Module I

Electrochemistry
and
Corrosion

Electrochemistry deals with

Chemical Change and Electrical Work
 By the 1700s, as the study of electricity became popular, (Leydon Jar)

History of Electrochemistry …..there was a type of

electrical fluid inherent
THE EXPERIMENT THAT SHOCKED THE WORLD in the body, which he
dubbed animal
electricity
LUIGI GALVANI

….the
electricity was
RESTORE LIFE BACK INTO THE DEAD ? intrinsic to the
Could the dead be brought back to life?
frog and the
What would it mean for the nature of the soul, metals simply
if humans were nothing more than electrical generators? acted as a
Italian physician, anatomist conduit
1737-1798
Laid the foundations of a new science, electrophysiology (ion current and its
recording), and opened the way for the invention of the electric battery
 Scientists could create a
ALESSANDRO VOLTA steady source of electricity
for the very first time
Frogs’ muscles were simply
reacting to the electricity, not
producing it. He set out to prove
Galvani wrong, and sparked a
controversy that divided the
Italian scientific community.
The generation of an electric
current did not require any animal
parts, Volta put together a rather
Italian Physicist messy stack of alternating zinc and
silver discs, separated by brine-
Lived 1745 – 1827. The Voltaic Pile: Volta’s own
soaked cloth. He built the pile,
illustration enclosed with the
which consisted of as many as
letter to Banks (RSC)
thirty disks

Volta set to work, trying many different combinations of metals. Silver touching copper?
Electrical current. Iron touching zinc? Electrical current.
With this evidence, Volta argued that the two metals created an electrical current; thus, the
metals alone were responsible for the twitches. Bi-metal electricity left no room for intrinsic
animal electricity
 William Nicholson
Using Volta’s Pile Anthony Carlisle
(chemist)
1753 -1815 In May 1800 he with Anthony (Surgeon)
Carlisle discovered electrolysis,
the decomposition of water into
hydrogen and oxygen by voltaic current.
……….. electricity can decompose
water into hydrogen and oxygen
caused as big a stir as any scientific
discovery ever made.
It demonstrated the existence of a 1768 - 1840
relationship between electricity and
the chemical elements.

To which, Michael Faraday would

give quantitative expression in his
two laws of electrolysis in 1834.
Davy used current
supplied by the pile to production of electricity by the
separate compounds voltaic pile depended on the
into their parts, occurrence of chemical reactions,
discovering several new not just on the contact of different
kinds of metals, as Volta had MICHAEL FARADAY,
elements. (Electro-
synthesis) thought. Davy was Faraday’s mentor
 An electrical telegraph was a point-to-point
text messaging system

It was the first

electrical telecommunications syste
m, the most widely used of a number
of early messaging systems
called telegraphs, devised to send
text messages more rapidly than
written messages could be sent.
Samuel Thomas von Sömmerring
1755-1830

By 1809 Samuel von Soemmering had built and demonstrated a

functional telegraph using bubbles to indicate the sent letter. It
required a separate wire for each encoded character, but cleverly
allowed the wires to be configured to send two letters at a time.
Soemmering even noted that the volume of hydrogen at one
electrode was double that of the production of oxygen at the other,
and assigned commonly used letters like vowels to the hydrogen
electrodes to make them easier to distinguish.
Johann Wilhelm Ritter Ritter invented the dry voltaic cell in 1802 and
German physicist an electrical storage battery the following year.
1776-1810
Ritter was the first to establish an explicit
connection between galvanism and chemical
reactivity. He correlated the electrical effects
produced by various metal couples on the
muscle with differences in the metals’s ease of
oxidation. His suggestion that current was due
to a chemical interaction between the metals
was the first electrochemical explanation of this
phenomenon. (discovered Electroplating )

https://krc.cecri.res.in/hoe
Bordeaux mixture—a combination of copper sulfate, lime, and water—is an effective
fungicide and bactericide that has been used for decades to control diseases of fruit
and nut trees, vine fruits, and ornamental plants.
1807 GROTTHUS put forward a theory on the electrolytes and the movement of charges
(separation of the charges on H and O in water molecule).

1807 DAVY discovered potassium using a battery (with 2 000 elements!) by electrolysing
molten potash. He then discovered sodium and calcium. Moreover, he was the first to identify
the role played by the reactions at the electrodes and the decomposition of the electrolyte.

1824 DAVY made use of zinc to protect against the corrosion of copper or iron parts in ships.

1826 BECQUEREL observed the polarisation effects of electrodes caused by hydrogen

evolution. He then proposed the use of depolarizers in two-compartment batteries.

1833 FARADAY, a student of DAVY, introduced the vocabulary of electrochemistry (electrode,

anion-anode and cation-cathode) and observed the link between the mass of compound
produced or consumed and the amount of charge passed (laws of electrolysis).

1836 DANIELL made up the two-compartment battery called the DANIELL cell, which is still the
main reference example given of an electrochemical battery in a number of educational books.
Anyway this is its only use since the electric power that this battery can provide is quite
negligible.

1837 JACOBI invented galvanoplasty, which has numerous applications today

1839 GROVE discovered the reversibility of water electrolysis reactions, and laid the basis of
the first fuel cell, which was not to undergo any significant development until the NASA
program in the 1960’s.

1859 PLANTE invented the lead-acid battery, which is still widely used because it can deliver
high levels of electric power at a low cost. Of course, its manufacturing process underwent
many improvements, but its main principle remained unchanged.

1868 LECLANCHE discovered the saline battery based on zinc and manganese dioxide which is
also still very successful today. Incidentally, it is interesting to note that LECLANCHE, having
failed to secure funding in France to develop his project, expatriated himself to Belgium,
where he then made his fortune.

1874 KOHLRAUSCH wrote his theory on the conductivity of electrolytes.

1886 HALL in the United States, and HEROULT in France both developed the aluminium
electrolysis process. The simultaneous nature of these discoveries did entail a certain degree
of polemics, but what is even more unsettling is the fact that both men were born the same
year and also died the same year. Would they now be together in Heaven with beautiful,
gleaming aluminium wings?

1887 ARRHENIUS developed his theory on acido-basic reactions and on ionic dissociation.

1889 NERNST worked out the thermodynamics of electrochemistry.

1897 BOTTGER developed the hydrogen electrode (first measurements of pH).

1899 The first electric car (JAMAIS CONTENTE) was developed. It reached a record speed
of 100 km h��1 (over the stretch of only a few kilometres).

1902 COTTRELL wrote the equations which rule the electrode kinetics with mass transport
by diffusion.

1905 TAFEL found an empirical law of electrode overpotential as being a function of the
current on various metals.

1906 CREMER invented the glass bulb pH electrode, which is still widely used.

1914 EDISON developed the Ni/Fe alkaline secondary battery.

1922 HEYROVSKY worked out the theory for the mercury electrode in polarography, an
electrochemical analysis method which, after a few improvements, meant that ultra-
traces could be analysed in heavy metals for instance. He was awarded the NOBEL prize
for his work in 1959.

1924-1930 BUTLER and VOLMER laid the foundations of the charge transfer theory at an
electrode.
Syllabus: ELECTROCHEMISTRY
History,
Introduction and Types of electrodes
Single electrode potential and its measurement using SHE as reference.
Electrochemical series and its application
Nernst equation derivation and its Application + numerical probelms
Analytical application of Nernst equation (potentiometric titration)
Reference electrode (Calomel and glass electrode) Construction + Working
Li+ion battery, Mechanism + Construction + advanatge + Use
Corrosion-Electrochemical corrosion – mechanism. Galvanic series
Cathodic protection - electroless plating –Copper and Nickel plating.

Prerequisites
Students should know oxidation, reduction, redox reactions and balancing of redox reaction.
Reading Assignments
http://www.dummies.com/education/science/chemistry/how-to-balance-redox-equations/
https://medium.com/countdown-education/7-simple-steps-to-balancing-redox-reactions-
dcf1b843ed1a