Topic 9: ELECTROCHEMISTRY

COURSE CONTENT

 Oxidation number or state

 Explanation of electrolysis
 Electrode potential
 Balancing of redox equations by ion-electron method
 Balancing redox equations by oxidation number change
method
 Learning Outcomes
 Give the characteristics of a redox reaction.
 Define oxidation and reduction in terms of a change in
oxidation number.
 Define cathode, anode, electrode potential and S.H.E.
(Standard Hydrogen Electrode).
 Define the standard electrode potential of an electrode.
 Use the ion-electron method/oxidation number method to
balance chemical equations.
RASHID JAMIL
Assistant Professor of Chemistry
Electrochemistry:
study of the interchange between chemical change
and electrical work

Electrochemical cells:
systems utilizing a redox reaction to produce or use
electrical energy
Oxidation and Reduction
 Not All Reactions are Redox Reactions

- Reactions in which there has been no change in

oxidation number are NOT redox reactions.

Examples:
1 5 2 1 1 1 1 1 5 2
Ag N O 3 ( aq )  Na Cl ( aq )  Ag Cl ( s )  Na N O 3 ( aq )
1 2 1 1 6 2 1 6 2 1 2
2 Na O H ( aq )  H 2 S O 4 ( aq )   Na 2 S O 4 ( aq )  H 2 O ( l )
 OXIDATION NUMBER

The apparent charge on an atom in a species.

1. Oxidation no. of an element in its free state is zero.

Na, Be, K, Pb, H2, O2, P4
2. In monatomic ions, the oxidation number is equal to the
charge on the ion.
Li+, Fe3+, O2-
3. The oxidation number of oxygen is usually –2. In H2O2, it
is –1. In OF2, it is +2)
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds where it
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 Neutral compound is zero
• Polyatomic ion; it is equal to its ionic charge.
 OXIDATION NUMBER

SO4–2 NO3–1
CrCl3 Cr2(SO4)3
K2CrO4 K2Cr2O7
Cr2O3 [Cu(NH3)4]SO4
K4[Fe(CN)6] K3[Fe(CN)6]
 Balancing Redox Equations

Two systematic methods are available, which are

based on the fact that the total electrons gained in
reduction equals the total electrons lost in oxidation.

The two methods:

1. Use oxidation-number method

2. Use half-reactions
Balancing Redox Equations

Oxidation Number Method

HNO3 + HI → NO + H2O + I2
 Balancing Redox Equations
MnO4–1 + C2O4–2 + H+ → Mn+2 + CO2 + H2O
The correct coefficients of reactants for the balanced
redox reaction are?

MnO4–1 C2O4–2 H+
a) 2 5 16
b) 16 5 2
c) 5 16 2
d) 2 16 5
 Balancing Redox Equations

K2Cr2O7 + HCl → KCl + CrCl3 + Cl2 + H2O

The correct coefficients of reactants for the balanced
redox reaction are?

K2Cr2O7 HCl
a) 1 7
b) 1 14
c) 2 7
d) 2 14
 Balancing Redox Equations

MnO2 + HCl → MnCl2 + H2O + Cl2

The correct coefficients of reactants for the balanced
redox reaction are?

MnO2 HCl
a) 1 7
b) 1 14
c) 2 7
d) 1 4
 Balancing Redox Equations
Ion-Electron Method
Balancing in Acidic Medium

a. Balance elements other than H and O.

b. Balance O by adding H2O.

c. Balance H by adding H+.

d. Balance charge by adding electrons.

 Balancing in Basic Medium

a. Balance elements other than H and O.

b. Balance O by adding OH‒

c. Balance H by adding H2O.

d. Balance charge by adding electrons.

Balancing Redox Equations

Ion - Electron Method

MnO4–1 + C2O4–2 → Mn+2 + CO2

 Balancing Redox Equations

2BrO3–1 + 12H+ → Br2 + 6H2O

How charge can be balanced in the above half
reaction?

a) by adding 10 e− on the right side

b) by adding 10 e− on the left side
c) by adding 12 e− on the right side
d) by adding 12 e− on the left side
 Balancing Redox Equations

MnO4–1 + 8H+ → Mn+2 + 4H2O

How charge can be balnced in the above half
reaction?
a) by adding 6 e− on the right side
a) by adding 5 e− on the left side
a) by adding 8 e− on the right side
a) by adding 8 e− on the left side
 Electrolysis
The process in which
electrical energy is
used to cause a
nonspontaneous
chemical reaction to
occur.
ELECTROLYSIS OF MOLTEN NaCl
 ELECTROLYSIS OF Conc. aq. NaCl Solution
An aq. soln. of NaCl contains four different types of ions.
Ions from sodium chloride Na+ (aq) and Cl- (aq)
Ions from water H+ (aq) and OH- (aq)
At the cathode:
H+ ions gains electrons from the cathode to form hydrogen gas,
which bubbles off. Na+ ions remain in solution.
2H+(aq) + 2e- → H2(g)
At the anode:
Cl- ions are discharged as chlorine gas, which bubbles off. The OH-
ions remain in solution.
2Cl- (aq) → Cl2(g) + 2e-
Selective discharge of cations during electrolysis
Cations lower down the reactivity series are more readily
discharged.
Selective discharge of anions during electrolysis
Sulphate (SO42-) and nitrate (NO3-) ions remain in the
solution and are not discharged during electrolysis. If a solution
containing SO42-, NO3- and hydroxide (OH-) ions is
electrolyzed, the OH- ions will be discharged.
4OH- (aq) → 2H2O (l) + O2 (g) + 4e-
 Products of Electrolysis
Using inert electrodes (Platinum or graphite)
Electrolyte Cathode Anode
PbBr2(l) Pb (s) Br2 (g)
NaCl(l) Na (s) Cl2 (g)
NaCl (aq) H2 (g) Cl2 (g)
CuSO4 (aq) Cu (s) O2 (g)
KNO3 (aq) H2 (g) O2 (g)
H2SO4 (aq) H2 (g) O2 (g)
 Products of Electrolysis
When electrodes also take part in the reaction

Electrolyte Copper Cathode Copper Anode

Cu (s) dissolves to
CuSO4 (aq) Cu deposits
form Cu2+ ions
Electrolyte Silver Cathode Silver Anode
AgNO3 (aq) and Ag (s) dissolves to
Ag deposits
HNO3 (aq) form Ag+ ions
GALVANIC / VOLTAIC CELLS
A spontaneous REDOX
reactions takes place,
electrons are
transferred and energy
is released.
• The oxidation occurs
at the anode.
• The reduction occurs
at the cathode.
Zn (s) + Cu2+ (aq) → Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode Cathode

In the cell, electrons leave the anode and flow through

the wire to the cathode.
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.
 STANDARD ELECTRODE POTENTIAL
• The potential set up when an electrode is dipped in one
molar solution of its own ions at 298K is called standard
electrode potential or standard reduction potential, denoted
by Eo.

• Electrode potential, of any element, can be calculated by

comparing it with (SHE).
 STANDARD HYDROGEN ELECTRODE (SHE)
• Consist of Pt foil, coated with finally divided platinum black.

• Foil is suspended in one molar solution of HCl.

• hydrogen gas at 25co and at 1 atm. pressure is bubbled.

• Platinum acts as electrical conductor.

• Potential of SHE is considered as zero.

 Standard Hydrogen Electrode

2H+ + 2e‒ → H2 0.00 ( SHE)

OR

H2 → 2H+ + 2e‒ 0.00 ( SHE)

Measurement of
Electrode
Potential
Zn-Electrode

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

E0cell = 0.76 V
 Measurement of Electrode Potential
Anode (oxidation): Zn(s) → Zn2+(1M) + 2e–
Cathode (reduction): 2e– + 2H+(1M) → H2(1 atm)
Overall Reaction: Zn(s) + 2H+(1M) → Zn2+(1M) + H2(1 atm)
Standard emf (E0cell) = + 0.76
E0cell = Eocathode – Eoanode
E0cell = Eo(H+/H2) – Eo(Zn+2/Zn)
0.76 = 0 – Eo(Zn+2/Zn)
Eo(Zn+2/Zn) = – 0.76
Measurement of
Electrode
Potential
Cu-Electrode

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

E0cell = 0.34 V
 Measurement of Electrode Potential
Anode (oxidation): H2(1 atm) → 2e– + 2H+(1M)
Cathode (reduction): Cu2+(1M) + 2e– → Cu(s)
Overall Reaction: Cu2+(1M) + H2(1 atm) → Cu(s) + 2H+(1M)
Standard emf (E0cell) = + 0.34
E0cell = Eocathode – Eoanode
E0cell = Eo(Cu+2/Cu) – Eo(H+/H2)
0.34 = Eo(Cu+2/Cu) – 0
Eo(Cu+2/Cu) = +0.34
 Electrochemical Series
Element Electrode Std. Red. Potential (E0)
Li Li+ + e‒ → Li ‒3.045
Ca Ca2++2e‒ →Ca ‒2.87
Mg Mg2+ + 2e‒ → Mg ‒2.37
Zn Zn2+ + 2e‒ → Zn ‒0.76
Fe Fe2+ + 2e‒ → Fe ‒0.44
H2 2H+ + 2e‒ → H2 0.00 ( SHE)
Cu Cu2+ + 2e‒ → Cu +0.34
Ag Ag+ + e‒ → Ag +0.799
Br2 Br2 + 2e‒ → 2Br‒ +1.08
Cl2 Cl2 + 2e‒ → 2Cl‒ +1.36
F2 F2 + 2e‒ → 2F‒ +2.87
 Applications of Electrochemical Series

1. To compare the relative oxidizing and reducing

powers.
2. To compare the relative activities of metals.
3. To calculate the standard emf of any voltaic cell.
4. To predict whether a redox reaction is spontaneous.
 Applications of Electrochemical Series
Higher the standard reduction potential, lesser will be the
reducing strength.
Li is strongest reducing agent in aqueous solution.
The lesser the standard reduction potential of a metal, greater
will be its activity.
A more active metal displaces a less active one from its salt
solution.
Those metals which have positive oxidation potential (lie above
SHE) will displace hydrogen from dil. acids.
STANDARD CELL POTENTIAL
Ecell  (cathode) − Ered
 = Ered  (anode)

= 0.34 V – (– 0.76 V )
= +1.10 V
OR
 = Eoxi (Anode) + Ered
Ecell  (cathode)

= 0.76 V + 0.34 V
= +1.10 V