ELECTROCHEMISTRY

Electrochemistry is that branch of chemistry which deals with the study of

production of electricity from energy released during spontaneous chemical
reactions and the use of electrical energy to bring about non-spontaneous
chemical transformations

ELECTROCHEMICAL CELLS

These are devices that convert chemical energy of some redox reactions to
electrical energy. They are also called Galvanic cells or Voltaic cells.

An example for Galvanic cell is Daniel cell. It is constructed by dipping a Zn rod

in ZnSO4 solution and

a Cu rod in CuSO4 solution. The two solutions are connected externally by a

metallic wire through a voltmeter and a switch and internally by a salt bridge.

A salt bridge is a U-tube containing an inert electrolyte like NaNO3 or KNO3 in a

jelly like substance. The functions of a salt bridge are:

1. To complete the electrical circuit

2. To maintain the electrical neutrality in the two half cells. The reaction

taking place in a Daniel cell is

These reactions occur in two different portions of the Daniel cell. The reduction
half reaction occurs on the copper electrode while the oxidation half reaction
occurs on the zinc electrode. These two portions of the cell are also called
halfcells or redox couples. The copper electrode may be called the reduction half
cell and the zinc electrode, the oxidation half-cell.

Functioning of cell when external opposite potential is applied:

Electrode Potential
The tendency of a metal to lose or gain electron when it is in contact with
its own solution is called electrode potential. When the concentrations of
all the species involved in a half-cell is unity then the electrode potential is
known as standard electrode potential.
According to IUPAC convention, standard reduction potential is taken as
the standard electrode potential.
In a galvanic cell, the half-cell in which oxidation takes place is called
anode and it has a negative potential.
The other half-cell in which reduction takes place is called cathode and it
has a positive potential. In a cell, the electrons flow from negative
electrode to positive electrode and the current flows in opposite direction.
Cell potential:
The potential difference between the two electrodes of a galvanic cell is
called the cell potential and is measured in volts.
The cell potential is the difference between the electrode potentials
(reduction potentials) of the cathode and anode.
The cell electromotive force (emf) of the cell is the potential difference
between the two electrodes, when no current is flow through the cell.
By convention, while representing a galvanic cell, the anode is written on
the left side and the cathode on the right side.
Metal and electrolyte solution are separated by putting a vertical line and
a salt bridge is denoted by putting a double vertical line.
For Daniel cell, the cell representation is
Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
Under this convention the emf of the cell is positive and is given by the
potential of the half-cell on the right hand side minus the potential of the
half-cell on the left hand side i.e.
Ecell = Eright – Eleft
Or, Ecell = ER – EL .
Measurement of Electrode Potential
The potential of individual half-cell cannot be measured. We can measure
only the difference between the two half-cell potentials that gives the emf
of the cell. For this purpose a half-cell called Standard Hydrogen Electrode
(SHE) or Normal Hydrogen Electrode (NHE) is used.
It consists of a platinum electrode coated with platinum black. The
electrode is dipped in an acidic solution of one molar concentration and
pure hydrogen gas at 1 bar pressure and 298K is bubbled through it.
It is represented as Pt(s)/H2(g)/H+ (aq).
By convention, the electrode potential of SHE is taken as zero. To
determine the electrode potential of an electrode, it is connected in
series with the standard hydrogen electrode and the emf of the
resulting cell is determined by the equation,
Ecell = ER – EL
Since the electrode potential of SHE is zero, the value of Ecell is equal to
the electrode potential of the given electrode.

If the standard electrode potential of an electrode is greater than zero

(i.e. +ve), then its reduced form is more stable compared to hydrogen
gas.
Similarly, if the standard electrode potential is negative then hydrogen gas
is more stable than the reduced form of the species.
Electrochemical series :
It is a series in which various electrodes are arranged in the decreasing
order of their reduction potential.
In this table, fluorine is at the top indicating that fluorine gas (F2) has the
maximum tendency to get reduced to fluoride ions (F– ). Therefore
fluorine gas is the strongest oxidising agent and fluoride ion is the
weakest reducing agent.
Lithium has the lowest electrode potential indicating that lithium ion is the
weakest oxidising agent while lithium metal is the most powerful reducing
agent in an aqueous solution.
Nernst Equation
Nernst proposed an equation to relate the electrode potential of an
electrode (or, emf of a cell) with the electrolytic concentration. He
showed that for the electrode reaction:

In Daniell cell, the electrode potential for any given concentration of Cu2+
and Zn2+ ions, we write For Cathode:
Equilibrium Constant from Nernst Equation
For a Daniel cell, the emf of the cell at 298K is given by:

When the cell reaction attains equilibrium, Ecell = 0

Electrochemical Cell and Gibbs Energy of the Reaction

Electrical work done in one second is equal to electrical potential multiplied by

total charge passed.

Also the reversible work done by a galvanic cell is equal to decrease in its Gibbs
energy. Therefore, if the emf of the cell is E and nF is the amount of charge
passed, then the Gibbs energy of the reaction,

ΔG = – nFEcell

If the concentration of all the reacting species is unity, then Ecell = E0cell .

So, ΔG0= –nFE0cell

Thus, from the measurement of E0cell, we can calculate the standard Gibbs
energy of the reaction.

Conductance of Electrolytic Solutions

Resistance (R): The electrical resistance is the hindrance to the flow of

electrons. Its unit is ohm (Ω). The resistance of a conductor is directly
proportional to the length of the conductor (Ɩ) and inversely proportional to the
area of cross-section (A) of the conductor.
Resistivity :It is defined as the resistance offered by a conductor having unit
length and unit area of crosssection.

Conductance (G): It is the inverse of resistance.

i.e. G = 1/R.

Its unit is ohm-1 or mho or Siemens (S)

Types of Conductance:
There are of two types of Conductance –

Electronic or metallic conductance and electrolytic or ionic conductance.

Electrical conductance through metals is called metallic or electronic

conductance and it is due to the movement of electrons. It depends on the
nature and structure of the metal, the no. of valence electrons per atoms and
temperature.

For electronic conductance, when temperature increases, conductance

decreases.

The conductance of electricity by ions present in solutions is called electrolytic

or ionic conductance.

It depends on i) the nature of electrolyte ii) size of the ion produced and their
solvation iii) the nature of the solvent and its viscosity iv) concentration of the
electrolyte and v) temperature (As temperature increases electrolytic conduction
also increases).

Note: Substances which allow the passage of electricity in molten state or in

solution state are called electrolytes. On the passage of electricity, they undergo
chemical decomposition.

Measurement of the conductivity of ionic solutions

Conductivity cell :It consists of two platinum electrodes coated with platinum
black. The electrodes are separated by a distance Ɩ and their area of crosssection
is A. The resistance of such a column of solution is then given by the equation:
The quantity Ɩ/A is called cell constant (G*). It depends on the distance between
the electrodes and their area of cross-section. Its unit is m-1

The cell constant of a conductivity cell is usually determined by measuring the

resistance of the cell containing a solution whose conductivity is already known
(e.g. KCl solution).

i.e. Cell constant = Resistance x Conductivity

Once the cell constant is determined, we can use it for measuring the resistance
or conductivity of any solution.

The set up for the measurement of the resistance is shown in the figure. It
consists of two resistances R3 and R4 , a variable resistance R1 and the
conductivity cell having the unknown resistance R2 . The Wheatstone bridge is
fed by an oscillator O (a source of a.c. power in the audio frequency range 550 to
5000 cycles per second). P is a suitable detector (a headphone or other electronic
device) and the bridge is balanced when no current passes through the detector.:

.
Once the cell constant and the resistance of the solution in the cell is determined,
the conductivity of the solution is given by the equation:

Molar conductivity (λm) :

It is the conductivity of 1 mole of an electrolytic solution kept between two

electrodes with unit area of cross section and at a distance of unit length. It is
related to conductivity of the solution by the equation,

Variation of conductivity and Molar conductivity with concentration

(dilution)

Both conductivity and molar conductivity change with the concentration of the
electrolyte. We know that when a solution is diluted, its concentration decreases.
For both strong and weak electrolytes, conductivity always decreases
with dilution. This is because conductivity is the conductance of unit
volume of electrolytic solution. As dilution increases, the number of ions
per unit volume decreases and hence the conductivity decreases.

For both strong and weak electrolytes, the molar conductivity increase with
dilution (or decrease with increase in concentration), but due to different
reasons.

For strong electrolytes, as dilution increases, the force of attraction between

the ions decreases and hence the ionic mobility increases. So, molar conductivity
increases.

When dilution reaches maximum or concentration approaches zero, the molar

conductivity becomes maximum and it is called the limiting molar conductivity
(λ0m).

For strong electrolytes, the relation between λm and concentration can be given
as: λm = λ0m - A√c Where ‘c’ is the concentration and A is a constant depends
on temperature, the nature of the electrolyte and the nature of the solvent.

All electrolytes of a particular type have the same value for ‘A’.

For weak electrolytes, as dilution increases, the degree of dissociation

increases. So the number of ions and hence the molar conductivity increases.
The variation of λm for strong and weak electrolytes is shown in the following
graphs:

For strong electrolytes, the value of λ0m can be determined by the extrapolation
of the graph. But for weak electrolytes, it is not possible since the graph is not a
straight line. So their λ0m values are calculated by applying Kohlrausch’s law of
independent migration of ions

Kohlrausch’s law of independent migration of ions

The law states that the limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contributions of the anion and the
cation of the electrolyte. Thus if an electrolyte on dissociation gives n(+) cations
and n(-) anions, its limiting molar conductivity is given as:

Applications of Kohlrausch’s law

1) Determination of λ0m of weak electrolytes: By knowing the λ0m values of

strong electrolytes, we can calculate λ0m of weak electrolytes.

For e.g. we can determine the λ0m of acetic acid (CH3COOH) by knowing the
λ0m of CH3COONa, NaCl and HCl as follows:

2. Determination of degree of dissociation of weak electrolytes

Electrolytic Cells and Electrolysis

In an electrolytic cell, the electrical energy is converted to chemical energy. The

dissociation of an electrolyte by the passage of electricity is called electrolysis.
For e.g. when CuSO4 solution is electrolysed by Cu electrodes, Cu is deposited at
the cathode and Cu2+ ions are liberated from the anode. Quantitative Aspects of
electrolysis – Faraday’s laws

1) Faraday’s first law It states that the amount of substance deposited or

liberated at the electrodes (m) is directly proportional to the quantity of
electricity (Q) flowing through the electrolyte.

One Faraday is the charge of 1 mole of electron or it is the amount of electricity required to deposit
one gram equivalent of any substance. Its value is 96500 C/mol.

2) Faraday’s second law It states that when same quantity of electricity is passed through
solutions of different substances, the amount of substance deposited or liberated is directly
proportional to their chemical equivalence. For e.g. when same quantity of electricity is passed
through solutions of two electrolytes A and B, then

Products of electrolysis

The products of electrolysis depend on the following factors:

i) The nature of the electrolyte: The electrolyte may be in molten state or in

aqueous solution state. For e.g. if molten NaCl is electrolysed, Na is deposited at
the cathode and chlorine is liberated at the anode
ii) The type of electrodes used: If the electrode is inert (e.g. Pt, gold,
graphite etc.), it does not participate in the electrode reaction. While if the
electrode is reactive, it also participate in the electrode reaction.

iii) The different oxidising and reducing species present in the electrolytic cell
and their standard electrode potentials. Some of the electrochemical processes
are very slow and they do not take place at lower voltages. So some extra
potential (called overpotential) has to be applied, which makes such process
more difficult to occur. For e.g. during the electrolysis of NaCl solution, the
possible reactions at anode are:

Batteries

A battery is basically a galvanic cell in which the chemical energy of a redox

reaction is converted to electrical energy.

They are of mainly 2 types – primary batteries and secondary batteries.

a) Primary cells: These are cells which cannot be recharged or reused. Here
the reaction occurs only once and after use over a period of time, they become
dead E.g. Dry cell, mercury button cell etc.

1. Dry Cell: It is a compact form of Leclanche cell. It consists of a zinc

container as anode and a carbon (graphite) rod surrounded by powdered
manganese dioxide (MnO2) and carbon as cathode. The space between the
electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc
chloride (ZnCl2). The electrode reactions are:

2. Mercury cell :Here the anode is zinc – mercury amalgam and cathode is
a paste of HgO and carbon. The electrolyte is a paste of KOH and ZnO. The
electrode reactions are:
b) Secondary cells : A secondary cell can be recharged and reused again and
again. Here the cell reaction can be reversed by passing current through it in the
opposite direction.

Lead Storage cell:The most important secondary cell is lead storage cell, which
is used in automobiles and invertors. It consists of lead as anode and a grid of
lead packed with lead dioxide (PbO2) as the cathode. The electrolyte is 38%
H2SO4 solution.

Fuel cells

These are galvanic cells which convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy. One example
for fuel cell is Hydrogen – Oxygen fuel cell, which is used in the Apollo space
programme. Here hydrogen and oxygen are bubbled through porous carbon
electrodes into concentrated aqueous sodium hydroxide solution. To increase the
rate of electrode reactions, catalysts like finely divided platinum or palladium
metal are filled into the electrodes.

Advantages of Fuel cells

1. The cell works continuously as long as the reactants are supplied.

2. It has higher efficiency as compared to other conventional cells.

3. It is eco-friendly (i.e. pollution free) since water is the only product formed.

4. Water obtained from H2 – O2 fuel cell can be used for drinking.

Corrosion :It is the process of formation of oxide or other compounds of a

metal on its surface by the action of air, water-vapour, CO2 etc.

Some common examples are: The rusting of iron, tarnishing of silver, formation
of green coating on copper and bronze etc. Most familiar example for corrosion is
rusting of iron. It occurs in presence of water and air. It is a redox reaction. At a
particular spot of the metal, oxidation takes place and that spot behaves as
anode. Here Fe is oxidized to Fe2+ .

Methods to prevent corrosion

1. By coating the metal surface with paint, varnish etc.

2. By coating the metal surface with another electropositive metal like zinc,
magnesium etc.

The coating of metal with zinc is called galvanisation and the resulting iron is
called galvanized iron. 3. By coating with anti-rust solution. 4. An
electrochemical method is to provide a sacrificial electrode of another metal (like
Mg, Zn, etc.) which corrodes itself but saves the object (sacrificial protection).