Books

1. P. W. Atkins, Elements of Physical Chemistry, Oxford University

Press, 2007.

2. M. S. Bhatnagar, A Text book of Polymer Chemistry

3. C. N. Banwell, E. N. McCash, Fundamentals of Molecular

Spectroscopy, tata McGraw-Hill Education, 1994.

4. A. R. West, Solid State Chemistry and its applications, second

edition, John Wiley & Sons Ltd., 2014.

1
Electrochemistry

2
 Electrochemistry is all about the chemistry between
two chemical species, where one loses electron and
the other accepts that!

Such exchange of electrons is known as REDOX processes.

3
4
5
6
 Example:
Identify the species that are getting oxidized or reduced:

ClO3 - + I - I2 + Cl-

NO3- + Sb Sb4O6 + NO

7
(in acidic medium)

8
9
10
electrons

11
12
 DO it yourself!

Balance the following reaction occurring in acidic media:

MnO-4 (aq) + Fe2+ (aq) Mn2+ (aq) + Fe3+ (aq)

13
Balancing the following reaction in basic medium:

BH4- + ClO3- H2BO3- + Cl-

Let’s assume the reaction taking place in acidic medium!

Oxidation half reaction:
-1 +1
BH4- + 3H2O H2BO3- + 8e- + 8H+

Reduction half reaction:

+5 -1
ClO3- + 6e- + 6H+ Cl- + 3H2O

14
Cancelling the electrons and adding

(BH4- + 3H2O H2BO3- + 8e- + 8H+) ×3

( ClO3- + 6e- + 6H+ Cl- + 3H2O ) × 4

3BH4- + 4ClO3- 3H2BO3- + 4Cl- + 3H2O

Lets assume the reaction taking place in basic medium!

( BH4- + 8OH- H2BO3- + 8e- + 5H2O ) × 3

( ClO3- + 6e- + 3H2O Cl- + 6OH- ) × 4

3BH4- + 4ClO3- 3H2BO3- + 4Cl- + 3H2O

15
 Assume that someone has predicted oxidation number of boron like this:
-5 +3
BH4- + ClO3- H2BO3- + Cl-

Try it out to see whether there will be any change in the final balanced equation!

Our next reaction was the following to be balanced in acidic medium

MnO-4 (aq) + Fe2+ (aq) Mn2+ (aq) + Fe3+ (aq)

16
 Balancing redox reaction

Oxidation half cell reaction:

5Fe2+(aq) 5F3+(aq) + 5e-
Reduction half cell reaction:

MnO4-(aq) + 5e- + 8H+ Mn2+(aq) + 4H2O

MnO4-(aq) + 5Fe2+(aq) 8H+ Mn2+(aq) + 5Fe3+(aq) + 4H2O

How to form an electrochemical cell out of such redox reaction?

17
Will this type of cell give steady electricity?

We will not be able to see electron flow in the above cell!

18
19
Ion migration is required to complete the circuit

20
 Classification of electrochemical cells
Electrochemical cells

• Electrolytic cells • Galvanic cells

• Electrochemical reaction is driven by • Electricity is produced
external electricity out of chemical reaction
• reaction is non-spontaneous • reaction is spontaneous

Given a spontaneous redox reaction, you will now be able to draw a

well labeled diagram of a Galvanic cell out of it!

21
 Some important electrochemistry terms:

Electrochemical cells: two electrodes in contact with redox electrolyte solution

Electrodes: electron conducting materials, where electron exchange take place

between solid materials and solutions

Electrolyte: ion conducting systems

Anode: electrode involved in oxidation reaction

Cathode: electrode involved in reduction reaction

…..and finally the definition of electrochemistry becomes

Chemical reactions taking place in a solution at the interface between electrode

and electrolyte

22
 A specific type of Galvanic cell:
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

e- e-
Zn Cu
salt bridge
anions cations

cations
anions
cotton/porous plugs
ZnSO4 (aq)
anode cathode
CuSO4 (aq)
Zn(s) Zn2+(aq) Cu2+(aq) Cu (s)
23

For a graphic understanding you may watch http://www.youtube.com/watch?v=J1ljxodF9_g

The same Galvanic cell can
be set up using a porous
membrane

Only SO42- ions can move

from one half cell to the other

Such type of cells were used to power telegraphs

Hundreds of years ago!

24
This type of cells are known as Daniell cell:

Concentric cylinders of metallic zinc and copper

dipped in zinc and copper sulphate solution
separated by porous membrane.

25
 A Daniell cell -
Zn rod
+

porous
earthenware

Cu cylinder J. F. Daniell
dil (England, 19th century)
H2SO4

CuSO4 (aq)

Steady electricity can be obtained when the two terminals are connected.
26
 Spontaneity of electrochemical cells

The question is how can we know which electrochemical reactions

would produce electricity spontaneously when connected with a
circuit?

• It depends whether t he reaction is thermodynamically favorable!

That essentially means, we have to predict in which direction, an

electrochemical reaction would proceed according to the
thermodynamic considerations!

27
 Chemical reaction, equilibrium and ΔG

Consider the following chemical reaction occurring reversibly at const. T and P,

aA (aq) + bB (aq) cC (aq) + dD (aq)

At equilibrium,
{C}ceq {D}deq Please note: {C} denotes
K= the activity of species C
{A}aeq {B}beq
At any time,
{C}c {D}d
Q= Q: reaction quotient
{A}a {B}b
If at any time Q > K, the reaction shifts towards left side!
If at any time Q < K, the reaction shifts towards right side!
If Q = K, equilibrium is reached.

28
 Chemical equilibrium
or, in other words chemical equilibrium is reached when

{C}c {D}d {C}ceq {D}deq

Q= = =K
{A}a {B}b {A}aeq {B}beq

At this condition, ΔG = 0 is true for the reaction

aA (aq) + bB (aq) cC (aq) + dD (aq) [at equilibrium]

and ΔG ≠ 0 is true for the same reaction at any time other than equilibrium!
aA (aq) + bB (aq) cC (aq) + dD (aq) [not at equilbrium]
Reaction is running reversibly but not under equilibrium so ΔG ≠ 0

29
Chemical equilibrium
Previous scenario can be explained mathematically like this:
under constant T & P

δG < 0
δξ
δG > 0
δξ

δG = 0
δξ
eq point
equilibrium
reactant end product end
ξ
Free energy does not change with extent of reaction at equilibrium point

30
 Gibbs energy (ΔG) and reaction quotient (Q):

There exists a fundamental equation for a reversible chemical reaction:

ΔG = ΔG0 + RTlnQ

ΔG0 is defined as the standard free energy of the reaction at 25o C,

at 1 atm pressure and all solutes (non-ionic) have concentration
= 1 M (if aqueous) under pH = 7.0

At equilibrium, ΔG = 0 and Q = K, so the above equation becomes

ΔG0 = - RTlnK

31
 ΔG, Q & electrochemical cell potential (E):

In mechanics, ‘potential’ implies the ability/capacity of performing a work.

Similarly, free energy (ΔG) is defined is the maximum amount of non-expansion

work (Wa) that can be extracted from a closed system, where Wa is maximum
when the closed system undergoes a completely reversible change.

Wa, max = ΔG
In an electrochemical reaction, this non-expansion work is directly related to the
electrochemical potential (E) or the capacity of electrochemical work done by the
reaction.
-nFE = ΔG
Here, n = number of moles of electron transferred in the cell reaction
F = Faraday’s constant of charge of 1 mol electrons = e-NA

32
Gibbs energy and Nernst equation
We know,
ΔG = ΔG0 + RTlnQ
or, -nFE = -nFE0 + RTlnQ

or, E = E0 – (RT/nF)lnQ The Nernst equation!

Gibbs energy accounts for a cell’s voltage!

E0 is the cell potential at standard condition, known as standard cell potential

E is known as cell potential or electromotive force (EMF) or cell voltage

If the above equation is applied for a half cell reaction , then
E becomes the half cell potential or simply the electrode potential.
E0 becomes standard half cell potential or simply the standard electrode potential

33
Working form of Nernst equation:
E = E0 – (RT/nF)lnQ R = 8.314 Jmol-1K-1
T = 298 K
So, we can write
Ecell = E0 – (RT/nF)lnQ F = 96485 Cmol-1
cell

Ecell = E0cell – 2.303(RT/nF)log10Q 2.303(RT/nF)

Ecell = E0cell – (0.059 V/n)log10Q = 0.059 V

n

It is interesting to note that when a reversible electrochemical reaction is at equilibrium,

ΔG = 0, so Ecell = o That means cell cannot perform any external work!

So, E0cell = (0.059 V/n)log10 K

We will be able to measure the equilibrium constant (K) of that reversible

electrochemical reaction at equilibrium provided we know the E0cell !
Ecell = Ered (R.H.E) – Ered (L.H.E)
34
 Derivation of Nernst Equation for Electrode potential:

In 1889 Nernst derived a quantitative relationship between the electrode

potential and the concentrations of metal ions are involved.

• The maximum work available from a reversible chemical process is equal

to the maximum amount of electrical energy that can be obtained; it
shows decrease in free energy.
Wmax = – ΔG------------------------------------[1]
And
Wmax = difference in potential between two electrode x total
quantity of charge flowing through the cell

Total quantity of charge flowing through the cell = (No. of moles of

electrons) x (Faradays constant)

35
E cell
36
Spontaneity and cell potential
-nFE = ΔG (relationship between Gibbs energy and electrochemical potential)
Ox (1) + Red (2) Red (1) + Ox (2)

From the above diagram, we can see that an electrochemical reaction will proceed
spontaneously from left to right when ΔG < 0 and Ecell > 0

The reaction will proceed as above till the equilibrium is reached!

37
Electrodes
Following are the examples of few common types of electrodes used in Galvanic cells

Note that each reaction taking place at electrode represents a half-cell reaction
and the half cell potential (Ered or Eox) is termed as Galvani potential difference
38
 Electrode potential
The cell potential (Ecell) of a Galvanic cell can be measured experimentally

The cell potential (Ecell) of a Galvanic cell can also be predicted theoretically
Ecell = E0cell – (0.059 V/n)log10Q (provided we know E0cell and activities)

Standard cell potential (E0cell) can be obtained by two ways:

RTlnK (provided we know K)

One way is E0cell =
nF
The other way is E0cell = E0red + E0ox (provided we know E0red & E0ox)

How to know E0red & E0ox ?

There is no way we can measure E0red/ox for redox half cell reactions!

39
Standard reference potential and standard half cell potentials

Using the standard hydrogen electrode (SHE), we can measure the standard half cell
potentials of other redox half cell reactions!

Ecell reading

salt bridge

X n+ reference
electrode SHE

X m+

Under standard condition, Ecell of the Galvanic cell will be

the E0half cell of the unknown half cell!

40
 Standard reduction potentials and IUPAC conventions

With respect to SHE, any redox couple will have its standard half cell potential
either positive or negative.
That means some half cells will under go oxidation and some will undergo reduction.

To avoid confusion, according to IUPAC, the standard half cell or electrode potentials
are expressed as reduction potential only!

The convention is

Oxidized species + ne- Reduced species (under standard condition)

O2 (g) + 4H+ + 4e- 2H2O (E0 red = + 0.40 V)

Zn2+ (aq) + 2e- Zn (s) (E0 red = - o.76 V)

Eo half cell = E0 standard reduction potential = Eostandard electrode potential

41
Standard electrode potentials
(basically the std. reduction potential at 298 K and under std. condition)

42
Standard electrode potentials (make yourself familiar with such table)

43
 Significance of standard electrode potentials
Zn2+ (aq) + 2e- Zn (s) (E0 = - o.76 V)
O2 (g) + 4H+ + 4e- 2H2O (l) (E0 = + 0.40 V)
Which chamber should contain the zinc electrode to make a spontaneous cell?

salt bridge

Cathode
Anode

an ox! red cat!

at anode oxidation takes place reduction takes place at cathode 44

 Standard cell potential and standard electrode potential
Previously we saw:
E0cell = E0red + E0ox (old convention)

But here we are talking about std. reduction potential only! So the std. reduction
potential at anode needs to be sign reversed to represent oxidation.
So according to the IUPAC convention,

E0cell = E0cathode - E0anode (New convention)

Zn2+ (aq) + 2e- Zn (s) (E0 = - 0.76 V) at which electrode?

O2 (g) + 4H+ + 4e- 2H2O (l) (E0 = + 0.40 V) at which electrode?

45
Significance of standard electrode potentials
Rule of thumb: Half reaction with higher Eo will always oxidize the other

Zn2+ (aq) + 2e- Zn (s) (E0 = - o.76 V)

O2 (g) + 4H+ + 4e- 2H2O (l) (E0 = + 0.40 V)

salt bridge

Cathode
Anode

2Zn (s) 2Zn2+ (aq) + 4e- O2 (g) + 4H+ + 4e- 2H2O

E0cell = E0cathode - E0anode

= + 0.40 - (- 0.76) = +1.16 V Is that cell reaction spontaneous?

What is the expression of Ecell in this case?

46
Calculating std. cell potential from st. electrode potential
Calculate E0cell of the following reactions pairs assuming standard conditions
and spontaneous cell reactions. All values are provided in std. reduction potential.

Formula: E0cell = E0cathode - E0anode

Example I

Pb2+ (aq) + 2e- Pb (s) (E0 = - 0.13 V)

Zn2+ (aq) + 2e- Zn (s) (E0 = - 0.76 V)

Example II

K+ (aq) + e- K (s) (E0 = - 0.83 V)

2H2O (l) + 2e- 2OH- (aq) + H2 (g) (E0 = - 2.93 V)

47
How to represent a Galvanic cell (battery) on paper?
It’s a pretty demanding job to draw a cell diagram like below, every time!
Zn2+ (aq) + 2e- Zn (s) (E0 = - o.76 V)
O2 (g) + 4H+ + 4e- 2H2O (l) (E0 = + 0.40 V)

salt bridge

Cathode
Anode

2Zn (s) 2Zn2+ (aq) + 4e- O2 (g) + 4H+ + 4e- 2H2O

Scientifically we can represent the cell in the following manner (IUPAC):

Zn (s) Zn2+ (aq) O2 (g) H+ H2O (l) Pt (s)

anode cathode
electrode phase electrode
left hand side salt bridge phase right hand side
boundary boundary
(an ox left) (red cat right)
48
Systematic cell notations:

Previous cell can be represented in detailed manner like below:

Zn (s) Zn2+ (aZn2+ = 1, aq) O2 (g) H+ (aH+ = 1, aq) H2O (l) Pt (s)

Example: III
Write down the complete cell reaction from the notation below:

Example: IV
Write down the cell notation from the half cell reactions below:

K+ (aq) + e- K (s) (E0 = - o.83 V)

2H2O (l) + 2e- 2OH- (aq) + H2 (g) (E0 = - 2.93 V)

49
Metal/insoluble salt electrode:
Example: IV
Write down the half and complete cell reactions from the notation below:

Ag (s) Cl- (aq) AgCl(s) Ag+ (aq) Ag (s)

Ag (s) + Cl- (aq) AgCl (s) + e-

Ag+ (aq) + e- Ag (s)

AgCl (s) + e- Ag (s) + Cl- (aq) (E0 = +0.22 V)

Ag+ (aq) + e- Ag (s) (E0 = + o.8 V)

What is the complete cell reaction and standard cell potential?

Ag+ (aq) + Cl- (aq) AgCl (s)
E0cell = E0cathode - E0anode = (0.8 – 0.22) V= 0.58 V

50
Standard electrode potential
A convention is adopted to assign the standard half cell or electrode potentials

H+ (aq) + e- (Pt) ½ H2 (g)

The standard half cell potential or Eo red of the above the reaction
is set as 0.0 volt (by definition)!

0.059 V 1
EH+/H = E0H+/H – log 10 (activity of pure H2 gas is unity)
n [aH+]

Under standard condition of [aH+] = 1.0 and at 298 K and 1 atm pressure,
the above equation becomes

EH+/H = E0H+/H = 0.0 Volt

So the standard reduction potential of hydrogen electrode is zero volt

51
 Determination of solubility product
Consider the cell: Ag (s) Ag+ (aq) I- (aq) AgI (s) Ag (s)
Cell reaction:
AgI (s) Ag+ (aq) + I- (aq) AgI (s) + e- Ag (s) + I- (aq) (E0 = -0.15 V)
Ag+ (aq) + e- Ag (s) (E0 = + o.8 V)
Nernst equation:
[aAg+ (aq)] [aI- (aq)]
Ecell = E0cell – 0.059 V log 10
[a AgI (s)]

If the above cell reaction is reversible then the Keq is called the solubility product
[aAg+ (aq)]eq [aI- (aq)]eq
AgI (s) Ag+ I-
(aq) + (aq) Keq = Ksp =
[a AgI (s)]eq
We know, an electrochemical cell at equilibrium means Ecell = 0
E0cell -
So, E0cell = 0.059 V log10 Ksp or, Ksp = anti log =
0.059 V

In this way we can determine, the Ksp for a sparingly soluble salt used in electrodes
52
pH electrode
Consider the following electrochemical cell:

Pt(s) H2(g) H+ (aq, a = ?) H+ (aq, a = 1.0) H2 (g) Pt (s)

Ecat = 0.0
0.059 V [aH+]
Ean = - log 10
1 1
= 0.059 V pH Ecell
pH =
0.059 V
Ecell = 0.059 V pH

These days, we don’t use hydrogen gas electrode, but

we use glass based ion selective electrode for pH reading.
Commercial cells: Leclanchē’s battery (primary cells)

Zn (s) Zn2+ (aq), NH4Cl (aq) MnO2 (s), Mn2O3 (s) C (s)

An irreversible cell
Non-rechargeable cell

(wet cell)

Zn (s) Zn2+ (aq) + 2e- Eo red = - 0.76 V

MnO2 (s) + 2e- + H2O Mn2O3 (s) + 2OH- Eo red = o.64 V

used in devices such as flashlights and portable radios.

Commercial dry cells: (primary cells)

In modern era, instead of aqueous NH4Cl medium, NH4Cl paste is

used in dry cells.

(dry cells)
 Alkaline batteries (primary)
Zn (s) Zn2+ (aq), KOH (aq) MnO2 (s), Mn2O3 (s) Ni(s)

KOH paste is used (dry cell)

At anode:
Zn (s) Zn(OH)2 + 2e-

MP3 players, CD players,

digital cameras, toys,
flashlights, and radios.

Li-ion batteries are completely reversible, known as secondary batteries

Commercial cells: Plantē’s battery (secondary cells)
Pb (s) PbSO4(s) H2SO4 (aq) PbSO4 (s) PbO2 (s)

Reversible cell reaction, so rechargeable batteries!

separator membrane
- +
H+ H+ HSO4-
Pb PbO2
HSO4- H+
H+
HSO4-
HSO4-
H+ HSO4-
H+

PbSO4 PbSO4
(aq. H2SO4)

In commercial lead-acid batteries six such chambers are stacked in parallel.

Up to 400 A of current is produced in few seconds.
Cell reactions in lead acid batteries
Balance the cell reaction in sulfuric acid medium

Pb (s) + PbO2 (s) PbSO4 (s)

At anode:

Pb (s) PbSO4 (s)

At cathode:

PbO2 (s) PbSO4 (s)

Net reaction:

The net reaction is reversed when the cell is recharged!

 Hydrogen fuel cells

H2 (g) 2H+ (aq) + 2e- Eored = o.0 V

½ O2 (g) + 2H+ (aq) + 2e- H2O (l)

Eored = o.4 V
Overall cell reaction:
½ O2 (g) + H2 (g) H2O (l)
We can design a cell in which, hydrogen
can be oxidized at anode and oxygen
can be reduced at cathode and we
can obtain a cell voltage!

Such type of cell is known as hydrogen

fuel cells that can power an automobile
Hydrogen fuel cells
Ideal vs non-ideal solutions
B B
A A
A A B B A A
A B B B
A B B
A A B B A B
A

molecules of A molecules of B mixture of molecules of A and B

molecular molecular molecular
interaction = UAA interaction = UBB interaction = UAA, UBB & UAB

We call the solution of A and B ideal if 2UAB = UAA + UBB

In electrochemistry, we deal with ions in electrolytic solutions. Obviously, for
ionic interaction, in a solution:
2UAB ≠ UAA + UBB

Ionic solutions are non-ideal!

Non-ideal solution and activity coefficient
In an ideal mixture or solution
µi = µ0i + RTlnxi (where xi is the mole fraction of the ith component)

B B
A A
A A B B
A A B B A A
B B
A A B B B
A B
A
µA = µ0A µB = µ0B
µA = µ0A +RTlnxA
In a non-ideal solution µB = µ0B +RTlnxB
µi = µ0i + RTlnxifi xifi = ai (activity)
fi is called activity coefficients
 Activity coefficients of solvent and solute

Cl-
H2O solvent
A NaCl aqueous solution Cl-

Cl-
µCl- = µ0Cl- + RTlnxCl-fCl- Cl-
(considering Cl- only)
µH2O = µ0H2O + RTlnxH2OfH2O

if xCl- 0 then xH2O 1

Since pure substance’s activity = 1, automatically fH2O 1
So a solution tends to be ideal in infinite dilution!
At infinite dilution, xH2O (mole fraction) = cH2O (molarity) = mH2O (molality)

Ionic solutions are non-ideal even in dilute (finite) solution

 Activities in a non-ideal solution
Electrolytic solution of electrochemistry are essentially non-ideal
Ionic species are present at finite (even though dilute) solution

µi = µ0i + RTlnxifi = µ0i + RTlnai Where ai is called ‘activity’

ai = xifi = mi γ ci
i = γi (m0 = 1 m solution and c0 = 1 M solution)
m0 c0
γi : denotes the activity coefficient when
mi: concentration in molality
concentration of solute is expressed
ci: concentration in molarity in molality or molarity (dimensionless quantity)
For simplicity:
µi = µ0i + RTlnmiγi = µ0i + RTlnciγi
 Activity coefficient of an electrolyte
Let’s assume a non-ideal aqueous solution of NaCl (1:1 electrolyte) and
complete dissolution

NaCl (aq) Na+ (aq) + Cl- (aq)

So, we can write:

μNaCl,aq  μ  μ salt      
Na , aq Cl  , aq or,
also, 0
μ NaCl,aq  μ 0

Na ,aq
 μ 0
Cl  ,aq or, salt
0
 0  0
from the definition,

µsalt = µ0salt + RT lnasalt and µ+ = µ0+ + RT lna+ and µ- = µ0-+ RT lna-

Also, we know that

i  i
0
 RT ln mi  i
 Activity coefficient of an electrolyte
salt      
salt
0
 RT ln asalt   0  RT ln m    0  RT ln m 

salt
0
 RT ln asalt   0   0  RT ln m   m 
Since,

salt
0
  0   0
We have
asalt  m   m  = (m+.m-)(γ+ .γ-)

unfortunately, since we cannot isolate an anion or a cation we have no way to

measure experimentally the value of γ+ or γ- !
Mean activity coefficient of an electrolyte:
We assume a mean activity coefficient denoted as: γ±
and the assumption becomes: γ+ = γ- = γ± (mean activity coefficient)

For NaCl (1:1) electrolyte,

So, asalt  m   m  = (m+.m-)(γ+ .γ-) = (m+.m-)(γ±)2

Therefore.
     
1
2   (for 1:1 electrolyte)

If NaCl is of m molal, then m+ = m- = m, so asalt = (m)2 .(γ±)2

It is possible to measure γ± experimentally!

 General expression for γ±
For any salt stoichiometry:

Now solve the following problem:

Solution of the problem:
Solution of the problem (continued):
Glass electrode

71
Mechanism of glass electrode:

72