CHAPTER 4

ELECTROCHEMISTRY
 OUTLINES
4.1 Types of electrochemical cell (Galvanic & Electrolytic)
4.2 Half-reactions and electrodes
4.2.1 Redox reaction
4.2.2 Calculation of standard cell potential, E°cell by Standard Reduction Potential
(SRP)
4.2.3 Symbolic representation of a cell (Cell Notation)
4.2.4 Predicting spontaneity of redox reactions
4.2.5 The Nernst equation
4.2.6 Concentration cells
4.2.7 Factors affecting the redox potential
4.3 Electrolysis
4.3.1 Factors affecting electrolysis and Electrochemical series
4.3.2 Faraday’s law and quantitative aspects of electrolysis
4.3.3 Applications of electrolysis (electro- refining, electroplating, manufacturing of
chlorine gas, sodium hydroxide and hydrogen from electrolysis of brine)
 Electrochemistry
 Electrochemistry is the branch of chemistry that
deals with the relationship between electricity (flow
of electrons) and chemical reactions.

 Reactions that involve transfer of electrons

(reduction and oxidation)

 Spontaneous reactions - galvanic cells or batteries .

 Nonspontaneous reactions - electrolytic or

electroplating cells. Why do reduction-
oxidation reactions occur?
Of course, it is all about
energy.
 • Interconversion of
electrical energy and
chemical energy
•Organic synthesis •Classified as Redox
•Catalyst reactions reactions (oxidation-
•Electroplating reduction)
•Energy/ cells/batteries •Involves spontaneous and
non-spontaneous reactions

Applications
Parts of galvanic cell
•Cathode
•Anode
•Electrolytes
Electrochemistry
•Voltmeter
•Salt bridge
Types of
Oxidation
electrochemical cell
•Loss electrons
•Oxidation number increased
Galvanic cell • Either loss of H or gain of O
•Spontaneous reactions
to produced electric Reduction
energy •Received electron
•Oxidation number decreased
Electrolysis cell •Either a gain of H or loss of O
•Non-spontaneous
chemical reaction using
outside sources of
electric energy
5
Galvanic Chemical reaction
cell
Generate electric current

Electrolytic
Use electric current
cell

Cause chemical reaction

OXIDATION
R OIL IS
E
D
LOSS REDUCTION
O
X RIG IS
GAIN 6
 Electrochemical processes are oxidation-
reduction reactions in which:
• the energy released by a spontaneous
reaction is converted to electricity or
• electrical energy is used to cause a
nonspontaneous reaction to occur
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4eOxidation

- half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e

7
8
Characteristics of VOLTAIC/GALVANIC
and ELECTROLYTIC cells.
 Galvanic/Voltaic Cells

anode cathode
oxidation reduction

spontaneous
redox reaction

10
Half cell reactions Overall reactions Half cell reactions
 Salt bridge electrolytes

•Not only water, but other liquids as well

can ionize various substances and result
in electrolytic solutions.

Precautions
•U-shape tube
•Contains a gel permeated with an •The dilution of acids is dangerous.
inert electrolyte solution: KCl, KNO3, If water is added to a concentrated
Na2SO4 and NH4NO3, acid, it can explode violently
•Used to complete a circuit by causing severe injuries.
connecting two electrolytes.
•Never pour water into
concentrated acid. Always add the
acid to the water. 11
Voltaic Cells

• The oxidation occurs

at the ANODE.
• The reduction occurs
at the CATHODE.
Voltaic Cells

• Once electron flows

from the ANODE to
the CATHODE, the
charges in each
beaker would not be
balanced and the
flow of electrons
would stop.
Voltaic Cells
• Therefore, we use a
salt bridge, usually a
U-shaped tube that
contains a salt
solution, to keep the
charges balanced.
Cations move toward
the CATHODE.
Anions move toward
the ANODE.
15
• Redox (reduction oxidation) are electron-
transfer reactions.

• Half reaction clearly/explicitly show the

electrons involved in redox reaction.

16
• Oxidation - half-reactions that involves loss of
electrons.

• Reductions - half-reactions that involves gain

of electrons.

17
18
SRP E°

SRP of a metal is the potential difference

of a metal – cation half cell connected to
hydrogen electrode under standard
condition, 1 M solution at 25 oC

A reference electrode, standard hydrogen

electrode (SHE)

19
 Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M and [Zn2+] = 1 M

Cell Diagram

phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode salt bridge cathode 20
 Standard Reduction Potentials
Standard reduction potential (E0) is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Reduction Reaction

2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

***SHE is used to measure the potential

of other electrodes
21
Standard hydrogen electrode (SHE)
 Standard Hydrogen Electrode
• Their values are referenced to a standard
hydrogen electrode (SHE).
• By definition, the reduction potential for
hydrogen is 0 V:
2 H+ (aq, 1M) + 2 e−  H2 (g, 1 atm)
 Standard Reduction Potentials (SRP)

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-

Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)
23
 Standard Reduction Potentials
0 = 0.76 V
Ecell

0 )
Standard emf (Ecell
0 = E0
Ecell 0
cathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

0 = E 0 + - E 0 2+
Ecell H /H2 Zn /Zn

0.76 V = 0 - EZn0 2+
/Zn
0 2+
EZn /Zn = -0.76 V

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V 24

 0 )
Standard emf (Ecell
0 0
E0 = Ecathode - Eanode
cell

The electrode potential or cell potential for copper or zinc

can be determined the same way using Daniel cell.

Zn + Cu2+  Zn 2+ + Cu Eo = 1.10V

E0cell = Eocathode – Eoanode = 1.10V

E0cell = EoCu – EoZn = 1.10V
E0Cu= Eocell– EoZn = 1.10 + (-0.76) = +0.34V
So, the half-cell reactions for standard reduction potentials
(SRP) for zinc and copper are written as follow:
Zn 2++ 2e  Zn EoZn = -0.76V
Cu2+ + 2e  Cu EoCu = +0.34V

***cell potential at cathode is larger than Eo anode

• E0 is for the reaction as
written
• The more positive E0 the
greater the tendency for the
substance to be reduced
• The half-cell reactions are
reversible
• The sign of E0 changes
when the reaction is
reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change
the value of E0 26
More positive Eº
more easily electron is
added
More easily reduced
Better oxidizing agent
More negative Eº
more easily electron is lost
More easily oxidized
Better reducing agent
Oxidizing and Reducing Agents
• The strongest
oxidizing agents have
the most positive
reduction potentials.
• The strongest
reducing agent have
the most negative
reduction potentials.
 Oxidizing and Reducing Agents

The greater the

difference between
the two, the greater
the voltage of the
cell.
 EXAMPLE !!!!

What is the standard emf of an electrochemical cell made

of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?
Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer
Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V Cd will oxidize Cr

Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2

Cathode (reduction): 2e- + Cd2+ (1 M) Cd (s) x3
2Cr (s) + 3Cd2+ (1 M) 3Cd (s) + 2Cr3+ (1 M)

0 = E0
Ecell 0
LargerE0 = cathode cathode - Eanode
Smaller E0 = anode 0 = -0.40 – (-0.74)
Ecell
0 = 0.34 V
Ecell
30
 EXAMPLE !!!!

A galvanic cell is constructed from the following half-cells, cadmium and silver.

Cd2+ + 2e Cd E0 = -0.40 V
Ag+ + e Ag E0 = +0.80 V

a) Identify the anode and cathode

b) Calculate the cell potential, E0cell
c) Write the overall cell reaction

Answers:
a) Cathode = Ag, anode = Cd
b) 1.20 V
c) Cd + 2Ag+ Cd2+ + 2Ag

31
 Learning check !!!!

A galvanic cell is constructed from the following half-cells,magnesium and

argentum.

Mg2+ + 2e Mg E0 = -2.37 V
Ag+ + e Ag E0 = 0.80 V

a) Identify the anode and cathode

b) Calculate the cell potential, E0cell
c) Write the overall cell reaction

0 = E0
Ecell 0
cathode - Eanode
Answers:
a) Cathode = Ag, anode = Mg
b) 3.17 V
c) Mg + 2Ag+ Mg2+ + 2Ag Larger E0 = cathode
Smaller E0 = anode
32
Cell Potentials
• For the oxidation in this cell,

E = −0.76 V
• For the reduction,

E  = +0.34 V
 Cell Potentials
 = E  (cathode) − E  (anode)
Ecell
= +0.34 V − (−0.76 V)
= +1.10 V
 Standard Cell Potentials - 2
The cell potential at standard conditions can be found through this equation:

Ecell
 = E (oxidation) + E (reduction)
 Cell Potentials -2
For the oxidation in this cell,
Zn(s)  Zn2+ + 2e
From the table Standard of Reductional Potential
Zn2+ + 2e  Zn(s) E = −0.76 V
Therefore
Zn(s)  Zn2+ + 2e E  = +0.76 V
For the reduction,
Cu2+ + 2e  Cu(s) E  = +0.34 V
 Cell Potentials - 2
Ecell
 = E (oxidation) + E (reduction)
= 0.34 V + 0.76 V
= +1.10 V
38
Consider a Daniel cell,

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

[Cu2+] = 1 M and [Zn2+] = 1 M
A shorthand notation or symbolic representation of a cell is used
to simplify the equation.

Cell Diagram
phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode salt bridge cathode
 Notation for a Voltaic Cell
components of anode components of cathode
compartment compartment
(oxidation half-cell) (reduction half-cell)

electrode phase of lower phase of higher phase of higher phase of lower electrode
oxidation state oxidation state oxidation state oxidation state

phase boundary between half-cells

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

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

graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq) | Mn2+(aq) | graphite

inert electrode
When half-cell involves gas, an inert electrode such as platinum is
used to serve as a terminal or electrode surface for the reaction to
occur.
2H+ + 2e  H2 (g) H+ | H2 (g) | Pt
Other examples that use platinum electrode are given below:

Pt | Cl- (aq) | Cl2 (g)

Fe3+ (aq), Fe2+ (aq) | Pt
 EXAMPLE !!!!

Write the cell notation for the reaction:

H2 (g) + Cu2+ (aq) Cu (s) + 2H+ (aq)

Solution:

We have to identify the half-cell reactions at anode and cathode before

we can write the cell notation. Hydrogen is oxidized at anode and copper
ion is reduced at cathode.

Anode : H2 (g) 2H+ (aq) + 2e

Cathode : Cu2+ (aq) + 2e Cu (s)

Cell notation : Pt l H2(g) l H+ ll Cu2+ l Cu

42
 Example
Write the notation for a voltaic cell consists of one half-cell
with a Cr in a Cr(NO3)3 solution, another half-cell with an
Ag in an AgNO3 solution, and a KNO3 salt bridge.
SOLUTION:
Oxidation half-reaction
e- Voltmeter
Cr(s) Cr3+(aq) + 3e-
salt bridge

Reduction half-reaction Cr Ag
Ag+(aq) + e- Ag(s) K+
NO3-
Overall reaction
Cr(s) + 3Ag+(aq) Cr3+(aq) + 3Ag(s) Cr3+ Ag+

Cr(s) | Cr3+(aq) || Ag+(aq) | Ag(s)

 Example
A voltaic cell houses the reaction between aqueous
bromine and zinc metal is given in the reaction below.
Calculate Eobromine given Eozinc = − 0.76 V.
Br2(aq) + Zn(s) Zn2+(aq) + 2Br−(aq) Eocell = 1.83V
SOLUTION:

anode: Zn(s) Zn2+(aq) + 2e E = +0.76

Eocell = Eooxidation + Eoreduction = 1.83V = Eobromine + 0.76V

Eobromine = 1.83 − 0.76 = 1.07 V

 Exercise
What is the standard potential of an electrochemical cell
made of a Cd electrode in a 1.0M Cd(NO3)2 solution
and a Cr electrode in a 1.0M Cr(NO3)3 solution?

Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V

Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V

46
• Standard reduction potential series is used to predict the
spontaneity of the reaction:
– Spontaneous
– Non-spontaneous

If the E0 cell > 0, the reaction is spontaneous

If the E0 cell < 0 , the reaction is non-spontaneous

47
 EXAMPLE !!!!

Predict whether the Pb2+ can oxidize aluminum or copper from standard reduction
potential table:
Cu2+ + 2e Cu E0 = +0.34 V
Pb2+ + 2e Pb E0 = -0.13 V
Al3+ + 3e Al E0 = -1.66 V

1) Pb can oxidize Al (metal below it) E 0 = E0 - E 0

cell cathode anode
3Pb2+ + 2Al 3Pb + 2Al3+
= -0.13 – (-1.66)
= 1.53 V (positive), so the cell potential is spontaneous

2) Pb can’t oxidize Cu but can reduce Cu

Pb2+ + Cu Pb + Cu2+
= - 0.13 – (0.34)
= - 0.47 V (negative), so, the cell potential is non-
spontaneous
 Exercise
By combining the following three half-reactions into
three balanced equations (A, B, and C), determine the
spontaneous reactions and calculate Eocell for each
spontaneous reaction.

(1) NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) Eo = 0.96 V

(2) N2(g) + 5H+(aq) + 4e- N2H5+(aq) Eo = -0.23 V
(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) Eo = 1.23 V
 Exercise
A galvanic cell is constructed from the following
half cell, Tin and Lead.
Sn4+ (aq) + 2e- Sn2+ (aq) E0 = 0.13 V
Pb2+ (aq) + 2e- Pb (s) E0 = -0.13 V

a. Identify anode and cathode.

b. Write the overall cell reaction.
c. Write the cell notation for the reaction.
d. Calculate the standard potential for the cell.
e. Which species is the stronger reducing agent?
 Exercise
Predict whether the cell reaction below is
SPONTANEOUS or NOT according to the Eºcell.

a. Al3+ + Cr Al + Cr3+
b. Fe + Zn2+ Fe2+ + Zn
c. Mg + Cd2+ Mg2+ + Cd
d. Sn + Ni2+ Sn2+ + Ni
e. Cr + Pb2+ Cr2+ + Pb
52
• Cell potential do not solely depend on the in SRP series but on
other factors such as;

Factors affecting the redox potential

Concentration of ions Temperatures

(electrolytes)

53
• Using base-10 logarithms, (2.303log A = ln A)
2.303 RT
Ecell = Ecell− log Q
nF

T = Temperature in K
R = gas constant, 8.314 J/K.mol
F = 96500 C/mol
n = Number of moles of electrons.
Q = [Product]/[Reactant]
 At room temperature (298 K),
2.303 RT
= 0.0592 V
F
Thus the equation becomes

0.0592
Ecell = Ecell − log Q
n
56
• Concentration cell – cell constructed from two half
cell of the same material.

• Oxidation- in more diluted site

• Reduction - in more concentrated site

 Concentration Cells

• When a voltaic cell using the same substance at both

electrodes, Eºcell = 0.
• Ecell will not be 0 as long as the concentrations are
different (Q ≠ 0).
 Concentration Cells
• Is an electrochemical cell with identical half-cells with
different ion concentration.

 As long as the concentrations are different, E will not be zero.

 Reduction occurs in more concentrated solution and oxidation takes place in less
concentrated solution.
 Concentration Cells
• From the Nernst Equation,
0.0592
Ecell = Ecell − log Q
n
0.0592 log [Product/dilute]
Ecell = Ecell −
n
[Reactant/concentrated]

• The product and reactant are determine from the

overall equation and cell notation.
Galvanic cell from two half-cells composed of the same
material but differing in ion concentrations.

0.0592
log
0.0592
log
61
 EXAMPLE !!!!

Will the following reaction occur spontaneously at 250C if

[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)

Oxidation: Cd Cd2+ + 2e-

n=2
Reduction: 2e- + Fe2+ 2Fe
2+/Fe – ECd2+/Cd
0
E0 = EFe 0

E0 = -0.44 – (-0.40) 0.0592

E = E0 - log Q
n
E0 = -0.04 V
0.0592 0.010
E = -0.04 V - log
2 0.60
E = 0.013 V

E > 0; Spontaneous
62
 EXAMPLE !!!!

A voltaic cell is constructed using Zn | Zn2+ (0.010 M) and H2 (0.30 atm) | H+

(2.5 M) cell.

a) Write the cell notation

b) Calculate the Ecell at 298K

Answer:
Balance equation; Zn + 2H+  Zn2+ +H2
a) Cell notation : Zn l Zn2+ ll H+ l H2(g) l Pt

63
Oxidation: Zn Zn2+ + 2e- E0 = -0.76V
Reduction: 2e- + 2H+ H2
0 = E0
Ecell 0
cathode - Eanode

E0 = 0 – (-0.76)
E0 = 0.76 V
0.0592
E = E0 - log Q
n
0.0592 [Zn2+]P (H2)
E = 0.76 V - log
2 [2H+]
0.0592 (0.010)(0.30)
E = 0.76 V - log
2 (2.5)
E = 0.86 V
64
 Concentration Cells
Calculate the cell potential of an electrochemical cell made of a
Cr electrode in a 0.01M Cr(NO3)3 solution and a Sn electrode in a
1.00M SnSO4solution?

Cr I Cr3+ (0.01M) II Sn2+ (1.00M) I Sn

Anode:(Ox) Cr2+ + 3e  Cr(s) E0 = −0.74V

2(Cr(s)  Cr3+ + 3e) E0 = +0.74V
Cathode:(Re) 3(Sn2+ + 2e  Sn(s)) E0 = −0.14V
Overall equation: 2Cr + 3Sn2+ → 2Cr3+ + 3Sn

E°cell = Eoxidation + Ereduction = 0.74 + (−0.14) = 0.60V

 Concentration Cells
Mol of electron, n = 6
Q = [product]/[reactant] = 0.01M/1.00M = 0.01

0.0592 log [Product]

Ecell = Ecell − n [Reactant]
0.0592 log [0.01]2
Ecell = 0.60 −
6 [1.00]3

Ecell = 0.60 + 0.0395 = 0.6395 = 0.64 V

 Concentration Cells
In a test of a new reference electrode, a chemist constructs a voltaic
cell consisting of a Zn/Zn2+ half-cell and an H2/H+ half-cell under the
following conditions. Calculate Ecell at 298 K.
[Zn2+] = 0.010 M [H+] = 2.5 M P = 0.30 atm
H2
2H+(aq) + 2e- H2(g) Eo = 0.00 V P x [Zn2+]
Q= H2
Zn2+(aq) + 2e- Zn(s) Eo = -0.76 V
[H+]2
Zn(s) Zn2+(aq) + 2e- Eo = +0.76 V
(0.30)(0.010)
Q=
0.0592 V (2.5)2
Ecell = Eo cell - log Q
n Q = 4.8x10-4
Ecell = 0.76 - (0.0592/2)log(4.8x10-4)
= 0.86 V
 Concentration Cells
A concentration cell consists of two Ag/Ag+ half-cells. In half-cell A,
electrode A dips into 0.0100 M AgNO3; in half-cell B, electrode B dips
into 4.0x10-4 M AgNO3. What is the cell potential at 298 K?

Ag+(0.010 M) Ag+(4.0x10-4 M)

[Ag+]
Ecell = Eo 0.0592 V log dilute
cell -
[Ag+]
1 concentrated

Ecell = 0 V - 0.0592 log 4.0x10-2

= 0.0828 V
 Exercise
Consider the following electro chemical cell.
Al I Al3+ (0.25M) II Fe3+ (0.45M),Fe2+(0.05M) I Pt

a. Which electrode is cathode?

b. Write the overall reaction.
c. Determine the Ecell at 298 K?
d. Identify the oxidizing agent in the reaction.
 Exercise
A voltaic cell is set to measure the concentration of Cu2+
ions. The Ecell at 25°C was measured to be 0.65V. The
concentration of Co2+ ion in another half cell is 0.25M.
E°cell for the reaction is 0.62V. Calculate the concentration
of Cu2+.
 Exercise
Consider a voltaic cell in which the following reaction
occurs.
O2(g) + 4H+(aq) + 4Br-(aq) → 2H2O(l)+ 2Br2(l)

Calculate the cell voltage when PO is 1.0 atm,

- + 2
[Br ] = [H ] = 0.10M. and liquids concentration are
constant and consider as 1.
 Exercise
Consider a voltaic cell in which the reaction is
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

It is found that the voltage is 0.56V when pressure of H2

is 1.0 atm and [Zn2+] = 1.0M. What must be the
concentration of H+ in the half cell.
73
 Factors Affecting The Redox Potential
 Concentration of Ions (Electrolytes):*
Ecell decrease as the concentration of ions in the
cell decrease.

 Temperature:*
Ecell decrease with increasing temperature.

 Complex ion formation:

Formation of complex ion reduces the
concentration of free ions; the cell potential decrease.
 Acidity:
Ecell decrease with increasing acidity using hydrogen
half-cell reaction in Nernst equation. A higher cell
potential indicates the higher the pH of the solution.
75
Electrolysis is the process in which electrical energy is used to cause a
nonspontaneous chemical reaction to occur.

Electrolysis of molten NaCl

76
 Is a process of dissociation or
Electrolysis decomposition of electrolyte to produce
elements using an electric current to
force a chemical reaction.

Position of ions in
electrochemical series

Types of electrodes

Concentration of
electrolytes

Is a cell, which an electric

Charge (C) = current (A) x time (s) current is applied to drive a
non-spontaneous reaction

Mole electrons = charge x 1 mole electron

96,500 C

77
**Opposite to galvanic cell.
78
Factor Affecting Electrolysis

Position of ions in
electrochemical series

Types of electrodes

Concentration of electrolytes
• Electrolysis of molten NaCl
– Na+ is attracted to cathode and form sodium metal
(reduction)
• Na  Na+ + e spontaneous reaction
• Na+ + e  Na non-spontaneous reaction
– Cl- migrates to anode and discharged to Cl2 gas.
• Cl2 + 2e  2Cl- spontaneous reaction
• 2Cl-  Cl2 + 2e non-spontaneous reaction

Overall reaction: 2Na+ + 2Cl-  2Na(s) + Cl2 (g)

Diagram
 Electrolysis of NaCl solution
 Consists of Na+, H+, Cl-, OH- ions
 Cations and anions are competing to discharged at cathode
and anode - the lower the position in the series, the easier
for the ion to be discharged.
 H+ ion is discharged at cathode producing H2 gas, while Cl- is
discharged at anode to produce Cl2 gas due to overvoltage.

Oxidation : 2Cl- (aq)  Cl2 (g) + 2e (anode)

Reduction : 2H2O(l) + 2e  H2 (g) + 2OH-(aq) (cathode)
Overall : 2Cl-(aq) + 2H2O(l)  Cl2 (g) + H2 (g) + 2OH-(aq)
• Two types of electrodes:
– Inert electrode – does not take part in reaction.
• Eg.: carbon (graphite) and platinum
– Active electrode – metals; involve in reaction if the
solution is made of the same element.

• During electrolysis, electrode that act as anode can

undergo oxidation (becomes thinner – formed ions),
and ions in solution are reduced at cathode.
Electrolyte Electrodes At cathode At anode
Acidified water Pt H2 O2
Molten NaCl C Na Cl2
Aqueous NaCl C H2 Cl2
Concentrated NaCl C H2 Cl2
Molten NaOH Pt Na O2
Aqueous NaOH Pt H2 O2
Aqueous CuSO4 Cu Cu -
Aqueous CuSO4 Pt Cu O2
Aqueous AgNO3 Ag Ag -
Aqueous AgNOv Pt Ag O2
85
 Faraday’s Law
• The mass of product formed at the electrode is
proportional to the quantity of current passes
through the cell and the molar mass of the
substance.

• 1 mole of electron flow through a Down cell produces

1 mole of Na at cathode
– Na+ + e  Na

• 2 moles of electrons from chlorine ion form 1 mole of

Cl2 gas at anode
– 2Cl-  Cl2 + 2e
 Faraday’s Law
• A current (A) that passes through is measured over a
period of time
Charge (C) = Current (A) x time (s)

• Charge on 1mole of electrons is 96500 C, the no. of

moles of electrons passes through the cell is

Mole electrons = charge x (1 mole electron/96 500 C)

 EXAMPLE !!!!
How much Ca 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?
Anode: 2Cl- (l) Cl2 (g) + 2e-

Cathode: Ca2+ (l) + 2e- Ca (s)

Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

2 mole e- = 1 mole Ca

C s 1 mol e- 1 mol Ca
mol Ca = 0.452 x 1.5 hr x 3600 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca x 40.0 g/mol Ca

= 0.50 g Ca
88
89
 Applications

Electro-refining and Manufacture of Cl2 , H2

electroplating & NaOH

90
 APPLICATION OF ELECTROLYSIS

1. Electro-refining &
Electroplating
 If electrode is not inert, it
can be coated with a thin
layer of the metal being
reduced, if its reduction
potential is greater than
that of water.
 This is called electroplating
 Ecell = 0, so a small voltage is
needed to push the
reaction.
 APPLICATION OF ELECTROLYSIS
2. Manufacture of Cl2, H2 and NaOH

• Production of Cl2 and NaOH by electrolysis of aqueous NaCl is

called chlor-alkali process.
• Chloride ions are oxidized at anode to formed chlorine gas as a
product. Then, sodium ions react with hidroxide ions to
produced aqueous NaOH as 2nd product. Lastly, H2O produced
H2 gas and hydroxide ions at cathode.
• Chlorine is used in plastic industry and domestic water
treatment.
• NaOH is used in making paper, textiles, soap and detergent.
93
 Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation

number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
94
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5. Group IA metals are +1, IIA metals are +2 and fluorine is

always –1.

6. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to the charge on the
molecule or ion.
HCO3−
Identify the oxidation numbers of O = −2 H = +1
all the atoms in HCO3− ?
3x(−2) + 1 + ? = −1
C = +4
95
 Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?

1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72- Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O7 2- Cr3+

3. Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+
96
 Balancing Redox Equations
4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- 2Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O 97
 Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation: 6Fe2+ 6Fe3+ + 6e-

Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.

14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3

9. For reactions in basic solutions, add OH- to both sides of the

equation for every H+ that appears in the final equation.
98
 Voltaic and Electrolytic cell.

voltaic cell electrolytic cell

Oxidation half-reaction Oxidation half-reaction

Sn(s) Sn2+(aq) + 2e- Cu(s) Cu2+(aq) + 2e-
Reduction half-reaction Reduction half-reaction
Cu2+(aq) + 2e- Cu(s) Sn2+(aq) + 2e- Sn(s)
Overall (cell) reaction Overall (cell) reaction
Sn(s) + Cu2+(aq) Sn2+(aq) + Cu(s) Sn(s) + Cu2+(aq) Sn2+(aq) + Cu(s)
 Electrolysis
• Electrolysis is the process in which electrical energy is
used to cause a NON-SPONTANEOUS chemical
reaction to occur.
• Ecell < 0 and ∆G > 0.
Anode (Positive Electrode):Oxidation Process
Cathode (Negative Electrode):Reduction Process
• Voltage used greater than the cell potential.
• Used for electroplating.
Electrolysis

Oxidation half-reaction
2H2O(l) 4H+(aq) + O2(g) + 4e-

Reduction half-reaction
2H2O(l) + 4e- 2H2(g) + 2OH-(aq)

Overall (cell) reaction

2H2O(l) H2(g) + O2(g)
Electrolysis
Electrolysis
 Calculating on Plating
1. Charge (Coulombs) = Current (Ampere) x time
(second)
q=Ixt (1 A = 1Coulombs/sec)
2. Mole of e = Charge/Faraday
n = q/F (1F = 96500C/mol)
3. Use the stoichiometry of the reaction to find the
mole of element or compound.
4. Mole to grams of compound.
 Calculating on Plating
MASS (g)
of substance
oxidized or M (g/mol)
reduced

AMOUNT (MOL)
AMOUNT (MOL)
of substance Faraday
of electrons
oxidized or constant
transferred
reduced (C/mol e-)

balanced CHARGE (C)

half-reaction
time (s)
CURRENT (A)
Calculating on Plating
How much Ca 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?
Anode: 2Cl- (l) Cl2 (g) + 2e-
Cathode: Ca2+ (l) + 2e- Ca (s)
Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)
mol Ca = 1/2 x 2 mol e
C x 1.5 hr x 3600 s 1 mol e 1 mol Ca
mol Ca = 0.452 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca
= 0.50 g Ca
Calculating on Plating
A technician is plating a faucet with 0.86 g of Cr from an
electrolytic bath containing aqueous Cr2(SO4)3. If 12.5 min is
allowed for the plating, what current is needed?
Cr3+(aq) + 3e Cr(s)

0.86 g (mol Cr) (3 mol e-)

= 0.050 mol e-
(52.00 g Cr) (mol Cr)

0.050 mol e- (9.65x104 C/mol e-) = 4.8x103 C

4.8x103 C X 1min
= 6.4 C/s = 6.4 A
12.5 min 60s
 Exercise
1. Calculate the mass of copper which can be
deposited by the passage of 12.0 A for 25.0 min
through a solution of copper(II) sulfate.
2. How long would it take to plate 5.00 g Fe from an
aqueous solution of Fe(NO3)3 at a current of 2.00
A?
3. How long must 5.00 amp current be applied to
produce 15.5 g of Ag from Ag+?
 Example
What products form during electrolysis of aqueous solution of the
following salts: (a) KBr; (b) AgNO3; (c) MgSO4?
The reduction half-reaction with the less negative potential and the oxidation
half-reaction with the less positive potential will occur at their respective
electrodes.
SOLUTION: (a) K+(aq) + e- K(s) Eo = -2.93 V
2H2O(l) + 2e- H2(g) + 2OH-(aq) Eo = -0.42 V
The overvoltage would make the water reduction -0.82 to -1.02 but the
reduction of K+ is still a higher potential so H2(g) is produced at the cathode.
2Br-(aq) Br2(g) + 2e- Eo = 1.07 V
2H2O(l) O2(g) + 4H+(aq) + 4e- Eo = 0.82 V
The overvoltage would give the water half-cell more potential than
the Br-, so the Br- will be oxidized. Br2(g) forms at the anode.
 Example
(b) Ag+(aq) + e- Ag(s) Eo = -0.80 V
2H2O(l) + 2e- H2(g) + 2OH-(aq) Eo = -0.42 V

Ag+ is the cation of an inactive metal and therefore will be reduced to Ag

at the cathode. Ag+(aq) + e- Ag(s)
The N in NO3- is already in its most oxidized form so water will have to be
oxidized to produce O2 at the anode. 2H O(l) O (g) + 4H+(aq) + 4e-
2 2

(c) Mg2+(aq) + 2e- Mg(s) Eo = -2.37 V

Mg is an active metal and its cation cannot be reduced in the presence of
water. So as in (a) water is reduced and H2(g) is produced at the cathode.
The S in SO42- is in its highest oxidation state; therefore water must be
oxidized and O2(g) will be produced at the anode.
 Comparison of Voltaic and Electrolytic
Cells Electrode

Cell Type DG Ecell Name Process Sign

Voltaic <0 >0 Anode Oxidation -

Voltaic <0 >0 Cathode Reduction +

Electrolytic >0 <0 Anode Oxidation +

Electrolytic >0 <0 Cathode Reduction -