ELECTROCHEMISTRY

❏ Electrochemistry is the branch of chemistry in which deals with the inter-relationship between electrical
energy and chemical changes.

❏ It is the study of production electricity from energy released during spontaneous chemical reactions and the
use of electrical energy to bring about non-spontaneous chemical reaction

❏ The chemical reaction occurring due to the passage of electric current is electrolysis (electrical energy is
converted into chemical energy)

Eg: Electrolysis of water, purification of impure cu metal

❏ The chemical reaction in which electric current is produced is called electrochemical reaction (chemical
energy is converted into electrical energy)

Eg: Batteries, fuel cells, galvanic cells

Redox Reaction

Oxidation : Loss of electron / increase in oxidation number

Reduction : Gain of electron / decrease in oxidation number

Oxidising agent : Those which oxidizes the other compound and removes hydrogen from the
compound. i.e. Reduction

Reducing agent : A substance which loses electrons to other substances in a redox reaction and
gets oxidized to the higher valency state. i.e. Oxidation
 Electrolytic cells
An electrolytic cell is an electrochemical cell that uses electrical energy to drive a non-spontaneous
chemical reaction. Usually used for refining metals. Eg. For the purification of Cu

These cells contain anode & cathode are connected to an external circuit.
 ELECTROCHEMICAL CELL
(Galvanic cell/Voltaic cell)
Electrochemical cell is device which converts chemical energy into electrical energy during a redox
reaction

Eg: Daniel cell

● It consists of a zinc rod dipped in ZnSO4 solution (anode half cell) and a Cu rod dipped in CuSO4
solution (cathode half cell)

● The two rods are connected by a metallic wire through a voltmeter

● The two solutions are connected by a salt bridge

● When the circuit is complete, electrons flow from Zn rod to Cu rod.

● At anode oxidation half reaction takes place

● At cathode Reduction half reaction takes place

At anode, Zn → Zn2+ + 2e- (oxidation half reaction)
At cathode, Cu²+ + 2e- → Cu (reduction half reaction)
Zn + Cu²+ → Zn²+ + Cu (cell reaction)
This cell converts the chemical energy liberated during the redox reaction to electrical energy and
has an electrical potential equal to 1.1 V when concentration of Zn²+ and Cu²+ ions is unity , such a
device is called a galvanic or a voltaic cell.
Salt Bridge
It is a U-shaped glass tube filled with a gelly like substance, agar-agar mixed with an inert electrolyte like KCl,
NH4NO3 etc...

Its functions are,

● It connects the two solutions and complete the electrical circuit (without mixing of the solutions.)

● It maintains the electrical neutrality of the solution in the half cells (by migrations of ions)

? Define anode and cathode of an electrochemical cell

✔ The electrode at which oxidation takes place is called anode and is negatively charged.

✔ The electrode at which reduction takes place is called cathode and which is positively charged.
Cell representation

A cell is represented by,

● writing the anode on left hand side and cathode on the right

● Anode is represented by writing the metal first and then the electrolyte.

● Cathode is represented by writing the electrolyte first and then the metal.

● Salt bridge is represented by two vertical lines

Representation of Daniel cell : Zn | Zn²+ || Cu²+ | Cu

Galvanic cells
A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into
electrical energy

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 half-cells or redox couples.

● The copper electrode may be called the reduction half cell

● The zinc electrode called the oxidation half-cell.

Electrode potential (E)

It is a measure of tendency of an electrode to lose or gain electrons.

The tendency of an electrode to lose electrons is called oxidation potential

The tendency to gain electrons is called reduction potential.

Oxidation potential is numerically equal to reduction potential but opposite in sign.

According to IUPAC convention, the reduction potential alone is called electrode

potential.
Standard electrode potential (E°)
It is the electrode potential measured under standard conditions. (ie, at 298 K, 1 atm pressure and 1
molar concentration.)

Cell potential or EMF of a cell (Ecell)

Cell potential or EMF of a cell (Ecell) is the difference between electrode potentials of two electrodes
in a galvanic cell.

E(cell) = E(cathode)- E(anode)

Standard Hydrogen Electrode (SHE)
It is a reference electrode used to measure standard electrode potential.

Its electrode potential is taken as zero.

SHE consists of a platinum electrode coated with platinum black.

The electrode is dipped in an acid solution of 1 M concentration

Pure hydrogen gas at 1 bar pressure is bubbled through the solution at 298 K.

If SHE acts as anode, the reaction is H2 2H+ + 2e-

If SHE acts as cathode, the reaction is 2H+ + 2e- H2

(SHE, anode representation Pt | H2(1 bar)|H+(1 M)

SHE, cathode, representation H+ | H2 | Pt )

Measurement of Electrode potential
The electrode whose potential is to be measured is connected with standard hydrogen electrode to
form a cell.

The EMF of the resulting cell is determined experimentally.

The electrode potential is then calculated using the equation.

E°cell = E°cathode - E°anode

For eg : To measure standard electrode potential (E°) of Zn electrode

● A Zn rod is dipped in 1M ZnSO4 solution. It is then connected to SHE through voltmeter. The two
solutions are connected by salt bridge. Voltmeter gives a cell potential of 0.76 V. The flow of electrons
is from Zn to SHE. Therefore, Zn acts as anode and SHE acts cathode.
● Eocell = Eocathode - Eoanode

● Eocell = EoH+/H2 – EoZn2+/zn

● 0.76 = 0 – EoZn2+/Zn

● EoZn2+/Zn = - 0.76 V

( For Cu, cell potential is 0.34V. Electrons flow from SHE to Cu. Therefore, SHE anode & Cu cathode

For Mg, cell potential is 2.36V. Electrons flow from Mg to SHE. Therefore, Mg anode & SHE cathode)
Electrochemical series
The arrangement of various elements in the increasing order of standard reduction potentials

(or E° values) is called electrochemical series or activity series

Applications

1) To calculate EMF of a cell

The metal with lower reduction potential acts as anode and the metal with higher reduction potential acts
as cathode.

E° cell = E° cathode - E° anode

2) To predict feasibility of a cell reaction.

If E° cell is positive, the cell reaction is feasible.

3) To predict whether a metal can liberate hydrogen from dilute acids.

Metals with negative E° values can liberate hydrogen from dilute acids. That is, metals placed above
hydrogen in electrochemical series can liberate hydrogen from dilute acids.
4) To compare the reactivity of metals.
A metal can displace another metal which lies below in the electrochemical series from its salt solution.
For eg: Zn can displace Cu from CuSO4 solution.

5) To compare the oxidising and reducing power of elements.

Element with greater E° value is easily reduced. Therefore, it will be a stronger oxidising agent. Fluorine
is the strongest oxidising agent. Element with lower E° value is easily oxidising. Therefore it will be a
stronger reducing agent. Li is the strongest reducing agent.
Nernst equation for electrode potential
It gives the relationship between electrode potential and concentration of the electrolyte.

For a general electrode reaction,

Mn+ + ne- M

E = Eo – (RT/nF) ln [M]/[Mn+]

where E is electrode potential, E° is standard electrode potential, R is gas constant, T is temperature in

kelvin, n is no. of electrons involved, F is Faraday constant, [M] is concentration of metal and [Mn+] is
concentration of metal ion.

But concentration of solid M is taken as unity, [M] = 1

Substituting the values of R (8.314 J/K/Mol), T (298K), F (96500C). We get,
Application of Nernst equation
1) Nernst equation for cell potential
Consider Daniel cell, Zn | Zn²+ || Cu²+ | Cu

Cell potential = E(cell) = E(cathode)- E(anode) Ecell = Ecu2+/cu – Ezn2+/zn

Applying Nernst equation for electrode potential,

Ecu2+/cu = Eocu2+/cu – (0.059/n) log (1/[cu2+])

Ezn2+/zn = Eozn2+/zn – (0.059/n) log (1/[zn2+])

Substituting these values we get,

Ecell = (Eocu2+/cu – (0.059/n) log (1/[Cu2+])) – (Eozn2+/zn – (0.059/n) log (1/[Zn2+]))

Ecell = (Eocu2+/cu - Eozn2+/zn) – (0.059/n)(log 1/[cu2+] - log 1/[zn2+])

Ecell = Eocell – (0.059/n) log ([zn2+]/[cu2+])

For a general reaction,
aA + bB cC + dD

Nernst equation for cell potential is,

Ecell = Eocell – (2.303RT/nF) log([C]c[D]d/[A]a[B]b)

Nernst equation for cell potential at 298K is,

Ecell = Eocell – (0.059/n) log ([product]/[reactant])

2) Relation between Eocell and equilibrium constant Kc
Consider Daniel cell

Cell representation : Zn | Zn²+ || Cu²+ | Cu

Cell reaction is,

Zn + Cu²+ → Zn²+ + Cu

Nernst equation for cell potential at 298 K is,

Ecell = Eocell – (0.059/n) log ([zn2+]/[cu2+])

At equilibrium, electrode potentials of 2 electrodes become equal

So, Ecell = 0
And, Kc = [zn2+]/[cu2+]
Substituting these values in Nernst equation,
0 = Eocell – (0.059/n) log Kc

In general,
Eocell = (2.303RT/nF) log Kc or Eocell = (0.059/n) log Kc
3) Relation b/w ∆Go and Eocell
∆G is the maximum useful work available from a system

∆G = -nFEcell

In standard state, ∆Go = -nFEocell

We know that, Eocell = (2.303RT/nF) log Kc

So we get,

∆Go = -nF (2.303RT/nF) log Kc

∆Go = -2.303RT log Kc

Conductance of electrolytic solutions
i) Resistance (R)

Its unit is ohm (Ω)

Resistance of a conductor is directly proportional to its length (l) and inversely proportional to its area
of cross section (A).

where is called resistivity or specific resistance. Its unit is Ωcm.

ii) Resistivity or specific resistance is defined as the resistance of a conductor of length 1cm and area of
cross section 1 cm².
iii) Conductance (G) is the inverse of resistance. Its SI unit is siemens. 1S = 1 Ω-1 (ohm-1 or mho)

Where inverse of resistivity is called conductivity (κ – kappa)

Conductivity or specific conductance (K) is defined as conduction of solution of length 1 cm and area of
cross section 1 cm2
Differences between Metallic conductors (electronic conductors) and
electrolytic conductors (ionic conductors)

Metallic conductors Electrolytic conductors

Flow of current is due to flow of electrons Flow of current is due to movement of ions.

Chemical decomposition of electrolyte takes

There is no chemical change
place.
There is no transfer of matter
There is transfer of matter in the form of ions
Metallic conductance decreases with
Electrolytic conductance increases with

increase in temperature increase in temperature.

Measurement of conductivity of ionic solutions

Conductivity of a solution is determined by measuring its resistance using Wheatston bridge.

For this, we face two problems,

a) Firstly, passing direct current changes the composition of the solution.

b) Secondly, a solution cannot be connected to the bridge like a metallic wire.

The first problem is resolved by using an alternating current (AC) source.

The second problem is solved by using conductivity cell (refer text)

The solution is taken in the conductivity cell and is connected as one arm of Wheatstone bridge.

Cell constant : Conductivity, K = (1/R)×(l/A) where (l/A) is a constant for a given cell and is called cell
constant. Its unit is cm-1
By adjusting resistances R₁, R3 & R4
null point is obtained.
At null point, R1/R3 = R2/R4
Unknown resistance, R2 = R1R4/R3
Reciprocal of resistance gives conductance.
Molar conductivity (ꓥm)

It is defined as the conductance of a solution containing one mole of electrolyte.

Its unit is scm2mol-1 or Ω-1cm2mol-1

If k is conductivity and V is volume in cm3 of solution containing one mole of electrolyte. Then,

ꓥm = KV or ꓥm = (1000K/M) where M is the molarity of the solution.

Variation of conductivity and molar conductivity with concentration
Both conductivity and molar conductivity change with the concentration of the electrolyte.

Variation of conductivity with concentrations

Conductivity is conductance of 1 mL electrolyte solution

Conductivity or specific conductance decreases with increase in dilution for weak and strong electrolytes.

This is due to number of ions per unit volume that carry the current in a solution decreases on dilution

Variation of molar conductivity with concentration

Molar conductivity is conductance of 1 mole electrolyte solution

Molar conductivity increases with decrease in concentration (on dilution) because the total volume V of solution
containing one mole of electrolyte also increases (ꓥm = 1000K/M = 1000K/(n/V) = (1000 x K x V) / n))

Conductivity reaches a maximum limiting value at zero concentration.

This limiting value of ꓥm at zero concentration is called limiting molar conductivity or molar conductivity at
infinite dilution (ꓥom or ꓥ∞m)
a) Variation for strong electrolytes
ꓥm of strong electrolytes increases slightly with dilution.

Reason :- Before dilution, the interionic attraction b/w ions are very high. On dilution, inter-ionic
distance increases & inter-ionic attraction decreases, so speed of ions increases hence conductivity
increases

ꓥm of strong electrolytes found to obey Debye - Huckel - Onsagar equation.

ꓥm = ꓥom - A√c

where A is a constant & c is molar concentration (eq. is in the form of, y = mx + c)

ꓥm = - A√c + ꓥom

A plot of ꓥm against √c is linear ( Slope = -A, intercept = ꓥom )

The value of ꓥom can be obtained by extrapolating the graph to √c = 0

b) Variation for weak electrolytes

ꓥm of weak electrolytes increases rapidly with dilution.

Reason :- With dilution, degree of dissociation increases and no. of ions in solution increases

ꓥm against √c graph is not linear

The value of ꓥom can not be obtained by extrapolating the graph
Differences between strong electrolytes and weak electrolytes

Strong electrolytes Weak electrolytes

They are completely ionised in They are only partially ionised in
solution solution
They show high values of They show low values of
conductance conductance
ꓥm increases slightly with dilution ꓥm increases rapidly with dilution
ꓥm against √c graph is linear ꓥm against √c graph is not linear
The value of ꓥom can be obtained The value of ꓥom can not be
from the graph. obtained from graph
 Kohlrausch law of independent migration of ions
It states that “limiting molar conductivity of an electrolyte is equal to the sum of individual contributions (or molar ionic
conductivities) of cations and anions of the electrolyte”

ꓥom = ‫ט‬+λo+ + ‫ט‬-λo-

‫ט‬+ and ‫ט‬- are no. of cations and anions formed from one molecule of electrolyte. λo+ and λo- limiting molar conductivities
of cation and anion respectively

For NaCl, ꓥo(NaCl) = λoNa+ + λoCl-

Applications of Kohlrausch law

1) To calculate limiting molar conductivity (ꓥom ) of weak electrolyte

According to Kohlrausch law, ꓥo(CH3COOH) = λoCH3COO- + λoH+

ꓥom of acetic acid can be calculated if we know ꓥom values of CH3COONa, HCl, NaCl
 ꓥo(CH3COONa) + ꓥo (HCl) - ꓥo (NaCl) = λoCH3COO- + λoNa+ + λoH+ + λocl- - λoNa+ - λoCl-
= λoCH3COO- + λoH+
= ꓥo(CH3COOH)
2) To calculate degree of dissociation of weak electrolyte

Degree of dissociation (α) is the fraction of the total no number of molecules of the electrolyte which
undergoes ionization

α = ꓥcm/ꓥom

where ꓥcm molar conductivity at concentration c and ꓥom limiting molar conductivity

3) To calculate dissociation constant of weak electrolyte

Dissociation constant, Ka = cα2/(1- α) = cꓥ2m / ((ꓥmo)2(1-ꓥm/ꓥom) = cꓥ2m / (ꓥmo(ꓥm - ꓥom)