PRINCIPLE OF PHYSICAL

CHEMISTRY

Chap 1: Atoms, molecules & ions

Chap 2: States of matter
Chap 3: Thermochemistry
Chap 4: Chemical Kinetics
Chap 5: Chemical Equilibrium
Chap 6: Electrochemistry
Electrochemistry
1. Introduction
2. Redox reaction
3. Chemical cells
4. Cell potentials
5. Faraday’s Law
6. Nernst equation
CELL POTENTIALS
Standard reduction potentials
 Standard reduction potentials are commonly denoted
by the symbol E°
 Voltage associated with a reduction reaction at an
electrode when all solutes are 1 M and all gases are at
1 atm
CELL POTENTIALS
Standard reduction potentials (cont)
 Voltage related to e- e-
redox reaction 1.10 V

 Sum of electrical
Zn Cu
potentials at Zn &
(1.0M) (1.0M)
Cu electrodes

ZnSO4 CuSO4
anode cathode
CELL POTENTIALS
Standard reduction potentials (cont)
 Impossible to measure
potential of just a single
electrode H2 (g)
at 1 atm
 Hydrogen electrode, serves
as reference (SHE, Standard
Hydrogen Electrode)

Pt

1.0 M HCl
CELL POTENTIALS
Standard reduction potentials (cont)
Under standard condition: 1.0M HCl
& 1 atm H2 (g), potential for the
reduction of H+ at 25oC is taken to be H2 (g)
zero at 1 atm

2 H+ (1.0M) + 2 e-  H2 (1 atm)
Eo = 0 V

Pt

1.0 M HCl
CELL POTENTIALS
Standard reduction potentials (cont)
Pt electrode:

1. Provides a surface for dissociation of H2 molecules

H2  2H+ + 2e-

2. Serves as an electrical conductor to the external circuit

CELL POTENTIALS
Standard reduction potentials (cont)
SHE is used to measure the potentials of other electrodes

Cell diagram: Zn(s) Zn2+(1M) H+(1M) H2(1 atm) Pt(s)

CELL POTENTIALS
Standard reduction potentials (cont)
Anode (oxidation):
Zn (s) → Zn2+ (1M) + 2e-

Cathode (reduction):
2H+ (1M) + 2e- → H2 (1 atm)

Overall reaction:

Zn (s) + 2H+ (1M) → Zn2+ (1M) + H2 (1 atm)

CELL POTENTIALS
Standard reduction potentials (cont)

Standard emf, Eocell is composed of contribution from

anode and cathode

Eocell = Eocathode – Eoanode

 CELL POTENTIALS
Standard reduction potentials (cont)

In previous example: Eocell = Eocathode – Eoanode.

Eocell = EoH+/H2 – EoZn2+/Zn
Eocell = 0 – ( – 0.76 V)
Eocell = 0.76 V
CELL POTENTIALS
Standard reduction potentials (cont)

Cell diagram: Pt(s) H2(1 atm) H+(1M) Cu2+(1M) Cu(s)

CELL POTENTIALS
Standard reduction potentials (cont)
Anode (oxidation):
H2(1 atm) → 2H+(1M) + 2e-

Cathode (reduction):
Cu2+(1M) + 2e- → Cu(s)

Overall reaction:
H2(1 atm) + Cu2+(1M) → 2H+(1M) + Cu(s)
CELL POTENTIALS
Standard reduction potentials (cont)
Eocell = 0.34 V

Eocell = Eocathode – Eoanode

Eocell = EoCu2+/Cu– EoH+/H2
0.34 V = EoCu2+/Cu – 0
EoCu2+/Cu = 0.34 V

standard reduction potential for copper: 0.34 V

 CELL POTENTIALS
Standard reduction potentials (cont)

For Daniell cell:

(a primary voltaic cell with a copper anode and a zinc-amalgam cathode,
giving a standard electromotive force when either copper sulphate or
sulphuric acid is used as the electrolyte.)

Eocell = Eocathode – Eoanode

Eocell = EoCu2+/Cu– EoZn2+/Zn
= 0.34 V – (– 0.76 V)
= 1.10 V
CELL POTENTIALS
CELL POTENTIALS
Standard reduction potentials (cont)

 Sign of Eo can be used to predict the extent of a redox

reaction at equilibrium
• Positive Eo : favor the formation of products
• Negative Eo : favor the formation of reactants

 In the list of standards reduction potentials, SHE has an

value of 0.00 V; below SHE, negative value; above SHE,
positive value
CELL POTENTIALS
Standard reduction potentials (cont)
1. Eo values apply to half-cell reactions as read from left to
right direction
2. More positive Eo is greater the tendency to be reduced,
thus highest positive value: strongest oxidizing agent
3. Half-cell reactions are reversible; electrode can act as
anode or cathode
4. Changing the stoichiometric coefficients does not affect
value of Eo
5. Sign of Eo changes but magnitude remains as we reversed
the reaction
ELECTROCHEMISTRY
1. Introduction
2. Redox reaction
3. Chemical cells
4. Cell potentials
5. Faraday’s Law
6. Nernst equation
FARADAY’S LAW
Thermodynamics of redox reaction
 Eocell related to thermodynamic quantities (Go and K)

 In galvanic cell, chemical energy converted to electrical

energy to do work

 Electrical energy is the product of emf of the cell & total

electrical charge (in coulombs) that passes through the
cell

Electrical energy = Volts x Coulombs

= Joules
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
 The equality: 1J = 1V x 1C
 Total charge is determined by number of e- passed
through the cell
Total charge = no of e- x charge of 1 e-
 It is convenient to express the total charge in molar
quantities. Charge of one mole of electrons is called
Faraday constant (F)

 1 F = 6.022 x 1023 e-/ mol e- x 1.602 x 10-19 C/e-

= 9.647 x 104 C/mol e-
~ 96500 C/mol e-
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
Total charge = nF

n: number of moles of e- exchanged between the oxidizing

agent & reducing agent in the overall redox equation

 Measurement of emf (Ecell) is the maximum voltage the

cell can achieve therefore electrical work done (wele)
which is the maximum work that can be done (wmax) is
given by
wmax = wele = – n F Ecell

 Negative sign: electrical work done by the system

FARADAY’S LAW
Thermodynamics of redox reaction (cont)
 Free energy is the energy available to do work. The
change in free energy (∆G) represents the maximum
amount of useful work can be obtained in a reaction:

∆G = wmax = wele = – n F Ecell

∆G = – n F Ecell
∆G negative: spontaneous reaction
∆G positive: non-spontaneous reaction
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
For reactions in which reactants & products in standard
states (1 M & 1 atm)
∆Go = – n F Eocell

∆Go is related to its equilibrium constant, K

∆Go = – RT ln K
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
Combination of both equations:

– n F Eocell = – RT ln K

Eocell = – RT ln K
–nF

Eocell = RT ln K
nF
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
When T = 298 K, the equation can be simplified by
substituting R and F
Eocell = RT ln K
nF
= (8.314 J K-1 mol-1) (298 K) ln K
n (96500 J V-1 mol-1)

= 0.0257 V ln K or
n
= 0.0592 V log K
n
FARADAY’S LAW
Thermodynamics of redox reaction (cont)
Exercise 3

Consider the redox reaction

Zn2+(aq) + H2(g)  Zn(s) + 2H+ (aq)

Calculate Eocell and ∆Go and determine the spontaneity of

this reaction.

Given:
Zn2+(aq) + 2e  Zn(s) Eo = -0.76V
2H+(aq) + 2e  H2(g) Eo = 0.00V
ELECTROCHEMISTRY
1. Introduction
2. Redox reaction
3. Chemical cells
4. Cell potentials
5. Faraday’s Law
6. Nernst equation
NERNST EQUATION
Effect of concentration on emf
Consider a redox reaction of the type

aA + bB → cC + dD

We have
∆G = ∆Go + RT ln Q where

∆G = - nFE and ∆Go = - nFEo

So - nFE = - nFEo + RT ln Q
NERNST EQUATION
Effect of concentration on emf
Dividing the equation with –nF:
[product]
E = Eo – RT ln Qc [reactant]
nF
E = cell potential (V) under specific conditions
Eo = cell potential at standard-state conditions
R = ideal gas constant = 8.314 J/mol-K
T = temperature (Kelvin)
n = number of moles of electrons transferred in the balanced equation
F = Faraday‘s constant
lnQc = the natural log of the reaction quotient at the moment in time
NERNST EQUATION
Effect of concentration on emf

At 298 K, the eq. can be written as:

E = Eo – 0.0257 ln Q
n OR
E = Eo – 0.0592 log Q
n
NERNST EQUATION
Effect of concentration on emf
 During the operation of galvanic cell, e- flow from anode to
cathode, resulting in product formation & decrease in
reactant concentration, thus Q increases & E decreases.

 At equilibrium, no transfer of e- so E = 0 & Q = K

 Nernst equation enables us to calculate E as a function

of reactant & product concentrations
NERNST EQUATION
Effect of concentration on emf
For Daniell cell; Zn (s) + Cu2+ → Zn2+ + Cu (s)

The Nernst equation for this cell at 25oC is

[product]
E = Eo – 0.0257 ln [Zn2+]
n [Cu2+]
[reactant]
NERNST EQUATION
Effect of concentration on emf
E = Eo – 0.0257 ln [Zn2+]
n [Cu2+]
The reaction quotient is therefore Q = [Zn2+]/[Cu2+]
Hence, if the ratio of [Zn2+]/[Cu2+] < 1
• ln [Zn2+]/[Cu2+] will be negative
• 0.0257 ln [Zn2+] will be positive
n [Cu2+]
• Thus the E > Eo

If Q < K ~ spontaneous reaction

NERNST EQUATION
Effect of concentration on emf
• Since electrode potential depends on ion concentrations, it
is possible to construct a galvanic cell from two half-cells
composed of the same materials but differing in
concentrations ~ concentration cell

• According to Le Chartelier’s principle, tendency for the

reduction increases with increasing concentration of ions

• So reduction will be occurred in the more concentrated

compartment
NERNST EQUATION
Effect of concentration on emf
[oxidation]
E = Eo – 0.0257 ln [diluted]
n [concentrated]
[reduction]
o
• E = 0 (same electrode & same solution)
• E usually small & decreases continually as the
concentrations in two compartments approach each
other
• E = 0 when the concentrations are the same
• Spontaneous if ∆G < 0 and Ecell > 0
• Non-spontaneous if ∆G > 0 and Ecell < 0
ELECTROCHEMISTRY
Example
Predict the results of passing a direct electrical current through
an aqueous solution of sodium hydroxide. Calculate the cell
potential.
Given:
Na+(aq) + e  Na(s) Eo = -2.71V
2H2O(l) + 2e  H2(g) + 2OH–(aq) H2O basic
Eo eq.
= -0.83V
- cathode
4OH– (aq)  O2(g) + 2H2O(l) + 4e Eo = +0.40V
2H2O(l)  O2(g) + 4H+(aq) + 4e Eo =eq.
H2O acidic +1.23V
- anode
 Answer:

Species in solution: Na+, OH– and H2O

Possible oxidation reactions at anode:

4OH– (aq)  O2(g) + 2H2O(l) + 4e
2H2O(l)  O2(g) + 4H+(aq) + 4e H2O acidic eq. - anode
Based on standard reduction potential:

(less +ve)
4OH– (aq)  O2(g) + 2H2O(l) + 4e Eo = +0.40V
2H2O(l)  O2(g) + 4H+(aq) + 4e Eo = +1.23V
Species in solution: Na+, OH– and H2O

Possible reduction reactions at cathode : S.R.P

Na+(aq) + e  Na(s) Eo = -2.71V
2H2O(l) + 2e  H2(g) + 2OH–(aq) Eo = -0.83V
H2O basic eq. - cathode (more +ve)
Overall reaction:

Anode: 4OH– (aq)  O2(g) + 2H2O(l) + 4e

Cathode: 2{2H2O(l) + 2e  H2(g) + 2OH–(aq)}
– 2
4OH (aq) + 4H2O(l) + 4e  O2(g) + 2H2O(l) + 2H2(g) +
4OH–(aq) + 4e

2H2O(l)  O2(g) + 2H2(g)

Overall reaction:
2H2O(l)  O2(g) + 2H2(g)

Eocell = Eocathode – Eoanode

= -0.83 V – (+0.40 V)
= -1.23 V
Conclusion:
Net cell reaction is
2H2O(l)  O2(g) + 2H2(g)
Hydrogen gas is produced at cathode, oxygen gas is
produced at anode.
The cell potential is -1.23V.
Exercise 4
Calculate the emf (E) and predict the spontaneity of the
following reaction at 25oC

Cu(s) Cu2+ (aq) (0.024 M) Ag+(aq) (0.0048 M) Ag(s)

Eo Cu2+/Cu = - 0.34 V and Eo Ag+/Ag = 0.80 V

Exercise 5

Consider the following reaction at room temperature

Co(s) + Fe2+ (aq, 0.83 M) Co2+ (aq, 0.12 M) + Fe(s)

Given: Eo Co2+/Co = – 0.28 V and Eo Fe2+/Fe = – 0.45 V

By using Nernst Equation, determine the cell potential (emf)

(E) and predict the spontaneity of this reaction