Electrochemistry

Electrochemistry 1
 Electrochemistry
• Electrochemical cell: Galvanic / Voltaic OR Electrolytic cells

1. Galvanic/ Voltaic: Involves spontaneous redox reaction, leading to movement of

electrons, finally generating electricity. Example: Daniell cell.

2. Electrolytic cell: Involves non spontaneous redox reaction with application of external

voltage, leading to decomposition of normally stable or inert chemical compounds.

Example: high-purity aluminium, copper, zinc and lead is produced industrially in

electrolytic cells.

Electrochemistry 2
 Redox Electrochemistry
Oxidation Reduction

Loss of electrons Gain of electrons

Occurs in one half cell Occurs in the other half cell

Metal-1 dipped in a solution (electrolyte Metal-2 dipped in a solution (electrolyte

– 1) of its own ions – 2) of its own ions
Metal-1 has a tendency to undergo Metal-2 has a tendency to undergo
oxidation because it has a high oxidation reduction because it has a high
potential reduction potential
Electrochemistry 3
 Line Notation

• solidAqueousAqueoussolid

• Anode on the leftCathode on the right

• Single line indicates different phases

• Double line indicates porous disk or salt bridge

• If all the substances on one side are aqueous, a platinum electrode is

indicated

Electrochemistry 4
 Line
Notation
An abbreviated
representation of an
electrochemical cell

(Ex. Line notation for the Daniell cell)

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

Anode Anode Cathode Cathode
material
| || | material
solution solution
Electrochemistry 5
The electrochemical Daniell cell is represented as:
Zn(s) | Zn2+(a1 M) || Cu2+(a2 M) | Cu(s)
Oxidation reaction Zn(s) ⎯⎯→ Zn2+(a1 M) + 2e-
Reduction reaction 2e- + Cu2+(a2 M) ⎯⎯→ Cu(s)

Total cell reaction Zn(s) + Cu2+(a2 M) ⎯⎯→ Cu(s) + Zn2+(a1 M)

External circuit: The movement of electrons from anode to cathode gives rise to current flow through
external circuit

Internal connection: A salt bridge is employed to provide ionic contact between two half-cells with
different electrolytes. A salt bridge allows the flow of negative or positive ions to maintain a steady-state
charge distribution between the oxidation and reduction half cells, while still keeping the contents
Electrochemistry 6
separate.
Electrochemistry 7
Electrode potential is defined as the potential that exists between the metal and its own ions

in an aqueous solution at their equilibrium when they are in contact with each other.

Oxidation potential: The potential generated due to oxidation at the electrode in equilibrium is

termed as oxidation potential.

Reduction potential: The potential generated due to reduction at the electrode in equilibrium

is termed as reduction potential.

Standard electrode potential: It is defined as the potential that exists between the metal and

its aqueous solution of 1M concentration at 298K and 1atm pressure.

• Standard reduction potential is measured with the help of Standard Hydrogen Electrode, E0 = 0 V
Electrochemistry 8
 Reduction potential
• More negative i.e. less positive E° means
• Low reduction potential
• Higher oxidation potential

• Will act as the anode

• More positive i.e. less negative E° means

• High reduction potential

• Lower oxidation potential

• Will act as the cathode

Electrochemistry 9
 Oxidation potential
• More negative i.e. less positive E° means
• Low oxidation potential
• Higher reduction potential

• Will act as the cathode

• More positive i.e. less negative E° means

• High oxidation potential

• Lower reduction potential

• Will act as the anode

Electrochemistry 10
 Cell potential
• The difference in electrical potential between the anode and cathode

✓ cell voltage
✓ electromotive force (emf)
✓ cell potential

• The ability of the anode to push the electrons and the ability of cathode to attract the
electrons together constitutes the driving force or electrical pressure that sends electrons
through the circuit.
• This driving force is known as the electromotive force (EMF) or cell potential (Ecell)
with which the cell works. Its unit is Volts (V).
Electrochemistry 11
 Cell Potential
• Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

• The standard cell potential (E°cell ) is the sum of the

potential at each electrode.

• E°cell = E°Zn  Zn2+ + E°Cu2+  Cu

• (i.e. oxidation potential of anode + reduction potential

of cathode)

• We can look up reduction/oxidation potentials in a

table called the electrochemical series
E˚cell = E˚cathode – E˚anode (considering
Electrochemistry
only reduction potentials) 12
 Cell Potential
• Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

• The standard cell potential (E°cell ) is the cell e.m.f

measured when the reactants and the products are on
their standard states i.e. 1M for dissolved species, 1
atm pressure for gases & pure substances for solids and
liquids.

• We can look up reduction/oxidation potentials in a

table called the electrochemical series
E˚cell = E˚anode – E˚cathode (considering
Electrochemistry
only oxidation potentials) 13
 Cell Potential
• Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

• We can look up reduction/oxidation potentials in a

table called the electrochemical series

• It is important to identify which electrode is anode

and which one is cathode, before using the formula
for calculating the standard cell potential (E°cell )
E˚cell = E˚anode + E˚cathode
(Oxidation potential) (Reduction potential)
(considering oxidation potential of anode and reduction potential
Electrochemistry 14
of the cathode)
• The current is the rate at which electrons pass through the cell,

measured in amperes (A)

• The movement of electrons from anode to cathode gives rise to

current flow through the external circuit.

Electrochemistry 15
Decreasing reduction potentials

Reduction
Potentials

Electrochemistry 16
Decreasing reduction potentials

Reduction
Potentials

Electrochemistry 17
Standard Cell potential numerical

Electrochemistry 18
Standard Cell potential numerical

Electrochemistry 19
• Electrical energy produced in a cell = n x F x E

Where,

n = Number of moles of electrons exchanged in the

electrochemical reaction (mol)

F = Faraday's constant, 96500 coulombs/mol

E = Cell potential or EMF in volts

Electrochemistry 20
• The maximum amount of work that can be produced by an

electrochemical cell (wmax) is equal to the product of the cell potential

(Ecell) and the total charge transferred during the reaction (nF):

wmax = ─ n F Ecell

• Work is expressed as a negative number because work is being done

by a system (an electrochemical cell with a positive potential) on its

surroundings. Electrochemistry 21
• The change in free energy (ΔG) is also a measure of the maximum

amount of work that can be performed during a chemical process

ΔG = wmax

• Consequently, there must be a relationship between the potential of

an electrochemical cell and ΔG, this relationship is as follows:

ΔG = ─ n F Ecell
Electrochemistry 22
• A spontaneous redox reaction is therefore characterized by

a negative value of ΔG (i.e. ΔG < 0) and a positive value of

E°cell.

• When both reactants and products are in their standard

states, the relationship between ΔG° and E°cell is as follows:

ΔG° = ─ n F E°cell
Electrochemistry 23
• Thermodynamic relationship between ΔG°, ΔG and the temperature
for a system is given as:

ΔG = ΔG°+ RT ln Q
• R= 8.314 J.mol-1.K-1, Q is the reaction quotient which at equilibrium is
equal to the equilibrium constant, K.

• Thus, the above equation becomes ΔG= ΔG°+ RT ln K. But, at

equilibrium, ΔG= 0, thus the expression can be rearranged to the
familiar

ΔG°= ─ RT ln K
Electrochemistry 24
 Deriving the Nernst equation
• From the thermodynamic relationship:
G = G° + RTln(Q)
• By substituting:
G = ─ nFEcell , ΔG° = ─ n F E°cell
─ nFEcell = ─ nFE°cell + RTln(Q)

Ecell = E°cell ─ (RT/nF)ln(Q) ln x = 2.303 log x

R = 8.314 J.mol-1.K-1
T = 298 K
Ecell = E°cell ─ (0.0592/n)log(Q) F = 96500 C

The Nernst Equation

Electrochemistry 25
 A Discharged Cell

• As the reaction in the cell proceeds, eventually, the reaction reaches a stage of

equilibrium, at which point the emf of the cell drops to zero

• Such a cell with E = 0 is a discharged or a ‘dead’ cell

Electrochemistry 26
 The Nernst Equation
(Non-standard conditions)
• The Nernst equation is used for calculating the emf of an electrochemical

voltaic cell under non-standard conditions

• The Nernst equation is given as:

• n = the number of electrons involved in the balanced reaction at the

anode or the cathode

Electrochemistry 27
 The Nernst Equation
(Non-standard conditions)
• The Nernst equation is used for calculating the emf of an electrochemical

voltaic cell under non-standard conditions

• The Nernst equation can also be given as:

• n = the number of electrons involved in the balanced reaction at the anode

or the cathode Electrochemistry 28

 The Nernst Equation
(Non-standard conditions: Example)
• For the redox reaction:
Zn (s) + Cu2+ (aq) Zn2+(aq) + Cu (s) E˚cell = + 1.1 V

• If [Cu2+] = 5.0 M, and [Zn2+] = 0.05 M, then at these concentrations the emf of the cell using the

Nernst equation is:

Electrochemistry 29
 The Nernst Equation
(Non-standard conditions: Example)
• For the cell: Zn│Zn2+║Ag+│Ag . Calculate Ecell Given: E˚cell = + 1.55 V

Hint: Write the reactions at anode and cathode, and then the balanced
redox reaction, here ‘n’ = 2

Zn (s) + 2Ag+ (aq) Zn2+(aq) + 2Ag(s)

• If [Ag+] = 5.2 × 10─6 M, and [Zn2+] = 1.3 × 10─3 M, calculate the emf of the

cell

• Using the Nernst equation:

Ans. Ecell = 1.273 V

Electrochemistry 30
• Given: E°Ag  Ag + = ─ 0.8 V ; E°Zn 2+ Zn = ─ 0.76 V

Ans. [Ag +] = 6.1 x 10─5 M

Electrochemistry 31
Nernst equation numerical

Electrochemistry 32
Nernst equation numerical

Electrochemistry 33
 Faraday’s Laws of Electrolysis

• If you wished to electroplate an object, you might ask

yourself the following questions:

• How can one determine how much metal is being

plated?

• How long should one leave the object being plated in

the electroplating cell?

• What size electric current should be used?

Electrochemistry 34
 Faraday’s Laws of Electrolysis
• Michael Faraday was a 19th century English chemist.

• His studies yielded two laws relating amount of electric current

and the chemicals produced by the current or used to produce
it.

• These laws enable us to:

• Work out the amount of energy required to discharge a metal

ion and place it out on an object or

• To calculate the amount of metal produced in an electrolytic

cell.
Electrochemistry 35
 Faraday’s Laws of Electrolysis – First Law
• The First law states that: The mass of metal produced at the
cathode is directly proportional to the quantity of electricity
passed through the cell

mQ

• Electric charge, Q, is measured using the unit coulomb.

• In practice we cannot measure the charge directly but we can

measure the current which is charge flowing per unit time. The SI
unit of current is ampere (A) which is defined as current flowing
through a conductor in one second
Electrochemistry 36
 Faraday’s Laws of Electrolysis – First Law

• Thus, the electric charge passing through a cell may be calculated

from measurements of the current, I, through the cell and the
time, t, for which the current flows.

Charge (coulombs) = current (amps) x time (seconds)

Q = It

Electrochemistry 37
Faraday’s Laws of Electrolysis – Second Law

• The second law states that: When the same amount of

charge is passed through different electrolytes the mass

of metal deposited (or the substance liberated) at the

cathode are directly proportional to their respective

chemical equivalent/equivalent weight

• Ex. Consider the three ions Ag+ , Cu2+ , Cr3+

Electrochemistry 38
Faraday’s Laws of Electrolysis – Second Law
• In order to produce one mole of metal: one, two, or three
moles of electrons must be consumed.

• Faraday found that there was a certain charge associated

with one mole of electrons.

• This amount of charge is now called the Faraday and is

equivalent to 96 487 (or 96 500) Coulomb.

1 Faraday = 96 500 Coulomb

Electrochemistry 39
Faraday’s Laws of Electrolysis – Second Law
In order to produce one mole of metal, one two or three moles
of electrons must be consumed.

1 mole of Ag+ (aq), Cu2+ (aq) and Cr3+ (aq) will require 1, 2 and 3
moles of electrons respectively for reducing to the metallic form.

Mathematically, the second law can be expressed as:

Amount of charge = no. of moles of metal ions (n) x charge

on the metal ion (z) x 1 Faraday (F)
(From 2nd law)
Q = nzF and Q = I t
(Important (From 1st law)
formulae It = nzF (by equating both)
for
numerical) Electrochemistry 40
 Faraday’s Laws of Electrolysis
(Important
expressions Q = n z F
for numerical
solving) Use this formula when the charge, Q is expressed in Coulombs

‘m’ is the mass of the metal

OR deposited in grams; ‘M’ is the
molar mass of the metal

Q = n z

Use this formula when the charge, Q is expressed in Faradays

‘m’ is the mass of the metal

OR deposited in grams; ‘M’ is the

Electrochemistry molar mass of the metal 41
 Faraday’s Laws of Electrolysis
Also, n = m / M,

where m = mass of the metal deposited on the cathode (in

grams) &

M = the atomic weight of the metal deposited at the cathode

(Important
Thus, Amount of charge, Q ( in coulombs) = formula for
numerical)

Thus, the mass of the metal being deposited at the cathode, can
be calculated

Similarly, the atomic weight of the metal can be calculated if all

other quantities in the above equation, are known
(Important
formula for
It = numerical)
Electrochemistry 42
Faraday’s Laws of Electrolysis – Questions
1. Calculate the number of mole of copper produced in an electrolytic
cell if a current of 5.0 amperes flows through a solution of copper
ions for 10 minutes.
2. Calculate the time taken to deposit 1.00 g of copper onto an object
that is placed in a solution of copper nitrate, Cu(NO3)2, and has a
current of 2.50 A flowing through it.
3. In an operating electrolytic cell, a current of 150 000 A is used.
Calculate the mass of aluminium that would be produced if this cell
operates continuously for 1 day.
4. The electrolysis of a solution of chromium ions using a current of
2.2 A for 25 minutes produced 0.60 g of chromium. Calculate the
charge on the chromium ion.
5. Calculate the masses of metal produced when 600 Faraday of
charge is used to reduce the ions of aluminium, silver and zinc.
Electrochemistry 43
Faraday’s laws numerical

Electrochemistry 44
Faraday’s Laws of Electrolysis – Solutions
1. n (Cu) = I t / z F
n (Cu) = 5.0 x 10 x 60 / 2 x 96 500
n (Cu) = 1.6 x 10-2 mol
That is, 1.6 x 10-2 mole of copper would be produced

2. t = n (Cu) z F / I
t = (1.00 / 63.5) x 2 x 96 500 / 2.5
t = 1216 seconds
That is, it takes 20 minutes 15 seconds to deposit 1.00 g of copper

3. n (Al) = I t / z F
n (Al) = 150 000 x 24 x 60 x 60 / 3 x 96 500
n (Al) = 44 767 mol
m (Al) = 44 767 x 27 = 1 208 705 g
That is, 1.2 tonne of aluminium is produced per day

Electrochemistry 45
Faraday’s Laws of Electrolysis – Solutions
4. z (Cr) = I t / n F
z (Cr) = 2.2 x 25 x 60 / (0.60 / 52) x 96 500
z (Cr) = 2.96
As the charge on an ion is a small integer, it must be 3+.
The ion is Cr3+.

5. Q = m z F / M
As Q = 600 F, then m = 600 M / z
m (Al) = 600 x 27 / 3 = 5400 g
m (Ag) = 600 x 107.9 / 1 = 64 740 g
m (Zn) = 600 x 65.4 / 2 = 19 620 g
The same 600 F of charge would produce different masses of these
metals; 5.4 kg of Al, nearly 20 kg of Zn and almost 65 kg of Ag.

Electrochemistry 46
Question
If 306C of charge is passed through a solution of Cu(NO3)2 during
an electrolysis experiment, what is the number of moles of copper
metal deposited at the cathode?
Cu(NO3)2 → Cu2+ + 2NO3- , thus. z = 2 Cu → Cu2+ + 2e-

Q = n z F, n = Q / z F

= 306
2 ×96500

 0.00158 moles Cu deposited at the cathode

Question
If 612 C of charge is passed through a solution of
Cu(NO3)2(aq), calculate the number of moles of copper metal
deposited.
Electrochemistry Answer = 0.00317 mol 47
Faraday’s laws numerical

Electrochemistry 48
Question
How many minutes will it take to deposit 0.00235 mol of metallic gold
by electrolysis of Au3+(aq) using a current of 0.214A?

Au3+ + 3e- → Au, z = 3

t = n (Au3+) z F / I
t = 0.00235 x 3 x 96 500 / 0.214
t = 3179 seconds
= 53 minutes
Thus, it takes 53 minutes to deposit 0.00235 moles of metallic gold in the
given cell

Electrochemistry 49
Question
How many hours will it take to deposit 0.0047 mol of gold by electrolysis
of Au3+(aq) using a constant current of 0.214 A?

Answer: 1.77 hours t = n (Au) z F / I ; z = 3

Question
How many kilograms of Ca (atomic weight = 40.08 a.m.u) will be
produced in an electrolytic cell of molten CaCl2 if a current of 0.452 A
is passed through the cell for 1.5 hours?

Answer: 5× 10─4 kg Ca m=ItM/zF

Electrochemistry 50
Question
Calculate the mass (in grams) of palladium (Pd) produced by the
reduction of Pd2+ ions during the passage of 3.20 amperes of
current through a solution of palladium (II) sulfate for 30.0 minutes.
(Atomic weight of Pd = 106.4 a.m.u)

Answer: 3.18 g m=ItM/zF

Question
On passing 0.1 Faraday of electricity through aluminum chloride
(AlCl3) how many grams of aluminum metal will be deposited at the
cathode ( atomic weight of Al = 27 a.m.u) Q (in Faraday) = m z / M
Answer: 0.9 g Al Therefore, m = Q M / z
Electrochemistry 51
Faraday’s laws numerical

Electrochemistry 52
Question

Calculate the mass in grams of aluminum produced by

electrolysis of molten aluminum chloride, if a current of 500 mA
passes for 1.50 hr. ( atomic weight of Al = 27 a.m.u)

m = I . t . M /z . F

Answer: 0.252 g

Electrochemistry 53
Question

An aqueous solution of Palladium (Pd) was electrolyzed for 1 hr

with a current of 1 A to produce 1.985 g of Pd at the cathode.
Calculate the charge on the Pd ion in this salt ( atomic weight of
Pd = 106.4 a.m.u)

Answer: 2+

Electrochemistry 54