Basics of electrochemistry and

it’s application in problem

solving

Dr. Mehul R. Khimani

P P Savani University
NH 8, GETCO, Near Biltech Company, Kosamba, Dhamdod, Gujarat 394125
 Contents
• Introduction
• Voltaic Cell
• Daniel Cell
• IUPAC recommended writing of cell diagram
• Measurement of EMF
• Standard hydrogen half-cell or Standard Hydrogen Electrode (SHE)
• Reference electrodes
• Relation between emf and free energy
• Nernst equation
• Examples
What is electrochemistry?

Electrochemistry

Electrochemical cell Electrolytic cell

 Why do you want to study electrochemistry?

• Electroplating

• Production or Purification of metal

• Working of batteries and cell

 Cell terminology
Current is the flow of electrons through a wire
or any other conductor.

Electrolyte
Electrolyte is the salt solutions in a cell.

Strong Weak
LOANS (Completely dissociate) (Partially dissociate)
Left Send of electron to outer circuit e.g. K2SO4, NH4Cl e.g. CH3COOH
Anode
Oxidation Negative
Electrode is the material (a metallic od/bar/strip) which conducts solution.

Anode is the electrode at which oxidation occurs. It sends electrons into the outer circuit. It has
negative charge and is shown as (–) in cell diagrams.
Cathode as (+) is the electrode at which electrons are received from the outer circuit. It has a positive
charge and is shown in cell diagrams.

Anode compartment is the compartment of the cell in which oxidation half-reaction occurs. It
contains the anode.

Cathode compartment is the compartment of the cell in which reduction half-reaction occurs. It
contains the cathode.

Half-cell : Each half of an electrochemical cell, where oxidation occurs and the half where reduction
occurs, is called the half cell.
 Oxidation/Reduction
Oxidation

2 Na + Cl2 → 2Na+ + 2Cl–

0 0 +1 -1

Reduction

Over all reaction is known as Oxidation-Reduction reaction or Redox reaction.

Half components of the redox reaction is known as Half-reactions

E.g. Zinc bar is dipped in a solution of copper sulphate, Redox reaction taking place on
zinc bar itself

The net reaction is

Zn + Cu2+ → Zn2+ + Cu
Electrode potential or emf : When an electrode is in contact with the solution of its ions in a
half-cell, it has a tendency to lose or gain electrons which is known as electrode potential.

Unit : volts (V)

Oxidation potential : Lose electrons

Reduction potential : Gain electrons

Ered = - Eoxi

Standard electrode potential : The potential difference developed between metal electrode
and solution of ions of unit molarity (1M) at 1 atm pressure and 25 °C (298 K) is called
standard electrode potential.
Voltaic (galvanic) cell

Construction
Anode: Zn metal is dipped in
ZnSO4 solution.

Cathode: Cu metal is immersed in

CuSO4 solution.

Connect electrodes by a copper

wire.

Salt bridge : K2SO4

Flow of electron
External circuit : Anode to
Cathode
Solution : Cathode to Anode (Due
to transfer of SO42-)
Oxidation half-reaction (at Anode) Zn → Zn2+ + 2e–
Reduction half-reaction (at cathode) Cu2+ + 2e– → Cu

Over all reaction Zn + Cu2+ → Zn2+ + Cu

The cell will operate till either the zinc metal or copper ion is completely used up.
 Daniel Cell
Named after the British chemist John Daniel.

Typical voltaic cell without salt bridge.

Salt-bridge has been replaced by a porous pot .

Flow /exchange of ions through the porous pot.

Cell reaction

Zn(s) → Zn2+(aq) + 2e–

Cu2+(aq) + 2e- → Cu(s)

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

  December 2012

The Daniel cell is

a) Pt (S) | Zn(S) | Zn2+(aq) || Cu2+ (aq) | Cu (s) | Pt (S)
b) Pt (S) | Zn(S) | Zn2+(aq) || Ag+ (aq) | Ag (s) | Pt (S)
c) Pt (S) | Fe(S) | Fe2+(aq) || Cu2+ (aq) | Cu (s) | Pt (S)
d) Pt (S) | H2(S) | H2SO4(aq) || Cu2+ (aq) | Cu (s) | Pt (S)

December 2013
The cell voltage of Daniel cell Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s) is + 1.70 V. If reduce potential of
Cu2+ (aq) | Cu (s) is 0.34 V, the reduction potential of Zn2+ (aq) | Zn (s) is
e) 1.141 V b) -1.141 V c) 0.73 V d) -0.73 V

Solution

= -
1.07 = 0.34 -
 IUPAC recommended writing of cell diagram
Single vertical line (|) represents a phase boundary between metal electrode and ion
solution (electrolyte). E. g. Representation for Voltaic Cell
Phase boundary
Zn | Zn2+ Cu2+ | Cu
Anode half cell Cathode half cell

A double vertical line (||) represents the salt bridge, porous partition or any other means
of permitting ion flow while preventing the electrolyte from mixing

Concentrations of dissolved species, in each phase written in parentheses and the state of
each phase (usually s (solid), l (liquid), g (gas) or aq. (aqueous solution)) is included in a
subscript after the species name.

Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)

The symbol for an inert electrode, like the platinum electrode is often enclosed in a
bracket.
Inert Electrode
Mg | Mg2+ || H+ | H2(Pt)

Different species in the same phase are separated by a comma.

Ag (s), AgCl(s) | Cl- || Cl- | AgCl(s), Ag(s)

It is possible to express the external stimulus i.e. ion concentration, pressure into bracket.

Zn(s) | Zn2+ (aq) (1M) || Cu2+ (aq) (1M) | Cu (s) or Zn(s) | Zn2+ (aq, 1M) || Cu2+ (aq , 1M) (1M) | Cu (s)

The value of emf of a cell is written on the right of the cell diagram.
Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s) E = +1.1 V
 Sign of emf value
+ve sign : Electrons are transported from the positive electrode to the negative
electrode (a clockwise flow in external circuit).

–ve sign : emf acts in the opposite direction through the cell circuit

Concussion : The negative sign indicates the reaction takes place in the reverse direction.
 Calculating the emf of a cell

The emf of a cell can be calculated from the half-cell potentials of the two cells (anode and
cathode) by using the following formula

Ecell = Ecathode - Eanode = ER – EL

where ER and EL are the reduction potentials of the right-hand and left-hand electrodes,
respectively.
CSIR NET 2017

Solution

1) Check the given EMF is in reduction potential

2) Apply formula Ecell = Ecathode - Eanode

Note : Absolute values of these reduction potentials cannot be determined.

By connecting the half-cell with a standard hydrogen electrode (SHE) whose reduction
potential has been arbitrarily fixed as zero.
MEASUREMENT OF EMF OF A CELL
The emf of an unknown cell can be measured with the help of a potentiometer
 =
Emf symbol = E & unit is Volt ‘V’
Emf varies with the concentration of the reactants and
products in the cell solutions and the temperature of the
cell.

If you determined emf under standard conditions, it is

called the standard emf
 E2
Temperature = 25 °C

 E1
For liquid : Concentration = 1M, For Gas : Pressure = 1 atm
 

Standard hydrogen half-cell or Standard Hydrogen Electrode (SHE)

Used for : measure unknown emf of half-cell.

Construction : It consists of a platinum foil electrode with platinum black immersed in a 1 M

solution of HCl (H ion) maintained at 25°C.

Pt surface has strong ability towards absorption of H2(g)

Electrode will act as electrode of metallic hydrogen.

H2(g) at 1 atm enters the glass hood and bubbles over the ions
Pt electrode.

The H2(g) at the Pt electrode passes into solution, forming H+ ions and electrons.
 Measurement emf of both half cell of voltaic cell

Complete electrochemical cell Converted to half electrochemical cell

  Anode : Zn(s) | Zn2+ (aq) || H+ | H2 (1 atm), Pt = -0.76V

Cathode : Pt , H (1 atm) | H+ || Cu2+ | Cu = 0.34V

 SHE act as

Cathode (Electron flow from Zn to SHE) Anode (Electron flow from SHE to Cu)
2H+ + 2e– → H2 (Reduction) H2 → 2H+ + 2e– (Oxidation)

The standard hydrogen electrode can be placed on the left-hand or the right-hand side.

IUPAC adopted method to determine standard potential

SHE is always placed on the left-hand side during study.

Consider only standard reduction potentials.

 Reference electrodes
or
Secondary standard electrode

Silver-Silver Electrode Calomel Electrode Glass Electrode Quinhydrone Electrode

  = 0.2224 V   = 0.280 V   = 0.2875 V
 RELATION BETWEEN EMF AND FREE ENERGY

When a cell produces a current, the current can be used to do work–to run a
motor.
A relation between electrical energy and the maximum amount of work, Wmax

Maximum amount of work obtainable from the cell: The product of charge flowing per mole
and maximum potential difference, E, through which the charge is transferred.

Wmax = – nFE …….....(1)

Where, n is the number of moles of electrons transferred and is equal to the valence of the
ion max participating in the cell reaction.
F stands for Faraday and is equal to 96,500 coulombs and
E is the emf to the cell
According to thermodynamics
Wmax = – ΔG …….....(2)
Therefore from (1) and (2), we can write

ΔG =– nFE …….....(3)

According to Gibbs-Helmholtz equation, the decrease in free energy of a system at constant

pressure is given by the expression

−  ΔG = − ΔH − 𝑇 …….. (4)
where – ΔH is the decrease in heat content of the system or heat of the reaction at constant
pressure.
Substituting the value of ΔG from (3)

nFE
  = −ΔH − 𝑇
   𝑇
nFE = −ΔH + nF ………………. (5)

  ………………. (6)
E=− + 𝑇 

Where,   p = the temperature coefficient of the emf of the cell at constant pressure.

The value of electrical energy would be equal to, more or less than the heat of reaction.
 December 2011

The standard electrode potential (EO) of Fe3+/Fe2+ and Fe2+/Fe electrodes are +0.77 V and
-0.44 V, respectively at 300 K. The EO of Fe3+/Fe electrode at the same temperature is

a) 1.21 V b) 0.33 V c) -0.11 V d) -0.04 V

Solution
Using Latimer diagram
+0.77V -0.44V 3 x E3 = -0.11
Fe3+ Fe2+ Fe
O.S. +3 +2 0 E3 = -0.11 / 3

E3 = -0.036 ≈ -0.04 V
n3FE3 = n1FE1 + n2FE2

n3E3 = n1E1 + n2E2

  December 2011

Fuel cell provide clean electrical energy to automobile and stationary power sources.
Normally hydrogen combined with oxygen to give electrical energy and water. If we used
butane instead of hydrogen at 1.0 bar and 298 K, the following reaction occurs :
C4H10(g) + O2(s) 4CO2(g) + 5H2O(l)
If we have change in Gibbs free energy of this reaction is 2746.06 KJmol -1, involving 26
electrons, its open circuit voltage is
a) 1.55 V b) 1.09 V c) 3.15 V d) 2.06 V

Solution

ΔG =– nFE
2746.06 x 1000 J/mol = 26 x 96500 C x E
E = 2746060 / 26 x 96500
E = 1.09 J / mol x C
E = 1.09 V
  June 2017

The electrochemical cell potential (E), after the reactants and products reach equilibrium is
(Eo is the standard cell potential and n is the number of electrons involved)

a) E = EO + b) E = EO - RTlnF c) E = EO d) E = 0

Solution
ΔG = – nFE

At equilibrium ΔG = 0

0 = – nFE

E = 0 (n and F have no. of electrons transfer and Faraday constant, respectively)

  June 2018

The standard cell potential for the reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(S) is +1.10V. The Gibbs
free energy change during the reaction is (F = 96500 C/mol)
a) -21.2 KJ/mol b) 212 KJ/mol c) -212 KJ/mol d) 212 J/mol
Solution
ΔG = – nFE
ΔG = – 2 x 96500 x 1.10
= - 212300 J/mol
= - 212.3 KJ/mol
 NERNST EQUATION
Experimentally potential of a single electrode or half-cell varies with the concentration of
ions in the cell.

Derived mathematical relationship which enable us to calculate half-cell potential, E, from

the standard electrode potential, E°, and temperature

∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛𝑄 ……………. (1)

Where, ∆G = Gibbs free energy
∆GO = Standard Gibbs free energy
R = Universal gas constant
T = Absolute temperature
Q = Quotient
At equilibrium Q = K, (K is the equilibrium constant of the redox cell
reaction) and substituted in equation (1)
Walter Nernst
∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛K ……………. (2)
 ∆𝐺 = - nFE and ∆GO = -nFEO
- nFE = -nFEO + 𝑅𝑇 𝑙𝑛K ……………. (3)
  E = EO - 𝑙𝑛K ……………. (4)

  E = EO - 𝑙og K

  E = EO - 𝑙og K ……………. (5)

Where, R = 8.314 J mol-1 K-1

T = 298 K
F = 96,500 coulombs
Eo = standard electrode potential
n = number of electrons transferred in the half-reaction
K = Equilibrium constant for the half-cell reaction as in
equilibrium law i.e. [Product] / [Reactant]
  June 2011

If the ratio of composition of oxidized and reduced species in electrochemical cell, given as ,
the correct potential difference will be

a) E – EO = b) E – EO = c) E – EO = d) E – EO =

Solution

  E = EO - 𝑙n   E - EO = - 𝑙n
Oxi + e- Red   E - EO = (1)   (

  =   E - EO =

  E - EO = - 𝑙n
   June 2012

The correct Nernst equation for the concentration cell :

Pt (H2) | HCl | AgCl | Ag || Ag | AgCl | HCl | Pt (H2) without Liquid Junction would be

a) E = b) E = c) E = d) E =

Solution
From Nernst equation
Pt (H2) | HCl | AgCl | Ag Ag | AgCl | HCl | Pt (H2)   E = EO - 𝑙og
Oxi Red Oxi Red
E = EO - 𝑙og
Anode : ½ H2 H+ + e-
( 𝑎± )1 E = EO - 𝑙og
Cathode( 𝑎
:H +
± )2
+ e- ½ H2 E = 𝑙og (EO = 0)
Anode : Ag + Cl- AgCl + e-
( 𝑎± )2
Cathode : AgCl + e- ( 𝑎- ± )
Ag + Cl
1
H
+
+ Cl- H+ + Cl-
( 𝑎± )2 ( 𝑎± ) ( 𝑎± )1 ( 𝑎± )1
  December 2012
Calculate the equilibrium constant for an electrochemical reaction
2Fe3+ + Sn2+ 2Fe2+ + Sn4+
EO(Fe3+/Fe2+) = 0.75 V, EO (Sn4+/Sn2+) = 0.15 V, [2.303RT/F = 0.06V]
a) 1010 a) 1020 a) 1030 a) 1040
Anode : Sn2+ Sn4+ + 2e-
Cathode : 2Fe3+ + 2e- 2Fe2+
2Fe3+ + Sn2+ 2Fe2+ + Sn4+
Solution For EO = EOcathode - EOanode
∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛Keq = 0. 75 – 0.15 = 0.60 V
At equilibrium ∆𝐺 = 0 and ∆GO = -nFEO n=2
\ 0 = -nFEO + 𝑅𝑇 𝑙𝑛Keq Substitute both value in eq. 1
\ nFEO = 2.303𝑅𝑇 𝑙ogKeq 16.67 x 2 x 0.6 = 𝑙ogKeq
\ = 𝑙ogKeq 20.004 = 𝑙ogKeq
\ = 𝑙ogKeq Keq = Antilog (20.004)
\ 16.67nEO = 𝑙ogKeq …….. (1) Keq = 1.0 x 1020 = 1020
  June 2013
Which is correct Nernst equation for Redox reaction
O + ne- R
a) E = EO - ln b) = c) = d) =
Solution
E = EO - 𝑙n
E = EO - 𝑙n
E - EO = - 𝑙n
E - EO = 𝑙n
(E – EO) = 𝑙n
=
  December 2013
Consider the cell
Zn(s) | Zn2+ (a = 0.01) || Fe2+ (a = 0.001), Fe3+ (a = 0.01) | Pt

Ecell = 1.71 V at 25 °C for the above equilibrium constant for the reaction
Zn(s) + 2Fe3+ Zn2+ + 2Fe2+ at 25 °C would be close to
a) 1027 b) 1054 c) 1081 d) 1040
Solution   For Ecell= 𝑙og
 ∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛K
eq 1.71 = 𝑙og
At equilibrium ∆𝐺 = 0 = 1.71 𝑙og
and ∆GO = -nFEO = 1.71 𝑙og 0.0001
0 = -nFEO + 𝑅𝑇 𝑙𝑛Keq = 1.71 𝑙og 10-4
\ nFEO = 2.303𝑅𝑇 𝑙ogKeq
\ = 𝑙ogKeq = 1.71 𝑙og 10 = 1.71 – 0.0591 x 2 = 1.5918
\ = 𝑙ogKeq
\ 33.82 x EO= 𝑙ogKeq
\ 33.82 x EO= 𝑙ogKeq
\ 33.82 x 1.5918 = 𝑙ogKeq
\ 53.864 = 𝑙ogKeq
\ Antilog (53.864) = Keq
\ Keq = 7.3 x 1053 ≈ 1054
  December 2014
For the cell reaction,
Sn(s) + Sn4+(aq) 2Sn2+(aq)
Separate electrode reaction could be written with the respective standard electrode
potential data at 25 °C as

Sn4+(aq) + 2e- Sn2+(aq), EO = + 0.15V

Sn2+(aq) + 2e- Sn(S), EO = - 0.14V

When RT/F is given as 25 mV, calculate logarithm of equilibrium constant (lnK) is

a) 22.6 b) 226 c) 2.26 d) 0.226
Solution : Calculate same as above
  December 2014

The correct ∆𝐺 for the cell reaction involving steps

Zn(S) Zn2+(aq) + 2e-
Cu2+(aq) + 2e- Cu(s) is

a) ∆𝐺O - ln b) ∆𝐺O + ln c) ∆𝐺O - ln d) ∆𝐺O + ln

Solution
  Zn(S) Zn2+(aq) + 2e-
Cu2+(aq) + 2e- Cu(s)
  Zn + Cu2+ Zn2+
(S) (aq) + Cu(s)

According to Nernst
  ∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛

∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛, Concentration Activity ∆𝐺O + ln

  December 2015
Given the Eo (Cl2/Cl-) = 1.35V and Ksp(AgCl) = 10-10 at 25°C, EO corresponding to the electrode
reaction

½ Cl2(g) + Ag+(soln.) + e- AgCl(s) is [2.303RT/F = 0.06V]

a) 0.75 V b) 1.05 V c) 1.65 V d) 1.95 V

 \ EO= 𝑙og10-10 / 16.67 x 1
Solution
 ∆𝐺 = ∆𝐺O + 𝑅𝑇 𝑙𝑛K
sp \ EO
= -10 𝑙og10 / 16.67 x 1
At equilibrium ∆𝐺 = 0 \ EO= -10 / 16.67 (log10 = 1)
and ∆GO = -nFEO \ EO= -0.59 V
0 = -nFEO + 𝑅𝑇 𝑙𝑛Ksp
\ nFEO = 2.303𝑅𝑇 𝑙ogKsp ½ Cl2(g) + e- Cl- (Cathode)
\ = 𝑙ogK AgCl Ag +
+ Cl -
(Anod)
sp

\ = 𝑙ogKsp
\ 16.67x n x EO= 𝑙ogKsp \ EO = EOcathode - Eoanode
\ EO= 𝑙ogKsp / 16.67 x n \ EO = 1.35 – (-0.59)
  December 2015
Given (i) Zn + 4NH3 Zn(NH3)42+ + 2e- EO = 1.03 V
(ii) Zn Zn2+ + 2e- EO = 0.763 V
The formation constant of the complex Zn(NH3)42+ is approximately 2.303RT/F = 0.0591
a) 1 x 105 b) 1 x 107 c) 1 x 109 d) 1 x 1012

  December 2018
The equilibrium constant of the following reaction
Sn(s) + Sn4+(aq) 2Sn2+(aq) at 300K is close to
(Given : EOSn4+/Sn2+ = +0.15 V and EOSn2+/Sn = -0.15 V , R = 8.314 JK-1mol-1, F = 96485 C mol-1)
a) 106.08 b) 108.08 c) 1010.08 d) 1012.08
 Conclusion
•  Examples based on

Ecell, ∆𝐺, 𝑙ogKsp, 𝑙ogKeq, 𝑙𝑛, 𝑙𝑛

 Conductivity, Specific conductivity, molar conductivity, Cell constant

Graph of conductometric titration, potentiometry titration

Only Formula