Topic

10
Electrochemistry:
 Electrochemistry:
10.1 Galvanic cell
Objectives:
At the end of this topic, students should be able to

Draw a galvanic cell

Describe the operation of galvanic cell
Write cell notation, half-cell equation and overall equation
Draw and explain the standard hydrogen electrode (SHE)
Calculate Eocell
Predict the spontaneity of a redox reaction
Electrochemistry
Defination The study of electrochemical
reactions that involves
interconversion of electrical energy
and chemical energy.

What reaction Electrochemical reactions deal with

involve ? redox reactions (reduction and
oxidation)

Reduction
Redox reaction
Oxidation
2 types of electrochemical cell
Galvanic Cell

Step 1:
-Draw a galvanic
cell

-State Energy Chemical energy electrical energy

change

-State Spontaneous redox reaction

Spontaneity of
the reaction
2 types of electrochemical cell
Electrolytic Cell

Step 1:
-Draw a
electrolytic cell

-State Energy Electrical energy chemical energy

change

-State Non-Spontaneous redox reaction

Spontaneity of
the reaction
Spontaneity
Spontaneous
reaction
1) Definition A reaction that has a natural tendency
to occur and does not require an
energy input for it to occur.
2) Example Galvanic cell, rusting of iron

Non-
Spontaneous
reaction
1) Definition A reaction that cannot happen
naturally and needs an energy input to
help it to occur.
2) Example photosynthesis, electrolytic cell
Galvanic Cell/ Voltaic Cell
Definition
What is ?

1.Redox Reaction involving both oxidation

reaction and reduction occur at the same
time.

2.Oxidation Process that occurs when species

donates electrons, with an increase in
oxidation number.
3.Reduction Process that occurs when species
gains electrons, with an decrease in
oxidation number.

4.Oxidising Species that undergoes reduction or

agent gains electrons.
(oxidant)

5.Reducing Species that undergoes oxidation or

agent donates electrons.
(reductant)
6.Electrode Conductor (carbon rod or metal) that
allows electrons to pass through it.

7.Anode Electrode at which oxidation occurs.

8.Cathode Electrode at which reduction occurs.

Remember
RED CAT
= REDuction at CAThode
 Oxidation no: decrease
Undergo Reduction
+2 0

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

0 +2

Oxidation no: increase

Undergo Oxidation

Zn is oxidised to Zn2+ Cu2+ is reduced to Cu.

Reducing agent: Zn Oxidising agent: Cu2+

The oxidising agent is reduced, and the reducing agent is

oxidised.
 Oxidation no: decrease
Undergo Reduction rxn

+1 0
Cu(s) + 2 Ag+(aq) Cu2+(aq) + 2 Ag(s)
0 +2

Oxidation no: increase

Undergo Oxidation rxn

Cu is oxidised to Cu2+ Ag+ is reduced to Ag.

Reducing agent: Cu Oxidising agent: Ag+

The oxidising agent is reduced, and the reducing agent is

oxidised.
 Galvanic Cell
Electron moves from
the anode to the
cathode e-
e-
Anode: electrode at which
oxidation occurs

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

Cathode: electrode at which

reduction occurs

anode cathode
Cu2+(aq) + 2 e- Cu(s)

Half-cell Half-cell
A half-cell consists of an
electrode immersed in a
Salt bridge solution of ions.
 Half-cell reactions; and overall reaction
Step1 :
Write cell Anode [oxidation]
reaction
Zn(s) Zn2+(aq) + 2e-

Cathode [reduction]
Cu2+(aq) + 2e- Cu(s)

Step2 :
Combine cell
reaction Zn(s) Zn2+(aq) + 2e- Half-cell
reactions
Cu2+(aq) + 2e- Cu(s)
Overall cell
reaction
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
 Salt bridge
An inverted U tube containing a gel permeated
with solution of an inert electrolyte such as
saturated KCl, Na2SO4, NH4NO3, or KNO3

Functions

helps to maintain
electrical neutrality of
electrolytes
Completes the
electrical circuit
Zn2+ Cu2+
 How does the cell maintains its electrical neutrality?
Anode Cathode

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

Zn2+ ions formed Cu2+ ions used up
Anode has excess of +ve Cathode has excess of -ve
charge charge.
NO3- ions from salt bridge K+ ions from salt bridge
move into electrolyte of move into electrolyte of
anode compartment cathode compartment

Electrical neutrality
is maintained
Cell notation
What is cell Cell notation in chemistry is a
notation? shorthand way of expressing a certain
reaction in an electrochemical cell.

How to write cell - Anode on the left and cathode on the

notation right
- Salt bridges are represented by
double vertical lines
- A single vertical line indicates a
phase boundary (boundary different
phase)
- Species in the same phase are
separated by commas
 Galvanic Cell Notation

Types of half cell

A) Active electrodes involved in the electrode half-reaction

(most metal electrodes)

Ex: Cell notation: Zn(s)/ Zn2+(aq) (as oxidation)

* Phase and Concentration

must be written in the cell
notation
Cell notation: Zn(s)/ Zn2+(aq,1.0M) // Cu2+(aq,1.0M) /Cu(s)

// - salt bridge / - boundary different phase

* Phase and Concentration must be written in the cell
notation
 B) Inactive (inert) electrodes not involved in the electrode
half-reaction

Ex : Pt electrode in Fe3+ /Fe 2+ soln.

Fe3+ + e- Fe2+ (as reduction)

Cell notation: Fe3+ (aq), Fe2+ (aq)/Pt(s)

C) Electrodes involving gases a gas is bubbled over an

inert electrode

Ex : H2 gas over Pt electrode

H2(g) 2H+ + 2e- (as oxidation)

Cell notation: Pt(s) / H2(g) / H+(aq)

Cell diagram:

Pt(s) / Br-(aq) / Br2(l) // Cl-(aq)/ Cl2(g)/ Pt(s)

 Electrode potential
Standard electrode potential
Cell potential
Standard cell potential
? volt
V
C
D(+)
A(-)

B E
 Electrode potential
A Zn plate immersed in its own
ions

Zn(s) Zn2+(aq) + 2e
Zn
Zn metal loses e,
Zn2+ Zn2+ gains electrons
Equilibrium exist between
Zn and Zn2+

The electrical potential difference produced between the

electrode and the solution in a half cell is called electrode
potential of the metal.
Standard electrode potential, (E)

The standard electrode potential (E) is the potential

difference between the electrode and the solution in a half
cell measured at standard conditions. It is also known
as Standard Reduction potential

Standard Condition
concentration : 1.0 M ,
Pressure : 1 atm,
Temperature : 25C.

The standard reduction potential value are arranged in a

certain order and the list is known as the Standard
Reduction Potential (SRP) table
 Cell potential Ecell
The cell potential (Ecell) is the potential difference
between the two half cells in an electrochemical cell.

It is also known as

cell voltage, measured

cell electromotive by a
voltmeter
force (emf),
cell potential
Standard cell potential Ecello
Standard Cell potential is the cell potential
measured at standard conditions

Standard Condition
concentration : 1.0 M ,
Pressure : 1 atm,
Temperature : 25C.

Ecell = Ecathode - Eanode

or
Ecell = Ered + Eox
 Ecell = Ecathode - Eanode

But how to measure E?

E is measured by
pairing that half-cell with
standard hydrogen
electrode (SHE).
SHE consists of H2 gas at 1
atm, bubbling around a
platinum electrode which is
immersed in 1 M solution of
H+ solution at 25C.
 Standard hydrogen electrode (SHE)
SHE is used as a standard reference
electrode to measure the electrode
potentials of other half-cell.
SHE is assign as zero potential (0.00 V)

The electric potential of the half reaction is

due to either

2H+(aq) +2e H2(g) E =0.00V

or

H2(g) 2H+(aq) +2e E =0.00V

 Ways to measure E
Determination of Standard reduction potential of Zn2+(aq)/
Zn(s)

076V e- flows
- + from Zn to
SHE
Anode: Zn
Cathode:Pt(SHE)

Ecell = Ecathode -Eanode

0.76 = EH+/H2 - EZn2+/Zn

0.76 = 0 - EZn2+/Zn
EZn2+/Zn = -0.76 V
 How to measure E
Determination of Standard reduction potential
of Cu2+(aq)/ Cu(s)

e- 0.34V
e- e- flows from
- SHE to Cu
+
Anode:Pt(SHE)
Cu
Cathode:Cu
1 M CuSO4

Ecell = Ecathode -Eanode

0.34 = ECu2+/Cu - EH+/H2
0.34 = ECu2+/Cu - 0
E = + 0.34 V
All written in reduction form.

Standard Electrode Potentials (Eo)

ALSO KNOWN AS
Standard Reduction Potentials (Eo)

REMEMBER :
THE SRP TABLE NOT GIVEN.
 Standard Electrode Potential
The sign of E0 changes when the reaction is reversed

Reduction : Ag+ (aq) + e Ag(s) E = +0.80 V

Oxidation : Ag(s) Ag+ (aq) + e E = -0.80 V

Changing the stoichiometric coefficients of a half-cell

reaction does not change the value of E0

Reduction : Br2(l) + 2e 2Br-(aq) E = + 1.09 V

1/2Br2(l) + e Br-(aq) E is also + 1.09 V

 Uses of Standard Electrode potential
What is the a) Build up the electrochemical
use(s) series

b) Determine anode and cathode.

c) Calculate the cell potential (Ecell)

d) Calculate the cell potential (Ecell)

e) Predict the possibility of a

spontaneous reaction

f) Compare the relative strength of

reducing or oxidising agent
Uses of Standard Electrode potential
a) Electrochemical series

Half reaction E V
Na+(aq) + e Na(s) -2.71
Zn2+(aq) + 2e Zn(s) -0.76
2H+(aq) + 2e H2(g) 0.00

Cu2+(aq) + 2e Cu(s) +0.34

Ag+(aq) + e Ag(s) +0.80

Cl2(g) + 2e Cl-(aq) +1.36

F2(g) + 2e 2F-(aq) +2.87
b) Determine anode and cathode

A half cell with a +ve E is able to attract electrons

towards it.
Thus, the element with more +ve E becomes cathode.
Element with more -ve E becomes anode.

More +ve

Cu2+ (aq) + 2e Cu(s) E = + 0.34V

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

Cathode: Cu Anode: Zn
c) Calculate the cell potential (Eocell) or emf of
a voltaic cell.

Ecell = Ecathode - Eanode

Cu2+(aq) + 2e Cu(s) E = +0.34 V

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

Ecell = Ecathode - Eanode Cathode:Cu

Anode: Zn
= +0.34 - (-0.76)

= +1.10 V
d) Test on spontaneity of reaction

E cell Reaction
>0V
spontaneous
(+ve value)

<0V Non-spontaneous
(-ve value)

0V In equilibrium
e) Compare the strength of reducing and oxidising agents

Oxidising Reducing
agent agent Eo
Cr 3+(aq) + 3 e Cr (s) -0.74 V
Ag+(aq) + e Ag (s) +0.80 V
Br2 (aq) + 2 e 2 Br- (aq) +1.07 V

The more +ve E , the stronger the oxidising agent

The more -ve E , the stronger the reducing agent

ORDER OF DECREASING STRENGTH

Strength of oxidising agent (oxidant) : Br2 > Ag + > Cr3+

Strength of reducing agent (reductant) : Cr >Ag >Br-
 Electrochemistry:
10.2 NERNST EQUATION
Objectives:
At the end of this topic, students should be
able to
Use Nernst equation, to determine
i) cell potential, Ecell
ii) concentration or partial pressure of a species
iii) equilibrium constant, K when Ecell = 0

Predict the spontaneity of a cell reaction

 Nernst Equation
Used to calculate cell potential at non- standard
conditions (Ecell)
2.303RT
E cell E cell
o
log Q
nF
At 25C

0.0592
E cell E o
cell log Q
n
Q = reaction quotient

cell emf depends on the concentrations of ions in the cell,

the temperature of solutions and pressure of gases
involved.
 For the cell reaction,
aA(aq) + bB(aq) cC(aq) + dD(aq)

Solution :

Step 1: 0.0592
Write Nernst equation E cell E cell
o
log Q
n
Step 2: Thus,
Substitute Q= [C]c[D]d
[A]a[B]b
E cell E cell
o 0.0592
log
C D
c d

Into the Nernst

equation n A a B b
For the reaction in gas phase,
aA(g) + b(B(aq) cC(aq) + dD(g)
0.0592
E cell E cell
o
log Q
n

Thus,
E cell E cell
o 0.0592 C PD
c
log a b
d

n PA B

*** cell emf depends on the concentrations of

ions in the cell, the temperature of solutions and
pressure of gases involved.
 At equilibrium there is no net transfer
of electrons,
Ecell = 0
Q becomes Kc(equilibrium constant)

0.0592
Thus, 0 E cell
o
log Kc
n
Main use: A) To calculate Ecell at non-standard conditions
Example: Calculate the Ecell for the following equation
Zn(P) / Zn 2+ (1.8M) // Cu 2+ (0.2M) / Cu(s)

Solution:
Step 1: Anode (oxi) : Zn(p) Zn 2+ (aq) + 2e
Write equation at Cathode (red): Cu2+(aq) + 2e Cu(s)
anode and cathode
and overall equation Zn(p) + Cu 2+(aq) Zn2+(aq) + Cu(s)

Step 2 : Ecell = Ecathode - Eanode

Calculate Ecell = 0.34 (-0.76) = 1.10 V

Step 3 : Ecell = Eocell 0.0592 log [Zn2+]

Calculate Ecell using n [Cu2+]
Ecell = 1.10 0.0592 log [1.8]
Nernst equation
2 [0.2]
= 1.072 V
B) To calculate each electrode potential at non-standard
conditions

Example:
Calculate electrode potential for zinc half cell (E Zn2+/Zn ) using
Nernst equation.
Eo Zn2+/Zn = -0.76 V and [Zn2+] =0.1 M. Answer: -0.79 V

Solution:
C) To determine the spontaneity of a reaction
Will the following reaction occur spontaneously at 25C if
[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Given : EoFe2+/Fe = -0.44v, EoCd2+/Cd = -0.40v
Fe2+(aq) + Cd(s) Fe(s) + Cd2+(aq)
Solution:
Step 1: Anode (oxi) : Cd(s) Cd2+ (aq) + 2e
Write equation at Cathode (red): Fe2+ (aq) + 2e Fe(s)
anode and cathode
and overall equation Cd(s) + Fe 2+
(aq) Fe(s) + Cd 2+
(aq)

Step 2 : Ecell = - 0.44 (- 0.40) = -0.04 V

Calculate Ecell
Ecell = Eocell 0.0592 log [Cd2+]
Step 3 : n [Fe2+] Ecell =+ve
Calculate Ecell using Ecell = -0.04 0.0592 log [0.01]
Nernst equation 2 [0.60]
Spontaneous
= 0.013V
 D) To determine pH of a solution
Calculate pH of a galvanic cell built from the hydrogen electrode
and zinc plate in 1 M zinc nitrate.
[Zn2+] = 1 M PH2 = 1 atm Ecell= + 0.58 V
Solution:
Step 1:
Write equation at Anode (oxi) : Zn(s) Zn 2+ (aq) + 2e
anode and cathode Cathode (red): 2H+(aq) + 2e H 2 (g )
and overall equation Zn(s) + 2H+(aq) Zn2+(aq) +H2(g)
Step 2 : Ecell = +0.76 V
Calculate Ecell
Ecell = Eocell - 0.0592 Log [Zn ]PH2
2+

Step 3 : n [H+]2
Calculate
0.58 = 0.76 - 0.0592 log [1]
concentration [H] 2 [H+]2
+
using Nernst eqn
[H+] = 9.11 x 10-4 M pH = - log[H+] = 3.04
and cal. pH
 E) To calculate equilibrium constant Kc
Calculate the Kc for the following reaction:
Sn2+(aq) + 2Ag+ (aq) Sn4+ (aq) + 2Ag(s)
Solution:
Step 1:
Write equation at anode
Anode (oxi) : Sn2+(aq) Sn4+(aq) + 2e
and cathode and overall Cathode (red): 2Ag+ (aq) + 2e 2Ag (s)
equation
Sn2+(aq) + 2Ag+(aq) Sn4+(aq)+2Ag(s)
Step 2 :
Calculate Ecell
Ecell = +0.65 V

Step 3 : Ecell = Eocell 0.0592 log [Sn4+]

Calculate Kc using Nernst 2 [Sn2+][Ag+]2
-equation
At equilibrium there is no
= 0.65 0.0592 log Kc
net transfer of electrons,
- Ecell = 0 2-2
Kc = 9.108 X 10 mol dm6
21

- Q becomes Kc
 Electrochemistry:
10.3 ELECTROLYTIC CELL
Objectives:
At the end of this topic, students should be
able to
Draw and describe an electrolytic cell
Explain the factors on the selective discharge of a species
at the electrode
Explain the electrolysis of molten salt, water, concentrated
and dilute NaCl, aqueous Na2SO4.
Predict the products of electrolysis.
Define and apply Faradays first law.
10.3 Electrolysis

electricity decomposition
 Electrolysis Cell
electrical energy chemical energy

Electrolyte
(M+X-)

Non-
spontaneous
No salt bridge is used reaction
 A. ELECTROLYTIC CELL
It is made up of 2 electrodes immersed in an electrolyte.
A direct current is passed through the electrolyte from an
external source.
Electrons move from anode to cathode

Anions are attracted to anode.

Cations are attracted to

cathode.
Non-spontaneous reaction

The electrolyte will be

decomposed or electrolysed into its
components.
 Definitions
a) Electrolysis is a chemical process that uses electricity
to cause a non-spontaneous redox reaction to occur.
b)Electrolyte is a liquid(aqueous solution/molten state) that
can conduct electricity due to its mobile ions.

Examples: NaCl solution, molten PbBr2

c) Electrode conductor that allows electrons to pass through it

Examples: metal, graphite/carbon rod

d) Anode: Electrode at which oxidation takes place.

e) Cathode: Electrode at which reduction takes place.

What is
electrolysis?
-Defination Electrolysis is a chemical process that
uses electricity to cause a non-
spontaneous redox reaction to occur.

Electrolyte is a liquid(aqueous
solution/molten state) that can conduct
electricity due to its mobile ions.

Electrode conductor that allows

electrons to pass through it
 Qualitative Electrolysis
Factors affecting selective discharge at electrodes:
i) Standard reduction potential
the more +ve E , the easier the species to be
reduced at the cathode.
the less +ve E , the easier the species to be
oxidised at the anode.
ii) Concentration of ions
the more concentrated the ion, the easier the
species to be discharged at the electrodes.
iii) Nature of electrodes
Special type of electrodes used will influence the
species to be discharged. (inert or active)
 ELECTROLYSIS USING INERT ELECTRODES
i) Electrolysis of molten Salt
eg 1: molten NaCl(l) consists of Na+(l) and Cl-(l)
Solution:
Cathode (Red) :
++

anode cathode Na+(l) + e Na(l)

Product at cathode: Na

Cl Na+ Anode (Oxi) :

Cl Na+
Cl Na+
2Cl-(l) Cl2(g) + 2e
molten NaCl Product at anode: Cl2

Overall: 2Na+(l) + 2Cl-(l) 2Na(l) + Cl2(g)

 eg 2 : molten Al2O3(l) consists of Al3+(l) and O2-(l)
Solution:
Cathode (Red)
+ +

anode cathode Al3+(l) + 3 e Al(l)

Product at cathode: Al
O2 2 Al3+
O
O2 Al 3+
Anode (Oxi)
Al 3+

2 O2-(l) O2(g) + 4e
molten Al2O3
Product at anode: O2

Overall: 4Al3+(l) + 6O2-(l) 4Al(l) + 3O2(g)

 ii) Electrolysis of water

2H2O(l) O2(g) + 4H+(aq) +

Oxidation Half-Reaction :
- 4e-
2H2O(l) + 2e H2(g) + 2OH-
Reduction Half-Reaction :
(aq)
Overall (cell) Reaction : 2H2O(l) 2H 2(g) + 2O2(g)
 iii) Electrolysis of Aqueous Solution
Aqueous salt solutions contains anion, cation and water.

Both water and anions are attracted to the anode,

competing with each other to be oxidised.

Both water and cations are attracted to the cathode,

competing with each other to be reduced.

Hence for aqueous solutions, the products at

electrodes depend on which species are
selected to be discharged.
 Electrolysis of Aqueous solution, diluted NaCl
and concentrated NaCl.

NaCl(aq)
a) Electrolysis of dilute aqueous NaCl solution
NaCl(aq) Na+(aq) + Cl-(aq)
Species present: H2O, Na+, Cl-,
Cl- and H2O are attracted to the anode
Na+ and H2O are attracted to the cathode.

Cathode(reduction) Anode(oxidation)
( more +ve ) (more ve)
Na+(aq) + e Na(s) E0 = -2.71V Cl2(g) + 2e 2Cl-(aq) E0 = +1.36V

2 H2O(l) + 2e 2OH-(aq) + H2(g) 4H+(aq) + O2(g) + 4e 2H2O(l)

E0 = -0.83V E0 = +1.23V

2 H2O(l) + 2e 2OH-(aq) + H2(g) 2 H2O(l) 4H+(aq) + O2(g) + 4e

Product at cathode : H2(g) Product at anode : O2(g)

 Overall reaction

Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)

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

Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e-

6H2O (l) 2H2 (g) +O2(g) + 4H+(aq) + 4OH- (aq)

=
4 H2 O

Overall
2H2O(l) O2(g) + 2H2(g)
Reaction:
b) Electrolysis of concentrated NaCl solution
NaCl(aq) Na+(aq) + Cl-(aq)
Species present: H2O, Na+, Cl-,
Cl- and H2O are attracted to the anode
Na+ and H2O are attracted to the cathode.
2nd factor: [Cl-] is high, Cl- ions will be selected to be oxidised.
Cathode(reduction) Anode(oxidation)
more +ve 2nd factor: more conc.
Na+(aq) + e Na(s) E0 = -2.71V Cl2(g) + 2e 2Cl-(aq) E0 = +1.36V

2 H2O(l) + 2e 2OH (aq) + H2(g)
-
4H+(aq) + O2(g) + 4e 2H2O(l)

E0 = -0.83V E0 = +1.23V
2 H2O(l) + 2e 2OH-(aq) + H2(g) 2 Cl-(aq) Cl2(g) + 2e
Product at cathode : H2(g) Product at anode : Cl2(g)
 Overall reaction

Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)

Anode: 2Cl- (aq) Cl2 (g) + 2e-

Overall 2H O(l) + 2Cl- Cl2(g) + H2(g) + 2OH-(aq)

2
reaction:
c) Electrolysis of aqueous Na2SO4 solution
Na2SO4 (aq) 2Na+(aq) + SO42-(aq)
Species present: H2O, Na+, SO42-
Na+ and H2O (cathode) SO42- and H2O (anode)
Cathode(reduction) Anode(oxidation)
more +ve more -ve
Na+(aq) + e Na(s) E0 = -2.71V S2O82-(aq) + 2e 2 SO42-(aq)
E0 = +2.01V
4H+(aq) + O2(g) + 4e 2H2O(l)
2 H2O(l) + 2e 2OH-(aq) + H2(g) E0 = +1.23V
E0 = -0.83V
2 H2O(l) + 2e 2OH-(aq) + H2(g) 2 H2O(l) 4H+(aq) + O2(g) + 4e

Product at cathode : H2(g) Product at anode : O2(g)

The S in SO42- is in its highest
oxidation state: so SO42- cannot be
oxidized.
Overall Reaction: 2H2O(l) O2(g) + 2H2(g)
d) Electrolysis of aqueous CuSO4 solution
CuSO4 (aq) Cu2+(aq) + SO42-(aq)
Species present: Cu2+, SO42- , H2O,

Cu2+ and H2O (cathode) SO42- and H2O (anode)

Cathode(reduction) Anode(oxidation)
more +ve
Cu2+(aq) + 2e Cu(s) E0 = + 0.34V The S in SO42- is in its highest
oxidation state: so SO42- cannot
2 H2O(l) + 2e 2OH (aq) + H2(g)
-

E0 = -0.83V be oxidized.

Cu2+(aq) + 2e Cu(s) 2 H2O(l) 4H+(aq) + O2(g) + 4e

Product at cathode :Cu(s) Product at anode : O2(g)

Overall
Reaction: 2Cu (aq) +2H2O(l) 2Cu(s) + O2(g) +4H (aq)
2+ +
e) Electrolysis of aqueous AgNO3 solution
AgNO3 (aq) Ag+(aq) + NO3-(aq)
Species present: Ag+, NO3- , H2O,

Ag+ and H2O (cathode) NO3- and H2O (anode)

Cathode(reduction) Anode(oxidation)
more +ve
Ag+(aq) + e Ag(s) E0 = +0.80V N atom in NO3- is at highest
oxidation state (+5), cannot be
2 H2O(l) + 2e 2OH-(aq) + H2(g) oxidized. H2O must be oxidized.
E0 = -0.83V

Ag+(aq) + e Ag(s) 2 H2O(l) 4H+(aq) + O2(g) + 4e

Product at cathode :Ag(s) Product at anode : O2(g)

Overall
Reaction: 4 Ag+(aq) +2H2O(l) 4 Ag(s) + O2(g) +4H+(aq)
 3rd factor: Types of Electrodes used
Application : ELECTROPLATING

Anode Cathode

Ag Ag+ + e Ag+ + e Ag
 COMPARISON

Galvanic Cell Electrolytic Cell

+ -
e- e-
e- e-
- + + -

Anode Cathode Anode Cathode

 DIFFERENCES
Galvanic cell Electrolytic cell
Chemical energy electrical Electrical energy chemical
energy energy
Cathode : terminal +ve Cathode : terminal ve
Anode : terminal -ve Anode : terminal +ve

Spontaneous reaction Non-spontaneous reaction

Salt bridge is used No need to use salt bridge

SIMILARITIES
Oxidation occurs at anode, reduction occurs at cathode.
Anions move towards anode, cations move towards
cathode.
Electrons flow from anode to cathode.
Quantitative
Electrolysis
 Faradays First Law:
.states that the amount of substance formed
during electrolysis is directly proportional to
the quantity of electric charge ( in coulombs,
C) that flows through electrolyte.
m Q

The amount of charge, Q = I t

Where, I = current in ampere, A

t = time, s

Unit Q in C
 Faradays constant
1 Faraday is the amount of electric
charge carried by one mole of e.

1F 1 mole electrons

1F = 96 500 C mol-1
 Cell Cell 2 Cell 3
1
Cathode: Cathode: Cathode:
Ag+ + e- Ag Al3+ + 3e- Al Zn2+ + 2e- Zn

1 F 1 mole Ag 3 F 1 mole Al 2 F 1 mole Zn

Example 1:
What mass in grams of Cu will be produced at the
cathode from an electrolysis of Cu2+ solution by using
a) 0.15 F of electric charge b) 2.00 A for 20.0 min
[Ar(Cu) = 63.5, 1F = 96 500C]
Solution:
Step 1: a) Cu2+(aq) + 2e Cu(s)
Write equation at
cathode 2F 1 mole Cu
0.15F x 0.15
Step2:
Calculate mole of Cu = 0.075 mol Cu
produced using 0.15F
Mass Cu = 0.075 X 63.5
Step 3:
Calculate mass of Cu
= 4.76 g
4M
Solution:
b) Q = It
Step 1:
Calculate Q using = 2 X 20 X 60
Faradays First Law: = 2400 C

Step 2:
= 0.02487 F
Write equation at
cathode Cu2+(aq) + 2e Cu(s)

2F 1 mole Cu
Step3:
Calculate mole of Cu 0.02487F x 0.02487 mole Cu
produced using
= 0.01244 mol Cu
0.02487F
Mass Cu = 0.01244 X 63.5
Step 4:
Calculate mass of Cu = 0.79 g 5M
Example 2:

We can use electrolysis to determine the gold content of a

sample. The sample is dissolved, and all the gold is
converted to Au3+(aq), which is then reduced back to Au(s)
on a weighed electrode. The reduction half-reaction is

Au3+(aq) + 3e Au(s).

What mass of gold will be deposited at the

cathode in 1.00 hour by a current of 1.50 A?
Solution: Q = It
= 1.5 X 60 X 60
Step 1:
Calculate Q using = 5400 C
Faradays First Law: = 0.05596 F

Step 2: Au3+(aq) + 3e Au(s)

Write equation at
3F 1 mole Au
cathode
0.05596F 1/3 x 0.05596 Au
Step3: = 0.0187 mol Au
Calculate mole of Au
produced using 0.05596F
Mass Au = 0.0187 X 197
Step 4:
= 3.68 g
Calculate mass of Au
 Example 3:

An aqueous solution of copper(II) nitrate was electrolysed

using a current of 1.5A for 60 min at 25oC and 1 atm.
Calculate:
a) Mass of copper metal deposited at the cathode
b) Volume of gas evolved at the anode

a)
Cu2+(aq) + 2e Cu(s)
Q = It
= 1.5 ( 60 x 60) 2F 1 mole Cu
= 5.4 x 103 C 0.05596F 0.02798 mole Cu
= 0.05596 F
Mass Cu = 0.02798 X 63.5

= 1.78 g
b) At the anode

2H2O(l) O2(g) + 4H+(aq) + 4e

4F 1 mol O2

0.05596F 1 X 0.05596 mol O

2
4
= 0.01399 mol O2

pV = n RT

V = nRT = 0.01399 X 0.08206 X 298

P 1
= 0.342 dm3