Consider the electrolysis of aqueous NaCl

(example from previous slide)

N.I.E: 2 Cl-(aq) + 2H2O(l) à H2(g) + Cl2(g) + 2OH-(aq)

What if there was no water ?

- pure (molten) NaCl at T > 800 degrees

- now only one possible cathode reaction

- now Na+ will be reduced at the cathode

This is how Na(s) is produced

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5.2 Examples of Electrolysis
Electrolysis of Molten NaCl (Downs Cell)

At high temperatures,
ionic solids melt to
form liquids that
conduct electricity.

Elemental sodium and

chlorine gas is
generated.

CaCl2 is added to lower the melting point of the mixture (lower

operating costs) 34
Example: If a molten mixture of MgCl2 and KBr is electrolyzed,
what products will form at the cathode and the anode, respectively?

Strategy/Method:
1. List all of the species present.

Mg2+ Cl− K+ Br− No H2O !!

2. Determine which species will be reduced (OA) and which

species will be oxidized (RA)
Mg2+ Cl- K+ Br-
SOA RA OA SRA
Highest reduction potential Lowest reduction potential 35
3. Write the relevant
(oxidation and reduction)
half reactions:

Mg2+ + 2e- à Mg
2 Br- à Br2 + 2e-

Products:
Br2 at the anode and Mg at
the cathode.

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Electrolysis of KI
KI (aq) ® K+ (aq) + I– (aq) (colorless solution)

Relevant reactions:
K+ (aq) + e– à K (s) E° = – 2.925 V

2 H2O + 2 e– à H2 (g) + 2 OH– (aq) E° = – 0.828 V

I2 (aq) + 2 e– à 2 I– (aq) E° = + 0.536 V

Possible reactions:
1) 2 K+ (aq) + 2 I– (aq) à I2 (aq) + 2 K (s) E °cell = -3.461 V

2) 2 H2O (l) + 2 I– (aq) à I2 (aq) + H2 (g) + 2 OH– (aq)

E °cell = -1.364 V
37
For a non spontaneous reaction, we need to supply the minimum
potential to achieve a reaction.

For the KI solution, we need to supply

voltage exceeding 1.364 V to drive
reaction (2)

38
Cathode: 2 H2O + 2 e– à H2 (g) + 2 OH– (aq)

Presence of OH– is detected with an indicator

Phenolphthalein turns pink/violet in basic solution

Formation of H2 is observed due to:

1) bubbles
2) volume displacement

Anode: 2 I– (aq) à I2 (aq) + 2 e–

Side rxn: I2 (aq) + excess I– (aq) ßà I3– (aq) (brown colour)

Reaction at the anode is observed as change in color
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5.3 Electroplating
Deposition of a thin layer of metal on the surface of the
electrode acting as the cathode
Electroplating a fork:

Cathode (fork):
Ag+(aq) + e- à Ag (s)

Anode (silver bar):

Ag (s) à Ag+(aq) + e-

40
 Electroplating nickel on steel

Power source

NiCl2 (aq)
Ni steel
Ni2+

Possible cathode reactions:

1. Ni2+ (aq) + 2 e- à Ni (s) - 0.257 V
2. 2 H2O (l) + 2 e- à H2 (g) + 2 OH- - 0.828 V
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Possible anode reactions :

1. Ni2+ (aq) + 2 e- à Ni (s) - 0.257 V

2. 4 H+ (aq) + O2 (g) + 4 e- à 2 H2O (l) +1.229 V
3. Cl2 (g) + 2 e- à 2 Cl- (aq) +1.358 V

Anode ½ rxn: Ni (s) à Ni2+ (aq) + 2 e-

Cathode ½ rxn: Ni2+ (aq) + 2 e- à Ni (s)

42
5.4 Batteries
What is a battery?

A device that converts the chemical energy (of its cell

components) → electrical energy.

It contains two materials that cannot undergo an oxidation-

reduction reaction directly, but that can do so if electrons are
allowed to travel from one material to the other through an
outside circuit (while ions simultaneously travel within the cell).

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Primary (Nonrechargeable) Batteries

Alkaline Battery
powers devices such
as flashlights, toys,
portable radios, etc.

Anode (oxidation): Zn(s) + 2 OH-(aq) → ZnO2(s) + H2O(l) + 2 e-

Cathode (reduction): MnO2(s) H2O(l) + 2 e- → Mn(OH)2(s) + 2 OH-(aq)

Battery is discarded when the cell reaction has reached equilibrium (i.e.
battery is dead)

44
Primary Lithium Battery

Widely used in watches and implanted medical

devices (i.e. pacemakers)

Anode (oxidation): 3.5 Li(s) → 3.5 Li+ + 3.5 e-

Cathode (reduction): AgV2O5.5 + 3.5 Li+ 3.5 e- → Li3.5AgV2O5.5

45
 Secondary (Rechargeable Batteries)

Lead-Acid Battery:
Six cells connected in series
Each cell delivers ~2.1 V (for a total of 12V)

Pb(s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2 e-

PbO2(s) + 3 H+(aq) + HSO4-(aq) + 2 e- → PbSO4(s) + 2 H2O(l)

Discharging:

Recharging:

Common problems: loss of capacity due to corrosion, formation of large PbSO4

crystals which prevent recharging.
46
Flameless Ration Heater

Each pouch contains:

7.5 g of Mg-Fe (iron filings)

95% Mg and 5% Fe
~ 0.5g of NaCl

Spontaneous
Add approximately 30 mL of water: exothermic rxn

Mg (s) + 2H2O (l) à Mg(OH) 2 (s) + H2 (g) + heat

47
Flameless Ration Heater (Redox Reaction)

Mg (s) à Mg2+ + 2 e- EºA = -2.356 V

2H2O(l) + 2 e- à 2OH-(aq) + H2(g) EºC = -0.828 V

Mg (s) + 2H2O(l) à Mg2+ + 2OH-(aq) + H2(g) Eºcell = 1.528 V

Mg(OH)2
Eºcell = EºC - EºA

NaCl: acts as an electrolyte and forms the “voltaic cell”

The reaction is catalyzed by: Fe(s)
Without catalysis, the reaction is much too slow to generate
appreciable heat.
48
Flameless Ration Heater (Thermochemisty)

What is the enthalpy of reaction (under standard conditions) ?

Mg (s) + 2H2O(l) à Mg2+ + 2OH-(aq) + H2(g)

ΔHf◦ (kJ/mol) 0 -285.84 -461.96 -229.94 0

ΔH◦ rxn = [(-461.96) + 2(-229.94) + 0 ] – [2(-285.84) + 0]

ΔH◦ rxn = -350.16 kJ/mol

In reality, the energy released by this reaction is approximately

80 W/min = 4.8 kJ/min

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THE END

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