the treatment group for up to 5 min. It was
concluded that intravascular sonotherapy decreased cellular proliferation
and reduced in-stent hyperplasia, thus giving intravascular sonotherapy a
potential to reduce in-stent restenosis.
Sonoelastography is an imaging modality that has been used to recog-
nize tumours of the breast, thyroid and prostate. Both axial strain elastog-
raphy and axial shear strain elastography (ASSE) have shown significant
potentials to differentiate between benign and malignant tumours.
Johnson et al. (2016) evaluated quantitative ultrasound elastography
of benign and malignant musculoskeletal soft-tissue masses. Quantitative
evaluation data showed that shear-wave velocity measurement was repro-
ducible and that malignant masses had slower longitudinal shear-wave
velocities than benign masses. It was concluded that the sample size of
this pilot study formed the basis for larger study designs.
Chaudhry et al. (2016) studied the effect of interstitial fluid pressure (IFP)
on ultrasound axial strain and ASSE. IFP developed a novel contrast mecha-
nism in both the axial strain and ASSE images. This in formation would be
important for a better elucidation of elastographic images of tumours.
Smith (1995) had discussed several applications of ultrasound for
medical treatment, some of which are uterine fibroid ablation, cataract
treatment, surgical removal of tissue and haemostasis, transdermal drug
delivery, healing of bone fracture, physiotherapeutic uses, sonophoresis,
sonoporation, gene therapy, bacterial growth control, dental treatment,
thrombolysis and so forth. All these applications work under specific
dosage or exposure of the ultrasound waves. Low doses can be used for
beneficial effects, whereas high doses cause cell death.
Cancer therapy using HIFU is also very common. Generally, lower
frequency sound waves are used for this purpose. Higher frequency sound
waves were earlier used for cancer treatment but due to their adverse
effects they are not used nowadays. Ultrasound is widely used in the diag-
nosis of certain health conditions, for example elastographyis beneficial in
differentiating healthy tissues from unhealthy tissues. Ultrasound waves
are also used for the detection of abnormalities in different body parts.
Medical Applications329

Misaridis et al. (2005) presented a coded excitation ultrasound imaging

system based on a commercial scanner. It had a coded sequence of 4-MHz
probe employed for the clinical treatment of the coded (excitation and
compression) scheme. The clinical images demonstrated an improvement
in contrast and penetration depth. Both axial and lateral resolutions were
preserved. An improvement of more than 10 dB in the signal-to-noise ratio
of the images was observed with the highest acquisition depth of 15 cm.
Therapeutic ultrasound is different from diagnostic ultrasound as it is
used for the treatment of affected organs. Many developments have been
made for safe application of ultrasound such as advances in transducer
design, determination of acoustic power and so forth. Chemotherapy plays
a very significant role in cancer therapy but there are still some disadvan-
tages mainly due to the adverse effects of the anticancer drugs and growing
resistance to drugs. Therefore, if ultrasound is employed in conjunction
with anticancer agents, it can enhance their efficiency and, thereby, lower
the dose amount required and lead to lesser side effects. It can also assist
in dealing with drug resistance. Yu et al. (2004) and Rosenthal et al. (2004)
also demonstrated that SDT can be given using either conventional low-
range ultrasound or by HIFU. Pitt et al. (2004) found that ultrasound also
enhances intracellular drug accumulation by the process of sonoporation.
As ultrasound has the ability of tissue penetration, this can be used for the
treatment of solid tumours present deep inside the body.
The development of excessive skin is a major side effect of acute
weight loss. The main evidence-based treatment for this problem of
excessive skin is by plastic surgery. Therefore, other treatments need to
be developed. Bjerså et al. (2015) investigated the effects of ultrasound
therapy on excess skin present on the upper arms after underground
bariatric surgery. Fourteen patients were treated for 30 min with active
ultrasound by ­CellsonicTM on one arm. The other arm was considered as
control. The effect was studied by determining the arm volume, circumfer-
ence and ptosis. Majority of patients reported positive experiences and no
side effects were observed. In addition, relief of symptoms related to skin
such as pain, looseness and reduced skin burst were also reported.
Ultrasound is widely used for treating most soft-tissue problems,
mainly lesions of tendon, ligament and bursa. Clinical evidences of ultra-
sound in soft-tissue injuries mainly deal with pain and swelling treatment
but do not have much effect on wound healing. Ultrasound was also used
in the treatment of musculoskeletal pain (Beckermann et al., 1993).
330Sonochemistry

Veronick et al. (2016) studied the effect of low-intensity pulsed ultra-

sound (LIPUS) to help in bone fracture repair and to treat non-union
defects. Ultrasound was also evaluated as a means of generating a trans-
dermal physical force that could initiate osteoblasts that had been encapsu-
lated within collagen hydrogels and led to bony defects. It was also shown
that ultrasound generates a physical force and when applied to hydrogel,
results in their deformation. The effect became intense as ultrasound inten-
sity was increased and hydrogel stiffness was reduced.
Albornoz et al. (2011) carried out in vitro animal studies using LIPUS
leading to osteoinductive effects and observed that it enhanced the healing
process and accelerated the bone strength. LIPUS was found to be more
effective in smokers and diabetic patients.
Voigt et al. (2011) studied the use of low-frequency ultrasound having
range 20–40 kHz as adjunctive therapy for acute wound healing. The
main objective of this study was to find out the effect of low-frequency
ultrasound employed as an adjunctive therapy in complete treatment and
decrease of size of chronic lower limb wounds. They showed that there
was a favourable influence of early healing in patients suffering from
venous stasis and diabetic foot ulcers by the use of both high- and low-
intensity ultrasound.
Bommannan et al. (1992) mainly focussed on:

• Mechanism of sonophoresis
• Pathway of drug permeation in the presence of ultrasound
• Any side effects on skin features and morphology

Electron microscopy was used to follow the permeation of an elec-

tron-dense, colloidal tracer, that is lanthanum hydroxide (LH). Experi-
ments have been carried out on using the hairless guinea pig. Colloidal
LH suspensions were put on different skin locations, which were then
immediately exposed to ultrasound having range at 10–16 MHz, for dura-
tion of 5–20 min. It was observed that LH penetrates the skin through the
stratum corneum (SC) under ultrasound exposure and LH passed through
the epidermis to the upper dermis, even after only 5 min of ultrasound
exposure.
Mitragotri et al. (1995) studied the effect of different ultrasound-related
phenomena, such as cavitation, thermal effects, production of convective
velocities and mechanical effects, in the sonophoresis. It was found that
Medical Applications331

in all the ultrasound-related phenomena, cavitation has the most important

role in transdermal drug delivery under the frequency range 1–3 MHz and
intensity range 0–2 W cm−2. Confocal microscopy demonstrated that cavi-
tation results in the keratinocytes of the SC upon ultrasound irradiation. It
was considered that oscillations of the cavitation bubbles cause disorder
in the SC lipid bilayers, thereby, increasing transdermal transport. This
hypothesis was supported by using skin electrical resistance measure-
ments. It was concluded that sonophoretic efficiency depends directly on
the passive permeant diffusion coefficient, and not on the permeability
coefficient through the skin. Specifically, permeants passively diffuse
through the skin. Seven permeants were used for the study and these were
estradiol, testosterone, progesterone, corticosterone, benzene, butanol and
caffeine.
Transdermal drug delivery has many advantages as compared to oral
drug delivery such as relief from pain and persistent drug release. However,
the use of this technique is restricted to low-skin permeability due to the
presence of SC, which is the outermost layer of the skin. Here, sonopho-
resis comes into scene as it temporarily enhances skin permeability so
that various drugs can be transmitted noninvasively. Different studies of
sonophoresis in transdermal drug delivery have been carried out focusing
on parameter optimization, delivery process, transport route or delivery
of drug including hydrophilic and high-molecular weight compounds.
Depending on different studies, various possible mechanisms of sonopho-
resis have been proposed. For example, cavitation is considered to be the
most significant mechanism for drug delivery in sonophoresis.
Alam et al. (2010) studied the effect of ultrasound as a safe and an
effective technique for facial and neck skin tightening. It was observed
that a single ultrasound treatment of the forehead led to brow height eleva-
tion of slightly < 2 mm. Mild erythema and oedema were observed in most
patients.
Anand and Kaczkowski (2009) studied the noninvasive method of esti-
mating the local in situ acoustic heating rate using the heat transfer equa-
tion. The heating rate is determined by experimentally calculating the time
needed to increase the temperature from a baseline temperature to boiling
temperature. The heat transfer equation is solved to obtain the heating
rate that is a consequence of boiling. The beginning of boiling is noninva-
sively determined by observing the time instant of onset of acoustic emis-
sions in the ultrasonic range due to violent collapse of bubbles. This study
332Sonochemistry

has potential for its applicability in therapy planning and monitoring for
appropriate therapeutic dose optimization.
Burgess et al. (1986) discussed the role of ultrasound in the treatment of
glaucoma using HIFU. They summarized results for 170 patients suffering
with refractory glaucoma and the treatment with HIFU. The results were
studied in terms of the effectiveness of different treatments resulting in
complications and category of the patients based on factors such as age
and etiology.
Transdermal drug delivery has proved to be an efficient alternative to
the conventional drug delivery techniques such as intake and injection.
The SC limits the penetration of substances through the skin and acts as a
barrier, but when ultrasound is applied to the skin the permeability of skin
is improved, which assists in better drug delivery through the skin (Lavon
and Kost, 2004).
Hyperthermia (HT) is widely used in the treatment of cancer and other
benign diseases. Ultrasound technology proves to be advantageous as it
allows efficient control of spatial and dynamic heating compared to other
commonly used heating methods. Some of the advantages of ultrasound
in this aspect are appropriate range of energy penetration in soft tissue
and the capacity to shape the energy deposition methods (Diederich and
Hynynen, 1999).
Farinha et al. (2006) reported ultrasonic skin permeation employing
Sontramedical corporation, Franklin, MA device (SonoPrep) and used it
as a method to reduce skin impedance for electrophysiology analysis. It
was concluded that SonoPrep ultrasonic skin permeation decreased skin
impedance to lower levels.
HIFU can be used for nonsurgical treatment for body contouring by
the process known as liposonix. It destroys adipocytes percutaneously.
Fatemi (2009) studied its efficiency and effectiveness. This technique is
used to transmit energy through the skin surface at a very low intensity,
but it concentrates this energy to the targeted focus in the subcutaneous fat.
(Most important part is that at the epidermis, the intensity of the ultrasonic
energy is so low that it causes no damage.) The targeting of the ultrasound
rays at fixed depth under the epidermis, results in adipose tissue destruc-
tion. As soon as adipocytes are disrupted, chemotadic signals initiate
body’s inflammatory response mechanisms. Macrophage cells reach the
area to digest the lipids and cell debris. This ultimately leads to reduction
in the overall volume of adipocytes. Liposonix has proved to be a safe and
Medical Applications333

beneficial technique for nonsurgical body shaping by decreasing the fat

content.
The influence of exposures varied in terms of intensity and duration
of HIFU on nerve conduction were studied in rats by Foley et al. (2008).
HIFU has proved to be an alternative for other clinical method for initi-
ating nerve conduction block.
Fry et al. (1954) studied production of focal destructive lesions in the
central nervous system with ultrasound.
Gebauer et al. (2005) studied the efficiency of ultrasonic waves in 85
cases with a minimum fracture age of 8 months. The results showed that
the LIPUS can influence healing rates similar to those obtained by surgical
methods with not much risks and complications.
Gelet et al. (2000) discussed the criteria for measuring response of
transrectal HIFU ablation of prostate cancer using progression-free prob-
ability calculations. The results showed that 62 % of the patients did not
report disease progression even after 60 months of transrectal HIFU abla-
tion. Therefore, it was concluded that transrectal HIFU prostate ablation
can be a potential alternative for patients suffering from localized prostatic
adenocarcinoma.
Hundt et al. (2007) evaluated the effect of HIFU on inducing cell
disruption in the case of squamous cell carcinoma. Continuous HIFU and
short-pulse HIFU modes were applied to tumour cells. Major changes were
exhibited in the MR images of the continuous HIFU mode as compared to
the short-pulse HIFU mode. It was observed that tumours exposed to the
continuous HIFU mode showed areas of necrosis, whereas in the short-
pulse HIFU mode, areas of coagulation necrosis were observed. Gene
expression analysis was also carried out. In the continuous HIFU mode,
23 genes were shown to be up regulated and 5 genes were down regulated
where as in the short-pulse HIFU mode, 32 genes were up regulated and
16 genes were found to be down regulated. This study offered a potential
to obtain molecular targets for imaging and therapeutic treatment.
Magnetic resonance imaging (MRI)-guided focussed ultrasound
(MRgFUS) surgery is widely used as a noninvasive thermal ablation tech-
nique that makes use of MRI for target definition, treatment methodology
and closed-loop monitor of energy storage. Altogether, FUS and MRI
as a therapy delivery system help to focus the target and control in real
time. This combination helps in treating targeted tissue without damaging
other healthy tissues. This gives MRgFUS a potential as an alternative
334Sonochemistry

to surgical resection or radiation therapy of cancerous cells in the treat-

ment of uterine fibroids, breast, liver, prostate cancer, brain cancer and
many more. FUS, with or without the use of microbubbles, can alter cell
membrane permeability temporarily and transmit various compounds for
targeted drug delivery (Jolesz, 2009).
Jung et al. (2011) evaluated the complications arising due to HIFU
in patients suffering from hepatic and pancreatic cancer. It was observed
that all patients experienced skin redness, oedema and pain in the exposed
areas. Major complications observed include biliary obstruction, symp-
tomatic pleural effusion, pneumothorax and fistula formation between an
abdominal wall abscess and the ablated hepatic tumour. The complications
were mainly shown around the targeted lesions or along the ultrasound
beam pathway.
Kieran et al. (2007) showed the use of high-intensity pulse-focused
ultrasound for tissue ablation using cavitational mechanisms and that too
without significant thermal effective creation of nonthermal lesions. It
was concluded that further research is required to regulate the parameters
for in vivo cavitational tissue ablation, incorporating the effect of tissue
perfusion.
Kim et al. (2007a) compared the Cyberwand, which is a new intracor-
poreal lithotrite that employs coaxial ultrasonic elements working at two
frequencies with LithoClast Ultra(R), which was considered as the most
efficient commercially available intracorporeal lithotripsy device. An in
vitro model system was used to study the efficiency of stone penetration
for both the devices. It was observed that the mean ± SD penetration time
for the Cyberwand was much shorter than for the LithoClast Ultra(R).
Both the devices had no difficulties with high temperature or occlusion. It
was concluded that the Cyberwand is more efficient lithotrite than Litho-
Clast Ultra(R).
Kinsey et al. (2008) explored the feasibility and efficiency of a multi-
sectoral tubular array transurethral ultrasound applicator. It was used for
prostate thermal therapy of prostrate with potential to facilitate angular
and length control of heating under magnetic resonance guidance without
mechanical moving of the applicator. This multisectoral tubular array
transurethral ultrasound technique showed potential for fast and good
targeting of prostate ailments.
Klingler et al. (2008) showed that HIFU allows targeted homoge-
neous ablation of tissue. The feasibility of HIFU ablation of small renal
Medical Applications335

tumours under laparoscopic monitoring was determined. The histological

study showed irreversible and homogeneous thermal damage within the
exposed site. A few tumours which were treated showed complete ablation
of the entire tumour and a few tumours had a 1- to 3-mm border of viable
tissue just near to the HIFU probe. One tumour also revealed a central area
having 20 % vital tissue. No intra- or postoperative complications were
observed.
Lowe and Knudsen (2009) compared ultrasonic, pneumatic and inte-
grated intracorporeal lithotripsy for percutaneous nephrolithotomy. It was
observed that integrated lithotripters showed superior efficiency compared
to individual ultrasonic and pneumatic lithotripters.
Ultrasound also finds use in liposuction technology (Mann et al., 2008).
HIFU can be used in pulmonary vein isolation (PVI), but certain safety
concerns are needed. Therefore, an esophageal temperature (ET)-guided
safety algorithm was used with HIFU. In this treatment, HIFU was repeat-
edly used until PVI was completed. A touch-up radiofrequency ablation
was applied, when PVI failed. Periprocedural ET control monitoring and
endoscopy were carried out 2 days after ablation. It was concluded that
the safety algorithm failed to prevent lethal complications. HIFU did not
meet the safety standards needed for treatment of atrial fibrillation (Neven
et al., 2010).
Thuroff et al. (2003) studied the use of HIFU for treatment of local-
ized prostate cancer. A phase II/III prospective multicentric clinical trial
was applied to study the safety and efficacy of HIFU. They concluded that
HIFU can be used for the primary treatment of localized prostate cancer.
Tempany et al. (2003) analysed MRI-guided focused ultrasound surgery
for the case of uterine leiomyomas. Periodic sonications were given to nine
targets. Temperature-sensitive phase-difference MRI controlled the target
area and measured rise in tissue temperature. MR images and hysterec-
tomy specimens were studied. MR thermometry was successful in all the
sonication cases. Focal necrotic lesions were observed in all cases at MR.
Drug-delivery vehicles that integrate ultrasonic and molecular targeting
are known to locally concentrate a drug at a specific location. The drug-
delivery vehicles known as acoustically active lipospheres (AALs) are
microbubbles encapsulated by a shell of oil and lipid. Toxicity analysis
demonstrated that paclitaxel-containing AALs showed more antiprolifera-
tive effect after insonation than paclitaxel-free AALsat the same concen-
tration. Ultrasound and molecular targeting are combined to transmit the
336Sonochemistry

drug to the endothelium and interstitium of chorioallantoic membrane

vasculature in vivo (Tartis et al. 2006).
White et al. (2007) studied the transcutaneous delivery of intense ultra-
sound (IUS) energy to focus on the facial superficial musculoaponeurotic
system (SMAS), to develop discrete thermal injury zones (TIZs) in the
SMAS, and showed the relative sparing of nearby nontargeted layers
superficial and deep inside the SMAS layer. The results showed that repro-
ducible TIZs were generated selectively in the SMAS at 7.8 mm depths
and the surrounding tissues and epidermis were spared. Higher-energy
settings and high-density exposures developed a higher degree of tissue
shrinkage. It was concluded that in human cadaveric facial tissue, IUS can
noninvasively produce TIZs of reproducible area, size and dimension in
the SMAS layer.
Mechanical tissue fractionation was achieved using high-intensity
ultrasound pulses in a process known as histotripsy. Histotripsy finds
great potential for noninvasive tissue removal. The primary mechanism
for histotripsy includes cavitation. Xu et al. (2008) studied the evolution
of a cavitating bubble cloud formed by a histotripsy pulse with 10 and 14
cycles at peak negative pressures exceeding 21 MPa. Bubble clouds are
produced inside a gelatin phantom and at a tissue–water interface. The
dynamics of bubble clouds produced by histotripsy was observed.
Kim et al. (2007 b) studied the biomedical applications of super para-
magnetic iron oxide (SPIO) nanoparticles encapsulated within chitosan
using sonochemical method. Microspheres made up of SPIO polyglu-
cosamine (chitosan) were prepared as a novel MRI-detectable material.
The synthesis followed a sonochemical method. The ferrofluid, solu-
tion containing SPIO-embedded chitosan, was sprayed on the surface
of an alkaline solution to prepare SPIO-chitosan microspheres. About
100–150 μm microspheres were injected into the blood vessel, which were
further transmitted to the kidney. These microspheres were detected in MR
images of the kidney.
A one-step ultrasound initiated process starting with the bovine serum
albumin (BSA) and tetracycline was used to encapsulate the drug, usually
an antibiotic, in small spherical particles of BSA. The tetracycline loading
analysis exhibited that the highest tetracycline loading capacity was noted
to be 65 %. The antimicrobial activity of tetracycline encapsulated in BSA
microspheres was shown on two bacterial strains that are reactive to tetra-
cycline (Avivi et al., 2003).
Medical Applications337

Medical ultrasound is a diagnostic imaging technique used to see

internal body parts such as joints, vessels, muscles, tendons and so forth.
This technique also plays a significant role in transmitting drugs to the
targeted body parts without affecting the surrounding cells. Thus, sono-
chemistry is a branch of chemistry, which has a great potential in the
medical field. Hence, it can be concluded that sonochemistry has replaced
traditional methods of treating different kinds of diseases and it is the
widely used technique nowadays. If ultrasound is used by keeping in mind
its harmful effects and taking the measures to avoid them, then it is one of
the best techniques for certain medical applications.

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CHAPTER 12

INDUSTRIAL APPLICATIONS
ANIL KUMAR CHOHADIA1, YASMIN2, NEELAM KUNWAR3
1
Department of Chemistry, M. P. Govt PG College, Chitttorgrh, India
E-mail: [email protected]
2
Department of Chemistry, Techno India NJR Institute of Technology,
Udaipur, India, E-mail: [email protected]
3
Department of Chemistry, PAHER University, Udaipur, India
E-mail: [email protected]

CONTENTS

12.1 Introduction ����������������������������������������������������������������������������  341

12.2 Textile Industries  ��������������������������������������������������������������������  343
12.3 Sugar Industries  ����������������������������������������������������������������������  352
12.4 Pharma Industries   ������������������������������������������������������������������  354
12.5 Extraction ��������������������������������������������������������������������������������  359
12.6 Cleaning ����������������������������������������������������������������������������������  361
12.7 Welding �����������������������������������������������������������������������������������  364
References  �����������������������������������������������������������������������������������������  368

12.1 INTRODUCTION

In recent years, power ultrasound has been used in various industries such as
dyeing, pharma, sugar, leather, extraction and so forth for various purposes
such as desizing, washing, cleaning, bleaching, finishing, scouring, desca-
ling, drug delivery, welding and so on. It is also used in the enzymatic
scouring process, since it increases the mass transfer effect. Ultrasonic
342Sonochemistry

waves travelling in a liquid result in cavitation and thus, produce bubbles.

The bubbles exhibit rich dynamic behaviours such as translation, oscilla-
tion, growth and collapse in response to the varying acoustic pressure (Choi
et al., 2016). Due to the high temperature and pressure inside the bubbles
created by strong ultrasonic waves during strong collapse, water vapour
inside the bubbles is dissociated and chemical products such as ˙OH, ˙O
and ˙H radicals, as well as hydrogen peroxide and ozone molecules are
created inside the bubbles (Yasui et al., 2005). Energy caused by ultrasound
enhances the dispersibility of dyestuffs and auxiliaries and stimulates the
emulsifying ability and solubility of dyestuffs leading to higher homogeni-
zation of the auxiliaries and dyestuffs. Such types of studies on the uses of
ultrasound in the textile industry are quite new. Nowadays, several studies
are available on the use of ultrasound in textile industry (El-Shishtawy et
al., 2003; Merdan et al., 2004; Akalin et al., 2004; Vouters et al., 2004).
Main environmental benefits of using ultrasound are:

• Lower process temperatures (Energy savings)

• Shorter running times (Energy savings)
• Minimization of auxiliary consumption
It has been observed that ultrasonic technology enhances mass transfer
during some textile-processing steps such as desizing, scouring, bleaching,
mercerizing and dyeing of natural fabrics apart from cleaning of materials.
The cleaning action of ultrasonic energy is due to cavitations. There is an
implosion of vapour bubbles inside the cleaning auxiliaries and near the
surface to be cleaned. It produces such a stress on the surface to be cleaned
that the contaminants are destroyed and thus, impurities are removed.
Stable cavitations may also cause the dispersion of the particles of
contaminant removed from the surface. Such an ultrasonic system for the
continuous washing of textiles in liquid layers has been designed. High-
power operation without the interaction of perturbing undesired vibration
modes has shown very good washing behaviour. Attempts have been made
to use acoustic cavitation for washing textiles and ultrasonic cleaning has
been widely used to remove very small contaminant particles adhering to
solid substrates.
Soltani et al. (2015) used a porous clay-like support for immobilizing
ZnO nanostructures (as a sonocatalyst) for the decolourization of methy-
lene blue dye in the aqueous phase. They concluded that the ZnO–biosilica
nanocomposite can be a suitable sonocatalyst for the sonocatalytic
Industrial Applications343

decolourization of coloured solutions with high reusability potential and

cost efficiency.

12.2  TEXTILE INDUSTRIES

Textile applications of ultrasound include a number of processes such as

bleaching open-width fabric, scouring, bast fibre separation, removing
weaving sizes, nonwoven fabric consolidation, preparation for dyeing,
chemical coating, heat treatment and so forth.
Some fundamental processes are affected by ultrasound, which leads to
a better design for the dyeing process in a pilot plant as well as commercial
scale-up applications. The use of ultrasound in dyeing industries may replace
expensive thermal energy and chemicals required for the treatment of waste-
water. It is also likely to improve the quality of dyed fibre; thus, the competi-
tiveness of textile industry is favourably enhanced by the use of ultrasound.
Washing time to wash reactive dyes off of a stationary fabric can also
be reduced by over 60 % by using ultrasound. This saving may be reflected
in increase in the productivity, decrease in water consumption and also in
steam consumption, if the washing is to be done with hot water.
Ultrasound increased diffusion coefficients by 30 % and permeability
coefficients by more than 300 %, thereby enhancing the dye penetration.
The apparent activation energy of dye diffusion was also lowered approx-
imately to its one-fourth, which shows a potential for reducing dyeing
temperatures. Its use also increased the reactivity of fibre-reactive dyes.
Some promising results were also obtained in the dyeing of nylon with
acid dyes, polyester dyed with disperse dyes, and so forth.
Wet processing of textiles requires large quantities of water, and elec-
trical and thermal energy. Majority of these wet processes involve the use
of different chemicals for assisting, accelerating or retarding their rates,
and therefore, these processes must be carried out at higher tempera-
tures to transfer mass from processing liquid medium to the surface of
the textile material and that too in a reasonable time. Similar to all the
other chemical processes, these transport processes are time- as well as
temperature-dependent. However, compromising with these conditions
could adversely affect product quality. Ultrasonics may be utilized to
reduce processing time and energy consumption, and also for maintaining
or improving product quality. An improvement and acceleration of textile
processes using ultrasound has been reported.
344Sonochemistry

Intensity of the waves is found to be greatly affected by the temperature

of the medium. As the temperature of the liquid was kept higher, the effects
of intensity were reduced. the effect of cavitation reaches its maximum at
about 50 °C in water. The effect of cavitation is several hundred times
greater in a heterogeneous system as compared to homogeneous systems.
Applications of ultrasound are related to preparation of auxiliary baths
for processes such as preparation of sizes, emulsions, dye dispersions and
thickeners. Starch solution can be prepared more rapidly and at a lower
temperature in the presence of ultrasound. It was observed that starch-
sizing agents prepared with ultrasound were superior to conventionally
prepared starch solution. Ultrasonic waves are also used to prepare solu-
tions and emulsions of lubricants for fibre that help in reducing interfibre
friction and static electricity.
Oil–water emulsions were prepared using an ultrasound device, which
remained stable for more than 200 h, whereas conventionally prepared
emulsion separated into phases after 12 h only. Ultrasound has also been
used in the preparation of paraffin/styrene emulsions to obtain a homo-
geneous emulsion. It was observed that reduced particle size of 1 μ was
obtained as compared to 3  μ obtained by the conventional method. All
such applications make use of the dispersion effect of ultrasound.
The dispersing action of ultrasound is commonly used for cleaning
purpose on commercial scale in the cleaning of machine parts. Other
examples include needles in knitting machines, spinnerets forming the
chemical fibres, open-end yarn-spinning rotors, and so forth.

12.2.1 DYEING

Reactive dyes are mostly used in dyeing and printing of cotton fibres. Reac-
tive dyes have a specific reactive nature due to the presence of some active
groups. These groups form covalent bonds with –OH groups of cotton either
through substitution and/or addition mechanism. Some conventional eco-
friendly methods for dyeing cotton with reactive dyes are available which do
not require thermal energy and result in high dye fixation, but at least 12 h or
more batching time is required for dye fixation. Khatri et al. (2011) proposed
cold pad-batch dyeing method for dyeing of cotton fabric with reactive dyes
and reduced this time using ultrasonic energy. The dyeing of cotton fibre
was carried out with reactive red-195 and Reactive Black-5 under ultrasonic
Industrial Applications345

radiation. They also showed that such use of ultrasonic energy significantly
reduces not only the batching time and the concentrations of alkalis but also
the colour strength, relative straightening of fibre and dye fixation was also
enhanced with no adverse effect on colour fastness of the dyed fabric.
Both low- and high-frequency ultrasonic waves have been used to study
their effects on the quality of dispersion of dyes, dye absorption by textile
materials and the change in solubility of water-soluble dyes. This disper-
sion had a longer life as compared to conventional stirring. Ultrasound also
affects the quality of dispersions and the particle size of the dispersion.
Kubidus (1962) also reported a change in the solubility of direct dyes
in cold water. An increase in the solubility of two direct dyes, blue-M and
brown-mX, was also observed, on using low-frequency ultrasound, but
there was no change observed in the solubility of direct sky blue dye. The
effectiveness of the treatment was found to depend upon the nature of dyes
and their physicochemical properties, particularly their solubility in water.
Alexander and Meek (1953a, 1953b, 1953c) dyed cotton with direct
dyes, wool with acid dyes, and nylon and acetate with disperse dyes in the
presence of ultrasound at 17.3 kHz. It was concluded that it is more bene-
ficial on hydrophobic fibres dyed with water-insoluble dyes. Ultrasound
was found to be less effective for water-soluble dyes. Quality dyeing was
also obtained with water-soluble systems on a larger scale with ultrasound.
The influence of ultrasound on the dyeing system has been proposed to
show the following three effects:

• Dispersion: This process involves breaking up of micelles and

high-molecular weight aggregates into uniform dispersions in the
dye bath.
• Degassing: This process involves expulsion of gas (dissolved or
entrapped) or air molecules from fibre capillaries and interstices at
the crossover points of fabric into liquid and removal by cavitation,
thus facilitating dye-fibre contact.
• Diffusion: This process involves accelerating the rate of diffusion
of dye inside the fibre by piercing the insulating layer covering the
fibre and accelerating the interaction or chemical reaction, if any,
between dye and fibre.

Ultrasound accelerates the rate of dyeing, increases the colour yield and
also improves quality of the fabric by reducing the warp streaks. Dyeing
346Sonochemistry

of polyester and acetate fibres showed only a marginal increase in colour

yield but substantial increase in rate of dyeing.
Shimizu et al. (1989) dyed amorphous and unoriented nylon 6 films
at 20, 40 and 60 °C temperatures in an ultrasonic field at a frequency of
27 kHz. The absorption of all the dyes was found to increase while activa-
tion energy was decreased with ultrasound. The amount of decrease was
the largest for disperse dyes whereas it was the lowest for fibre-reactive
dyes. It was reported that high temperatures can be avoided during dyeing
synthetic fibres using ultrasound.
Kamel et al. (2009) also reported dyeing of cationized cotton fabric
with Solfix-E using colouring matter extracted from Cochineal dye using
ultrasonic techniques. Babar et al. (2017) presented the dyeing results of
lyocell fabrics dyed with conventional pad-batch and pad-ultrasonic-batch
processes. The dyeing of lyocell fabrics was carried out with two commer-
cial dyes namely Drimarine Blue CL-BR and Remazol Blue RGB. The
dyeing of acrylic fabrics was studied with both conventional and ultra-
sonic techniques using Astrazon Basic Red-5BL by Kamel et al. (2010).
Bamboo is a regenerated cellulose fibre and it is usually dyed with reactive
dyes such as Reactive Black-5 and Reactive Red-147. Batch-wise dyeing
of bamboo cellulose fabric with reactive dyes has been carried out using
ultrasonic energy by Larik et al. (2015).
Ultrasonic preparation of cationic cotton and its application in ultra-
sonic natural dyeing has been reported by Guesmi et al. (2013). Cation-
ization of cotton fabric was carried out under sonication of cellulose with
bromoacetyl bromide, followed by the substitution of the terminal bromo
groups by triethylamine. Ultrasonic energy has also been used in dyeing
polyamide (microfibre)/Lycra fabrics with reactive dyes. The polyamide
(microfibre)/Lycra blends were dyed using conventional and ultrasonic
dyeing techniques with three reactive dyes containing different chromo-
phore and reactive groups by Merdan et al. (2004). Ferrero and Periolatto
(2012) proposed that the ultrasound can be used for dyeing of wool with
acid dye at low temperature. Ultrasound energy was found to accelerate
dye uptake and interaction of fibre with reactive dye on knitted cotton
fabric at low temperatures (Tissera et al., 2016).
Hao et al. (2012) prepared a stable anionic nanoscale pigment suspen-
sion using a polymeric dispersant to colour cationize cotton with the
exhaust method. It was found that nanoscale pigment has higher adsorption
rate on using ultrasonic method, as it promotes the diffusion of pigment
Industrial Applications347

through the fibre–liquid boundary layer. The colour difference reveals

the fact that nanoscale pigment can be deposited on cotton surface more
uniformly under ultrasonic conditions with improved product quality. Sun
et al. (2010) investigated the acceleration efficiency of ultrasound during
dyeing process in an ultrasound cleaner. They showed that the ultrasound
pretreatment could slightly improve the dye exhaustion and fixation. Ben
et al. (2016) also improved the dyeability of modified cotton fabrics by the
natural aqueous extract from red cabbage using ultrasonic energy.
Textile dyeing assisted by ultrasonic energy has gained a significant
interest. Ultrasonic-assisted dyeing of cellulosic fibres has already proved
to be a better choice among conventional dyeing processes.

12.2.2  SCOURING AND BLEACHING

Conventional hydrogen peroxide bleaching process is an important and

a specific step for wet processors in textile industries, but it has certain
problems such as long time and high-energy consumption. On the other
hand, ultrasonic energy can be used as an alternative method in bleaching
(Mistik et al., 2005). Fibre damage was also relatively less when ultra-
sound was used as compared to conventionally scoured wool fibres. An
increase in the bleaching rate and reduction in required time was there in
peroxide bleaching under ultrasonication. The whiteness of the fabric was
also found to be improved over conventionally bleached fabrics. White-
ness was improved over conventionally scoured and bleached flax fibres
during processing of flax fibres—an application of ultrasound.
The scouring of raw wool fibres is a textile chemical processing that
needs a lot of detergents and water due to the presence of high amount
of impurities (Simpson and Crawshaw, 2002). Effluents produced by this
treatment are extremely polluted with chemicals and impurities washed
out from the fibres. Ultrasound washing can effectively remove different
substances from the textile surfaces without using surfactants because of
cavitations occurring at certain parameters of the ultrasound field.
This energy could destroy and remove the pollutants from textile
wastewater on textile surfaces even if additional auxiliaries are not used
(Makino et al., 1983). The synergistic effect between power ultrasound and
enzymes in an enzymatic scouring process has been reported by Agrawal
et al. (2010). They used scouring enzymes such as Fusarium solani pisi
348Sonochemistry

cutinase and pectate lyase. It was observed that ultrasound shortens the
enzymatic scouring process time dramatically. Rositza et al. (2011) worked
on enzyme-assisted ultrasound scouring of raw wool fibres. Kadam et al.
(2013) also analysed the wool scouring using ultrasound irradiation at
intermediate stages and compared it with the wool scoured without ultra-
sonic energy. No cuticle damage was detected on exposing wool fibre to
ultrasound as evident from scanning electron microscopy. Fibre diameter,
single fibre strength and moisture content also did not show any signifi-
cant change after ultrasound irradiation.

12.2.3  WASHING AND CLEANING

Washing of textiles using ultrasound is another process which is well

studied.
The use of ultrasonics for washing fabrics after dyeing and printing
has also been reported. An ultrasonic washing machine can be used to
wash sheets or strands of textiles. It has been reported that the washing of
flax can be improved by ultrasonic vibration. This method also removed
noncellulosic material more effectively than mechanical agitation and
thus, improved whiteness of the flax fibre.
Vigorous physical effects including microjet and micro-streaming
can be induced in heterogeneous systems by acoustic cavitation. Such
a process is useful for the removal of pollutants from contaminated soil
particles. Son et al. (2012) compared diesel removal efficiencies in ultra-
sonic, mechanical and combined soil-washing processes considering the
electrical energy consumptions for these processes. This type of combined
process showed synergistic effects for both removal efficiency and effec-
tive volume, and it also has the advantage of a short operation time as
compared to the sequential processes. Hence, the ultrasonic soil-washing
process with mechanical mixing can be considered a promising technology
for industrial use.
Ultrasound can be applied to washing of textile as a mechanical action
for soil removal. Polyester fabric was soiled with carbon black or oleic
acid as a model contaminant. It was washed with the original fabric in
aqueous solutions with and without alkali or surfactant by applying ultra-
sound, shaking or stirring action. The detergency and soil redeposition
were evaluated from the change in the surface reflectance due to washing
Industrial Applications349

of these artificially soiled fabrics. Ultrasound was found to remove the

particulate and oily soils quiet effectively in a relatively shorter time and at
low bath ratio as compared to shaking and stirring actions with increasing
ultrasound power (Gotoh and Harayama, 2013). It was observed that deter-
gency of both soils increased. It was also shown that ultrasound washing
caused little mechanical damage to the fabric using three standard fabrics.
Wet textile washing processes were set up for wool and cotton fabrics to
evaluate the potential of ultrasound transducers in improving dirt removal.
Textile samples were contaminated with an emulsion of carbon soot in
vegetable oil and aged for 3 h in fan oven. These fabrics were soaked for
3 min in a standard detergent solution before washing and then washed
in a water bath. The removal of dirt was evaluated through colorimetric
measurements. The total colour differences of the samples were measured
with respect to an uncontaminated fabric before and after each washing
cycle. Its percentage variation was calculated and correlated to the dirt
removal (Peila et al., 2015). They showed that the use of ultrasound trans-
ducers enhanced the dirt removal and the temperature is an important
parameter influencing the efficiency of the cleaning process. Much better
results were obtained at a lower process temperature.
The cleaning of wool is both energy- and time-consuming process. It
produces large amounts of waste water with high chemical and biolog-
ical oxygen demand. Cleaning occurs in a number of ways and that too
at different times during the production and use of a wool textile. Most
cleaning processes affect the quality of wool fabric by causing felting
shrinkage, particularly in case of fine wool. Wool cleaning using ultra-
sound provides a method of reducing the ecological and quality impacts.
It is an efficient mass-transfer mechanism that can help us in improving
the removal of contaminant and also in reducing the aggressive movement
of liquor in the cleaning bath; thus entanglement of wool fibres is checked
to a greater extent.
The use of ultrasonic irradiation within a bath containing water, wool
and detergent improves cleaning of wool and that too at lower cleaning
temperatures and with less detergent. The effect of ultrasonic irradiation
on the structure and properties of wool fibres and fabrics has also been
observed.
No adverse effects on colour or fabric tensile strength were reported
on the repeated use of ultrasound. A wool fabric having stains of coffee,
tea, red wine, orange carbonated sugar drink and engine oil can be cleaned
350Sonochemistry

using ultrasound. Colour measurement of the stain before and after cleaning
revealed that dirt can be better released using ultrasound. Both alkaline and
acidic detergents can be used for removing stain of all these types.
A significant benefit to the environment can also be achieved during
wool cleaning by ultrasonic irradiation as it reduces energy inputs and the
amount of detergent required for cleaning. As a result, the level of deter-
gent can be reduced in waste water.
A wool textile needs cleaning at multiple stages during its life cycle .
Raw wool is contaminated by dust, dirt, sweat, food, grease, oils, smells,
body fluids and so forth. These contaminants should be removed before
yarn production.

12.2.4 FINISHING

Finishing of textiles involving ultrasonics has been studied by several

researchers from time to time (Antonescu and Grunichevici, 1979; Kunert,
1979; Dupont and Co, 1984). Scinkivich et al. (1975a, 1975b) studied the
formaldehyde resin treatment of cotton fabric using ultrasound at 8 and
18 kHz frequency and measured the change in physical properties before
and after 60 washing cycles. The crease recovery angle was much higher
even after 60 washings with ultrasound than without ultrasound, but this
treatment resulted in a small decrease in tensile strength. A military fabric
was also treated with a liquid repellent fluorochemical finish in the pres-
ence of high-frequency ultrasonic waves (Last and McAndless, 1981).
This method resulted in an increase in finish add-on.
Dyeing kinetics of nylon-6 fibre with different reactive dyes was
compared using conventional and ultrasonic conditions (El-Shishtawy
et al., 2003) The time/dye uptake isotherms revealed the fact that enhanced
dye uptake takes place in the second phase of dyeing (diffusion phase). The
results fitted well with the integrated form of the first-order rate equation.
Ultrasonic efficiency in accelerating the dyeing rate relative to conven-
tional heating was examined for all dyes and it was found that ultrasonics
are most effective for a dyeing system particularly when it is difficult
to achieve high dye uptake. Time-dependent ultrasonic pretreatment of
nylon-6 fibres was observed to clarify the role of fibre fine structure. It
was observed that the percentage of nylon-6 fibre crystallinity becomes
higher in ultrasonically treated fibre as compared to the conventionally
Industrial Applications351

treated one. Increased crystallinity of the fibre due to ultrasonic dyeing

process would retard uptake of dye, but the enhanced effect of power ultra-
sonic may be high enough to overcome this side effect on the fibre.
Akalin et al. (2004) studied the effects of ultrasonic energy on the
wash fastness of reactive dyes having three different reactive groups. The
samples were applied with three types of washing processes simultane-
ously after dyeing with the traditional method—conventional, ultrasonic
probe and ultrasonic bath. A comparative study was made in these three
processes; three different fixing agents were used in the washing processes.
Different parameters such as colourfastness, staining fastness, magnitude
of total colour difference and lightness difference of the colour values of
dyed samples were measured.
Potential applications of ultrasound exist for finishing of textiles.
Specific applicators of ultrasonic energy were developed, which could
be adapted on jigger, a widespread textile finishing machine (Vouters, et
al., 2004). Their effects on fibre structure were observed and validated by
trials in dynamic conditions.
A facile one-step sonochemical route has been suggested for uniform
deposition of inorganic nanoparticles (NPs) on the surface of solid
substrates, including textiles. The antimicrobial finishing is very important
for medical textiles as decreasing the risk of hospital-acquired infections
are reduced by it. Petkova et al. (2016) reported a simultaneous sono-
chemical/enzymatic process for coating of cotton with zinc oxide (ZnO)
NPs as it produces ready-to-use antibacterial medical textiles in a single
step. A multilayer coating of uniformly dispersed NPs was obtained in this
process. The pretreatment of cotton fabrics with enzymes causes better
adhesion of the ZnO NPs on its surface. It was reported that NPs-coated
cotton fabrics inhibited the growth of Escherichia coli and Staphylococcus
aureus by 100 and 67 %, respectively.
Processing baths containing textile substrates are also affected by
ultrasonic waves. Ultrasonic equipment has been used in preparation
processes, for example desizing, scouring, bleaching, dyeing, finishing
and washing. The objective of using ultrasound is different in all these
processes, that is removing natural material or impurities (soil) from the
surface of the fibre in preparation and washing operations, to transport or
diffuse dyes or chemicals into the fibre in dyeing and finishing processes
as these processes are complex and so forth. In all these processes, the
rates were found to increase by the use of ultrasound; however, it is little
352Sonochemistry

difficult to conclude how ultrasound affects these widely diverse processes

but it is all attributed to cavitation process. The use of ultrasound in textile
wet processing has many advantages including energy savings, process
enhancement and reduced processing times.

12.3  SUGAR INDUSTRIES

Scaling is one of the major problems in evaporators, boilers and heaters

in various industries such as sugar, paper making, chemical fertilizer and
so forth. Industries use lot of liquids, which must be evaporated and this
causes scale formation. Scaling causes economic loss due to low heat-
transfer capacity. These losses were in billions annually in sugar factories
all over the globe. Scaling resulted in an increase in energy requirement
and decrease of production capacity. There was an estimated British
national economic loss of about 0.5 billion pounds in the late 1980s (Qiu
and Yao, 1999).
At present, various chemical, mechanical and physical methods are
commonly used for cleaning the scales. As this scale sticks to the walls
of tubes or vessels very strongly, its removal by an individual method
is not very successful and therefore, quite often, it requires synergistic
methods. Irrespective of the method used, it is important to stop evapora-
tion process. Evaporators tend to become worn and corroded. Different
methods of preventing scale formations have been proposed to solve this
problem, such as deploying some antiscalants, ion exchange and electric
or magnetic fields. Unfortunately, these methods have not been widely
adapted in the sugar industry for various reasons (Qiu and Hu, 2002). Since
ultrasound has been reported to have many effects on compounds in solu-
tion, its influence on scale in evaporators was studied. It has been reported
that ultrasound not only inhibited the formation of scale but also removed
the scaling efficiently. A newer technique with equipment of scale control
was developed and used in a sugar factory.
The transducers are installed on the outside of the bottom of the rect-
angular reaction pipe. The main part is a powerful ultrasonic wave gener-
ator. Its electro-circuit design is also special. Forty-eight transducers were
divided into 4 groups having 12 transducers per group. Each group of
these transducers is controlled by its own integrated circuit with a single
switch. Any group out of these four groups can be chosen to run so that
Industrial Applications353

ultrasonic power can be changed according to the requirement of operation

parameters. All transducers can tolerate high temperatures (95–105 °C)
and protect themselves automatically.
Ultrasonic frequency can be automatically monitored and in that condi-
tion, ultrasonic generator and transducer will run in a good condition for
a long time without much care. The operation of such equipment system
is also easy.
The ultrasonic equipment is normally placed between the juice sedi-
mentation vessel and the evaporator. Scale formation on the heating area
of heat-transfer equipment conforms to the mechanism of mass crystal-
lization. Heterogeneous nucleation provides more nucleation spots on a
clean heating surface because an uneven surface can decrease the surface
energy, which is necessary for nucleation. Adsorption action causes scale
nuclei to form on the uneven surface in the initial stage. The induction
period of nucleation of various scale-forming materials is shortened due to
ultrasonic cavitation; thus, crystal scale nuclei are produced in a relatively
shorter period of time. A large proportion of the nonsugar material (it may
be inorganic or organic impurities) can be deposited onto the nuclei, in
place of the surface of the heating tubes. Such deposits remain suspended
in the sugar solution and flow out of the evaporators with the syrup,
where these can be separated from syrups. Thus, the amount of precipitate
deposited onto the surface of evaporator tube scan can be greatly reduced
(Senapati, 1991; Chepurnoi, 1990; Qiu, 1994; Yao and Qiu, 1999).
Such an investigation was made on scale control by ultrasound in a
sugar factory using five evaporation systems. It was observed that heat
transfer coefficients (HTCs) of the evaporators were low, and deposition
of scale was a very serious problem. Therefore, lots of chemical reagents
were used to clean it, and two evaporators had to be cleaned in turn daily.
Seven parameters were investigated to know more about the perfor-
mance of the ultrasonic technique in the removal of scale. These are:

• HTC of evaporators
• Time to clean scale
• Viscosity of juice/syrup
• Efficiency of removing scale (ERS)
• Evaporation intensity (EI)
• Usage of chemical detergents
• Effects of ultrasound on white sugar
354Sonochemistry

It was found that the EI, HTC and ERS of syrup were improved. Inter-
estingly, the scale with ultrasound was found to be loose, soft and white
in colour (on drying), which could be easily removed by just tapping.
On the other hand, the scale without using ultrasound was dense, hard
and yellowish in colour after drying. This scale could not be removed
completely even using a steel brush. Therefore, the scaling could be
reduced to a significant extent using ultrasound and its physical character
was also changed.
Viscosity is a force between two layers of liquids, and therefore, it is
related to the force among molecular forces of liquid. Like any other sound
wave, ultrasound is transmitted via waves, which alternately compress and
stretch the molecular structure of the syrup while passing through it. As a
result, the average distance between the molecules in the syrup will vary as
the molecules oscillate about their mean position. The molecular distance
will increase, when the acoustic pressure is the pressure on rarefaction.
Otherwise, it decreases on the application of a sufficiently large negative
pressure on the syrup and the distance between the molecules exceeds the
critical molecular distance necessary to hold the liquid intact. As a result,
the syrup liquid breaks down; the inner friction force of molecules in syrup
decreases, resulting into a decrease the viscosity of syrup. A series of
physical and chemical changes are responsible for affecting the viscosity
of syrup during the evaporation process. The syrup was found to be less
viscous, when ultrasound was used.
The products received after the treatment of ultrasound were all within
the desired specifications although the colour, haze and impurity with
ultrasound were a little higher than that without ultrasound.

12.4  PHARMA INDUSTRIES

Chemical effects on the reaction system can be induced by ultrasonic

waves, such as the generation of free radicals, which increase the rate of
reaction. Besides this, ultrasound may have other mechanical effects on the
reaction system, such as increasing the surface area between the reactants
and accelerating dissolution rate. Sonochemistry has several applications
in the pharmaceutical industry including sonocrystallization, sonopho-
resis, lowering extraction time, solution atomization, melt sonocrystal-
lization, crystallization by sonication and particle rounding technology.
Industrial Applications355

Numerous other domains of ultrasound in the pharmaceutical industries

have been explored for future development, for example formation of
aerosols, enhancing inhalation drug delivery, sonochemical preparation
of biomaterials, enhanced drug delivery, drying conducive in polymer-
ization and depolymerization, extraction, chemotherapy, filtration, cell
therapy, homogenization and synthesis. It also has some significance in
transdermal drug delivery, haemotherapy and cell therapy.
The drug engineering has been aimed to alter and improve the primary
and physical properties of drugs such as particle size, shape, crystal habit,
crystal form, density, porosity and so forth, as well as secondary prop-
erties such as flowability, compressibility, compactibility, consolidation,
dust generation and air entrapment during processing. In the pharmaceu-
tical industry, efficient production of small and/or substantially uniform
particles is desired not only due to its impact on the performance during
processing and storage but also due to its impact after consumption by
patients. Micronization of drugs is routinely carried out for increasing
dissolution rate. For inhalation drug-delivery system, the particle size,
shape and surface properties determine its interaction with the container
and amount of dose deposited in lungs, which is generally the desired
site of action (Paradkar and Dhumal, 2011). Application of ultrasound
measurements as process analytical technology (PAT) tools for industrial
crystallization process development of pharmaceutical compounds has
been reported by Helmdach et al. (2015).
Ultrasound is a simple and effective technique for producing drug nano-
crystals. With the use of Barbell Horn Ultrasonic Technology (BHUT), the
process is directly scalable and can be used in the commercial produc-
tion of high-quality nanocrystals, nanoemulsions and liposomes for the
pharmaceutical industry. This technology is also making it possible to
implement laboratory accomplishments in an industrial production envi-
ronment, guaranteeing reproducible and predictable results at any scale.

12.4.1 SONOCRYSTALLIZATION

Crystallization is an omnipresent operation for the manufacture of fine

chemicals, pharmaceuticals or intermediates, whether derived from
chemical or biochemical processing. Nucleation and crystallization can
be mediated by acoustic cavitation and streaming. Sonocrystallization is
356Sonochemistry

mediated by the bubbles caused by such acoustic effects. These bubbles

are transient microreactors that facilitate faster chemical reaction and crys-
tallization. Significant energy is transferred to molecules suspended or in
solution over a very short time. Sonocrystallization is involved in one or
all of the crucial steps in the nucleation and crystallization process. The
sonocrystallization process involves:

• Improved mass transport, which improves clustering and templating

• Rapid cooling after cavitation collapse
• Transient high supersaturation close to the collapsing bubble
• Increase in pressure reducing the temperature for crystallization
• Shock waves to assist in nucleation
• Overcoming energy barriers for nucleation

The widely used explanation is the so-called hot-spot theory, which

attributes nucleation to local hot spots, created by the concentration of
kinetic energy in the collapsing cavity or due to rapid cooling afterwards.
Local temperatures in excess of 5000 K in the gas phase and 2000 K in the
liquid phase have been reported due to these hot spots. Heat dissipation
happens within 2 μm, and hence, cooling rates are of the order of 109 K·s−1.
Another popular mechanism is based on the fact that the pressure shock
wave caused by cavity collapse creates high pressures locally. There are
substances for which the solubility reduces with pressure, increasing local
supersaturation, which could induce nucleation. A hypothesis related to
the shock wave effect states that nucleation is initiated due to segregation
of the solute and solvent near the bubble wall. This is caused by high pres-
sures occurring in the ultimate phase of bubble collapse. There is also an
opinion that nucleation occurs during bubble expansion. Solvent evapo-
rating into the bubble or cooling of the liquid interface layer increases
local supersaturation, which could lead to nucleation around the cavity.
Electrical theory is also of interest which proposes that the consequences
of cavitation are caused by electrical charges on the cavity interface layer
(Fig. 12.1).
Sonocrystallization can be used mundanely for polymorph control,
improving crystal size distribution and morphology, reducing impuri-
ties and superior solid–liquid separation. It can also help in augmenting
secondary nucleation by disrupting crystals or agglomerates. Signifi-
cantly, sonocrystallization is a viable manufacturing option, whether it
Industrial Applications357

FIGURE 12.1  Crystal growth.

is continuous flow mode, batch mode or for in situ generation of seed

crystals. Crystallization of drug actives and intermediates is a ubiquitous
process for the removal of impurities and procuring a suitable solid state
form in readiness for formulation and milling. Generally, it is straight-
forward but quite often it can be a troubling process step. Crystallization
processes include cooling, evaporation, anti-solvent and salt formation
variants and so forth. A key challenge in pharmaceutical active crystalliza-
tion is manufacturing the desired solid form with the desired chemical and
physical properties.
Ruecroft and Collier (2005) studied the sonocrystallization particle
engineering for inhalation and improved respiratory medicines. Ultra-
sound-mediated amorphous to crystalline transition (UMAX) and disper-
sive crystallization with ultrasound (DISCUS) are being developed for the
manufacture of respiratory particles for asthma and chronic obstructive
pulmonary disease (COPD) drug products. The particles have optimal
size, shape, surface rugosity, surface free energy, crystallinity and stability.
UMAX can be used to manufacture combination particles, where two or
more mutually synergistic pharmaceutical ingredients can be processed
into highly crystalline particles. Compounds processed by these method-
ologies include corticosteroids, long-acting beta agonists (LABA), long-
acting muscarinic agents (LAMA) and combinations.
Dhumal et al. (2009) produced fine elongated crystals of salbutamol
sulphate by sonocrystallization for pulmonary delivery and compared
with micronized and spray-dried salbutamol sulphate for in vitro aero-
solization behaviour. Application of ultrasound during anti-solvent
358Sonochemistry

crystallization resulted in fine elongated crystals compared to aggre-

gates of large irregular crystals obtained without sonication. The major
drawback of simvastatin to formulate a dosage form is its poor aqueous
solubility. Therefore, Tripathy et al. (2016) used a solvent and carrier-
less technique (called melt sonocrystallization) and utilized it to form
tiny crystals of simvastatin with enhanced solubility in distilled water.
This technique has also been reported to improve solubility, micromeritic
properties and rheological properties of drugs such as piroxicam (Gupta
et al. 2013). Attempts have been made to control the release of simvas-
tatin by forming hydrogels (Park et al., 2013), porous polymer scaffolds
(Gentile et al., 2016) and by the formation of matrix tablets by using
gums (Mantry et al., 2013).
Melt sonocrystallized curcumin was developed by Khan et al. (2015),
and its therapeutic potential was validated by in vitro cytotoxicity studies
against human oral cancer cell line KB. Manish et al. (2005) also used
melt sonocrystallization technique for ibuprofen agglomerates and char-
acterization of their physicochemical, micromeritic and compressional
properties. By using melt sonocrystallization technique, an improvement
in compressional properties and reduction in sticking was also observed
due to the change in crystal habit.
Integrated drug substance and drug product design for an active phar-
maceutical ingredient using particle engineering has been suggested by
Kougoulos et al. (2011). Particle engineering techniques such as sono-
crystallization, high-shear wet milling and dry impact milling were used to
manufacture samples of an active pharmaceutical ingredient with diverse
particle size and size distributions.
The lack of systematic knowledge of physics underlying the ultra-
sound-assisted compaction of pharmaceutical powders prevented opti-
mizing the processing steps for industrial pharmacy utilization. Many
groups are involved in the application of ultrasound in compaction with
the aim to design a controlled release of a variety of active agents from
prepared systems taking the advantage of the physical changes occurring
during the ultrasound compaction (Motta, 1994; Rodriguez et al., 1998;
Fini et al., 1997; Sancin et al., 1999; Fini et al., 2002a, 2002b; Cavallari
et al., 2005) and the possibility to obtain a direct formation of tablets even
with powders of poor compactibility. Levina et al. (2000a, 2000b, 2002)
found that coherent ibuprofen or paracetamol tablets could be prepared by
ultrasound-assisted compaction at pressures as low as 20–30 MPa. Effect
Industrial Applications359

of ultrasound on the compaction of ibuprofen/isomalt systems has also

been reported by Fini et al. (2009).

12.5 EXTRACTION

Extraction techniques are commonly required before any analytical deter-

mination in samples.
One of the important requirements of most of the extraction tech-
niques is that solvents at high temperature or pressure must be used,
but such operations can be performed with ultrasonic processors at
ambient temperature and normal pressure, and relatively mild chemical
conditions.
Sonication is normally recommended for pretreatment of solid envi-
ronmental samples such as soils, sludges and wastes for the extraction of
nonvolatile and semi-volatile organic compounds. Sonication is consid-
ered as an effective method in comparison with different methods avail-
able for analyte extraction as not much sophisticated instrumentation is
required and solid liquid separations can be easily performed in a short
time using diluted reagents and that too at low temperatures. Most of the
applications of ultrasonic extraction have been carried out for organic
compounds, but ultrasound has also been used for element extraction.
Some examples of solid liquid extraction of some elements using ultra-
sound are given in Table 12.1.

TABLE 12.1  Percentages of Metals Extracted by Sonication.

Sample Element (%) References
Cabbage leave Cd (89), Pb (1) Dobrowolski et al. (1993)
Carbon Cu (69), Cr (2) Miller-Ihli (1993)
Lemon leaves Cd (67), Cu (88), Mn (98) Minami et al. (1996)
Orchard leaves Cd (100), Cu (88), Pb (98) Minami et al. (1996)
Prawns Se (88) Mierzwa et al. (1997)
Spinach Cu (98), Cr (74) Miller-Ihli (1993)
Talc As (59), Cr (61), Ni (74) Mierzwa and Dhindsa (1988)
Tomato leaves Mn (70), Fe (70), Cr (51) Miller-Ihli (1990)
Wheat flour Mn (97), Fe (88) Miller-Ihli (1990)
360Sonochemistry

It was observed that parameters, such as sonication time, vibrational

amplitude of the probe, acid concentration, particle size and solid concen-
tration in the liquid, affect ultrasound-assisted extraction processes.
However, strongly bound analytes should be more difficult to extract,
and hence, require more stringent extraction conditions.
It was observed that extraction efficiency could be increased with ultra-
sound by the addition of glass beads, which promote particle disruption by
focusing the energy released by cavitation and by physical crushing. The
use of a bubbling gas during sonication gives rise to formation of more
H2O2 and hydroxyl radicals (˙OH) and thus, aids to analyte extraction
from oxidizable materials.
Near-field cavitation breaks down cell walls, so that cell contents are
released into the surrounding liquid. Such a method is used to extract
active antigens for making vaccines. Ultrasonic extraction is done with
cooling so that it may cause minimal degradation of active contents.
Perfumes from flowers, essential oils from hops, juices from fruits and
chemicals from plants can be extracted sonochemically. The demand for
natural products from agricultural and marine bioresources is growing
rapidly worldwide. The quality and yield of the extracts of natural prod-
ucts is also improved by ultrasound-assisted extractions. One of the best
uses of ultrasound is in preparing tinctures, which are normally mixtures of
water and ethanol-containing extracts from different medicinal herbs. The
time taken by conventional methods in obtaining a tincture ranges from 1
to 2 weeks, depending on a particular herb. The same or sometimes even
better-quality tincture can be obtained by ultrasonically assisted extrac-
tion in hours instead of days (Vinatoru et al., 1997; Toma et al., 2001;
Vinatoru, 2001). It has also been proved to be successful on industrial
scale in preparing water–alcohol extracts of medicinal herbs. The cavita-
tion bubbles collapse near herb cell walls creating shock waves and liquid
jets in the presence of ultrasound. This causes the cells walls to break
and release their contents into the solvent. This speeds up and improves
the diffusion process, which is very slow under normal solvent extraction
conditions.
The usefulness of ultrasound was also demonstrated in mayonnaise
and ketchup manufacturing (Povey and Mason, 1998). The power of
ultrasound was fully employed to create emulsions in food-processing
processes. Recently, the ultrasonic power has been used to emulsify
normally immiscible liquids and produced a biodiesel from oil seed oils
Industrial Applications361

(Stavarache et al., 2003, 2004; Maeda et al., 2003, 2004). The advantages
of using ultrasound to perform the transesterification of vegetable oils with
methanol or ethanol to give biodiesel are shorter reaction time, reduced
catalyst requirement, lowering of reaction temperatures and so forth.
The extraction conditions for Memecylon edule shoots in order to
achieve the highest polyphenols levels and antioxidant activities were
based on the suitable solvent and duration of sonication (Falleh et al.,
2012). Zou et al. (2011) showed the optimization of ultrasound-assisted
extraction of anthocyanins from Mulberry. Wang et al. (2011) made
use of ultrasound-assisted extraction to extract three dibenzylbutyro-
lactone lignans, including tracheloside, hemislienoside and arctiin from
Hemistepta lyrata.

12.6 CLEANING

Ultrasonic cleaning is an oldest industrial application of power ultrasound.

Here, high-frequency sound waves (above the upper range of human
hearing or about 18 kHz) are utilized to remove a variety of contaminants
from materials immersed in aqueous media. These contaminants can be
dirt, oil, grease, buffing/polishing compounds, mold release agents and
so forth. Materials that can be cleaned by this technique include metals,
glass, ceramics, and so forth. It is powerful enough to remove contami-
nants without damaging the substrate. It provides excellent penetration
and cleaning in the smallest cracks, chasm, cranny and between tightly
spaced parts in a cleaning tank.
Micro-sized bubbles originate and grow in process of cavitation due to
alternating positive and negative pressure waves generated in the solution.
These bubbles subjected to alternating pressure waves continue to grow
till they attain a resonant size., There is a tremendous amount of energy
stored inside the bubble just before its implosion.
Temperature and pressures inside a cavitating bubble are extremely
high and, as a result, implosion occurs near a hard surface, which changes
the bubble in the form of a jet about one-tenth of the bubble size, and it
travels at very high speed up to 400 km·h−1 towards the hard surface. With
the combination of these factors, that is pressure, temperature and velocity,
the jet detaches any contaminants from the substrate. Due to this inher-
ently small size of the jet and relatively large energy, ultrasonic cleaning
362Sonochemistry

process has the capability to reach into small cranny cracks and chasm and
remove any entrapped material (dirt) very efficiently.
Ultrasonic transducers used in the cleaning industry have a frequency
range of 20–80 kHz. Low-frequency transducers create larger bubbles
with more energy and tend to form larger dents, whereas cleaners with
higher frequency will form much smaller dents.
A mechanical vibrating device is required so that positive and nega-
tive pressure waves are produced in the aqueous medium. Manufacturers
of ultrasonic instruments used a diaphragm attached to high-frequency
transducers. These transducers are vibrating at their resonant frequency
because of a high-frequency electronic generator source and induced
amplified vibration of the diaphragm, which is the source of positive and
negative pressure waves propagating through the solution transmitted
through water. Oscillation of stable cavitational bubbles and the resultant
micro-streaming also contribute to cleaning as these pressure waves create
the cavitation processes.
Ultrasonic transducers are mainly of two types:

• Piezoelectric
• Magnetostrictive

Both these types of transducers have same function, but they are
dramatically different in their performance. A ceramic (usually lead
zirconate) crystal is sandwiched between two strips of tin and it creates
a displacement in the crystal on applying the voltage across the strips.
This is called piezoelectric effect. When such transducers are mounted to
a diaphragm on surface such as walls or bottom of a tank, the displacement
in the crystal results in a movement of the diaphragm. Thus, a pressure
wave is generated and it is transmitted through the medium. However,
piezoelectric transducers have several disadvantages as far as industrial
cleaning is concerned.
On the other hand, magnetostrictive transducers are established for
their ruggedness and durability and, as such, these can be used in indus-
trial applications. Zero-space magnetostrictive transducers consist of
nickel laminations which are attached tightly together with an electrical
coil placed over the nickel stack. A magnetic field is created when current
flows through this coil. This is similar to the deformation of a piezoelectric
crystal, when a voltage is applied. When an alternating current is passed
Industrial Applications363

through the magnetostrictive coil, the nickel stack vibrates at the frequency
of the current.
There are some advantages of zero-space magnetostrictive transducers
and these are:

• They are silver brazed for permanent bonding with no damping

effect.
• A consistent performance is provided throughout the life of this unit
and there is no degradation of transducers.
• The high mass of this type of transducers results in high energy, but
less load sensitivity.
• Its thick diaphragm prevents its erosion and wear through.

It is very important to select a solution (or solvent) to be used in ultra-

sonic cleaning. Water is considered as an excellent solvent as it is nontoxic,
nonflammable and also environmental friendly. Ultrasonic cleaning is
better used for relatively hard materials such as metals, ceramics, glass,
plastics, and so forth as these materials reflect the sound rather than
absorbing it. Thus various things such as ball bearings, carburetor parts
and vessels having complex internal cavities can be effectively cleaned.
The layers of maximum cavitational intensity repeat approximately every
1.3–3.8 in. producing quite uniform cleaning throughout. However, the
parts may be moved during exposure for getting more uniformity.
Power density of ultrasonic cleaners is relatively low (usually
< 10  W·in.−2 of the driving area). If an attempt is made to overdrive, these
may be loss of the far field effect, and it causes pronounced cavitation
resulting in wear at the driving surface.
The choice of cleaner frequency is normally decided on the basis of
its application. As cavitational shock intensity is higher at lower frequen-
cies (2.5 kHz), such cleaner will have harsher cleaning ability than with a
higher-frequency cleaner (40 kHz). However, such lower frequencies are
likely to damage some delicate parts, and therefore, 40 kHz cleaners may
be preferred for cleaning of semiconductors and in that case, cleaning is
also simpler and silent.
Standard industrial cleaners typically have power ranging from one
hundred to a couple of thousand watts , depending on capacities of tank.
Although higher kilowatt systems with larger tank capacities are available
for the past few decades, low-power and low-cost cleaners have become
364Sonochemistry

available in the past few years making ultrasonic cleaning readily acces-
sible to restaurants, shops and laboratories.
At present, there seems to be no dramatic breakthroughs in the process
of ultrasonic cleaning; however, tank materials and design can definitely
be further improved to extend the life of ultrasound cleaners and enhance
the cleaning process. Since the process of cavitational choice of optimum
cleaning parameters can be tricky, behaviour depends on nature of solvents
and temperature and thus, further advancement in this area is possible in
years to come.

12.7 WELDING

Some of the welding techniques are discussed in detail in the following

sections.

12.7.1  PLASTIC WELDING

People may come in contact daily with some or the other ultrasonically
welded plastic parts. The process of plastic welding was developed
in the past few years and it was quickly accepted for assembling toys
and different thermoplastic appliances. A big breakthrough came with
discovery of far field welding, so as to make welding of rigid thermoplas-
tics possible and it was later extended beyond welding of plastic films
known at that time.
Ultrasonic welding is a fast and clean process, as it does not require
consumables. It is quite extensively used in the automobile industry for the
assembly of various parts such as taillights, dashboards, heater ducts, in
which plastics have almost replaced the traditional use of glass and metal.
High-frequency vibration produces large amount of heat which melts
the plastic. Ultrasonically induced heat is generated precisely and selec-
tively at the interface of the parts to be joined without indiscriminate
heating of the surrounding material. Therefore, less energy is required for
welding resulting in little distortion and degradation of material. Since the
heat is generated within the plastic and it is not conducted in surrounding
materials, such as tools, ultrasound welding can be accomplished in
completely inaccessible places.
Industrial Applications365

Most of the thermoplastics have the desired characteristics suitable for

ultrasonic welding. This is all due to their ability to transmit and to absorb
vibration, as well as their low thermal conductivity which facilitate local
build-up of heat.
Heating in plastic is a function of ultrasonic stress which varies as the
square of amplitude of this stress. The contact area between the parts to be
joined is reduced, just to maximize the effect stress in the welded region.
The parts are clamped together during welding and are kept there for a
fraction of a second after ultrasonic exposure. This will allow the plastic to
solidify and then they are unclamped. Normally ultrasonic welding takes
less than a second for its completion.
Ultrasonic plastic welding (UPW) requires much higher power densi-
ties (about hundreds of watts per square inch), as compared to ultrasound
cleaning. Plastic welding horns operate at amplitudes at about 10 times
higher than cleaning for such power densities. Very sharp mechanical
resonances are exhibited due to high energy storage. They must accommo-
date a wide variety of loads depending on the application, and mechanical
loading may vary during the welding. In this case, a new class of equip-
ment had to be developed to satisfy these requirements taking ultrasonic
power technology to a new level.
Modern ultrasonic plastic welders normally operate around 20 kHz at
power outputs below 1000 W. They lock automatically on the horn reso-
nance, and hold vibrational amplitude constant for different mechanical
loads. Another improvement is using mechanical amplitude transformers
which facilitate matching of equipment to the load. Ultrasonic exposure is
controlled by accurate electronic timers.
Progress has been made in the past few years in the size of plastic
parts that can be welded ultrasonically, particularly using higher-power
equipment and improvement in ultrasonic horn. Such improvements in
joint design have extended the area of ultrasonic welding to more difficult
plastics and shapes. The development in ultrasonic welding process has
been mainly affected by ultrasonic staking, spot welding and inserting of
metal parts into plastics.
Ultrasonic welding of woven and nonwoven fibres deserve special
consideration. Thermoplastic textiles can be sewn ultrasonically with up to
35 % natural fibre content. The advantages include absence of thread and
its colour-matching problems, execution of several stitches at the same
time and numerous other variations of concurrent cut and seal operations.
366Sonochemistry

UPW is a welding technique, where two phases are present:

• Vibration phase
• Consolidation phase

In the vibration phase, an ultrasonic vibration perpendicular to the

joining interface is applied to heat the thermoplastic by frictional and visco-
elastic heating above its melting temperature. After intermolecular diffu-
sion, it is again cooled down to room temperature under applied pressure
during consolidation phase. This process is completed within 10 s or so.
This heating process of UPW is a combination of interfacial friction
heating and viscoelastic heating (Tolunay et al., 1983; Zhang et al., 2009;
Levy et al., 2012). The frictional heating process for amorphous and semi-
crystalline thermoplastics is through surface asperities which results in a
large proportion of the heating process in the beginning, whereas above the
glass transition temperature, major role is played by viscoelastic heating
(Zhang et al., 2009; Benatar et al., 1989).

12.7.2  METAL WELDING

Commercial equipment for ultrasonic metal welding was available in the

late 1950s. The process of metal welding, known as micro-bonding, was
accepted in the semiconductor industry for welding of miniature conduc-
tors. Development in the design of equipment and the requirement for
better ways of welding of high-conductivity metals has created interest
in the use of ultrasonics for this purpose. Now, equipment is available to
weld even thicker and larger parts, depending on the material and configu-
ration of the part.
Interestingly, ultrasonic metal welding is a relatively cold process.
Although some heating occurs, but this type of metal welding depends
more on cleaning than on melting of the material. Ultrasonic shear causes
abrasion of the surfaces to be joined, breaking contamination including
dispersing oxides. The exposed, plasticized, metal surfaces are brought
together under pressure and solid-state bonding takes place. Ultrasonic
welding resembles spin welding or pressure welding with a major differ-
ence that there is no gross movement of parts or large displacement of
material.
Industrial Applications367

Ultrasonic metal welds require low heat and welding temperatures are
below the melting temperatures of the metals and relative distortion is also
low. It avoids embrittlement and the formation of high-resistance interme-
tallic compounds, when welding dissimilar metals.
As no role is played by electrical conductivity in this process, those
applications that are difficult or almost impossible with resistance welding
can also be successfully done ultrasonically. Worth mentioning examples
are welding of high-conductivity metals (electric grade aluminium and
copper) and also metals of different resistivities (copper and steel). Simi-
larly, welding of parts that are quite different in heat capacities (foil to thick
sections) is much difficult with heat dependent methods but it can be easily
achieved using ultrasound. Another important use is in sealing of liquid
filled containers and packing heat-damageable contents and explosives.
Ultrasonic metal welding has the desirable characteristics of UPW but
it also has more competition from other metal joining methods. Apart from
microbonding, it is mainly found useful in electric and electronic indus-
tries particularly in the assembly of electric motors, transformers, switches
and relays. Replacement of copper by aluminium is associated by ultra-
sonic welding, as there are not many reliable alternate methods for joining
aluminium conductors.
Far field welding is not practical as metal welding requires shear ultra-
sonic motion parallel to the plane of the weld. Therefore, the method is
more suitable for producing spot welds and line welds. Here, continuous
seaming of metal foil and sheet is also possible.
Ultrasonic power densities at the contact with the welding tip are rela-
tively very high and it is in the order of 10,000 W·in−2. High power density
causes tip wear and makes ultrasonic welding almost impractical for
welding of hard metals, which due to requirement for the mutual abrading
ability must not be too different in hardness and therefore, compatibility of
materials also pose a limitation on its use.
Ultrasound finds great use in different industrial processes. Various
industries such as textile, dyeing, leather, food, pharma, and so forth are
employing this technique on a wide scale. Different industrial processes
such as drying, freezing, extraction, and so forth, also use sound waves. The
basic reason for the wide range use of ultrasound in industrial processes is
because of their ability to enhance rate of reaction, product yield, easiness
and feasibility of operation. The use of sonochemistry has proved that it
has a great potential in various industries.
368Sonochemistry

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24–28.
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23(5), 647–664.
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CHAPTER 13

SONOCHEMISTRY: A VERSATILE
APPROACH
RAKSHIT AMETA1
1
Department of Chemistry, J.R.N. Rajasthan Vidyapeeth (Deemed to
be University), Udaipur, India E-mail: [email protected]

Organisms like dolphins and bats use sound waves to develop an unseen
picture of things around them to move around safely. This depends on
the reflection of ultrasound wave and its detection by these animals. This
technique is called echolocation.
Individual particles are held together by some attraction forces, which
may be of physical and chemical nature. These forces include surface
tension in liquids, van der Waal forces, and so forth. These attraction
forces must be increased so as to deagglomerate and disperse fine parti-
cles in liquid media. Such a process is used in different products such as
shampoo, ink, beverages, paints, varnish and other polishing materials.
Ultrasonic cavitation generates higher shear forces that have enough
energy to break down some particle agglomerates into single dispersed
particles. High-intensity ultrasound is found effective for such dispersion
and deagglomerization of powders in liquids.
Emulsions are dispersion of two or more immiscible liquids. Here
also, high-intensity ultrasound power is required to disperse a liquid phase
(dispersive phase) in the form of very small droplets into another phase
(continuous phase). Emulsification is a very important process as it is
used in the preparation of wide range of intermediates as well as final
products such as cosmetic, skin lotion, varnishes, paints, lubricants, fuels,
pharmaceuticals, creams, etc., which are in the form of emulsion either
completely or partially. The cavitation bubbles generate intensive shock
waves on implosion in the liquid in dispersing zone. It forms liquid jets
of high liquid velocity. As a result, microemulsion is obtained with an
average droplet size less than 1 µ.
372Sonochemistry

Fibrous cellulosic materials can be broken into fine particles by ultra-

sonic exposure by processes such as milling and grinding that lead to
breakage of the wall of the cell structure and, therefore, the intracellular
materials such as starch, sugar are released into the liquids. With ultra-
sonic treatment, much more intracellular material will be available to the
enzymes that will convert starch into sugars. Ultrasonic treatment can
also be used for digestion, fermentation and other conversion of organic
matter, where surface area exposed to the enzymes is increased resulting in
enhancement of the rate of these processes accompanied by higher yields.
In this way, the production of ethanol from biomass can be increased. The
process of extraction of proteins by enzymes and other potential bioactive
compounds within the body of plants and seeds by a solvent can be dramat-
ically improved. Ultrasound can also help us in wet milling and micro
grinding of bigger particles, where it has many additional advantages as
compared to other traditional milling techniques, such as ball mills, disc
mills, bead mills and jet mills. Processing volume can be reduced by ultra-
sonication, which allows the processing of high concentration. It is an effi-
cient technique for preparing micro-sized and nanosized materials such as
metal oxide, calcium carbonate and different ceramics.
Conversion of oil into biodiesel through transesterification is also
increased in terms of rate and yield in the presence of ultrasound. Animal
fats can also be used for such conversion. In the ultrasonic method produc-
tion, batch processing is changed to continuous processing making the
process cost-effective. Vegetable oils and animal fats are converted to
biodiesel through base-catalysed transesterification of fatty acids with
methanol or ethanol providing respective methyl and ethyl esters. The
time taken in the processing and separation can be reduced significantly
along with the higher yield of biodiesel (around 99 %) by ultrasonic
radiations.
Degassing is also one of the important applications of ultrasonics,
where it removes smaller suspended gas bubbles from the liquid and the
level of dissolved gas is brought below its natural equilibrium level. It
is also used for the detection of leaks in bottles and cans as immediate
release of CO2 confirms leakage in container filled with carbonated bever-
ages. Cavitation generated by ultrasonic power is used as an eco-friendly
technique to remove dust, soap, oil, grease and so forth. It can also be used
for cleaning of continuous materials such as tubes, wires, cables, tap and
others.
Sonochemistry: A Versatile Approach373

Cheese, milk, ice cream, and so on can be made healthier for human
consumption by using ultrasound. Small bubbles of water can be injected
into the fat so as to reduce the fat content making it better in quality
along with keeping intact the properties of the products and their external
appearances. The processing time is also reduced from minutes to seconds.
Such a method is also used for injecting additives such as menthol, fruits,
berries, etc.
If ultrasound is applied in crystallizer in nucleation stage, it provides
much clear and higher-quality crystal. In addition, the crystals will be of
uniform size. Most probably, convection caused by microjets plays an
important role here.
Grignard reagents are quite useful in organic synthesis. During
conventional preparation of this reagent, one has to use the pure form of
magnesium as well as distilled dry ether; whereas no prior treatment of
magnesium is required and commercial sample of ether can also be used,
if the reaction is carried out in the presence of ultrasound. A strong base
such as lithium diisopropylamide can be obtained using lithium metal by
ultrasonic exposure. This type of preparation is not possible otherwise.
If a reaction is to be carried out in two phases and one reagent is soluble
in one phase while the other is soluble in other phase. In such cases, phase
transfer catalysts are required. These reactions can be carried out even in
the absence of phase transfer catalyst with high yield and reduced time,
provided these reactions are carried out in the presence of ultrasonic
radiations.
Ultrasound radiation creates cavitations or microjets depending on the
environment and these not only help in increasing the rate of reaction and
yield of the products, but also take care of the environment. In the presence
of ultrasound, a new route can be also developed apart from the traditional
pathway. It adds a new dimension in the field of sonochemistry known
as sonochemical switching. Sonochemistry can be utilized in a number
of diverse fields. It is developing as a green chemical technology and is
likely to occupy a prominent position as compared to other eco-friendly
techniques in the years to come.
INDEX

A microbubbles, 302
Rayleigh streaming (Region II), 304
Acetaminophen (AAP), 257
Schlichting streaming (Region III),
Acoustic wave technology (AWT), 254
304–305
Acoustically active lipospheres (AALs),
Anaerobic digestion
335
advantages, 296
Acrylic glass. See poly (methyl methacry-
biological processes, 296
late) (PMMA)
mechanisms of
Active manganese oxide, 231 acetogenesis, 306
wastewater, treatment of, 231 acidogenesis, 306
Adenosine-5′-triphosphate (ATP), 179 basic stages, 305
Advanced oxidation process (AOP), 232 hydrolysis stage, 306
Air-coupled ultrasonics, 283 methanogenesis, 307
Aldol condensation phases, 305, 305f
advantages, 47 methane, formation of, 296
carbon–carbon bonds, 46 sludge hydrolysis, 297–298
chalcones, preparation of, 48 traditional anaerobic digesters, 297
methylene moiety, 47 ultrasonic treatment
Amorphous calcium phosphate (ACP), 179 operating frequency, 311–312
Anaerobic digesters organic loading rate, 307–308
high-rate digester, 300 particle size, 309
anaerobic fluidized-bed reactor, 300 pH, 310
fixed-film digester, 301 sludge (solid) characteristics,
standard-rate digester, 299 308–309
types, 300 sonication time, 309
upflow anaerobic sludge blanket specific energy input, 310–311
reactor, 300–301 temperature, 309–310
mesophilic and thermophilic digestion, ultrasound, applications of
301–302 industrial wastewater, 316–317
standard-rate (cold) digester, 298 organic solid wastes, 317–319
two-stage digester, 301, 302f sewage sludge, treatment of, 312–316
ultrasonic pretreatment waste-activated sludge (WAS), 298
acoustic streaming, 304, 304f Anaerobic fluidized-bed reactor, 300
collapsing bubbles, 302–303 Artificial neural networks (ANNs), 256
Eckart streaming (Region I), 304 Attenuation, 17–18
extracellular matrix biofilm, 303 Audible sound, 10
376Sonochemistry

Axial shear strain elastography (ASSE), methane sulphonic acid, 61

328 Cleaning
Azodicarbonamide (ADC) wastewater, 247 magnetostrictive transducers, 362
mechanical vibrating device, 362
B micro-sized bubbles, 361
Baylis–Hillman reaction, 48–50 piezoelectric effect, 362
Benzoin condensation power density, 363
benzaldehyde, 51 ultrasonic transducers, 362
carbon–carbon bonds, 50 zero-space magnetostrictive transducers,
imidazolium salts, 51–52 363
Biginelli reaction, 52–54 Continuous plug-flow reactors (CPFRs), 41
Bis(indol-3-yl) methane (BIM), 259 Continuous stirred tank reactors (CSTRs),
Blaise reaction, 56–57 41
Bovine serum albumin (BSA), 336 Conventional methods, 116
Bulk waves, 10 Coordination compounds
AgBr nanoparticles, 136
C Al13–Fe and Al13–Fe–Ce polymers,
136
Cannizzaro reaction
anatase TiO2:PPy nanocomposites,
2-aminobenzimidazoles, 57
136–137
phase-transfer catalysts (PTCs), 55, 56
Au(III) reduction, rate of¸ 138
reaction rate, 56
Bi(III) supramolecular compound, 137
Carbon nanotubes (CNTs), 173
Cd(II) coordination polymer, 135
CNT-supported Rh nanoparticles, 174
chromium(VI) and uranium(VI), 133
polymers, 211
Co-B catalysts, 132
surface oxidation, 173
cryptomelane phase, 133
Cavitation
micro-hexagonal rods, 134–135
causes, 18
Mn–ferrite nanoparticles, 133–134, 134f
factors affecting cavitation
modify activated carbon (AC), 133
intensity of sonication, 19
nano-sized lead(II) coordination
pressure and bubbled gas, 20
solvent, 20 polymer, 137
temperature, 19 Pb(II) two-dimensional coordination
ultrasound, frequency of, 19 polymers, 137
Cavitation bubbles, 302 platinum nanoparticles, 135
Cellulose nanocrystals (CNCs), 288 rhodium(I) and iridium(I), 131–132
Ceric ammonium nitrate (CAN), 75 single-crystalline material, 135
Chain-growth polymerization, 198 ZnO nanoparticles, 138
Chemical warfare agent (CWA), 244, 245 Curtius rearrangement, 61–62
Claisen–Schmidt condensation
activated barium hydroxide, 60
D
aromatic aldehyde, 58 Dichlorodiphenyltrichloroethane (DDT),
Cs-doped carbon, 60 254
Cs-Norit carbon, 60 Diels–Alder reaction, 62–63
cycloalkanones, 59 Dimethyl methylphosphonate (DMMP),
cyclopentanone/cyclohexanone, 59 244–245
1,5-diarylpenta-2,4-dien-1-ones, 60 Dodecylbenzenesulphonate (DBS), 260
Index377

E low-intensity ultrasound, 273

meat, 276–277
Eckart streaming (Region I), 304
osmotic dehydration, 273
Electrogenerated chemiluminescence
pasteurization, 271
(ECL), 191
processes
Electromechanical transducers
cleaning, 281–282
magnetostriction, 28f
drying, 278–279
advantages and disadvantages, 29
extraction, 280–281
applications, 29
freezing and crystallization, 279–280
Joule’s effect, 27
product identification, 282–283
magnetic field, 27
rehydration properties, 290
magnetic flux lines, 28
sonic waves, 290
nickel-based alloys, 30
thermophysical properties, 289
Villari effect, 27
ultrasound treatment, 290
piezoelectric
WPI and WPC, 289
energy, transformation of, 30
Formetanate hydrochloride (FMT), 254
history, 30
Fourier Transform Infrared Spectroscopy
materials, 31–34
(FTIR), 205
Emerging technologies, 271
Energy, 9 Frequency dispersion, 12
Engineered nanomaterials (ENMs), 160
Enzyme-linked immunosorbant assay
G
(ELISA), 181 Galton’s whistle, 24, 25f
Extracellular polymeric substances (EPS), Gas-driven transducers, 24–26
303 Glassy carbon electrode (GCE), 186
Extraction, 359–361 Graphene
cyclic voltammetry test, 184
F G-Au, 186
Fixed-film digester, 301 graphene oxide, 186–188
Flavin mononucleotide (FMN), 177 graphite flakes, 184
Flow cell mechanochemical effect, 185, 185f
continuous stirred tank reactors mesographene, 186
(CSTRs), 41 mesographite, 186
immersible, 43 nanomesh, 184, 185f
plug-flow reactors, 42 reduced graphene oxide, 188–189
submersible cleaning systems, 43 sheet, 183, 184f
Fluorine-doped tin oxide (FTO) glass, 170 Graphene nanoribbons (GNRs), 175, 176f
Food industry, 272 Graphene oxide (GO), 186–188
Food technology Graphene oxide nanosheets (GOS), 187
beverages, 274 Guided waves, 10
bread, 275
cheese and tofu, 275–276 H
emulsions, 289 Halloysite nanotubes (HNTs), 209
high-frequency ultrasound, 273 Heck reaction
inactivation aryl bromide, 65
enzymes, 286–288 Pd–biscarbene complex, 64
microorganisms, 283–286 ultrasonic irradiation, 65
378Sonochemistry

Henry reaction, 66–67 ultrasonic transducers, 362

Heterocycles zero-space magnetostrictive trans-
imidazole derivatives, 96–97 ducers, 363
isoxazole derivatives, 98–99 environmental benefits, 342
oxadiazole derivatives, 101–102 extraction, 359–361
oxazole derivatives, 99 pharma industries, 354–359
pyrazole derivatives, 97–98 sugar industries
selenazole derivatives, 100–101 heterogeneous nucleation, 353
tetrazole derivatives, 102–103 scale, removal of, 353
thiadiazole derivatives, 102 scaling, 352, 354
thiazole derivatives, 99–100 transducers, 352–353
triazole derivatives, 101 viscosity, 354
High-intensityfocussed ultrasound (HIFU), textile industries
323–324 dyeing, 344–347
High-resolution transmission electron finishing, 350–352
microscopy (HRTEM), 122 oil–water emulsions, 344
Hydroxyapatite nanoflowers (HAFs), 166, scouring and bleaching, 347–348
167f washing and cleaning, 348–350
Hypersound, 10 washing time, 343
Hyperthermia (HT), 332 wet processes, 343
ultrasonic energy, cleaning action of, 342
I welding
metal welding, 366–367
Ibuprofen, 258 plastic welding, 364–366
Imidazole derivatives, 96–97 Industrial wastewater, 316–317
Inactivation Infrasound, 10
enzymes Insulation ring, 36
apple cubes, 297 Interstitial fluid pressure (IFP), 328
cellulose nanocrystals (CNCs), 288 Intracoronary sonotherapy (IST), 327
free radical production, 286–287 Ionic liquids (ILs), 94–96
high-intensity ultrasound, 286 Isoxazole derivatives, 98–99
manothermosonication, 286, 287
starch solution, viscosity of, 297 J
ultrasound processing, 288
Joule’s effect, 27
ultrasound, advantages of, 287
microorganisms
K
bactericidal effects, 285
high-power ultrasound, 285 Knoevenagel condensation reaction
manosonication, 284 aromatic aldehydes, 69
thermal processing, 285 electron-donating groups, 68, 69
Industrial applications ethyl cyanoacetate, 68
cleaning 2,4-thiazolidinedione and rhodanine, 70
magnetostrictive transducers, 362 US-PTC method, 70
mechanical vibrating device, 362
micro-sized bubbles, 361 L
piezoelectric effect, 362 Lamb waves, 12
power density, 363 Lanthanum hydroxide (LH), 330
Index379

Laurylpyridinium chloride (LPC), 261 liposonix, 332–333

Liposonix, 332 liposuction technology, 335
Liquefied petroleum gas (LPG), 205 low-intensity pulsed ultrasound
Liquid whistle, 26, 26f (LIPUS), 330
Liquid-driven transducers, 26 macrophage cells, 332
Longitudinal waves, 10 magnetic resonance imaging (MRI), 333
Lossen rearrangement, 70–71 mechanical tissue fractionation, 336
Low-intensity pulsed ultrasound (LIPUS), microbubbles, 325
330 noninvasive method, 331
Low-intensity ultrasound (LIU), 82 pharmaceutics, 324
pulmonary vein isolation (PVI), 335
M safe and effective technique, 331
Magnetic fluorescent nanospheres skin permeation, 332
(MFNs), 180 sonodynamic therapy (SDT), 323,
Magnetostrictive transducers 325–326
advantages and disadvantages, 29 sonoelastography, 328
applications, 29 sonosensitizers, 326
Joule’s effect, 27 super paramagnetic iron oxide (SPIO),
magnetic field, 27 336
magnetic flux lines, 28 superficial musculoaponeurotic system
nickel-based alloys, 30 (SMAS), 336
Villari effect, 27 thermal injury zones (TIZs), 336
Mannich reaction transdermal drug delivery, 331, 332
β-amino-carbonyl compound, 71, 74 ultrasound-activated thrombolysis, 325
β-aminoketone derivatives, 73 veterinary medicine, 324
magnetite nanoparticles (MNPs), 72, 73 Metal welding, 366–367
three-component reaction, 73 Michael addition reaction
Medical applications, ultrasound long-chain dicationic ammonium salts,
acoustically active lipospheres (AALs), 76
335 2-pyrrolidinon-3-olates, 78
aspect, 325 p-toluenesulphonamide, 77
axial shear strain elastography (ASSE), sodium hydroxide and PTC, 76
328 ultrasound, use of, 75
bovine serum albumin (BSA), 336 α,β-unsaturated ester, 77
chemotherapy, 327 Micro-bonding, 366
clinical evidences, 329 Mizoroki–Heck reaction. See Heck
Cyberwand, 334 reaction
drug-delivery vehicles, 335 Monocrotophos (MCP), 252
electron microscopy, 330 Monomers, 198
heating rate, 331 Multiwalled carbon nanotubes
high-intensityfocussed ultrasound (MWCNTs), 173, 174, 211
(HIFU), 323–324, 325, 332, 335
histotripsy, 326 N
hyperthermia (HT), 332 N,N′-dimethylformamide (DMF), 203
interstitial fluid pressure (IFP), 328 Nanocubes
intracoronary sonotherapy (IST), 327 Ag/AgCl hybrid, 171
380Sonochemistry

CoSn(OH)6, 171 nanosheets, 177–178

Cu2O, 172 nanospheres, 179–180
SnO2–Co3O4 hybrids, 171–172, 172f nanotubes. see Nanotubes
Nanoflakes, 180–181 nanowires, 181–182
Nanoflowers shapes, 162–163f, 164
CdS, 164 Nanometer, 160
3D Cd(II) coordination polymer, 166 Nanoparticles
HAFs, synthesis of, 166, 167f CdSe, 191
8-hydroxyquinoline aluminum, 165 CNT-supported Rh, 174
Pb(II) coordinated compound, 165, 166, formation of, 160, 161f
167 plate-like hydroxyapatite (HAp), 168,
ZnO nanostructures, 164–165 168f
Nanomaterials silver nanoparticles, 174–175
miscellaneous sonication treatment, 161
CdSe nanoparticles, 191 Nanoporous materials, 182–183
ECL, 191 Nanoribbons
iron pentacarbonyl, 190 graphene nanoribbons (GNRs), 175,
nanoplatelets, 190 176f, 177
OMS-2 material, 190 properties, 176
PbS nanobelt, 191 Nanorods
nanocubes
CeVO4, 167–168
Ag/AgCl hybrid, 171
CuSO4, 170–171
CoSn(OH)6, 171
NiMoO4 nanorods, 170
Cu2O, 172
plate-like hydroxyapatite (HAp)
SnO2–Co3O4 hybrids, 171–172, 172f
nanoparticles, 168, 168f
nanoflakes, 180–181
ZnO nanorods, 170
nanoflowers
ZnO nanostructures, 168–169, 169f
CdS, 164
3D Cd(II) coordination polymer, 166 Nanosheets, 177–178
HAFs, synthesis of, 166, 167f Nanospheres, 179–180
8-hydroxyquinoline aluminum, 165 Nanotubes
Pb(II) coordinated compound, 165, CNTs
166, 167 CNT-supported Rh nanoparticles, 174
ZnO nanostructures, 164–165 surface oxidation, 173
nanoporous materials, 182–183 FeSbO4, 175
nanoribbons iron oxide, 175
graphene nanoribbons (GNRs), 175, MWCNTs
176f, 177 amine-grafted/epoxy-grafted, 174
properties, 176 carboxylate functionalized, surface
nanorods of, 173, 174
CeVO4, 167–168 silver nanoparticles, 174–175
CuSO4, 170–171 TiO2 and TiO2-ZrO2, 174
NiMoO4 nanorods, 170 Nanowires, 181–182
plate-like hydroxyapatite (HAp) Naphthol blue black (NBB), 235
nanoparticles, 168, 168f Naproxen (NPX), 257
ZnO nanorods, 170 Nα-[(9–fluorenylmethyl)oxy]carbonyl
ZnO nanostructures, 168–169, 169f (FMOC), 61
Index381

O thiadiazole derivatives, 102

thiazole derivatives, 99–100
Octahedral molecular sieve (OMS-2), 189,
triazole derivatives, 101
190
ionic liquids (ILs), 94–96
Olive mill wastewaters (OMWs), 317
Knoevenagel condensation reaction
Organic synthesis
aromatic aldehydes, 69
aldol condensation
electron-donating groups, 68, 69
advantages, 47
ethyl cyanoacetate, 68
carbon–carbon bonds, 46
2,4-thiazolidinedione and rhodanine,
chalcones, preparation of, 48
70
methylene moiety, 47 US-PTC method, 70
Baylis–Hillman reaction, 48–50 Lossen rearrangement, 70–71
benzoin condensation Mannich reaction
benzaldehyde, 51 β-amino-carbonyl compound, 71, 74
carbon–carbon bonds, 50 β-aminoketone derivatives, 73
imidazolium salts, 51–52 magnetite nanoparticles (MNPs), 72,
Biginelli reaction, 52–54 73
Blaise reaction, 56–57 three-component reaction, 73
Cannizzaro reaction Michael addition reaction
2-aminobenzimidazoles, 57 long-chain dicationic ammonium
phase-transfer catalysts (PTCs), 55, salts, 76
56 p-toluenesulphonamide, 77
reaction rate, 56 2-pyrrolidinon-3-olates, 78
Claisen–Schmidt condensation sodium hydroxide and PTC, 76
activated barium hydroxide, 60 ultrasound, use of, 75
aromatic aldehyde, 58 α,β-unsaturated ester, 77
Cs-doped carbon, 60 miscellaneous
Cs-Norit carbon, 60 benzothiazoles and benzimidazoles,
cycloalkanones, 59 107
cyclopentanone/cyclohexanone, 59 dibenzothiophene, 105
1,5-diarylpenta-2,4-dien-1-ones, 60 α-enone systems, 106
methane sulphonic acid, 61 homoallylic alcohols, 105
Curtius rearrangement, 61–62 ruthenium-catalysed oxidation, 106
Diels–Alder reaction, 62–63 sonochemical processes, 108
Heck reaction phase-transfer catalysis, 92-93
aryl bromide, 65 pinacol coupling reaction
Pd–biscarbene complex, 64 aromatic aldehydes and ketones, 79,
ultrasonic irradiation, 65 80
Henry reaction, 66–67 ultrasound, effect of, 79
heterocycles Zn–ZnCl2 reagent, 79
imidazole derivatives, 96–97 Reformatsky reaction
isoxazole derivatives, 98–99 benzaldehyde, reaction of, 81
oxadiazole derivatives, 101–102 disadvantages, 80
oxazole derivatives, 99 ethyl iodoacetate, 81
pyrazole derivatives, 97–98 low-intensity ultrasound (LIU), 82
selenazole derivatives, 100–101 zinc-catalysed reaction, 80
tetrazole derivatives, 102–103 sonochemical switching, 103-105
382Sonochemistry

sonogashira coupling, 83-85 P

Strecker synthesis, 85
Paracetamol, 257–258
sugars, 93-94 p-chloronitrobenzene (p-CNB), 230
Suzuki reaction, 85–87 Pectin-coated Fe3O4 magnetic nano-
Ullmann reaction, 87–90 spheres (PCMNs), 180
Vilsmeier–Haack reaction, 90–91 Pentachlorophenol (PCP), 243
Wittig reaction, 91–92 Perchloroethylene (PCE), 241
Organometallic compounds Perfluorooctanoic acid (PFOA), 261
categories, 138 Perfluorosulphonates, 260
heterogeneous sonochemistry Pharma industries
lithium, 148–151 sonocrystallization
magnesium, 151–152 crystallization processes, 357
mercury, 142–145 electrical theory, 356
potassium, 151 hot-spot theory, 356
sodium, 151 melt sonocrystallization technique,
transition metals, 153–154 358
zinc, 145–148 particle engineering techniques, 358
homogeneous sonochemistry process, 356
clustrification, 138–139 drug engineering, 355
ligand substitution, 139–140 drugs, micronization of, 355
secondary sonochemical reactions, Pharmaceutically active compounds
140–141 (PhACs), 257
sonocatalytic reactions, 141 Phase-transfer catalysis (PTC), 92–93
Oxadiazole derivatives, 101–102 Physical modifications, 162
Oxazole derivatives, 99 Piezoelectric effect, 362
Oxidative desulphurization (ODS), 246 Piezoelectric transducers, 32, 32f
energy, transformation of, 30
Oxides
history, 30
activated barium hydroxide, 122
materials
Ag, 119
ceramic, 31
CeO2 nanorods, 122, 122f
dipoles, 33
chromium oxide (Cr2O3), 125
direct effect, 32
CoAl2O4, 123–124 disks, 33
copper oxide nanoparticles, 120–121 frequency, 34
1,5-diarylpenta-2,4-dien-1-ones, inverse effect, 32
122–123 ions, 31
facile and surfactant-free method, 123 polymers, 31–32
Fe3O4 nanoparticles, 119 quartz, 32–33
HRTEM, 122, 122f unit cell, 31
LiCoO2 compound, 123 Pinacol coupling reaction
manganese dioxide, 124, 125, 125f aromatic aldehydes and ketones, 79, 80
mesoporous TiO2, 118, 119 ultrasound, effect of, 79
single-step sonochemical synthesis, 121 Zn–ZnCl2 reagent, 79
titanium isopropoxide (TIP), 118 Plastic welding
vanadium pentoxide, 123 consolidation phase, 366
ZnO, 119–120 heat, 364, 365
Index383

phases, 366 electrical properties of, 200

vibration phase, 366 Fe3O4, 201
woven and nonwoven fibres, 365 isopropyl alcohol, 202
Plate waves, 12 nanocomposites, 203
Poly (methyl methacrylate) (PMMA) nano-EB, 201
anionic surfactant and monomer concen- nanosticks, 202
tration, 207 silver wire, 201–202
HBC10 concentration, 208–209 sonochemical synthesis, 200–201
HNTs, 209 Y2O3 and IL, 201
homopolymerization of, 207 ZM nanoparticles, 203
oxygen flow rate, 208 polymer–semiconductor devices, 214
Polyaniline (PANI) polymer surface, 213–214
electrical properties of, 200 poly (methyl methacrylate) (PMMA)
Fe3O4, 201 anionic surfactant and monomer
isopropyl alcohol, 202 concentration, 207
nanocomposites, 203 HBC10 concentration, 208–209
nano-EB, 201 HNTs, 209
nanosticks, 202 homopolymerization of, 207
silver wire, 201–202 oxygen flow rate, 208
sonochemical synthesis, 200–201 polypyrrole (PPy)
Y2O3 and IL, 201 emulsion polymerization, 204
ZM nanoparticles, 203 Fe3O4 nanoparticles, 204
Polyaromatic hydrocarbons (PAHs), 238, LPG sensor, 206
239 sensing performance, 204–205
Polyethylene glycol (PEG), 175 TiO2:PPy, 205
Polymers ZnO nanoparticles, 205, 206f
carbon nanotubes, composites of, 211 polythiophenes (PTP), 206–207
categories, 198 polyurethane (PU), 209–210
chain-growth polymerization, 198 polyvinyl alcohol (PVA), 210–211
coordination polymers, 212–213 step-growth polymerization, 198
degradation, 200 thin film-based photo anodes, 214
high-intensity ultrasonic wave, 218 ultrasound irradiation, 199
macromolecular radicals, 216–217 Polypyrrole (PPy)
methyl cellulose, 219 emulsion polymerization, 204
methyl orange (MO), 219, 220f Fe3O4 nanoparticles, 204
molecular weight, 216 LPG sensor, 206
poly(vinyl acetate), 216 sensing performance, 204–205
polyvinyl alcohol (PVA), 217–218 TiO2:PPy, 205
poly(vinyl pyrrolidone), 217 ZnO nanoparticles, 205, 206f
rate of, 218–219 Polythiophenes (PTP), 206–207
ultrasonic degradation, 216 Polyurethane (PU), 209–210
ultrasonic irradiation, 219 Polyvinyl alcohol (PVA), 117–118,
use of, 220 210–211
monomers, 198 Primary sonochemistry, 162
organic polymers, 199 Pulmonary vein isolation (PVI), 335
oxide films, 215 Pulp and paper mill effluent (PPME), 316
polyaniline (PANI) Pyrazole derivatives, 97–98
384Sonochemistry

R p-chlorobenzoic acid (p-CBA),

242–243
Rayleigh streaming (Region II), 304
p-chlorophenol, 242
Rayleigh wave, 12
pentachlorophenol (PCP), 243
Reduced graphene oxide (rGO), 177,
perchloroethylene, 241
188–189
TCE, 239
Reformatsky reaction
2,4,6-trichlorophenol, 240
benzaldehyde, reaction of, 81
dyes
disadvantages, 80
acid blue 25 (AB-25), 236–237
ethyl iodoacetate, 81
azo dyes, 234
low-intensity ultrasound (LIU), 82
basic violet 16 (BV 16), 235
zinc-catalysed reaction, 80
crystal violet (CV), 235–236
Rod waves, 12
eosin Y and rhodamine B, 236
naphthol blue black (NBB), 235
S
reactive blue 19 dye (RB 19), 237
Schlichting streaming (Region III), reactive yellow 145 (RY 145), 236
304–305 rhodamine B, 237
Screen-printed carbon electrodes (SPCEs), textile dyes, 234
184 hydrocarbons, 237–239
Secondary sonochemistry, 162 miscellaneous, 261–263
Selenazole derivatives, 100–101 nitrogen-containing compounds
Shear waves, 10 azodicarbonamide (ADC), 247
Sidewall acoustic insulator. See Insulation 2-butyl-4,6-dinitrophenol, 247–248
ring 4-chloro-2-nitrophenol (4C2NP), 248
Single-crystal ultrasonic transducer H2O2 oxidant, 248
acoustic couplant, 38 p-nitrophenol (PNP), 247
backing block, 36 pyridine, 246–247
electric connectors, 37 pesticides
electrical shield, 37 acoustic wave technology (AWT), 254
insulation ring, 36 acoustical processor reactor, 253
matching layers, 37–38 aeroxide P25, 254
piezoelectric crystal, 35 alachlor, 253
tuning coil, 36 azinphos-methyl and chlorpyrifos, 253
wear plate, 38–39 carbaryl (1-naphthyl-N-methyl carba-
Soluble chemical oxygen demand (SCOD), mate), 254
313, 314 diazinon and malathion, 252
Sonic waves, 15 dichlorodiphenyltrichloroethane
Sonochemical switching, 103–105 (DDT), 254
Sonochemical wastewater treatment diuron, 255
chloro compounds formetanate hydrochloride (FMT), 254
CCl4, 240 fresh water pollution, 252
chlorobenzene (ClBz), 242 monocrotophos (MCP), 252–253
2-chloro-5-methylphenol (2C5MP), organophosphate, 252, 253
240–241 pharmacological drugs
degradation products, 240 acetaminophen (AAP), 257
2,4-dichlorophenol (2,4-DCP), antipyrine, 256–257
241–242 artificial neural networks (ANNs), 256
Index385

atenolol, 256 cavity collapse, 4

bis(indol-3-yl) methane (BIM), 259 chemical reactions, 4
carbamazepine (CBZ), 256 nanomaterials, 5
cephalexin, 257 polymers, 5
cetirizine dihydrochloride, 259 ultrasonic horn, 4
17α-ethinylestradiol (EE2), 256 homogeneous, 3
17β-estradiol (E2), 256 organisms, 371
fluoxetine (FLX), 258 ultrasound
Ibuprofen, 258 applications, 2
naproxen (NPX), 257 concept of, 1
paracetamol, 257–258 liquid molecules, 2–3
PhACs, 257 medical field, 2
sonoelectrolysis, 259 sonochemical switching, 373
tinidazole (TNZ), 258 Sonodynamic therapy (SDT), 323
phenols Sonogashira coupling, 83–85
catalytic wet air oxidation, 250 Sonoluminescence, 16
dispersed nano-metallic particles Sonolysis, 9
(NMPs), 250 Sonosensitizers, 326
Fenton’s reagent, 250 Sound navigation and ranging (SONAR), 1
hydrogen peroxide and copper Sound
sulphate, 251 categories, 10
major hazard, 249 energy, transmission of, 9
nonylphenol, 251–252 Stable cavitation, 12
peracetic acid and heterogeneous Step-growth polymerization, 198
catalyst, 251 Strecker synthesis, 85
ZnO-immobilized horseradish peroxi- Sugar industries
dase (HRP), 250 heterogeneous nucleation, 353
sulphur-containing compounds scale, removal of, 353
chemical warfare agent (CWA), 244, scaling, 352, 354
245 transducers, 352–353
crude oil, 244 viscosity, 354
dimethyl methylphosphonate Sugars, 93–94
(DMMP), 244–245 Sulphides
hydrodesulphurization process, 244 Bi2S3 nanorods, 129
oxidative desulphurization (ODS), CuInS2 (CIS) nanoparticles, 129
246 InCl3, sonication of, 129
ultrasound-assisted oxidative desul- MoS2, 126–127, 126–127f
phurization process (UAOD), 246 PbS hollow nanospheres, 127–128, 128f
surfactants, 259–261 Sb2S3 nanorods, 131
Sonochemistry single-crystalline Sb2S3 nanorods,
cavitational phenomenon, 3 synthesis of, 128–129, 128f
crystallizer, 373 WS2 nanorods, 129–130
degassing, 372 zinc sulfide–silica (ZSS), 130–131
emulsions, 371 ZnS/PS microspheres, 130
fibrous cellulosic materials, 372 Super paramagnetic iron oxide (SPIO), 336
high-frequency sound, 2 Superficial musculoaponeurotic system
heterogeneous (SMAS), 336
386Sonochemistry

Surface acoustic waves (SAWs), 11–12, 87 piezoelectric crystal, 35

Suzuki reaction, 85–87 tuning coil, 36
wear plate, 38–39
T ultrasonic, 24
Tetrabutylammonium fluoride (TBAF), 96 Transient cavitation, 12
Tetrazole derivatives, 102–103 Transmission electron microscopy (TEM),
Textile industries 208
dyeing Triazole derivatives, 101
cotton fibre, 344, 346 Trichloroethylene (TCE), 239
low- and high-frequency ultrasonic Tube reactor, 44
waves, 345 Tuning coil, 36
dispersion, 345
degassing, 345 U
diffusion, 345 Ullmann reaction, 87–90
lyocell fabrics, 346 Ultrasonic cleaning bath, 39–40, 39f
bamboo cellulose fabric Ultrasonic plastic welding (UPW), 365
finishing Ultrasonic probe
antimicrobial finishing, 351 direct sonication, 40
nylon-6 fibre, 350 indirect sonication, 40–41
oil–water emulsions, 344 Ultrasonic transducers, 24
scouring and bleaching, 347–348 single-crystal ultrasonic transducer
washing and cleaning acoustic couplant, 38
colour measurement, 350 backing block, 36
polyester fabric, 348 electric connectors, 37
raw wool, 350 electrical shield, 37
soil-washing process, 348 insulation ring, 36
wool, cleaning of, 349 matching layers, 37–38
washing time, 343 piezoelectric crystal, 35
wet processes, 343 tuning coil, 36
Thermal injury zones (TIZs), 336 wear plate, 38–39
Thiadiazole derivatives, 102 tube reactor, 44
Thiazole derivatives, 99–100 Ultrasound, 10
Titanium isopropoxide (TIP), 118 advantage of, 233
Transducers applications, 2
electromechanical transducers attenuation, 17–18
magnetostriction, 27–30 cavitational bubbles, 13, 15
piezoelectric, 30–34 acoustic cavitation, 16
gas-driven, 24–26 disadvantage, 15
liquid-driven, 26 growth and implosion, 13f
single-crystal ultrasonic transducer regions, 13–14
acoustic couplant, 38 sonochemical reactions, 16
backing block, 36 cavitation, types of
electric connectors, 37 stable cavitation, 12
electrical shield, 37 transient cavitation, 12
insulation ring, 36 concept of, 1
matching layers, 37–38 distortion, 10
Index387

food technology, 5, 291 coagulation/flocculation, 232

guided waves, 11 membrane filtration, 229–230
frequency dispersion, 12 oxidation, 227–229
plate waves, 12 sorption process, 231
rod waves, 12 sonochemical
surface acoustic waves, 11–12 chloro compounds, 239–244
industrial applications. see Industrial dyes, 234–237
applications hydrocarbons, 237–239
liquid molecules, 2–3 miscellaneous, 261–263
longitudinal/transverse waves, 10, 11f nitrogen-containing compounds,
medical applications. see Medical appli- 246–249
cations, ultrasound pesticides, 252–255
medical field, 2 pharmacological drugs, 255–259
scattering, 17 phenols, 259–252
shear waves, 10–11 sulphur-containing compounds,
244–246
sonolysis, 9
surfactants, 259–261
treatment, 5, 6
Water pollution, 226
ultrasonic waves, types of, 10
Wear plate, 38–39
Ultrasound-assisted oxidative desul-
Welding
phurization process (UAOD), 246
metal welding, 366–367
Upflow anaerobic sludge blanket reactor,
plastic welding
300–301 consolidation phase, 366
heat, 364, 365
V phases, 366
Villari effect, 27 vibration phase, 366
Vilsmeier–Haack reaction, 90–91 woven and nonwoven fibres, 365
Volatile suspended solids (VSS), 315 Whey protein concentrate (WPC), 289
Whey protein isolate (WPI), 289
W Wittig reaction, 91–92
Wastewater treatment
methods
Z
biological treatment, 226–227 Zinc sulfide–silica (ZSS), 130–131