Introduction to electrochemistry

- Basics of all techniques -

Electrochemistry is the study of phenomena at
electrode-solution interfaces
(a) Galvanic and (b) electrolytic cells
Two quite different aspects of the field of
electrochemistry
Reactions and electrodes
• The overall chemical reaction taking place in a cell is
made up of two independent half-reactions, which
describe the real chemical changes at the two electrodes.
• Most of the time one is interested in only one of these
reactions, and the electrode at which it occurs is called
the working (or indicator) electrode, coupled with an
electrode that approaches an ideal nonpolarizable
electrode of known potential, called the reference
electrode. In experiments, the current is passed between
the working electrode and an auxiliary(or counter)
electrode.
• Three electrodes are frequently placed in three
compartments separated by a sintered-glass disk.
Three-electrode cell and notation
for the different electrodes
 Reference electrode
● The potential of the working electrode is
monitored relative to a separate reference
electrode, positioned with its tip near the
working electrode.
● The internationally accepted primary reference is
the standard hydrogen electrode (SHE) or
normal hydrogen electrode (NHE), which is
Pt/H2(a=1)/H+(a=1,aqueous)
●By far the most common reference is the saturated
calomel electrode (SCE), which is
Hg/Hg2Cl2/KCl(sat’d in water)
Its potential is 0.242 V vs. NHE.
Scope Introduction
of electrochemistry
Introduction
– Investigation of chemical phenomena associated
with a charge transfer reaction
– To assure electroneutrality two (or more) half-
reactions take place in opposite directions
(oxidation/reduction)
– If the sum of free energy changes at both
electrodes is negative electrical energy is released
 battery
– If it is positive, external electrical energy has to be
supplied to oblige electrode reactions 
electrolysis
Factors affecting electrode reaction rate

In general, the electrode reaction rate is governed by

rates of processes such as:
(1) Mass transfer (e.g., from the bulk solution to the
electrode surface).
(2) Electron transfer at the electrode surface.
(3)Chemical reactions preceding or following the
electron transfer.
(4)Other surface reactions.

◆ The magnitude of this current is often limited by

the inherent sluggishness of one or more
reactions called rate-determining steps.
Conditions for electrochemical
experiments
Reproducible experimental conditions must
be given
Interfering side effects must be avoided as
Migration effects
High solution resistance
-these effects can be minimised by adding an inert
supporting electrolyte (around 1 mol/L)
Undefined or large diffusion layer
– A complete study of the electrode process requires
the measurement of kinetic as well as
thermodynamic parameters.
Faradaic and nonfaradaic processes

• Charges (e.g., electrons) are transferred

across the electrode-solution interface and
causes oxidation or reduction to occur. Since
these reactions are governed by Faraday’s
law, they are called faradaic processes.
• Under some conditions, processes such as
adsorption and desorption can occur, and the
structure of the electrode-solution interface
can change with changing potential or
solution composition, these processes are
called nonfaradaic processes.
Capacitance and charge of an
electrode
• The behavior of the electrode-solution
interface is analogous to that of a capacitor.
When a potential is applied across a
capacitor, charge will accumulate on its
electrode plates.
• At a given potential there will exist a charge
on the metal electrode, qM, and a charge in
the solution, qs. At all times, qM=-qs.
• At a given potential the electrode-solution
interface is characterized by a double-layer
capacitance, Cd, typically in the range of 10 to
40μF/cm2.
The nature of electrode reactions
• Electrode reactions are heterogeneous and take
place in the interfacial region between electrode and
solution  diffusion layer
• The charge separation at each electrode is
represented by a capacitance
• the difficulty of charge transfer by a resistance
• The electrode can act as (1) a source of electrons
(cathode)  reduction ,(2) a sink of electrons
transferred from species in solution (anode) 
oxidation
• The amount of electrons transferred is related to the
current flowing between the two electrodes
Thermodynamics and kinetics
• Thermodynamics and kinetics
– The potential at which a reduction or
oxidation takes place (measured relative to the
normal hydrogen electrode) is given by the Nernst
equation
E = E0 – (RT/nF) i ln ci
i : stoichiometric numbers: positive for reduced species,
negative for oxidised species
E0 : standard electrode potential
ci : concentration (ai has to be applied if activity coefficient is
not 1)
Thermodynamics and kinetics
●The concentration of species at the
electrode interface depends on its mass
transport coefficient kd and
●The rate of the electrode reaction is
expressed by the standard rate constant k0
which is the rate when E = E0
– reversible reaction  k0 >> kd
– irreversible reversible reaction  k0 <<
kd,
an overpotential  has to be applied
additionally to overcome this kinetic barrier
●A behaviour in between these extremes is
called quasireversible reaction