Electrochemistry

Electrochemistry is the branch of chemistry which deals with the relation

between chemical energy and Electrical energy.

Two types of cells:

1. Galvanic cell (Voltaic cells)
2. Electrolytic Cell
 Galvanic cells (also called Voltaic cells)
 use spontaneous chemical reactions to generate electrical
energy in the form of an electrical current
e-

Anode Cathode
e.g. Zinc electrode Salt Bridge e.g. Copper electrode

- +

Electrolyte, e.g. Electrolyte, e.g.

ZnSO4 CuSO4

Most batteries are made from

• Made up of two half cells Voltaic cells!
• Oxidation (loss of electrons) occurs at the negative anode
• Reduction (gain of electrons) occurs at the postive cathode
• Salt bridge acts to complete the circuit by joining the two half cells together
 For the example above, the reactions occuring are:
Anode: Zn(s)  Zn2+(aq) + 2e- Cathode: Cu2+(aq) + 2e-  Cu(s)

The shorthand notation for this cell is:

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

The cell potential, E, is a measure of how well a cell reaction can push and pull
electrons through a circuit

The electrical energy generated by the spontaneous reaction is proportional to the

cell potential.

The standard cell potential (the cell potential measured when all the species are in
their standard states) is given by:

E°cell = E°cathode - E°anode

 • The more negative the reduction potential is, the more readily
the element acts as a reducing agent, i.e. is itself oxidised

• Reduction occurs at the electrode with higher potential and oxidation

occurs at the electrode with the lower potential
• Unit of potential is the volt (V) and unit of charge is the Couloumb (C)
These are related by: 1V = 1J/C
• The charge of one mole of electrons is given by the Faraday constant,
F (F = 96,500 C mol-1)
We can combine the standard cell potential and Faradays
constant to give us an equation for ΔG°
ΔG° = -n F E°cell
where ΔG° is the change in Gibbs Free Energy
n is the number of moles of electrons
F is Faradays constant
E°cell is the standard cell potential
 Have relationship between Gibbs Free Energy and Equilibrium constant:

ΔG° = - RT lnK

ΔG for a reaction depends on the concentration by:

ΔG = ΔG° + RT ln Q where Q is the reaction quotient = [product]

[reactant]

But ΔG = -n F Ecell and ΔG° = - n F E°cell

-nFEcell = -nFE°cell + RT ln Q

Dividing across by nF gives: Ecell = E°cell – RT ln Q

Nernst Equation
nF
i.e. the cell potential at any conditions depends on the potential under standard state
conditions and a term for the potential at nonstandard-state conditions
Question
Which of the following statements relating to electrochemistry are correct?

(i) Oxidation involves the loss of electrons

(ii) Reduction involves the gain of electrons
(iii) Galvanic cells use electricity to produce chemicals
(iv) The anode in a Galvanic cell is positive
(v) Oxidation always occurs at the cathode
Answer: (i) and (ii)
Question
The standard potential of the Ag+/Ag electrode is +0.80 V and the standard potential of
the cell Fe(s)|Fe2+(aq)||Ag+(aq)|Ag(s) is +1.24 V. What is the standard potential of the
Fe2+/Fe electrode?

Half reactions Fe  Fe2+ + 2e- Oxidation reaction - Anode

Ag+ + e-  Ag Reduction reaction - Cathode

E˚cell = Ecathode - Eanode

Eanode = Ecathode - E˚cell
Eanode = 0.80 V – 1.24 V
Eanode = -0.44 V
Question
If the standard cell potential at 298 K is 1.10 V for the following reaction
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s), then what is the change in Gibbs Free
Energy?

ΔG° = -n F E°cell
Half reactions: Zn  Zn2+ + 2e-
Cu2+ + 2e-  Cu

n = no of moles of electrons = 2

F = Faradays constant = 96,500 C/mol

E°cell = 1.10 V = 1.10 J/C

ΔG° = - (2) (96500 C/mol) (1.10 J/C)

= - 212300 J/mol
= - 212.3 kJ/mol
Question
The equilibrium constant for the reaction is 1.8 × 1019 at 298K.
Ni(s) + Hg2Cl2(s)  2Hg(l) + 2Cl-(aq) + Ni2+(aq)

What is the value of the standard cell potential E°cell for this reaction?
ΔG° = -RT ln K
= - (8.314 J K-1 mol-1) (298 K) ln (1.8 × 1019)
= - 109847.8 J mol-1
= - 1.098 × 105 J mol-1

ΔG = -n F E°cell

E°cell = -ΔG°
nF
= -(-1.098 × 105 J mol-1) = 0.57 J/C = 0.57 V
(2 mol) (96500 C)
 Electrolytic Cells
 In an electrolytic cell, a non-spontaneous redox reaction is
made to occur by pumping electrical energy into the system
- DC Source
+
Could be Voltaic
CATHODE - cell + ANODE

Reduction occurs at the Oxidation occurs at the

cathode anode
M + + e-  M X-  X + e-

• External source must provide a greater potential than that for

the spontaneous reverse reaction
• Electrolysis = process in which electrical energy is used to
cause a non-spontaneous chemical reaction to occur
 Electrolytic Cells
 The simple electrolytic cell consists of
 two electrodes, dipping into
 a solution containing positive and negative ions
 The external battery or DC source acts as a pump
 It pushes electrons to the cathode and removes
electrons from the anode
 Metal ions in solution travel to the cathode and
gain electrons (reduction)
 Non-metal ions travel to the anode and give up
electrons (oxidation)
 The process is called electrolysis 10
 Electrolytic Cell Reactions

 In aqueous solution, a number of anode and

cathode half reactions are possible
 At the cathode:
1. Reduction of a metal cation to the metal:
Cu2+(aq) + 2e-  Cu(s) Eored = +0.339V
Common when transition metal cations present; does
not occur if cation is difficult to reduce (Eored < -0.828V)
2. Reduction of a water molecule to hydrogen gas:
2H2O + 2e-  H2(g) + 2OH-(aq) Eored = -0.828V
Occurs if cation is difficult to reduce 11
 Electrolytic Cell Reactions
 At the anode:
1. Oxidation of an anion to the non-metal:
2I-(aq)  I2(s) + 2e- Eoox = -0.534V
Does not occur if anion is difficult to oxidize
(Eored < -1.229)
2. Oxidation of a water molecule to oxygen gas:
2H2O  O2(g) + 4H+(aq) + 4e- Eored = -1.229V
Occurs if anion is difficult to reduce
3. Oxidation of the anode material
Cu(s)  Cu2+(aq) + 2e- Eored = -0.339V 12
 Electrolysis of water

Oxidation Half-Reaction 2H2O(l) O2(g) + 4H+(aq) + 4e-

Reduction Half-Reaction 2H2O(l) + 2e- H2(g) + 2OH-(aq)
Overall (cell) Reaction 2H2O(l) 2H2(g) + O2(g)
 Electrolysis of Sodium Chloride
 Possible anode half reactions:
2Cl-(aq)  Cl2(g) + 2e- Eoox = -1.360V
2H2O  O2(g) + 4H+(aq) + 4e- Eored = -1.229V
 At high concentrations, the chlorine oxidation half reaction is
favoured
 Possible cathode half reactions:
2H2O + 2e-  H2(g) + 2OH-(aq) Eored = -0.828V
Na+(aq) + e-  Na(s) Eored = -2.714V
 The water reduction half reaction has a much lower Eored value
and is favoured
 Overall cell reaction:
2Cl-(aq) + 2H2O  Cl2(g) + H2(g) + 2OH-(aq) Eocell = -2.188V
 Electrolysis of Sodium Chloride

 Chlorine gas is produced at the anode

 Hydrogen gas is produced at the cathode
 Sodium ions remain in solution
 Hydroxide ions are formed in the solution
 Commercially, this process is used to
manufacture
 Chlorine
 Hydrogen
 Sodium hydroxide
15
 Electroplating

 In many electrolytic cells, metal is deposited at the

cathode
 An object can be electroplated by making it the
cathode
 Copper, chromium and silver are often plated onto
brass, nickel, or other metals by this method
 The process is also used to purify copper, as the last
step in the manufacture of copper from copper ore

16
 Electrolysis of metals
 Salts will conduct electricity when melted, as well as when in
solution, e.g.: 2NaCl(l)  2Na (l) + Cl2(g)

 Aluminum is produced by electrolysis of alumina, Al2O3

 The melting point of Al2O3 is too high for direct electrolysis,
so it is dissolved in molten Na3AlF6 (cryolite) at 980oC
 The cathode is iron
 The anode is carbon
 Cathode reaction: Al3+ + 3e-  Al(l)
 Anode reaction: 2O2-  O2(g) + 4e-
 (The oxygen reacts with the carbon anode to form carbon
17
dioxide gas)
 Quantitative Relationships

 The amount of a substance produced or used in an

electrochemical cell will be determined by the
amount of electricity flowing in the cell
 Cathode reaction:
Ag+(aq) + e-  Ag(s)
 One mole of electrons will produce one mole of
silver
Cu2+(aq) + 2e-  Cu(s)
 Two moles of electrons will produce one mole of copper

18
 Electrical Units

Quantity Unit
Potential Volt (V)
Current Ampere (A) Rate of flow of electrons
Charge Coulomb (C) 1 Amp for 1 second
Energy Joules (J) #Volts  #Coulombs

1 mole of electrons = 96500 Coulombs = 1 Faraday

19
 Faraday’s Law of Electrolysis: the quantity (moles)
of product formed by an electric current is stoichiometrically
equivalent to the amount (moles) of electrons supplied

Faradays
Current + Time Charge Moles of electrons
constant

Using Faradays Law!

Molar mass
Mass product Moles product
 Faraday’s Laws

 In an electrolysis, the amount of product produced or

reactant consumed is proportional to the length of time
that a constant current is passed in the circuit
 To produce one mole of product, or to consume one
mole of reactant, requires n moles of electrons, (where n
is the number of electrons gained or lost by one atom or
ion). This is 96,500n Coulombs

21
 Faraday’s Laws

 Faraday’s Laws provide a relationship

between
 The current flowing in an electrolytic cell
(Amperes)
 The time that the current flows (seconds)
 The amount of material deposited or consumed
(moles)

22
 Applying Faraday’s Laws

1 mole
e- -
+

AgNO3 CuSO4
solution solution
cathode cathode

1 mole Ag (108g) ½ mole Cu (32g)

deposited on deposited on
cathode cathode
23
 Applying Faraday’s Laws

 What current will deposit 0.155g of silver from a solution of

silver ions in 11.0 minutes ( 660 seconds)?
Ag+(aq) + e-  Ag(s)

# moles silver produced = 0.155g  108 g/mol = 1.44  10-3

mol
# moles of electrons = 1.44  10-3 mol
Total charge = 1.44  10-3 mol  96500 Coulombs/mol = 139C

 Current = Charge (Coulombs)  time (seconds)

 Current = 139C  660 seconds = 0.211 Amps
24
 Applying Faraday’s Laws

How much copper will be deposited if a current of 0.150A is

passed through a solution of copper sulfate for 20.0 minutes?
Cu2+(aq) + 2e-  Cu(s)
Two moles of electrons will be required to deposit each mole of copper
 Total charge (C) = current (A)  time (s)
= 0.150A  1200s = 180 C
 # moles (Faradays) = 180 C  96500 C/mol = 1.87 x 10-3 mol
 #moles of copper deposited
= ½  1.87  10-3mol = 9.33 x 10-4mol
 Mass of copper = 9.33 x 10-4mol  63.5 g/mol
= 5.92  10-2g
25
 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- Cu  Cu2+ + 2e-

 2 moles of electrons required to reduce 1 mol Cu2+
charge = 306 C
No of moles e- =
Faradays constant 96500 C/mol

= 0.00317 moles of electrons

From reaction stoichiometry, 2 moles electrons ≡ 1 mole Cu

 0.00158 moles Cu deposited
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.
Answer = 0.00317 mol
 Question
How long will it take to deposit 0.00235 mol of metallic gold by
electrolysis of KAuCl4(aq) using a current of 0.214A?

KAuCl4(aq)  Au(s) Au3+ + 3e-  Au

 For every 1 mol Au produced, 3 mol electrons required

 For 0.00235 mol Au need 0.00705 mol electrons

Charge
No of moles electrons =
Faradays constant

Charge = moles electrons × Faradays constant

= 0.00705 mol × 96500 C/mol
= 680 C
Charge = current × time Time = Charge/Current
= 680 C / 0.214 A 1C = 1As
= 680 As / 0.214 A
= 3179 s
= 53 mins
Question
How long will it take to deposit 0.0047 mol of gold by electrolysis of KAuCl4 using a
constant current of 0.214 A?

Answer: 106 minutes

Question
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?

Answer: 0.5 g Ca
Industrial Applications of
Electrolysis

29
 What chemical species would be present in a
vessel of molten sodium chloride, NaCl (l)?

Na+ Cl-

Let’s examine the electrolytic cell for molten NaCl.

30
 Molten NaCl
Observe the reactions at the electrodes
- +
battery

Cl2 (g) escapes

Na (l)
NaCl (l)
Na+
Cl- Na+

Cl-
(-) (+)
electrode electrode
half-cell Cl- Na+ half-cell
Na+ + e-  Na 2Cl-  Cl2 + 2e
31
-
 Molten NaCl
At the microscopic level
- +
battery
e-

NaCl (l)

cations anions
migrate Na+ migrate
toward Cl- Na+ toward
(-) (+)
e-
electrode Cl- electrode
(-) (+)

cathode Cl- Na+ anode

Na+ + e-  Na 2Cl-  Cl2 + 2e-

32
Molten NaCl Electrolytic Cell

cathode half-cell (-) X2

REDUCTION Na+ + e-  Na

anode half-cell (+)

OXIDATION 2Cl-  Cl2 + 2e-

overall cell reaction

2Na+ + 2Cl-  2Na + Cl2
Non-spontaneous reaction!
33
The Downs Cell for the Electrolysis of Molten
Sodium Chloride

34
If the products are mixed, the result is household bleach.
2 NaOH(aq) + Cl2(g) = NaCl(aq) + NaOCl(aq) + H2O

Houghton Mifflin Company and G.

Hall. All rights reserved. 35
The Mercury Cell for Production of Chlorine and Sodium Hydroxide

36
A schematic diagram of an electrolytic cell for producing
aluminum by the Hall-Heroult process.

37
Fig. A schematic
diagram of an
electrolytic cell
for producing
aluminum by
the Hall-Heroult
process.

Houghton Mifflin Company and G.

Hall. All rights reserved. 38
 The Hall Process for Aluminum

 Electrolysis of molten Al2O3 mixed with cryolite –

lowers melting point

 Cell operates at high temperature – 1000oC

 Aluminum was a precious metal in 1886.

 A block of aluminum is at the tip of the

Washington Monument!
 graphite anodes e- 
+
from
power
CO2 source
bubbles Al+3 Al+3 -
O-2  e-
O-2 O-2
Al2O3 (l)
Al (l)

Draw
carbon-lined steel vessel off
acts as cathode Al (l)
Cathode: Al+3 + 3e-  Al (l)
Anode: 2 O-2 + C (s)  CO2 (g) + 4e- 40
 The Hall Process

Cathode: Al+3 + 3e-  Al (l) x4

Anode: 2 O-2 + C (s)  CO2 (g) + 4e- x 3

4 Al+3 + 6 O-2 + 3 C (s)  4 Al (l) + 3 CO2 (g)

The graphite anode is consumed in the process.

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