7

Introduction to
electrochemistry

1.1 The scope of electrochemistry

7. 7. 7 A definition of electrochemistry

If you happened to take down a copy of the Oxford English Dictionary,

you would learn, although you would not be greatly illuminated by the
fact, that electrochemistry is 'the science of the application of electricity to
chemistry'. One of the earliest references in 1829 in a journal called Natural
Philosophy offered 'Electro-Chemistry, one of the connecting branches be-
tween remote divisions of the Philosophy of Nature'. (Ho hum!)
As an introduction to this textbook let me suggest that electrochemis-
try is the science of the interaction of phases containing electrons and
phases containing ions. This book treats the myriad permutations of that
simple definition. In terms of what is happening, therefore, electrochemis-
try (or electrodics, as some would have it) lies between the science of ionic
solutions (ionics) and the science of electrons in solids (electronics).

7.7.2 Electrochemistry and science

This is a chemistry book in a series on Physical Chemistry, but it is

important to stress that electrochemistry is not merely physical chemistry,
nor even chemistry, but genuinely spans a swathe of science from biology
through chemistry to physics and materials science. Why is this? The world
is full of interfaces and the majority of them are charged. Simply under-
standing how these charges move and interact is a basic goal of physics.
Putting them together into cells (the use of the word 'cell' came from
biological parallels made by early electrochemists) brings in the materials
science of electrodes and the organic and inorganic chemistry of the species
in the cell. Other types of interfaces - those in colloids, for example -
obey the same rules. Some of them - again, for example, colloids - have

D. B. Hibbert, Introduction to electrochemistry

© D. Brynn Hibbert 1993
2 Introduction to electrochemistry

taken on such a life of their own that they are taught and considered
separately from electrochemistry.

7.7.3 Electrochemistry and physical chemistry

While it is most useful for the planners of courses to draw a line round a bit
of knowledge and call it 'electrochemistry' and slot it into physical chemis-
try, it is worth dwelling on the commonality of the subjects. It may be that
as a fledgling electrochemist you know more than you realised. Consider
the following.

(1) Electrochemistry obeys all the same laws of nature as the rest of
science. So we would expect, for instance, the thermodynamics of cells to
be much the same as the general thermodynamics encountered early in a
chemistry course, perhaps with a few twiddles to take care of the charges
and voltages, and so on.
(2) The transfer of an electron from an electrode to a molecule must
be done at an interface. The bit of physical chemistry called 'surface
chemistry' or 'catalysis' will hopefully aid our deliberations. This may be of
little use to the student, as interfacial chemistry intrudes into the average
course less and later than electrochemistry.
(3) If you know anything about ions, then think of an electrode as a
super-big one with a charge that can be varied from outside.
(4) The kinetics of electrode reactions can be treated in an entirely
analogous way to solution reactions but with the added dimension of
potential, whose job it is to change the free energy of anything that is
charged. Thus, the theory of Marcus of the kinetics of outer sphere redox
reactions works just as well for electrochemical reactions of transition
metal complexes at electrodes.
(5) The idea that potential may change the rate of a reaction by
turning up the pressure on electrons to enter or leave part of a molecule
should be familiar to organic chemists in another guise. Do you remember
why the acidity of chlorinated propanoic acids increases in the order
CH3 CH 2COOH, CICH 2 CH 2 COOH, CI 2CHCH2 COOH, CI3 CCH 2 COOH?
Chlorine, being more electronegative, withdraws electrons from up the
other end of the molecule, leaving the 0- H bond short of the wherewithal
and so the hydrogen falls off more easily and so we say that it is more
acidic. We can control the acidity somewhat by changing the inductive
effect of the atoms in the rest of the molecule. In electrochemistry this is
achieved by changing the potential at an electrode. Thus, a connection is
made with the Br(llnsted law for proton transport.

The above discussion is not making the case for the complete submersion
of electrochemistry into physical chemistry. Hopefully it will show that
 Introduction to electrochemistry 3

electrochemistry is not such an alien being but a subject that fits neatly into
science.

1.2 History

7.2. 7 From then to now

The history of electrochemistry is a remarkably short one for a subject that

is steeped in archaic terms and that has a curiously dusty feel about it.
Leaving aside the possibility that visiting space folk may have left flashlight
batteries or the discoveries of Babylonian cells (see panel on electro-
chemical archaeology), electrochemistry is 200 years old (1791-1991). As
with many who make the very first discovery of something, Luigi Galvani
got the explanation wrong of why his frogs' legs twitched when sparks were
generated from an electric machine. Luckily Volta quickly came to the
rescue (see panel on electrolysis), but it was about 50 years before Michael
Faraday made his famous remark about 'what use is a newborn baby?' to
the reasonable request as to what one could do with this new electricity.
Volta in 1800 made the first battery, which became known as a Voltaic pile,
but at the time Volta wrote: 'To this apparatus, much more similar to the
natural electric organ of the torpedo or the electric eel, etc., than to the
Leyden flask, I would wish to give the name "Artificial Electric Organ"'.
Electrochemists breathe a sigh of relief that we still are not delving into the
mysteries of 'artificial electric organs'!
Faraday's laws came in 1834, and in the same year Sir William Grove

Cold fusion: or illusion?

On 23 March 1989 an astounded world heard claims by Fleischmann

and Pons that they had caused nuclei to fuse in a test-tube. Were
they right? Three years later and, alas, the subject is as murky as it
was then.
Back in 1989 we saw an unusual phenomenon. Not cold fusion,
but the dissemination of scientific results by television, newspapers
and electronic bulletin boards. No peer-reviewed papers and very few
hard facts led to enormous speculation. Anyone who had the
remotest theory or opinion could appear on a chat show. The dream
of the free lunch had almost come true.
What did Fleischmann and Pons claim? They said that when
hydrogen is evolved at a palladium electrode from a solution of
LiOD in D 2 0, the deuterium atoms that penetrate the lattice
undergo nuclear fusion.
4 Introduction to electrochemistry

You will see in Chapter 8 that the evolution of hydrogen in

alkaline solution has the following mechanism:
H20 + e - Hads + OH-
2 Hads - H2
The unusual thing about palladium as an electrode material is that it
can hijack the adsorbed hydrogen formed in the first reaction into
the metal lattice. Between two deuterons the reaction is posited to be
20 + 20 _ 3T (1.01 MeV) + IH (3.02 MeV)
20 + 20 _ 3He (0.82 MeV) + In (2.45 MeV)
At different times groups around the world have claimed to
detect excess heat, neutrons, tritium and helium-3. At later times
some of the same groups admitted they were wrong. There were
problems. Simply making up a cell and switching on the current did
not appear to do much. It was necessary to run the experiment for
up to 3 months before sudden spikes of heat were seen. It was
argued that the lattice needed to become saturated with deuterons,
or that dendrites of impurity metals needed time to grow on the
cathode.
The bubble did not so much burst, for no accepted alternative
explanation has been forthcoming, as gradually deflate. Many of the
top echelons of the University of Utah, where the whole furore
started, have left. Stanley Pons resigned from the University; Martin
Fleischmann retired, having reached a suitable age.
Now, in 1993, very few would support the theory that a nuclear
process does indeed take place. That something very funny goes on is
true but few think it is nuclear.
Looking back, they were heady days. I liked best the headline in
The Sydney Morning Herald newspaper of 29 April 1989, which read
AUST STRIVES TO WIN RACE TO COLO FUSION. I estimated
that had cold fusion been real, Australia was striving to come about
47th.

invented the fuel cell. By 1894 Ostwald was declaring to anyone who would
listen that electric power was far superior to that provided by combustion
engines because of the Carnot cycle inefficiencies inherent in the latter.
Another 50 year lull then ensued in which electrochemistry stood still
enmeshed in the success of Nernstian thermodynamics. Why this happened
no one is sure. Perhaps it was the lack of good apparatus and instruments
(the measurement of voltage was an art not suited to dynamic electro-
chemistry) or the failure of theories to explain what was happening as
 Introduction to electrochemistry 5

current flowed. The subject only picked up again in the 1950s, and the last
half of the twentieth century has seen rapid advancement on several fronts
- experimental, theoretical and in applications.

7.2.2 So what use is electrochemistry?

It is always tempting to ask the question 'What is the use of X' in a

textbook on X. It allows the author to pontificate on how the modern
world would not be the way it is were it not for the fact that people who did
X are alive and well and doing X all over the place. This is indeed my thesis
but one I shall try and justify and not simply assert. Let us look at three
areas of electrochemistry: the production of chemicals; the production of
electrical energy; and corrosion. The majority of chemicals are produced
from oil by catalytic reactions. However, a few key substances are pro-
duced electrochemically - namely sodium hydroxide, chlorine and alumi-
nium. As we shall see in Chapter 12, there are more, but these are the most
important. Before aluminium was produced by the Hall-Heroult process it
was made by a chemical process at about US$ 100 per pound (excuse the
non-SI units). Now it is around US$ 2 per pound. All in all, the US
electrochemical industry uses 6% of the country's generated electricity to
make chemicals worth US$ 30 billion. It is an irony that the electrically
powered vehicle would be more widely used had it not been for the internal
combustion engine, but that in turn would not have been so popular if
Plante had not invented the lead-acid battery. As more and more
rechargeable batteries are developed, and whenever the really efficient fuel
cell is invented, the world's use of electrical power derived from stored
chemical energy is bound to increase. Meanwhile reflect on the fate of
those who have heart pacemakers were not small implantable lithium cells
available.
Finally, if you thought US$ 30 billion was a lot, then ponder the
estimated US$ 200 billion that is lost because of corrosion. Most modern
motor cars succumb to rust before their engines give way and, in general,
the reversion, slow or not so slow, of thermodynamically unstable metals
to their oxides is a curse and an inevitability.

7.2.3 Whither electrochemistry

Electrochemistry is going along quite nicely here in the last decade of the
twentieth century. I expect batteries to continue to improve to the point
where their use will be seen in everything requiring energy, from small
appliances to vehicles. Industrial applications will also grow, with a shift of
emphasis in research to making small amounts of high-cost speciality chemi-
cals. Electrochemical sensors will be more selective, rugged and smaller, and
6 Introduction to electrochemistry

so will be used for process control, medical monitoring and environmental

analysis. They will be aided by advances in computing and data handling
(chemometrics). Corrosion will have no electrochemical solutions but our
understanding of the processes involved will direct us to materials having
better properties.
On the theoretical front our interpretation of reactions at a molecular
level will improve, particularly in respect to adsorption and solvation. This
understanding will be extended to biological and macromolecular systems.
The electrochemistry of new materials - for example, ceramics and orga-
nic conductors - will provide gainful employ for many researchers and I
expect the gamut of analytical spectroscopies (including electron spin
resonance and surface photoelectron spectroscopies) to be brought to bear
on various problems.
Finally, ignore the foregoing. Things may be turned upside down at a
stroke, as indeed things nearly were with the advent of the putative cold
nuclear fusion (see panel).

1.3 A quick tour of electrochemistry

7.3. 7 Basic concepts

In the rest of this chapter I shall introduce a few basic terms to put a
diligent reader (that bizarre individual who actually starts a textbook at
Chapter 1) in the right frame of mind to take in the ideas that follow in the
next thirteen chapters. As I stated in the first subsection, electrochemistry
is all about the interface between electrons and ions, and it is the different
facets of this interface and its general environment that is the subject of the
first part of this text. Figure 1.1 shows a schematic of a cell that you will see
many times during the course of the book. It is labelled with the chapters
that deal with bits of it that may provide a logical flow through to some
measure of understanding.

7.3.2 Electrolytes and electrodes

Electrochemistry takes on the task of explaining what the solution side of

our interface looks like before any electrochemistry goes on (Chapter 2).
The fact that ions in water are solvated and interact like mad is important.
The phase that conducts ions is known as the electrolyte. When a lump of a
solid containing electrons (the electrode) is introduced into the solution, it
causes even more problems for the system to reorganise itself to achieve an
equilibrium state (Chapter 3). It can manage this, but what happens if it
can swap electrons with the electrode?
 Introduction to electrochemistry 7

f Batteries
Ch.13

~
~
Industrial
electrochemistry
Ch.12

Synthesis
Ch.ll

Figure 1.1 A schematic view of an electrochemical cell labelled with the topics of
Chapters 2-14

7.3.3 Voltage and cells

The voltage (E) established as a species in solution equilibrates with

electrons in the solid (e.g. a silver ion at a silver electrode Ag+ + e ~ Ag)
is related to the free energy (..1G) of the process that occurs by the equation
..1G = -n FE (1.1)
where n is the number of electrons transferred per mole and F is a
constant. If two electrodes and their electrolytes are brought together as
8 Introduction to electrochemistry

at
cathode

/ anode

'''/
Species

Electrode

Figure 1.2 The processes of oxidation and reduction at an electrode

shown in Figure 1.1, a cell is formed and the overall voltage is related to the
free energy of the overall reaction (made by adding up the two electrode
reactions so that the electrons cancel) by Equation (1.1). All of this is
covered in Chapter 4. In chemical terms reduction occurs at the electrode
that donates electrons and oxidation at the electrode that accepts electrons.
(That is, the definitions are in terms of what happens to the species in
solution.) This is illustrated in Figure 1.2. Notice that negative ions (an-
ions) can be reduced at an electrode, just as positive ions (cations) may be
oxidised. In fact there is no restriction on what may react and how. The
following is a list of electrochemical equilibria. Note also that when we
speak of equilibrium, what we mean is that the rate of oxidation of a
species at an electrode is the same as the rate of reduction (just like the
usual definition in terms of forward and back reactions).
Ag+ +e ;::= Ag (one species in solution one is the
electrode)
Fe3+ + e ;::= Fe2 + (both species are cations in
solution)
[Fe(CN6)]3- + e ;::= [Fe(CN6)]4- (both species are anions in
solution)
 Introduction to electrochemistry 9

Pt0 2 + H 20 +2e ~ PtO + 2 OH- (two species are on the

electrode)
2 H 20 + 2 e ~ H2 + 2 OH- (neutral, anion and
gaseous species)
2 CH2CHCN + 2 H 20 + 2 e ~ (CH 2CH2CH)2 + N2 + 20H-
(organic reaction)
CO 2 + 6 H+ +6e ~ CH3 0H + H 20 (gas and organic
species)

The latter reaction is an example of an equilibrium that cannot be realised

in practice. Methanol can be electrochemically reacted to give carbon
dioxide and water, but so far no one has found any way at all to persuade
the cathodic reaction to go.

7.3.4 Dynamics and current

Whereas the poor electron has no option but to react (or not) at the
electrode, the species in solution have freedom to move. How and why
they move is also important to electrochemistry and is treated in Chapter 5.
If the species in solution are charged, they can move in response to the
electric field that is set up whenever there is a voltage difference between
the two electrodes. Any species can diffuse - that is, move - because
there is a concentration difference between two points in the cell. Such a
concentration difference arises when an electrochemical reaction happens
at the electrode surface - that is, when a current flows. The current (I) is
related to the rate of reaction by Faraday's Law:
rate (mol S-1) = 1/ n F (1.2)
with nand F being the same as in Equation (1.1). If you think of charge
flowing around the circuit, then the current flowing in the wires and
measured by the ammeter must also flow through the solution at the same
rate, and also through the interfaces via the electrochemical reaction
(Equation 1.2). It may have dawned on you that in a cell, if electrons go
from the electrode to a species in the electrolyte at one electrode, then at
the other electrode electrons must flow from the species to the electrode at
the same rate. So, if the equilibrium is disturbed and a net current flows,
there must be net oxidation at one electrode (called the anode) and net
reduction at the other (called the cathode).
The relationship of the current to the voltage is derived by applying
the principles of chemical kinetics to the problem, and these dynamical
aspects of electrochemistry are done to death in Chapter 6. Exactly how
reactions proceed in some important reactions is covered in a chapter on
reaction mechanisms (Chapter 8).
10 Introduction to electrochemistry

It is important to be able to measure what is going on and Chapter 7

deals with the various ways of doing electrochemistry .

• PROBLEM

1.1 Write a textbook of electrochemistry .

• ANSWER

1.1 Now read on.