A GUIDE

TO PROBLEMS
IN MODERN
ELECTROCHEMISTRY
1: /onics
A GUIDE
TO PROBLEMS
IN MODERN
ELECTROCHEMISTRY
1: /onics

Maria E. Gamboa-Adelco
Superior, Colorado

and
Robert J. Gale
Louisiana State University
Baton Rouge, Louisiana

SPRINGER SCIENCE+BUSINESS MEDIA,LLC

ISBN 978-0-306-46668-7 ISBN 978-1-4419-8600-9 (eBook)
DOI 10.1007/978-1-4419-8600-9
©2001 Springer Science+Business Media New York
Originally published by Kluwer Academic / Plenum Publishers, New York in 2001

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To all students of Electrochemistry
PREFACE

The main goal when writing the textbook Modern Electrochemistry -in its
original version of 1970 (by Bockris and Reddy), and later in its second edition
of 1998 (by Bockris, Reddy and Gamboa-Aldeco)- was to present, in a lucid
way, the complex and multidisciplinary area of Electrochemistry. The aim was
to start at a low level and increase the complexity of concepts, theories, and their
applications. The result is a detailed presentation of topics such as ion-solvent
and ion-ion interactions (Volume 1: lonics), and thermodynamics and kinetics of
electrodic processes (Volumes 2A and 2B: Electrodics). In this effort, the
involvement of various other disciplines -such as mathematics, biology and
engineering- were considered as well as numerous applications, such as fuel
cells, production of metals, batteries, soil remediation and photo-splitting of
water, to mention a few.
The textbook is addressed to anyone interested in learning
Electrochemistry, with occasional previews of advancing frontier topics. It is
written for students or anyone who, because of their work or personal interests,
would be presented with the challenge of learning Electrochemistry. Since the
goal was to teach, the authors followed the format of an excellent textbook,
Physical Chemistry, written by Peter Atkins (W.H. Freeman). Therefore, in the
second edition of Modem Electrochemistry, exercise headings addressed to
assimilate the acquired knowledge were included at the end of each chapter.
Thus, any student willing to improve hislher understanding of this field could be
challenged by solving the many exercises found through the book.
It has been always an incentive for students to find whether hislher efforts
to solve exercises give correct results, or to find tips for problems that he/she
finds more difficult. These are the main reasons for the appearance of the
present book. As part of the textbook Modern Electrochemistry J: /onics, A
Guide to Problems in Modem Electrochemistry: Part 1 Ionics compiles many

vii
viii PREFACE

of the solutions to the exercises and problems presented in the text, as well as
many new problems. During its preparation, the authors wanted to emphasize
three points; first, the variation in complexity of the exercises, which allows the
student to acquire the knowledge in little steps; second, the numerous exercises
and problems that give the student plenty of practice to assimilate the concepts
in the book; and third, the variety of topics presented in the book, which covers
fundamental concepts through applications in modern technology.
The exercises in each chapter have been divided into three categories. The
fIrst category contains simple Exercises, which can be completed with a basic
understanding of the related text. These Exercises allow for practice in using the
chapter's equations and should take about 15 minutes each to solve. Exercises
represents 37% of the total number of exercises and problems, with an average
of 30 exercises per chapter. In the second category, the degree of complexity
increases. This is not because of the length of the answers, but because of a
more profound understanding of the concepts is required. Because of their
higher complexity, the Problems require more time to solve, but can each be
completed within one hour. There are about 44 of these Problems in each
chapter, representing 60% of the total number. Finally, the third category
includes tasks that are more difficult. To solve these Micro-Research Problems,
a further effort of the student is needed. This may imply research on his/her own
for data or deeper concepts in reference or more advanced texts. There is only
one of these problems included in each chapter.
At this point it is important to stress that, in addition to the efforts of the
authors, more than thirty Electrochemistry professionals contributed to the
preparation of the problems. Thanks to them, the authors, with substantial
assistance from J. O'M. Bockris, were able to compile and organize more than
500 exercises and problems for the whole book, including those in A Guide to
Problems in Modern Electrochemistry: Part 2 Electrodics. Just writing this
many questions -without considering their solutions, complexity, and variety of
topics- constitutes a tremendous effort. The authors would like to thank each
one of the participants of this volume who make this book an asset for the
student of Electrochemistry: Bock, Bockris, Casidar, Constantinescu,
Contractor, Herbert, Kim, Mussini, Tejada, Trassati, and Xu.
Finally, one of the authors (Gamboa-Aldeco) thanks Prof. John O'M.
Bockris, for his encouragement, guidance, insistence, and recompilation of the
problems ofthis book.
CONTENTS

CHAPTER 1

NOMENCLATURE ................. . ...... ....................................... ..

CHAPTER 2

ION-SOLVENT INTERACTIONS...... ..... . .................... . ...... ... .... 9

Exercises ................................ . ... . .. ... ...... . ... .................... 9

Problems ...... '" . .. . . . . .. ... . . ... . ... .. . .. . . .. .. . . . . ... .. . ... .. . . . . ... . . . . .. .. . 43
Micro-Research Problems ......... .. . .... . .. ... .......... . .. ... . . .. ... . .. . .. . 84

CHAPTER 3

ION-ION INTERACTIONS.. . ...... ..... .. .. ... ... ... ... ...... .... .. .. . ... ... .... 89

Exercises ................................... . ........ . .... ..... .................. 89

Problems ...... . .. . .. ... . .. . . . . . . . .. .. . .. . . .. . . . .. . . .. ... .. . .. . .. . . .. .. . . .. . .. . .. 119
Micro-Research Problems ..... . .. .. .. ... . ... ..... .... .. .... ... .. ' " ... ....... 150

CHAPTER 4

ION TRANSPORT IN SOLUTIONS .. .... ...... .. .......... .. . ... ..... ...... . 155

Exercises .. ... ......... .. ................... . .. . '" ... ... ... ...... ... ... ... ... ... 155
Problems ..... .... ... . " ... .. . . . . .. . ... .. . . .. .. . .. . .. . .. . .. . .. . .. . .. . .. . ... . .. .. . 186
Micro-Research Problems ...... ... '" .. . . .. . .. . .. ... . . . .. . .. . .. . . .. .. . ... . ... 219

ix
x CONTENTS

CHAPTER 5

IONIC LIQUIDS. .. ... ... ... ... .. . ...... .. .. . .. .. . . .. ... ... ... .. ... ... .. . ... ... ... 225

Exercises ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

Problems .. . .. .. ...... . .. .. .. . ........ . ..... ........ . .. .. .. . ...... ............... 252
Micro-Research Problems .. . .... . . ..... .. .. . ...... ..... ....... ..... ... ... .. .. 282

INDEX ... ... ..... .. .. ....... .......... .... ... ....... ..... ..... ....... ... .. .. .... ...... 287
CHAPTER 1

NOMENCLATURE

For each symbol the appropriate SI unit is given. Multiples and

submultiples of these units are equally acceptable, and are often more
convenient. For example, although the SI unit of concentration is mol m-3,
concentrations are frequently expressed in mol dm-3 (or M). The abbreviation SI
units comes from Systeme International d'Unites, a system developed by the
General Conference on Weights and Measures based on the mksa (meter-
kilogram-second-ampere) system.

Symbol Name SI unit Other units

frequently used

GENERAL

A area of an electrode-solution interface m 2

OJ activity of species i
Cj concentration of species i molm-3 M,N
c" bulk concentration mol m-3 M,N
E energy J
F force N
glJ radial pair distribution function
v frequency Hz, S-l
m mass kg
n number of moles
N number of molecules

M. E. Gamboa-Adelco et al., A Guide to Problems in Modern Electrochemistry

© Springer Science+Business Media New York 2001
2 CHAPTER 1

Symbol Name SI unit Other units

frequently used

P pressure Pa atm
r, d, I distance m A
T thennodynamic temperature K °c
t time s
U potential energy J
V volume m3
v velocity m S-I
W work J
Xi molar fraction of species i
Ji reduced mass
p density Kgm- 3
A. wavelength m
v wavenumber m- I
0
() angle
y surface tension Nm- I dyncm- I

ION AND MOLECULE-RELATED QUANTITIES

a distance of closest approach m A

q Bjerrum parameter m
Zi charge number of an ion i
ai polarizability of species i m 3 molecule- I
fJ compressibility Pa -I
j.J dipole moment Cm D (debye)
esucm
tel Debye-HUckel reciprocal length m- I

THERMODYNAMICS OF A SIMPLE PHASE

energy of activation J mol- I

relative molar Gibbs free energy Jmol- I
relative molar enthalpy Jmol- I
equilibrium constant of the reaction
charge C
relative entropy J K -I mol -1 eu
NOMENCLATURE 3

Symbol Name SI unit Other units

frequently used

X electric field Vm"'

Pi chemical potential of species i Jmol"'

Pi electrochemical potential of species i J mol"'

p charge density C
& dielectric constant
If! electrostatic potential between two V
points

ACTIVITIES IN ELECTROLYTIC SOLUTIONS AND RELATED

QUANTITIES

a± mean activity
Y;, j; activity coefficient of species i
Jv y± stoichiometric mean molar activity
coefficient
I ionic strength

MASS TRANSPORT

Di diffusion coefficient of species i m 2s"'

Jj flux density of species i mol m"2s"'
Vd drift velocity ms"'
17 viscosity gcm"' sol poise

CHARGE TRANSPORT PROPERTIES OF ELECTROLYTES

q; charge of species i c
R resistance of the solution o
lIR conductance S orO"'
specific conductivity Sm"'
molar conductivity of an electrolyte S m2 mol"'
4 CHAPTER 1

Symbol Name SI unit Other units

frequently used

A.; ionic conductivity or ionic species i

A equivalent conductivity
I; transport number of ionic species i
in an electrolytic solution
U abs absolute mobility
U;, (u conv); conventional (electrochemical)
mobility of species j

KINETIC PARAMETERS

I electric current
j current density
k,k rate constants

STATISTICS AND OTHER MATHEMATICAL SYMBOLS

Pr probability
<x> average value of variable x
<Xl> mean square value of variable x
X nns root-mean-square value of variable x
() fraction number
erf{y) error function
X:t mean value of variable x
r(n) Gamma function
NOMENCLATURE 5

Useful Unit Conversion Factors

Potential Length Volume Mass Force Energy

IV 1m 1m3 I g IN IJ
I J C- I 100 em 1000dm3 10-3 kg I kg m S-2 I kg m2 S-2
lAO 1000mm 1000 liters 1000mg 105 dynes I Nm
I COS-I 106 IJm 105 gem-I S-2 107 ergs
109 nm 0.239 cal
10 1o A 6.242x101S eV
10 12 pm I C 2 0 S-I
IVC

Electric
Pressure Viscosity dipole Charge Current Temperature
moment

IPa I gem-I S-I ICm IC IA K=oC+273 .15

I Nm- 2 I dyne s em-2 3.00x1029 D 2.998x109 esu I C S-I °c = 5/9(Op -
32)
10 -5 bar I poise
9.87 Ix 10-6 atm
7.502xlO-3 mmHg
7.502xlO- 3 torr

Conversion Factors Between c.g.s. and m.k.s.a. Units:

IC = 2.998x10 9 esu or statC I A = 2.998x10 9 statA

Ierg = I esu2 em-I I V = 0.333x1O-2 statV
I D = 10- 18 esu em I n = O.lllx1O- 11 stat n
I esu em-I = I statV I F = 9xIO II em
6 CHAPTER 1

Useful Constants

Symbol Name Value

Co speed of light 2.998xlOs m S-I

eo electron charge 1.602xlO- 19 C
F Faraday's constant = eoNA 9.649x10 4 C mol -I
h Plank's constant 6.626xI0· 34 J s
k Boltzman's constant l.381x10- 23 J K- 1
NA Avogadro's number 6.022x10 23 mol- I
R gas constant 8.314 J mol- I K- 1
£0 permittivity of free space 8.854xI0- 12 C 2N -I m-2
41t£o 1.112xlO- 1O C 2 J -I m- I
OK absolute zero of temperature -273.15°C
1t pi 3.14159 ...

Other Data

Dielectric 20°C 25°C 30°C Dipole moment of water:

constant f.Iw = 1.87 D

Water 80.1 78.3 76.54 Quadruple moment of

aEw water:
--= -0.356 K .)
aT Pw = 3.9xlO·s D cm
Cyclohexane 2.02 2.02
Carbon 2.24 2.23 Polarizability of water:
tetrachloride llw =1.46x I 0-24 cm3
Benzene 2.28 2.27
Ammonia 17.35 16.9
I-Propanol 20.1
Ethanol 24.30
Methanol 33.62 33.63
Nitrobenzene 35.74 34.82
NOMENCLATURE 7

Masses and Radii

H Be B C N 0 F
1.008 9.012 10.811 12.011 14.007 15.999 18.998
(+2)35 (+3)23 (-4)260 (-3)171 (-2)132 (-)136
(+4)160 (+3)16
(+5)13

Li Mg Al Si P S CI
6.941 24.305 26.982 28.086 30.974 32.062 35.453
(+) 59 (+2)66 (+3)51 (-4)2.71 (-3)212 (-2)184 (-)181
(+4)0.42 (+3)44
(+5)35
Na Ca Br
22.990 40.08 79.904
(+) 95 (+2)99 (-)195

K Sr I
39.098 87.62 126.905
(+)133 (+2)112 (-)216

Rb Ba
85.468 137.3
(+)149 (+2)134

Cs
132.905
(+)167
mass
~ H20 radius
18 . 015~
138 pm
CHAPTER 2

ION-SOL VENT INTERACTIONS

EXERCISES

Review of Sections 2.1 to 2.4 of the Textbook.

How is an electrochemical system constituted? Describe the two ways

mobile ions can create an interphase. What is the difference between hydration
and solvation? Briefly, describe the three main approaches to the study of
solvation. Draw a schematic of the water molecule. What is Iibration? Define a
dipole and its moment. Explain how the water molecule is considered a dipole.
What is the role of free orbitals in the water molecule? What is a hydrogen
bond? Describe the ice and liquid water structures. Mention the seminal
contributions of Bernal and Fowler, as well as of Frank and Wen, to the
understanding of water structure. Write the basic equation for the interaction
energy between particles and describe each one of its terms. How does an ion
affect the structure of water? Draw a schematic showing the primary, the
structure-broken and the bulk regions of water around an ion. What are the
radius and the dipole moment of water? What energy changes are described in
the Bernal-Fowler theory of ion-solvent interaction?

2.1 A positive charge +eo, and a negative charge -eo are separated by 53 pm.
Calculate their dipole moment. (Cf. Exercise 2.29 in the textbook)
(Contractor)

9
M. E. Gamboa-Adelco et al., A Guide to Problems in Modern Electrochemistry
© Springer Science+Business Media New York 2001
10 CHAPTER 2

Answer:

The dipole moment is given by:

J.J = (charge )( separation of charges)

=(1.602Xl0- 19 C)(53xl0-12 m)x ID_ 30 =2.S4D(2.1)

3.336xl0 Cm

Comment. According to Bohr's model, in the hydrogen atom the proton and the
electron are separated 0.53 A in the ground state. They form a dipole with a
moment of2.54 D.

2.2. Water often is subjected to extremely strong electric fields as, for
example, in the solvation of ions. By considering the total H-bond energy of
water, calculate the electric-field strength that will break up H-bonded
water. (d. Exercise 2.33 in the textbook) (Bockris-GamboaAldeco)

Data:

From Section 2.4 in the textbook: 10 kJ mor l < WH-bonding < 40 kJ mor l

Answer:

The relationship between energy and electric field is:

Wa - b =qXd (2.2)

Considering q to be the charge of the proton, and the average hydrogen-

bonding energy as 25 kJ mol -I, the electric field strength needed to break the
hydrogen bond is

W -I
X=~= 25000Jmoi x I mol x_IV_C
eod (1.602XIO- 19 C }lm) 6.022x10 23 11 (2.3)

-1
=0.260 Vm
ION-SOLVENT INTERACTIONS 11

2.3 (a) Show that the electrostatic interaction potential energy between two
charges ql and q2 can be represented in the non-conventional form,
although widely used equation,

332 z}z2
u=--- (2.4)
& r}-2

where U is the potential energy given in units of kcal mol -I, '1-2 is the
distance between the charges expressed in angstroms (A), &is the relative
dielectric constant of the medium (unitless), and z/ and Z2 are given by the
equation q i = Z i eo where qi represent the charge expressed in electronic
charge units (esu). (b) What is the Coulombic interaction energy in kcal
mor l between a proton and an electron separated by 1 A in vacuum? (d.
Exercise 2.27 in the textbook) (Contractor-Casidar)

Answer:

(a) The corresponding potential-energy equation given in SI units is:

U=_I_Qlq2 (2.5)
41r&o& rl-2

where Ql and Q2 are expressed in coulombs (C), rl_2 in meters (m), & is unitless,
Eo, the permittivity of free space, is a constant equal to 8.854xIO- 12 C2r 1m- l , and
U is the potential energy given in units of 1. However, this expression can be
written in cgs units as (cf. Chapter 1)

2
U = _q_1q_2_ = _z_1z.. .;2;.. e. . ;O,- (2.6)

where U is given in ergs, the electron charge, eo, is given in esu or electrostatic
units and rl_2 in cm. With rl_2 given in A, substituting the value of eo,
multiplying by Avogadro's number, NA, and applying some conversion factors
gives,

U= E~~:[A]( 4.8xI0-10 esu r (6.022X10 23 mOl-I) (2.7)

12 CHAPTER 2

10 8 A I erg 11 Ical Ikcal

x - - x ---=-- x x --- x ---
Icm lesu 2 cm -I 10 7 erg 4.186J 1000cai

or

[
U kcalmol
-I] = 332 zIz2
[] (2.8)
& rl-2 A

(b) When rl_] = I A and & = I, then,

U[ kcal mOl-I] = 332(I)(IA)

(1)(-1) -332 kcal mol-1 (29)
.

Review of Section 2.S of the Textbook

What are the thermodynamic, transport, and spectroscopic methods used to

study solvation? Define heats ofsolvation, sublimation and dissolution. Write an
equation for the change of chemical potential of dissolution. Describe a method
to determine tlG ~olvation ' llS ~olvation' and I1H ~olvation ' What is the importance
of these quantities?

2.4 Calculate the sum of the heats of hydration of IC and F ions. The lattice
energy is -194.7 kcal mol-I. The heat of the solution is - 4.1 keal mol-I. (Cf.
Exercise 2.11 in the textbook) (8ockris-GamboaAldeco)

Answer:

The heat of solvation of a salt is related to the heat of solution and the heat
of sublimation by the following equation (cf. Eq. 2.3 in the textbook):

I1H s s, alt = I1H so In - L sub (2.10)

However, the heat of sublimation is equal to the lattice energy but has an
opposite sign. Therefore,

I1H s salt
, = I1H so In + I1H lattice (2.11 )
ION-SOLVENT INTERACTIONS 13

Substituting the corresponding values,

-1 -1 -1
&f s s, alt = - 4.1 kcal mol -194.7 kcal mol = -198.8 kcal mol
(2.12)
-1
= - 832.2 kJ mol

Review of Sections 2.6 and 2.7 of the Textbook.

Why are measurements of partial-molar volumes important in

understanding solvation? Explain Conway's method to detennine ionic volumes
of individual ions. Write an expression relating the compressibility of the
solution to solvation. Explain how solvation numbers are obtained from
Passynski 's method. What important fmding did Orani contribute to Passynski' s
theory? How is the compressibility of a liquid measured?

2.5 The adiabatic compressibilities of water and of a 0.1 M NaI solution at

298 K are 4.524x10- 10 Pa- 1 and 4.428xl0-10 Pa-., respectively. Calculate the
hydration number of the NaI molecule when the density of the solution is
1.0086 g cm-3• (Cf. Exercise 2.18 in the textbook) (Kim)

Data:

130 = 4.524xl0- IO Pa- I P soln = 1.0086 g cm-3 T = 298 K

13 = 4.428xlO- IO Pa- I c = 0.1 mol dm- 3

Answer:

The hydration number of a salt can be obtained from (c.f. Eq. 2.11 in the
textbook):

(2.13)

where nw is the number of water moles and nNaJ the number of electrolyte moles.
The value of nNai is 0.1 mol in 1000 cm3 of solution. The value of n w, in
1000 cm3 of solution can be calculated as

(2.14)
14 CHAPTER 2

=[ (lOoocm 3 )( 1.0086gcm -3 ) - (0.1 mOI)( 148.9 gmol- I ) l~~;lg

= 55.14mol

Therefore, the hydration number ofNaI is,

ns =~(I_Ll=55.14mol[l_ 4.428Xl0- IO pa- I ]=1l.7 (2.15)

nNaJ 130 O.lmol 4.524xl0- 10 Pa- I

2.6 The adiabatic compressibility of water at 25°C is 4.524xl0- IO Pa- I •

Calculate the adiabatic compressibility of 0.101 M solution of CaCl2 of
density 1.0059 g cm-3 at 25°C, if the hydration number of the electrolyte is
12. (Cf. Exercise 2.19 in the textbook) (Contractor)

Data:

130 = 4.524xl0-10 Pa- 1 Psoln = 1.0059 g cm-3

eCoCI2 = 0.101 mol dm-3 ns = 12

Answer:

The hydration number in terms of compressibility data can be calculated

from (cf. Eq. 2.11 in textbook):

= (2.16)

where nw is the number of water moles and nCaCI2 the number of electrolyte
moles. The value of nw is calculated as

1.0059 g dm -3 - ( 0.10 1mol dm -3 )( III g mol -\ )

-\
(2.17)
18.016gmol
=55.21 mol in 1dm 3 of solution
ION-SOLVENT INTERACTIONS 15

Therefore,

P=PO[I- nCaC/ 2 nS ]=4.524XIO- 10 pa[I_(0.lOlmol)(12)]

nw 55.21mol (2.18)
= 4.42Sx10 -10 Pa

2.7 In the textbook are data on compressibility as a function of

concentration. Use the Passynski equation to calculate the total salvation
number of NaBr at infinite dilution. (cf. Exercise 2.21 in the textbook)
(Bockris-GamboaAldeco)

Data:

From Table 2.5 in the textbook, the compressibility of NaBr aqueous solutions
at different concentrations:

c(M) 5.2 2.0 1.1 0.1 0.05

26.93 35.99 39.75 44.23 44.47

f3w = 45.24 X 10-6 bar· l at 25°C

Answer:

The Passynski equation reads (cf. Eq. 2.11 in the textbook):

(2. 19)

where Po is the compressibility ofthe solvent (water), and pthe compressibility

of the solution; nj is the number of solvent (water) moles and n] the number of
salt moles. In 1 liter of solution there are approximately 55 mol of water (nw).
For a solution of 5.2 M NaBr,

[
ns = 1- 26.93xlO bar-6 -I) 55mol =4.28 (2.20)
45.24xlO-6 bar -I 5.2mol
16 CHAPTER 2

In the same way for the other solutions,

c(M) 5.2 2.0 1.1 0.1 0.05

ns 4.28 5.62 6.07 12.28 18.7

Plotting these values as in Fig. 2.1 and neglecting the last two points, gives
a straight line of equation,

ns =6.52-0.43c (2.21)

Therefore, when c ~ 0 the value of the total solvation number of NaBr at

infmite dilution can be obtained. This number is, from the graph, n;o = 6.52

2.8 Sound velocity in water is measured to be 1496.95 m S-I at 25°C.

Calculate the adiabatic compressibility of water in bar-I. (Cf. Exercise 2.20
in the textbook) (Xu)

Data:

co= 1496.95 m S-I T=298 K

20r-~-.--~-.--~-.~--'-~--~~~

18 ~
16
14
ns from
Passynski 12 •
AnllAtinn 10

6[_______--------J
4
2L-~~ __ ~-L __~-L~~~~__~~~
o 2 3 4 5 6
c (M)

Figure 2.1. Total solvation number of NaBr at different concentrations

according to Passynski's equation.
ION-SOLVENT INTERACTIONS 17

Answer:

The relationship between the compressibility of a liquid or solution and the

velocity of sound in it is (c.f. Eq. 2.12 in the textbook),

/3= 1 (2.22)
2
cOPw

Substituting values in Eq. (2.22),

-2
/3= I x Ikgms INm -2 10 5 Pa
x---x---
IPa I bar
(I496.95ms-lr(103kgm-3) IN

= 4.46xl0 -5 bar- 1 (2.23)

Review of Sections 2.8 to 2.11 of the Textbook

Describe the ultrasound method for the determination of hydration

numbers. Why does the mass-action law of chemistry not work for ions in
solution? What is an activity coefficient? How does the activity coefficient vary
with concentration? Explain how this variation can be used to determine
hydration numbers. Mention some drawbacks of this method. Describe briefly
how the determination of the mobility of ions can lead to information of
solvation numbers. Mention some difficulties found within this method. How
are spectroscopy techniques used to obtain hydration numbers? What regions of
the infrared spectrum give information about intermolecular and intramolecular
effects? What information in the infrared region can be obtained related to the
structure of water and its interaction with ions? Write Brag's equation for X-rays
analysis. Explain the difficulties found in attempting to utilize the powerful tool
of neutron diffraction to the study of solvation. What is a distribution function?
What is the relation of coordination waters and hydration waters? How are
distribution functions applied to determine coordination and hydration numbers?
How are these quantities determined? What is the contribution of Hewich,
Neilson and Enderby to the structure of ions and their solvation sheets? Describe
possible nonelastic-scattering effects in Raman spectroscopy. Mention some
important fmdings related to solution structure by Raman spectroscopy.

water is 44x10·5 cm 2 S·l V.,

2.9 Calculate the hydration number of Na + when the mobility of the ion in
and the viscosity of the solution is 0.01 poise.
18 CHAPTER 2

Tbe Stokes radius is given by r Stokes = Zj eo /6 m]U . (Cf. Exercise 2.23 in

tbe textbook) (Kim)

Data:

rNa-t- = 95 pm rw = 138 pm UNa -t- = 44xlO-s em 2 S-1 V-I

7Jsoln =O.Olpoise
dyns IN 1m 11 1m -9 -3
=O.oI--x x-x--x---=10 Jsem
5
em 2 10 dyn 1m 1Nm 100cm

Answer:

The hydration number of the ion ean be obtained from (cf. Eq. 2.23 in
textbook):

3 3
r Stokes - r crys
ns = (2.24)

The radius of the hydrated ion is obtained from the Stokes equation given
above (ef. Eq. 4.183 in textbook):

zje o
c)
(+ 1)(1.602XlO- 19 1J
rStokes =--= (9
61r7JU 61r lO - J s em -
3)( 5 2 I 1) x--(2 25)
44 x lO - em s - V - I CV .

-8
= 1.93x10 em

Therefore, Eq. (2.24) gives

2.4 (2.26)

2.10 An IR spectrum bas a peak with a wavenumber of 1.56lxl03 cm-'. (a)

What is tbe wavelengtb and frequency of tbe corresponding bond? (b) If
tbe spectrum originates from water, calculate tbe force constant between 0
and H. (cf. Exercise 2.34 in tbe textbook) (Bockris-GamboaAldeco)
ION-SOLVENT INTERACTIONS 19

Answer:

(a) The wavelength (A) and frequency (v) are related to the wavenumber (if) by
1
A=- and v = coif . Substituting the corresponding values gives:
if

A =1. = 2.808xl 0 -4 em (2.27)

if 3.561 x 10 3 em -I

and

v=cOif= ( 2.998x10 10 em s -I )( 3.561xlO 3 em -I )

(2.28)
14 -1
= I.068xlO s

(b) The frequency (v) and the force constant (k) are related through the equation

(cf. Eq. 2.24 in textbook) v=_I- fI, where ji is the reduced mass, given by
27r Vji
1.=_1_+_1_. Considering that the subscript J refers to the oxygen of the
ji ml m2
water molecule, and the subscript 2 to one of its hydrogens, then, the reduced
mass of water is given by

1 1 1
-=-+-=----- (2.29)
ji 16 1 0.94gmol-1

or

jl=0.94gmol- 1 Imol =1.56xI0-24 g (2.30)

6.022x10 23

Then, the force constant is,

k = ( 21tv ) 2 _
Il = 41t 2 ( 1.068 x 10 14 s -I) 2 ( l.56xlO - 2Kg7 ) x 1N -2
IKg ms
-1
=702.47Nm (2.31 )
20 CHAPTER 2

Review of Sections 2.12 to 2.14 of the Textbook

Define dielectric constant. Why does the dielectric constant decrease when
ions are added to a liquid? How does the dielectric constant vary as a function of
the distance from an ion? Write the equation proposed by Hasted relating
dielectric constants to solvation numbers. What is electrostriction? What
differences exist between cations and anions on the frequency at which water
undergoes relaxation? How are the dielectric constants of liquids and of ionic
solutions measured? How can these measurements be used to study the structure
of ionic solutions? Explain a method to determine the hydration energy of the
outer-hydration shell. How is this value relative to the total hydration energy?
What parameters determine the solvation number of ions? Mention an approach
to determine ionic solvation numbers.

2.11 If the primary hydration number of NaCI in 1 M solution is six, make a

rough calculation of the dielectric constant of the solution if the dielectric
constant of pure water is taken as 80. (cf. Exercise 2.6 in the textbook)
(Bockris-GamboaAldeco)

Answer:

An equation to calculate the dielectric constant ofa solution is (cf. Eq. 2.27
in the textbook):

E soln
_ (55-c;n s ) +6 (c;n
-80 --)
s
(2.32)
55 55

Substituting the corresponding parameters in Eq. (2.32),

55moldm -3 -( lmoldm - 3 )(6)1 [( Imoldm -3 )(6)1

Esol n =80 [ +6
-3 -3
55moldm 55moldm

=71.9 (2.33)

2.12 Solvation numbers for Na + and cr have been measured as 5 and 1,

respectively. With this information, and recalling that the number of moles
per liter of pure water is 55, calculate the dielectric constant of a 5 M
ION-SOLVENT INTERACTIONS 21

solution of NaCI. The dielectric constant of pure water is to be taken as 80

near room temperature. When the water molecules are held immobile in
respect to the variations of an applied field, & drops to 6. (Cf. Exercise 2.10
in the textbook) (Bockris-GamboaAldeco)

Data:

n s,Na+ =5 nw = 55mol in Iliter Ew,bulk =80

n s,cr =1 Ci =5M E w,saturated = 6

Answer:

According to Hasted, a simple equation to determine the dielectric constant

ofa solution is [cf. Section 2.12.1 in the textbook]:

n w,bulk n w,saturated
& so In = & w,bulk + & w,saturated (2.34)

The number of saturated water molecules can be taken as the number of

water molecules around the ions. In 1 liter of solution,

n w,saturated =C Na n s ,Na + CCI- n s ,CI-

+ +
(2.35)
=(5mol)(5)+ (5mol)(I) =30 mol
and the number of water molecules in the bulk of the solution is:

n w b, ulk =n w - n w,saturated = 55 mol- 30 mol = 25 mol (2.36)

Therefore,

& soln = (80 )25mol + 6 30mol = 39.6 (2.37)

55mol 55mol

Review of Sections 2.15.1 to 2.15.11 of the Textbook

Describe the Halliwell-Nyburg method to determine relative heats of

hydration of individual ions. Do opposite charged ions of equal radii have equal
heats of solvation? Draw a schematic of water as a quadrupole. Which are the
22 CHAPTER 2

steps involved in the ion-quadrupole model of ion-solvent interactions? Write

expressions for (a) the ion-dipole energy in the gas phase, (b) the energy
involved in the introduction of solvated ions into a cavity (Born term), and (C)
the full energy equations for cation- and anion-solvent interactions. What is
deformation polarizability? How are the equations for heat of ion-solvent
interactions modified by the induced-dipole effect? Explain a method to
determine the individual heats of hydration from values known for the salt. How
did Lee and Tai determine the absolute standard entropy of the proton in
solution? Draw schematics of the solvation model of Bockris and Reddy. What
is understood by dynamic solvation number? Explain the steps involved in the
cycle of ion-solvent interactions proposed by Bockris and Saluja. Write Born's
equation for solution energy. What is the meaning of each one of its terms?
Which are the difficulties presented by the Born's theory of solvation? What
does the acronyms SN, CN and NSCW represent? Write Bockris and Saluja's
equations for the interaction energies (a) of an ion with waters oriented along the
ionic field, (b) of an ion with nonsolvationally coordinated waters, and (c)
between lateral ions. What are the differences among the structure-breaking
energies proposed by (a) Bernal and Fowler, (b) Frank and Wen, and (c) Bockris
and Reddy? How do these models fit experimental data?

2.13 Calculate the absolute heats of hydration of Na + and cr using the

absolute heat of hydration of W of -1113.0 kJ mol -I. The heat of
interaction between HCI and water is -1454.0 kJ mol-I, the heat of solution
of NaCI is +3.8 kJ mol -I, and the heat of sublimation of NaCI is +772.8 kJ
mol-I. (Cf. Exercise 2.17 in the textbook) (Kim)

Data:

-I -I
L1H HC/ (hyd) = -1454.0 kJ mol L1H H + (hyd) = -1113.0 kJ mol
-I -I
L1H NaC/ (so In) = +3 .8 kJ mol L1H NaC/ (sub) = +772.8 kJ mol

Answer:

The heat of hydration ofHCI is (cf. Eq. 2.29 in the textbook):

-I
L1H HC/ (hyd) = L1H H + (hyd) + L1H C/ - (hyd) = -1454.0 kJ mol (2.38)

From Eq. (2.38),

ION-SOLVENT INTERACTIONS 23

&f cr (hy d)=-1454.0kJmOI- 1 - ( -1l3.0kJmOI- 1 )

(2.39)
= -341.15 kJ mol- 1

In the same way, &fNaC1(hyd) is also equal to:

till NaCI (hyd) = till Na + (hyd) + till cr (hyd) (2.40)

However, the heat of solvation of NaCI is also given by [cf. Fig.2.l3 in

textbook],

&f NaCI (hyd) = &f NaCI (so In) - &f NaCI (sub)
(2.41)
= +3.8kJ mol- 1 -772.8kJ mol- 1 = -769.0kJmol- 1

Therefore, the absolute heat of hydration ofNa+ ions is

-\
&f Na + (hyd) = &f NaCI (hyd) - &-I Cl- (hyd) = -769.0 kJ mol
(2.42)
- ( - 341.1 kJ mol -\ )
= -427.9 kJ mol -I

2.14 The cr ion has a radius of 181 pm. Find how much larger the ion-
dipole term is compared with the Born term. The dielectric constant in the
Born equation is to be taken as 80. Neglect any dependence of the dielectric
constant with temperature. (d. Exercise 2.2 in the textbook) (Bockris-
Gam boaAldeco)

Answer:

The ion-dipole interaction energy in the gas phase is given by (cf. Eq. 2.41
in the textbook):

(2.43)

where the term 41[&0 in the denominator has been introduced to write the
equation in the mksa system, i.e., the charge in Coulombs, the distance in
meters, and the free energy in joules per mol. For cr,
24 CHAPTER 2

4( 6.022xlO 23 mol-I )1-11(1.602XlO- 19 C )(1.87D)

W 1 _D = - (2.44)
(1.l12XlO- 1O C 2 J-I m -I )(18I pm+138 pm)2

-30 24 2
x 3.336x lO em x lO pm = -212.8 kJ mol-I
ID 1m2

The Born term is given in the mksa system by (cf. Eq. 2.40 in the textbook):

(2.45)

Substituting the corresponding parameters for cr and taking into account

that -
as =0,
aT

(6.022XlO 23 mol-I }_1)2 (1.602XlO- 19 C r I

W Be " - 2( 1.112, \0-10 C' ,-' m-, )[181 pm+2(1l'pm))( 1- .0 (2.46)1

10 12 pm
x - 150.2 kJ mol-I
1m

Therefore,

-1 -1
-212.8kJmol +150.2kJmol
= =0.417 (2.47)
-1
- 150.2 kJ mol

That is, the ion-dipole term is 41.7% larger than the Born term.

2.15 The interaction energy of the iodide ion with water dipoles in gas phase
is -171 kJ mol -1 at 298 K. Calculate the radius of the water molecule. Take
the iodide radius and the dipole moment of water from tables in Chapter 1.
(Cf. Exercise 2.3 in the textbook) (Contractor)

Data:
-1
rr =216pm Ilw = 1.87 D W1- D = -171 kJ mol
ION-SOLVENT INTERACTIONS 25

Answer:

The ion-dipole interaction in the gas phase is given in the mksa system by
(c.f. Eq. 2.41 in textbook):

(2.48)

Solving for rwand substituting the corresponding values,

(2.49)

= [_ 4( 6.022 x 10 23 mol-I )1- 11( 1.602 x 10 -19 C )(1.87D )

(1.l12XIO- 10 C 2 J-l m -l)( -171000JmOI- I )

x 3.336xl0
-30 Cm ]1/2 -2.16xl0-JOm=1.398xl0-IOm
ID
= 140 pm

2.16 The heat of interaction of chloride ion with water is -347.3 kJ mol -I ,
and the corresponding contribution to the Born charging process is -152.5
kJ mol -I. (a) If the dielectric constant of water at 298 K is 78.3, estimate its
rate of change with temperature at this temperature. (b) Calculate the
percent error introduced in the Born charging term if the dielectric
constant is assumed independent of temperature. (Cf. Exercise 2.4 in the
textbook) (Contractor)

Data:

-I
&/ cr -w = -347.3kJ mol r cr = 181pm T = 298K
-I
W BC = -152.5kJ mol rw = 138 pm Ew = 78.3

Answer:
26 CHAPTER 2

(a) The interaction energy involved in the process of introducing the primary
solvated ion formed in the gas phase into the solvent cavity, i.e., the Born term,
is given in the mksa system by (c.f. Eq. 2.42 in textbook):

(2.50)

Solving for DE I aT and substituting the corresponding values,

a& = &2 [2W BC (r; + 2r w )47Z"&0 +1-1.] (2.51)

aT T NA (Z i eo) 2 &

r
2 [2(-152500JmOI-1 )(181+276)XIO- 12 m
78.5
=--
298 K 6.022 x 10 23 mol -I ( 1.602 x 10 -19 C

1]
x ( 1.112xl0 -10 C 2 J -I m -I) + 1 - - =-0.32
78.5

(b) If the dielectric constant is assumed independent of temperature,

DEI aT = 0 , then,

( 6.022x 10 23 mol -I )( 1.602 x 10 -19 C )2

(2.52)

( 1)
x 1 - - - =-150147Jmol -I
78.5

The error introduced in neglecting DEI aT is calculated as:

ION-SOLVENT INTERACTIONS 27

(w Be )aYar - WBe x 100= -150.2 kJ mol-I + 152.5kJ mol-I

- - - - - - - - - - - - x 100 = -1.5%
WBe 152.5 kJ mol-I
(2.53)

2.17 When fluoride ions encounter water molecules, the ion-quadrupole

interaction energy is - 394.6 kJ mol -I. Calculate the quadrupole moment of
water at 298 K. (Cf. Exercise 2.5 in the textbook) (Contractor)

Data:

T=298 K f.Jw = 1.87 D &w = 78.3

-I
WF - _Q = -394.6 kJ mol rr =136pm rw = 138pm

Answer:

The ion-quadrupole interaction energy is given in the mksa system by (c.f.

Eq. 2.46 in textbook):

4N Az;eOpw
(2.54)
2(r; +rw )3 41rEo

Solving for Pw and substituting the corresponding values,

2(r;+rw )3 41rE O[ 4N A z of.Jw ) je

W j_Q + ----=.::........:........:.-........:.
Pw =

r
4N AZjeO (rj +rw)2 41rEo
(2.55)
2[ (136+ 138 )xlO -12 m (1.l12XIO -10 C 2 J- I m -I )

4 ( 6.022 x 10 23 mol -I )( 1.602 x 10 - 1 9

C)

r
-I 4( 6.022x10 23 mOl-I)
x
1
- 394.7 k J mol +---------
[(136+ 138)xI0-12 m
28 CHAPTER 2

( 1.602Xl0- 19 C){1.870) 3.336xl0

-30}
Cm 10
x x x------------
(1.l12Xl0-10c2J-lm-l) 10 3.336xl0- 30Cm

-10
=3.8xl0 Dm

2.18 Evaluate the heat of solvation for the ions K+, Ca+2, F, and cr on
terms of the ion-dipole approach. Neglect the quadrupole effect of water.
The variation of the dielectric constant of the solution with temperature is
O.ilS6 KI. (Cf. Exercise 2.15 in the textbook) (Kim)

Data:

r K + =133pm rr =136pm f: w (298 K) = 78.3

rCa +2 = 99 pm rcr = 181 pm Of: =0.356K-I

aT
Answer:

The heat of solvation for cations expressed in the mksa system is (cf. Eq.
2.47 in the textbook),

(2.56)

Therefore, the enthalpy change for the solvation ofK+ in water is

-I 4.186kJ 4x6.023x10 23 mol -I ( +1 )

IV{ K + = 20kcaI mo I x - {
-w lkcal (133XlO-12m+138XlO-12mr
ION-SOLVENT INTERACTIONS 29

( 1.602XIO- 19 C)1.8D
3.336x 10
_30}
Cm
x x------ (2.57)
(1.l12XIO-IOc2J-Im-l) ID

6.023x10 23 mol -I (+1)2 (1.602 x 10 -19 C )2

{
2( 133xI0- 12 m+ 138xlO- 12 m)( 1.112xI0-10 C 2 J-I m -I)

298K
x ( 1- - 1 - - - 0.356 K -I ] } = -375.5 kJ mol -I
78.3 78.3 2

Correspondingly, the heat of solvation for Ca+2 is - 1389.7 kJ mOrl. The

heat of solvation for F- and cr can be obtained from a similar equation, Eq.
(2.48) in the textbook, giving, - 326.1 and - 226.0 kJ mor l, respectively.

2.19 Calculate the differences of the heat of hydrations when using the ion-
quadrupole model or the ion-dipole model for the ions K+, Ca+ 2, F, and Cr.
(Cf. Exercise 2.16 in the textbook) (Kim)

Data:

r K+ = 133 pm r cr = 181pm
-10
r Ca +2 = 99pm rw = 138pm Pw = 3.9x10 Dm
rr = 136 pm J.i w = 1.87 D

Answer:

The heat of interaction for negative ions and water expressed in the mksa
system is (cf. Eq. 2.47 in the textbook):

(2.58)
30 CHAPTER 2

The difference between the quadrupole and the dipole model for water is
4N AZjeoPW +
given by the term . Thus, for K ,
2(rj +rW )3 41rEO

4x6.023xlO 23 mol -1 (+)1 ( 1.602 x 10 -19 C )

-12 -12 )3
2 ( 133xlO m+138xlO m

(2.59)

-1
= 113.4kJ mol

Similarly, the difference of heat of hydration between the dipole and the
quadrupole model for Ca2+ is 339.1 kJ mOrl. For anions, the difference between
the quadrupole and the dipole model for water is (cf. Eq. 2.48 in textbook)
4N Az;eoPW I
--..:..::.-..:........::....::....:~- . Thus, for F, this term gives -108.84 kJ mol- , and for
2(r; +rW )3 41rEO
cr is -71.16 kJ mol -I.

2.20 Calculate the concentration of a NaCI solution at which the so-called

"Gurney co-sphere" is reached, that is, when the separation between ions is
equal to the radii of the primary solvation sheaths. Consider that for a 1:1
electrolyte, the average separation between ions is given by

(2.60)

where d is given in A and c in mol dm-3 • (Cf. Exercise 2.7 in the textbook)
(Xu)

Answer:

When the average separation between the ions is equal to the radii of
primary solvation sheath, then the incompressible spheres are in contact and the
Gurney co-sphere is reached. The radii of the primary solvation sheath for the
chloride and sodium ions are:
ION-SOLVENT INTERACTIONS 31

rh ,Na+ =rNa+ + 2r w =0.98x10-S cm+2(1.38XlO-S cm)

(2.61)
=3 .74xlO-S cm

rh,cr =rcr + 2r w =1.8lx10- S cm+2(1.38X10-S cm)

(2.62)
= 4.57x 10 -s cm

The mean separation distance of these ions is (3.74 +4.57) x 10.8 cm = 8.31
x 10-8 cm. Applying Eq. (2.60) to fmd the concentration,

3 3
c = ( 9.40 ) = ( 9.40 ) = 1.45 M (2.63)
d 8.31

2.21 Suppose the results from Exercise 2.20 are true. Calculate the solvation
number of NaCI. Comment on the reliability of the results. (Cf. Exercise 2.8
in the textbook) (Xu)

Answer:

In Exercise 2.20, all the water molecules in the 1.45 M NaCI solution (i.e.,
at the most 55.56 mol dm- 3) are assumed to be in the primary sphere ofthe ions.
Therefore, the solvation number is:

55.56 mol water

ns = =19 !!! (2.64)
(2 x 1.45 )mol ions

This is a very high value, and indicates that at high concentrations, the
average separation relation of Exercise 2.20 oversimplifies the situation. Other
effects such as electrostriction should be taken into account in the calculation of
ns·

2.22 A Raman spectrum shows that in a 4.0 M NaCI solution about 40% of
the water molecules are in the primary sheath. (a) Estimate the average
solvation number, ns. (b) If the SB region consists of only one layer of water
molecules, is there any bulk water left in this solution? (Cf. Exercise 2.9 in
the textbook) (Xu)
32 CHAPTER 2

Data:

rCl. =181 nm r", = 138 nm. eNaCl = 4.0 mol dm·3

rNa + = 95 nm n., %=40 %

Answer:

(a) The total number of moles of water in the primary sheath in 1 liter ofthe 4.0
M solution is:

solvation moles = (n w )( n s %) = (55.56 mol)( 0.40) =25.00 mol (2.65)

Since there are 4.0 moles of electrolyte in 1 liter of this solution, thus, the
total solvation number is:

n = 25 .00 mol water = 6.0 (2.66)

s
4 mol electrolyte

(b) Considering an average ionic radius of {r Na + + r CI- )/2 =

(95nm+ 181 nm)/2 = 138nm, it holds that (cf. Eq. 2.85 in textbook):

2 (2.67)
tr rw
= 36 water molecules per ion

This means that in I liter of solution there are 8 mol of ions present, and
thus, the total number of moles of water in the SB regions of the ions is:

. ) ( 36 mol of SB water) = 288 mol of SB water

( 8 mol of IOns (2.68)
mol of ion

Now, 288 mol» 55.56 mol, which is the number of water moles in 1 liter
of water if there were no electrolyte present. Therefore, there is no free bulk
water at this concentration. The solution at this point is so concentrated that ions
in it have to share water molecules in the SB region.

2.23 Using the equation provided by the Born theory, calculate the free
energy of ion-solvent interaction for K+, Ca+1, F and cr in water. The ionic
ION-SOLVENT INTERACTIONS 33

radii are 133, 99, 136 and 181 pm, respectively, and the dielectric constant
of water is 78.3 at 298 K. (Cf. Exercise 2.13 in the textbook) (Kim).

Data:

r K+ = 133pm rr =136pm
&w (298 K) =78.3
rCa +2 =99pm rcr =181pm

Answer:

The energy change due to the solvent interaction with the ion expressed in
the mksa system is (cf. Eq. A2.1.6 in the textbook):

!!.G J-S =
NA (Z j eo )2 [ 1 - - 1) (2.69)
2rj 41i&o &

-I
= -515.9 kJ mol (2.70)

Correspondingly, the ion-solvent interaction free energy for Ca+2, F" and cr
in water are -2772.3, - 504.5, and 379.1 kJ mort, respectively.

2.24 (a) Lithium and chloride ions have ionic radius of 59 and 181 pm,
respectively. Calculate the work of charging Lt and cr in vacuum. (b)
Calculate now the work of charging Li+ in water with a relative dielectric
constant of 80 at 293 K. (Cf. Exercise 2.28 in the textbook) (Contractor)

Answer:

(a) The work of charging a Li+ ion in vacuum is (cf. Eq. A2.1.4 in the textbook)
34 CHAPTER 2

(6.022Xl0 23 mol- 1 )(+ 1)2 (1.602 x 10-19 C r (2.71)

2(1.l12Xl0-10c2J-lm-l )(59xlO-12 m)

-1
=1178 kJ mol

and the work of charging a cr ion in vacuum is:

(2.72)

-1
=384 kJ mol

The work of charging is less in the case of the chloride ion because its
radius is larger. Note also that the sign is the same in both cases.

(b) The work of charging a Li+ ion in water is (cf. Eq. A2.1.5 in the textbook)

-1
=14.7 kJmol

A polar medium like water reduces the electrostatic force between two
charges by a factor of E in comparison to the vacuum situation. Hence, less work
needs to be done to charge the Li+ ion in water.

Review of Sections 2.15.12 to 2.15.15 of the Textbook

Describe the entropy changes accompanying hydration according to Bockris

and Saluja's model. Write equations for the entropy of (a) an ion in the gas
phase, (b) the Born charging, (c) translation of an ion in a liquid, (d) SC water,
(e) NSC water, and (t) SB water. Explain which one of the three models,
namely, Bernal-Fowler, Frank-Wen or Bockris-Reddy, for hydration entropy
best describes experimental facts. What conclusions related to the structure of
ION-SOLVENT INTERACTIONS 35

hydration water can be withdrawn from this analysis? How does the
compensation effect of entropy and enthalpy affect the free energy of solvation?

2.25 Using the Born equation as representing a part of the free energy of
hydration of ions, derive an expression for the entropy of Born hydration.
What would be the entropy of Born hydration of the iodide ion, which
radius is 216 pm? Consider that the variation of the dielectric constant with
temperature is equal to 0.4 K -1, and that the value of the dielectric constant
is 80. (Cf. Exercise 2.12 in the textbook) (Bockris-GamboaAldeco)

Data:

&=80 a&jaT=OA

Answer:

The free energy according to the Born equation expressed in the mksa
system is (cf. Eq. A2.1.6 in the textbook):

(2.74)

A well known thermodynamic relationship establishes that,

M=-( at..G)
aT p
(2.75)

Therefore,

(2.76)

and the entropy change due to the interaction of r with water is

6.023x 10 23 mol -I (_1)2 ( 1.602 x 10 -19 C ) 2 2

M --w = (...!...) OAK- I
2( 216xlO- 12 m)( 1.112xI0- IO c 2 J-Im -\)
I
80
36 CHAPTER 2

-I -I
= 20.1Jmol K (2.77)

2.26 Calculate the entropy change due to ion-solvent interaction for the ions
K+, Ca+ 2, F and cr in water. Consider the relation os/ aT = 0.356 K -I for
water. (Cf. Exercise 2.14 in the textbook) (Kim).

Data:

r K + =133pm rr =136pm s w (298 K) = 78.3

rCa +2 =99pm rcr = 181pm os/ aT =0.356 K-1
Answer:

The entropy is calculated from the thermodynamic relationship,

/),S = _( adO) (2.78)

aT p

Applying this equation to the equation giving the energy change due to
solvent interaction with the ion (cf. Eq. A.2.l6 in the textbook):

/),S;-S =-( adO J-S) = NA (z;e o )2 12 ( as) (2.79)

aT p 2r; 41t'so s aT p

The entropy change due to the interaction ofK+ with water is, then,

6.023x10 23 mol -I (+ 1)2 ( 1.602xlO -19)2

C
LIS + =--:------:--:-----'------"'--:-
K -w 2(133XIO-12 m)(1.l12XIO-IO C2 J-1m -I)
(2.80)
2
1 ) -I -I -1
x( - 0.356K = 30.3J mol K
78.3

Correspondingly, the entropy changes for Ca+2, F- and cr in water are

162.9,29.6 and 22.3 J mol-1Ki, respectively.
ION·SOLVENT INTERACTIONS 37

2.27 Self diffusion coefficients of certain ions are given in the textbook (e.g.,
DLi+ = 1.0xlO' s cm 2 S-l and D 1_ = 1.47xlO-s cm 2 S-l). The diffusion coefficient
is related to the rate constant of diffusion by the equation I 2 = 2Dk- l • (a)
What kind of value for the jumping distance of an ion during diffusion, I,
would be reasonable? (b) Calculate the times (T) the Li+ and the r ions
reside in one place. Consider T = k-I . Comment on your results. (Cf.
Exercise 2.35 in the textbook) (Bockris-GamboaAldeco)

Data:

From Table 2.26 in the textbook:

Answer:

(a) The parameter I represents the main distance an ion can jump from one site
to another site during the diffusion process. A reasonable value for I would be of
the order of the radius or diameter of the considered ion. Thus, in general, the
value of I can be taken to be of the order of 100 nm.

(b) From the given equation,

2 -1
I =2Dk =2DT (2.81)

where D is the diffusion coefficient, k is the rate constant for diffusion and T is
the mean jump time to cover the mean jump distance (seconds per jump). Since
the radius of Li+ is 59 pm, then I ~ 60 pm and Tis,

2 (
60xl0- cm 10)2
I - 12
T =-= = 1.8xlO s= 5ps (2.82)
2D 2(1.0X10 - 5 cms - l )

In the same way, the radius of the r ion is 216 pm. Thus, I ~ 200 pm and

I
2 (200xlO-10)2
cm
-12
T=-= ( )=13 .6XlO s=13.6ps (2.83)
2D -5-1
2 1.47xl0 cms
38 CHAPTER 2

The Li+ ion, being such a small ion, can move much faster than the much
bigger iodide ion, spending less time (small r) in jumping the mean jump
distance.

Review of Sections 2.16 to 2.20 of the Textbook

Define primary- and secondary-hydration numbers. How are these two

quantities distinguished from each other? Name several methods used to
determine solvation numbers. What influences do hydration waters have on the
different types of molecular orbitals? Draw a schematic of hydration heats of
transition-metal ions vs. atomic numbers. What characteristics are present in
these plots? Explain. Under what circumstances do second hydration waters
bond with greater strength than the first hydration waters? Which are the three
computational approaches used to study ionic solvation? Compare their
effectiveness to determine solvation numbers. Mention the works of Dang,
Malenkov, Heinzinger-Palinkas, and Guardia-Padro. What are the phenomena of
salting-in and salting-out? How can these phenomena be explained in terms of
the orientational polarizabilities of the nonelectrolyte and water? Write
equations for the primary and secondary solvation numbers. What is
Setchenow's constant? Mention the importance of salting-in and salting-out
phenomena in industry. What parameters are responsible for the occurrence of
anomalous salting-in? How is the degree of salting-in affected by the size of the
ion? What are dispersion forces? How does the presence of these forces affect
the solubility of nonelectrolytes in ionic solutions? What is understood by the
hydrophobic aspect of solvation? Explain how solute-solute interactions lead to
hydrophobic effects.

2.28 Calculate the change of solubility of 2,4-dinitrophenol in water due to

the primary solvation when 0~1 M NaCI is added to the solution and the
solvation number of NaCI is assumed to be 5. (Cr. Exercise 2.25 in the
textbook) (Kim)

Answer:

From the equation of change of solubility for non-electrolytes (cf Eq. 2.13 7
in textbook);

S-So cns (o.lmoldm-3 )(5)

---"- =- - - = - = -0.009 (2.84)
So 55.55 55 .55moldm-3
ION-SOLVENT INTERACTIONS 39

This equation indicates that the solubility of 2,4-dinitrophenol in water

decreases by 0.009 x 100 = 0.9% when NaCI is added to the solution.

Review of Sections 2.21 to 2.27 of the Textbook

What is dielectric breakdown? When does this phenomenon occur? What is

the importance of this phenomenon? How does Szklarczyk's theory explain
dielectric breakdown? What is electrostriction? Where does the electrostriction
take place in a solution? Does electrostriction affect ions and molecules as well
as water? How do polyions affect the solvent structure? How is hydration in
poly ions measured? Describe the reverse micelles technique to study protein
dynamics. What is the relation between the structure of biological materials
(e.g., coil-like film and helix) and its content of water? Does water in biological
systems have a different structure from water in vitro? What do spectroscopic
studies say about water in biological systems?

2.29 The definition of compressibility is /3 = -1.(

V ap
av) . On
T
the

approximated assumption that /3 is constant with pressure, find V as a

function of P. Why is your equation applicable only over a limited range of
pressure? (Cf. Exercise 2.22 in the textbook) (Bockris)

Answer:

From the given equation,

/3=_1.(
V ap
av) T
(2.85)

At constant temperature, Eq. (2.85) can be written as,

dV
-=-/3dP (2.86)
V

Integrating this equation under the assumption that /3 is independent of

pressure,

or InV=-/3P+A 1 or (2.87)
40 CHAPTER 2

where AI and A] are constants. This equation is applicable only over a small
range of pressure because f3 is known to be dependent on pressure (cf. Section
2.22.3 in the textbook) up to pressures ofthe order of 109 Pa.

2.30 Calculate tbe pressure exerted by an Na+ ion on a water molecule in

the first hydration shell. Consider the cross section of the ion as the area
where the force is applied. (GamboaAldeco)

Data:

rNo + = 95 pm rw = 138 pm

Answer:

Pressure is defined as force/unit area, or

p=F (2.88)
A

The force is written in the mksa system as (cf. Eq. 2.162 in the textbook)

2 eo J.l cos ()
F=-...:..--- (2.89)
3
4Jr&o& r

Since the angle between the centers of the ion and the water molecule is
zero, then cos () = 1. Considering the dielectric constant in this region to be
equal to 6, and the distance between the ion and the molecule equal to the sum
of their radii, i.e., 95 + 138 = 233 pm, then,

2 eo J.l cos (J
F=-~--
. 3
4 Jr&oer

-30
x 3.336x 10 em x 1 N m = 2.28x 10 -ION
10 IJ

The area where the force is applied is Jr; = 7t(95xl0-12 m)2 = 2.83xlO-20 m2.
Therefore, the pressure is
ION·SOLVENT INTERACTIONS 41

-10
P = 2.28x 10 N x 1Pa = 8.04xl0 9 Pa (2.91)
2.83xI0- m 2 INm 2
20

2.31 Calculate the change of solubility of ethyl ether in water due to the
secondary solvation shell, when 1 M NaCI solution is added to the solution.
The dielectric constants of ethyl ether and 1 M NaCI solution are 4.33 and
70, respectively, the density of ethyl ether is 0.7138 g cm-3, and the
polarizability of water is 1.46 x xlO-14 cm3• The polarizability of non-
electrolytes can be determined from the following equation:

(t: NE -1)
aNE = (2.92)
41iN

where N is the number of molecules of the non-electrolyte (NE) in one cm3•

(Cf. Exercise 2.26 in the textbook) (Kim)

Data:

&ethyl-ether = 4.33 &NaC/ 70

= aw = 1.46 xlO-24 cm3
Pethyl-ether = 0.7138 g cm-3 CNaCl = 1 mol dm-3 rNa + = 95 pm
rC/_ = 181 pm rw=138pm

Answer:

The change of solubility of a nonelectrolyte in water due to the secondary

solvation shell can be calculated from (cf. Eq. 2.151 in textbook);

8-8 0 N Ac4tr(zjeO)2 (a w -aNE)

= (2.93)
80 1000 &2 kTrh

To determine the polarizability of the ethyl ether it is needed to determine

first N, the number of ethyl ether molecules in 1 cml,

Pethy/N A (0.7138 g cm -3)( 6.022 x 10 23 mOl-I)

N =----=...:....-----:........:.-------~
(2.94)
(MW)ethy/ 74.13gmol- 1
21 -3
=5.8xI0 cm
42 CHAPTER 2

From Eq. (2.92)

4.3 -I -23 3
ae1hyl = ( 21 -3) = 4.53x10 cm (2.95)
41l" 5.8x 10 cm

Finally, rh is

(2.96)

Considering that ri == (rNa+ + rCl.)/2 = 185 pm, then,

rh = 138 pm + 2(138 pm) = 414 pm = 4.14xlO-8 cm (2.97)

Substituting Eqs. (2.95) and (2.97) into Eq. (2.93)

S -So ( 6.022 x 10 23 mol- 1 )( Imoldm -3)

r
- - = --'-------'--'------'-
So 1000cm 3dm- 3

(1)2 ( 1.602 x 10 -19 C {1.46 - 45.3)x 10 -24 cm 3

x (2.98)
( 8.854x 10- 12 C 2 J -1 m -1 ){70)2 ( 1.381 x 10 -16 erg K -1 )

7
I 10 erg
x x---~ 0.009
(298K)( 4.14xlO- IO m) lJ

2.32 Determine the dielectric constant of a 50% amine solution. Consider

the dielectric constant of the pure amine to be 4.3, and that of pure water
78. What is the dielectric constant of a solution 30% of this amine?
(GamboaAldeco)

Answer:

The relationship between dielectric constant and concentration is a linear

one (cf. Eq. 2.170 in the textbook),

&=&0 (1-&) (2.99)

ION-SOLVENT INTERACTIONS 43

At c = 0, & = &0 = 78. And at c = 1, 4.3 = &0 (1-8), or 8 = 0.95. Thus,

& = 78 (1- 0.95 c) (2.100)

At 50% concentration of amine, & = 78 [1- 0.95 (0.50)] = 41 , and at 30% ,

& = 78 [1- 0.95 (0.30)] = 56.

PROBLEMS

2.33 For a given water molecule, what is the maximum number of hydrogen
bonds that can be form with other neighboring water molecules? Are these
hydrogen bonds identical in bonding nature? Explain. If there were a
difference in bonding nature for these hydrogen bonds, how would you
differentiate them experimentally? The word maximum is emphasized
because in liquid state the actual number of hydrogen bonds per molecule is
less. Even in the crystal ice-II there are dangling hydrogen atoms that do
not participate in hydrogen bonding. (Cf. Problem 2.17 in the textbook)
(Xu)

Answer:

One single water molecule can form at the most four hydrogen bonds with
other water molecules. They are of two different types: two can be formed with
the hydrogen atoms of the reference water molecule, and the other two with the
lone pairs of its oxygen atom. The former two are electron-acceptor and the
latter two are electron donor. These two types of hydrogen bonds can be
distinguished by the O-H distance: 99 nm for the H ... H type, and 177 nm for the
H ...O type (cf. Fig. 2.9 in textbook)

2.34 (a) Calculate the dipole moment associated with water in the
hypothesis of fully ionic 0-8 bondings, i.e., considering a -2eo charge on the
o atom and a +leo charge on each 8 atom. Draw the associated vector.
Refer to the drawing in Fig. 2.2 for angles and distances in the water
molecule. (b) Knowing the dipole moment of water, write an equation
expressing it in terms of the fractional charge on either end of the dipole, /.
and the distance between the center of charge and the atomic nucleus, x. (c)
Determine f and x in the hypothesis of a tetrahedrical angle (i.e., 1201)
between 8-0-8, and draw the corresponding dipole moment vector. (Cf.
Problem 2.24 in the textbook) (Mussini)
44 CHAPTER 2

H H
Fig. 2.2. Angles and distances in
the water molecule.

Answer:

(a) The dipole moment is given by f-l = qd . Under the hypothesis presented here,
the dipole moment can be represented as in Fig. 2.3(a), and it is calculated as:

f-l = qa = 2 eoc cos ()2 = 2( 1.602 X10 -19 C )(97X 10 -10 cm )cos 105
2 (2.101)
-27
= 1.89xl 0 C em

(b) From the dipole moment of water, 1.87 D,

-28
f-lw = 2e oft=1.87D 3 .336xlO Ccm (2.102)
ID

Solving for the parameter f,

-9
1= 1.94xlO (2.103)
x

with x given in cm. See Fig. 2.3(b).

(e) With the angle between H-O-H equal to 120°, a new set of variables (a', b'
and c ') is assigned. With b = b', and a' = x, the distance a ' is

a'= x = b' tan {120/2 )= 46 pm (2.104)

and the parameter lis,

ION-SOLVENT INTERACTIONS 45

o o

Ii Ii
Ii

(a) (b) (c)

Fig. 2.3. The parameters f.J and fin the water molecule according to Problem 2.34.

-9
f = 1. 94 xl 0 = 0.42 (2.105)
-10
46xl0 cm

Finally, the dipole moment becomes,

f.i w =2e oft =2( 1.602 x 10-19 C )(0.42)( 46xlO- 10 cm)

(2.106)
=6.l9x 10 -28 C cm =1.86D
See Fig. 2.3(c).

Comment This problem follows the 1933 Bernal and Fowler approach, which is
still very appreciable. However, more complicated charge distributions, e.g.,
quadrupole ones, have been proposed in latter years.

2.35 (a) Using data for the solution enthalpy (Allso/n ) and lattice enthalpy
(AIl/alike = -Lsub) in the Table below, calculate the hydration heats for
various alkali halides (AIls). Comment on the possible source of major
error. (b) Using cation radii data, explain the trend and the sign of AIlso/n.
What is the driving force of the solution process when AIlsoin > O? (Cf.
Problem 2.11 in the textbook) (Xu)

LiCI LiBr NaCI NaBr KCI KBr

AIlso/n (kJ mol -I) -37.0 -48.8 +3.89 -0.6 +17.22 +19.9
LlSso/n (kJ mol -I KI) +48 +43 +110 +100 +135 +140
AIl/alike !kJ mol -Il -852 -815 -787 -752 -717 -689
46 CHAPTER 2

Answer:

(a) The heat of solvation of the salt is given by (cf. Fig. 2.13 in textbook):

!:!J{ s ,salt =!:!J{ so In +!:!J{ lattice (2.107)

where it was considered that Lsub = -iJHlaltice. Thus, for LiCI,

-1 -1 -1
iJHs,LiCI =-37.0kJmol -852 kJ mol = 889kJ mol (2.108)

In the same way for the other salts:

LiCI LiBr NaCl NaBr KCl KBr

iJHs.sall (kJ mol -I) -889 -864 -783 -753 -700 -669

Since iJHs,sall has dominant contribution from iJH1allice. the major possible
source of error should come from this parameter. Besides, iJHsoln can be
accurately measured.

(b) In the solution process: MX (s ) ~ M + (aq) + X - (aq), the parameter that

indicates whether or not the salt dissolves is L1Gsoln . The more negative L1Gsoln is,
the more stable the ions are in solution. Now, L1Gsoln has two contributions, one
from the enthalpy of solution, iJHsolm and another from the entropy of solution,
iJSso1n, i.e., AG soln =!:!J{ soln - TAS soln .
The first term, iJHso1n , is the result of the stabilization of the ions due to the
ion-solvent interaction (iJHs.sall), and the de-stabilization of the ions due to
disruption of the lattice (LJHlallice)' The major contributors to the stabilization
factor (Born charging term, ion-dipole/quadrupole terms and induced dipole
terms) are proportional to 1';-n , with n = {1...4} and r being the radius of the
ion. Thus, the smaller the ion, the stabilization of the ions due to solvent-ion
interactions becomes greater, and therefore, iJHsoln becomes more negative. A
large negative iJHsoln means a large negative L1Gsoln '
In the opposite case, i.e., when very large cations are present, e.g. K+, the
stabilization due to solvent ion-interactions cannot cover the de-stabilization due
to the disruption of the lattice. This results in small negative numbers or even
positive values for iJHsoln' In such cases iJSsoln becomes the sole driving force in
ION-SOLVENT INTERACTIONS 47

the dissolution process, because only a large LiSsoln will assure that L1Gsoln < 0
and therefore that the salt dissolves.

2.36 Using the data in the table below, calculate the heats of solution,
LJJIsolm and the heats of solvation, LJJI., for AgCI, AgBr and AgI and
rationalize their low solubility. (Cf. Problem 2.7 in the textbook) (Xu)

Answer:

The dissolution reaction of a salt in solution is:

AgCI AgBr AgI

K (equilibrium constant) 1.77xlO- IO 7.7xl0-13 1.5x10-16
LlSsoln (kJ mol -I K -I) 32.98 51.34 73.59
LJJI,attlce (kJ mol -I) -912 -900 -886

+ -
MX(s)~M (aq)+X (aq) (2.109)

Its equilibrium constant is

(2.110)

and the free energy of solution is given by,

I1G soln =-RTlnK (2.111)

The free energy of solution can be split into an enthalpy term and an
entropy term:

I1G soln = I1H soln - TI1S soln or I1H soln = I1G soln + TI1S soln (2.112)

In addition, the heat of sublimation (Lsub) is equal to the negative of the

lattice enthalpy (&llal/ice). Thus, the heat of solvation of the salt is (cf. Fig. 2.13
in the textbook),

I1H s ,salt = I1H so In + I1H lattice (2.113)

48 CHAPTER 2

Thus, for AgCI, the free energy of solution from Eq. (2.111) is

~Gsolo =-(S.3IJmOl- I K- 1 )(29SK)ln1.77XIO- 1O

(2.114)
= 55 .61 kJ mol -I

and the enthalpy of solution, from Eq. (2.222) is,

Mf solo = 55.61 kJ mol -I + ( ) ( 32.98x 10 -3 kJ mol -I K -I)

298K

-I
= 65 .44 kJ mol (2.115)

The heat of solvation from Eq. (2.113) is,

-I -I -I
i1H s ,salt = 65.44 kJ mol - 912 kJ mol = -846.5 kJ mol (2.116)

In the same way, for the other two salts:

AgCl AgBr AgI

L1Gsoln (kJ mol -1) 55.61 69.10 90.27
i1Hsoln (kJ mol -1) 65.44 84.40 112.20
i1Hs,salt(kJ mol -1) -846.5 -815.6 -773 .8

Since L1Gsoln > 0, then the three salts are insoluble, with AgI being the most
insoluble salt. In the three cases i1Hsoln > 0, and the entropy change, L1Ssoln is not
positive enough to make the process happen (see table above). The stable lattice
of these salts --marked by the large negative value of i1Hlallice- makes it
difficult for the solvent to grab the ions away.

2.37 The densities of aqueous NaCI solutions at 25°C are given as a

function of NaCI molality in the table below. The density of pure NaCI is
2.165 g cm-3• Calculate the partial molar volumes of: (a) NaCI (V 2 ) , and
(b) water (VI ),and plot these values as a function of NaCI molality. (c)
Compare the limiting cases, i.e., VI when m 7 0, and 2 when m 7 v
saturation, with those of pure water and pure NaCI molar volumes, V/ and
ION-SOLVENT INTERACTIONS 49

v/, respectively. (d) Calculate j/2 for m = 0.5 mol kg-3 and m = 2 mol kg-3.
(Cf. Problem 2.23 in the textbook) (Mussini)

o 0.99707 3.09392 1.10849

0.11094 1.00158 3.9873 1.13600
0.23631 1.00663 5.24324 1.17290
0.56874 1.01970 5.4952 1.18030
0.85382 1.03071 5.8023 1.18880
1.47458 1.05353 5.82267 1.18888
2.51393 1.08963

Answer:

(a) The volume of the solution can be divided into (cf. Eq. 2.6 in the textbook):

(2.117)

where Vm•2 is the apparent NaCI molar volume in the solution and Vm. J is the
molar volume of the solvent. The apparent molar volume is a quantity that can
be obtained from the experimental values of density of the solution.
Differentiating Eq. (2.117) with respect to n2. keeping nJ constant,

(2.118)

Now, the total volume of the solution can also be divided into:

(2.119)

where VI and V2 are the partial molar volumes of water and NaCI,
respectively. However, the partial molar volumes cannot be determined directly
from experimental data, although can be related to the corresponding apparent
molar volumes. The partial molar volume is defined as (oV / an i ) n .
j

Therefore, V2 = (oV / on2)n . Then,

1
making use of Eq. (2.118), the partial
50 CHAPTER 2

molar volume of NaCI (V2 ) can be written in tenns of the apparent molar
volume ofNaCI (Vm.2) as:

+Vm,2 (2.120)

The condition of constant n I can be observed by considering always an

amount of solution corresponding to 1 kg of solvent, i.e., nl = 1000 g /18.0152 g
mol-I = 55.51 mol, an advantageous conditions because in this case n2 = m.
The parameter, Vm•2 can be obtained from Eq. (2.117) (cf. Eq. 2.6 in the
textbook:

Vm .2 (2.121)
n2

The total volume of the solution, V, can be obtained from the data of
solution density. Thus,

msoln mw +mNaCI mw +n2 (MW)NaCI

V =-- = =------==.:....
Psoln Psoln Psoln
(2.122)
1kg + n2 ( 0.0585 kg mOl-I)

Psoln

For CNaCl= 0.11094 mol kg-\ and p= 1.00158 kg dm-3 , Eq. (2.122) becomes,

lkg +(0.11094mol)( 0.0585 kg mol-l ) -3

V= =1.0049dm (2.123)
(1.00158kgdm -3 )

and Eq. (2.121) becomes,

Vm 2 =
'
1
O.11094mol
[1.00490dm 3 - lkg
O.99707kgdm-3
1 (2.124)

= O.OI770dm 3 mol- l
ION-SOLVENT INTERACTIONS 51

The values of V and Vm.2 at different concentrations are shown in the

following table for 1 kg of solvent:

d
Molality8 Densityli V" Vm.2 dVm./dn/ -
Vz
f -
VI
g

o(water) 0.99707
0.11094 1.00158 1.0049 0.01770 0.00103 0.0178 0.0181
0.23631 1.00663 1.0071 0.01781 0.00101 0.0181 0.0181
0.56874 1.0197 1.0133 0.01823 0.00096 0.0187 0.0181
0.85382 1.03071 1.0187 0.01842 0.00092 0.0192 0.0181
1.47458 1.05353 1.0311 0.01908 0.00084 0.0202 0.0180
2.51393 1.08963 1.0527 0.01980 0.00070 0.0215 0.0180
3.09392 1.10849 1.0654 0.02019 0.00062 0.0221 0.0180
3.9873 1.1366 1.0850 0.02059 0.00050 0.0226 0.0179
5.24324 1.17290 1.1141 0.02120 0.00032 0.0229 0.0179
5.4952 1.18030 1.1196 0.02123 0.00029 0.0229 0.0179
5.8023 1.18880 1.1267 0.02133 0.00025 0.0228 0.0179
5.82267 1.18888 1.1276 0.02142 0.00024 0.0228 0.0179
NaCl 2.165
amoINaclkg",/v cdm J edmJ Imof 'dm 31mol
bkg",,'/dm3"',. ddm 31mol fdm 31mol

The next step is to fmd the value of (av m,2/ On 2) D. . This can be done
from the slope of a Vm.2 vs. n2 curve. Plotting Vm•2 against n2 (or m) gives the
graph in Fig. 2.4. The data fit the second-degree polynomial:

0.022

0.021

0.020
Vm.2
0.019

0.018 V m.2 = -6.85x10· 5 m 2

+ 0.001042 m + 0.017609
0.017
0 2 3 4 5 6

Figure 2.4. The apparent NaCI molar volume vs. molality

52 CHAPTER 2

Vm ,2 =-0.0000685n~ +0.001042n2 +0.017609 in dm3 mol-' (2.125)

Differentiating this equation with respect to n2 (or m) gives:

( oVm .2) = -0.0001370n2 + 0.001042 in dm3 mol- 2 (2.126)

on2 n1

Now we have the parameters to fmd V:1' Thus, substituting the

corresponding values into Eq. (2.120) for m = 0.11094 mol kg-' and using the
values of Vm,2 calculated before,

V2 =0.11094 moI{[- 0 .0001370(0.11094)+ 0.001042]dm 3 mol-2 } (2.127)

3 -I 3-1
+0.01770dm mol =O.01781dm mol

(b) Once the values of the partial-molar volume of the solute are known, the
partial-molar volume of water, VI' can be calculated from Eq. (2.119), i.e.,

- V- n 2 V2
VI =----'::........::::.. (2.128)
nl

For mNaCl = 0.11094 mol kg-I,

_ 1.0049dm 3 - (O.l1094moi)( 0.01781dm 3 mOL-I)

VI =----------~------~ (2.129)
55.51mol
3 -1
= O.01807dm mol

The corresponding values of V2 and VI at different molalities of NaCI are

given in the previous table. Figure 2.5 shows the corresponding plots of V2 and
VI as a function of mNaCl..

(c) Limiting case I: m -7 0, VI -7 yowaler

ION-SOLVENT INTERACTIONS 53

o 2 6
0.026
-----------------------
VO N8C1

0.024

• • •••
•
V2 0.022

•• •
0.020

0.Q18 ~

... --------------------
0.0184

- 0.0182 VOwater
V1
0.0180

0.0178
• •• • • ••
0.0176

o 6

Figure 2.5. Partial-molar volumes of water (C\) and of NaCI (V2 )

vs. the molarity of the solution.

-I
o MW water 18.016 g mol
= -----'---- = 0.0181 dm - 3 mol- 1 (2.130)
V water
-3
Pwater 997.07 gdm

This value is shown in Fig. 2.5. There is a good agreement between

(VI )m~O and Vwater-
Limiting case II: m 7 sat, V2 7 VONaC!
-I
o MW Nael 58.50 g mol -3 -I
V NaCl = 0.02702 dm mol (2.131)
PNaCl 2165 g dm -3

This value is shown in Fig. 2.5. It shows that (V2 ) m~oo < V NaCl·

(d) (V2 )m=O.5molkg- I = 18.6cm 3 mol- I and (V) 2 m=2.0molkg- I

-- 210
•
cm 3 morl.
54 CHAPTER 2

2.38 (a) Justify that in dilute solutions, the solvation number is given by

ns = 55.56 (1-~)' where c is the electrolyte concentration in mol dm-3 ,

e ~o
P is the compressibility of the electrolyte, and Po the compressibility of the
pure solvent. (b) The compressibility values of LiCI, NaCI, KCI and MgCh
solutions are given in the table below. The compressibility of the pure
water, under the experimental conditions, is 44.65xl0-6 bar-I. Calculate the
total solvation number of these electrolytes. (Cf. Problem 2.21 in the
textbook) (Xu)

C PLiCI xl 06 PNaCIxl06 PKCI xl06 PMgCI2 xl06

(mol dm-3) {bar-I} {bar-I} {bar-I} {bar-I}
0.05 44.49 44.45 44.46 44.21
0.09 43.88
0.10 44.30 44.20
1.00 40.60 40.04 39.84
1.05 35.94
2.00 37.15 36.64
4.10 29.88
5.00 29.93 26.75

Answer:

(a) The volume of an aqueous solution can be divided into two parts according
to its compressibility: a compressible volume and an incompressible volume.
The incompressible volume, v, consists of the volume of water molecules
that are in the primary shell. If the number of water molecules around a single
ion is n." and e is the concentration of ions in mol litef 1, then, the total number
of water molecules in the primary shell is ens. Thus, the incompressible volume
of water is v = Vo en s' where Vo is the molar volume of water. From the
definition of compressibility (cf. Eq. 2.9 in the textbook):

P = _J...[ a(v -v)] = _J...( av) (2.132)

V ap T V ap T

where V is the total volume of solution given by V ~ 55. 56 V0 (for diluted

solutions), and (V-v) is the volume of the compressible water. However, this
compressible water should have the compressibility value of pure water, i.e., Po:
ION-SOLVENT INTERACTIONS 55

/3 - 1 [8(V-V)] _ 1 (8V) (2.l33)

o- - V- v 8P T - - V- v 8P T

Therefore,

-
/3 V -v v Vocns cns
= - - = 1-- = 1- ---.:.---.:.- 1 - - - (2.l34)
/30 V V 55.56Vo 55.56

or

ns =(1_L)55.56 (2.l35)
/30 c

(b) Using the above relationship, for 5.00 M LiCI,

ns = ( 1_29.93xlO -6 bar -\ 1 55.5moldm -3 =3.7 (2.136)

-6 -\ -3
44.65xl0 bar 5.00moldm

The values of total solvation number of the other electrolytes are listed next:

c(mol dm'3) LiCI NaCI KCI MgClz

0.05 4.0 5.0 4 .7 11.0
0.09 11.0
0.10 4.8 5.6
1.00 5.0 5.7 6.0
1.05 10.3
2.00 4.7 5.0
4.10 4.5
5.00 3.7 4.5

2.39 (a) Calculate the transport numbers, t+. of Li\ Na\ K+, and Mi+ in
dilute chloride solutions. Use the mobility data, f.4 and #' in the following
equations and table:

#+
t+ = - - - (2.l37)
#+ +#-
56 CHAPTER 2

and

(2.138)

Ion cr
4.01 5.19 7.62 5.42 7.91

(b) Estimate the term A in the following equation that relates the solvation
numbers of the ions in the chloride salts based on their transport numbers
(cf. Eq. 2.17 in textbook):

M +A (2.139)
2. 79a o

Use the values of (Vs)+ and (Vs). given in Table 2.6 in the textbook. (Xu)

Answer:

(a) Using the Eq. (2.137) for transport number for the first solution, LiCl,

1+ =_J.L_+_= 4.01 =0.33 (2.140)

J.L+ +J.L- 4.01+7.91

In the same way, INa+ =0.39; t K + =0.49; t Mg 2+ =0.41

(b) Comparing Eq. (2.16) in the textbook with Eq. (2.139)

(2.141)

Substituting the corresponding values for LiCl,

ALiel =1-(0.33(140.7)_1-0.33(92.4)) (2.142)

18 1 1
ION·SOLVENT INTERACTIONS 57

_..l.(
18
0.33 (6.9 )_1-0.33 (35.5)) = 0.34
1 1

In the same way for the other electrolytes: ANaCl = 0.082; A KCI = -0.18;
A MgC12 = 0.12.

2.40 Suppose tbat tbe transport numbers obtained in Problem 2.39 are
independent of concentration. Calculate tbe absolute ion solvation number,
n+ and n .• for (a) LiCI and (b) MgClz. Use tbe value of M/2 .79ao from
Table 2.6 in tbe textbook, tbe value of A obtained from Problem 2.39, and
tbe total solvation number n., given by ns =Iz+ In+ +lz_ln_, obtained in
Problem 2.38. (Xu)

Answer:

(a) From Problem 2.38, ns for a solution of 0.05M Liel is ns,LiCI = 4.0. Thus,

(2.143)

Substituting this equation in the equation that relates the solvation numbers
of the ions in salts based on their transport numbers (cf. Eq. 2.17 in the
textbook):

(2.144)

Rearranging terms in Eq. (2.144),

(-Izt++-I](n s -n - )- (I-t+
- - ]n
I I -
L
= M
2.79 a 0
+A (2.145)

Substituting the parameters A = 0.34 from Problem 2.39 and L1EI2.79ao =

0.112.79 from Table 2.6 in the textbook, and solving for no,

(0.33)( 4.0-n_ )-(1-0.33 )n_ =..Ql..+0.34 (2.146)

2.79
58 CHAPTER 2

Solving for n_ gives, n _ = 0.94 . Also, n+ = n s - n_ = 4.0 - 0.94 = 3.1

(b) Similarly, for 1 M MgCh, ns.MgCl2 = 10.3 from Problem 2.38:

(2.147)

Considering the parameters A = 0.12 from Problem 2.39 and t1EI2 .79ao =
112.79 from Table 2.6 in the textbook, Eq. (2.145) for MgCh is written as

0.41(10.3_2n_ )-(1-0.41)n_ =.lQ...+0.12 (2.148)

2 2.79

LiCI MgCh
cr cr
3.1 0.94 7.04 1.63

2.41 The following table lists the measured dielectric constants at 25°C for
1.0 M LiCI, NaCI, and KCI solutions. Calculate the percentage of water in
the primary sheath. Compare your results with those of the compressibility
method and comment on their reliability. (Cf. Problem 2.22 in the textbook)
(Xu)

LiCI NaCI KCl

Eat 25°C 64.9 66.7 68.1

Answer:

From the model of Hasted et aI., (cf. Eq. 2.27 in the textbook),

55.56- ci n s cins
E=80 +6-- (2.149)
55.56 55.56

where 55.56 stands for the number of moles of water in 1 dm3, and Cj is given in
mol dm-3 . Thus, solving for ns,
ION-SOLVENT INTERACTIONS 59

55.56(80-& )
(2.150)
74ci

Therefore, the primary hydration number for LiCI is,

ns (L I'Cl)-- 55.56(80-64.9)_
-11 (2.151)
74(1.0)

This result indicates that about 11155.56 or 20% of water molecules are in
the primary sheath. In the same way for NaCI and KCl, about 10/55.56 or 18%
and 9/55.56 or 16% of water molecules respectively are in the primary sheath.
Comparing these values with the corresponding ones obtained from the adiabatic
compressibility method (cf. Table 2.5 in textbook: niLiCl) = 4.9, niNaCl) =
5.7, and ns(KCl) = 5.7, the solvation numbers obtained through the dielectric
constant method are higher.
The major error source is the oversimplification of the model, where water
molecules are classified ·into two groups with distinct demarcation. It does not
consider the reduced dielectric constant in the structure breaking region.

2.42 Calculate the heat of interaction between the three individual ions, cr,
Na+ and Br-, and water, i.e., Mi cl - -w ,I!J{ .,
iVa
+
-w
, Mi B -
r -w
• Use the
following experimental values of the heats of interaction between a salt and
water at 25 DC:

Salt KF KCI NaF NaBr

.&lsalt-w (kJ mol -1) -827.6 -685.3 -911.2 -741.8

Consider the Born model as valid. (Cf. Problem 2.5 in the textbook)
(Constantinescu)

Answer:

The heat of interaction between individual ions and water is related to the
heat of interaction between the salt by (cf. Eq. 2.32 in the textbook)
Mi salt-w = Mi A + -w + I!J{ x - -w . The Born model involves the postulate that
ions that have equal crystallographic radii also have equal interaction with the
60 CHAPTER 2

solvent. The pair KF is chosen to start the calculations because the radii of the
K+ and F" ions are almost equal (see tables in Chapter 1). Thus,

MI KF- w =M1 K + -w +M1 F - -w (2.152)

Since rK+ "'" rr, then,

AI{ KF-w -827.6kJmol- 1

AI{ + "",AI{ - = - - - = - - - - --
K -w F -w 2 2 (2.153)
= -413.8 kJ mol-1

Once these values are obtained, the other values can be calculated:

M1 KCI - w =M1 K + +M1 cl - (2.154)

-w -w

or

AI{ cr -w = AI{ KCI-w - AI{ K + -w = -685.3 - (- 413.8)

(2.155)
= -271.5 kJ mol-I

In the same way,

MI NaF-w = MI lYa (2.156)

AT +
-w +M1 F - -w

or

AI{ AT
lYa
+
-w =AI{NaF-w -AI{F- -w =-911.2-(-413.8)
(2.157)
-I
= -497.4 kJ mol

and,

M1"aB
lV, r-w =M1 Na + -w +M1-
Br - w (2.158)

or

Al{B - =AI{NaBr-w -AI{" + =-741.8-(-497.4)

r -w l Va -w (2.159)
= -244.4 kJ mol-I
ION-SOLVENT INTERACTIONS 61

Comment. The differences between the Born values for heats of ion-solvent
(heats of solvation) and these "experimental" values are numerically too high, in
some cases nearly 50% too high. To reduce this difference between the theory
and the experimental values, the ion-dipole and the ion-quadrupole theory were
developed. The basis of these theories is knowledge of the structure of the
solvent in the bulk and in the region around the ions.

2.43 (a) Write an expression for the potential in a point P of the electric
field created by a dipole of moment J.I. (b) Using the expression developed in
(a), write an expression for the potential energy of ion-dipole interaction.
(c) Calculate the potential energy, E p , of ion-dipole interaction between
water and a z-valent cation, as a function of the distance r, the ion charge Zj,
the angle (), and the relative permitivity &. (d) Perform a complete
calculation for the limiting cases, i.e., Zj = 1, 0 = 0, r = 2 A, & = 4.5, and Zj = 1,
o = 0, r = 6 A, & = 80. Assume that the relative positions are as in the Fig.
2.6, with the negative end of the water dipole facing the positive ion. (e)
Assuming the intermediate values of & increase exponentially with r, draw a
complete Ep vs. r curve for the interval 2 < r < 6, and mark the region in
which the thermal energy, -RT, is competitive with the electric interaction.
(cf. Problem 2.25 in the textbook) (Mussini)

Answer:

(a) The potential generated by one q charge at a distance r in vacuum is given by

q
v=-- (2.160)
41r&or

and the potential generated by more q; charges,

(2.161)

Therefore, the potential generated by the dipole in Fig. 2.6(b) in a point P at

a distance r from the center of the dipole is,

(2.162)
62 CHAPTER 2

H
(~.- .....
, + ..................
\ .
. . ........... .

Figure 2.6. Relative positions of the atoms in a water molecule

according to Problem 2.43.

Now, if a < < r (i.e., the point P is far away from the dipole). then r2 - r I ;: a
cos B. and r2r. ;:/, and

v q a cosO J.i cosO

(2.163)
""'-4----2-"'" 2
1rEO r 41l'eor

(b) The potential energy in vacuum is given by,

(2.164)

and in a medium of relative permittivity e.

(2.165)

(c) Thus, using Eq. (2.165) to calculate Ep as a function ofr inA, Z;, B. and e,

(1.86D )z( 1.602 x 10- 19 C )( 6.022 x 10 23 mOl-I)

(,,1' 1
= x
(Ul2X 10 -10 C' J- 1m -1 )"
ION-SOLVENT INTERACTIONS 63

-30 ( 1010 1)2

xcosBx 3.336xl0 em x - - - - = 538.405zcosB (2.166)
ID 1m 2

where Ep is given in kJ morl.

(d) For Zi = 1, B = 0°, r =2 A, and & = 4.5,

E _538.405{I)COSOO -299kJ . -1
- -. rn~ (2.167)
p 4.5(2)2

and for Zi = 1, r = 6 A, and & = 80,

538.405(I)cOSO O -I
E = O.2kJrnol (2.168)
p 80(6)2

(e) If & increases exponentially with r, then the equation that satisfies this
condition is

Br
&=Ae (2.169)

To evaluate the constants A and B, we make use of the conditions that at r =

2 A, & = 4.5, and that at r = 6 A, & = 80. Thus, from the two equations
ln4.5=lnA+2B and In80=lnA+6B, the constants A = 1.067, and B =
0.719. Substituting these values into Eq. (2.169),

& = 1.067 e O. 719r (2.170)

Therefore, the corresponding equation of Ep is:

E = 504.600z cosS -I
in kJrnol (2.171)
p 2 O.719r
r e

where r is given in A. A plot of this equation is given in Fig. 2.7. When Z = 1

and B= 0°.
64 CHAPTER 2

30r-----~------~--~--~--~~

25

20

5 RT

3 4 5 6
r (A)

Figure 2.7. Potential energy due to the dipole in Fig. 2.6 as a

function of the distance r.

The value of RT = (8.314 J mor l K 1)(298 K) = 2.481 kJ mol -I is marked

by a broken line in Fig. 2.7. The thermal energy, RT, becomes competitive when
the distance between the point P and the dipole is larger than 3.5 A.

2.44 (a) Calculate the heat of ion-solvent interaction considering only the
Born term, i.e., ..&IBc. for cr ions at 298 K. The dielectric constants of
water at three different temperatures are:

Temperature <"9 20 25 30
80.1 78.3 76.54

(b) Considering that chloride ions are surrounded by four water molecules
in the gas phase calculate their ion-dipole interaction energy. (c) Calculate
..&Ii _w for chloride ions using the ion-dipole model at 298 K. (Cf. Problem 2.8
in the textbook) (Contractor)

Answer:

(a) The Born term for ion-solvent interaction is (cf. Eq. 2.42 in textbook):
ION-SOLVENT INTERACTIONS 65

(2.172)

To estimate the derivative (OE / oT) p

we use the central difference formula
[cf. Numerical Methods for Mathematics, Science and Engineering, by J. H.
Mathews, Prentice-Hall, 2nd Ed., (1994), p. 318]:

OE I 76.54-80.1 -0.356K-1 (2.173)

oT 25C 30C-20C

Substituting values for the cr-water interaction intoEq. (2.172):

6.023 x 10 23 mol- I (_1)2 (1.602 x 10- 19 e r

Mf BC(CI - -w) = - 2[ 181 x 10- 12 m+(2)138 x 10-12 m J( 1.112 x 10-10 e 2 J-Im -I)

X[I __I__ 298K(0.356K- I )]=-147.5 kJ mol-I (2.174)

78.3 78.3 2

(b) From the equation (cf. Eq. 2.41 in the textbook):

(2.175)

(18IXIO- 12 m+138xlO-12 m
-30
r (1.112XIO- IO e 2 J- I m- l )

x 3.336 x 10 em _ 204.8 kJ mol-I

10

(c) The enthalpy of ion-water interaction for negative ions is (cf. Eq. 2.48 in the
textbook):

-I
!!J{ i-w = 30 kcal mol (2.176)

4N A Zi eo f.J w N A (Z i eo) 2 [ 1 T (OE) 1

- (r; +rW )2 47rEO - 2(r; +2rw )4JrE O 1-~- E2 oT p
66 CHAPTER 2

Substituting the corresponding parameters, and making use ofEq. (2.174),

!l.H c/- -w = (30 kcal mol -\ ) 4.186 kJ

1 kcal (-\2 -\2 ) 2
195x1O m+138xI0 m

(1.602 x 10 -19 C )1.8 D 3.336 xlO -30 em 1 kJ

x x-------
( 1.112 x 10 -\0 C 2 J -\ m -\ ) 1D 1000 J

-147.5 kJ mol -\ =- 209.8 kJ mol -1 (2.177)

2.45 Estimate the error introduced in calculating the heat of interaction

between NaBr and water when the distortion of the charge distribution of
water molecules due to the electrical field is ignored. Consider the values of
dipole moment, quadrupole moment, and polarizability of water as
indicated in the Table section. The dielectric constant of water at 25°C is Sw
= 78.5, and (OE w / or )= -0.356 KI. (Cf. Problem 2.9 in the textbook)
(Contractor)

Answer:

For positive ions (cf. Eq. 2.52 in the textbook) the heat of ion-water
interaction is:

Evaluating this equation for Na+ ions,

!!JI + =(20 kcal mol-I )4.l86kJ ( 2.179)

Na -w 1kcal
4(6.023XI0 23 mol-I )(+I)(1.602XIO- 19 C)1.8D 30
3.336x 10 - em
---~-----~--~----~---- .------+
(95XIo- 12 m+138xlO-12 mr (l.l12XIO- IO C 2 J-l m -l) ID
ION-SOLVENT INTERACTIONS 67

r
4(6.023Xl0 23 mol-I )(+I)(1.602XIO- 19 e)3.9xlO- 10 Dm -30
+ 3.336x 10 em

2(95Xl0- 12 m+138xl0- 12 m (1.l12XI0- 1O e 2 J-I m -I) ID

6.023 x 10 23 mol -I (+ 1)2 ( 1.602 x 10 -19 e )2

2[95XIO- 12 m+(2)138xlO- 12 m J( 1.112xl0-10 e 2 J-I m -I)

X[l __l__ 298K (0.356K -I )]

78.3 78.3 2

4( 6.023xl0 23 mol-I )( 1.46 x 10- 24 em 3 }+1)2 (1.602XIO-19 e r

r
1m 3

2(95XIO-12 m+138xlO- 12 m (1.112XIO-10 e 2 I- 1m -I) 10 6 em 3

= - 441.11 kJ mol-I

For negative ions (cf. Eq. 2.53 in textbook) the heat of ion-water interaction
is:

(2.180)

Therefore,

& _ =(30kealmol- 1 )4.186kJ

Br -w I keal

r
4(6.023XI0 23 mol-I )1-11(1.602XIO- 19 e)1.8D 30
3.336 x 10 - em
----~----------~~~----------~------
(195XIO- 12 m+138xlO-12 m (1.112XI0- 10 e 2 J-I m -I) ID

4( 6.023 X10 23 mol-I )1-11(1.602XIO-19 e )3.9XIO-10 Dm

3.336 x 10 -30 em
ID
68 CHAPTER 2

6.023x 10 23 mol- I (- 1)2 ( 1.602 x 10 -19 C r

2[195XIO- 12 m+(2)138xl0- 12 m ](1.112XI0-1O c 2 J-1 m- l )

x [1- _1__ 298K (0.356K -I )] (2.181)

78.3 78.3 2

r
4 ( 6.023x 10 23 mol -I )( 1.46 x 10 -24 em 3 ) (_1)2 ( 1.602 x 10 -19 C ) 2

2(195XIO- 12 m+138xl0- 12 m (1.112XIO- 10 c 2 J-1 m- l )

= - 300.00 kJ mol -I

Therefore, the total heat ofNaBr-water interaction is,

-1 -1
AH NaBr-w = AH ,,+ -w
/Ya + AHBr - -w = -441.11kJ mol - 300.00kJ mol

=-741.09 kJ mol-l (2.182)

The energy due to ion-induced dipole interactions involves the term

4N Aa(z;eo)2 +
- . Evaluating this term for Na and Br", the total ion-
2(r; +rw )4 4Jr&o
induced dipole interaction is 137.72 kJ mOrl + 33.01 kJ mOrl = -170.73 kJ
mort. Thus, the error in AHNaBr-w committed by ignoring these terms is:

170.73 x 100 = 23.04% (2.183)

741.09

2.46 In a cation-solvent interaction model, cf. Fig. 2.37 in textbook, the

"solvated-coordinated water" has two sites capable of forming hydrogen
bonds with water molecules in the SB region. Are these two sites identical in
bonding? For the "non-solvated coordinated water" there are three sites for
hydrogen bonds. Are these three sites identical? Explain. (Cf. Problem 2.18
in the textbook) (Xu)

Answer:

The two sites in the solvated coordinated water are both acceptor in nature.
On the other hand, in the non-solvated coordinated water one of the sites is
ION-SOLVENT INTERACTIONS 69

electron donor in nature since it is on one of the lone pairs of oxygen that is
disoriented from the ion.

2.47 An ion of charge zen and radius r is transferred from a solvent of

dielectric constant &j to a solvent of dielectric constant sf' Derive an
expression to calculate the free energy change associated with this transfer
using the Born model. (cf. Problem 2.14 in the textbook) (Contractor).

Answer:

The process of transferring an ion from one solvent molecule to another

solvent molecule, is equivalent to subtract the individual transfer of the ion from
vacuum to each one of the solvents. Thus,

!3.G i~ f =G f - Gi = (G f - G vacuum )- ( G i - G vacuum )

(2.184)
= !3.G vacuum~ f -!3.G vacuum~i

Therefore, from Born equation (cf. Eq. A.2.1.6 in the textbook),

!3.G Hf =[_ N A {zeo )2

2r
1
(1 _ _
&f
ll-[- NA {zeo )2
2r
(1 __
1
&i
II (2.185)
= N A {zeo )2 (_1 -~l
2r &f &i

2.48 What is the free energy change involved in transferring chloride ions
from water to a nonpolar medium like carbon tetrachloride with a
dielectric constant of 2.23 at 25°C? Is this an energetically favorable
process? Comment on your answer. Make use of the equation developed in
Problem 2.47. (cf. Problem 2.15 in the textbook) (Contractor)

Answer:

Using the equation developed in Problem 2.47:

!3.G Hf
NA {zeo )2 (_1___11 (2.186)
2r &f &i
70 CHAPTER 2

which is valid when the charge is given in electrostatic units, the distance in
centimeters and the free energy in ergs per mol. Introducing the term 47rco in the
denominator changes the charge units to coulombs, the distance to meters, and
the free energy to joules per mol:

I1G · j =
N A(ze o )2( -1- - 1- J (2.187)
I~ 47rco 2r Cj ci

Substituting values into this equation:

6 .. 023xl0 23 mol -\ (_1)2 ( 1.602xl0 - \ 9

C) 2
LlGHj
(2.188)

( I
x ---
2.23 78.54
1) =+167.22kJmol -1

Since I1G H j is a large positive number, the process is not favorable . This
result can be understood qualitatively even without involving the Born model.
Water has a large dipole moment and therefore the ion-dipole interactions are
quite strong in this solvent. The opposite occurs in carbon tetrachloride with low
dielectric constant. Therefore, the ions would prefer to be in water.

2.49 Living cells are surrounded by bilayered membranes, and aqueous

environments are present on both sides of the membrane. The interior of
the membrane is highly non-polar in nature. Based on the result of Problem
2.48, explain why the transportation of charges across a bilayered
membrane in a living cell is difficult. (Cf. Problem 2.16 in the textbook)
(Contractor)

Answer:

On either side of the membrane, which is non-polar in nature, aqueous

environment is present.
Transporting a charged ion across a membrane involves two processes (see
Fig 2.8): (1) transporting the ion from the first aqueous environment to the non-
polar membrane medium, and (2) transporting the ion from the non-polar
membrane to the other side where a second aqueous medium exists. According
to Problem 2.48, process (1) is not a favorable process, though process (2) is a
ION-SOLVENT INTERACTIONS 71

Non-polar
bilayered
membrane
Polar
environment

(2)

Figure 2.8. A bilayered membrane

favorable one. Thus, it is difficult to transport the charged ions across the
membrane. To help this two-step process, living cells use protein pumps that are
located across the membrane to transport charged ions through them.

2.50 Estimate the error introduced by ignoring the size of the solvent
molecules in calculating the heat of the Born-charging process during the
interaction of a Cs+ ion with water. (Contractor)

Answer:

The Born-charging contribution (cf. Eq. A.2.1 .6 in the textbook) taking into
account the size of the solvent molecule is given by

(2.189)

At constant temperature, the above equation can be written as,

K
tlG Born .l (2.190)

In the same way, if the size ofthe solvent is ignored, then,

K
tlG Born ,2 = - - (2.191)
(ri)
72 CHAPTER 2

The error involved in calculating LlOBom without considering the size of the
solvent can be calculated as:

K K
LlO Born , 2 - LlO Born, ) ri ri + 2rw 2rw 2x1.38
= = 1.63 (2.192)
LlO Born,) K ri 1.69
ri + 2rw

That is, 1).0 Born is 63% larger when the size of the solvent is ignored.

2.51 (a) Calculate the volumes of a bare ion and a solvated ion sheathed by
water. Make the calculation for Li\ Na+ and K+. Use the corresponding
ionic radii. (b) If the structure-breaking region consists of two layers of
water molecules, calculate the volume of water that has been affected by a
single ion. (Cf. Problem 2.19 in the textbook) (Xu)

Answer:

(a) The volume of the bare ion is calculated as:

4 3
Vi =-Jrri (2.193)
3

To calculate the volume of the solvated ion, it is assumed that one layer of
water molecules (SN) constitute the solvation sheath. Thus,

(2.194)

For Li+ ion,

V Li+ = 3Ji
4 ( -8) 3
0.59xlO cm = O.86x10
-24
cm
3
(2.195)

and Eq. (2.194) becomes,

4 (-8 -8 )3=1.57x10 -22 cm 3

V Li ++ SN =3Ji 0.59x10 +2x1.38xlO (2.196)
ION-SOLVENT INTERACTIONS 73

The value of Vi and Vi+ SN for the other ions are given in the table at the end of
this problem.

b) The volume of water affected by an ion constitutes the volume of solvation

waters and structure breaking region, i.e., VSN+ SB. Thus,

V;+SN+SB =V; +V SN+SB (2.197)

or

V SN+SB =V;+SN+SB -V; (2.198)

Since the SB region consists of two layers of water molecules,

(2.199)

For Li\

V SN+SB =f"{ [ 0.59xlO -. +6( 1.38 x 10 -. ) r-( 0.59 x 10 -. )' } (2.200)

= 2.92xl0 -21 cm 3

The values of Vi, Vi+SN and VSN+ SB for the three ions are listed in the
following table:

Vi (cm 3) 0.86 X 10-24 3.59 x 10.24 9.85 X 10-24

Vi + SN (cm 3) 1.57 X 10-22 2.14 x 10.22 2.86 X 10-22
VSN+SB ( cm3) 2.92 X 10-21 3.36 X 10.21 3.76 X 10-21

2.52 Using the results of Problem 2.51, calculate the percentage of bulk
water in 0.05 M NaCI solution. What is the percentage if the concentration
is 0.5 M? Comment on the significance of the results. (Cf. Problem 2.20 in
the textbook) (Xu)
74 CHAPTER 2

Answer:

Using the results of Problem 2.51 (b), the volume of water affected by a
single cr ion is determined from Eq. (2.199),

VSN +SB =-;-1l"[ (r; + 2r w-SN + 4r w-SB r -r/ 1 (2.201)

~~ ..{[J.81X 10 -8 cm+ 6( l.3Sx 10 -8 em )]' -( l.3Sx 10-8 em )' }

= 4.29xlO -21 cm 3

Therefore, in 1 dm 3 of 0.05 M NaCI solution, the total volume of water

affected by cr and Na+ ion is:

(V SN + SB )Tolal =0.05N A l(VSN +SB )Na+ + (V SN + SB )cr J

= (0.05 mOI)( 6.022 x 10 23 mol-I )( 3.36 x 10 -21 cm 3 + 4.29 x 10 -21 cm 3 )

=230.38 cm 3 or 0.23 dm 3 (2.202)

3
This indicates that 0.23dm x 100 = 23% is the percentage of water
Idm 3
volume affected by the ions and 77% is the volume of free water. If the
concentration would increase 10 times, to 0.5 M, the above method predicts that
there would not be more free water. This warns that in concentrations above 1.0
M the rules applicable in dilute solutions no longer hold true because the bulk
water has practically disappeared.

2.53 Consider a dilute gas of polar molecules (permanent dipoles) in an

electric field generated from the charge on the plates of a condenser [Figs.
2.9(a) and 2.9(b»). Different forces affect the alignment of the molecules (a)
What are these forces? (b) The number of dipoles per unit solid angle at an
angle () to the applied field, no, [Fig. 2.9(c») is given by the Boltzmann
distribution law:

-WlkT
nO = Re and dn 0 = Re - W I kT d.Q (2.203)
ION-SOLVENT INTERACTIONS 75

+ +
+ +
~

+ +
+ +
+ +
(a) (b)

+
{c}

Figure 2.9. Permanent dipoles in an electric field of a condenser.

where R is a proportionality constant, W is the work done by the molecule

in aligning with the field

(w =- P X ext cos () ) (2.204)

and .Q is the solid angle to the external field [Fig. 2.9(c»). Consider the
dipoles oriented at angles ()11 ()], ••• The dipole moments in the direction of
the field are only fJCOS()11 fJCos()], ••• [Fig. 2.9(b»). Thus, the average moment
<p> is defined as

7r

fpcosBdne
0
(p) (2.205)
7r

fdne
0

Substitute in this equation the equivalent of dnoand W. (c) Substitute now

76 CHAPTER 2

dO.=2" sinB dB=-2" d(cosB) (2.206)

(d) If x = cosB, what are the new limits of the integrals? (e) For small fields,
the exponential becomes a small number and it can be expanded by a
Taylor's series, i.e., tl'y = 1 + Ay + ... Use this expansion in your equation.
(1) Determine now the quotient (J.i.) / J.i., and then find an expression for
<J.i.>.
(g) Using the equation you developed, calculate the average dipole
moment that gaseous water exhibits in the direction of an external field of
3xlO' V m-I when subject to electrical orienting and thermal randomizing
forces at 25°C. (Cf. Exercise 2.30 in the textbook) (Contractor-
GamboaAldeco)

Answer:

(a) The electric field arising from the charge on the plates tends to line up the
dipoles with their positive heads oriented toward the negative plate, but at the
same time, thermal collisions between the dipoles are trying to knock them out
of alignment. Hence the dipoles strike a compromise between the electrical
orienting force and the thermal disorienting force.

(b) Substituting Eqs. (2.203) and (2.204) into Eq. (2.205)

r J.i. (cos() )Re (cosO)p X <XI IkT dO.

(J.i.) =--"0_ _ _----==--_ __ (2.207)
f; Re(cosO)pX <xl IkT dO.

(c) Substituting now Eq. (2.206) into Eq. (2.207) and simplifying,

r J.i. (cos () )( - 2" ) Re (cosO) p

(J.i.) = --'0'--_ _ _ _ _ _ _ _ __
Xexi I kT d cos B

f;(_2,,)Re(cOSO)PXexllkT dcos(}
(2.208)
1J.i. cos
0
7r
( ())
e (coso) p X IkT d cos ()
<XI

1e (coso)
0
7r
p X ext I kT d
cos
()

(d) If x = cos B, then, when () = 0 =>x = 1, and when () = " =>x = -1.
Therefore, Eq. (2.208) becomes
ION-SOLVENT INTERACTIONS 77

(2.209)

(e) For small fields, xIJ,Xext/kT«I, and eXIlXextlkT ~1+xIJ,Xext/kT.

Thus, Eq. (2.209) becomes

r+1 f.lX( 1+ Xf.L X ext

LI kT
1 dx
(2.210)
r+1( 1+ Xf.L X ext
LI kT
ldx
(I) The quotient (f.L) / f.L is obtained by dividing Eq. (2.210) by f.L:

J:I xdx+ J:I X2 f.LX-

-I -I kT
ext dx
(f.L) f.L X ext
= (2.211)
f.L J:I dx + J:I Xf.L X 3kT
-I -I kT
ext dx

or

2-
f.L X ext
(f.L)= (2.212)
3kT

(g) Finally, the average dipole moment of gaseous water is, from Eq. (2.212),

(1.87D)2(3XI0 7 Ym- l ) -I -30

(f.L)= IJY 3.336x10 Cm
(2.213)
3(1.38IXIO-23 JK- 1 298K) IC D

=O.028D

2.54 In Problem 2.53, the average dipole moment of a gas-phase dipole

subjected to electrical and thermal forces was determined. This treatment
78 CHAPTER 2

can be applied satisfactory to a gas of water molecules that are not involved
in mutual interactions. However, the dipole moment of a network structure
such as liquid water cannot be determined through the same equation.
Water is quasi-crystalline in the sense that there are in liquid water large
groups ("icebergs") of water molecules associated by hydrogen bonding. A
structural unit may be distinguished, that consists of a central water
molecule tetrahedrically linked to four other molecules by hydrogen bonds
(Fig. 2.10). When such a structure is placed in an electrical field, the whole
subgroup aligns. Now, not the dipole moment of isolated molecules matters,
but the dipole moment of the subgroups, J.igrollp" The effective moment of the
group as a whole is equal to the dipole moment of the central molecule plus
the components of the dipole moments of the four neighboring water
molecules of the tetrahedral unit. In other words, the effective moment is
the vector sum of the dipoles in the group, i.e.,

(2.214)

where g is the number of nearest-neighbor water molecules linked with the

central molecule and cos y is the average of the cosines of the angles
between the dipole moment of the central water molecule and those of its
bonded neighbors. Finally, it is possible to apply the same arguments
applied before to the gaseous molecules and use the equation developed in
Problem 2.53 (i.e., Eq. 2.212), to obtain:

/ ) = J.i
2(1+ g -cosy yX
(2.215)
\ J.i group 3 kT

where X is the total field that operates on the group, and is given by

··d
' r0atoms

Figure 2.10. "Icebergs· of

water molecules.
ION-SOLVENT INTERACTIONS 79

- 3&-
X=--Xext (2.216)
2&+1

If the average cosy = 113, and the tetrahedral clusters are subjected to
an external field of 2. 7xl 08 V cm-I, estimate the effective moment of a dipole
cluster of water at 298 K. (Cf. Exercise 2.31 in the textbook) (Contractor-
GamboaAldeco)

Answer:

Substituting values in Eq. (2.215),

(l.S7D)2 [1+4(!))2
(f.igroup)= 3 3(7S.5) (2.7X10 8 vcm- l )
3( l.3Slx10- 23 JK- 1 29SK ) 2(78.5 + 1)

-I -30
x~ 3.336xl0 C m lOOcm =205.SD (2.217)
IC D 1m

2.55 Consider the interface between the metallic plates of a capacitor (with
charge density qM) and the dielectric material aligned in between the two
plates (with a charge density qdipole on each extreme) (See Fig. 2.11). (a)
Using Gauss's law, prove that the net field that is set up in the dielectric
material as a result of the external field and the internal counterfield is

-x ext = q M - qdipole
(2.2IS)
eo
In this equation, the charge qtlipole can be approximated as

qdipole = 47re OnaX ext (2.219)

where a is the polarizability of the molecules (susceptibility of the molecules

to deform into dipoles). (b) Considering that X ext = V / d , and that the
80 CHAPTER 2

capacity is C = q M / V = EE 0 / d , find a relationship between the dielectric

constant as a function of the polarizability of the molecules. Now, the term
qdipole should include both, the permanent as well as the induced dipoles
(those produced by the distortion of molecules subject to an electrical field).
Therefore, q dipole = q perm + q ind • The first term is given by

q perm = n ( f.J group ) (2.220)

where

f.J
2(1+ g -cosy )2 X
(f.J group) (2.221)
3kT

(see Problem 2.54), and

- 3e- (2.222)
X=--Xext
2e+l

The second term is

(2.223)

(c) Find an expression for the dielectric constant in terms of aind and f.J. (d)
Calculate the deformation polarizability of water at 25°C if there are 10-3
moles of deformable molecules per unit volume. Use the average of the
cosines of the angles between the dipole moment of the central molecule and
that of its bonded neighbors as 113. (Cf. Exercise 2.32 in the textbook)
(Contractor-GamboaAldeco)

Answer:

(a) Gauss's law says that the electric field normal to the surface (Gaussian
surface) of any volume is 1/eo times the charge in the volume. The volume
chosen for this problem is a brick-shaped volume with two of its faces of unit
area parallel to the capacitor plate, and enclosing the charges qM and - qdipole (see
Fig. 2.12). The net charge in the volume is qM- qdipole and the net electric field is

X ext = q M - qdipole (2.224)

eo
ION-SOLVENT INTERACTIONS 81

+
+

+
+
Charge Oriented
density, qM dipole layer

Figure 2.11. Dielectric

molecules at a metallic
plate of a capacitor.

(b) From Eq. (2.219), qdipole =4m'onaX ext, then

q M -47l'sOnaX ext
Xext (2.225)
So
or rearranging terms,

qM
Xext =-~:..:.::..-- (2.226)
EO + 41l"EOna

Substituting X ext = V / d and rearranging Eq. (2.226),

qM EO + 41l"Eona
- - = --'-----'-- (2.227)
V d

For a parallel-plate condenser C =q / V =EE 0 / d , then,

(2.228)
V d d

or

E=I+4nna (2.229)
82 CHAPTER 2

Brick-shaped volume

Charge -qdipole from

end of dipole layer

Field directed towards

",.~"~m'~'~' _'4*" other capacitor plate
X.XI = (qM-qaipol.)!EO

Net charge in brick

shaped volume = qM - qdlpole

Capacitor plane

Figure 2.12. Gaussian surface.

(c) With q dipole = q perm + q ind , then

qdipole qperm qind

a =--"----- ---=----+---"-=-- (2.230)
4JreOnX ext 4JreOnX ext 4JreOnX ext

where

_ (
2(
) _ f-ll + g cos y
-)2 3e -
q perm - n f-l group - n X ext (2.231)
3kT 2&+ I

and
3& -
qind =4 Jr&Onaind - - X ext (2.232)
2&+1

Therefore,

2( - )2
f-ll + g cosy 3& 3&
a= +aind-- (2.233)
4 Jr& 0 3 kT 2 &+ I 2 &+ I
ION-SOLVENT INTERACTIONS 83

Substituting Eq. (2.233) in Eq. (2.229),

&=1+ nJ.i
2(I+gcosy
-)2 3& +aind 4Jm3& =I+~~
&0 3 kT 2& + I 2& + I &0 2& + I

x( .u 2 (I+gCOsy)2 + 41Z'&oa ind

1 (2.234)

3kT

or

(& -I )(2&+ I)
(2.235)
3&

This is Kirkwood's equation for the dielectric constant of a condensed

medium. It takes into account the short range interactions between polar
molecules that lead to the formation of molecular groups oriented as a unit under
the influence of electric fields.

(d) Using Kirkwood's equation,

aind =
(&-1)(2&+1)
-
J.i2 (I+gcosy y
12mm 121Z'&okT
(2.236)
(78.5-1)(157+1) Imol
121Z' ( 78.5 )( 10 -3 mol em -3 ) 6.022x10 23

(L87D)' (1+4( {))'

x
(3.336XIO- 30cm
D2
r (100cm)3}
(Im)3
= 6.7lx110
-21
em
3
84 CHAPTER 2

MICRO-RESEARCH PROBLEMS

2.56 The orlgm of the hydrogen bond is the intermolecular dipole

interaction caused by the polarized covalent bond. The existence of this
additional intermolecular force accounts for the abnormally high boiling
point of water (cf. Section 2.4 in the textbook). (a) Using the
electronegativity (z) data provided below, as well as the boiling points (b.p.)
of different hydrides in Figure 2.13, rationalize semi-quantitatively the
elevation of boiling point of NH3, H 20, and HF in terms of bond
polarization. Consider the total intermolecular force caused by H-bond to
be proportional to tbe total number of H bonds times the dipole moment of
an individual H bond, which in turn varies approximately with the
difference in electro negativity between the hydrogen and the anion, i.e., LiX
= Xx - XII-

H N o F Zn
Electronegativity, X 2.2 3.0 3.4 4.0 1.6

(b) The elevation of boiling point is by no means unique to hydrogen.

Explain the abnormal boiling point of ZnF2 (Fig. 2.14) in the light of the
"zinc bond". Compare the "zinc bond" with the hydrogen bond in the
hydrides studied above and account for the especially strong effect of the
"zinc bond" on the boiling point. Assume that each ZnF2 molecule can form
six "zinc bonds" (this number is derived from the largest possible
coordination number zinc could have). (Cf. Micro research problem 2.2 in
the textbook) (Xu)

Answer:

(a) To a fIrst approximation, we can suppose that the boiling point elevation is
proportional to the total effect of H-bond on the boiling point. This effect
can be accounted as the product of the polarization of single H-X bond
times the number of H-bonds formed. The polarization is approximately
given by LiX, while the number of hydrogen bonds is known from structural
studies. Now, the increase in boiling point for every hydrogen bond of unit
dipole moment should be independent of the hydride, that is
ION-SOLVENT INTERACTIONS 85

100

50

b.p. 0
(DC)

-50

-100

2 3 4 5 6

Main period

Figure 2.13. Boiling points of hydrides

il(b.p. )[degree~H- bondt1 (ilX t 1]

il(b.p.) (2.237)
= =constant
(numberof H - bonds)( ilX )

1600

1400

1200
b.p.
(DC)
1000

------.---.
800 • ZnBr2 Znl2

600
2 3 4 5 6
Main period

Figure 2.14. Boiling points of zinc halides.

86 CHAPTER 2

The calculated values are tabulated below. With rather fair consistency
considering the roughness of the treatment, a H-bond of unit dipole moment
contributes approximately with 20 to 30 degrees increase in boiling point. The
only disagreement is with the H-N bond (22 degrees). This can be explained if it
is considered that not all the four H bonds are formed. If instead of four it is
considered only three H bonds, the change in boiling point is approximately 29
degrees, which is in better agreement with those of H-O (31 degrees) and H-F
(28 degrees).

HF HO (in H2O) NH (in NH 3)

AX (= Xw Xx) 1.8 1.2 0.8
Maximum A(b.p.) 100 150 70
(degrees)
Number ofH bonds 2 4 4 (or 3)
in molecule
A(b.p.)
27.8 31.2 21.8
[deg(H-bon~-1 (AX tl ] (or29.1)

(b) Because the Zn-F is severely polarized due to the big difference between the
atom electronegativities, Zn is rendered as very "electron thirsty". As a result,
Zn begins to interact with neighbor electron-rich fluorides of neighboring ZnF2
molecules, in the same way as hydrogen does in hydrides. This intermolecular
force, realized with Zn as bridging atom between F of different ZnF 2 molecules,
is essentially the same as the H-bonds. Similar calculation as with hydrides
shows a decrease of boiling point of ZnF 2 of 52 degrees (in degrees per Zn bond
and per .1X):

AX (= XZn - Xx) 2.4

Maximum A(b.p.) 650
(degrees)
Number of Zn bonds 6(?)
in molecule
A(b.p.)
52
[deg(zn-bon~-l (AX tl ]
ION-SOLVENT INTERACTIONS 87

The value of !l(b.p.) for ZnF2 is much higher than any of the above hydrides
(compare both tables). The reason might be the partial ionic nature of the Zn-F
bond. The difference in electronegativity is so large, that this may indicate that
the Zn-F bond is partially dissociated, that is, it is partially electrostatic in
nature. This means that the Zn bond is to some extent non-directional, and
works in a much wider range, in contrast to the H bond, which is directional and
stoichiometrical, that is, only affects the nearest neighbors. As a consequence,
much more F atoms interact with a given Zn atom (in comparison with a given
H atom), explaining the further increase in boiling point.
CHAPTER 3

ION·ION INTERACTIONS

EXERCISES

Review of Sections 3.1 to 3.3 of the Textbook.

Describe and give examples of ionophore, ionogen, strong and waek

electrolyte. Why is the charge density around a reference ion not zero when the
whole solution is electroneutral? Explain succinctly the Debye-HOckel approach
to their ionic-cloud theory. Mention the main steps involved in this theory as
well as the assumptions involved in its development. Write the linearized
Poisson-Boltzmann equation and the time-average spatial distribution of the
excess charge density around a reference ion. What is the total ionic-cloud
charge around a reference ion? Draw the variation of the electrostatic potential
and the excess-charge density as a function of the distance from the central ion.
What does 1(-1 represent? Write expressions for the Debye-Huckel length, the
total electrostatic potential, the potential due to the isolated central ion, and the
potential due to the ionic cloud. What is the physical meaning of effective
thickness of the ion atmosphere?

3.1 (a) Write down the full Taylor expansion of t!' and e-x • (b) Find the
percentage difference between t!' and l+x for x = 0.1, 0.5 and 0.9. (Cf.
Exercise 3.32 in the textbook) (Bockris-GamboaAldeco)

Answer:

89
M. E. Gamboa-Adelco et al., A Guide to Problems in Modern Electrochemistry
© Springer Science+Business Media New York 2001
90 CHAPTER 3

(a) The expansions are:

2 3
eX =l+x+~+~+ ... (3.1)
21 3!

2 3
-x x x
e =1-x+---+ ... (3.2)
21 31

(b)
x eX l+x x
e -(I+x)xlOO
x
e
0.1 1.1052 1.1 0.47%
0.5 1.6487 1.5 9.02%
0.9 2.4596 1.9 22.57 %

3.2 Evaluate the electrostatic potential f// and the work of charging Cu +2
ions from a state of zero charge to a charge of Zil!o in water at 25°C.
(Contractor)

Data:

z;=2 T=298 K
&= 78.3 r Cu +2 = 72 pm

Answer:

The work of charging an electrical conductor is (cf. Eq. 3.3 in the textbook),

z ·eo
W=-'-f// (3.3)
2

and, the electrostatic potential If/, is given by the equation (cf. Eq. 3.30 in the
textbook),

(3.4)
ION-ION INTERACTIONS 91

Substituting this value into Eq. (3.3),

(2 )(1.602XlO -19 e)
w= (0.51 v)x 2 = 8.18xlO -20 J (3.5)
2 1ve

3.3 (a) The excess charge of an ionic atmosphere varies with distance out
from the central ion. Starting from the expression for the excess charge
density, show that the net change in a spherical shell of thickness dr is

-/(J" 2
dq = -zieOe K rdr (3.6)

(b) At a certain distance from a central ion, there will be a ring with a
maximum charge. Find the distance of this ring from the central ion. (Cf.
Problem 3.7 in the textbook) (Bockris-GamboaAldeco)

Answer:

(a) The excess charge density is given by (cf. Eq. 3.35 in the textbook),

-/(J"
e
(3.7)
r

Therfore, the total charge in a spherical shell of thickness dr at a distance r

from the reference ion is given by p, times the volume in this shell, i.e., 4n?dr,
or,

(3.8)

Substituting p, from Eq. (3.7) into Eq. (3.8) gives the equation we are
looking for, i.e.,

2 -/(J"
dq = -ZjeOK re dr (3.9)
92 CHAPTER 3

(b) The excess charge in a spherical shell of thickness dr, that is dq/dr, has a

maximum when .!!....( dq ) =o. Thus, differentiating Eq. (3.9),

dr dr

2
d q =.!!.... dq =.!!.... ( _Z i eo K 2 re -Kr )
dr 2 dr dr dr (3.10)
=-zieOK 2 (-Kr
e -rKe -Kr ) =0

e
-Kr =rKe
-Kr (3 .11)

or

(3 .lla)

3.4 The potential of the ionic atmosphere according to the limiting law (i.e.,
low concentration) is given by IJI cloud = - Z i eOK / E, where tel is the so-
called Debye-Hilckel length. Explain why tel is called in this way and draw
a figure showing the meaning of this term in terms of the concept of "ionic
atmosphere." (Cf. Exercise 3.27 in the textbook) (Bockris-GamboaAldeco)

Answer:

The term tel represents the distance at which a spherical shell around an ion
contains the maximum value of charge. Since tel represents a distance and has
units of length, it is referred to as the Debye-Huckel length. A scheme showing
this concept is given in Fig. 3.1. In this figure, dq represents the charge enclosed
in a dr-thick spherical shell, and r the distance from the reference ion.

dq

Figure 3.1. Charge in a dr-thick

spherical shell as a function of distance.
ION-ION INTERACTIONS 93

3.5 The Debye-Hiickellength, ,el, is (cf. Eq. 3.43 in the textbook):

(3 .12)

(a) Analyze the units of this equation. What are the units of /C-l? (b) How
should this equation be modified to have units in the mksa system?
(GamboaAldeco)

Answer:

(a) The equation is written in the cgs system (cf. Exercise 2.3). The
corresponding units are [E] 7dimensionless, [k] 7 erg K -\ [11 7 K, [n;o ]7
cm-J , [z;] 7 dimensionless, and [eo] 7 esu (or electrostatic units). The
corresponding analysis of units is,

(3 .13)

Therefore, ,el is given in cm.

(b) To write this equation in the mksa system, the numerator has to be multiplied
by 4"Eo. Thus, the corresponding units are [E] 7dimensionless, [Eo] 7 c2 rim-I,
[k] 7 J KI, [11 7 K, [n;0]7 m-J , [z;] 7 dimensionless, and [eo] 7 C. The
equation reads now,

(3.14)

The analysis of units ofEq. (3.14) is,

94 CHAPTER 3

(3.15)

3.6 Calculate the thickness of the ionic atmosphere in 0.1 M solutions of an

uni-valent electrolyte in the following solvents at 25°C : nitrobenzene, with
& = 34.8, ethyl alcohol, with & = 24.3, and ethylene dichloride, with & = 10.4.
(Cf. Exercise 3.24 in the textbook) (Constantinescu)

Data:

C = 0.1 M &nitrobenzene = 34.S &ethylene dichloride = 10.4

Iz+ I = Iz.I =I &ethyl alcohol = 24.3 T=29S K

Answer:

The thickness of the ionic atmosphere, Ttl, in the mksa system is given by
(cf. Eq. 3.14 in Exercise 3.5 and Eq. 3.43 in the textbook),

(3.16)

where nio is given in m· 3. If the concentration of the ions of the i-th kind, Ci, is
given in mol liter" I (= mol dm- 3) then,

Ci
( I
mol
dm -3
n.o ( m
I
-3)
= N A (mol-I) x 1000dm 3
1m
3
(3.17)

Solving for n/,

(3 .IS)

Substituting nio from Eq. (3.IS) into Eq. (3.16),

ION-ION INTERACTIONS 95

(3.19)

For a 1:1,0.1 M electrolyte, LC;z; =c(I)2 +c(_1)2 =2c=0.2M.

Therefore,

r(
&(8.854XIO-12c2J-Im-1 )(1.381x10- 23 JK-1 )
1(
-I
r
= (IOOOdm 3 m -3 )( 1.602 x 10 -19 C 6.023x10 23 mOl-I)
(3 .20)
1/2
x 298K ] = ~ 1.086xIO -10 m
-3
0.2moldm

Substituting the different values of &for the different solvents gives

Solvent & K' (m)

Nitrobenzene 34.8 6.404xl0-10
Ethyl alcohol 24.3 5.352xl0-10
Ethylen dichloride 10.4 3.50lxl0-1o

3.7 Calculate the potentials due to the ionic cloud around cations in the
following aqueous solutions at 25 °C: 10-3 M NaCI, 0.1 M NaCI, 10-3 M
CaCI2, and 10-3 M CaS04' Considering your results from this problem as
well as those of Exercise 3.6, what conclusions can you make with respect to
the variation of the dielectric constant and the potential of the ionic cloud?
(Cf. Exercise 3.1 in the textbook) (Kim)

Answer:

The potential due to the ionic cloud is obtained from the following equation
written in the mksa system (cf. Eq. 3.49 in the textbook),
96 CHAPTER 3

If/ cloud = (3 .21)

-I
47rEOEK

l ]
where ,ci is (cf. Eq. 3.14 in Exercise 3.5):

1/2

K -I = EEOkT
(3.22)
2",02
eO £...n; z;
;

For 10-3 M NaCl,

=[(10-3 moldm- 3 }+1)2 +(10-3 moldm- 3 )(_1)2 ] (3.23)

x ( 6.022x 10 23 mOl-I) 1O::~ 3 1.205 x 10 24 m- 3

Substituting the corresponding values into Eq. (3.22),

K -I = [ (78.3 l( 8.854 x 10 -12 C' J,-I m -I )

(1.602XIO -19 C)
(3.24)
(1.381XIO- 23 JK- 1 }298K)]1/2 -9
---------- =9.607xlO m
(1.205Xl0 24 m -3 )

Substituting now Eq. (3.24) into Eq. (3 .21),

(3.25)
\jl cloud = - ( 10 2 1 1) ( 9 )
1.112xl0- C J- m- (78.3) 9.607xlO- m
ION-ION INTERACTIONS 97

x I VC = 1.915x10-3 V
11

In the same way for the other solutions,

,(1
~>?z; 'l/cloud

i
(m-3) (m) (V)
10-) MNaCI 1.205xlO24 9.607xI0-9 1.915xIO-)
10-1 MNaCl 1.205xl026 9.607xI0- 1O 1.9 I 5xlO,2
10,3 M CaCh 3.614x1024 5.546xlO-9 6.635xlO,3
10-3 M CaS04 4.818x1024 4.803xlO-9 7.66IxlO'3

Comment: The thickness of the ionic atmosphere increases with increasing the
dielectric constant, c, of the solvent. It decreases with increasing the electrolyte
concentration and with increasing the valence of the ions in the electrolyte. On
the other hand, 'l/cloud increases with the increase of the concentration of the
electrolyte and with the valence of the ions.

3.8 Consider a 0.001 N aqueous KCI solution. Calculate the potentials at

distances K- 1/2, ,(1 and 3 ,(1 due to the K+ ion, its ionic atmosphere, and the
total potential. (Cr. Exercise 3.2 in the textbook) (Bockris-GamboaAldeco)

Answer:

The value of ,(1 for a I: I, 10-3 M electrolyte was calculated in Exercise 3.7
as 9.607xlO,9 m. The potential at a distance r = ,(1/ 2 due to the K+ ion, is given
in the mksa system by (cf. Eq. 3.44 in the textbook):

x I VC = 0.00383V (3.26 )
11

The potential due to the ionic cloud is given in the mksa system by (cf. Eq.
3.49 in the textbook):
98 CHAPTER 3

If/ cloud = - -I
4m'O&K

(+I)(1.602XlO- 19 C)
= x 1VC (3 .27)
(1.l12XI0- IO C 2 J-Im -I )(78.3)(9.607XlO-9 m) IJ

= -0.00192 V

The total potential at a distance r from the ion is given by the sum of the
potentials due to the central ion and its ionic cloud, i.e., (cf. Eq. 3.45) in the
textbook),

If/ total = 0.00383 V -0.00192 V = +0.00192 V (3.28)

Using the same equations, the values of If/iol> If/c/oud, and 1f/'010/ for r = Ttl and
3Ttl are,

r 'l/;on If/c/oud If/IOIO/

(V) (V) (V)
O.5TtI +0.00383 -0.00192 +0.00192
Ttl +0.00192 -0.00192 0
3 Ttl +0.00064 -0.00192 -0.00128

Comment: At K-/ the effect of the ion cloud is equivalent to the effect of the
central ion, with opposite charge, and both effects cancel out each other.

3.9 Calculate the change of chemical potential of the following solutions:

10-3 M NaCI, 0.1 M NaCI, 10-3 M CaClz, and 10-3 M CaS04' Consider the
Debye-Hiickel limiting law at 25 DC applies. Use the results from Exercise
3.7. (Cf. Exercise 3.18 in the textbook) (Kim)

Data:

If/c/oud (V) If/c/oud (V)

10-) MNaCI 1.915xl0-j 10-) MCaCl 2 6.635xlO-)
10- 1 MNaCI 1.915xlO-2 10-3 MCaS04 7.661xl0-3
ION-ION INTERACTIONS 99

Answer:

The chemical potential difference is given in the mksa unit system by (cf.
Eqs. 3.3 and 3.49 in the textbook):

(3.29)

Therefore, for Na+ in 10-3. M NaCI,

(6.022XI0 23 mol-I )(+I)(1.602XIO- 19 C)

APi-I =
2 (3.30)

x(1.915X 10 -3 V) x.J....!... = -92.39 J mol-1

1CV

Similarly,

c(M) If/cloud (V) Api-l (J mol -I)

Na+ (NaCl) 0.001 1.915xlO-3 - 92.39
Na+ (NaCl) 0.1 1.915xl0-2 -923.9
Ca+2 (CaCh) 0.001 6.635xl0-3 -640.2
Ca+2 ( CaS0 2) 0.001 7.661xl0-3 -739.2

3.10 Derive the linearized Poisson-Boltzmann equation. (Cr. Exercise 3.33

in the textbook) (Bockris)

Answer:

The excess charge density in the volume element dV is given by (cf. Eq.
3.10 in the textbook):

(3.31)

where nio is the number of ions in the bulk, Zi the ion charge, 'fir the electrostatic
potential in the volume element dV. Thus, when

Zi eo'fl r «kT (Debye-HUckel assumption) (3.32)

100 CHAPTER 3

the exponential in Eq. (3.31) can be expanded in a Taylor series. If only the fIrst
term of the series is taken into account, then,

IkT Zjeol{/ r
e -z .eolfl r
I ~ 1_ --=--=--=- (3.33)
kT

Substituting Eq. (3.33) into Eq. (3.31),

(3.34)

where the fIrst term, L n~ Zj eo, has been removed because it represents the

charge in the electrolyte solution as a whole and is equal to zero. Equation (3.33)
is the linearized-Boltzmann equation. On the other hand, the Poisson equation
for a spherical symmetrical charge distribution is (cf. Eq. 3.4 in the textbook),

Pr = _~_I_~(r2 dl{/ r ) (3.35)

41l" r2 dr dr

Equating Eq. (3.34) and (3.35),

(3.36)

Defining K 2 == 41l" Ln~ Z; e ~ , and substituting it into Eq. (3.36),

ekT j

(3.37)

and this is the linearized Poisson-Boltzmann equation.

ION-ION INTERACTIONS 101

Review of Section 3.4 in the Textbook.

Defme activity coefficient and mention its relationships to the activity and
the chemical potential of species i. Define the mean ionic-activity coefficient.
What is the ionic strength of a solution? Mention two methods to determine
solute activities and their drawbacks.

3.lt (a) Compare the ionic strengths of 1:1, 2:1, 2:2 and 3:1 valent
electrolytes in solutions of molarity c. (b) Based on these results, find a
relationship between the ionic strength and molarity. (Cf. Exercise 3.5 in
the textbook) (Constantinescu)

Answer:

(a) The ionic strength for a single electrolyte solution is given by (cf. Eq. 3.83 in
the textbook),

(3.38)

Applying Eq. (3.38) to the given solutions :

Type z+ z. c+ c. I
1:1 (AB) c c
.!.[c(1)2 + c(I)2
2
]= c
2:1 (AB 2) 2 c 2c
.!.[C(2)2 +2c(I)2 ]=3C
2
2:2 (AB) 2 2 c c
.!.[c(2)2 + c(2)2 ]= 4c
2
3: I (AB3) 3 c 3c
.!.[C(3)2 +3c(I)2 ]=6c
2

(b) From the above results,

I = constant x concentration (3.39)

102 CHAPTER 3

3.12 Calculate the ionic strength of the following solutions: (a) 0.04 M KBr,
(b) 0.35 M BaCh and (c) 0.02 M Na2S04 + 0.004 M Na3P04 + 0.01 M AICh.
(Cf. Exercise 3.6 in the textbook) (Constantinescu)

Answer:

From the results of Exercise 3.11,

(a) 0.04 M KBr is a 1: 1 (AB) type electrolyte and thus, 1= C = 0.04 M

(b) 0.35 M BaCh is a 2: 1 (AB 2) type electrolyte and thus, 1= 3c = 3(0.35) =

1.05M

(c) 0.02 M Na2S04 + 0.004 M Na3P04 + 0.01 M AICh is a mixture of

electrolytes, thus (cf. Eq. 3.83 in the textbook),

I =.l LCjZ; (3.40)

2 j

=;'[c Na + (1)2 +C SO ;2 (2)2 +C pO ;3 (3)2 +C A/ +3 (3)2 +c cr (1)2 ]

= .l[O.052(1)2 +0.02(4 )+0.004(9)+ 0.01(9)+ 0.03(1)2

2
]= 0.144M

3.13 Calculate the mean ionic-activity coefficients of the following salts in

aqueous solutions at 298 K: 10-3 M NaCI, 0.1 M NaCI, 10-3 M CaCI2, and
10-3 M CaS04. Consider the Debye-Hiickel limiting law at 25°C. (Cf.
Exercise 3.9 in the textbook) (Kim)

Answer:

The activity coefficient according to the Debye-Htickellimiting law (cf. Eq.

3.88 in the textbook) is given by the following expression in the mksa unit
system,

The parameter B in the mksa unit system is (cf. Eq. 3.86 in the textbook),
ION-ION INTERACTIONS 103

2]I12 [ 2(6.022XI0 23 mOl-I)

B= ( 2N A e o
880 kT = (78.3)( 8.854 x 10 -12 C 2 J -I m -I )

1
I12 (3.42)

( 1.602XIO-19 C)2
x = 1.041 x 10 8 mol- I12 m I12
(1.38IXIO- 23 JK- 1 )(298K)

or,

3/2 (1000dm 3 )1/2

B=1.041x10 8 mol- I12 m 112 ~ _ _ _ __
(3.43)
dm 3/2 1m 3/2

Substituting this value of B in Eq. (3.41)

( 1.602 X10 -19 C r

(3.29IXI0 9 M- I12 m- 1 )(z+z_ )1 I12
x 0~
2(78.3)( l.38xl0 -23 J K -I )(298K)

=( 0.512M- I12 )(z+z_ )1 1/2

Therefore, for 10-3 M NaCI, z+ = I, z_ = -I and 1 = c = 10 -3 M (cf. Exercise

3.11)

logf± =-( 0.512M-1/2 )IIII-II( 10-3 )I12 = -0.0162

::::::> f+ =0.963 (3.45)

104 CHAPTER 3

Similarly for the other electrolytes,

Solution I logJ±
10-3 M NaCI (1 :1) 1= c= 10-3 M -0_0162 0_963
10- 1 M NaCI (1:1) 1= c= 10- 1 M -0.162 0_689
10-3 M CaCI2 (2:1) 1= 3c= 3xlO-3 M -0_0561 0_879
10-3 M CaS04 (2:2) I=4c=4xl0- 3 M -0.129 0_743

3.14 What are the units of the constants A and B used in the Debye-Hiickel
theory when the equations are given in the mksa system, i.e.

logf± =-A ( Z+L ) 1 1/2 (3.46)

where

2
N AeO
A= B (3.47)
2.303 87r808RT

and

B=
( 'f'
2N A e o
880kT
(3.48)

Are these the units given in Tables 3.3 and 3.4 in the textbook?
(GamboaAldeco)

Answer:

From Eqs. (3.42) and (3.43) in Exercise 3.13, the units of B in the mksa
system are

(3.49)

However, the units in Table 3.3 in the textbook are expressed in

[B) ~ M- Ill cm-I. For example, from Exercise 3.13, at 25°C, B =
3.291xl09 M- 1/2 m-I. Converting m- I into cm- I gives,
ION-ION INTERACTIONS 105

B=3.291xl0 9 M- 1/2 m- 1 x~=0.3291xI08 M- 1/2 cm- 1 (3 .50)

100cm

which is the value given in the textbook for B at this temperature. In the mksa
system, A is

(3.51)

~mo
1-112 m 312

The units of A in Table 3.4 in the textbook are A -7 M -Ill. In our same
example at 25°C,

[A]= I ( 6.023 x 10" mol-I )( 1.602 x 10-19 C )'

2.303 2( 1.1 12xlO -10 C 2 J -I m -I )(78.3)( 8.314J mol- I )(298K)

x( 1.041 x 10 8 mol- 1/2 m 1/2 )

3/2 (IOOOdIn 3 ) 1/2 (3.52)

= 0.01619mol- 1/2 m 3/2 x...;;.dIn~_....:...-_ _---.:__ = 0.512M- I12
dIn 3/2 1m 3/2

This is the value given for A in Table 3.4 in the textbook at 25°C.

3.15 (a) Evaluate the Debye-Hiickel reciprocal length, Kl in 0.001 M

solution of NaCI in water at 25°C. Use the constant B = 0.329lxl08 M -Ill
cm-I. (b) How does Kl varies if the concentration of this solution is doubled
keeping all the other conditions the same? (c) How does Kl varies if instead
of NaCI the solution under study is 0.001 M CdClz? (Contractor)

Answer:

(a) The Debye-Huckel reciprocal length is given in terms of the constant B (cf.
Eq. 3.85 in the textbook),
106 CHAPTER 3

(3.53)

For a 1:1 electrolyte, I = c (cf. Exercise 3.11), and from the textbook the
value of Bat 298 K is 0.3291x108 M -1/2 cm- I, Therefore,

K = 0.3291xl0
8
M
-1/2
cm
-1 ..J O.OOIM = 1.041xl0
6
cm
-1
(3.54)

or

-1 -7 -9
K =9.609xI0 cm=9.609x10 m (3.55)

(b) Doubling the concentration ofNaCI will result in doubling the ionic strength
(I = 2 c/). Therefore,

-1 I I
K =--=--- (3.56)
BJI B..{'i;

and K / will decrease by a factor of I / '"~

2 . Therefore, K
-1
= 6.794xl0 -9 m,

(c) Replacing 0.001 M NaCI by 0.001 M CdCh will result in tripling the ionic
strength (I = 3c) since CdCh is a 2:1 electrolyte (cf. Exercise 3.11). Therefore,
-1
I /
K will decrease by a factor of 1 '" 3 . Thus,
~
K = 5.547xl0 -9 m

3.16 Estimate the dielectric constant of water in an aqueous solution of

5x10-4 M KCI at 25°C using the Debye-Huckellimiting law. Comment on
the result obtained. (Contractor)

Answer:

From the equation of activity coefficient in the mksa system (cf. Eq. 3.80 in
the textbook), i.e.,

(3.57)

the value of Ii can be obtained if the values of f ± and K are known. The activity
coefficient can be obtained from (cf. Eq. 3.90 in the textbook),
ION-ION INTERACTIONS 107

(3.58)

Since this is a I: I electrolyte, the ionic strength is given by I = c (cf. Exercise

3.11), i.e., I = c = 5x I 0-4 M. Therefore,

logi±,KCI =-O.5115M -1/2 V5xlO

I -4 M =-0.0114
~ i±,KCI =0.974 (3.59)

The value of 1C is obtained from the following equation expressed in the

mksa system (cf. Eq. 3.19 in Exercise 3.6),

]1/2 [
r
-I [ &&okT e(8.854XIO-12c2J-Im-l)

1C = 1000e~ N ~Ci z;
A = (1000dm 3 m -3 )( 1.602 x 10 -19 C

x (1.38IXIO- 23 JK -I )(298K) 1112

( 6.023xl0 23 mol -I )( 2x5xl0 -4 moldm -3 )

=.re-(1.535Xl0-9 m) (3.60)

or

(6.515XI0 8 m )
1C=----- (3.61)
.re-

Substituting Eqs. (3.59) and (3.61) into Eq. (3.57),

In 0.974 =
IIII-II( 1.602x10-19 C r (6.515XIO-8 m )

( 1.112x 10 -10 C 2 J -I m -I )(2)( 1.381 x 10 -23 JK -I )(298) e 3/2

(3.62)

Solving for e gives,

108 CHAPTER 3

& =(702.9 )2/3 =79.05 (3.63)

Comment: The literature value for the dielectric constant of water is 78.3 at 298
K. The result shows the validity of the Debye-Htickellimiting law.

3.17 (a) Calculate the mean activity ofa 0.0001 M KCI solution. (b) What is
the activity change of KCI if 0.01 mol of ZnCh is ad"ed to 1 liter of the
above solution? (c) After the addition of the ZnCh salt, will the Debye-
Huckel reciprocal length increase or decrease? Explain. Consider J± = Yc±*
(Cf. Exercise 3.30 in the textbook) (Xu)

Answer:

(a) The activity coefficient for a 1:1 electrolyte,fKC/, is given by (cf. Eq. 3.91 in
the textbook),

log!±,KCI =-A(z+z_)JI =-A.[;

(3.64)
= -0.5115M -1/2 .JO.OOOIM = -5.12xlO-3

or

!±.KCI =Yc±.KCI =0.988 (3.65)

Therefore, the activity ofKCI is,

a± .KCI = c±.KCIY c±.KCI = (0.0001)(0.988) = 9.88xlO- 5 (3.66)

(b) After the addition of I mol ZnCh to one liter of the above solution, the ionic
strength is,

I=].Iciz; =].[0.000IM(I)2 +0.000IM(I)2 +0.01(2)2 +0.02(1)2]

2 i 2
= 0.0301M (3.67)

Then,

log!±,KCI = -0.5115M -1/2 (I )(1 ).J 0.0301 M = -0.0887 (3 .68)

ION-ION INTERACTIONS 109

or

i±.KCI =Yc± ,KCI =0.815 (3.69)

and the activity of KCI is,

a±,KCI = c± ,KCIY c±,KCI = (0.0001)( 0.815)= 8.15x10 -s (3.70)

(c) The Debye-Hilckel reciprocal length, 1(-1, ofKCl will decrease when ZnCh is
added to the solution. The increase of electrostatic force in the solution contracts
the ionic atmosphere.

3.18 Calculate the Debye-Hilckel reciprocal len~ths for the following

solutions at 298 K: 10-3 M NaCI, 0.1 M NaCI, 10- M CaCI2, and 10-3 M
CaS04. Use the constant values given in the textbook. (Cf. Exercise 3.23 in
the textbook) (Kim)

Data:

T=298 K B = 0.329Ix108 M-I12 cm- I

Answer:

The Debye-Hilckel reciprocal length, !C 1, is given by (cf. Eq. 3.85 and Table 3.3
in the textbook),

-\ 1
I( = =----------- (3 .71)
B.fi (0.3291XI0 8 M-1I2 cm -\ ).fi

NaCI is a 1: 1 type electrolyte. Thus, for C = 10-3 M, and considering the

results from Exercise 3.11 , I = C = 10-3 M, and I(
-\
= 9.607x10 -7 cm . In the
same way for the other solutions,

z:z I 1(-1

NaCIIO- 3 M 1:1 c= 10-3 M 9.607xI0-' cm

NaCllO- 1 M 1: 1 c= 10- 1 M 9.607xl0-8 cm
CaCh 10-3 M 2:1 3c= 3xlO-3 M 5.546xlO-7 cm
CaS04 10-3 M 2:2 4c=4xlO-3 M 4.803xI0-7 cm
110 CHAPTER 3

3.19 Calculate the highest concentration at which activity can be replaced

by concentration in (a) NaCl, and (b) CaS04 solutions. Assume that a 10%
error can be tolerated from the Debye-Huckel limiting law at 25°C.
Comment on these results. (Cf. Exercise 3.8 in the textbook)
(Constantinescu)

Answer:

A permitted error of 10% in the activity means that the corresponding

activity coefficient may be as low as 0.9. The Debye-HOckel limiting law
establishes that (cf. Eq. 3.90 in textbook),

(3 .72)

The value of A at 25°C is 0.5115 M -\12 and can be obtained from Eq. (3.89)
or Table 3.4 in the textbook.

(a) For NaCl, a 1: 1 valent aqueous electrolyte, I = c (cf. Exercise 3.11). Thus,
the highest allowed concentration is,

2
log(0.9) ] -3
c =[ - =8.0xlO M (3 .73)
0.5115M- I12 11 11- 11
(b) For CaS04 that is a 2:2 valent aqueous electrolyte 1= 4 c (cf. Exercise 3.11).
Therefore, the highest allowed concentration is,

I[ log (0.9 ) ]2
c =- - = 1.3xlO -4 M (3.74)
4 0.5115M -1/21211_21

Comment. The higher the valence of the electrolyte, the lower the limit of
concentration at which activity can be replaced by the concentration.

3.20 Explain how the determination of the vapor pressure of water can give
rise to the activity of the electrolyte dissolved therein. Start from the Gibbs-
Duhem equation. (Cf. Exercise 3.17 in the textbook) (Bockris)
ION-ION INTERACTIONS 111

Answer:

The Gibbs-Duhem equation of thermodynamics establishes that,

(3 .75)

For a two components system, i.e., water and electrolyte,

(3 .76)

The chemical potential of each component is given by,

o or, (3 .77)
J-li = J-li +RT Inai

where dJ-li is the chemical potential at standard conditions, and ai is the activity
of the component. Applying Eq. (3 .74) to the electrolyte and water, and
substituting into Eq. (3.76) gives,

(3.78)

or
(3 .79)

Integrating the left-hand side from a low concentration of electrolyte, Ce, to a.,
and the right-hand side from -J to aw,

ae all'

fd In a e = - f n W d In a W (3 .80)
o I ne

Integrating the left-hand side ofEq. (3 .80),

(3 .81)

The activity of the solvent can be written in terms of the vapor pressure of
the pure solvent, PII'*' and the vapor of the solvent when it is a component of a
solution, Pw,
112 CHAPTER 3

(3.82)

Therefore, writing Eq. (3.81) in terms of the corresponding vapor pressures

of the solvent,

(3 .83)

The integral in Eq. (3 .83) needs to be solved graphically. To do this, one

plots n1/ne against In P1/Pw · , and the area will give the value of In a/ceo

Comment: According to the limiting law, the plot of f ± against l2 should give
a straight line of slope -A z_z.. Beside the valence of the ions constituting the
particular electrolyte under consideration, the equation contains no reference to
the specific properties ofthe salts that may be present in the solution.

Review of Section 3.5 of the Textbook.

Under what conditions does the Debye-Hilckel limiting law apply? What
are the inadequacies of this law? Explain how the theory was improved to allow
for concentrated solutions of electrolyte. Following this theory, write equations
for charge density, charge in the ionic cloud, potential at a distance r from the
central ion taking into account the size of the ion, and the contribution from the
ionic atmosphere to the potential. How are the individual and mean-ionic
activities modified when the ion-size parameter, a, is considered? What range of
values can a acquire? Can a be calculated through models? Discuss the success
or failure of the introduction of the parameter a to the Debye-Hilckel theory.
Name the contribution of Milner and Gouy to the ionic solution theory.

3.21 Calculate the mean activity coefficients for 1:1, 1:2, and 2:2 valent
electrolytes in water of ionic strengths 0.1, and 0.01 at 20°C. The mean
distance of closest approach of the ions is 3 A. Use the extended Debye-
Hiickellimiting law and the corresponding constant values provided in the
textbook. Comment on your results. (Cf. Exercise 3.15 in the textbook)
(Constantinescu)
ION-ION INTERACTIONS 113

Data:

From Tables 3.3 and 3.4 in the textbook:

A = 0.5070 M -112 B = 0.3282x108 M -112 cm-·

Answer:

The extended Oebye-Huckellimiting law establishes that (cf. Eq. 3.120 in

the textbook):

1/2
A ( z+z_ ) ]
logf± = - - - - - - (3.84)
1+ Ba] 1/2

Therefore, for a I: 1 electrolyte,

0.5070M- I12 IIII- II(O.lM)1I2

logf± = - ( . 8 112 I )( 8)
1+ 0.3282xlO M- cm- 3x10- cm (0.IM)1I2 (3.85)

= -0.1223

f± =0.7546 (3.86)

Similarly,

Electrolyte ] = O.OIM ] =O.IM

logf± f± /ogf± f±
I:1 -0.0462 0.8992 -0.1223 0.7546
1:2 -0.0924 0.8083 -0.2446 0.5694
2:2 -0.1848 0.6534 -0.4892 0.3242

Comment: The mean-activity coefficient decreases with increasing ionic

strength and increasing valence of the ions.

3.22 In Exercise 3.7, the Debye-Hiickel reciprocal length, J{I, of 0.001 M

NaCI solution was calculated as 9.607x10-9 m. Find the corresponding value
of the size parameter, a, in the textbook. What conclusion related to the size
of the ionic cloud could you draw from the comparison of these two values?
(Kim)
114 CHAPTER 3

Data:

a = 0.40 x 10-9 m (cf. Table 3.9 in the textbook)

Answer:

The difference between the equations of J: according to the point-charge

model (cf. Eq. 3.90 in the textbook) and the fmite-size model (cf. Eq. 3.121 in
the textbook) is

(3.87)
-1
l+a / K

When this term tends to l(i.e., when K' » a), then the equation for log/x
in the finite-ion-size model (cf. Eq. 3.121 in the textbook) approaches the
corresponding equation for the point-charge model (cf. Eq. 3.90 in the
textbook), i.e.,

-I
K »a
(3 .88)

In this example, 10-3 M NaCI solution, the ratio

- - - - - - - - - - - = 0.9897::::; 1 (3.89)
-1
l+a / K 1+( 0.40xl0-9 m/9.607xl0-9 m)

This means that, at this concentration, the ion atmosphere has such a large
radius compared with that of the ion that one can ignore the finite size of the
latter.

3.23 Calculate the product lCa for the following solutions of CsCI: 10-4,
Sxl0-4, 10-3 , Sxl0-3 , 10-2, Sxl0-2, and 10-1 M at 25°C. Find the maximum
concentration at which Ka < 0.1, i.e., the concentration at which the limiting
law is applicable. Assume that the distance of closest approach between two
ions is equal to the sum of the ionic radii of the cation and the anion plus
one diameter of water. (Cf. Exercise 3.28 in the textbook) (Bockris-
GamboaAldeco)
ION-ION INTERACTIONS 115

Data:

a=rcs + +rcr + 2r w =169+181+2(138)=626pm

B = 0.3291 M"1 /2 cm- 1 (cf. Table 3.3 in the textbook)

Answer:

The parameter K is given by K = BI1 / 2 (cf. Eq_3.85 in the textbook). Since

CsCI is a 1: 1 electrolyte, then, I = C (cf. Exercise 3.11). Thus,

r
Ka=Ba'l/c= ( 0.3291M -1/2 cm -1)( 6.26xl0 -12) r
cm'l/c (3.90)

For 10-4 M CsCl,

Ka = (0.3291x 10 8M -1/2 cm -1)( 6.26x 10 -8 cm )~ 10 -4 M = 0.0206 (3 .91)

In the same way for the other concentrations,

c(M) Ka
IxI0 04 0.0206
5xlO-4 0.0461
IxlO- 3 0.0652
5xlO-3 0.1457
lxlO- 2 0.2060
5xlO-2 0.4607
IxlO- 1 0.6215

The maximum concentration at which Ka < 0.1 , and therefore the

concentration at which the Debye-HOckel limiting law is applicable, is, then,
about Ix10-3 M.

Review of Sections 3.6 to 3.8 of the Textbook.

Explain why the activity coefficient increases at high concentrations, i.e., at

C > -IN. Write an expression for the activity coefficient, feb to consider the
116 CHAPTER 3

solvent removal to the ions' aphere. Explain why the unlinearized Poisson-
Boltzmann equation leads to logical inconsistency in the ion-solution theory.
What is the difference between the Guntelberg charging process and the Debye
charging process? What is an ion-pair? What is the physical meaning of the
distance q according to the Bjerrum theory? Mention the main forces involved in
the ion-pair formation as well as the main parameters that increase the
occurrence of this phenomenon. How does ion-pair formation affect the Debye-
Huckel theory?

3.24 Calculate the effect of water molecules on the activity coefficient in 1 M

NaCI. The water activity in the solution is 0.96686, and the hydration
number of the electrolyte is 3.5. The density of the solution is 1.02 g cm-3•
Consider the parameter a = 4 pm. (Cf. Exercise 3.11 in the textbook) (Kim)

.Answer:

For a 1:1 electrolyte (cf. Eq. 3.130 in the textbook),

logf± =-
Arcr-2.303-logaw
nh
+2.303/og
nw +n
(3.92)
1 + Ba" c n n w + n - nh

where n is the number of electrolyte moles in solution, nw is the total number of

water moles in solution, and ns is the number of water moles in the solvation
sheets of the ions. Thus, in 1 liter (or 1000 cm3) of solution, n = 1mol, and

Vsolo Psolo - n(MW) NaCi

nw =
(MW)w
(lOoocm 3 )( 1.02g cm -3 ) - (lmol)( 58.5g mOl-I)
(3.93)
-I
18.02g mol
= 53.4mol

ns =3.5n=3.5mol (3.94)

The activity coefficient without considering the effect of water, i.e., the frrst
part ofEq. (3 .92) is:
ION-ION INTERACTIONS 117

log/± =-
1 + Ba.Jc

( 0.5115M -1/2 ).JlM

(3.95)
1 + ( 0.329lx 10 8 M -1/2 em -I )( O.4x 10 - 7
em) viM
r.:;-;

= -0.2208

or It = 0.6014 .
The terms related the hydration of the ions are, from Eq. (3 .92):

nh 3.5 mol
-2.303-loga w =-2.303 logO.96686 =0.1178 (3 .96)
n 1mol

nw + n 53.4mol+ Imol
+ 2.30310g----- = +2.30310g--------
nw +n-nh 53.4mol+lmol-3.5mol (3.97)
= 0.0665

Adding these results to Eq. (3.95) gives,

log I± = -0.2208 + 0.1178 + 0.0665 = -0.0365 (3.98)

or f ± = 0.9194. Therefore, the error when hydration is not considered is

0.9194 - 0.6014 x 100 = 35% .
0.9194

3.25 According to the Bjerrum theory, at what concentration does KCl

manifest 10% association in (a) ethanol, and (b) water? Use data obtained
in tables in the textbook. (Cf. Exercise 3.12 in the textbook) (Bockris-
GamboaAldeco)

Data:

()= 10%
From Tables 3.18 and 3.9 in the textbook:
Gethanol = 24.30 &Water = 78.3 a=0.36 run
lIS CHAPTER 3

Answer:

(a) The concentration can be obtained from n?in Eq. (3.147) in the textbook
written in the mba system,

(3.99)

The parameter b in the above integral is obtained from Eq. (3.14S) in the
textbook. Thus, for the ethanol solution,

z+=-e~ 1111-11
b- -~------------~--~-------------

r
- 41r&oa&kT - ( 1.112x 10 -10 C 2 J -I m -I )( 0.36x 10 -9 m )(24.3)

(1.602XIO- 19 C
x~~--------~----- ( 2.307 1 (3 .100)
(1.3SIXIO- 23 JK- 1 )(29SK) 0.36xI0-9 m

=6.41

The value of the integral in Eq. (3 .99), can be found in Table 3.16 in the
textbook. Thus, interpolating the value of b = 6.41 gives,

b
feY y -4 dy = 1.409 (3.101)
2

Therefore, n? from Eq. (3 .99) is,

nj
o = [41r
-
[ z+z_e~ ]3 bfe y _4dyj-1
Y
(3 .102)
() 41r&0&kT 2

=[41r( 2.307xlO-9 m
0.1
r (1.409)]-1

=4.596xI0 23 m 3
ION-ION INTERACTIONS 119

or,

3
( 4.596xI0 23 m- 3 )x 1m x Imol =7.6x10- 4 M (3.103)
1000dm 3 6.022x 10 23

(b) In the same way, for water, with a dielectric constant of 78.3, b = 1. 989, and
b
Table 3.16 in the textbook indicates that feY y -4 dy = o. Therefore, KCl does
2
not reach 10% association in water at any concentration.

Review of Sections 3.9 to 3.15 of the Textbook.

Mention the basis of the McMillan-Mayer theory for liquids. What type of
catastrophe does one encounter when trying to calculate the energy of attraction
between one central ion and ions surrounding it? What is the justification for
adding the term e- Kr to the calculation of intermolecular energy by Mayer?
Explain the Monte Carlo approach. Explain the difference between the Monte
Carlo (MC) procedure and the Molecular Dynamic Simulation (MD). Mention
some of the drawbacks of the computer-simulated procedures. Explain what a
correlation function represents and mention some of its advantages. What is the
Mean-Spherical approximation? Give some reasons for the discrepancy between
theories of solutions and experimental data at high concentrations. Mention the
contribution of Daves, Wertheim, and Haymet to the electrolyte theory. Under
what conditions does Raman spectroscopy help detect the presence of ion pairs?
Explain what is referred as "primitive" and "mound" model in the ionic solution
theories. Describe different ways matter interacts with electromagnetic radiation.
Write the Beer-Lambert law. Describe the Raman effect. What information
about molecules can be obtained from Raman spectroscopy, infrared
spectroscopy and nuclear magnetic resonance?

PROBLEMS

3.26 (a) When the Debye-Hiickel model was developed, an important

hypothesis was made for mathematical convenience, i.e., that Z,-eo'l/r « kT.
Considering a 1: 1 electrolyte solution at 25 °c as an example, reassess the
validity of the hypothesis. (b) What is the physical nature of the above
hypothesis? (Cf. Problem 3.2 in the textbook) (Xu)
120 CHAPTER 3

Answer:

(a) Using the point charge version of Debye-Htlckel model expressed in the
mba unit system (cf. Eq. 3.33 in the textbook),

(3 .104)

Now, the approximation indicates that

(3.105)

Substituting the value of If/r and rearranging tenns,

(3 .106)
47rE oEkT r

Consider now a I: I aqueous electrolyte at 25°C, and a value of ,{i in dilute

solution of 10-8 m (cf. Table 3.2 in the textbook. It can be proved that ,{i has a
negligible effect on the results in diluted solutions.) The left-hand side (l.h.s.) of
Eq. (3.106) as a function of the radius r becomes,

e
-Kr {I)2 (1.602 xlO- 19 C r
47rE o&kT r (1.112 X 10- 10 C 2 J-I m -I )(78.3)( 1.381 xlO- 23 JK -I)

-rllO m -rllO m
e m)e r
-I -I

x 1 =(7 . 162xlO- 10 (3 .107)

(298 K) r

The hypothesis establishes according to Eq. (3.106) that,

- r 10-1
(7.162XIO- 10 )e r «I (3.108)

with r given in meters.

Evaluating the l.h.s. ofEq. (3.108) for different values ofr, gives the results
shown in the following table:
ION-ION INTERACTIONS 121

rx 108 (m) l.h.s. ofEq. (3.108) l.h.s.ofEq.

(3.108)
0.001 71.55 0.5 0.087
0.05 1.36 1 0.026
0.1 0.65 2 0.0049
0.2 0.29 3 0.0012
0.3 0.18 4 0.00033
0.4 0.12

Plotting the l.h.s. of Eq. (3.104) against the distance from the center ion
gives the graph in Fig. 3.2.
The validity of the hypothesis depends on the value of r. Close to the
vicinity of the center of the ion, the hypothesis does not hold true, but as r
increases, the function on the l.h.s. of Eq. (3.104) rapidly drops, and becomes
much smaller than one. In Problem 3.28(a), it will be proved that the vast
majority (more than 70%) of the ionic-cloud charge lies beyond a sphere of a
radius ,c/. In other words, more than 70% of the contribution to the ion
atmosphere comes from a distance r > ,c/. Under such conditions, the
mathematical description employing the above hypothesis correctly reflects the
average picture. However, as the solution becomes more concentrated, the value

1.5rr-----.----.---..........- - . - - - - . . . . - - - - ,

I.h.s 1.0
ofEq.
(3.108)
~

0.5

0.0 ........... ,... ,.," ",.....,"", ......,' .... ..

o 1 2 3
rx10 8 (m)

-Kr
Figure 3.2. Plot of (z i eo) 2 e in Eq. (3.107) VS. the distance
41Z'& o&kT r
from the central ion.
122 CHAPTER 3

of It! decreases (cf. Table 3.2 in the textbook), and the original hypothesis loses
its validity. The breakpoint occurs at a concentration of about 10-3 M.

(b) To a first approximation in diluted solutions, when r = It!, and It! = 10-8 m,

-rIIO"
e = 0.37 (3.109)

. _rIlO-8
Takmg e as 0.37, Eq. (3.108) becomes,

-10
2.64 x 10 m « 1 (3.110)
r

or

r» 2.64xlO- 10 m (3.111)

Therefore, the hypothesis adopted in the Debye-HUckel model is merely a

dimensional demand: only the ionic species that are 2.64xlO- 1O m away from the
center of the ion are considered in the model.

3.27 (a) Using the "point-charge" version of the Debye-Hiickel model,

derive the radial distribution of total excess charge, q(r), from the center of
the ion to a distance r. (b) Compare the shape of the graphs of q(r) and
dq(r), and comment on their differences. (Cf. Problem 3.20 in the textbook)
(Xu)

Answer:
(a) According to the point-charge version of the Debye-HUckel model, the
excess charge density in an element of volume dV at a distance r from the
central ion is (cf. Eq. 3.35 in the textbook),

(3.112)

The excess charge in a dr-thickness shell of radius r is (cf. Eq. 3.36 in the
textbook),

(3.113)
ION-ION INTERACTIONS 123

The total excess charge in the sphere of radius r is obtained by integrating

Eq. (3.113) from r= 0 to r = r,

(3.114)

If Kr = x , then,

q(r)=-zjeO f.r=O
r -x
xe dx (3.115)

This integral can be solved by parts, i.e. , fVdu = vu - f udv . Thus, considering v
= x, dv = dx, du = e-xdx, and u = -e-X, then,

( -x + Ir=oe
r -x) -xe -e -xIr=O
dx =-ZjeO (-x
r
q(r )=-ZjeO -xe )

(3 .116)
=-ZjeO -Kre( -KT
-e
-KT
Ir=O
r )

or,

(3.117)

(b) Evaluating Eqs. (3.113) and (3.117), give the results shown in the next table:

Kr -dq(r)/z;eoKdr -q(r}/ z;eo

0 0 0
0.2 0.164 0.018
0.4 0.268 0.062
0.5 0.303 0.090
0.6 0.329 0.122
0.8 0.359 0.191
1 0.368 0.264
2 0.271 0.594
3 0.149 0.801
4 0.073 0.908
5 0.034 0.960
124 CHAPTER 3

Figure 3.3. Comparison of q(r) and dq(r) functions .

Plots of dq(r) and q(r) functions against KT, give the graphs in Fig. 3.3 . The
amount of the total excess charge in the sphere of radius r around the ion, q(r),
increases monotonously with r. On the other hand, the amount of dq(r) shows a
maximum at r = !C/. When r -7 00, q(r) reaches its limiting value of -z;eo.

3.28 (a) Using the results from Problem 3.27, calculate the total excess
charge within the sphere of the radius of the Debye-Hfickel reciprocal
length, !C/. How much of the overall excess charge has been accounted for
within the sphere of radius !C1? (b) Plot q(r) vs. r for an aqueous solution of
to-3 M I: I electrolyte at 25°C. What distance from the ion encloses 95% of
the excess charge? (Xu)

Answer:

(a) From Problem 3.27, Eq. (3.117), the excess charge from the center of the ion
up to a radius r is

(3.118)

Therefore, at r = !C/,

(3 .119)
ION-ION INTERACTIONS 125

A sphere of radius r = K/ encloses only approximately a quarter of the

total charge. Most of the excess charge is distributed out of the imaginary ionic
cloud of radius K/.

(b) From Table 3.2 in the textbook, K- / for an aqueous solution of 10-3 M 1: 1
electrolyte at 25°C is 9.6 nm. Thus, from Eq. (3.118),

() [ (
q r =-Z j eO 1- 1+ 9.6nm e
r) -rI9.6nm 1 (3.120)

Evaluating q(rYz;eo as a function of r,

r(nm) q(ryz;eo r(nm) q(ryz;eo

1 0.005 40 0.936
5 0.096 45 0.948
9.6 0.264 50 0.966
20 0.616 60 0.986
30 0.819 70 0.994

Plotting q(rYz;eo as a function of r gives the graph in Fig. 3.4. The graph
shows the radial distribution of total-excess charge, q(r)/z;eo, around the center
ion. The limiting value of q(r) at r ~ 00 is, without surprise, -z;eo. An excess
charge of95% is obtained at about 45 om from the center of the ion.

1.0

0.8

0.4

0.2

10 20 30 40 50 60 70
r from center of ion (nm)
Figure 3.4. Total excess charge as a function of the distance
from the central ion.
126 CHAPTER 3

3.29 Find an equation relating the mean activity coefficient of thallous

chloride with the molarity of this electrolyte in solutions containing KCI.
The table below shows the solubility of TICI in water and in the presence of
various concentrations of potassium chloride solutions at 25°C. Consider
the activity of TICI to be approximately constant in this range of
concentration.

KCI concentration 0 0.025 0.050 0.10 0.20

(mol kg.l)

TICI solubility 1.607x10'2 8.69xlO-J 5.90xlO-J 3.96xlO-J 2.68xlO-J

(mol kg.l)

Consider that, for dilute solutions, f ± "" Y ± (cr. Problem 3.30). (Cf. Exercise
3.12 in the textbook) (Constantinescu)

Answer:

The mean activity coefficient is given by (cf. Eq. 3.55 in the textbook),

y±
or (3 .121)

and by (cf. Eq. 3.90 in the textbook),

(3 .122)

The logarithm function can be expanded as log x zx - 1. Thus, Eq. (3.122)

becomes,

(3.123)

or

(3.124)

For diluted solutions,f± ""y±(see Problem 3.30). Thus, substituting Eq.

(3.124) into Eq. (3 .121),
ION-ION INTERACTIONS 127

_1_=_1__ Az+z_ .JI (3.125)

m± a± a±

This equation indicates that a plot of lIm:t vs. //12 should give a straight line
with slope Az+z/a± and intercept I/a", whenever a± is constant. From any of these
parameters, it is possible to determine a±. The different values of mOe can be
obtained from the definition of this variable, i.e.,

(3.126)

-2 -I
For TICI in pure water, m Tl + = m Cl- = 1.607 x 10 mol kg , and m±,TlCI
1.607xlO-2 mol kg-I . For the solution containing 0.025 mol kg' I KCI,
-3 -3 -I -3
mcr =8.69xI0 +0.025=33.7xI0 mol kg and m Tl + =8.69 x 10
mol kg-I. Therefore,

m±,TlCI = ~( 8.69 x 10 -3 )( 33.7 x 10 -3 ) = 17.1x 10 -3 mol kg -I (3.127)

The values of m± for the other solutions are given in the table below. The
second parameter to determine is the ionic strength of the solutions. For the
solution of TICI in water, / = c = 1.607x10-2 mol kg-I, (cf. Exercise 3.11). The
ionic strength of the solution containing 0.025 mol kg-I ofKCI is,

(3.128)

In the same way for the other solutions,

mTlCl (mol kg-I) mKCI (mol kg-I) m:t {mol kg· l ) / (mol kg,-') l.t
16.07xlO-3 0 16.07xlO-3 16.07xI0-3 0.8963
8.69xlO-3 0.025 17.lxI0-3 33.69xl0-3 0.8424
5.90xlO-3 0.050 18.2xlO-3 55.90xlO-3 0.7915
3.96xlO-3 0.100 20.2xlO-3 103.96xl0·3 0.7131
2.68xl0-3 0.200 23.3xl0-3 202.68x 10-3 0.6183
128 CHAPTER 3

Figure 3.5. Mean activity coefficient of TICI as a function of its

concentration.

Plotting now I I m± vs . .[j gives the graph in Fig. 3.5. The fact that the
graph gives a straight line validates Eq. (3 .125). The equation corresponding to
this graph is,

_1_ = 69.41-59.88..[i (3.129)

m±

Therefore, a:J:= 1/69.41 = 0.01441, and from Eq. (3.121),

0.01441
r ±.TlCI = (3 .130)
m±.TICI

The last column in the above table gives the values of r ± at different
concentrations of KCI.

3.30 The chemical potential of a given species in a real system, i.e.,

interacting particles, is given by:

(3.131)
ION-ION INTERACTIONS 129

wbere x; is tbe concentration of tbe species i in mol-fraction units, Pi tbe

o
cbemical potential under standard state conditions and /; is tbe activity
coefficient wben tbe concentration is expressed in mol fraction. However,
tbe same equation can be written in terms of molality (m) or molarity (c) of
species i as

Pi (real)=p? (m)+RTlnmiYm.i (3.132)

(3.133)

Derive tbese two equations and find p? (m ), p? (c), Ym,;, and Ye,; in terms
o
of Pi and!;. (GamboaAldeco)

Answer:

(a) The molality is defined as the number of moles of solute (n) divided by the
mass of the solvent, i.e., water, (nw),

n n
m=--=---- (3.134)
mw nwMW w

Dividing and mUltiplying by the total number of moles, i.e., n, = n + nw ,

(3.135)

where x and Xw are the mol fractions of the solute and water, respectively.
Obtaining x from Eq. (3.135) and substituting it in the equation for p;{realj, i.e.,
Eq. (3.131) gives,

(3.136)

The next step is to separate the argument of the logarithm and identify the
different terms. However, to maintain the argument of the logarithms
dimensionally correct, it is needed to multiply and divide by mO, which is
defmed as mO == I mol kg-I. Thus,
130 CHAPTER 3

o
J.1 i (real) = J.1? + RT In mx w MW wIi m 0
m (3.137)
o 0 m
=J.1i + RTInMWwm +RTln/ixw-o
m

Defining

(3.138)

and

ri,m =/;Xw (3.139)

gives,

o
J.1 i (real) = J.1 i (m) + RT In -i-
m·
rm ,i (3.140)
m

or, when mj is given in mol kg-I (cf Eq. 3.64 in the textbook),

J.1 i (real) = J.1? (m ) + RT In m i r m i (3.141)

Comment: For diluted solutions Xw -7 1. Then, from Eq. (3.139) Y;,m -7 t.

(b) The molarity is defined as the number of moles of solute, n, divided by the
volume ofthe solution, V, i.e.,

n
c=- (3.142)
V

Dividing and mUltiplying Eq. (3.142) by the total number of moles, n"

n n, xn,
c=-x-=- (3 .143)
V n, V

Obtaining x from Eq. (3.143) and substituting it in the equation for J.1;{real),
i.e., Eq. (3.131), gives,
ION-ION INTERACTIONS 131

Ili (real) = Il~ + RT IneVfi (3.144)

where V is the molar volume of the solution defined as V =V / n t . Multiplying

and dividing by CO defined as e O =1mol dm -3 ,
0 - e 0 -0
o e
Ili ( real ) =Ili +RTlneVfio=Pi +RTlnVe +RTlnfi o (3.145)
e e

Defining

o()
Ilic · =Pi + RTlnVc
0 -0 (3.146)
and

Yi,c =Ii (3.147)

gives,

(3.148)

when ej is expressed in mol dm-3 (cf Eq. 3.63 in the textbook).

3.31 Derive an expression for the solvent activity in diluted solutions. Hint:
start with the Gibbs-Duhem equation considering the solution as a binary
system. Then, apply the Debye-Hilckellimiting law. (Cf. Exercise 2.21 in the
textbook) (Xu)

Answer:

If the solution is considered a binary system, then system A represents the

solvent (water), and system B the electrolyte. Thus, the Gibbs-Duhem equation
reads (cf. Eq. 3.95 in the textbook);

(3.149)

Now, the chemical potentials of the two systems are given by,

o o
PA =P A + RT In a A and Il B = PB + RT In a B (3.150)
132 CHAPTER 3

and their derivatives:

(3 .151)

Therefore, Eq. (3.149) becomes,

(3.152)

Since the solution is diluted, nA can be regarded as a constant. Therefore,

integrating Eq. (3.152),

(3 .153)

or

(3.154)

The integral on the left side of Eq. (3.154) is simply

(3.155)

The evaluation of the integral on the right-hand side ofEq. (3.154) is more
complicated because aB (or CB) is a function of nB' The activity of the electrolyte
is defined as (cf. Eq. 3.55 in the textbook),

(3.156)

where IB the activity coefficient, and XB is the concentration expressed in mole

fraction, i.e.,

nB cB
x B = - - = - = ---=-- (3.157)
nB +nA cB +cA

The next step is to fmd IB' the activity coefficient of the electrolyte. This
variable can be taken as the mean of the activity coefficients of the positive and
negative ions constituting the electrolyte, i.e., Is = Ir Thus, considering the
condition that the solution is very diluted and that the electrolyte is of the I: I
ION-ION INTERACTIONS 133

type, the Debye-Htlckel limiting law can be applied (cf. Eq. 3.90 in the
textbook), i.e.,

(3.158)

where the condition I = CB for a 1: 1 electrolyte was considered (cf. Exercise

3.11). Thus, taking logarithms on both sides of Eq. (3.156) and substituting the
values ofxB and/B, from Eqs. (3 .157) and (3.158)

(3.159)

Since the solution is diluted, CB + CA ~CA , and

CB C-
InaB :::.In--2.303A,,CB (3 .160)
cA

Differentiating Eq. (3 .160),

dlnaB:::' [ -I - U5IA] dCB (3 .161)

cB rc;
Substituting Eqs. (3 .155) and (3 .161) into Eq. (3.154), and considering that
aB = CB gives

or
0.767 A~(CB)3 -cB
In a A = - -- - - ' ' - - - - - - (3.163)
CA

3.32 An electrochemical cell is represented by

I
Ag(s ),AgBr(s) KBr(aq) II Cd (N0 3 )2 I
(aq,O.OIM) Cd(s) (3.164)
134 CHAPTER 3

The standard potentials on the hydrogen scale of the pairs Cd+2/Cd and
AgBr/Ag are -0.40 V and +0.07 V respectively. At 2S DC, the reading
potential of the cell is - 0.62 V. Show that

0.035
r ±.KCI = (3.165)
c± .KCI

when the Debye-Hiickel ion-cloud model holds well. (Contractor)

Answer:

The reactions on the right- and left-hand sides of the cell are:
+2 -
r.h.s. Cd (aq) + 2 e ~ Cd(s) E 10 = -0.40V (3.166)

I.h.s 2Ag(s) + 2Br (aq) ~ 2AgBr(s) + 2e E 10 = -0.07V (3 .167)

+2 -
2 Ag (s) + Cd (aq) + 2 Br (aq) ~ 2 AgBr (s) + Cd (s) E 10 = -0.47 V (3 .168)

The measured potential is given by (cf. Eq. 3.103 in the textbook)

E = E o + -In
RT ( a Cd +2 a B 2) - (3.169)
nF r

where E = -0.62 V, and n = 2. The value of a Cd +2 can be obtained from the

activity coefficient equation, i.e. (cf. Eq. 3.90 in the textbook). Considering that
Cd(N03h is a 2: 1 electrolyte, the ionic strength on the r.h.s of the cell is given
by 1 = 3c (cf. Exercise 3.11). Thus,

logf± ,Cd ( N0 3 ) 2 =-A(z+z_).JI

(3.170)
= -0.509M -\ 1+211-11"'0.03M = 0.18

or

(3.171)

Since f± = r c± (cf. Problem 3.30),

ION-ION INTERACTIONS 135

(3.172)

Substituting the values of E, £1, n, and a Cd +2 from Eq. (3.172) into Eq.
(3.169),

( 8.314JmOI- 1 K- 1 )(298K)
-0.62V=-0.47V+ ( ) lCV ( 0.0067a -
x--ln B
2)
(2) 96500Ctnol- 1 11 r

(3.173)

Solving for a Br - ,

a Br- = 0.035 (3.174)

Since a Br - = r c± C KBr , therefore,

0.035
rc±.KBr = - - (3.175)
cKBr

3.33 The following electrochemical cell gives a potential of -0.218 V at

2SoC:

Ag I AgCl(s) I AgCI(aq.,sat.) I AgCI(aq,sat .inO.05M CaC/2 ) I AgC/(s) I Ag

(3.176)

The solubility product of AgCI is known to be 1.77xl0-10 at room

temperature. (a) Calculate the individual activity coefficient of cr in the
CaCI1 solution. (b) Is there a way to obtain the individual activity
coefficient for Ag+ in the same solution? (Cf. Problem 3.6 in the
textbook)(Xu)

Answer:

(a) The potential of the cell is related to the activities of the active species in
both compartments of the cell by (cr. Section 3.4.8 in the textbook),
136 CHAPTER 3

RT Ag + ) right (a (3.177)
E cell = E soln2 - E solnl = - I n - - - - - - ' ' - -
F ( a Ag + ) left

The subscript left refers to the solution of AgCl in water (left side of the
cell), and the subscript right to the solution of AgCl in 0.05 M CaCh (right side
of the cell).
On the left side of the cell, AgCl(aq.,sat.) is in equilibrium with AgCI(s).
The solubility reaction of AgCl is:

Ag"(aq.) + Cr(aq.) -?AgCI(s) (3.178)

and the corresponding solubility product (remember that the activity of pure
substances is I!):

(3.179)

From Eq. (3.179),

( aAg +) left =(a cr ) =~l.77xIO-IO

left
=1.33xI0- 5 M (3.180)

Substituting this value of (a A

g
+ )
left
into Eq. (3.177), and solving

for(a A
g
+) right :

( 8.314JmOI- I K- I )(298K) Ag+ ) .

right
(a
Ecell = -I In -5 = -0.218V (3.181)
96500Cmol 1.33 x 10

( aA + ) . = 2.73xlO -9 . (3.182)
g right

Now, on the right side of the cell, AgCI in 0.05 M CaCl2 solu~~m is in
equilibrium with AgCI(s). Neglecting the chloride from AgCl, the activity of
chloride on the right side of the cell is,
ION-ION INTERACTIONS 137

Ks =(a Ag + )
right
(acr )rIg. ht =2.73x1O-9 (acr )rIg. ht =1.77xlO- 10 (3.183)

-10
(a cr ). = 1.77xl0 =0.065 (3.184)
rIght 2.73x 10-9

The activity coefficient of chloride on the right side of the cell is given by

( ) _tacr ) right
(3.185)
r cr right - ( C _)
CI right
With tcCI-)
right
~2xO.05=0.10,

(r _) = 0.065 = O.65M-1 (3.186)

CI right O.lOM

(b) From the equation relating activity coefficient and ionic strength (cf. Eq.
3.90 in the textbook),

(3.187)

The ionic strength in the right side of the cell neglecting the concentration
of Agel, is (cf. Eq. 3.83 in the textbook),

I =.!.
2 i
Lei z; =.!.2 (c cr c
+ 4 Ca +2 )

(3.188)
= .!.[2( 0.05)+ 4( 0.05 )]= 0.15M
2

Considering that Eq. (3.187) holds for the right-hand side of the cell,

(logf± )AgCl,right =-0.5115M- 1I2 (1)(I)v'0.15M =-0.20 (3.189)

or

(J± ) AgCl ,right = 0.63 (3.190)

138 CHAPTER 3

The individual activity coefficients of Agel are related by,

(3 .191)

Therefore,

(3.192)

or

(j ± ) Ag + ,right = 0.61 (3.193)

3.34 (a) If the finite sized center ion has a size parameter a, what is the
radial distribution of total excessive charge, q(r) and dq(r)? (b) Use the
correspondance principle to confirm the validity of this expression. (c) Does
the Debye-Htickel reciprocal length, K I , depend on a? Use the results from
Problem 3.27. (Cf. Problem 3.10 in the textbook) (Xu)

Answer:

(a) The spatial distribution of the charge density is given by (cf Eq. 3.34 in the
textbook),

e 2
Pr =--1( Ifr (3 .194)
4"
If the ion is considered to have a finite size, a size parameter 0 can be
assigned to it. Thus, the potential at a distance r from the finite-sized central ion
is (cf. Eq. 3.113 in the textbook),

ICtl -I(T
zieO e e
If r = - - - - - - - - (3.195)
e 1+1(0 r

Substituting Eq. (3 .195) into Eq. (3 .194) gives,

(3.196)
ION-ION INTERACTIONS 139

The excess charge in a dr-thickness shell of radius r is (cf. Eq. 3.36 in the
textbook),

(3.197)

Substituting Pr from Eq. (3.196) into Eq. (3.197) gives

2
() Z i eo I( K ( a-r )
dqr=- re dr (3.198)
1 + Ka

The total excess charge in the sphere of radius r is obtained by integrating

Eq. (3.198) from 0 to a distance r. Therefore,

(3.199)

Solving the integral by parts as in Problem 3.27,

q(r)= Zjeoelal ( -Kre -/(f" -e -/(f"

~
I
r )
(3.200)
1+1(0 r=a

K1I
ZieO e (
q(r) = - Kre
-/(f"
- e
-/(f"
+ Kae -K1I + e -KIl )
(3.201)
1+l(a

(b) To confIrm the validity of this expression, we make use of the

correspondonce principle. The general version of a theory, in this case Eq.
(3.201), must reduce to the approximate version under the conditions of
applicability of the latter (cf. Section 3.5.3 in the textbook). In other words, does
Eq. (3.201) reduces to Eq. (3.117) in Problem 3.27 under the appropriate
conditions? Thus, when 0 = 0, Eq. (3.201) becomes,

q( r) =- Z j eo ( - Kre
-/(f"
- e
-/(f"
+1
)
(3.202)

This is the expression for the center ion as a point charge. This similitude
validates the expression in Eq. (3.201).
140 CHAPTER 3

(c) The parameter If' represents the distance from the ion at which a spherical
shell of infinitesimal thickness, dr, contains the maximum value of charge (cf.
Sec. 3.3.8 in the textbook). Thus, K-' is obtained when the function dq has a
maximum value, i.e., when!!..... dq = o. Thus, differentiating Eq. (3.198), and
dr dr
equating to zero,

d dq(r) Zj e OK 2 dq(r) K(a-r}

---= re
dr dr I+Ka dr
(3 .203)
2
= ZjeOK [_rKeK(a-r} +eK(a-r}]=o
I+Ka

Therefore,

K(a - r} K(a-r} -1
rKe =e r=K (3.204)

This indicates that, although the center ion is considered now to have a fmite
size, the distance at which dq(r) has a maximum occurs still at If'. In other
words, the value of IfJ is independent of the ion size.

3.35 Evaluate the Debye-Hiickel constants A and B for ethyl alcohol. Use
the calculated values to determine approximately the mean activity
coefficients for 1:1, 1:2, and 2:2 valent electrolytes in this solvent at ionic
strengths of 0.1 and 0.01 at 25°C. The mean distance of closest approach of
the ions, a, may be taken as 3 A in each case. The dielectric constant of ethyl
alcohol is 24.3. Comment on your results. (Cf. Problem 3.22 in the textbook)
(Constantinescu)

Answer:

The two constants, A and B, are defined in the mksa unit system as (cf. Eqs. 3.86
and 3.89 in the textbook),

2
and A= eO B (3.205)
2.30341r& oEkT

Substituting the corresponding values for the parameter B,

ION-ION INTERACTIONS 141

2 ( 6.022 xl 0 23 mol -I )( 1.602 x 10 -19 C ) 2 11/2

[

= 1.869xl0 8 mol- 112 m 1/2 (3.206)

or (cf. Exercise 3.13),

3/2 (1000dm 3 )1/2

B=(1.869XI0 8 mol-112m 112 )x~...o.....----,,--- (3.207)
dm 3/2 Im 3/2
=5.910xI0 9 M- 1/2 m- 1

The parameter A is given by,

A=--------~----'------------
(1.602XIO- 19 C r
(2.303 )(2 )(24.3)( 1.112x 10 - 10 C 2 J -I m - I )( l.381x 10 -23 JK -I )

x 1.869xl0 8 mol-112 m 112 =0.09365mol-1I2m3/2 (3.208)

298K

or

3/2 (1000dm 3 ) 112

A = (0 .09365mol-1I2m3/2 )x dm 3/2 2.96IM-1/2 (3.209)
dm Im 3/2

From the extended Debye-HOckel law (cf. Eq. 3.120 in the textbook), the
equation for the mean activity coefficient reads,

(3.210)

For a I: 1 valent electrolyte in a solution with ionic strength of I = 0.1, Eq.

(3.210) gives,
142 CHAPTER 3

(2.961M- 1/ 2 )(I)(I)(O.lM)1I2
log/± =
(3.211)
1+(5.910X10 9 M-1/ 2 m- 1 )(3xlO- IOm )(0.IM)I/2

=-0.600

or

I± =0.251 (3.212)

In the same way for the other solutions,

J = 0.1 M J=O.OI M
Electrolyte
logl± I± logft I±
1:1 -0.600 0.251 -0.253 0.559
1:2 -1.200 0.0631 -0.506 0.312
2:2 -2.400 0.00398 -1.012 0.097

Comment. According to this theory, the mean activity coefficient decreases

with increasing ionic strength of the solution. The decrement is greater as the
valence of the ions increases. The unusual low values of mean activity
coefficients obtained indicate the necessity to introduce other corrections that
could reflect better the ion-ion interactions (cf. Chapter 3 in the textbook).

3.36 The radius of the ionic atmosphere is represented by ttl, the Debye-
Huckel length. When the solution is diluted, the ions are far apart, and the
central ion sees a smoothed-out cloud of charge around itself. However,
when the concentration increases, the distance, e, between ions decreases,
and one is confronting a situation in which the radius of the atmosphere is
less than the average distance between ions. (a) Write an expression
showing the average distance between ions, e, as a function of the
concentration, c. (b) Compare the distances e and ttl for a low
concentrated solution, e.g., 10-5 M, and for a very concentrated solution,
e.g., to-l M, for a 1:1 electrolyte. (c) Find the concentrations for a 1:1 and a
2:2 electrolyte at which e > ttl, i.e., when the "disaster of coarse-
ION-ION INTERACTIONS 143

grainedness" occurs. (d) Do you think an ionic-atmosphere model applies

when f > Kl? (Cr. Problem 3.9 in the textbook) (Bockris-GamboaAldeco)

Answer:

(a) Consider the concentration c of a 1: 1 electrolytic solution. In this solution,

there are a total of2c ions, or,

3 -I lOOOdm 3
2cmoldm xN A mol x =2000N AC ions in 1 m3 (3.213)
1m 3

Therefore, the volume occupied by a single ion is, 1I2000NA c m3. Now, to
determine the distance between ions, e, consider a model where the ions are in a
cubic array, and each ion occupies a volume given by a cube of side P, as
shown in Fig. 3.6. In this array, the side of the cube is the same as the distance
between the ions. Then, the volume occupied by one single ion is

v=p 3 = m3 (3.214)
2000N AC

and the side of each cube in meters when the concentration is given in mol dm·3
is, then,

Figure 3.6. Cubic array of ions. The parameter

Prepresents the distance between ions.
144 CHAPTER 3

1I3
f =( 1 m3 ] =9.398xlO -10 c -1/3 (3.215)
2000N AC

(b) The Debye-Hilckel distance, ,cl is given by the equation (cf. Eq. 3.85 in the
textbook),

(3.216)

r
For a I: 1 electrolyte, I = C (cf. Exercise 3.11). Therefore, ,cl in meters is,

K- 1 =( 0.329lxl0 8 M- 1I2 cm -I rc x IO o;m

l
1
(3.217)
= 3.0386x 10 -10 C -1I2

Using Eq. (3.217), when c = 10-5 M. then K-\ = 9.609xlO-S m and f =

4.3621xlO-s m. Under this conditions, K-\ > f. Thus, it is quite legitimate to
argue that the central ion sees a smoothed-out cloud of charge around itself and
one can use the Poisson equation with its implications of a continuous charge
distribution. However, as the electrolyte concentration is increased, the situation
ceases to be so satisfactory. For example, in a 10-2 M solution of the same
electrolyte, K-\ = 3.0386xlO-9 m and f = 4.362 IxlO- 9 m. At this concentration,
,cl < f. The central ion experiences a discrete charge, not a smoothed-out cloud
of charge. Thus, as the concentration increases, the ion cloud at a given distance
from the ion, contains a number of ions which increases as the concentration
increases. In other words, the cloud gets increasingly coarse grained.
Smoothness decreases, discreteness increases.

(c) The "disaster of coarse grainedness" occurs when ,cl < f. For a 1:1
electrolyte at 25°C, f and ,cl are given by Eqs. (3.214) and (3.216). Thus,

3.0386xlO- lO c -112 <9.398xlO- lO c -113 (3.218)

Solving Eq. (3.217) for c gives, c> 0.0011 M. For a 2:2 electrolyte I = 2c
(cf. Exercise 3.11), and the Debye-Hilckellength given in meters is

K = BJI = B.[2"; = O.329Ix10 8 .J2 rc (3.219)

or
ION-ION INTERACTIONS 145

(3.220)

From this equation and Eq. (3.216),

2.148x 10 -10 c -1 / 2 < 9 .398x 10 -10 c -1 / 3 (3.221)

Simplifying terms shows that the disaster of coarse grainedness" for a 2:2
electrolyte occurs when c > 0.00014 M.

(d) No. The increase of grainedness leads to large fluctuations of the

electrostatic potential, If/, with time. Hence, the model of a continuous,
smoothed-out charge density, i.e., the ionic cloud, must break down when this
phenomenon occurs.

3.37 The experimental values of the mean activity coefficients for CaCI2 at
various concentrations at 25°C are given in the Table below:

c(M) Ix (experimental)
0.0018 0.8588
0.0061 0.7745
0.0095 0.7361

Calculate the mean-effective-ion size, a. Calculate the mean-activity

coefficient without considering and considering the ion size parameter, and
comment on your results. (Contractor)

Answer:

For CaCI2> 1= 3c (cf. Exercise 3.11). Thus, from the point-size model (cf.
Eq. 3.91 in the textbook),

(3 .222)

At 0.0018 M,

log! ± = -( 0.5115M -1/2 )1 2 11- 1IJ3{0.0018M) = -0.07517 (3 .223)

or
146 CHAPTER 3

f± =0.8411 (3 .224)

where A = 0.5115 M- l12 was taken from Table 3.4 in the textbook. At this
concentration, the difference between Iiexperimental) and this calculated value
is only 2%. This good agreement indicates that it is possible to determine the
parameter a from this value of/r.{experimental) using the modified equation, and
then recalculating the mean-activity-coefficient value for the other
concentrations. Thus, from the finite-ion-size model (cf. Eq. 3.120 in the
textbook),

(3 .225)

Solving for a and substituting the corresponding values (B = 0.3291x108

M -1/2 cm- l from Table 3.3 in the textbook),

1 (AZ+Z_ JI )
a = - B JI log f ± + 1 = - -0.-32-9-I-x-IOR8-M---:iI~/2;-c-m-:J1.J-;=3(;::0=.0=0=18=M~)

x[
0.5115M -1I21211_11~3( 0.0018M)
+1
1
logO.8588
-8
= 5.671xlO em (3.226)

With this value of a, fr is re-calculated at each concentration using the

finite-ion-size model, i.e., Eq. (3.225),

( 0.5115M-C1 / 2 )i111-11.Jk
logf± = (3.227)
1 +( O.3291x10 8 M- 1/ 2 em -1)( 5.67lxI0-8 em ).Jk
The next table shows J: for all the other concentrations using the point-size
model as well as the fmite-ion size model. The table includes the percentage
difference between these values and the experimental ones, calculated as:

(3.228)

and
ION-ION INTERACTIONS 147

I ± (re-calc) - f± ( exp )
% re- calc x 100 (3.229)
I±(exp)

c(M) Ir(exp) Ir o/Ocolc Ir %re-colc

point-size finite-ion
model size model
0.0018 0.8588 0.8411 2.1% 0.8588
0.0061 0.7745 0.7271 6.1% 0.7755 0.1%
0.0095 0.7361 0.6718 8.7% 0.7391 0.4%

The fmite-ion-size model gives a better agreement with experimental

values, compared to the point-ion model.

3.38. (a) Find the maximum potential at which the Poisson-Boltzmann

equation can be linearized in a 1:1 electrolyte at 25 Dc. (b) After
linearization, the charge density in the atmosphere is proportional to the
potential. Can you see any fundamental objection to having a p not
proportional to vi! (Cf. Problem 3.1 in the textbook) (Bockris-
GamboaAldeco)

Answer:

(a) The Debye-HOckellaw is valid at low concentrations, up to -om N for 1: 1

electrolytes in aqueous solutions (cf. Section 3.5.1 in the textbook.) At this
concentration, ,(1 = 3.04 run (cf. Table 3.2 in the textbook.) Substituting this
value in the corresponding equation for If/c1outb expressed in the mksa system (cf.
Eq. 3.49 in the textbook),

ZjeO
1(1.602Xl0- 19 c)
If/ cloud =
41l'&0&K -I ( 1.112x 10 -10 C 2 J -1m - I )(78.3)( 3.04x 10 -9 m )

x 1CV = -0.00605 V (3 .230)

lJ

(b) A charge density proportional to If/ is consistent with the law of

superposition of potentials. However, a p not proportional to If/ would be the
148 CHAPTER 3

result of a non-linear relationship between p and If/ (cf. Section 3.7 in the
textbook), which implies an invalidity in the law of superposition of potentials.

3.39 (a) As alternative to the Bjerrum's model of ion dissociation, use the
results of the Debye-Hfickel model to develop a qualitative but facile
method to predict ion-pair formation. (Hint: compare the Debye-Hfickel
reciprocal length, Itl, with the effective distance for ion formation, q). (b) In
lithium batteries, usually non-aqueous solutions constituted by lithium salts
dissolved in organic solvents are used as electrolytes. The dielectric
constants of such solvents range between 5 to 10. Using this information,
estimate if ion paring occurs in these batteries, and compare with similar
calculations in water. (Cf. Problem 3.13 in the textbook)(Xu)

Answer:

(a) The Debye-HUckel reciprocal length, Itl, defines a territory within which
there is a considerable amount of counter ions (cf. Section 3.3.8 in the textbook).
On the other hand, the effective distance for ion-pair formation defined by q in
the Bjerrum's model encloses a territory within which two ions of opposite
charge may associate into an ion-pair (cf. Eq. 3.8.3 in the textbook). Therefore, a
fast method to predict ion-pair formation would be comparing the parameters q
and It' . Thus, if q > It', ion pair formation occurs in solution, but if q < It', ion
pair does not form.

(b) The effective distance for ion-pair formation, q, is given by the Bjerrum
equation in the mksa unit system as (cf. Eq. 3.144 in the textbook),

(3.231)

Considering a I : 1 electrolyte at 25°C,

q=
(1.602XlO- 19 C r 1

2(1.l12XIO-IOc2J-lm-1 )(1.38IXlO-23 JK- 1 )(298K)& (3.232)

2.804xIO-8 m
ION-ION INTERACTIONS 149

If the electrolyte is water, & :::: 78, and q = 3.6xlO· 1O m. Under these
circumstances in diluted solutions K'l "" 10-8 m (cf. c < 10-3 M in Table 3.2 in the
textbook), and thus, q < < K'l. This means that counter ions are beyond the
distance of ion-pair formation, and thus this phenomenon is unlikely to occur.
Now, if the electrolyte has a dielectric constant of, say, 10, as in
poly(tetraglycol-dimethylether) in lithium batteries,

1/2 {(10 )(8.854X 10-12 C2 J-Im -I)

-I &&okT
=[ =
eo2"
L;ni0zi2 (1.602 x 10- C )2
K ]
19

1/2

(1.381XIO-23 JK- I )(298K)

x----------~------------------------------ (3.233)
[( 2x1O-3 moldm -3 )( 6.022 x 1023 mol-' )'0::,,:,,3]

-9
= 3.43xlO m

From Eq. (3.232), q = 5.61xlO-9 m when & = 10. Thus, q > K'l . This
indicates that most of the counter ions are within an effective distance, and ion-
pair formation is likely to occur.

3.40 (a) Describe the correlation function, as applied to ionic solutions and
state two entirely different types of methods of calculating correlation
functions. (b) Describe the "point" of knowing this quantity and comment
on the meaning of the statement: "From a knowledge of the correlation
function, it is possible to calculate solution properties, which may, in turn,
be compared with the results of experiment. Hence, the calculation of the
correlation function is the aim of all new theoretical work on solutions."
(Bockris-GamboaAldeco)

Answer:

(a) The correlation function is a measure of the effect of species j in solution in

increasing or decreasing the number of i ions in a given small volume of
solution. Two methods to determine correlation functions are: Method I to
determine correlation functions: By computer simulation MonteCarlo or
150 CHAPTER 3

Molecular Dynamic methods. Method 2 to detennine correlation functions: By

experiment, using X-rays and neutron diffraction measurements.

(b) The main advantage is that there are no models assumed in the experimental
detennination of the correlation functions. In the case of computer simulated
methods, correlation functions are obtained by assuming a certain pair-
interaction law. In any case, once the correlation functions are obtained,
different properties of the studied system can be detennined without the
experiment being troublesome, faster, and at lower costs. Thus, in a very general
although complex way, the solution properties are found in tenns of correlation
functions. Since there are no model assumptions involved in the experimental
detennination of correlation functions, this approach is the aim of the
detennination of properties in solution.

MICRO-RESEARCH PROBLEMS

3.41 (a) One could use the Debye-Hiickel ionic atmosphere model to study
how ions of opposite charges attract each other. Based on this model, derive
the radial distribution of cation concentration (n+) and anion concentration
(n_) around a central positive ion in a dilute aqueous solution of a 2:2
electrolyte. (b) Plot these distributions, and compare this model with the
Bjerrum's model of ion association. Comment on the applicability of this
model to the study of ion-association behavior. (c) Using the data in Table
3.2 in the text, compute the cation and anion concentrations at the Debye-
Htickel reciprocal lengths at various concentrations. Explain the
applicability of the expressions derived. (Cf. Micro-research 3.1 in the
textbook) (Xu)

Answer:

(a) The individual cation or anion concentration in a volume element dVaround

a given ion, is given by the Boltzmann distribution law, i.e. (cf. Eq. 3.7 in the
textbook),

(3.234)

where n? is the bulk concentration or the calculated concentration throughout

the whole solution, and U is the change in potential energy of the i particles
when their concentration in the volume element dV is changed from the bulk
ION-ION INTERACTIONS 151

value n? to n;. If only the electrostatic contribution to the potential U is

considered, then, (cf. Eq. 3.8 in the textbook),

(3.235)

where '1/, is the electrostatic potential. Using the approximation that

Zjeo'l/r «kT,

zjeO'l/r) ~l-~~~
Zjeo'l/r
~p ( (3.236)
kT kT

For a 2:2 electrolyte, n O = n~ = n~ and the expression for cation and

anion concentrations in the volume element dV becomes,

n+ = n o ( 1- 2 eO '1/ r ) for cations (3.237)

kT

n_ = n O( 1+ 2ekTO'l/r) .
for anIons (3.238)

The next step is to find an appropriate expression for the electrostatic

potential. Since the solution is diluted, the expression of 'l/r for the point-charge
model can be applied. Hence, (cf. Eq. 3.33 in the textbook),

-Kr
ZjeO e
'l/ r = - - - - (3.239)
& r

where Z; is the valence of the central ion, i.e., +2. Thus, inserting 'l/r from Eq.
(2.239) into Eqs. (2.237) and (2.238), gives, for cations,

n+ =nO[I_ 4e~
&leT
e-
r
Kr
1 (3.240)

or
152 CHAPTER 3

~=I_~_e __
4 2 -Kr
(3.241)
nO ckT r

and for anions,

o 4 eO2 e -Kr) (3.242)

n_ = n ( 1+ ekT -r-

or

4 2
~=I+~_e __
-Kr
(3.243)
nO ckT r

(b) Figure 3.7 shows the profile of n+ / nO and n./ nO against the distance r from
the center ion, where K J was taken to be approximately 30 om (cf. Eqs. 2.242
and 2.243). The figure shows that, the closer to the central ion, the larger the
deviation from the bulk value, nO, is. For the cations, the deviation means
depletion, and for the anions, it means accumulation. This result is in agreement
with the Debye-HOckel's picture of ionic cloud.

16 ~

1•
\
nlnO
io

'-------.... -

r from positive center ion (nm)

Figure 3.7. Radial distribution of cation and anion density

around a positive center ion (+2). The deviation from the
bulk value dies gradually with distance (hence the center
ionic field) .
ION-ION INTERACTIONS 153

In the Bjerrum's model of ion association, the same issue was handled, i.e.,
the distribution of anions and cations around a positive center ion [cf. Section
3.8 in the textbook]. While the initial reasoning is essentially the same, i.e., both
theories consider an electrostatic distribution of ions, these two models are based
on different approximations. The Bjerrum's model does not consider the ion-ion
interaction when handling the electrostatic potential U responsible for the ion
association, i.e., the contribution to U from other ions than the central one is
ignored. This makes the Bjerrum model only good for diluted solutions.
On the other hand, the Debye-HOckel model considers inter-ionic effects,
but to simplify its equations, it assumes that Z i eolf/ r «kT, which holds only
when r is large. In other words, the Debye-HOckel theory does not reflect a
realistic view of ion distribution in the close neighborhood of the center ion.
This disadvantage disqualifies this model for the study of the ion-association
phenomenon, because the ion-pair formation only occurs in the close vicinity of
the central ion. The advantage of this model is that it applies to larger
concentrations than the Bjerrum's model.

(c) The cation and anion concentration at the Debye-HOckel reciprocal lengths
for NaCI can be calculated from Eqs. (2.241) and (2.243). Thus, for 10-4 M, the
cation concentration is,

(3.244)

which means that there is a small depletion of cations near the central ion. In the
same way, the anion concentration is,
154 CHAPTER 3

indicating that there is a small accumulation of anions at r = K'/ . Similarly for

higher concentrations,

Concentration (M) K'/ (nm) n.Jn~ nJn~

(Zj e O)2 e -Kr /ukT
1004 15.2 0.9307 1.069 0.069
10-3 4.81 0.7809 1.219 0.219
10-2 1.52 0.3068 1.693 0.693
10-\ 0.48 ~-1.l95~ 2.195 2.195

The result for n j nO when the concentration is 10-\ M makes no sense,

because it gives a negative value and the concentration cannot be negative. To
check the origin of this unreasonable result, one should look at the
approximation used in the derivation of these equations. One may recall, that in
expanding the exponent, exp (-z;eo\j!j / kT), the hypothesis z;eo\j!r «kT or
(z;eoie -
I(f /erkT« 1, was made. The last column in the table shows that at
10-2 M the calculated value is already not much less than one, and at 10-\ M the
value is larger than one. This indicates that at these high concentrations the
hypothesis does not hold true, showing the reason for the appearance of negative
concentrations. The theory is not valid any more.
CHAPTER 4

ION TRANSPORT IN SOLUTIONS

EXERCISES

Review of Sections 4.1 and 4.2 ofthe Textbook

Define flux, diffusion, migration and hydrodynamic flow. What forces are
responsible for the movement of mass and charge, and the diffusional flux of
species? Write equations defining these forces. What is steady state? Write
Fick's first law of steady-state diffusion. In this equation, what does the
parameter D represent? Is D a constant? Write expressions for the average
distance, the mean square distance, and the mean distance. Write the Einstein-
Smoluchowski equation, and explain its importance in diffusion. Write Fick's
second law of time-dependent diffusion. How does this equation transform after
applying Laplace transformation? Name three conditions applied to solve Fick's
second law. Write the solution to the second Fick' s law showing the space and
time variation of concentration in response to a constant-unit flux that extracts
ions from the system considered. How does this equation vary if now (a) the
flux is constant but different from one, (b) the flux acts as a source of ions, (c)
the flux varies as a cosine function, or (d) the flux varies as a step function?
What is the Einstein-Smoluchowski fraction? What are the advantages and
limitations of this equation? Write equations relating the jump frequency with
the diffusion coefficient and with the activation-free energy. Briefly, describe
two atomistic models of diffusion. Draw a diagram of the energy barrier for an
ion jump. What is the velOcity-autocorrelation function?

155
M. E. Gamboa-Adelco et al., A Guide to Problems in Modern Electrochemistry
© Springer Science+Business Media New York 2001
156 CHAPTER 4

4.1 (a) Calculate the steady-state diffusional flux of cr ions to tbe surface of
an electrode if tbe concentration gradient is 0.5068 mol dm-3 em-I. (b)
Calculate tbe magnitude of tbe diffusion current for tbe oxidation of
cbloride ions. Consider D cl_= 2.032xI0-5 cm2 S-I. (Contractor)

Answer:

(a) The steady-state diffusional flux is given by (cf. Eq. 4.16 in the textbook):

J- j = -Di de
dxj = - (
2.032x10 -S cm 2s -1)( 0.5068moldm -3 cm -I )
2 (4.1)
Idm 100dm -4 -2 -1
x--x =-1.030xl0 molm s
10cm 1m2

(b) The magnitude of the diffusion current is

i D = zF J j =I-II( 96500C mol- I )( 1.030 x 10-4 mol m -2s -I )

(4.2)
IA -2
x - - = 9.940A m
ICs -I

4.2 A certain radioisotope is leaking out from a defect in a storage tank. If

tbe diffusion coefficient of tbe isotope is 3x10-5 cm2 sot, calculate tbe mean
distance traveled by it in 24 bours if transport occurs only by diffusion.
(Contractor)

Answer:

From the Einstein-Smoluchowski equation (cf. Eq. 4.20 in the textbook),

4.3 In an instantaneous-pulse experiment, the electrode material is

radioactive and hence, detectable by a Geiger counter. The pulse is
produced witb an electronic device generating a current of 10 A on a 0.1
cm 2 electrode during 0.1 second. A Geiger counter placed at 1 em from the
ION TRANSPORT IN SOLUTIONS 157

electrode, registers the trace of the radioactive uni-:valent ion at 450 seconds
after the pulse. The diffusion coefficient of the released ions is of the order
of 10-9 m2 S-I. (a) Draw two diagrams showing the experiment at t = 0 and at
t = 450 s after the pulse. (b) Write an equation giving the quantity of ions
produced during a single pulse, i.e., A.. (c) Determine A. for the conditions of
the described experiment. (d) Calculate the limiting sensitivity of the
instrument, that is, the minimum concentration of ions detected by the
instrument. (Cf. Exercise 4.6 in the textbook) (Xu)

Data:

/= 10 A d= 1 cm (pulse = 0.1 s
Area = 0.1 cm2 D = 10-9 m2 S-I (= 450 s

Answer:

(a) The diagrams showing the experiment at 0 s and 450 s are given in Fig. 4.1 .

(b) The amount of the ion produced during a pulse is,

/ (pulse
A. = ---''--- (4.4)
FA

where F is the Faraday constant and A the electrode area.

(c) Inserting the corresponding values in Eq. (4.4),

t= 0 1= 450 sec
CI
$ CI $
e ~ e

1 em
~ ~
Ib ~
*
Ib

Electrode
<
E!ectrooe
0.1 em2 0.1 em2

Figure 4.1. Schematics of the experiment described in Exercise 4.3 at t =0 sand t =450 s.
158 CHAPTER 4

(10A)(0.ls) lCs -I -4 -2
A =---'-----'-"'-----'------- = 1.036xlO mol cm (4.5)
(96500C mol-I )( 0.1 cm 2 ) lA

(d) At the distance of the Geiger probe, i.e., d = 1.0 cm, the instrument detects
radioactive material after 450 s. The concentration of the ion after the pulse at a
distance x and after a time t is given by the equation (cf. Eq. 4.91 in the
textbook),

C=_A
.J trDt
exp(_L]
4Dt
(4.6)

Inserting the corresponding values in Eq. (4.6),

1.036molm -2 [ (0.0Im)2 J
c= ~tr( 10-9 m2s -I )(450S) exp - 4( 10-9 m 2 s -I )(450S) (4.7)

=6.5xlO-22 molm- 3

or

-22 I -3 6.022x10 23 ions 1m 3

. x 10
c= 65 mo m x x----
1mol 1000dm 3 (4.8)
-3
= 0.39 ion dm

This is the limiting sensitivity of the Geiger counter.

4.4 The diffusion coefficient of an ion in water is 1.5xl0's cm 2 S· I. It seems

reasonable to take the distance between two steps in diffusion as roughly
the diameter of a water molecule, i.e. 320 pm. With this assumption,
calculate the rate constant in S·I, for the diffusion of the ion. (Cf. Exercise
4.41 in the textbook) (Bockris-GamboaAldeco)

Answer:

The diffusion coefficient of the ion is related to the frequency of its jumps
by (cf. Eq. 4.106 in the textbook),
ION TRANSPORT IN SOLUTIONS 159

(4.9)

and from this equation,

2D
( -5 cm 2s -I)
1 1.5x1O
10 -1
k =- = =1.5xl0 s (4.10)
,2 (320x10-10)2
cm

Review of Section 4.3 of the Textbook.

Define potential, potential difference, and electric field. What does the
minus sign in the electric field equation indicate? Define ionic conduction. How
does an electric field act on ions in solution? What force would oppose the
applied electric field in an ionic solution? Explain how a steady flow of charge,
i.e., current, is maintained in an electrolyte. Define reduction and oxidation.
State Kirckhoff's law and Faraday's law. Write expressions for current density
as a function of the flux of ions, ], and the electric field, X. Defme specific
conductivity and resistance of a solution. State Ohm's law. What are the
conditions required so that an electrolytic conductor can be represented by
Ohm's law? What is the relationship between specific conductivity and the
conductance of an electrolytic solution? Define molar conductivity and
equivalent conductivity. What is the defmition and importance of equivalent
conductivity at infinite dilution, and how is this quantity determined
experimentally? State Kohlrausch's law. What is the convention adopted for the
sign of the current flow? Do positive and negative ions in the same solution
migrate independently?

4.5 A solution of 100 ml volume containing originallyl0-1 M of Fe+3 ions is

reduced at a constant current density of 100 mA cm-1 employing planar
electrodes of 10 cm 1 area. Calculate the time after which the concentration
of Fe+3 decreases by 10%. (Cf. Exercise 4.42 in the textbook) (Bock)

Data:

o -2
V= 100 cm3 c Fe +3 =10 M ( C +3) = 0.9 c ~ +3
Fe I re
j = 100 rnA cm-2 Aeleclrode = 10 cm2
160 CHAPTER 4

Answer:

The current j passed through the circuit is related to the charge Q passed
during the time t by

. Q (4.11)
J=-
tA

According to Faraday's law, the charge passed is also equivalent to

Q=nzF (4.12)

where n is the number of Fe+3 ions converted into Fe+2 , i.e.,n = (co - e)V=
(1-0.9) l V, and z is the number of electrons involved in the reduction reaction
of Fe+3, i.e., Fe+3 + Ie- ~ Fe+2 , and thus, z = 1. Combining Eqs. (4.11) and
(4.12) and substituting the corresponding values,

nzF (1- 0.9)e 0 VzF

t = - - = -'-----'---- (4.13)
jA jA

(0.1)( 10 -5 mol em -3 )( 100 em 3 YI) 6500C eq -\ 1A

=
3 -2)
(100XIO- Aem
x
10em 2
x---=9.6s
1Cs-\

4.6 In the calibration of an amperometer, a coulometer of H2 was connected

in series in the circuit. After passing a current, 95.0 ml of H2 were collected
in one hour at 19°C and 744 mm Hg. Calculate the current passed.
(Tejada)

Data:

VH]=95.0 ml T=292 K
PH] = 0.978 atm t= 3500 s

Answer:

The number of moles of hydrogen collected are:

ION TRANSPORT IN SOLUTIONS 161

(0.978atm)(0.095dm -3 )
PV ~
n=-= =3.92xl0 mol (4.14)
RT (0.081atmdm -3 mol -I K -1 )(292K)

From Eq. (4.13),

nzF (3.92X 10 -3 mol )(2)( 96500C mOl-I)

1=-= =O.209A (4.15)
t 3600s

4.7 A metallic wire transports a current of 1 A. How many electrons pass

through one point of the wire per second? (Tejada)

Answer:

The current is given by the number of electrons per second that pass
through the wire times the charge of the electrons, that is I = Ne eo. Solving for
Ne and substituting values, it is found that,

I IA ICs -I -18 -1
Ne =- = x - - = 6.24xlO electrons s (4.16)
eo 1.6022 x 10-19 C lA

4.8 Table 4.11 in the textbook lists data on equivalent conductivity

measured at various concentrations. Calculate the conductance of these
solutions if they were measured in a conductivity cell with 1 cm1 electrodes
separated 1 cm apart. Comment on the results obtained. (Contractor)

Answer:

The conductance is given by (cf. Eq. 4.134 in the textbook)

A
G=a- (4.17)
I

and the equivalent conductivity by (cf. Eq. 4.137 in the textbook)

162 CHAPTER 4

A=~ (4.18)
cz

Combining Eqs. (4.17) and (4.18) to obtain the conductance as a function of

the equivalent conductivity,

A = ( AScm eq
G = Acz- 2 -1)( czeqdm -3 )( Icm )x Idm 3
3
(4.19)
I 1000cm

The obtained conductances are tabulated below:

Concentration (eq liter· i ) G(S)
0.001 146.9 1.469xlO04
0.005 143.5 7.175x10 4
0.01 141.2 14.12 xl04
0.02 138.2 27.64 xl04
0.05 133.3 66.65 xl04
0.1 128.9 128.9 xlO4

Comment: The conductance of the solution increases as the concentration of the

electrolyte increases. This is intuitively to be expected. However, the equivalent
conductivity decreases with increasing concentration. Increasing ion-ion
interaction with increasing ion population is responsible for this effect.

4.9 A conductance cell having a constant k (=VA) of 2.485 cm-) is filled with
0.01 N potassium chloride solution at 25°C. The value of the equivalent
conductivity for this solution is 141.2 S cm 2 eq-I. If the specific conductivity,
0; of the water employed as solvent is 1.0xl0-6 Scm-I, what is the measured
resistance of the cell containing the solution? (Cf. Exercise 4.18 in the
textbook) (Constantinescu)

Data:

k = 2.485 cm- 1 A so1n = 141.2 S cm2 eq-l

c= 0.01 N (jWOle r = LOx I 0-6 S cm- 1

Answer:

The specific conductivity is given by (cf. Eq. 4.134 in the textbook),

ION TRANSPORT IN SOLUTIONS 163

1 I k
asoln =--=- (4.20)
RA R

or,
R=_k_ (4.21)
a so In

The value of Uso/n is also related to the equivalent conductivity by (cf. Eq.
4.137 in the textbook),

3
asoln = AsolnCZ = ( 141.2Scm 2eq -\)( O.Oleqdm -3)()
1 x ldm 3 (4.22)
1000cm
-3 -\
=1.412xl0 Scm

From Eq. (4.21),

-\
R = __2_._48_5_cm
_ _ _ = 1760.a (4.23)
1.412xlO-3 Scm-\

Comment: Since a wot., < < Uso/n, no correction is needed.

4.10 The specific conductivity of water at 298 K is 0.SS4xl0-7 n -I cm- I •

Calculate (a) the degree of dissociation and (b) the ionic product of water.
Consider the molar conductivity of u+ and On- to be 349.8 n -I cm 2 mor l
and 197.8 n ·1 cm 2 mol -I respectively. (Contractor).

Data:

a w = 0.554xIO- 7 n -I cm- I Am.H+ =349.8 n -I cm2 mor l

T=298 K Am.OH- = 197.8 n -I cm2 mor l

Answer:

(a) Let a be the degree of dissociation of the reaction

(4.24)
164 CHAPTER 4

The concentrations onr and OH- in water are given by

CH + = COH - =a Cw (4.25)

where Cw is the concentration of water, i.e., 55.56 M. Now, the specific

conductivity of water is given by

aw = a H + + a OH- (4.26)

and each individual-specific conductivity is related to the corresponding molar

conductivity by (cf. Eq. 4.136 in the textbook) a i = A. m ,i C i' Thus, Eq. (4.26)
becomes,

a w = A. m ,H + CH + + A. m ,oH - C OH - (4.27)

Substituting Eq. (4.25) into Eq. (4.27),

(4.28)

The degree of dissociation is, then,

a=------
A.m,H+ +A.m,OH- CW

7 3
- -0.554xlO-
----- Scm -I
- - - - - - - - - xlOOOcm
--- (4.29)
{349.8+ 197.8)Scm 2 moC I 55.56moldm -3 Idm 3
-9
=1.822xlO

(b) Taking into account Eq. (4.25), the dissociation constant of water is
calculated as

Kw =C H + COH - =a 2 Cw
2 = ( 1.822xlO-9 )2 {55.56M)2
(4.30)
= 1.023xlO -14 M 2
ION TRANSPORT IN SOLUTIONS 165

4.11 The relation between resistance and specific conductivity, i.e., R = l/uA
= k/u (cf. Eq. 4.134 in the textbook) gives a geometric definition of the cell
constant k. However, different factors such as lack ·o f ideal distribution of
current lines and change of surface and distance parameter with constant
use of the cell, might alter the value of the cell constant. Thus, the cell
constant must be frequently re-determined by standardization with
solutions of known specific conductivity. The most widely used solution is
diluted KCI, for which internationally approved Reference Tables are
available (ITS-90 Temperature Scale). With a given cell of plate surface 1.8
cm 2 and distance between plates of 0.8 cm, the following two conductance
measurements at 298.15 K were performed: Sample 1: 0.01 M KCI, G =
2.845 mS [0( ITS-90) = 1408.23 ~S cm'I]; Sample 2: 0.01 M KZS04, G =
5.414 mS. (a) Calculate the specific conductivity and the equivalent
conductivity of Sample 2. (b) Compare the ideal cell constant to the real
one. (Trassati)

Data:

Sample I: 0.01 M KCI, G = 2.845 mS [0( ITS-90) = 1408.23 ~S cm'l]

Sample 2: 0.01 M K2S04 , G= 5.414 mS
A = 1.8 cm2 /=0.8cm T=298.15K

Answer:

(a) From the standardization step given in Sample I the real cell constant can be
calculated:

-I
k = .!.... = u = 1.40823 mS cm 0.4950 cm -\ (4.31)
A G 2.845mS

The specific conductivity of Sample 2 is, then,

I ( 5.414mS )( 0.4950cm -\ ) =2.680mScm -I

u=G"A= (4.32)

and the equivalent conductivity of Sample 2 is,

'\
A = !!... = 2.680 mS cm x -1000cm 3 2 -I
- - - = 268.0 S cm eq (4.33)
-3 3
cz 0.01 eqdm Idm
166 CHAPTER 4

(b) The real cell constant as calculated in (a) is knol = 0.4950 cm- I, and the ideal
cell constant is

I 0.80cm -1
k ideal = - = = 0.44cm (4.34)
A 1.8cm 2

The percentage difference between k nol and kideal is,

[( 0.4950 - 0.44) /0.44 ]x 100 = 13% .

4.12 Use the data in Table 4.11 in the textbook to verify Kohlrausch's law.
(Contractor)

Answer:

Kohlrausch's law indicates that there is a linear relationship between A and

e ll2 up to a concentration of -0.01 N (cf. Section 4.3 .9 in the textbook). The
intercept on the y-axis of this curve gives .110 (or Ai, the equivalent conductivity
at infmite dilution. The corresponding values of A at different concentrations are
given in the next table. Figure 4.2 plots these results as well as the value of .110.

0.001 0.03162 146.9

0.005 0.07071 143.5
0.Ql 0.l000 141.2
0.02 0.l414 138.2
0.05 0.2236 133.3
0.1 0.3162 128.9

The equation of the graph in Fig. 4.2 considering it as a straight line is A =

149.5 - 0.79 ell], with A"" = 149.5 S cm2 eq-I. In this particular case, the law is
valid for concentrations up to 0.02 eq dm-3.

4.13 A conductance cell containing 0.01 M potassium chloride had a

resistance of 2573 0 at 25°C. The same cell when filled with a solution of
0.2 N acetic acid had a resistance of 5085 O. Calculate (a) the cell constant,
(k = IIA), (b) the resistivity of the potassium chloride and acetic acid
solutions, and (c) the ratio of conductivities, a = AlAo, of the acetic acid
ION TRANSPORT IN SOLUTIONS 167

145

A = 149.5 - 0.79 c '12

130
•
125~~~~~~~~~~~~~~--~

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

CI12(eq dm·3)112

Figure 4.2. Verification of Kohlrausch's law

solution. At 2S °c, the equivalent conductivities at infinite dilution of the

individual ions Wand CH3COO- are 349.82 and 40.9 0 -I cm 2 eq-I,
respectively. The specific conductivity of 0.01 N KCI solution is 0.0014114
0- 1 cm- I. (Cf. Exercise 4.16 in the textbook) (Constantinescu)
Data:

Solution I: KCI CJ = 0.01 N RJ = 25730

Solution 2: CH3COOH C] = 0.2 N R]= 5085 0
0(0.01 N KCl) = 0.0014114 0-' cm-' T= 25°C
o -I 2 -I o -I 2 -I
AH + = 349.820 cm eq A _ =40.90 cm eq
CH,COO

Answer:

(a) The specific conductivity is given by (cf. Eq. 4.134 in the textbook),

I k
a=-=- (4.35)
RA R

where k is the cell constant. Thus,

-3 -I -I )
k=Ra= ( 25730 )( 1.411xlO 0 cm =3.63cm -I (4.36)
168 CHAPTER 4

(b) The resistivity is given by (cf. Fig. 4.55 in the textbook),

I R
P=-=- (4.37)
a k
For KCI and CH3COOH,

25730
P KCf = _I = 7090em (4.38)
3.63cm

50850
PCH 3 COOH = _I 14010em (4.39)
3.63cm

(e) The equivalent conductivity of the acetic acid solution is given by (Fig. 4.55
in the textbook),

3 3
A=.!!....=_I_= I x 10 cm
cz pcz (1401.0cm)( 0.2eqdm -3 )(1) Idm 3 (4.40)
2 -I
=3.57Scm eq

The equivalent conductivity of the acetic acid solution at infmite dilution,

AO, is given by the law of independent migration of ions (cf. Eq. 4.144 in the
textbook):

o 0 0
ACH 3COOH =ACH3COO- + AH+
(4.41)
2 -I
= 349.82 + 40.9 = 390.7 Scm eq

Therefore, the ratio of conductivities for CH3COOH is,

2 -I
A 3.57 Scm eq
-= = 0.00914 (4.42)
2 -I
390.7 Scm eq
ION TRANSPORT IN SOLUTIONS 169

Review of Section 4.4 of the Textbook

What is the relationship between drift velocity and absolute mobility?

Define conventional mobility. Write relationships between conventional,
specific, molar and equivalent conductivity. What is the importance of these
relationships? Write the Einstein equation. How is the diffusion coefficient
related to the absolute mobility? Write Stokes' law. How is this law modified
when instead of a spherical particle a cylindrical particle is considered? What is
the main inconvenience of using Stokes' law in describing the movement of
ions? Write the Stokes-Einstein and the Nernst-Einstein relations. Establish their
importance in electrochemistry and the main factors that limit their validity.
How does the diffusion coefficient vary with the concentration for a 1: 1
electrolyte? What is a phenomenological equation? Write Walden's rule. When
is the product A17 not a constant? Write equations for the jump frequency in
terms of the energy of activation. What does the parameter f3 represent? Why is
it said that the jumping frequency is anisotropic in the presence of a field? What
is the relationship between the ionic current density and the electric field? How
do high-field and low-field Tafel approximations apply to the current density
equation? Write Ohm's law. Under what conditions does this equation apply?
Defme electrochemical potential. Write the Nernst-Planck flux equation and
establish its importance in electrochemistry.

4.14 Calculate the absolute and the electrochemical (or conventional)

mobilities of sodium ion when the drift velocity is S.2x10-s em 5"1 under an
electrical field of 0.10 Vern-I. (Cf. Exercise 4.29 in the textbook) (Kim)

Answer:

The absolute mobility is given by (cf. Eq. 4.149 in the textbook),

5.2xI0-5 cm s-1
=-=- =
vd Vd
Uabs =--------------------------
F ZjeO X III( 1.602 x 10 -19 C )( O.lOV cm -1 ) (4.43)

The electrochemical mobility is given by (cf. Eq. 4.152 in the textbook),

170 CHAPTER 4

-5 -I

u conv =UabsZjeo
Vd

X
5.2xlO cm s
=-=-= (
O.IOYcm
-I) (4.44)

=5.2x10· IO mV -1s - 1

4.15 Calculate the conventional mobility of sodium ion in an aqueous

solution knowing that tbe diffusion coefficient oftbe ion is 1.334xl0-5 cm 2 S-I
at 2S 0c. (Cf. Exercise 4.30 in tbe textbook) (Kim)

Answer:

From the Einstein equation, the absolute mobility is (cf. Eq. 4.172 in the
textbook),

D l.334xIO-5 cm 2 s- 1 1J 1m2
Uabs =-= x--x
kT (1.38lxIO- 23 JK- I )(298K) INm 10 4 cm 2 (4.45)

= 3.24xIO Il mN-ls- 1

and thus, the conventional mobility is (cf. Eq. 4.152 in the textbook),

-
u conv =UabsZjeo = ( 3.24x10 11 ms -1 N -I )I II(1.602xlO -19 C)
(4.46)
xIN
- -mx - -
1J= 5•19x10-8 m 2 V -I s -I
1J ICY

4.16 Calculate the radius of tbe solvated sodium ion in a~ueous solution
wben tbe absolute mobility oftbe ion is 3.24xl08 cm dyne-I s- . Tbe viscosity
of tbe solution is 0.001 poise. (Cf. Exercise 4.31 in tbe textbook) (Kim)

Answer:

From Stoke's law (cf Eq. 4.177 in the textbook),

_ _ _ _ _: - -_ _ _ _ _ _- : - X I poise (4.47)
r=--=--
6 1tll U abs 8
61t(O.OIPOise)( 3.24x10 cms -I dyn -1) 19cm -Is-I
ION TRANSPORT IN SOLUTIONS 171

-2
Igcms 1m -10
x-::.._--x--=1.64xl0 m
1dyne 100cm

4.17 Calculate the equivalent conductivity of a 0.10 M NaCI solution. The

diffusion coefficient of Na+ is 1.334xlO-5 cm 2 S-1 and that of the cr is
2.032xlO-5 cm 2 5"1. (Cf. Exercise 4.20 in the textbook) (Kim)

Answer:

From the Nernst-Einstein equation (cf. Eq. 4.187 in the textbook),

F2

r
A=_z-{D+ +D_}
RT
111(96500cmot-1
( ) ( 1.334x 10 -5 + 2.032 x 10 -5 )om 2 s -, (4.48)
8.314J K -I mot- I {298K}

IV IA 11 1m2 -2 2-1
x--x--x--x 1.265xl0 8m eq
IA ICs- 1 IVC 10 4 cm 2

4.18 Calculate the conductivity of NaI in acetone. The viscosity of acetone is

0.00316 poise. The radii of the Na+ and r ions are 260 and 300 pm,
respectively. (Cf. Exercise 4.21 in the textbook)(Kim)

Answer:

The conductivity of the solution is given by the addition of the individual

conductivities, i.e., (cf. Eq. 4.144 in the textbook),

(4.49)

These individual conductivities can be calculated by Walden's rule (cf. Eq.

4.196 in the textbook), i.e.,

zeOF
),:f/ = constant = - - (4.50)
6m-
172 CHAPTER 4

Consider that,

1poise 1V 1A lJ
-----x --- x ---x--
19cm -Is -1 IAn ICs -1 IVC
(4.51)
2 -2 4 2
lkg m s 1000g 10 cm 1poise
x ---'=----x - - x - - - -
lJ lkg 1m 2

Solving for ANa+ and substituting the corresponding values into Eq. (4.50),

111( 1.602xl0- 19 C )(96500cmol- 1 ) 1poise

ANa+ -~----~~----~x--~---
(4.52)
61r(260XI0- IO cm )(O.00316 Poise) 10-7 nC 2 cm-3
2 -I
=99.8 Scm eq

In the same way for iodide, Ar =86.5Scm 2 mol- l . The conductivity ofNaI in
. th 2 -1
acetone IS, en, ANa! = 99.8 + 86.5 = 186.3 S em eq .

4.19 Walden's empirical rule states that the product of the equivalent
conductivity and the viscosity of the solvent should be constant at a given
temperature. (a) Explain the data in the table below obtained for NaI
solutions in different solvents at 25°C. (b) Calculate the radius of the
moving entity in acetone applying Walden's rule. (Cf. Problem 4.10 in the
textbook) (Bock)

Solvent Ethanol Acetone Isobutanol

5.247xl0-8 5.686xlO-8 4.883xl0-8
24.3 20.70 15.80

Answer:

(a) Walden's rule is given by the equation (cf. Eq. 4.196 in the textbook),
ION TRANSPORT IN SOLUTIONS 173

zeOF
ATJ = cons tan t = - - (4.53)
61U

This equation shows that the product of the equivalent conductivity and the
viscosity is a constant. However, this is subjected to the condition that the
moving entity is the same independently of the solvent. Furthermore, the radius
in the above equation enters through the Stokes-Einstein relation, which
assumes that the moving entities are spherical ions (cf. Section 4.4.7 in the
textbook). However, if there is a great difference between the dielectric
constants of the solutions considered, then, several factors should be considered
that may lead to deviations from the rule. On the one hand, different solvents
produce different solvation of the ions, and thus, different radii of the moving
entities. In addition, the degree of ion association increases with lowering the
dielectric constant of the solvent, and thus, the concentration of free ions varies
from solvent to solvent. In the three cases depicted in the table above, isobutanol
has the lowest dielectric constant, and thus, it shows the largest deviation in the
A TJ product.

(b) From Walden's rule, i.e., Eq. (4.53),

zeOF III( 1.6x10-19 C )(96500cmol- 1 ) -8

r=--=-------------- 1.4xl0 cm (4.54)
6trATJ 6tr(5.686XIO-Sc2cm-lmOI-leq-l)

4.20 Calculate the concentration gradient of a univalent ion in 0.10 M

solution at 25°C when the electric field is lOS Vern-I. (Cf. Exercise 4.2 in the
textbook) (Kim)

Answer:

From the Nemst-Plank equation (cf. Eq. 4.226 in the textbook),

"] = DczF X Dde (4.55)

RT dx

When the flux is zero, "] = 0 , and

de ezF X (4.56)
dx RT
174 CHAPTER 4

Therefore, the concentration gradient is,

de (O.lomoldm -3 )III( 96500Cmol- 1 )( lOS V cm -I ) lJ

-= x--
dx (4.57)
( 8.314J mol-I K -I )(298K) I CV

=3.9x10 S M cm -1

Review of Section 4.5 of the Textbook

Define transport number. Mention the factors on which the conduction

current of an ion depends. Write the modified Nernst-Planck equation for
diffusion and diffusion flux.. What is an indifferent or supporting electrolyte?
What is the importance in electrochemical measurements of this type of
electrolytes? What is eleetroneutrality field? What are diffusion potential,
concentration cell, liquid-junction potential and membrane potential? How is
the flux of one ionic species affected by the flux of the other species in solution?
Describe three methods to measure transport numbers. What are the Onsager-
phenomenological equations? What do Lij and Lii represent in these equations?
Write an equation for diffusion potential as a function of transport numbers.
Write the Planck-Henderson equation for diffusion. Is the transport number
independent of concentration of the considered species?

4.21 A 0.2 N solution of sodium chloride was found to have a specific

conductivity of 1.75xl0-2 S cm- 2 eq-J at 18°C, and a cation-transport
number of 0.385. Calculate the equivalent conductivity of the sodium and
chloride ions at this temperature. (Cf. Exercise 4.17 in the textbook)
(Constantinescu)

Answer:

The transport numbers of the ions are related to the mobilities by (cf. Eq.
4.236 in the textbook),

u conv ,;
t· =---- (4.58)
I LU conv ,;
Since Uconv,i is directly proportional to the equivalent conductivity (cf. Eq.
4.163 in the textbook) then,
ION TRANSPORT IN SOLUTIONS 175

A; A;
=--=- (4.59)
t·
I LA; A

The equivalent conductivity of the solution is given by (cf. Eq. 4.163 in the
textbook)

-2 -\ 3
A=~=1.75xl0 Scm x 1000cm 875S
=.cmeq2 -\
(4.60)
-3
ZC 0.2eqdm Idm 3

Therefore, the equivalent conductivities of the individual ions are given by,

ANa+ =t Na + A= ( 0.385 )( 87.5Scm 2 eq -I) =33.69 Scm 2 eq -1 (4.61)

The equivalent conductivity of the chloride ion can be calculated by

Acr =A-ACI orby:

2 -\) 2 -I
Acr =tcr A= ( 1-0.385 )( 87.5Scm eq =53.81 Scm eq (4.62)

4.22 Estimate the concentration of indifferent electrolyte (e.g., K1S04)

which must be added to a 10-6 M HCI solution in order to study the
diffusion of protons knowing that the cation mobilities at 25°C for 0.1 M
-4 2 -\-\
solutions are: uconv,H+ =33.7IxlO cm V s , and uconv,K+

-4 2 -\-\
6.84 x 10 cm V s . (Cf. Exercise 4.11 in the textbook) (Bock)

Answer:

There are four different species in solution, K+, H+, cr and S04-2• Their
charges are IZK + I= IZH+ I= IzCI.1 = 1, and Izso./-21 = 2, and their concentrations,
CH- = CCI- = 10-6 M and CK~ = 2CSO-l_2 = 2CK2S0-l. The transport number of K+ is,
then, (cf. Eq. 4.234 in the textbook)
176 CHAPTER 4

i K + iK+
tK+ = =--
iK+ +iH+ + icr + i SO-2 Lii
•
(4.63)
Z K+ Fc K+ U conv, K+ X
=
Lii

Similarly,

i H+ iH+
t H+ = =--
iK+ + j H+ +i cr + i SO-2 Li;
4

(4.64)
ZH+FcH+ U conv, H+ X
=
Li;

where (cf. Eq. 4.159 in the textbook) J; =ziFciuconv,i X . The role of the
indifferent electrolyte is to carry the major part of the current. To assure that this
is the case, the ratio of the transport number of K+ to the transport number of W
should be large. Considering this number to be, say 200, then the ratio of tKJtH+
obtained from Eqs. (4.63) and (4.64), is,

tH+ Z H + C H + U conv ,H +

(4.65)

Solving for CK
2
so 4 ,

200( 10 -6 M )( 33x 10-4 cm 2V- l s -I )

CK 2 S0 4 = ( -4 2 _I -I) 4.9xlO- 4 M (4.66)
2 6.8xlO cm V s
ION TRANSPORT IN SOLUTIONS 177

4.23 A current of 5 mA flows through a 2 mm inner-diameter glass tube

filled with 1 N CUS04 solution in the anode compartment and
Cu(CH3SOO)2 solution in the cathode compartment. The interface created
between the two solutions moves 6.05 mm towards the anode in 10 minutes.
Calculate the transport number of the sulfate ion in this solution. (Cf.
Exercise 4.27 in the textbook) (Herbert)

Data:

I=SmA x = 6.0S mm Anode: I N CUS04

d=2mm t = 10 min Cathode: Cu(CH3SOO)2

Answer:

This is the Lodge's experiment to determine transport numbers. The charge

transported through the solution due to the migration of the sulfate ions equals
the charge of such ions existing within the volume V limited by the initial and
final position of the interface. Thus,

(4.67)

where V = filx = n(0.1 cm)2(0.60S cm) = 0.0190 cm3 • The transport number is
then, the ratio of q SO;2 to the total charge transported through the solution in
the time given (cf. Eq. 4.262 in the textbook):

qso;2 3 3
VFc (0.019OxIO- dm )(96S0oceq -I)
=-- = - =-'--------'--'-----"'--
It It (SmA) (4.68)
-3
x I eq dm x 1000rnA x I min = 0.611
10min les -\ 60s

Comment: The mobile interface method illustrates an approach to determine the

contribution of individual ionic species to conductivity.

4.24 Calculate the junction potentials for the following situations at 298 K:
(a) 0.10 M HCIIO.OI M HCI, t+ = 0.83, and (b) 0.10 M KCI / 0.01 M KCI, t+ =
0.49. (Cf. Exercise 4.44 in the textbook) (Kim)
178 CHAPTER 4

Answer:

The Planck-Henderson equation for liquid-junction potential considering a

z:z electrolyte is (cf. Eq.4.290) in the textbook),

(4.69)

(a) For this solution, t+ = 0.83, and thus, t = I - 0.83 = 0.17. Then,

-Lhl'
( 8.314JmOI- 1 K- 1 )(298K)
=..:.------..:........--
96500C mol- l
( ) (om)
0.83-0.17 In -
0.10
x1C
-V
lJ
- (4.70)

= -O.039V

(b) For this solution, L = 0.49, and thus, t. = I - 0.49 = 0.51. Then,

(8.314JmOI- 1K- 1 )(298K) (0.01) ICV

-.1",= (0.49-0.51)ln - x - - (4.71)
96500Cmol- 1 0.10 lJ
=+O.0012V

Review of Section 4.6 of the Textbook

What is the relaxation approach? Why is it said that the ionic cloud is egg
shaped? What are relaxation field and electrophoretic force? Draw a diagram of
the forces acting on a moving ion. Write expressions for the electrophoretic
velocity, relaxation time, relaxation force, relaxation velocity, and drift velocity
on an ion. Write the Debye-Huckel-Onsager equation for a symmetric
electrolyte. What is the importance of this equation? How would you improve
this theory? What are the contributions of Justice, Fouss and Blum, and Lee and
Wheaton to conductance theory?

4.25 Estimate the electrophoretic velocity of a sodium ion in 0.01 M NaCI

solution under an electrical field of 0.1 V em-I. The viscosity of the solution
is 0.00895 poise. (Cf. Exercise 4.3 in the textbook) (Kim)

Answer:

The electrophoretic velocity is given by (cf. Eq. 4.300 in the textbook),

ION TRANSPORT IN SOLUTIONS 179

zeo X
(4.72)
vE = -I
61tK II

The Oebye-Htlckel reciprocal length for a I: I electrolyte of concentration

om Mis (cf. Table 3.2) Ttl = 3.04 mm. Substituting values into Eq. (4.72),

III( 1.602 x 10-19 C )( 0.1 V cm -I)

vE = (4.73)
61f( 3.04x 10 -7 cm )( 0.00895 poise )
7 2 -2
I poise 1] 10 gcm s . 312 10-6 -1
x x--x = • x ems
Igcm -Is -I I VC IJ

4.26 Estimate the time for an ionic cloud to relax around a sodium ion in 0.1
M NaCI solution when the drift velocity is S.2xl0-s em sol under an electrical
field of 0.10 V em-I. (Cf. Exercise 4.39 in the textbook) (Kim)

Answer:

The relaxation time is obtained from (cf. Eq. 4.303 in the textbook):

(4.74)

The absolute mobility is given by (cf. Eq. 4.149 in the textbook)

Vd
Uabs =-=- (4.75)
F

The electrical force needed in Eq. (4.75) is obtained from

F=ZjeO X=III( 1.602x 10-19 C )( O.IOV cm - I)

7 (4.76)
11 10 erg Idynecm -13
x--x x 1.6xl0 dynes
ICV 11 I erg
180 CHAPTER 4

Substituting Eq. (4.76) into Eq. (4.75),

5.2xlO- 5 cms- 1 8 -I -I
Uabs = = 3.25x 10 cm s dynes (4.77)
-13
1.6 x lO dynes

The Debye-HUckel reciprocal length for a 1: I electrolyte of this

concentration is 0.96xlO-9 m (cf. Table 3.2 in the textbook). Thus, the relaxation
time becomes,

TR
( O.96x lO -7 cm
=~~------------~--~~--~----------~-----
r
2( 3.25x 10 8 cm s -I dyne -1 )( 1.381 x 10 -16 erg K -I )(298K) (4.78)

x I erg -_ 34
• x10-
10
s
I dyne cm

4.27 A rigorous treatment of the mobility of the ions considers three forces
operating on the ion: (i) an electric force arising from the external field, (ii)
a relaxation force from distortion of the cloud around a moving ion, and
(iii) an electrophoretic force arising from the fact that the ion shares the
electrophoretic motion of its ionic cloud. Considering these three forces,
calculate the conventional mobility of a sodium ion in 0.01 M NaCI solution
at 298 ·K. Take the viscosity of the solution as 0.00895 poise, the dielectric
constant of the solution as 78.3, and the radius of the sodium ion as 260 pm.
(Cf. Exercise 4.22 in the textbook) (Kim)

Answer:

The conventional mobility considering the three forces operating on the ion
is given by (cf. Eq. 4.316 in the textbook),

(4.79)

where UO is the result of the externally applied field only and excludes the
influence of interactions between the ion and the ionic cloud. The terms UE and
UR refer to the electrophoretic component of the mobility and to the relaxation
field mobility, respectively. The term UO can be considered as the mobility at
ION TRANSPORT IN SOLUTIONS 181

infmite dilution, given by the expression for the Stokes mobility, that is, (cf. Eq.
4.183 in the textbook)

o zeo Ill( 1.602xlO- 19 C) Ipoie lJ

U =--= x x--
610"1] 67r( 260xlO- 12 m )(0.00895Poise) 19cm -Is -I ICY (4.80)
2 -I
1000gm s
x--"---x--= .
100cm 365 x 10-4 cm 2 y -I-1
s
lJ 1m

The electrophoretic component of the mobility is (cf. Eq. 4.316 in the

textbook),

(4.81)

or

Il l(1.602XIO- 19 C) 1poise
uE = x
61t(0.00895Poise)( 3.04xI0-9 m) Igcm -Is-I (4.8Ia)
2 -I
x--x
lJ 1000gm s IOOcm
x--= .
3 12 x 10-5 cm 2y -I-1
s
ICY lJ 1m

where the Debye-Hilckel reciprocal length for a 1:1 salt at a concentration 0.01
M is considered as 3.04xI0-9 m (cf. Table 3.2 in the textbook). The relaxation
component of the mobility given in the mksa system is (cf. Eq. 4.316 in the
textbook),

o 2
1 U eow

r
uR =
47r8o 6EkTK-1 1.112x10-IOC2J-lm-1

(3.65XlO-4 cm 2 y-1s -1)( 1.602x10-19 C

0.5859
x x-------- (4.82)
6(78.3)( l.38lx10-23 JK-1 )(298K) 3.04xI0-9 m

=7.165xI0--6 cm 2 y- l s-1
182 CHAPTER 4

o 2
I u eOw

r
UR =
41l"&o 6FlcTK-1 1.112x10-IO C 2 J-1m-1

(3.65XI0-4 cm 2 y-1s -1)( 1.602x1O-19 C

0.5859
x x----- (4.82)
6(78.3)( 1.38 lx 10-23 JK-1 }298K) 3.04xI0-9 m

=7.165xI0-6 cm 2 y- 1s-1

where w = 0.5859 for a I: I electrolyte is a correction factor introduced by

Onsager (cf. Table 4.18 in the textbook). Then, substituting Eqs. (4.80)-(4.82)
into Eq. (4.79) gives the conventional mobility,

u conv = 3.65xlO -4 - ( 3.12xlO -5 + 7.165xlO -6 )

(4.83)
-4 2 -1-1
= 3.26xl0 cm V s

Review of Section 4.7 of the textbook. Defme relaxation time. What is the
physical meaning of this variable? Draw a schematic showing how to measure
the electric conductance of ionic solutions by alternating currents of different
frequencies. What is relaxation time of the asymmetry of the ionic cloud? What
is the Debye effect? Describe the three parts in which the dielectric constant of
water can be divided into according to Kirkwood. How does the dielectric
constant vary with frequency? Explain. Describe the effects of ions on the
relaxation times of the solvents. What is understood by optical permitivity and
"dielectrically saturated"?

4.28 An investigator wants to study the Debye-effect of a diluted NaCI

solution at room temperature, but he has no clue about what frequency
range he should look at. Please help him. The diffusion coefficient of 0.001
M NaCI solution is 1.5xl0·9 m1 S·I. (Cf. Exercise 4.43 in the textbook) (Xu)

Answer:

The Debye-HUckel reciprocal length for a 1: 1 electrolyte of concentration

0.001 Mat 298 K is, 1(1 = 9.6xlO·9 m (cf. Table 3.2 in the textbook). According
to the Einstein-Smoluchowski equation, the relaxation time of the ionic cloud is
given by (cf. Eq. 4.27 in the textbook),
ION TRANSPORT IN SOLUTIONS 183

(4.84)

Therefore, the corresponding frequency / at which the ion cloud relax is given
by,

1 1 6
/=-= ( -8 ) =5.2xlO Hz (4.85)
21IT 2 3.1xlO s

In order to observe the Debye effect, the applied frequency must be much
higher than the above relaxation frequency, so that the relaxation of the ionic
cloud cannot catch up with the applied field. Therefore, the investigator needs to
look at the range above 107 Hz.

Review of Section 4.8 of the Textbook

Mention advantages of water as a solvent. Mention examples of industrial

reactions where it is not possible to use water. Mention advantages and
disadvantages of nonaqueous electrolytic solutions. Explain the parabolic-type
curve observed in conductivity vs. concentration graphs for electrolytes in
nonaqueous solvents. Explain the presence of temperature-dependent minima
and maxima for salts in nonaqueous solvents. Mention relaxation processes
related to changes of dielectric constant with frequency for nonaqueous solvents.
What are the disadvantages of using Raman and NMR spectroscopies in the
study of nonaqueous solvents? Mention advantages of liquid ammonia as
solvent. Explain by the use of the Debye-Huckel-Onsager equation why the
specific conductivities of nonaqueous electrolyte solutions are smaller than the
specific conductivities of aqueous solutions at the same electrolyte
concentrations. Explain via Bjerrum's theory the increase of ion association in
nonaqueous solvents. What new dependence equivalent to Kohlrausch equation
for aqueous electrolytes is applicable for nonaqueous electrolytes? What are
non-Coulombic forces and what is their importance in ion-pair formation? What
is a triplet? Under what conditions do these entities appear?

4.29 In acetonitrile, the equivalent conductivity of a very diluted solution of

KI is 198.2 S cm 2 eq'! at 25°C. Calculate the equivalent conductivity of KI
in a similar concentration range in acetophenone. The viscosity of
184 CHAPTER 4

acetonitrile is 0.00345 poise, and that of acetophenone is 0.0028 poise. (Cf.

Exercise 4.23 in the textbook) (Bockris-GamboaAldeco)

Data:
o 2 -I
7lacetophenone = 0.0028 poise A K1 ,acetonitrile = 198.2 Scm eq
7Jacetonitrile = 0.00345 poise

Answer:

At infinite dilution (cf. Eq. 4.340 in the textbook),

o
u 7J = constant (4.86)

The equivalent conductivity is related to the conventional mobility by (cf.

Eq. 4.163 in the textbook) A = Fu conv . Therefore, Eq. (4.86) becomes,

o
A 7J = constant (4.87)

From the data of acetonitrile,

Ao ( 2 -1)( 0.00345 pOIse. )

acetonitrile 7J acetonitrie = 198.2 Scm eq
(4.88)
2 -I
=0.684Spoisecm eq

For acetophenone,

2 -I
o _ 0.684Spoisecm eq -2 4 S 2 -I
(4.89)
Aacetophenone - - 4 cm eq
0.0028 poise

Comment: Walden's rule, i.e., Eq. (4.87), has to be carefully used. In the form
presented in this problem, it is valid only under the assumption that the radii of
the moving ions are the same in both solvents. This is the same as saying that
the structures of their solvation sheets are similar in both solvents. A more
generalized way for this rule is uOr7J = constant.
ION TRANSPORT IN SOLUTIONS 185

Review of Sections 4.9 to 4.11 ofthe Textbook

How does a polymer become a conducting polymer? What are the

characteristics of conducting polymers? What is a dopant? Explain the ·
conductivity in polymeric structures thorough polaron formation. What are
redox polymers, loaded ionomers, and electronically-conducting polymers?
Name applications of electronically conducting polymers in electrochemical
science. Why is the proton considered a different sort of ion? What is meant by
the conductance and mobility anomalies of the proton? Describe the Grotthuss
mechanism for proton movement. Draw a Morse curve for the water-proton
system. Write an equation for the frequency at which the proton crosses the
potential barrier, i.e., k. Is Eyring's theory on proton mobility in water
successful in predicting the experimental values of mobility? What is quantum-
mechanical tunneling? Is it reasonable to assume that proton can tunnel as the
electron does? How did Conway-Bockris-Linton theory explain proton mobility?
How does this theory explain the large mobility of protons in ice?

4.30 When it comes to practical applications, the actual conductance (the

inverse of the resistance, R) instead of the specific conductivity is the
important variable. This is the reason why polymer electrolytes have drawn
so much attention as a potential player for alkali-metal batteries although
their specific conductivities are usually low (_10-5 Scm-I) compared with
the non-aqueous electrolytes (_10-2 Scm-I). Calculate the conductance of 1.0
M LiS03CF3 in poly(ethylene oxide) and propylene carbonate, respectively.
The former is fabricated into a film of thickness 10 f.1m, and the latter is
soaked with porous separators of thickness 1 mm. (Cf. Exercise 4.15 in the
textbook) (Xu)

Data:

CLiS03CF3 = 1.0 M O'poly(ethylene oxide) 10-5 S cm-1

= lpoly(ethylene oxide) = 10 f.1m
O'propylene carbonate = 10
-2 S cm-1 [propylene carbonate = 1 mm

Answer:

Considering an electrode of unit area, the conductance of the polymer

electrolyte is [(cf. Eq. 4.l34 in the textbook),

2
A -5 -I lcm
Gpoly(ethyleneoxide) =0'-=10 Scm ---=0.01 S (4.90)
[ O.OOlcm
186 CHAPTER 4

while the non-aqueous electrolyte has a conductance of

2
A -2 -1 Icm
G propylene carbonate = u- = 10 Scm = 0.1 S (4.91)
I O.OOlcm

Comment: The good processability of polymer materials has partially made up

for their inferior specific conductivity (1000 times smaller), reducing the gap in
conductance to only 10 times. Other advantages of polymer electrolytes such as
anti-leaking, safety, etc, make these materials serious candidates for industrial
applications.

PROBLEMS

4.31 Does the valence of the ion affect the statement that the ionic-diffusion
coefficient can be considered as a constant? To find out, take electrolytes of
the z:z type, for example 1:1 and 2:2, and compare the variation of their
diffusion coefficients over the concentration range 0.01 - 0.1 mol dm· 3• (Cf.
Problem 4.2in the textbook) (Xu)

Answer:

The diffusion coefficient is given by (cf. Eq. 4.19 in the textbook):

D = BRT ( 1+ din f ±
d Incj
1 (4.92)

where the activity coefficient is given by the Debye-Hilckellimiting law, i.e. (cf.
Eq. 3.90 in the textbook),

(4.93)

I I I I
For z:z type electrolytes, z + = z _ =z and c+ = c. = c. Thus, the ionic
strength of this type of electrolytes is (cf. Eq. 3.83 in the textbook),

(4.94)
ION TRANSPORT IN SOLUTION 187

Substituting Eq. (4.94) into Eq. (4.93),

logf+ = _Az 3 Fc (4.95)

and Eq. (4.92) transforms into

D =BRT(1-AZ 3 dFc ) (4.96)

dine

Combining the derivatives d Fc / de = 1/2 Fc ,and dine/de = 1/ e gives,

d Fc / dine = e /2 Fc = Fc / 2 . Substituting this equation into Eq. (4.96),

(4.97)

For an aqueous solution at 25°C, the parameter A = 0.51 M') (cf. Table 3.4
in the textbook). Thus, for a I: 1 electrolyte, the ratio of diffusion coefficients of
the 0.01 M solution to the 0.1 M solution is,

1-( 0.255M- 1 )(1)3 .JO.IM

D(O.IM)
= =0.94 (4.98)
D(O.OIM) 1-( 0.255M- 1 )(1)3 .JO.OIM

and for a 2:2 electrolyte,

1-( 0.255M- 1 )<2)3 .JO.IM

D(O.IM)
= =0.45 (4.99)
D(O.OIM) 1-( 0.255M- 1 )(2)3 .JO.OIM

In the case of a I: 1 electrolyte there is only a ca. 5% change in its diffusion

coefficient over the range of concentrations from 0.01 to 0.1 M. Hence, the
diffusion coefficient of this type of electrolyte can be viewed as a constant. On
the other hand, for a 2:2 electrolyte, there is a change of ca. 55%, and its
diffusion coefficient cannot be considered constant in this range of
concentrations.
188 CHAPTER 4

4.30 (a) Derive and plot the relations for the variation of the ion
concentration at the electrode surface (x = 0) under the conditions of (a)
constant flux, and (b) instantaneous pulse. For the constant flux problem,
consider fluxes of 1 and 10-1 mol cm- s-., with an initial concentration of 1
mol cm-3, and a diffusion coefficient of 1.5xl0-5 cm1 S-l . For the
instantaneously pulse problem, consider a total concentration of 10-1 mol
cm-1, and make the calculation at the electrode surface and at a distance
0.03 cm from the pulse source. (c) In the constant flux-induced diffusion,
the time when the ion concentration at the electrode surface reduces to zero
is called transition time, designated as T. Derive an expression for T and
comment on its physical significance. Assume that in the constant flux
experiment the concentration change is only caused by diffusion, i.e., the
contribution of ion migration to concentration change is suppressed and
therefore negligible. (Cf. Problem 4.15 in the textbook) (Xu)

Answer:

(a) In the case of constant flux-induced diffusion (cf. Eq. 4.72 in the textbook),

c=c o-~[2 rzexp[-L)-~erfc(

JD V-;; 4Dt JD !x21l
V4lli (4.100)

At the electrode surface, x = 0, and thus, x 214Dt = o. Therefore,

exp ( x2 /4 Dt ) =1and (x / JD )erfc ~ x2 /4 Dt =o. Under these conditions,

Eq. (4.100) reduces to,

c=c
°Hi
-2..1. -
1iD
(4.101)

If the initial concentration value is CO = 1 mol cm-3, and A. = 10- 1 mol cm-2 S- I,
then,

-3 - 2 (-I
10 mol cm -2s -I)
t

(1.5xl0 -5 cm 2s -I)
c = 1 mol cm (4.102)
1i

The values of c at A. = 10- 1 and 1 mol cm-2 S- I as a function of time are given
in the next table, and Fig. 4.3 shows this variation:
ION TRANSPORT IN SOLUTION 189

t (f.ls) Constant flux Constant flux

A. 10- 1 mol em- 2 S-1
= A. = I mol em-2 S-1
c (mol em- 3) at x = 0 c (mol em- 3) at x = 0
o 1.000 1.000
I 0.971 0.709
2 0.959 0.588
3 0.949 0.495
4 0.942 0.417
5 0.935 0.349
6 0.929 0.286

(b) In the case of instantaneous-pulse induced diffusion at a distance x from the

pulse origin (cf_ Eq. 4.91 in the textbook),

c=
A
.J trDt exp
(x2]
- 4Dt
(4.103)

At the electrode surface, x = 0, and thus, exp(x 2/4Dt) = l. Equation (4.103)

reduces to,

A
c=-- (4.104)
trDt.J

1\."" = 149.5 S cm 2 eq-l

145

135
I\. =149.5 - 0.79 el12

130
•
125
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
c 112(eq dm-3)112

Figure 4_3_ Concentration at the electrode surface as a function of time

during constant flux.
190 CHAPTER 4

In this case A represents the total concentration, and thus has the units of mol
cm-2, in contrast with the constant-flux problem where it represented aflux
given in mol cm-2 S-I . Now, if A = 10- 1 mol cm- 2, Eqs. (4.103) at x = 0.03 cm and
Eq. (4.104) atx = 0 become respectively,

and
10 -I molcm-2
c=-r===============
I ( -5 2-I)
(4.106)
V1r l.5xl0 cm s t

The values of c at A = 10- 1 mol cm- 2 as a function of time are given in the
next table, and Fig. 4.4 shows this variation:

t (s) Pulse Pulse

A = 10- 1 mol em· 2 A = I mol em-2
c (mol em-3) atx = 0 em c (mol em- 3)at x = 0.03 em
5 6.51 0.32
10 4.60 1.03
20 3.25 1.53
30 2.65 1.61
40 2.30 1.58
50 2.06 1.53
60 1.88 1.46
70 1.74 1.41
80 1.62 1.35
90 1.53 1.30
100 1.45 1.25

(c) The expression for constant-flux induced diffusion is given in Eq. (4.101)
above. The transition time, t = 1; occurs when this concentration becomes zero,
i.e.,

c=c o~
-2A - = 0
1rD
(4.107)
ION TRANSPORT IN SOLUTION 191

0.8

0.6
cat x = 0
(mol cm· 3)
0.4

0.2

0.00
2 4 6 8
time (~)

Figure 4.4. Concentration at the electrode surface as a function of time

during an instantaneous pulse.

The transition time is, then,

(4.108)

Comment: From these two expressions it can be seen that as t > 1;

concentration assumes negative values, c < 0, which is only the mathematical
solution of the equation but has no physical significance. Therefore, constant
flux problems are time-restricted processes. They do not exist beyond To

4.31 In the same experiment with radioactive material described in Exercise

4.3, it was found that at a certain time the Geiger counter registered a
maximum ion flux, i.e., the intensity of the radiation had a maximum with
respect to time. It was also found that by placing the Geiger counter farther
away from the electrode, the time at which the maximum occurred became
longer and the peak intensity rapidly decreased. (a) Draw diagrams of
current vs. time plots at x = 1 cm, x > 1 cm, and x » 1 cm, where x is the
distance of the Geiger counter from the electrode. (b) Justify the
observation presented here. (c) Evaluate its usefulness in experimentally
measuring diffusion coefficients of ions. (Cf. Problem 4.1 in the textbook)
(Xu)
192 CHAPTER 4

Answer:

(a) In the experiment described in Exercise 4.3, a current pulse of 10 A is

generated for lOs on a 0.1 cm2 electrode surface. Schematics of the variation of
current vs. time at a given distance are shown in Fig. 4.5.

(b) The radiation intensity is proportional to the ion flux, that is, to the ion
concentration. The ion concentration varies with time and the distance from the
source. Thus, a maximum of the flux, i.e., the intensity, can be determined by
differentiating the concentration equation with respect to time and equating it to
zero. The equation describing the concentration as a function of time and
distance due to a pulse of flux is (cf. Eq. 4.91 in the textbook),

(4.109)

and its derivative,

a a
a; = .j ;rDt at exp (- 4 Dt2) + exp (- 4 Dt2) at [.j trDt )
OC A x x A

(4.110)
1 At -3/2] ( x2 )
"2 .j ;rD exp - 4Dt

Equating this derivative to zero,

x=1cm x>1cm x»1cm

Figure 4.5. Variation of current with time at different distances from the
electrode according to the experimental parameters described in Problem
4.31.
ION TRANSPORT IN SOLUTION 193

1 At- 3/2 ] exp ( - -X2)

- =0 (4.111)
2 J;D 4Dt

or

x2 I
---1=0 (4.112)
2Dt

Solving for t,

2
x
(4.113)
t max = 2D

which is the "rush" hour for the ion flux at x. As x increases (Geiger moved
away form the electrode) the time corresponding to this ionic "peak traffic" is
delayed. An interesting fact is that this rush hour is actually determined exactly
by the Einstein-Smoluchowski equation. This should not be a surprise as it has
been proved that Einstein-Smoluchowski equation describes the diffusion
behavior of the majority of the ions, and this majority quantity of ions constitute
the "peak traffic". Now, inserting Eq. (4.113) into Eq. (4.109), gives the
maximum ion concentration, i.e.,

Cmax = _A._l.exp
.J1T12 x
(_!) 2
= 0.484 A.
x
(4.114)

As the Geiger moves away from the electrode, the intensity of radiation,
which is proportional to the ion flux, decreases rapidly according to Eq. (4.114).

(c) The above experiment could be used to measure the diffusion coefficients of
ions, but the ions do not have to be radioactive as long as there are other ways to
determine the change of ion concentration (visible-UV, refractive indices, etc.)

4.32 The unit flux, i.e., 1 mol cm-2 s-., has been used in an attempt to
simplify the solution of the partial-derivative equation of Fick's second law.
(a) Calculate, for an univalent ion, the current density and the electrical
field this flux will cause. Make any reasonable assumption for your
calculations. Is this current density achievable in a real experiment? (b) 1
194 CHAPTER 4

mA cm-2 is the current density normally used in electrochemistry

laboratories. What is the flux in this case? (Cf. Exercise 4.1 in the textbook)
(Xu)

Answer:

(a) The unit flux means that 1 mol of ions passes through an area of I cm2 in I s.
Because each mole of uni-valent ions carries 1 Faraday or 96500 C of charge,
then the charge flux is:

Usually the conductivity of the electrochemical systems under study is

below 10- 1 Scm-I . If the linear relation between field and flux holds (most
unlikely!), then the field X will be given as,

-: 4-2
x=.!...= 9.65xIO Acm IV
=9.65xlO
4
Acm
-I
.ox--
(j 10 -I .0 -I cm -I IAn (4.116)
= 9.65x10 4 V cm -1

Almost no electrolyte system can withstand this high field. Therefore, unit
flux is only a thOUght convenience and not feasible in experiments.

(b) When j = O.OOIA cm -2 , then (cf. Eq. 4.127 in the textbook),

-: -2 ICs- 1 8 2
7=~= O.OOIAcm x =1.036xlO- molcm- s-1 (4.117)
zF II196500Cmol- 1 IA

4.33 A saturated solution of silver chloride has a resistance of 67.953 kO

when placed in a conductance cell of constant 0.180 cm- I at 25°C. The
resistance of the water used as solvent is 212.180 kO measured in the same
cell. Calculate the solubility, S, of the salt at 25°C. Consider the salt
completely dissociated in its saturated solution in water. The equivalent
conductivity at infinite dilution of Ag+ and cr are 61.92 and 76.34 S cm 2
eq-I, respectively. (Cf. Exercise 4.37 in the textbook) (Constantinescu)
ION TRANSPORT IN SOLUTION 195

Answer:

The solubility can be detennined from conductance measurements. The

equivalent conductivity is given by (cf. Table 4.55 in the textbook),

A=!!.... (4.118)
cz

If S is the solubility of the salt AgCl, then, SAgCl = CAgCl, and

0' AgCl
SAgCl =-....::....-- (4.119)
A AgClz

where O'AgCl is the specific conductivity of the salt. This parameter, O'AgCl, can be
detennined from the specific conductivity of the Agel solution, which consists
of two contributions,

0' so In =0' AgCl + 0' water (4.120)

The specific conductivity of the saturated solution is given by (cf. Fig. 4.55
in the textbook)

1 I k 0.180cm -I -6 -I
0' solo = - - = - = = 2.65x10 Scm (4.121)
RA R 67953f]

and that of water,

-I
0.180cm -6-1
0' water = =0.848xlO Scm (4.122)
212180f]

Therefore, the specific conductivity due to the salt is, from Eq. (4.120),

-6 -6 -6-1
0' AgCl = 0' solo -0' water = 2.65x10 -0.848xI0 = 1.80xlO Scm
(4.123)

On the other hand, the equivalent conductivity of the salt is given by

o 0 0 2 -I
A AgCl :::J A AgCl = A. + + A. _ = 61.92 + 76.3 = 138.26 Scm eq (4.124)
Ag Cl
196 CHAPTER 4

Therefore, from Eq. (4.119)

-6 -I 3
1.80xl0 Scm 1000 cm -5-3
SAgCl =-1-1---- 2---1 x - - - = 1.302xl0 eqdm (4.125)
1 138.26 Scm eq Idm 3

Comment: The method described here gives the ionic concentration in the
saturated solution, and it is only when dissociation is virtually complete that the
result is identical with the solubility. The solution has to be sufficiently diluted
(i.e., the solubility has to be small) for the equivalent conductivity to be similar
to the value at infinite dilution.

4.34 Calculate the relaxation times of the ionic atmospheres of 0.1 N

solutions of a 1: 1 electrolyte in nitrobenzene, ethyl alcohol, and ethylene
dichloride. Consider the Oebye and Falkenhagen equation, which indicates
that the relaxation time, TR, is related to the frictional coefficients K+ and K
of the two ions constituting a binary electrolyte:

(4.126)

where

K j =eozF / A, (4.127)

k is the Boltzmann constant, and Ifl is the thickness of the ionic atmosphere.
(Constantinescu)

Answer:

Equation (4.126) can be written as:

(4.128)

Substituting K+ and K from Eq. (4.127), into Eq. (4.128)

ION TRANSPORT IN SOLUTION 197

(4.129)
( _1)2
=3.09xI0- 14 _Z_K _ _
AkT

where iC' is in cm, A in S cm2 eq-I, k in J K -I and Tin K. For most solutions
other than acids and bases, A is about 120 S cm2 eq-I at 25°C (cf. Table 4.10 in
the textbook). The thickness of the ionic atmosphere, iC', is given by Eq. (3.43)
in the textbook. For a 0.1 N I: 1 electrolyte at 25°C, iC' in meters is given by (cf.
Exercise 3.6)

K
-I
= 1.086 x 10
-10 r-
'1/& (4.130)

For nitrobenzene with an &nilrobenzene = 34.8, iC' = 6.40xlO-8 cm (cf Exercise 3.6),

-8 (1)( 6.40xI0- 8 cm )2
T R nitrobenzene = 30.8x 10 --------'------'------
120S cm 2 eq -I ( l.38lx 10 -16 erg K -I )(298K)

-10
= 2.SSx10 s (4.131)

In the same way for the other solvents,

Nitrobenzene 34.8 6.40 xlO-g 2.55 xlO-\O

Ethyl alcohol 24.3 5.352xlO-8 1.786x10- 1O
Ethylene dichloride 10.4 3.50IxI0-8 0.764xI0- 1O

Comment: The existence of a fmite time of relaxation means that the ionic
atmosphere surrounding a moving ion is not a symmetrical one. The charge
density behind the ion is greater than that in front. The asymmetry of the ionic
cloud due to the time of relaxation results in a retardation of the ion moving
under the influence of an applied electric field. The influence on the speed of an
ion is called relaxation effect. The P. Oebye and H. Falkenhagen equation can be
\98 CHAPTER 4

found in Physik. Z. 29 (1928)121,401; H Flakenhagen and J. W. Williams, Z.

Physik. Chern. 137 (1928)399; and J. Phys. Chern., 33 (1929)1121.

4.35 The values of molar conductivity at infinite dilution for HCI, NaCI and
sodium acetate (NaAc) are 420, 126, and 91 S cm 2 mor l , respectively. The
resistance of a conductivity cell filled with 0.1 M acetic acid (HAc) is 520 0
(Solution 1), and drops to 1220 when enough NaCI is added to make the
solution 0.1 M NaCI (Solution 2). Calculate (a) the cell constant and (b) the
concentration of hydrogen ion (pH) in Solution 1. (Contractor)

Answer:

(a) The cell constant is given by the ratio k = 1/ A. From the specific
conductivity equation (cf. Eq. 4.134 in the textbook),

1 I
a=--=Gk (4.132)
RA

Therefore, for NaCl,

a NaCI = G NaClk (4.133)

where GNaCl is the conductance ofNaCI. Now, the total conductance, G, in a cell
is given by the addition of the conductances of its components. In the case of the
0.1 M NaCI + 0.1 M HAc solution, the total conductance is G = lIR2 , and
also, G = G NaCI + G HAc' Therefore,

I I -\
G NaCI =-----=0.006270 (4.134)
1220 5200

The specific conductivity ofNaCI can be approximated as,

00
crNaCI = Am,NaClcNaCI (4.135)

2
= ( 126Scm mol
-\ )(
O.lmoldm -3 ) xx Idm 3 3 =0.0126Scm -\
1000cm

Substituting the corresponding values of GNoCI and aNaCl from Eqs. (4.134)
and (4.135) into Eq. (4.133) and solving for k,
ION TRANSPORT IN SOLUTION 199

-I
k= (F NaCl = 0.0126Scm = 2.01cm
-1
(4.136)
G Nael 0.00627 S

(b) From the equilibrium reaction for acetic acid,

---+ + -
HAc H +Ac (4.137)
+-

the concentrations ofW and Ac· are given by

c H + = c Ac - = a c HAc (4.138)

where a is the degree of dissociation of 0.1 M HAc, and is given by,

Am
a=-- (4.139)
Ar:L)
m

The molar conductivity of 0.1 M HAc solution, Am." is given by (cf. Eq.
4.136 in the textbook) Am,1 =(FI ICI and the specific conductivity, (FI, by
(cf. Eq. 4.134 in the textbook), (F I = G I k . Therefore,

kG -I 3
A I = __ 1 = 2.01cm x 1000cm
m, cl (520n)( O.1moldm -3) Idm 3 (4.140)

= 38.7S cm 2 mol-I

The molar conductivity at infmite dilution can be determined by

Kohlrausch's law of the independent migration of ions, (cf. Sec. 4.3.10 in the
textbook) i.e.,

00 OCJ 00 CIJ 00 ex:>

Am ,HAc = A, m, H + + A, m , AC - =Am Hel ' + Am , NaAc - Am , Nael
(4.141)
2 -I 2-1
= ( 420+91-126 ) Scm mol =385Scm mol

Substituting Eqs. (4.140) and (4.141) into Eq. (4.139) gives the degree of
dissociation of acetic acid in Solution 1,
200 CHAPTER 4

2 -I
a=38.7Scm mol =0.100 (4.142)
385Scm 2 mol-I

and, thus, the concentration ofW is, from Eq. (4.138),

CH + = (0.100)( 0.1 M) = 0.01 M (4.143)

or

pHI =-logc H + (M)=-log(0.0IM)=2 (4.144)

4.36 The equivalent conductivity at infinite dilution of the divalent copper

ion is 55 S cm 2 eq-l, and its ionic radius, 72 pm. Calculate the primary
solvation number of Cu+2• The radius of a water molecule is 138 pm and the
viscosity of the solution is 10-2 poise. (Cf. Exercise 4.19 in the textbook)
(Herbert)

Answer:

The expression of the primary hydration number as the ratio between the
volume of the hydration sheath and the volume of the water molecule is (cf. Eq.
2.23 in the textbook),

(4.145)

where rs is the Stoke's radius, i.e., the radius of the ion and its primary solvation
shell, rj is the crystallographic radius of the ion, and r w is the radius of the water
molecule. The Stoke's radius can be obtained from the Einstein-Stokes-Nemst
equation (cf. Eq. 4.196 in the textbook), i.e., applied to a single ion,

ZjeOF
llA j =~.....:....- (4.146)
67trs

Therefore (cf. Exercise 4.16),

ION TRANSPORT IN SOLUTION 201

Zj eoF 121( 1.602 x 10 -19 C )( 96500C mOl-I)

rs
( -2 poise )( 55 Scm 2eq -I)
=---=
6trT/A,j 6n- 10 (4.147)
1 poise -8
x =2.98xl0 cm
10-7 nC 2 cm- 3

Substituting this value as well as the values ofr; and rw into Eq. (4.145) gives

r-( r
r
(2.98XIO-8 cm 0.72xlO-8 cm
nh = = 9.93 (4.148)
( l.38x 10 -8 cm

Comment: The mobility method is one of the most adequate for the
determination of the primary solvation number of ions, but the geometric
simplification may lead to some error.

4.37 A definition for specific conductivity frequently cited in

electrochemical literature (cf. Eq. 4.160 in the textbook) is,

where nl is the number of ions in a unit volume, (U COIIV )/ is the conventional

mobility, z/ is the valence state, and eo is the elemental charge. Starting
from the definition of specific activity, i.e.,

j
U :-=:;- (4.150)
X

derive Eq. (4.149). (Cf. Exercise 4.14 in the textbook) (Xu)

Answer:

The specific conductivity of a single ion is given by (cf. Eq. 4.128 in the
textbook) is,
202 CHAPTER 4

-jj
(J'.I =__
- (4.151)
X

where j j is the current density caused by the transport of the ionic species i, and
X is the electric field. The current density is defined as j j = i j / A , where A is

-
the area of the ion-flux cross. Furthermore, the current is defmed as the quantity
of charge, Qi, crossing the area A in the unit time t, i.e., I j = Qj / t . Thus,

"': Qj
j . =- (4.152)
I tA

Substituting j j into Eq. (4.151), gives

Qj
(J'j =~ (4.153)
tAX

Further, the charge Qi is given by

Qi = (number of ions crossing the area A) X (charge ofthe ion) (4.154)

where

(number of ions crossing the area A)

= (volume) X (number of ions per unit volume) = Vni (4.155)

The total volume needed in Eq. (4.155) is given by (see Fig. 4.6)

v = AVdt (4.156)

Therefore, the charge Qi becomes,

(4.157)

Substituting Qi into Eq. (4.153),

Vd,jnjZjeO
(J'j= (4.158)
X
ION TRANSPORT IN SOLUTION 203

• Volume, V ..
•• •• >•
Vd.i

• • • Ion flux
area, A

• • • •
< ct
:>
Figure 4.6. Cross area of an ionic flux.

Now, the conventional mobility is defined as (cf. Sec. 4.4.3 in the textbook)

(4.159)

Therefore, Eq. (4.158) becomes

(4.160)

Applying Kohlrausch's independent law, the total conductivity due to the

movement of all the ionic species is (cf. Eq. 4.143 in the textbook),

(4.161)

which is the definition of specific conductivity found in literature.

4.38 Using the data given in the table below, calculate the activation energy
for diffusion for the electrolytes KCI and tetraethylammonium picrate and
comment on their relative magnitudes. (Contractor)

Temperature (lC) AO of KCI AO of Tetraethylammonium-picrate

(S cm 2 efl) (S cm 2 eq-l)
o 81.8 31.2
18 129.8 53.2
100 406.0 196.5
204 CHAPTER 4

Answer:

The drift velocity is given by (cf. Eq. 4.199 in the textbook),

(4.162)

where I is the jump distance and k the jump frequency. The jump frequency can
be expressed as

k= Ae -Eo / RT (4.163)

where Eo is the activation energy and A the pre-exponential factor, independent

of temperature. Now, the velocity is equal to the conventional mobility (cf. Eq.
4.151 in the textbook),

Vd =u conv ' (4.164)

and U conv is related to the equivalent conductivity by (cf. Eq. 4.163 in the
textbook)

(4.165)

or at infinite dilution,

o
A =Fu conv (4.166)

Therefore, putting Eqs. (4.162)-(4.164) and (4.166) together,

A 0 = FIAe - Eo / RT o Ea 1
InA =lnFIA--- (4.167)
or
R T

According to Eq. (4.167), a graph of logAO vs. liT should give a straight
line with slope Eo I R. The values of logAO at different temperatures for the two
electrolytes are given below
ION TRANSPORT IN SOLUTION 205

6.

O 5.
InA
4.

4.

3.
0.0028 0.0036

Figure 4.7. Graph of In AO vs. T" for two electrolytes

for the detemination of their diffusion-activation
energy.

log AO (KCl) log AO (Tetraethyl

ammonium picrate)
0.00366 4.404 3.440
0.00344 4.866 3.974
0.00268 6.006 5.281

The corresponding plots and parameters are given in Fig. 4.7 and in the
following table:

Slope
KCI 1599 13.29
Tetraethylammonium picrate 1837 15.28

Comment: A higher value of activation energy is reasonable for the

tetraethylammonium picrate because of its much larger molecular size.

4.39 (a) Calculate the minimum concentration gradient necessary to obtain

a flux of [Ag(CN)zr towards a silver electrode when the electrode is held at
-0.5 V in a point 10 A from the electrode surface. The concentration of
[Ag(CN)zr at the surface of the electrode can be assumed to be 0.01 M,
206 CHAPTER 4

while the bulk concentration is 1.0 M and the temperature 300 K. Assume
that there is a significant field beyond 10 A from the electrode surface, and
the fraction of the current carried by [Ag(CN)lr is close to one (Fig. 4.8).
(b) If semi-infinite linear diffusion is assumed, calculate the thickness of the
diffusion layer. (Contractor)

Answer:

(a) Since the electrode is held at a negative potential, [Ag(CN)2f will migrate
away from the surface due to the electric field. To obtain a flux towards the
electrode, the diffusion flux must be at least equal to the migration flux (cf. Eq.
4.226 in the textbook),

dc Dco -
D-=--zFX (4.168)
dx RT

where Co is the surface concentration and X the electric field, i.e.,

- -8
X = 0.5VIlOx 10 cm . Thus,

( O.Olmoldm -3 )111(96500C mol-I )( 0.05x10 8 V cm -I) 11

dc
-= x--
dx (8.314JK- l mOI- 1 )(300K) ICV
6 -I
=1.9xl0 Mcm (4.169)

Figure 4.8. Schematic of the

process described in Problem 4.39
ION TRANSPORT IN SOLUTION 207

(b) Assuming semi-infinite linear diffusion,

(4.170)

where Cb is the bulk concentration, Co the concentration at the surface of the

electrode, and 0 the diffusion layer thickness. Then,

Cb -
-1.0M-0.OIM -51
. x10-7 cm
C
0= 0 ------- (4.171)
dc/dx 6
1.9xl0 Mcm- I

4.40 Estimate the diffusion coefficient of Na+ and cr in water at 298 K from
the equivalent conductivity at infinite dilution of NaCI, AONaCi = 126.46 S
cm 2 eq-l and the cation transport number, I'Na+ = 0.396. (Cf. Exercise 4.7)
(Herbert)

Answer:

From the Einstein relation (cf. Eq. 4.172 in the textbook) the diffusion
coefficient is related to the absolute mobility by,

Di =Uabs ,i kT (4.172)

The absolute mobility is related to the conventional mobility by (cf. Eq.

4.152 in the textbook),

uconv,i
Uabs,i = (4.173)

which is given in terms of the equivalent conductivity by (cf. Eq. 4.163 in the
textbook),

Ai
U .=- (4.174)
conv,1 F

Now, the transport number of the species i is given by (cf. Eq. 4.236 in the
textbook),
208 CHAPTER 4

(4.175)

Substituting Eq. (4.174) into Eq. (4.175),

(4.176)

Fom Eqs. (4.176) and (4.173), Eq. (4.172) becomes,

U conv jkT tjA OkT

Dj = ' =-'--- (4.177)
ZjeO FZjeO

For Na+,

t Na + A 0 kT (0.396)( 126.46Scm 2 eq -I )( l.381xl0 -23 J K -I )

DNa +
Fz Na + eo (96500C eq -I )(I)

(298K) IC ICV -s 2-1

x x - - x - - = 1.33xl0 em s (4.178)
(1.602XIO- 19 C) IVs 11

Similarly, for the cr ion, considering that let- = I- tNa+ = I - 0.396, gives,
-5 2-1
D cr = 2.03x10 em s .
Another way to calculate the diffusion coefficient is through the Nemst-
Einstein equation after one has calculated the equivalent conductivities of the
ions.

Comment: The answer is sustained by the assumption that chemical and

electrical forces encounter the same resistance in moving a given ion through the
solution, even if the mechanistic picture of a force acting on a single particle
cannot be applied to diffusion.

4.41 A student has to determine the equivalent conductivity at infinite

dilution of KCI, NaCI, KN03 , and NaN03 solutions, as well as the transport
ION TRANSPORT IN SOLUTION 209

numbers of the ions in these solutions. He managed to determine only

AO(KN03 ), AO(NaN03), f(Na+/NaCI), and f(K+IKCI), and wrote them in a
table:

NaCI KCI
121.4 144.9
0.396 0.490

Assuming that the determined values are correct, help him fill in the spaces
in the table without doing any further experiment. (Cf. Exercise 4.25)
(Herbert)

Answer:

Kohlrausch's law of the independent migration of ions leads to (cf. Eq.

4.3.10 in the textbook),

o 0 0 0 0 0
A. K + - A. Na + =A KCI - A NaCl =A KNO l - A NaNO l (4.179)

Also (cf. Eq. 4.175):

(4.180)

Equation (4.179) can also be written as,

000 0
A. K +
- A. Na + = A KNO l - A NaNO l
(4.181)
o 0 0 0
=1 K+ (KCI)AKCI -I Na+ (NaCI) -ANaCI

Equations (4.179) and (4.180) form a set of equations with variables A0NaCI
and A\cl. Thus, multiplying Eq. (4.179) by - lNa+(NaCI) and adding the two
equations,
210 CHAPTER 4

_to AO +/0 AO = _to AO +/0 AO

No + (NaCl) Kel No + (NaCl) NaCl No+ (NaCl) KNO, No+ (NaCl) NoN0 3
(4.182a)
(4. 182b)

or

o (1- I ~a + (NaCI) )( A~N03 - A~aN03 )

AKCI = 0 0
IK+ (KCl) -INa+ (NaCI) (4.184)

(1-0.396)(144.9 -121.4 )Scm 2eq -I 51 OS 2 -I

= =1 • em eq
0.490 - 0.396

and from Eq. (4.179),

o 0 0 0
A NaCI =AKCI -A KNO -ANaNo 3
(4.185)
2 -I
=151.0-144.9+121.4=127.5Sem eq

From equations similar to those in Eq. (4.180), the transport numbers of the
other ions are,

A,0 o AO
t
o = AT
IVa
+ I Na + (NaCl) NaCI
=
Na + (NaNO 3 A0
)

NaN0 3
AO
NaNO,
(4.186)
(0.396)(127.5Scm 2 eq - l )

= = 0.416
2 -I
121.4Scm eq
ION TRANSPORT IN SOLUTION 211

(4.187)

The anion transport numbers are computed by subtracting the cation

transport number from unity and the resulting values are:

NaCl KCl
121.4 144.9 127.5 151.0
0.416 0.511 0.396 0.490
0.584 0.489 0.604 0.510

Comment: At higher concentrations, ion-ion interactions make A. differ from A.0,

and the law of independent migration of ions is not strictly valid anymore.

4.42 The transport number of Ca+2 in a CaCI2 solution is tCa+l/CaC/l

0.438, and that of K+ in a KCI solution is t K + I KCI = 0.490. Calculate the

transport number of Ca+2 in a solution containing both, 0.001 M CaCI2 and
0.01 M KCI: Neglect the variation of t and A with concentration. (Cf.
Exercise 4.26 in the textbook) (Herbert)

Answer:

The transport number is related to the equivalent conductivity by the

relation (cf. Eq. 4.163 and Section 4.5.2 in the textbook)

Z·C · A.-
t. = I I I
(4.188)
I LZjCjA.j

Therefore, the transport number of Ca+ 2 in the mixture of solutions (0.001 M

CaCh + 0.01 M KC1) is,
212 CHAPTER 4

(4.189)

The next step is to calculate the different A.i in Eq. (4.189). For each separate
solution, the corresponding transport numbers are given by,

A. Ca +2
t Ca 2+ I CaCl 2 = (4.190)
ACaCl 2

A.cr
t Cl - I CaCl
2
= (4.191)
ACaCl 2

A. K +
t K + I KCl = - - (4.192)
A KCl

A.cr
t Cl - I KCl = - A (4.193)
KCl

Combining Eqs. (4.188) and (4.189),

A. Ca +2 t Ca 2+ I CaCl 2
---= (4.194)
t Cl - I CaCl
2

and substituting A. cr from Eq. (4.193),

A. Ca +2 t Ca 2+ I CaCl 2
---=---= (4.195)

Since t Cl- I KCl =1- t K + I KCl and t Cl- I CaCl 2 =1- t Ca +2 I CaCl 2

A. Ca +2 t Ca 2+ I CaCl 2
T---~-~--=-----~-- (4.196)
(1- t K + I KCl }A KCl 1- t Ca +2 I CaCl 2
ION TRANSPORT IN SOLUTION 213

or
t1 - tK + / KCI )t Ca 2+ / CaC/ 2 A KCI

1- t Ca +2 / CaC/ 2 (4.197)
(1 - 0.490 )( 0.438)A KCI
= =0.398A KC1
1- 0.438

Also, from Eq. (4.193),

t
A. CI- = t CI - / KCI A KCI = 1 - t K + / KCI )A KCI
(4.198)
= (1-0.490 )A KC1 = 0.5 10 A KCI

and from Eq. (4.192)

(4.199)

With these values, now it is possible to calculate the transport number of

Ca+2 in the mixture. Substituting Eqs. (4.197)-(4.199) into Eq. (4.188),

t +2 =
Ca mixture
121(0.00IM)(0.398A KC/ )

121( 0.00IM)(398A KC1 )+1 11(0.01 M)( 0.490A KC1 )+111 (0.012M)( 0.510A KC1 )
= 0.0673 (4.200)

where ccr =2cCaC/2 +cKCI =0.012Mwasused.

Comment: Even if equivalent ionic conductivities are affected by concentration

variation, this effect is lowered somehow by the transport numbers, which are
calculated as ratios of A.'s.

4.43 In Section 4.5.9 in the textbook the integration of the differential

equation for the diffusion potential (planck-Henderson equation) gave the
following result (cf. Eq. 4.289 in the textbook)

_ /). 'If = RT L ~ In Ci (i) (4.201)

F z; c;(O)
214 CHAPTER 4

Equation (4.201) was obtained considering (1) the activity coefficients

were taken as unity, (2) the transport numbers were assumed constant, and
(3) a linear variation of concentration with distance was assumed. If the
second assumption is removed and the transport numbers are considered to
vary with concentration as (cf. Section 4.5.2 in the textbook):

(4.202)

then the following equation for a 1:1 electrolyte would be obtained:

LC; (i)u;
_ dlj/ = _R_T In -=-;_ __ (4.203)
F LC; (O)u;
(a) Prove Eq. (4.203) for a 1:1 electrolyte. (b) Calculate the junction
potentials for the following situations: 0.1 M HCIIO.1 M KCI, and 0.1 M
HCI / 0.01 M KN03, considering the following data:

Ion (
Uconvcm S
2 -1 V-I) Ion (
UconvCm S
2 -1 V-I)
3.625x10-3 7.912x10-4
7.619xl0-4 7.404xl0-4

(Cf. Problem 4.16) (Kim)

Answer:

(a) The Planck-Henderson equation for diffusion potential is (cf. Eq. 4.284 in
the textbook),

RT t;
-dlj/ =-L-dlna; (4.204)
F ; z;

and the integral of this equation is (cf. Eq. 4.286 in the textbook),
ION TRANSPORT IN SOLUTION 215

d (I; c; ) dx
RT
-f:l.I{I=-L
F
J- I;
x=1 I;
; x=o z;
1

c; dx
(4.205)

Considering an ideal solution, i.e., I; <:; 1, Eq. (4.205) becomes

RT
-f:l.I{I=-L
x=1
J
I· 1 dc·
- ' - - - ' dx (4.206)
F ; x=o Z; c; dx

Considering a linear variation of concentration with distance [cf. Fig. 4.86 in the
textbook], i.e.,

c; = c; (0)+ [c; (i) - c; (0 )]x (4.207)

or

dc; =c; {l)-Ci (0) (4.208)

dx

Substituting Eq. (4.208) into Eq. (4.206),

RT"'X=JI Ii Ci (J)""Ci (0) (4.209)

-f:l.I{I=-LoJ dx
F ; x=OZi Ci

Now, substituting Ci from (4.207) into the denominator of the equation for Ii.
i.e., Eq. (4.202),

(4.210)

Substituting Eq. (4.210) into Eq. (4.209), and considering Zi = 1,

216 CHAPTER 4

x=1 :L[C; (i)-C; (O)]U;

= RT f; dx ( 4.211)
F x=o:LC; (O)U; + :L[C; (i)-C; (O)]XU;

X=ld{:L C; (O)U; + :L[C; (i)-C; (O)]U;X}

= RT f; ;
F x=o :LC; (O)U; + :L[C; (l)-c; (O)]XU;
;

= RT In{:L c; (O)U; + :L[C; (l)-c; (O)]U;X}X=I

F I I x=O

Evaluating Eq. (4.211) between the given limits gives the equation we are
looking for,

(4.212)

(b) For 0.1 the M HCVO.1 M KCI solution,

RT cK+u K + +ccrucr (S.314JmOI- I K- I )(29SK)

-LlIfI=-F In -I
c H + u H + +c cr u cr 96500Cmol

(O.1M)( 7.619xlO-4 em 2 s -IV-l )+(O.lM)( 7.912xI0-4 em 2s -IV-I)

xln----~--------------~------~--------------~
(O.IM)( 3.625x 10 - 3 em 2s -I V-I) + (0.1 M)( 7.912xlO- 4 em 2s -I V-I)

=-O.0266V
(4.213)

In the same way for the 0.1 M HCVO .Ol M KN0 3 solution,

(S.314JmOI- I K- I )(29SK)
~----------~----x
-I
96500Cmol
ION TRANSPORT IN SOLUTION 217

(0.01)( 7.619xl0-4 em 2s -\ V -\ )+(O.OIM)( 7.404 x 10 -4 )

x In = -O.0868V
( 0.1 )( 3.625xl0 -3 em 2 s -\ V -\) + (
O.IM
) ( 7.912xlO -4 )

(4.214)

4.44 A two compartment electrochemical cell contains NaCI in one

compartment and KCI in the other. The compartments are separated by a
porous partition. Concentration of both electrolytes are equal. If ANaO and
A KCI are the equivalent conductivities of the two solutions, show that the
liquid junction potential, EL (or -..1'1'), is given by

_ RTf A Nael
EL - -n (4.215)
F A KCI

(Contractor)

Answer:

The free energy change associated with the transfer process when one mole
of charge is passed, is given by, (cf. Eq. 4.283 in the textbook)

t· t·
dG= - Fd'l'=L-' dPi =RTL-' dlnai (4.216)
i zi i zi

This free energy change results in an electrochemical potential known as the

liquid-junction potential, EL • Consider that the liquid junction consists of a
continuous series of lamina. If the difference in activity on the two sides of the
lamina gives rise to a difference in chemical potential, dpi the liquid-junction
potential between the two faces of the lamina can be represented by dEL. Then,

(4.217)

The total liquid-junction potential can be obtained by adding the dEL across each
lamina, i.e.,
218 CHAPTER 4

a
RT II I;
EL = JdE L = - - JL-dlna; (4.218)
F a l ; z;

where aJ and alI are the activities in the two compartments I and II. If the mixing
fraction x is the fraction of solution II at a particular lamina, then the fraction of
solution I will be I-x, and x will vary between 0 and 1 going from pure I to pure
II. If Ci' is the concentration of the i-th species in solution I and Cj" is the
respective concentration in solution II, then at a lamina where the mixing
fraction is x,

(4.219)

The transport number of the ion in that lamina, Ii, is,

I; =---------------------- (4.220)
LC;U; +x LU; (c;' -c; )
I I

where Ui is the mobility. Substituting concentrations for activities, the

expression for liquid-junction potential becomes,

=_RTa: [';+(';'-,;)x].,
1 <Ix

F 0 ; =i (1- x ) ~ C; u; + x ~ u; c;' [c; + ( c;- - c; ) x ]

=_ RT JL 1
I
U; dx (4.221)
F 0 i =i (1 - x) L c; U i + xL U i c;'

or
ION TRANSPORT IN SOLUTION 219

~
E L =- RT, -,
:j (C;' -C;) LUjC;
1n -' ' - - - (4.222)
F LUj (C;' -C;) LUjC j
,

For the system under consideration, I contains NaCI and II contains KCI.
Considering also that the concentrations in the two compartments are equal then,
Eq. (4.221) becomes,

RTlUK+ -u cr )-lu Na + -u cr )In UNa + +u cr

EL = (4.223)
F {U K + +u cr )-(U Na + +U cr ) u K + +u cr

or

EL = RT In ANaCI (4.224)
F AKcl

Equation (4.222) is the needed expression.

MICRO-RESEARCH PROBLEMS

4.45. In an electrochemical experiment, a 10,3 M uni-valent ion solution is

constantly oxidized at the electrode in the presence of a large amount of
indifferent electrolyte. A current density of 1.0 mA cm,2 passes through the
anode constantly. The diffusion coefficient of the ion is 10'9 m2 S'l at 25 0c.
(a) Calculate the concentration of the ion at 0.05 seconds after the current is
switched on, and at distances of 1 /lm, 5.5 /lm and 20 /lm from the electrode.
Now calculate the concentration of the ion at 0.50 seconds after the current
is switched on and at distances of 25 /lm, 40 /lm and 100 /lm from the
electrode. Compare these results with those obtained at 0.05 seconds. (b)
Based on the above results, as well as the results from Problem 4.30, draw,
qualitatively, the three-dimensional distribution of the ions with respect to
both, the time, t, and the distance x from the electrode. (c) Draw a similar
three-dimensional distribution of the ions for an instantaneous pulse-
induced diffusion problem. (Cf. Micro Research 4.1 in the textbook) (Xu)
220 CHAPTER 4

Answer:

(a) The variation of the concentration of diffusing species with the distance x
from the electrode/solution interface with the time that has elapsed since a
constant consumption of ions is switched on is given by (cf. Eq. 4.72 in the
textbook),

c=c o -~[2 rIexp(-Ll-~ercf

.JD V--;; 4 Dt
1x2]
.JD Vill
(4.225)

The flux, which is constant, is given by

--:} = - i = 0.001Acm 2 1036 x 10- mo I cm 2-1

=.
8
s (4.226)
zF 96500C mol- I

At a distance of I J.lm from the electrode, the concentration of the ion after
0.05 s, is calculated from Eq. (4.223) with the following values for the
corresponding variables: t = 0.05 s, x = 1. Ox I 0-6 m,j = 1.036xlO'"" mol mo2 sol, c
= I mol mo3 , and D = 1.0xlOo9 m2 sol:

c [/ -005
- . s, x- J-I I
-10-6 m - mo m -3 - -
1.036xl0
-;=== molm
= =s- -
I -9 2-1
-4 2 -I

VIO m s

x
{~
2
-;r-exp -
0.05 s
[
10 -12 m
4( 10-9 m 2 s -I )(O.05S)
1 (4.227)

10-6 m
r==:::::::==:==ercf
I -9 2-1
V 10 m s

According to Table 4.6 in the textbook,

erjc(0.071) = 1- e1(0.071) = 1-0.0789 = 0.9211 (4.228)

then,
ION TRANSPORT IN SOLUTION 221

c [ t=0.05s ,x=10 -6 m ] =0.274molm -3 (4.229)

In the same way for the other concentrations at t = 0.05 S and t = 0.5 s,

t = 0.05 S t = 0.5 S
x(m) c(mol mol) x(m) c (mol mol)
1.0xl0-6 0.274 2.5xlOos 0.114
5.5xl0-6 0.616 4.0xlOos 0.671
2.0xl0os 0.986 1.0xlO-4 0.982

Comments: (1) The concentration is closer to the initial value as the distance
from the electrode surface increases. (2) At a certain distance, concentration
rapidly drops with time elapsing.

(b) From the initial and boundary conditions as well as the results of Problem
4.30, we know the following facts concerning the concentration change for the
constant flux problem in a 3D space at a time t and distance x :

c
c . ...........................................................

x=O

(a)
c c
c+--------
t=0

'----------+x '----------+x
(b) (c)

Figure 4.9. Variation of concentration with time and distance from the
electrode for the continuous oxidation of an univalent ion.
222 CHAPTER 4

(i) In the c-t plane at the electrode surface, x = 0, the concentration c varies as in
Fig. 4.4, or Fig. 4.9(a).

(ii) When the time becomes equal to the transition time zo, the concentration
becomes equal to zero at any distance from the electrode (cf. Problem 4.30c),
i.e.,

(4.230)

(iii) In the c-x plane, at any distance when t = 0, the concentration is equal to co,
[cf. Fig. 4.9(b) and 4.9(c)], i.e.,

c[t=zo,x=x]=CO (4.231)

At any time and at a distance far away from the electrode,

(4.232)

(iv) At any time after the oxidation starts, the slope of the c-x relationship at c =
ois the same.
With this information the 3D map of concentration varying with time and
distance from the electrode at constant flux drain of the ion can be built. Figure
4.10 shows this map.

Distance from the electrode, x

Figure 4.10. A c-t-x graph for a constant flux drain of an ion.

ION TRANSPORT IN SOLUTION 223

(c) Instantaneous pulse-induce diffusion. From Problem 4.30 and with the
concentration variation with distance from the electrode described in Fig. 4.31 in
the textbook, the following facts are known:

(i) At t = 0, the concentration everywhere but at the electrode surface is zero,

i.e.,

(4.233)

(ii) In the Cot plane at the surface of the electrode, the concentration varies as in
Fig. 4.4 or Fig. 4.11(a).

(iii) At any time greater than zero, the relation cox is shaped like a semi-bell, as
in Fig. 4.31 in the textbook or Fig. 4.11 (b)

(iv) At t = ct:J the concentration gradient disappears.

(v) At distance far from the surface of the electrode, the concentration of the ion
is zero, i.e.,

c[t=t,x»O]=O (4.234)

Figure 4.12 depicts the 3D map of concentration varying with time and
distance with instantaneous pulse-induce diffusion.

c c

x
(a) (b)

Figure 4.11. Variation of concentration with time and distance from the
electrode for instantaneous pulse-induced diffusion.
224 CHAPTER 4

Figure 4.12. A c-t-x graph for instantaneous pulse-

induced diffusion.
CHAPTER 5

IONIC LIQUIDS

EXERCISES

Review of Sections 5.1 and 5.2 of the Textbook

Define pure-liquid electrolyte. Discuss similarities and differences between

molten ice (Le., water) and molten sodium chloride. What are molten oxides?
Name similarities and differences between pure-liquid electrolytes and aqueous
solutions. What do X-rays and nuclear diffraction tell about structural
differences between fused salts and their corresponding crystals? How are the
ions distributed in a fused salt as compared to an ionic crystal? Describe the
diffraction-grating apparatus developed by Von Laue. Explain the meaning of
refraction and diffraction. Write Bragg's equation describing each of the
variables involved in the equation. Draw radial distribution functions as a
function of distance, and explain the meaning of the maxima and minima in the
plots. What does a pair-correlation function represent? How can pair-correlation
functions be used to determine properties of liquids? Why is neutron diffraction
preferred to X-rays in carrying out diffraction experiments with molten salts?
What are the disadvantages of using neutrons in studying fused salts? What is
the effect of voids in liquid salts on the pair-correlation functions? How do
computer approaches help to determine properties of ions in liquids and
solutions?

5.1 X-ray data on the internuclear distances in the solid and liquid forms of
alkali-halides are given in the textbook. In all cases, the internuclear

225
M. E. Gamboa-Adelco et al., A Guide to Problems in Modern Electrochemistry
© Springer Science+Business Media New York 2001
226 CHAPTER 5

distance contracts on melting. On the other hand, the volume of the solid
lattice increases when it becomes liquid. Using the data of internuclear
distances, find out the average contraction volume and compare it with the
average increase in volume of the lattice upon melting. What kind of
structure of molten salts does this suggest? (Cf. Exercises 5.23 and 5.24 in
the textbook) (Bockris-GamboaAldeco)

Answer:

Table 5.9 in the textbook gives values of the internuclear distance of

crystals and the corresponding molten salts. For example, for LiCI the
internuclear distance in the ionic crystal is 266 pm, and that in the molten salt is
247 pm. Since the volume is proportional to the cubic distance, then, the change
of volume upon melting is,

3 3
%AV= r/iq -rcrystal xl00= 247 3 -266 3 xl00=-199% (5.1)
3 3 .
r crystal 266

In the same way for the other salts given in Table 5.9 in the textbook,

Salt Internuclear distances % decrease

{Em) in volume
Crystal Molten salt
LiCI 266 247 19.9
LiBr 285 268 16.8
Lil 312 285 23 .8
NaI 335 315 16.9
KCI 326 310 14.0
CsCI 357 353 3.3
CsBr 372 355 l3.1
CsI 394 385 ~
Average: 14.3%

The average contraction volume for these salts considering the decrease of their
internuclear distances is 14.3%. The average increase in volume upon fusion for
some salts can be obtained from the data in Table 5.10 in the textbook:
IONIC LIQUIDS 227

Salt % increase of volume on fusion

NaCI 25
NaF 24
NaI 19
KCI 17
KBr 17
KI 16
RbCI 14
CdCh 20
CdBr2 28
NaN03 j.L
Average: 19.1%

The average increase in volume of the salts upon fusion is 19.1%. These
results indicate that the distances between atoms in the fused salts become
smaller as compare to the corresponding crystals, and thus, the total volume of
the sample should decrease by about the same amount. However, the total
volume of the sample increases by 19.1%, indicating that some volume is not
occupied by ions, and should correspond to free space in the sample.

Review of Sections 5.3 to 5.5 of the Textbook

Write the Bom-Huggins-Meyer equation for pair-wise addition potentials

for molten salts and explain each one of its terms. What is the contribution of
Woodcock and Singer to the molten-salt theory? What are the factors involved
in Saboungi's calculation? What are the improvements of the Saboungi's model
over previous models? How is the much later work of Saboungi considered an
improvement to the pioneer calculations of Woodcock and Singer? Explain the
hole model for fused salts. How are the holes produced? What does a
distribution function for the hole sizes represent? What is the breathing motion
of a hole? Which are the variables needed to specify a hole and how are they
different from those needed to specify an ion? Explain the meaning of mass of a
hole. What is the contribution of Ftlrth to fused-salt theory? Write the Ftlrth
equation for the work done in expanding a hole. Starting from the equation of
the probability of the location, momentum and breathing momentum of a hole as
a function of the Boltzmann-probability factor, derive the average radius of a
hole in fused salts. What are the conclusions arising from Ftlrth's theory of holes
in liquids? What are supercooled liquids? What is glass-transition temperature?
What is the contribution of Angell and of Cohen and Turnbull to molten-salt
theory? Describe the property ofJree volume and write a corresponding equation
for this variable. How does the equation of probability of finding a hole in the
228 CHAPTER 5

Cohen-Turnbull model differ from that in the Furth's model? What is the
available proof for the validity of the Cohen-Turnbull theory of glass-forming
molten salts?

5.2 Calculate the work of hole formation in molten sodium cbloride using
tbe Filrtb approacb. Take the surface tension of NaCI salt at 900°C as 107.1
dyne em-I, and the mean-bole radius of NaCI as 1.7xI0-8 em. (Cf. Exercise
5.10 in tbe textbook) (Contractor)

Answer:

The work of hole formation can be represented as (cf. Eq. S.33 in the
textbook),

2
W=4nr r (S.2)

where r and r are the mean-hole radius and the surface tension, respectively.
Therefore,

(
W=4Jr 1.7xlO
_8)2
cm (I07.ldynecm -1) x 1erg
-1 =3.89xlO -13 erg
ldynecm
-20
= 3.89x10 J (S.3)

or 23.4 kJ mol -1 .

5.3 Wbat is tbe bole radius of maximum probability found in molten

sodium cbloride at 900°C? Tbe surface tension of molten sodium cbloride
at tbis temperature is 107.1 dyne em-I. Compare your calculated value with
tbe mean-hole radius of tbe salt. (Contractor)

Answer:

The probability of the existence of a hole of radius r is given by (cf. Eq.

S.39 in the textbook),

16 7/ 2 6 _ar 2
Pr dr = 12 a r e dr (S.4)
ISJr 1
IONIC L1aUIDS 229

where

410/
a=-- (5.5)
kT

The distribution function given in Eq. (5.4) can be used to plot the
probability P, against the radius of the hole. The maximum value of P, in this
plot corresponds to the most probable size of the hole found in the sample. To
make the graph, r can take values from, say, 1.0xlO-8 em to 3.0xI0- em at
intervals ofO.2xl0-8 em. With this in mind, Eq (5.4) can be evaluated. The value
of a from Eq. (5.5) is,

4 1r ( 107.1 dyne em -I ) 1
a= x erg =8.314xlO I5 em -2 (5.6)
(1.38XIO- 16 ergK- I )(1l73K) Idyneem

The value of P, at 1.0x I0-8 em is

Pr =
16 (
8.314xlO
15
em
_2)7/2( 1.0xi0 _ Sem) 6
151r 1l2 (5 .7)

xe
-(S.314XIO ls em -2 )(I.OXIO-S emY
= 1373
. X 107 em -I

8r--r-----r--~~--~-.--~_,__.

7
6
5
p, dr x 10.7
4

3
2

1.0 1.5 2.0 2.5 3.0

r x 108 (em)

Figure 5.1 . Probability of the existence of a hole of radius r in

molten NaCI.
230 CHAPTERS

In the same way for the other values of r,

rx 108 (cm) Pr X 10 -7 Prx 10 -7

1.0 1.373 2.2 6.392
1.2 2.843 2.4 5.014
1.4 4.654 2.6 3.529
1.6 6.296 2.62 3.388
1.8 7.250 2.8 2.243
1.9 7.375 3.0 1.293
2.0 7.255 3.8 0.058

A corresponding plot of the probability against the radius of the ion is

given in Fig. 5.1 . The maximum in the plot of P r vs. r occurs at 1.9x10-8 cm,
which represents the most probable radius of the holes in molten NaCI. This
value is comparable to the mean-hole radius, I. 7x I 0-8 cm given in the textbook
in Table 5.15.

5.4 Calculate the mean-hole size of fused CsBr for which the surface tension
is 60.7 dynes cm- I at 900 Dc. (Cf. Exercise 5.3 in the textbook) (Bockris-
GamboaAldeco)

Answer:

The mean-hole radius in molten salts is given by (cf. Eq. 5.44 in the
textbook),

kT ff
(r}=0.51 -=0.51
( 1.38IXIO-16ergK-I)(1173K) Id
x---
ynecm
(5.8)
r 60.7dynecm -I I erg

= 2.63xlO -8 cm

Review of Section 5.6 of the Textbook

How are the transport phenomena of diffusion as well as the ion-ion

interactions in fused salts different from those in aqueous solutions? What is the
meaning of self-diffusion? How is it measured? What is the order of magnitude
of self-diffusion of Na+ in molten NaCI compared to that in crystal NaCI near
IONIC LIQUIDS 231

the melting point? Write empirical expressions for self-diffusion as a function of

temperature. Write an equation for the activation energy for self-diffusion. Write
similar equations for the viscosity of molten salts. What is the main conclusion
due to the general applicability of the Nanis-Bockris equation? Write the Stokes-
Einstein equation for diffusion. Does this equation apply successfully to ions in
molten salts? Why has the electrical conductivity of fused salts been widely
studied? What general trends referring to the size and valence of the ions can be
withdrawn from the equivalent conductivities of ions in molten salts? Do
experimental data for ionic liquids fit the Nemst-Einstein equation properly?
Under what conditions would the conductivity exceed the observed value?
Discuss the diffusion mechanism proposed by Borucka. Derive an equation
explaining the deviation from Nemst-Einstein equation in fused salts. Defme
transport number. What are the variables used to measure transport numbers in
fused salts? Describe some experiments by which this is done. Explain why the
direct determination of transport numbers in molten slats is more difficult in
comparison with the same determination in aqueous electrolytes. Would it not
be better to abandon them and use the approximate applicability of the Nemst-
Einstein equation relying on self-diffusion determinations?

5.5 The melting temperature of CaCI1 is 919 K and the pre-exponential

factor for self-diffusion of 36Cl is 1.8xlO-3 cm 1 S-I and of 4s Ca is 0.38xlO-3 cm1
S-I. Given these data, determine the self-diffusion coefficient of both ions in
the salt at 1200 K. Establish any needed assumption. (GamboaAldeco)

Data:

Tmp. = 919K Do.cl = 1.8xlO-3 cm2 S-I

T= 1200 K Do.co = 0.38xl0-3 cm2 S-I

Answer:

The diffusion coefficient can be obtained from (cf. Eq. 5.55 in the textbook)

(5.9)

Considering that the value of the activation energy is similar for both ions,
and that it does not change in this range of temperature, the Nanis-Bockris
equation at 919 K reads (cf. Eq. 5.53 in the textbook):
232 CHAPTERS

E~ =3.74RTm . p . =3.74( 8.314Jmol- 1K- 1 )(919K)

(5.10)
= 28575J mol-I

DCa+ 2 =0.38xl0-3 cm 2 s- 1 exp _

[ 28575Jmol -I]
(8.314JmOI-1 K -I )(1200K) (5.11)

-5 2-1
= 2.17xlO cm s

and for 36cr,

D cr (18 10 - 3 2 -I) [ 28575 J mol-I ]

= . x cm s exp - (8.314JmOI- 1 K- 1 )(1200K) (5.12)

= 10.3xlO -5 cm 2 s -1

5.6 The diffusion coefficient of the tracer cr ion in molten NaCI is 4.2xlO-5
cm 1 S-I at 1020 °c, and 6.7xlO-5 cm1 S-I at 840°C. (a) Calculate the values of
the activation energy and the pre-exponential factor for the diffusion
process. (b) Compare the E'D value with that obtained from the empirical
equation proposed by Nanis-Bockris, i.e., E'D = 3.74 RTm.p.. (Cf. Exercise
5.33 in the textbook) (Contractor)

Answer:

(a) The self-diffusion coefficient is given by (cf. Eq. 5.55 in the textbook),

D=Doexp (
-ED
Rr 1
"# (5.13)

The activation energy, F:D , and the pre-exponential factor, DQ, can be
obtained from the solution of two simultaneous equations given by Eq. (5 .13) at
IONIC LIQUIDS 233

two different temperatures, i.e., In DJ = In Do - E:D IRTJ and ., In D2 = In Do-

E:DIRT2. Subtracting these two equations,

ED 1 1
InDI -lnD2 = - -*- [ - - - - ) (5.14)
R TI T2

and substituting the appropriate values,

In6.7x10 -5 -ln4.2x10 -5 =-
*
ED (1 1)
- - - - - (5.15)
8.314JK-1 mol-1 ll13K 1293K

Solving for E ~ gives, E ~ = 31 kJ mol-I. Substituting this value of E ~ in

Eq. (5.13), and solving for In Do,:

E* 3 -I
InDO =lnDI +~=ln6.7xl0-5 + 31xl0 Jmol =-6.26
RTI (8.314 JK- 1 mol- 1 )(ll13K)
(5.16)

Equation (5.16) gives a value for the pre-exponential factor for this salt of
Do = 1.9x10-3 cm1 S-I.

(b) The melting point of NaCI can be obtained from Table 5.6 in the textbook.
Therefore,

E~ =3.74RTm. p . =3.74(8.314JK- l mOl- 1 )(1074K)=33.4kJmOI-1

(5.17)

This value is in good agreement with that found from experimental data of
diffusion· coefficients.

5.7 It is known that the equivalent conductivity of molten salts depends on

the size of the cation forming the salt. Using the data in the book, plot the
equivalent conductivities of molten salts of monovalent cations against the
radii of the corresponding cations. Which type of dependence did you find?
(Cf. Exercise 5.32 in the textbook) (Contractor)
234 CHAPTERS

200'---~~~~'-~-r~-r~-'

180
160
A2 140
(S em eq·1)
120
100
80
w ~ 100 1~ 1~ 1~ 1~

rcation (em)

Figure 5.2. Equivalent conductivity of molten salts of

monovalent cations as a function of the cation radii.

Answer:

The next table (cf. Table 5.24 in the textbook) shows the equivalent
conductivities of molten chlorides and the radii of the corresponding cations,
and Figure 5.2 shows the corresponding plot:

LiCI NaCI KCI RbCI CsCI

Radius of the cation (pm) 68 94 133 147 167
Equivalent conductivity (S cm2 eq·l) 183 150 120 94 86

The equivalent conductivities of monovalent cations show a linear

dependence with respect to the corresponding ionic radius.

Comment: The larger ions such as Cs+ and Rb+ need a larger hole to jump into
to be able to move. Consequently, their conductivities are smaller than those of
the smaller cations.

5.8 The equivalent conductivity of molten NaCI is 153 n -I cm 2 eqol at 1153

K, and the self-diffusion coefficients of Na + and cr ions in molten NaCI are
9.6xlOoS and 6.7xIO·s cm 2 sol, respectively. With these data evaluate
Faraday's constant. (Cf. Exercise 5.34 in the textbook) (Contractor)
IONIC LIQUIDS 235

Answer:

The Faraday's constant can be calculated using the Nemst-Einstein relation

(cf. Eq. 5.61 in the textbook),

A = F 2 (D + + Dcl - ) (5.18)
RT Na

or,

( 1530 -\ cm 2 eq - \ ) ( 8.314Jeq -\ K - \ ) ( 1153 )

F=
( 9.6+6.7 ) xlO -5 cm 2-\
s

~
-\
x Ie Os =94857 Ceq-l (5.19 )
1J

Review of Section 5.7 of the Textbook

Write a molecular-kinetic expression for viscosity of a fluid and explain the

model of viscous flow in fluids. How is the viscosity represented under this
model? How is this molecular-kinetic expression modified for ionic liquids?
Explain the significance of the mean-time between collisions in an ionic liquid
and write and equation for it. Write an expression for the viscosity of ionic
liquids as a function of the mean radius of the holes. Write the Stokes-Einstein
relation for the diffusion coefficient of holes. Starting from this relation, derive
an expression for the diffusion coefficients of ions in a fused salt and as function
of the volume expansion at the melting point. Derive Eq. (5.101) in the
textbook. Derive an expression for the heat of activation of hole formation, A, as
a function of the melting temperature of the salt. What are the assumptions
considered in this derivation? Mention some of the advantages and difficulties
the hole model has. Why is it said that the variation of the diffusion coefficient
with temperature at constant volume is an artificial state? How are the heats of
activation for hole formation and that for jumping-into-into-a-hole determined?
How does Swallin's model differ from the jumping-into-holes model? Why is
this model rejected as a possible model to explain conductivity in molten saHs?
Explain Rice and Allnutt's model for molten salts and mention some of its
drawbacks.
236 CHAPTER 5

5.9 For a hole in molten KCI at llOO K, calculate (a) its average radius, (b)
its mass, and (c) its lifetime. The melting point of this salt is 1045 K, and in
its liquid state, its surface tension is 89.5 dyn em-I, and its molar volume is
50.20 cm 3 mol -1. (Cf. Exercise 5.19 in the textbook) (Bockris-
GamboaAldeco)

Data:

T= 1l00K Vm,KCI = 50.20 cm3 mor J rKCI = 89.5 dyn cm- J

Tm.p = 1045 K MKCI = 74.6 g mor J

Answer:

(a) The average-hole radius is given by (cf. Eq. 5.44 in the textbook):

1/2 (1.381XIO-23 JK-I )(IlOOK) INm

(rh ) = 0.51 [
krT
)
=0.51 -3 _I xIJ- (5.20)
89.5xlO Nm
-10
= 2.10xlO m

(b) The apparent mass ofa hole is given by (cf. Eq. 5.28 in the textbook),

(5.21)

where p is the density of the liquid. Therefore,

1mol 0.0746kg 106cm3 -3

p = = x x = 1486 kg m (5.22)
V m,KCI 50.20cm 3 1mol 1m 3

Substituting Eqs. (5.20) and (5.22) into Eq. (5.21),

m h = '321Z' ( 2.lOx 10 _10)3

m (1486 kg m -3) = 2.88xl0 -26 kg (5.23)
IONIC LIQUIDS 237

(c) The lifetime of a hole is calculated by (cf. Eq. 5.93 in the textbook)

(5.24)

where (cf. Eq. 5.115 in the textbook)

A = 3.3 RTm.p. = 3.3(8.314 J K -I mol -1)(1045 K) = 28670 J mol ·1 (5.25)

Substituting Eqs. (5.20), (5.23) and (5.25) into Eq. (5.24),

(2.10XI0- 1O m) 27r( 2.88xlO -26 kg)

T=....:......----~

3 (1.38Xl0- 23 JK- 1 )(llOOK)

xexp [
28670 J mol -I 1__
x
1 _J_112_ _
(5.26)
( 8.314J K -I mol- I )(llOOK) 1 kg 1/2 m s-I

-12
= S.S6xlO s

5.10 Deduce an expression to calculate the number of holes per unit volume
of liquid in a molten salt in terms of its physical properties (e.g.,
temperature, density). (GamboaAldeco)

Answer:

The number of holes per unit volume of the liquid, nh, can be obtained from
the expression for viscosity of the hole-theory (cf. Eq. 5.94 in the textbook),

1] = -2 n h ( r h ) ( 2 mnkT ) 112 e AI RT (5.27)

3

The average radius of the hole is (cf. Eq. 5.44 in the textbook),

112
8 kT
(rh )=- - [ ) (5.28)
57r r
238 CHAPTER 5

The parameter A is given by [cf. Section5.7.6 in the textbook],

A = 3.3RTm . p . (5 .29)

and the mass ofa hole of average radius is (cf. Eq. 5.28 in the textbook).

(5.30)

Substituting these expressions into equation (5.27) and solving it for nh,

=(27)112 17e-A I RT (51<)5/2[(~)5/2l1l2

16 1< (kTp ) 112 8 kT

Arranging terms

nh = 2.234
~ Y512 11 2/( kT )712 P e -3.3T mp.. rr (5.32)

This equation gives the number of holes per unit volume, nh, as a function of the
surface tension, viscosity, density, temperature and melting point of the molten
salt.

5.11 Using the equation developed in Exercise 5.10, calculate for NaCI fused
salt at 1173 K, (a) the number of holes per cubic centimeter, (b) the number
of holes per mole of fused salt. The melting point of NaCI is 1074.1 K. Its
viscosity at its melting point is 1.67 cpoise, and at 1173 K, is 1.05 cpoise. The
density of the salt at 1173 K is about 1.52 g em -3, and the surface tension at
this temperature is 107.1 dyn em-I. (GamboaAldeco)

Data:

Tmp= 1074 K T/J074K = 1.67 ep PJl73 =1.52 g em- 3

T= 1173 K T/J173K = 1.05 cp YJl73K = 107.1 dyn em- l
IONIC LIQUIDS 239

Answer:

(a) The expression to calculate the number of holes per unit volume of liquid is
(cf. Eq. 5.32 in Exercise 5.10),

5/ 2 2
Y TJ -3 .3Tmp lT
nh = 2 .234 e (5.33)
(kT)1 1 2 P

Substituting the appropriate values for fused NaCI at 1173 K,

r
nh = 2.234 e -3.3(I074K)/(1173 K)

/2
(107.ldyn cm -I (0.0105poise)2
x
(l.38IXIO- 23 JK -I) 7/2 (1l73Kr/2 (l.52 g Cm -3)
(5.34)

x [1 g cm -I s -I ]2 [ 1J ]7/2 1dyn -2
1 poise 10 7 dyn cm 1g cm s

= 7.723xl0 21 holes
3
em

or,

21 holes 1mol
nh =7.723xl0 x------ (5.35)
cm 3 of liquid 6.022 xl 0 23 holes
= 0.0128 mol holes
3
em

(b) The number of holes per mole of fused salt is,

-I
M NaCI mol holes 58.5 g mol mol holes
nh = 0.0128 = 0.493 (5.36)
P1173K cm 30fliquid 1.52gcm -3 mol salt
240 CHAPTER 5

5.12 What fraction ofthe total volume is due to holes in the salt described in
Exercise 5.10? Does the hole model conforms to the observed experimental
increase of volume upon fusion? (GamboaAldeco)

Answer:

The volume of a hole of average radius is given by:

3/2
(1.38XIO- 23 JK- 1 )(1173K) ] [10 7 d cm)3/2
= 0.553 [ yn (5.37)
107.1dyncm -I lJ

-23 3
= 3.251xlO cm

and the volume of holes in 1 em 3 of liquid is

Vhnh =[3 .25IXIO-23 em

hole
3
](7.723xI0 21 holes
em 3 of liquid
1
(5.38)
3
= 0.251 em hole
3
em

The value obtained in Eq. (5.38) indicates that 25.1% of the total volume of
the liquid is occupied by holes. Table 5.10 in the textbook shows an increase of
volume of 25% upon fusion for NaCI. Therefore, the hole model used in this
calculation conforms to the experimental behavior of the fused salt.

Review of Sections 5.S and 5.9 of the Textbook

Draw a sketch of conductivity vs. composition for an ideal and real mixture
of molten salts. In a general way, how are deviations from ideality explained in a
mixture of molten salts? How is a eomplexed ion defined in molten salts? Define
transition time and write an equation for the electrode potential as a function of
the transition time. Explain a method based on transition times to determine the
concentration of complexes in mixtures of fused salts. What is the parameter
used to distinguish the existence of complexes in molten salts? What are some
spectroscopic and electrochemistry methods used to determine complexes in
molten salts? Describe the electrochemical process for the obtention of
IONIC LIQUIDS 241

aluminum. What do the two peaks found in the Raman spectrum of cryolite
represent? Explain how the coordination number is related to the value of the
wavenumber of the given peak in a Raman spectrum. How is it possible that
anions such as AIOF react at electrodes negatively charged, i.e., cathodes?
Which are the structures formed when AICh is added to SnCh? Describe briefly
how Nuclear Magnetic Resonance works. What information related to molten
salts is obtained from NMR? How is NMR used to study complexes of AICh?

5.13 What is the force constant of vibration, k, of the entities shown in the
Raman spectrum of molten Cryolite? The wavenumbers at which the peaks
appear are 554 cm- I and 575 cm- I , respectively (cf. Fig. 5.57 of the
textbook). Comment on your results. (Cf. Exercise 5.22 in the textbook)
(GamboaAldeco)

Answer:

The frequency of a given vibration is given by (Eq. 2.24 in the textbook):

(5.39)

where J.J is the reduced mass given by (cf. Section 2.11.2 in the textbook)

1111111
-=-+-=--+--=-+-=----- (5.40)
~ ml m2 MAl MF 27 19 11.l5gmo)-1

and the frequency v is given by,

v=co v (5.41)

r
Therefore, from Eqs. (5.39)-(5.41),

k554cm -I =(21tv)2 ~ =[ 21t( 3xI0 10 cm s -I )( 554cm -I )

(5.42)
-I ) 1 mol 5-2
x ( 11.15 g mol = 2.02xlO g s
6.022 x 10 23

In the same way at 575 cm- I ,

5 -2
k575cm-1 =2.17x10 g s (5.43)
242 CHAPTER 5

Comment: A high wavenumber indicates a large force constant. This means that
the bond strength between the two considered atoms, e.g., atoms A and B, is
stronger the higher the wavenumber is. If more atoms surround the central atom
A (higher coordination number), the bond strength between A and B decreases,
k becomes smaller, and thus the wavenumber decreases too.

Review of Section 5.10 of the Textbook

What is the effect of alkali metals dissolved in molten salts? Is the mobility
of molten salts very different from that of the corresponding ions dissolved in
aqueous solutions? What is the travelling lifetime of an electron in moving from
one ion to another? Describe the three steps followed to calculate electronic
conductance in molten salts according to Bockris and Emi.

5.14 Suppose the electrical conductivity of CaO is determined primarily by

the diffusion of the Ca+2 ions. Estimate the mobility and the conductivity of
this cation at 1800 Dc. The diffusion coefficient of Ca+2 ion in CaO at this
temperature is 10-14 m2 S-I. CaO has a NaCI structure with a parameter a =
4.522 A. (Cf. Exercise 5.31 in the textbook) (Contractor)

Answer:

In ionic materials like CaO, the mobility of the charge carriers (or ions) is
given by (cf. Eqs. 4.152 and 4.172 in the textbook),

ZjeOD (2)(1.602XIO- 19 C )(10- 14 m 2 s- l ) 1]

U e = U conv = =----.:...--------.:...~-----~
kT (1.381XIO- 23 JK -I )(2073K) ICV (5.44)

= 1.12x10 -13 m 2 V -1 s -1

The conductivity is given by (cf. Eq. 5.134 in the textbook),

CT=FNeu e (5.45)

The number of moles of electrons per cubic centimeter, Ne , is

IONIC LIQUIDS 243

number of Ca +2 ions per unit cell z

Ne =
volume of unit cell NA (
4.522xlO m
-10)3
x-- = - - - - - - - -
(5.46)

x 2 = 35910(molofelectrons)m-3
6.022 x 10 23 mol- I

Thus, the conductivity is calculated as,

(j = FN e u e = (96500 C mol- I )( 35910 mol m -3 )

X(1.l2XIO- 13 m 2 v- 1 s- l )x I~ =3.88xI0-4Sm-1
(5.47)

IC sin

Comment: The mobility is many orders of magnitude lower than the mobility of
electrons. Hence, the conductivity is very small compared to the electronic
conduction.

Review of Sections 5.11 and 5.12 of the Textbook

Why is a liquid medium a better place for reactions to occur than a gaseous
medium at the same temperature? Describe Lin's work and its importance in
industry. Which is the potential window in which aqueous solutions can be
examined before oxygen and hydrogen are evolved at low pH's? How is the
potential window in, say, molten NaCI? Mention advantages of having systems
with large potential windows. Is it possible to have the advantages of molten
salts at room temperatures? Describe the acid-base behavior of low-melting-
point liquid electrolytes such as those containing AICh. Mention some onium
salts. What are the structural characteristics of these salts? Explain why the
melting point of molten salts decreases as the complexity of the molecule
increases. Mention some disadvantages of the use of complex-molten salts. Why
is it said that protons act as contaminants in low-temperature-molten salts?

5.15 Ambient-temperature molten salts are made up from certain alkyl-

ammonium salts or alternatively, by a mixture of AICI3 with organic
compounds. Mention two advantages of these salts over traditional molten
salts. Suggest three solvents which would allow the electrochemical
oxidation of complex organics such as polymerized isoprene (rubber) at less
than 100°C. (Cf. Exercise 5.28 in the textbook) (Bockris)
244 CHAPTER 5

Answer:

Some of the advantages of ambient-temperature molten salts are: (I) They

melt several hundred degrees below room temperature resulting in a material
easier to handle. (2) They allow a much larger electrochemical window.
Examples of these materials are: tetraheptylammonium chloride (m.p. 264 K),
ethyl-diphenyl-sulfonium tetrafluoroborate (m.p. 308 K),and trimethyl-phenyl-
phosphonium iodide (m.p. 308 K).

Review of Section 5.13 of the Textbook

What is an oxide system? Discuss the structural similarities between water

and fused silica that make the conductivity of fused silica compounds lower than
molten salts. How is the transport process in molten silica? Which is the rate
determining process for transport in molten silica? What similarities and
differences exist between water and fused silica? Between fused salts and fused
silica? Explain the temperature dependence of EI] in liquid Si02 • Which are the
two ways water interacts with ions? How is the mechanism of dissolution of
non-metallic oxides. Draw a schematic of this process. What is a glass? What is
the effect of addition of metallic oxides to silica oxide? What is understood by
liquid silicate, frozen liquid, and devitrification when referring to silicates?
What happens when devitrification occurs? How is the concentration of metal
oxides in nonmetallic oxides expressed? Draw a schematic of changes of
activation energy for viscous flow as a function of the OIR ratio. What are the
species present at a ratio O/Si> 4? Why does the theory involving changes of
molecular species in the liquid silica structure as metallic oxide is added fail to
explain the behavior of the liquid silicate? What are the bases of the network
theory of liquid-silicate structure? Explain why this model fails in describing the
glassy state of silicate. Describe the discreate-polyanion model of liquid
silicates. How does this model explain better the observed experimental facts?
What are the disadvantages of this model? Which are the two structures
proposed by Tomlinson, White and Bockris to explain the silicate behavior in
the composition range from 12-33% M20? How do spectroscopic measurements
of Si04-4 lifetime help to understand the liquid silicate structure? What is the
type of silicate structure proposed to exist in the earth's interior? Describe the
metallurgical process of producing iron in a blast furnace. What is slag? What is
its importance in the manufacture of iron?

5.16 The heat of activation of simple molten salts is generally less than 10
kcal mol -I (42 kJ mol -I), while that of Si02 is 59 kcal mol -I (245 kJ mol -I)
(cf. Problem 5.32). Similarly, the heat of activation when a metal oxide is
IONIC LIQUIDS 245

added to liquid silica decreases 2 to 4 times (d. Fig. 5.71 in the textbook).
Explain these significant differences in the activation energies of molten
salts, silica, and silica with additives. Which are the most probable rate
determining steps in each case? (Cf. Exercise 5.15 in the textbook) (Bockris-
GamboaAldeco)

Answer:

Molten salts are constituted by ionic species such as Na+ and cr in NaCl.
Each one of these ions may easily jump into the holes formed in the liquid.
Liquid silica, on the other hand, is an associated liquid, constituted by chains of
Si04 segments. Thus, before jumping, some energy is needed to break one of
these segments from the chain,a step not needed in the transport of molten salts.
This extra energy is what makes the heat of activation of molten silica larger
than that ofthe molten salt. Now, when a metal oxide such as Na20 is added to
the liquid silica, the Na+ and 0-2 ions help in the breaking process of the chain
(cf. Problem 5.32), resulting in a decrease of the energy of activation. If the
transport process occurs through vacancies, then the most likely rate-
determining step (rds) for molten salts such as NaCI is the/ormation o/voids in
the liquid. For liquid silica, this step is constituted by the breaking of the chain
structure to give a transport entity. Addition ofNa20 facilitates this step.

5.17 Determine the average radius and the corresponding volume of the
hole formed in fused silica at 2100 K. Does a segment of the Si04 chain fit in
the average hole formed? The surface tension offused silica is 250 dyn cm- I ,
and the Si-Si distance is 3.2 A (d. Problem 5.23). (GamboaAldeco)

Answer:

The average radius of the holes formed in fused silica is (cf. Eq. 5.44 in the
textbook),

rEf
(r) = 0.51 V-;

(1.38lxl0- 23 JK- 1 )(2100 K) 10 7 dyncm

= 0.51 ------------------------x--------
-I
(5.48)
250 dyncm 11
-8
= 1.74xlO cm

and the corresponding volume (cf. Eq. 5.144 in the textbook),

246 CHAPTERS

3/2
( )
(Vh ) = 1.6 ~

( ( l.381xlO-
23
JK- \ ) (2100K) 10 7 dyncm ]3/2
= 0.51 x (5.49)
250 dyn cm -\ 11

-23 3
= 2.0lx10 cm

Comment: Consider that the radius of the Si04 segment is about half of the Si-
Si length. Then, the radius of the Si04 segment is 1.6 x 10.8 cm, which fits
adequately in the holes formed.

5.18 (a) Assess the total number of individual Si-O bonds in one mole of
Si02. (b) Give a chemical explanation of why the addition of Na20 to silicate
causes the breaking up of the tetrahedral network. (Cf. Exercise 5.13 in the
textbook) (Xu)

Answer:

(a) Since Si is tetra-coordinated, i.e., every Si is surrounded by 4 Si-O bonds,

the number of Si-O bonds (NSi-O) in 1.0 mol of Si02 is

1
+
,,5""-0_ Na+
Figure 5.3. Breaking of the Si0 2 network by a Lewis base.
IONIC LIQUIDS 247

6.022x 10 23 24
N Si-O =4N Si =4(lmol)x =2.5xlO bonds (5.50)
1mol

(b) The highly charged Si+4 is a strong Lewis acid in the molten state. This
Lewis acidic center is easily attacked by the base added, i.e., 0- 2 anions from
Na20, as shown in Fig. 5.3. The result of the reaction is that the bridging oxygen
is replaced by electronically richer oxygen anions, better satisfying the
electrophilic Si+4 center. The calculation in Problem 5.23 confirms the great
repulsion between two neighboring St4 centers at their equilibrium distance.

5.19 (a) Which is the O/Si ratio of 50% mol CaO in Si02 ? Of 10% mol
K 20? (b)What is the composition of a M 20 + Si02 mixture that has a O/Si
ratio of3.5? (GamboaAldeco)

Answer:

(a) A 50% mol CaO is written as:

I CaO + 1 Si02 -+ 3 0 : 1Si -+ 0 = 1. = 3 .

Si 1

Similarly, a 10% mol K 20 is written as:

I K20+9Si02 -+ 190:9Si
o 19
-+ -=-=2.1
Si 9

(b) To fmd the composition of a O/Si = 3.5 ratio, it is needed to find the value of
x in the following equation:

xM 2 0+(100-x)Si0 2 -+ o x + 2(100 -x) 3.5

Si 100-x
-+ x=33 .8 -+ 33.8 % M 20

5.20 A frozen liquid can also flow. Researchers have found that window
glass of many medieval churches in Europe has thicker bottom than top (as
large as in the millimiter range). This deformation is evidently caused by
the flowing of the silicate. Calculate how far the moving species in the glass
can travel in a millennium at room temperature. Does your calculation
explain the enlargement in the millmiter range? Which other force should
248 CHAPTER 5

be taken into account? Consider the glass to have a composition 40 % mol

Na20, with ring structures of approximatelly 10 A. At the temperature of
glass transition, Tgt the viscosity is 1'/ = 1012 Pa s. (Cf. Exercise 5.14 in the
textbook) (Xu)

Data:

40% mol Na20 ring structures of loA

1'/ = 10 12 Pa s t = 1000 years

Answer:

At approximatelly 40% Na20, the major species that are available for
moving is polyanions with ring structures, i.e., Sh09-6 (cf. Section 5.13.8 of the
textbook). Their sizes are of the order of loA. The mean square distance the ion
can travel during this time period is given by the Einstein equation (cf. Eq. 4.27
in the textbook),

(x) = .J2Dr (5.51)

Assuming that the viscosity of the glass at room temperature is of

comparable value to that of the glass-transition temperature, Tg , then, 1'/25 C
=1.0xl0 13 Pa s, and the diffusivity of the mobile species is given by (cf. Eq. 5.58
in the textbook),

( 1.381XIO-23 JK-l )(298K)

D = E- = x 1N m x 1Pa
6m]r 61Z'( 1.010 13 Pa s )( 10 -9 m) 11 1N m -2 (5.52)

=2.18xlO- 26 m 2 s-1

A millenium in seconds is:

365 days 24hr 3600s 10

1=1000 yearsx x--x--=3.15xI0 s (5.53)
1year 1day Ihr

Substituting the values of D and t into Eq. (5.51) gives,

IONIC LIQUIDS 249

(x )=~ 2 (2.1Sxl0 -26 m 2s -1)( 3.15xl0 10 s ) = 3.7xl0 -8 m (5.54)

-5
:::=10 rom

The above result can be even bigger when the gravitational force is taken
into account. In this case the mobile species do not diffuse randomly, i.e., in
every direction, but directionally, i.e., downward.

5.21 In the discrete- polyanion model of liquid silicate, the entities present
vary according to the amount of M10 added. Draw schematics of the
structures present at (a) 0% MzO, (b) 10% M10, (c) 30% M10, (d) 50%
MzO, (e) 60% MzO, and (f) 90% MzO. What is the Si:O ratio in each case?
(g) What is the meaning of an O/Si > 4? (h) How are these entities different
from those proposed by the network theory of liquid silicates? (Cf. Exercise
5.26 in the textbook) (GamboaAldeco)

Answer:

(a) At 0% M20 the theory proposes continueous 3-dimentional networks of Si04

represented by the drawing in Fig. 5.4.

" .......

Figure 5.4. Schematic of liquid silicate

. 0
At this composition, 100 SI02, and - =-200 =2 .
Si 100

(b) At 10% M20 the theory proposes Si04 network with some broken bonds, as
shown in Fig. 5.5. At this composition, 10 M20 + 90 Si02, and
o = ISO + 10 = 2. I
Si 90
250 CHAPTER 5

+ •
Ca··

Fig. 5.5 Schematic of the structure ofliquid silicate with 10% M20

(c) At 30% M20 the theory proposes [Si60 1S]-6 rings, as in Fig. 5.6. At this
composition, 30 M 20 + 70 Si02, and 0 = 140 + 30 = 2.4 .
Si 70

Figure 5.6. Schematic of the structure

of liquid silicate with 30% M20.

(d) At 50% M20 the theory proposes a mixture of, say, [SLtOd-s and [Sis0 2o s , r
as in Fig. 5.7. At this composition, 50 M20+ 50 Si02, and Q = 100+50 = 3.
Si 50

Figure 5.7. Schematic of the structure of liquid silicate with 50% M20.
IONIC LIQUIDS 251

(e) At 60% M20 the theory proposes chains of Sin0 3n+1-(2n+2) , like [Si20 7]-6 and
[ShOlOr8 as in Fig. 5.8. At this composition, 60 M20 + 40 Si02, and
0= 80+60 =3.5
Si 40

Figure 5.8. Schematic of the structure of liquid silicate with 60% M20 .

(I) At 90% M20 the theory proposes SiO/f and 0.2 , as in Fig. 5.9. At this
composition, 90 M20 + 10 Si02, and Q = 20 + 90 11
Si 10

Figure 5.9. Schematic of the

structure of liquid silicate with 90%
M 20.

(g) Since the saturated valency of Si is 4, an O/Si > 4 indicates that there is an
excess oxygen in the mixture, represented as 0.2 •

(b) Some of the main differences between the two models are: (i) In the network
theory, the cations and the anions are about the same size, in contrast to the
discrete-polyanion model, where big ring structures are proposed. (ii) The
network theory proposes only breaking of the silicate structure, while the
discrete-polyanion model accounts for the breaking of the network and then the
formation of different conglomerates.
252 CHAPTER 5

PROBLEMS

5.22 Using the pair-potentials of one of the pioneers in the modeling of

molten salts, i.e., Woodcock and Singer, as well as the corresponding
parameter in their work, calculate the equilibrium distance between Ie and
cr ions (rij) in molten KCI just above the melting point. (Cf. Exercise 5.8 in
the textbook) (Bockris-GamboaAldeco)

Answer:

The pairwise addition potentials in molten salts as described by Woodcock

and Singer are given by (cf. Eq. 5.10 in the textbook):

2
z'·Zj·eo ( ) c·',j· d·',j·
v·',j. = -....:....--+bexpB cr '· ,j . -r·' ,j. +--+--
6 8 (5.55)
~J ~J ~J

The parameters needed for Eq. (5.55) for K+-Cr as used by Woodcock and
Singer are given in Table 5.12 in the textbook, i.e.,: ~ = 3.048xl0·s cm, b =
0.338xlO· 12 erg. B = 2.97xlOs cm· l , C;j = -48.0xl0 erg cm6 , and d;j =
-73.0xl0·76 erg cms. The curve of V;.j against the separation distance, r;j, for
opposite charge ions passes through a minimum (cf. Fig. 5.12 in the textbook),
which correspond to the point of minimum energy for the system. One way to
calculate this minimum is to take the derivative of Eq. (5.55) and make it equal
to zero:

2
ZjZ jeO c·· d· ·
bBexpB ( a·' .j. -r·' ,j. ) -....!..:!....-....!..:!....=O
7 9
(5.56)
2
4lr&orj ,j r··
'.j r·, ,j ·

Arranging terms in Eq. (5.56):

2
ZjZ jeO 7 9 ( ) 2
--'--r·, ,j . -bBr·, ,j . expB a ,·.j. -r·, ,j. -c ,·,j ·r·
, ,j. -d ,·,j. =0 (5.57)
4JT&o

Substituting the corresponding parameters,

IONIC LIQUIDS 253

(2.307XlO- 19 ergcm )ri~j (5.58)

- (I •00 X 10 -4 ergcm -I) ri,je

9 2.97xI0 8 em- 1 (3.05xI0- 8 em - r)
-60 6) 2 -76 8
+ ( 48xl0 ergcm ri,j +73x10 ergcm =0

The substitution of values of r;J into Eq. (5.58) gives as result the values in
the next table, where:

C = [( 48xlO -60) ri,j

2 + 73xlO -76 ]

r/J A B c I.h.s. Eq. (5.58)

(em)
1.0 xlO· g 0.02 x 10.73 -0.04 x 10.12 1.21 x 10-74 -2.94 x 10.73
2.0 xlO, s 2.95 x 10.73 -l.l5 x lO. n 2.65 x 10.74 -8.28 x 10-73
2.3 xlO· s 7.85 X 10-73 -1.66 x IO- n 3.27 X 10-74 -8.42 X 10.73
2.4 xlO· s 10.6 X 10.73 -1.87 x lO. n 3.49 X 10-74 -7.75 X 10.73
2.5 xlO· s 14.1 X 10-73 -1.94 x lO. n 3.73 X 10.74 -4.93 X 10-73
2.6 xlO· s 18.5 X 10-73 -2.05 x IO- n 3.97 X 10.74 -1.60 X 10-73
2.7 xlO· s 24.1 X 10.73 -2.14 x lO. n 4.23 X 10.74 +3 .12x 10.73
2.8 xlO· s 3l.l X 10.73 -2.20 x lO. n 4.49 x 10.74 +9.55 x 10.73
2.9 xlO·s 39.8 X 10-73 -2.25 x lO. n 4,77 X 10-74 +17.77 X 10-73
3.0 xlO· s 50.4 X 10.73 -2.27 x lO. n 5.05 X 10.74 +28.20 X 10.73

A plot of the last column of the above table against the separation distance
is given in Fig. 5.10. The l.h.s. of Eq. (5.58) equals zero when r = 2.62x10-s cm,
which corresponds to the distance of minimum energy between the K+ and cr
ions.

5.23 A pairwise potential widely used in both Monte Carlo and MD

calculations (d. Eq. 5.10 in the textbook),
254 CHAPTER 5

z·z . ( ) 6 8
.. _'_j +B·I,j. expC·I ,j.
<l> I,j. {r}=A I,j (T .
I ,j
. -r·I,j. +D·I ,j ·r·-
I ,j
· +E·I,j·r·-·
I ,j
r·I,j.
(5.59)

which describes the potential as function of distance between the two ions i
and j. The parameters Zi, Zj are the charges on i and j respectively, while {1';j
is the size parameter of the ion pair (normally the sum of the
crystallographic radii of i and J). A ij, Bij> C;j> D ij, and Eij are constants
estimated from studies on the crystal of the corresponding salt. (a) Identify
the term that dominates the attraction between a pair of opposite charged
ions at long range, and the term that prevents these two ions from "falling
into each other." (b) Which is the parameter in the second term that
determines the "steepness" of the repulsion felt by these two ions once their
size parameters and center-to-center distances have been fixed? (c) In
molten silicate, the Si-Si equilibrium distance is ca. 3.2 A. Determine by
calculation whether the force due to the second term or the Coulombic like
charge repulsion dominates. What does the result connive at concerning the
stability of the silicate network? Consider: Aij = e/, Bij = O.19x10- 19 J, C ij =
3.44xlO lo m-I, and Tcrys,Si = 1.3lxlO-IO m. (Cf. Problem 5.18 in the textbook)
(Xu)

Answer:

(a) The terms in the equation are in turn: Coulombic term, nuclear repulsion
term, dipole-dipole attraction term, and ion-dipole attraction term. The last two

15

10

-I.h.s. of 5
Eq. (5.58)
o
-5

-10
2.2 2.4 2.6 2.8 3.0
r x108 (em)

Figure 5.10. Detennination of the equilibrium distance

between K+ and cr ions in molten KCI according to
Woodcock and Singer theory.
IONIC LIQUIDS 255

terms contain r- 6 and roB, and thus, can only exert influence in a very short range.
In the long range, only the fIrst Coulombic term works as major source of
attraction, i.e., between opposite charged particles. Thus, for the case where Z;Zj
< 0, the contribution of this term is negative, since the attraction lowers the
potential of the system. The second term, the nuclear repulsion term, prevents
these two opposite charge ions from "falling into each other." As r decreases,
the positive contribution of this term rises exponentially, making the potential of
the system higher than zero (no interaction state).

(b) The parameter that accounts for the repulsive interaction is Cij' known as the
"softness parameter". Considering the repulsive term in Eq. (5.59),

<1> I. .j. (rern )= Bl· .j . ex:pC l.j.Icr

\ l.j
. -rl .j .) (5.60)

Taking logarithms on both sides of this equation,

In<1> I .j. {rep}=lnB I. .j. +C I .j·cr I .j . -Cr

l .j l .j
· (5.61 )

The slope (or steepness) of the curve In <1> i .} {rep} against r is given by

O<l> i .} (rep)
-~--=-C · . (5.62)
8r l .j

Putting it in words, when two ions approach each other, the increase of the
repulsion potential depends on the value of C;.j'

(c) For molten silicate, at the equilibrium distance of 3.2xIO- IO m the two last
terms in Eq. (5.59) can be considered negligible. Thus,

<1> I..
,j
(r}=A I.,j. ziz) +B·I ,j.exp[CI ,j . (cr I.,j. -r·I ,j.)]
ri,} (5.63)
= <1>.l,j. (Caul) + <1> l,j
. . (rern )

Since force is defIned as (cf. Table 4.1 in the textbook) Force = - O<l> , then
8r

O<l> i ,} (Coul) Zi Z}
F(Coul)=- =A- . - - (5.64)
8r l,j 2
ri ,}
256 CHAPTER 5

and

F ( rep) = ()¢)i.j
8r
(rep)
= B·I.J.C I.J. exp [ (
C·I.J. (F I.J. - rI .J.
)]
(5.65)

At r = 3.2xlO'lO m, Eq. (5.64) and (5.65) become, in the mksa system,

r
2 2
F(Cou/)= zSieO
2 (5.66)
41Z'&or (1.l12X 10-10 C 2 J-Im -I )( 3.2x 10-10 m

-8
=3.604xlO N

and

F(rep)= ( O.l9xlO -19 J )( 3.44xlO 10 m -I)

(5.67)
xexp {3.44xlO 10 m -I [ 3.2-2 (1.31
) ] xlO -10 m }=0.4S1xlO -8 N

At the equilibrium distance of 3.2 A, the contribution to the repulsive force

is mainly from Coulombic like charge. The above results show the great
repulsion existing between Si+4 centers, and therefore, the possibility of breaking
up the network when a nucleophile is present (cf. Exercise 5.1S).

5.24 In the Furth-hole model for molten salts, the primary attraction is that
it allows a rationalization of the empirical expression E' = 3.74 RTm.p.• In
this model, fluctuations of the structure allow openings (holes) to occur and
to exist for a short time. (a) Using the probability curve obtained for NaCI
at 900°C in Exercise 5.3, probe that the mean-hole size turns out to be
about the size of the ions in the molten salt. (b) Determine the probability of
finding a hole that is two times the most probable hole size, and (c) the
probability of finding a hole that would allow paired-vacancy diffusion.
Comment on your results. (Cf. Problem 5.13 in the textbook) (Bockris-
GamboaAldeco)

Answer:

(a) The most probable hole size is given by the maximum in the plot Pr VS. r.
Thus, from Exercise 5.3, this graph was obtained for NaCI, with a maximum at a
IONIC LIQUIDS 257

hole radius of 190 pm. Now, the area under the whole curve Pr vs. r represents
the total probability of finding holes any size, i.e.,

(5.68)

The fraction of holes of sizes "around" the most probable (or must
populous) radius rmax is represented as rmax :I LIr, and is given by

(5.69)

The next step is to decided what the value of LIr is. To keep the hole size
close to the value of rmax, the variation is allowed to be, say I % of rmax' Thus,
I1r = O.Olrmax = 0.01(190 pm) ~ 2 pm, that is, 188 pm < rmax < 192 pm. To
evaluate the integral in Eq. (5.69), one makes use of the Pr vs. r plot in Fig. 5.1.
At rmax = 190 pm, Pr ma., = 0.007375 pm -J . Then the integral in Eq. (5.69) can
be approximated as

rl92pmpr ....,
JJ88pm ~ r ...., ( 211r ) = ( 0.007375 pm - I )4pm
dr""P ( ) =0.028 (5.70)

That is, about 3% of the holes have a radius between 192 pm and 188 pm. Since
rNa+= 95 pm and rC/_ = 181 pm, only one ion is allowed to jump into one hole.

(b) The probability of rmding a hole twice as large as the most probable hole
size is equivalent to finding the probability of the existence of a hole of radius
equal to rho/e = 2rmax = 2(190 pm) = 380 pm. At this value of r, an Pr holf! =
0.000058 pm- l is obtained from Exercise 5.3. With LIr = 2 pm,

r382pmpr
JJ78pm hole
dr~Pr hoI,
(2I1r)=(0.000058 pm- J )(4 pm)=0.00023 (5.71)

that is, 0.023% of the holes have a radius between 378 and 382 pm, which
corresponds only to approximately I % of the probability of finding a hole of
radius rmax.'
258 CHAPTERS

(c) To fit a pair Na+-Cr into a hole, one has to sum their radii, and consider the
decrease of the internuclear distance in the fused salt as compared to that in the
crystal. The internuclear distance between the two ions is
rNa + + r cr = 95 pm + 181 pm = 276 pm . The internuclear distance in fused

salts shrinks by approximately 5% (cf. Table 5.9 in the textbook). Thus,

r pa ir=0.95(276pm)=262pm . At this radius, Pr =0.0034pm- 1 is
fJ'I l'
obtained from Exercise 5.3. With Llr = 2 pm,

J
P'fJ'Il' +t>r Pr
P
'pair
- t>r hoI.
dr r::: Pr . (2Llr)= (0.0034 pm -I
fJ'I"
)(4 pm)= 0.014 (5.72)

i.e., 1.4% is the probability of finding a hole of the size ofa Na+-Cr pair. This
corresponds to about half the probability of finding a hole of rmax.

5.25 (a) A general equation for obtaining average values is ( x ) = r xPx dx •

This equation, together with the results of the hole model, was used in the
textbook to obtain the average radius of a hole for ionic liquids. Using a
similar procedure, derive the average surface area, (s), of the holes in ionic
liquids. (b) Determine again the average surface area of the holes, (s')" but
using this time the equation of the average radius of a hole. What
conclusions can you withdraw from comparing the surface areas (s), and
(s')? (c) Do similar calculations to determine the average volume of the

r
holes, i.e., ('" and (v'). Hint: The gamma function, defined as
r (n)= t n-I e- t dt has the following properties: (i) r(1/2) = .r;, (ii)

r (n+l) = n! , when n is a positive integral, (iii) r(n+1) = n r(n) when n is a

positive real. (Cf. Problem 5.3 in the textbook) (Xu)

Answer:

(a) The holes in ionic liquids can be viewed as spheres with radius r, and thus,
with surface area s = 4JlT2• The average surface area can be obtained from the
general procedure of obtaining average properties with known probability (cf.
Eq. 5.40 in the textbook). In this case, the probability ofthe existence of a given
hole is given by (cf. Eq. 5.39 in the textbook)

16 7 / 2 6 _ar 2
Prdr= 112 a r e dr (5.73)
157r
IONIC LIQUIDS 259

with a = 4 nr / dT (cf. Eq. 5.35 in the textbook). Therefore, the average-surface

area (s) is,

(5 .74)

If t=ar 2 , then r=(t/a)/2and dr=I/2(at)1/2 dt. Therefore, Eq. (5.74)

becomes,

1/ 2
() 321! r" 7 / 2 -t d
s =---Jo t e t (5.75)
15 a 0

·
The mtegra r" t 7 / 2 e -t dt IS
I JO · the gamma fun·
ctlon, r() r" t n- I e - t dt ,
n = Jo
when n = 9/2 (cf. Appendix 5.2 in the textbook). Thus,

ro t 7 / 2 e -t dt= r(9)
-
2
(5.76)

and Eq. (5.75) becomes,

112 r ( .2. )
(s) = 32 _1!_ (5.77)
15 a 2

To evaluate the gamma function we make use of its properties. Thus,

(5.78)

Substituting Eq. (5.78) and the constant a = 4nr / dT into Eq. (5.77),
260 CHAPTER 5

( s ) = 2. kT = 3.5 kT (5.79)
2 r r
(b) The average-hole radius, (r), is given by (cf. Eq. 5.44 in the textbook),

(r)= -
5tr
8ffT-r (5 .80)

If it is considered that all the holes are the same size, then the surface area of the
holes, s ', is given by,

2
,
(s )=4tr(r) =4tr
2
-~
( 8 kT ] 256 kT
=--=3.3-
kT
(5.81)
5tr r 25tr r r
which is in good agreement with the average surface area calculated in (a). This
means that all the holes are approximately the same size, i.e. , the average size.

(c) Similarly to Eq. (5.74), the average-hole volume can be calculated as

(v)= rv,Pr dr = r(i7/T 3 . 16 a7/2r6e-ar2 Jdr

o 0 3 15tr 112
64.[; 7/2
=--a
45
r
0
9
r e
_ar dr2
(5.82)

If t = ar 2 , (V) becomes,

32 \/ 2 32 \/ 2
(v) =__ tr_ roo t 4 e-t dt=--tr-r(5) (5.83)
45 a 3 / 2 JO 45 a 3 / 2

However, r(5)= 4/= 24. Thus,

IONIC LIQUIDS 261

Now, considering the average-hole radius, (r),

which supports the result in (b).

5.26 Using the results of Problem 5.25, calculate the work needed to make a
hole of average size at 900°C in any molten salt if the Furth's "nearly-
boiling assumption" holds. (Cf. Problem 5.3 in the textbook) (Xu)

Answer:

With FUrth' s assumption that molten salts are at nearly boiling state (i.e.,
the internal and external pressure experienced by the hole balance each other),
the work in forming a hole comes only from the surface work contribution (cf.
Eq. 5.33 in the textbook);

W=(s}r (5 .86)

The average surface area of holes in ionic liquids is given by the results
obtained in Eq. (5.79) in Problem 5.25(a), namely,

7 kT
(s)=-- (5.87)
2 r

Substituting (s) from Eq. (5.87) into Eq. (5.86),

262 CHAPTER 5

This is the work needed to fonn a single hole. For one mole of holes,

W =( 5.66x 10 -20 J )( 6.022x 10 23 mol -I ) =3.4lxl0 4J mol

-1 (5.89)

5.27 When a liquid supercools (i.e., does not crystallize when its
temperature drops below the thermodynamic melting point), the liquid-like
structure is frozen due to the high viscosity of the system. The state of
supercooled liquid is in a so-called visco-elastic state. If the crystallization
could be further avoided as temperature continues to drop, glass transition
happens at a certain temperature, Tg , where the "frozen liquid" turns into a
brittle, rigid state known as glassy state. A well accepted definition for glass
transition indicates its formation when the relaxation time of the system, T,
is 200 s, or its viscosity, 17, is 10 12 Pa s (an arbitrary standard, of course!).
(a) Calculate the average distance an ion can travel during the period of a
single relaxation time in a substance with room-temperature glass
transition. (b) A simple relation between relaxation time and viscosity exists
in all liquids down to the glass transition temperature, T = K17, where K has
a very small temperature dependence and can be regarded as a constant
independent of temperature. Obtain this constant and calculate the
theoretical upper limit of the viscosity of liquids, considering the fact that
the electronic relaxation time measured in the far-infrared region is 10-13 s.
(Cf. Problem 5.19 in the textbook) (Xu)

Answer:

(a) The mean square distance the ion can travel during this time period is given
by the Einstein equation (cf. Eq. 4.27 in the textbook):

(5.90)

where rrepresents a single relaxation time (T = 200 s) by the definition of the

glass transition temperature (Tg ) given above. Assuming the ion's radius is of
the order of 10- 10 m, a typical molecular size, then, its diffusivity is given by the
Einstein-Stokes equation (cf. Eq. 5.58 in the textbook):

( 1.381 x 10 -23 JK -I )(298K)

kT IN m IPa
D=--= x--x--- (5.91)
61tW 6 (10 12 pas)(1O- IO m) 1J INm - 2
IONIC LIQUIDS 263

Substituting this value of D into equation (5.90),

( x ) 2 =2 ( 2.18xlO -24 m 2 s - I ) ()
200 s =8.73xlO -22 m 2 (5.92)

or,

(5.93)

The value of (x) from Eq. (5.93) is smaller than the size of the ion.

(b) At the glass transition temperature, Tg, t' = 200 s and 7] = 10 12 Pa s, and the
constant K can be obtained from the given equation t' = K 7] • Thus,

t' 200s -10-1

K=-= =2xlO Pa (5.94)
7] 10 12 Pa s

For any liquid, as temperature goes up the viscosity drops, and the
relaxation time becomes shorter and shorter (cf. Eq. 5.94). However, the time
cannot become shorter than the electronic relaxation time, in this case, 10-13 s.
This value is therefore taken as the theoretical upper limit for relaxation time at
"extremely-high" temperatures (of course, no liquid can be heated up to this
temperature without chemical decomposition, hence it represents a theoretical
state). At this "extremely-high" temperature, the viscosity is,

t' lxlO- 13 s -4
7]=-= =5.0xlO Pas (5.95)
K 2xlO-10pa-1

This is the limiting value of viscosity of liquids at high temperatures.

5.2S Using the data in Table 5.1S in the textbook, determine the self-
diffusion coefficient of the given ions at 1100 K. What phenomenological
conclusions can you withdraw from these results? Give reasonable
explanations for your conclusions. (GamboaAldeco)
264 CHAPTER 5

Answer:

The table below shows the values of Do and E; for the diffusion
coefficient equation given in Table 5.18 in the textbook. The diffusion
coefficient can be calculated using these parameters by the equation (cf. Eq.
5.55 in the textbook),

(5 .96)

The values of D calculated using Eq. (5.90) are shown in the last column of
the following table:

Molten saltlTracer Do x 105

(cm2 S·I) E; Dx 105
(cm2 S·I)
(kJ mor l )
NaCIPNa 2.1 29.87 8.01
NaCIP 6Cl 1.9 31.09 6.34
KCl!,2K 1.8 28.78 7.73
KCl/36Cl 1.8 29.83 6.89
CaC12!,sCa 0.38 25.65 2.30
CaCli 6Cl 1.9 37.07 3.30
srCll9sr 0.21 22.51 1.79
SrCl 2P 6Cl 0.77 28.79 3.30
BaCl/ 4°Ba 0.64 37.49 1.06
BaChP6Cl 2.0 39.66 2.62
CdCI/ISCd 1.1 28.62 4.81
CaC1 2/36Cl 1.1 28.45 4.90

Conclusions: (i) The monovalent cations have larger D' s than the divalent
cations (e.g., DNa,NoCl and D ca,coCI2)' (ii) As the size of the cation in the same
group in the periodic table increases, the diffusion coefficient decreases (e.g.,
Dca CoCI2 and DBa'BoCd. (iii) The diffusion coefficient of the anion in the 1: 1 salts
is smaller than that of the cation (e.g., DNaNaCI and DCINoClo). (iv) The trend in
(iii) reverses in the 1:2 salts (e.g., D ca,coCl2 and DC/ coCI2 ). (v) The diffusion
coefficient of the anions in the I: I salts is twice as large as that in the 1:2 salts
(e.g., DCI' NoCl and DCI/coCI2).

Explanations: Comparing monovalent and divalent cations, the divalent cations

have more bonds to break before they can jump to another site. Their movement
through the liquid is therefore more difficult than a monovalent ion with less
IONIC LIQUIDS 265

bonds, explaining their smaller D's [c.f. (i) above). Larger ions need greater
local rearrangement at a site before they can jump into it. As a result, the total
energy involved in the moving process is larger and diffusion more difficult
(Le., smaller D.) This accounts for the decrease of D as the cations size increases
[cf. (ii) above], and for the decrease of anion's D as compared with the cation in
the 1:1 salts [cf. (iii) above]. The smaller D's of the divalent cations as
compared to that of the anions can be explained considering that the difference
of energy involved in the breaking of bonds is larger than that accounting for the
different size ofthe ions [cf. (iv) above]. The jump barrier energy ofthe chloride
ions is larger in the 1:2 salts than in the 1: 1 salts. This is due to the larger
attraction these ions have with the divalent cations, making their movement
more difficult and thus, decreasing their D's [cf. (v) above].

5.29 The conductance calculated from the Nernst-Einstein equation is

several tenths of percent more than that measured. An interpretation is that
the diffusion coefficient includes contributions from jumps into paired
vacancies and these (having no net charge) would contribute nothing to the
conductance while fully counting for the diffusion. (a) Using the Stokes-
Einstein equation, calculate the self-diffusion coefficient of the Na + and cr
ions and that of the paired Na+-Cr at 1173 K. (b) Calculate the real
equivalent conductivity, that is, the measured value whether pairs would
not be present. (c) Considering now the diffusion due to Na-CI pairs, find
the equivalent conductivity that would have been measured. How much
grater would the Nernst-Einstein equation indicate the conductivity to be
than it really is? Consider the mean-hole radius of the pair Na+-Cr as 262
pm and those ofNa+ and cr as 95 pm and 181 pm, respectively (cf. Problem
5.22). The viscosity of fused NaCI is 1.05 cpoise. (Cf. Problem 5.10 in the
textbook) (Bockris-GamboaAldeco)

Answer:

(a) From Stokes-Einstein equation (cf. Eq. 5.58 in the textbook),

kT (1.38XIO- 16 ergK- 1 )(1l73K)

D pair = - - - =
6""pair1] 6"( 262xl0- IO cm )(O.Ol05 Poise)
(5.97)
2 -2
1poise Igcm s -5 2-1
x x = 3.12xl0 cm s
-I -I 1
Igcm s erg
266 CHAPTER 5

2
In the same way, DNa + =8.6lxl0 ~ cm s
~
and D cr = 4.52xlO-5cm
21
s-
These two values were not obtained experimentally, and thus, correspond to
individual values of diffusion coefficients, i.e., D No +. ind and DCI-,ind.

(b) Using the Nemst-Einstein equation for a 1:1 electrolyte (cf. Eq. 5.61 in the
textbook):

A'= F2 (D +D _ )

r
+
RT Na ,ind Cl ,ind

(96500ceq - 1
= (8.61+4.52)xIO- 5 cm 2 s- 1 (5.98)
(8.314JmOI- 1 K-1 )(1173K)

1] IVn-1 2 -1
x--x = 125 Scm eq
ICV ICs- 1

(c) If the diffusion coefficients were detennined by tracer experiments instead of

calculated as done in (a), then, the equivalent conductivity would have been (cf.
Eq. 5.76 in the textbook)

2F2
Aca/c = A'+--Dpair
RT

(5.99)

IJ I vn- I 2 -1
x - - x - - - 184Scm eq
ICV ICs- 1

Comparing Eqs. (5.98) and (5.99) indicates that the Nemst-Einstein equation
would have given a value of the equivalent conductivity 47% larger than it is in
reality.

5.30 The relaxation time r and the viscosity 17 are variables whose
temperllture dependence follows a non-Arrhenius behavior, i.e., they are of
the type exp(BTtIT-To), instead of the well known Arrhenius trend, i.e.,
IONIC LIQUIDS 267

exp(E,/Rn. In this non-Arrhenius equation, To represents a characteristic

temperature, and the constant B is an important characteristic of the
structure of the liquid, whose inverse is known as the fragility of the liquid.
Thus, the larger the value ofB, the stronger (or the less fragile) the liquid is.
(a) Write the non-Arrhenius equations for relaxation time and viscosity. (b)
What type of plots would differentiate the Arrhenius from the non-
Arrhenius behavior? (c) Explain how the value of B differentiates these two
types of behavior. (d) How would the strong and fragile liquids be identified
in the most common plot of In 7J vs. lIT! (Cf. Problem 5.20 in the textbook)
(Xu)

Answer:

(a) The non-Arrhenius equations for the relaxation time and the viscosity are:

BTO BTo
7J=Aexp-- and T=A'exp--- (5.100)
T-To T-To

(b) To analyze the effect of B on the temperature-dependence of the variable, we

can compare an ideal Arrhenius relation with the case of an non-Arrhenius
equation. Taking the viscosity as an example, if its temperature dependence is
strictly Arrhenius, then,

E'l
7J = Aexp- (5.101)
RT
where E" is independent of temperature. Then,

E'l
In7J =lnA+- (5.102)
RT
or,

___ =_R_T = KT (5.103)

In 7J -In A E'l

where K is a constant independent of temperature. Therefore, a plot of

l/(In 7J - In A) vs. T should give a straight line passing through the origin if the
relation between 7J and temperature is of the Arrhenius type (Fig. 5.11).
Similarly, if the temperature dependence is non-Arrhenius,
268 CHAPTER 5

In 1] - In A

t{ Temperature

Figure 5.11. Arrhenius and non-Arrhenius

behavior of viscosity.

To
7]= AexpB-- (5.104)
T-To
or,

BTo
In7] = InA + - - - (5.105)
T-TO

Therefore,

TIl
---=----=KT-- (5.106)
In 7] -In A BT 0 B B

In 11 or InT

Figure 5.12. Behavior of strong and fragile liquids in a

In 7] or In r vs. 1lTgraph.
IONIC LIQUIDS 269

A plot of 1I(In 17 - In A) vs. temperature should be a straight line with a

negative intercept of 11B if the relation between 17 and T is of the non-Arrhenius
type (Fig. 5.11).

(c) For a series of similar systems, the larger B is, the smaller the intercept is,
and the closer the temperature dependence is to the Arrhenius behavior.
Therefore, strong liquids (larger B) have more Arrhenius-like temperature-
dependence of both, viscosity and relaxation time. On the other hand, the fragil
liquids have a more canonical temperature dependence of both, viscosity and
relaxation time (see Fig. 5.12).

(d) In a In 17 or In T vs liT plot, the strong and tragiJ liquids are viewed as
represented in Fig. 5.12.

5.31 The Addam-Gibbs theory assumes that the energy barrier to the
formation of a transport process is proportional to the product of the
activation free energy, Ap, and a certain critical size, z*, of a subsystem,
whose cooperation is needed in the transport. Hence, according to the
universal Boltzmann relation, the probability for such a process to happen
is,

(5.107)

where Ap, Sc' and To could be viewed as constants independent of

temperature but characteristic of the system. Prove that the temperature-
dependencies of the relaxation time T and viscosity 17 of super-cooled
liquids are both non-Arrhenius, i.e., of the exp(BTo / T - To) type, where To
is a characteristic temperature. (Cf. Exercise 5.29 in .the textbook) (Xu)

Answer:

The viscosity, which is resistance to the transport process, should be

inversely proportional to the probability of the process to happen with a pre-
exponential term A. Using Eq. (5.107), the viscosity can be written as,

[ · 1 [ 1
A apSe To BTo
17 = - = A exp = A exp (5.108)
P kC(T-T o ) T-To
270 CHAPTER 5

where B is a constant independent of temperature, i.e., B = dp Sc *lkC. The pre-

exponential term, A, mayor may not have temperature dependence, but its
influence on the temperature dependence is trivial as long as T »To, i.e., in the
state of most supercooled liquids and all true liquids. Thus, from T = K7], a
similar temperature dependence can be derived, for the relaxation time, i.e.,

T=A'exp [ -BTo
--
T-To
1 (5.109)

5.32 Ca(N03)z-KN03 or better known as CKN, is a well known molten salt

that easily vitrifies upon cooling. An attempt to ascertain the fragility of this
system (d. Problem 5.30) was made on a CKN sample with a glass
temperature of Tg of 80 °c (d. Problem 5.27). This sample was heated up to
120°C and its dielectric-relaxation time was measured by an impedance
bridge as 10-2 s. Using also the data from Problems 5.27 and 5.30 classify
this ionic liquid. (Cf. Exercise 5.30 in the textbook) (Xu)

Answer:

Using the equation Eq. (5.100),

BTo
T=A'exp--- (5.110)
T-To

When T = 00, the exponential in Eq. (5.110) becomes exp(BTol T-To) 7 1, and
therefore, T = A' . Thus, A' becomes the value of the relaxation time at
extremely high temperature. From Problem 5.27 it is known that A' = 10- 13 s. At
T = Tg = 80°C = 353 K, the relaxation time is T = 200 s, by definition of Tgo
Hence, from Eq. (5.110)

( -13)s exp---
200s= 10 BTo (5.111)
353-T o
In the same way, at T = 120°C = 393 K, the relaxation time is T= 0.01 s,

( -13)s e x393-
0.01 s = 10 BTo
p ---
To
(5.112)
IONIC L1aUIDS 271

From these two equations, the values of B and To can be obtained. Thus,
from Eq. (5.111),

-13 BTo
In 200 = In 10 + -----'- or BTO =35.2(353-To ) (5.113)
353- To

and from Eq. (5.112),

-13 35.2(353-To )
InO.01 = In10 +----'----'--'- (5.114)
353 - T o

or To = 250 K and B = 14.4. The value of B = 14.4 is a small value compared

with 100 for pure silicate (cf. Problem 5.27). Therefore, CKN is a rather fragile
liquid.

5.33 Calculate the transport numbers of the cation and the anion in molten
CsCI at 943 K. The experimental equivalent conductivity of the fused salt is
67.7 S COIl eq-l. The observed diffusion coefficients of Cs+ and cr ions in
molten CsCI are 3.5x10-5 COIl S-I and 3.SxlO-5 COIl S-I, respectively. (Cf.
Problem 5.IS in the textbook) (Contractor)

Answer:

According to the procedure to determine transport numbers in fused salts

based on conductivity measurements (cf. Section 5.6.7.3 in the textbook), the
first step is to determine the diffusion coefficient of the pair Na-Cl, Le., DNa-CI.
This can be calculated by applying the Nemst-Einstein equation to fused salts
(cf. Eq. 5.76 in the textbook):

2
A ' = A calc - -
2zF- D Cs-CI (5.115)
RT

or

DCs-CI = (A calc - A') RT2 (5.116)

2zF

where A ca1c , the calculated equivalent conductivity, is (cf. Eq. 5.75 in the
textbook)
272 CHAPTER 5

r
zF2 ( )
A calc = RT D Cs + + D Cl-

(1)( 96500C eq -I
-:---'------:---'---(3.5 + 3.8)x 10 -5 cm 2 s -I (5.117)
(8.314J mol-1K - I )(943K)

1J IV lA 2 -I
x--x--x--=86.7Scm eq
lCV IAn lCs-1

Substituting Eq. (5.117) as well as the value of A ' into Eq. (5.116)

(86.7 - 67.7)S cm 2 eq -I ( 8.314J mol-I K -I )(943 K)

D Cs - CI = 2 (5.118)
2(1)(96500ceq - l )
2 -I
x lC ns =800
. x 10-6 cms
2-1
1J

Once DCs-c/ is known, the next step is calculate the individual diffusion
coefficients, Dcs+ ind and Dc/-ind, of the independently jumping Cs+ and cr ions
(cf. Eqs. 5.80 and 5.81 in the textbook):

-5 -I -5-1
DCs +ind =D~s + -D Cs - CI =3.5xlO cms -0.8xlO cms
(5.119)
=2.7xl0-5 cms- I

and

-5 -I -5-1
DCrind =D~r -DCs-CI =3.8xl0 cms -0.8xlO cms
(5.120)
=3.0xlO- 5 cms- I

Finally, the transport numbers are determined from the Einstein relation (cf.
Eq. 4.172 in the textbook) and the relation between absolute and relative
mobilities (cf. Eq. 5.84 in the textbook):
IONIC LIQUIDS 273

DCS+ind 2.7xI0- 5 cms- 1

t Cs + = - - - - - - - - = - - - - - - - - - = 0.47 (5.121)
DCs+ind + Dcrind (2.7+3.0)xI0- 5 cms-1

and

(5.122)

5.34 (a) Using the observed and calculated values of the equivalent
conductivity at different temperatures given in Table 5.27 in the textbook
for NaCI, find out the temperature dependence of the coordinated diffusion
coefficient, i.e., the D Na- Ci vs. T plot (b) Determine the transport numbers of
Na + and cr in the molten salt. The self-diffusion coefficients of Na + and cr
in NaCI measured by the radiotracer method at Ill3 K are D Na+= 9.60xI0-5
cm2 S-I and D CI_ = 6.70xI0-s cm 2 S-I. (c) The difference between calculated
and observed equivalent conductivities is often phenomenologically
attributed to the association (either permanently or transient) of cations
and anions in the molten salt. What is the temperature dependence of this
"association degree", and how would you explain the seeming contradiction
with our knowledge about cation-anion interaction (cf. Problem 5.22)? (Cf.
Problem 5.9 in the textbook) (Xu)

Answer:

(a) The diffusion coefficients measured by the radiotracer method include the
contribution of the coordinated Na+ and cr pairs, i.e., DNa-CI. However, DNa-C1
does not contribute to the current carrying flux. Therefore, in order to obtain the
transport number, the independent diffusion coefficients of Na+ and cr are
needed. From Table 5.27 in the textbook, the difference between the measured
and the calculated equivalent conductivity can be used to derive the diffusion
coefficients of the coordinated jump of Na+ and cr. Thus, using the values of
equivalent conductivities at 1093 K, DNa-Ci is (cf. Eq. 5.76 in the textbook)

D Na - CI = RT2 (A ca1c - A') (5.123)

2zF

r
( 8.314JK- 1 mot- 1 )(I093K)( ) _I
= ')IS cm 2 eq -I
... xI VC
--xIcns
---
2(1)(96500cmOI- 1 lJ IV

=l.03xIO-5 cm 2 s- 1
274 CHAPTERS

In the same way for the other temperatures.

T{K2 1093 1143 1193 1293

A' (S cm2 eq'l) 138 147 155 171
A ca1c (S cm 2 eq'l) 159 177 198 240
A ca1c - A ' 21 30 43 69
DNa-cl !cm2 S'I~ 1.03xl0,5 1.53xlO,5 2.29x 10,5 3.98xlO's

Figure 5.13 shows the corresponding variation of DNa-Cl vs. T.

(b) The transport numbers for a 1: 1 salt as a function of the corresponding

independent diffusion coefficients can be calculated as (cf. Eq. 5.84 in the
textbook).

D; (ind)
t· =----~~~---- (5.124)
I D; (ind)+ D j (ind)

To determine the independent diffusion coefficients of Na+ and cr. we

make use of the equation (cf. Eqs. 5.80 and 5.81 in the textbook):

(5.125)

4 •

2 •
•
•
o~~----~----~--~--~~~
1100 1150 1200 1250 1300
T(K)

Figure 5.13. Temperature dependence of the coordinated

diffusion coefficient of fused NaCI.
IONIC LIQUIDS 275

From Fig. 5.13, DNa-CJ is found to have a strong temperature dependence.

The value of D Na-CJ at 1113 K can be obtained by a rough interpolation at this
temperature, i.e., DNa-cJ (l113K) = 1.23xlO-s cm2 S-I. Substituting the
corresponding values into Eq. (5.125),

-5-5
DNa+ ( ind ) =D~a+ -D Na - CI =9.60xlO -1.23x10
(5.126)
= 8.37 x 10 -5 cm 2 s -I

and

-5-5
Dcr ( ind ) =D~r -D Na- CI =6.70xI0 -1.23x10
(5.127)
=5.47xI0- 5 cm 2 s- 1

The transport numbers are, then, from Eq. (5.124),

8.37 x10- 5
t Na + =- - - - - - - - - = 0.60 (5.128)
8.37 xlO -5 +5.47 xlO- 5

and

t cr =I - 0.60 = 0.40 (5.129)

(c) As shown in the table above, the difference of Acalc - A' increases with
temperature. This is the same as saying that the "association degree" rises with
temperature. Furthermore, one would conclude that association between cation
and anion is an endothermic process, which is favored as temperature rises. This
contrasts our knowledge about ion interaction, because it is known that
Coulombic attraction dominates the cation-anion pairing.
The reason for this discrepancy is that the "association" used here no longer
involves the ion-pair formation in solvent-containing electrolytes, where both
ions have "real" interactions and must stay for a relatively long time in the
solvent sheath. In solvent-free electrolytes like molten salts, the "association" is
much broader, including the paired jumps of both ions without interaction.
When temperature goes up, the portion of "paired jump" increases as the total
diffusion coefficient increases.
276 CHAPTERS

5.35 Consider the data in Figs. 5.50 and 5.51 in the textbook on diffusion
coefficients as a function of temperature and pressure for the diffusion of
134CS ion in molten NaN03• Using these data find the heats of activation for
the processes of hole-/ormation and jump-into-a-hole. Discuss whether they
conform more to the jump-into-a-hole (FOrth) model, or the shuffle-along
(Swallin) model of transportation. (GamboaAldeco)

Answer:

The heat of activation for the processes of hole formation (LVrH ) and
jumping-into-a-hole (LVrJ ) are given by the equations (cf. Eqs. 5.116 and 5.117
in the textbook),

- R[ aIn D
a(l/T)
1
p
AU*-
=ilI1H AU*-
+ilI1J (5.130)

and

-R[ alnD
a(l/T)
1 V
= Mf~ (5.131)

From Fig. 5.51 in the textbook, the corresponding pressure and temperature
values at a constant molar volume of, say, 45 cm3 mor\ are :

Vm = 45 cm3 mol -I
T 350 °c (623 K) 370 °c (643 K) 390 °c (663 K) 420 °c (693 K)
P oatm 400 atm 730 atm 1200 atm

Using these pairs of data of temperature and pressure, the corresponding values
of diffusion coefficient can be obtained from Fig. 5.50 in the textbook:

liT {K') 0.00161 0.00153 0.00151 0.00144

[loglO D (cm2 s-I)]v 5.365 5.375 5.385 5.405
= -4.635 = -4.625 = -4.615 = -4.595
[In D (cm 2 S-I~JV -10.672 -10.649 -10.626 -10.580
IONIC LIQUIDS 277

The corresponding graph at constant volume is given in Fig. 5.14. The slope
of the corresponding curve is

[ oIn D
o(lIT)
1 V
= -538.61 K (5.132)

Substituting this value into Eq. (5.131),

!ili J;t. = - (
8.314 JK - \ mol - \ ) (
- 538.61 K ) = 4.478 kJ mol -I (5.133)

Now, from the same Fig. 5.50 in the textbook, the diffusion coefficients at
different temperatures and at a constant pressure of 800 atm are,

]IT(K J) 0.00161 0.00153 0.00151 0.00144

[logJO D (cm2s· I)]p 5.265 5.320 5.380 5.450
= -4.735 = -4.680 = -4.620 = -4.550
[In D (cm 2s")]p -10.903 -10.776 -10.638 -10.477

Plotting In D vs. T at constant pressure gives the plot shown in Fig. 5.14.
The slope of this curve is

-1 0.4 ,....--,--~-.---~--r--~-,---,

-10.5

-10.6
In D (cm2 s")
-10.7

-10.8

-10.9
0.00145 0.00150 0.00155 0.00160
1fT (1("')

Figure 5.14. Plots of logarithm of the diffusion coefficient as

a function of temperature at constant pressure and constant
volume for the diffusion of 13..CS ion in molten NaN03 .
278 CHAPTER 5

[ oInD
o(l/T)
1
p
= -2520.88 K (5.134)

Substituting this value as well as the value of Mf/ from Eq. (5 .133) into Eq.
(5.130), and solving for MfH~'

'" (
MfH =- 8.314JK -\ mol -\ )(-2520.88K ) -4478Jmol -\
(5.135)
-I
= 16.480 kJ mol

If Mf/ / MfH~ < 0.3, then the make-hole-then-jump-in model makes sense. In
this case, from Eqs. (5.133) and (5.135),

-\
4.478kJmol
= 0.271 < 0.3 (5 .136)
-\
16.480kJ mol

which means that the make-hole-then-jump-in model better describes the process
of transportation of 134CS ion in molten NaN03•

5.36 Figures 5.29 and 5.68 in the textbook show two plots of viscosity as a
function of temperature for a molten salt and liquid SiOz. Determine the
energy of activation for these two systems. What are the relative diffusion
coefficients at their melting pOints considering the Do's to be approximately
equal? Comment on your results. (GamboaAldeco)

Answer:

The activation energy, Err, can be obtained from the equation,

or
'"
E1] 1
In1] = In1]o + - - (5.137)
R T

This equation indicates that the slope of a In 1] vs. liT plot is equal to E,/IR.
Therefore, from the plot of viscosity as a function of temperature in the range
1000 to 1250 K for the molten salt in Fig. 5.29 in the textbook, m = E'I~/R =
2500 Kor
IONIC LIQUIDS 279

E77'" = ( 2500K )( 8.314JK -I mol -I ) =20.79kJmol -1 (5.138)

In the same form, from the slope of the plot for Si02 in Fig. 5.68 in the
textbook in the range 2200-2300 K" m = E,/,IR = 29500 K or,

E77'" = ( 29500K )( 8.314JK -I mol -I ) = 24S.26kJmol -1 (5.139)

Considering E,/, "" ED" (cf. Eq. 5.60 in the textbook), then, the self-
diffusion coefficient can be approximated as,

-E,; I RT
D=Doe (5.140)

D m.s .
D Si02

(5.141)

Evaluating Eq. (5.141)

Dm .s . [ 20790J
D Si02 ""exp - ( 8.314JK-1 mo/-I )(1074K)
(5.142)

+ 245260J ] = l.SxlOS
( 8.314JK-1 mo/- I )(2073)

This equation indicates that the diffusion coefficient of the molten salt is
about lOs times greater than that of the liquid Si02.

Comment: The diffusion coefficient is directly related to the mobility of the

species (cf. Eq. 4.172 in the textbook). The mobility and, therefore, the specific
280 CHAPTER 5

conductivity of the molten salt are expected to be 105 times greater than that of
the liquid Si02 (cf. Table 5.44 in the textbook). The big difference in
conductivities is because molten salts are constituted by ionic lattices that upon
melting form highly conductive ionic liquids, in contrast to Si02 that fusses into
an associated liquid.

5.37 Assuming a 3~coordination exclusively for B as well asa planar

structure in borate glasses (a) determine the formula of the glass, and (b)
calculate the moles of base (e.g.Na20) needed to form a chain structure.
(Xu)

Answer:

The three coordinated boron has all its bonds on the same plane, therefore
the borate glass has a sheet-like structure as shown in Fig. 5.15. The Lewis
center, B+3 in this case, can be attacked by oxygen anions and the network gets
ruptured as shown in Fig. 5.16. It can be seen that one mole ofNa20 breaks one
mole of B-O bonds. To transform the 2D sheets into ID chain, one out of the
three B-O bonds must be broken for every boron center, i.e., the ring has to be
broken in one point. Since 1.0 mole of pure borate, B20 3, has

3NB =3(lmol)(6.022xl0 23 ) = 1.8xl024 B-O bonds (5 .143)

Therefore for every mole of borate to form aiD chain, mole of B-O
bonds need to be broken, and the amount of Na20 needed is 1 mole. So, the
component of ID borate glass should be:

(5.144)

and its formula, NaB02•

0\ /0
8-0-8
/ \
"
o 0
or:
/
'0
8-0-8 etc ....

I
Figure 5.15. Planar structure of Na 20 considering only a 3-coordination.
 >--f<
IONIC LIQUIDS 281

:0.2

+ (Na)"!·

Na+

+
>-O'+Na + Na+'0--a(

Figure. 5.16. Attack of Na20 to borate glass.

5.38 According to Adam-Gibbs theory, the constant B in the non-Arrhenius

equation for viscosity (d. Problem 5.31) is given by,

(5.145)

where LJp, Sc·, k and C are the activation energy for the transport process,
the configurational entropy of the subsystem, the Boltzmann constant, and
a proportionality constant in a heat capacity-temperature relation,
respectively. As found in Problem 5.31, the value of B determines the
fragility of the liquid, which can be classified into three categories: strong
(large value of B), intermediate (medium value of B), and fragile (small
value of B). Pure silicate belongs to the strong class, with a B value of ca.
100. As Na20 is added, the fragility increases and the resultant glass passes
via intermediate (B < SO), to fragile (B < 10). Interpret this transformation
on a structural level. (Xu)

Answer:

As Na20 is added to the pure silicate, the Si-O bonds are broken up, and
large chunks of silicate are disintegrated into relatively small pieces with either
chain or ring structure. When the structural unit becomes smaller, so does the
sub-system whose cooperation is required for the transportation process to
happen in the Adam-Gibbs theory. Hence, Sc· , the configurational entropy,
becomes smaller. On the other hand, as the network is being broken up,
viscosity drops, either holes needs much smaller activation energy to form, or
silicate pieces of certain sizes need smaller activation energy to jump into the
282 CHAPTER 5

fonned hole. Both effects, i.e., reduced values of Sc· or ,1p., leads to smaller B
values, or in other words, to a more fragile nature ofthe glass.

MICRO-RESEARCH PROBLEMS

5.39 (a) What is the difference between "average-hole radius, (r)," and
"radius of the most populous hole, r 1IfIVC"? Calculate the most-popular-hole
radius rWUlJO and compare it with (r). (b) If (r) ~ r"""" does this mean that the
majority ofthe holes possess a homogeneous radius? (c) If the answer in the
above question is negative, what parameter is needed to describe the
dispersity of the hole sizes? Quantitatively confirm the validity of the
approximation that "all holes are of the same size in molten salts". Using
the data in Table 5.15 in the textbook, find the above dispersity for KCI
molten salt at 900°C. [Hint: Numerical integration may be needed to solve
question (c»). (Cf. Micro Research 5.2 in the textbook) (Xu)

Answer:

(a) The most popular radius, rmax, refers to the radius of the holes whose number
is larger than the number of holes of any other radius. This number does not
necessarily (and often defmitely not!) stand for majority compared with the total
number of holes present. In other words, the probability takes a maximum at this
radius (see Fig. 5.13). The value of rmax differs from that of (r) unless the
distribution ofr is roughly symmetrical against rmax (Fig. 5.14) Unlike (r), rmax is
not an average value. Since a maximum in the probability corresponds to rmax,
this parameter can be derived from the general procedure for obtaining an

P,

Figure 5.13. Plot of the probability against

the hole radius, showing the difference
between "average hole radius· and the radius
of the "most populous hole".
IONIC LIQUIDS 283

P,

wider
distribution

Figure 5.14. Plot of the hole probability against

the hole radius. When the distribution is
symmetrical, then <1/ = f mox.

extremum as described next. The probability of having a radius between r and

r + dr is known to be (cf. Eq. 5.39 in the textbook):

Pr ur
J 16 7/2 6 -ar 2 J
= r are ur (5.146)
15v1l'

Differentiating Pr with respect to r, one gets,

-d P = - 16
- a 7/2 (6 r 5 e -ar 2 -2ar 7 e -ar 2 )

dr r 15.[;
(5.147)
= -16- a 7/2 (6 r 5- 2ar 7) e -ar 2
15.[;

Equating Eq. (5.147) to zero and solving it for r,

2 3
rmax =- (5.148)
a

Inserting now the value of the parameter a (Eq. 5.35 in the textbook), i.e., a =
4nrl kT,

rmax = ~ 3kT =0.49 ~ kT (5.149)

4nr r

Eq. (5.149) represents the most populous-hole radius, which is very close to
the average radius, (r) of 0.51 JkT / r derived in Eq. (5.44) in the textbook.
284 CHAPTERS

(b) The closeness of r max to ( r ) indicates that the distribution is almost

symmetrical. However, this does not indicate that the majority of the holes
possess a radius in the neighborhood of 0.51 ~ kT / r . This would be equivalent
to thinking that the hole radius has a very narrow distribution. Figure S.14 shows
the comparison of symmetrical distributions with widely and narrowly dispersed
hole-size. In the wide distribution, the average value is always somewhere near
r max, although a large quantity of holes still may possess radii either much larger
or smaller than (r). On the other hand, in the narrow distribution all the holes
have approximately the same size. A wider dispersed hole-size distribution may
have the same average properties than the narrow dispersed distribution, but its
holes possessing radii close to (r) are far from being majority. In this case, the
approximation that "all holes are of the same size" will not hold true. Therefore,
the closeness of r max to (r) is not enough to guarantee a narrowly dispersed hole-
size around (r).

(c) There may be more than one way to solve this problem, and the following is
only a possible path. It is already known, by definition, that the total probability
for holes of all possible sizes is unity, which is the whole area under the curve Pr
vs. r, i.e.,

(S.IS0)

To actually reflect the dispersity of the hole sizes, one needs to know the
probability of existence of holes of sizes "around" the most populous radius rmax'
In other words, one needs to fmd out the radius variation, Llr, that makes the
probability for holes of radii between rmax - Llr and rmax + Llr be, say, SO% of the
total probability for holes of all possible sizes. In this way, the larger Llr is, the
more dispersed is the hole radius distribution. Now that the hole dispersity is
defined as Llr, the problem becomes to solve Llr from the following equation:

(S. ISI)

The integration r max

rmar -~
+~ Pr dr can only be evaluated through numerical

methods. The value of Pr can be obtained from Eq. (S.39) in the textbook, i.e.,
IONIC LIQUIDS 285

16 7 / 2 6 _ar 2
P ---a r e (S.IS2)
r - IS.[;

KCl has a surface tension of 89.5 dyne cm-I (cf. Table S.IS in the textbook.)
From Eq. (S .149), rmax at 900 °c is

( 1.38 x 10 -16 ergK -I )( 1173K )

rmax =0 .49~k; =0.49 -I (S .IS3)

89.Sdynecm
= 2.08x 10 -10 m

With this data, Eq. (S.1S1) can be written as,

(S .IS4)

By trial-and-error, !lr is found to be O.4xlO- IO m. This result means that the

radius of SO% of the holes, is in between 1.68x 10·\0 m and 2.48x 10-\0 m. This
corresponds to a very narrowly dispersed distribution (Fig. S.IS) since!lr is
smaller than half of the size of the studied ion. A relation between various !lr
and (max -6..r
rmox
+~Prdr is plotted in Fig. S.16. This figure shows that as !lr increases

<r> = 2.17x1 0.10 m

6
rmax = 2.08x10·10 m

5 6

Figure 5.15. Plot of the hole probability against the hole radius for
fused KCI at 900 °C.
286 CHAPTER 5

0.8

P, for holes of radius 0.6

between
(rmax - oM) and (rmax + oM)
0.4

0.2

0.0
0.0 0.5 1.0 1.5 2.0
oM (A)

Figure 5.16. Plot of f.rr.... -81'

mar
+I'v d 0
Pr r against l.rfor fused KCI at 900 C.

from OAxlO' lO m to LOx I 0. 10 m, the integration rapidly increases from 0.50 to

0.91. Therefore, the approximation that all the holes present have the same
radius is effective and close to truth.
INDEX

a, see Size parameter a Charge density, 147

Activation energy; see Energy of activation Charge of a dipole, 79
Activity, 110, 116 Charge, excess; see Excess charge
mean, 108 Chemical potential, 98, 128
solvent, 131 Compressibility, 15,39,54
Activity coefficient, , 116, 129, 135,214 adiabatic, 13, 14, 16
mean, 112, 126, 134, 140, 145 Concentration gradient, 156, 173, 188, 205,
Addam-Gibbs theory, 269, 281 214,219
Amperometer, 160 Condenser, 74
Anode, compartment, 177 Conductance, 161, 165, 185, 265
Arrhenius behavior, 266 cell, 166
non-266, 269, 281 Conductivity, 166, 171
Association of ions, 150, 273 cell, 161, 162, 194, 196
Association of molecules, 117 electrical, 242
equivalent, 161 , 162, 171, 172, 174, 183,
Bjerrum's theory, 117, 148, 150 211,217,233,234, 265, 271 , 273
Boiling assumption in Furth model, 261 equivalent at infinite dilution, 167, 194,
Boiling points, elevation of, 84 200, 203, 207,208
Boltzmann, molar, 163, 198
distribution law, 74 specific, 162, 163, 165, 167, 174, 185,
relation, 269 201
Bond, number of, 246 Constants, 6
Bond polarization, 84 Conversion factors, 5
Born Correlation function, 149
entropy of _ hydration, 35 Correspondence principle, 138
term, 23, 25, 64 Coulometer, 160
theory, 32,35, 59,69 Crystallization, 262
Current, 160, 161 , 177, 191 , 206
Capacitor, 79 density, 193,219
Cathode, compartment, 177
Cation-solvent interaction model, 68 Debye effect, 182
Cell, Debye-Falkenhagen equation, 196
constant, 162, 165, 166, 198 Debye-HUckellimiting law, 98,102, 106,
resistance, 162, 166 110,112,114, 119,131,140

287
288 INDEX

Debye-Huckel reciprocal length, 92, 93, Electrochemical cell, 133, 135,217

105, 108, 109, 113, 124,138, 142, 150 Electrolyte, indifferent, 175
Debye-HUckel theory, 104,119,131 , 148, Electronegativity, 84
150 Electronic charge units, II
point charge version" 122 Electrophoretic force, 180
Density, ofNaCI solutions, 48 Electrostatic potential, 90
Dielectric constant, 20, 41 , 42, 58,69, 80, Energy, see also Heat
95 ofactivation, 244, 276,278,281
effect oftemperature, 25, 64 of activation for diffusion, 203, 232
of water, 20, 21, 106 barrier, 269
Diffusion, 158, 188,242,263; see also of interaction, 22, 24, 59,66, 71
Diffusion coefficient potential, 11 , 61
activation energy, 203, 232 Enthalpy, of solution, 45
coefficient, 182, 186, 191,207,219; Entropy
see also Diffusion coefficient of Born hydration, 35
current, 156 change due to ion-solvent interaction, 36
of ions, 186 configurational, 281
jumping distance, 37 Excess charge, 91 , 122, 124, 138
pair-vacancy _ in molten salts, 256
pre-exponential factor, 232 Falkenhagen equation, 196
of protons, 175 Faraday's constant, 234
rate constant of, 37 Fick's second law, 193
self-, 263; see also Diffusion Flux, 191 , 193, 205
coefficient, self- constant, 188, 219
semi-infinite linear, 206 instantaneous pulse, 188, 219
Diffusion coefficient, 37, 156, 157, 158, Force
170, 171 , 232,265,271,278 Coulombic, in molten salts, 254
pressure dependence, 276 electric, 180; see also Electric force
self-, 37, 231, 234, 242, 265, 273 electrophoretic, 180
temperature dependence, 273, 276 relaxation, 180
Diffusion layer, 206 Force constant, 18, 241
Diffusion, steady state flux, 156 Fragility ofliquids, 267, 270, 281
Dipole charge, 79 Free energy, activation, 269
Dipole moment, 9, 43, 61 Free energy of ion-solvent interaction, 32,
average, 75, 78 69
effective, 79 Frequency, 18
Dipole orientation, 75 Frictional coefficient, 196
Disaster of coarse grainedness, 142 Frozen liquid, 262
Discrete-polyanion model of liquid silicate, FUrth model, 228, 256, 261 , 276
249
Dissociation, Gamma function, 258
degree of, 163 Gauss's law, 79
of ions, 148 Geiger counter, 156, 191
Distance, Gibbs-Duhem equation, 110, 131
of closest approach, 112, 114, 142 Glass, 247, 280
of equilibrium in molten salts, 252 borate --' 280
Distance, mean, 156, 262 temperature, 270
Drift velocity, 169, 179 transition, 262
Glassy state, 262
Effective distance, q, 148 Grainedness, 142
Electric field, 10, 61,169, 173,178,193 Gurney co-sphere, 30
external, 79
internal, 79 Heat, see also Energy
Electrical forces, 74, 77, 180 of Born-charging process, 71
INDEX 289

Heat (cont.) Liquid silicate, 249

of hydration, 12,22,24,25,28,45 Living cells, 70
ion-dipole interaction, 28, 29
ion-quadrupole interaction, 27, 29 Mass of a hole, 235
of solution, 12, 22, 47 Masses of atoms, 7
of solvation, 47 Membrane, bilayered, charge transport
of sublimation, 22 Metal oxide, 245
Hole, in molten salt, 228, 245, 282 Mobility, 17, 55, 175, 180,214
density, 237, 238 absolute, 169, 170
lifetime, 235, 256 conventional, 169, 170, 180, 201
mass, 235 electrochemical; see Mobility,
probability, 256 conventional
radius, 228, 230, 235, 245, 256, 258 of molten salts, 242
average, 282 Molten salt, 225
most-popular, 282 ambient temperature, 243
surface area, 258 structure, 226
volume, 239, 258 Monte Carlo calculation, 253
work to make a-, 261
Hole-formation process, 276 Nanis-Bockris equation, 232, 256
Hydration number, 13, 14, 17, 1\6; see also Nernst-Einstein equation, 265
Solvation number Network theory of liquid silicate, 249
primary, 20, 58
Hydrogen bond, 10,43, 84 O/Si ratio, 247, 249
Hydrogen scale, 134 Oxidation
of ions, 156,219
Icebergs, 78 of organic complexes, 243
Impedance bridge, 270
Instantaneous-pulse experiment, 156 Pair- potential, 252
Instrument sensitivity, 157 Pair vacancy in molten salts, 256, 265
Internuclear distance, 225 Pairwise potential, 253
Ion-dipole interaction, 23, 28, 61 , 64 Panial molar volume, 48
Ionic-activity coefficient, mean, 102 Passynski equation, 15
Ionic atmosphere, 91, 92, 180 , 196 Permanent dipole, 74
thickness, 94 pH, 198
size, 113, 142 Planck-Henderson equation, 213
Ionic liquids, 225 Point charge, 122
Ionic product, 163 Poisson-Boltzmarm equation, 99,147
Ionic strength, 101 , 102, 140 Polar molecule, 74
Ion-ion interactions, 89 Polarizability , 79
Ion-pair formation, 148,265, 273 of non-electrolytes, 41
Ion-solvent interactions, 9 of water, 41, 80
Ion-transport in solution, 155 Potential, 61 , 97, 147
Ion valence, 186 diffusion, 213
IR spectrum, 18 due to ion, 97
Isotope, 156 due to ionic cloud, 95, 97
junction, 177, 214,217
Jumping distance, during diffusion, 37, 265 pair-, 252
Jump-into-a-hole process, 276 pairwise, 253
Junction potential; see Potential, junction standard, 134
Potential energy, 61
Kohlrausch's law Pressure by an ion, 40
Probability of transport process, 269
Lattice energy, 12
Lattice entropy, 45 q; see Effective distance q
290 INDEX

Quadrupole moment of water, 27 Temperature, melting, 231

Thermal forces, 74, 77
Radial distribution, 138, 150 Time,
Radioisotope, 156, 191; see also Isotope life _ of hole, 235
Radius, 7, 172 relaxation, 179, 196,262,270
of hole, 228; see also Hole, radius transition, 188
of ion, 170 Transport number, 55, 57, 174, 177, 207,
of molten salt, 233, 235, 209,211,214,271 , 273
Raman spectrum, 31, 241 Transport process, 269, 281
Rate constant, 159
Rate determining step in conduction in Units, 1,93, 104
molten salts, 245 SI, I
Reduction of ions, 159
Relaxation Valence of ions, 186
force, 180 Vapor pressure of water, 110
time, 179, 196,266,269 Velocity
Residence time of ions, 37; see also Time, drift; see Drift velocity
residence electrophoretic, 178
Resistance, 165, 194 of sound, 16
of cell; see Cell, resistance Visco-elastic state of supercooled liquid,
Resistivity, 166 262
Viscosity of molten salt, temperature
sa region, 31, 68, 72 dependence,278
Shuffle-along model, 276 Vitrification, 270
Silicate network stability, 254 Volume
Singer theory, 252 of hole; see Hole, volume
Size parameter a, 113, 138, 145 partial molar, 48
Solubility , 194 of solid lattice, 226, 239
product, 135 solvation, 72, 73
of salts, 47,126
Solubility, change of, 38, 41 Walden's empirical rule, 172
Solvation Water, 10
energy, 24 boiling point, 84
number, 15,20, 31,54,56 radius, 24
absolute, 57 Wavelength, 18
primary, 200 Wavenumber, 18,241
sheath, 31 Woodcock, 252
Solvent molecules, size of, 71 Work
Stokes-Einstein equation, 265 of charging, 33, 90
Stokes radius, 18 of making holes, 261
Structure breaking region, see sa region
Supercooled liquid, 262, 269 X-ray, 225
Surface tension, 228, 230
Swallin model, 276 Zinc bond, 84
Taylor expansion, 89