Electrochemistry and its application

Electrochemical cells
►Galvanic cells → converting chemical to electrical Energy
►Electrolytic Cells → converting Electrical to Chemical Energy

1. Commercial Production of elements/compounds:

Chlorine, Hydrogen, Oxygen, Sodium, Magnesium, Aluminum, NaOH
2. Impure metals are refined: Cu, Au, Pb
3. Articles are plated for protective and decorative purposes:
Jewelry, Tableware, Car bumpers, Tin cans, Shoes
4. Batteries and Fuel Cells as clean energy devices
5. Corrosion control
6. Anodizing of Aluminum
Electrochemical Cells
Charge on a single electron = 1.602x10-19 C
Charge on 1 mole electrons = 9.65x104 C = 1 F
 Electrolytic Cell
Calculate the mass of copper in g produced during the passage of 2.50 amperes of
current for 50.0 minutes through a solution of copper(II) sulfate.

1. Calculate total charge flowing in C / s

for 50 min.
(2.50 A)(1Cs-1 /1A)(50min)(60s/1min) = 7500 C

2. Convert Charge in C into moles of e:

(7500 C)(1 mol e /9.65x104 C) = 0.0777 moles e

3. Convert moles of e into moles of Cu,
using Cu2+ + 2e → Cu
(0.0777 mole e)( 1 mol Cu2+ / 2 moles e) = 0.03886 mol Cu2+

4. Convert moles of Cu into g of Cu

(0.03886 mole Cu )( 63.5 g/1mol Cu ) = 2.47 g
 Problem based on Faraday Law
Calculate the mass of copper in g produced during the passage of 2.50 amperes of current for 50.0
minutes through a solution of copper(II) sulfate.

g of Copper deposited=
[(2.50 A ) (1 C.s-1 /1A )][( 60 s / min] [50 min] X
[(1mole e / 9.65x104 C)][(1 mole Cu / 2mole e)][( 63.5 g / I mole Cu)] = 2.47 g Cu

Electro-refining of Cu and anode mud

 Which rod accumulates more electrons

Cu(s) → Cu2+ (aq) + 2e

Zn(s) → Zn2+ (aq) + 2e
Working of Galvanic Cell

Cell Diagram

What is the function of Salt Bridge ?

Overall Voltage of the Cell; Ecell = EOx + ERed
Displacement Reaction: Dissolving Zn and Plating out of Cu

Zn in CuSO4 solution
 Write Cell reactions

Write the cell diagram

1. What do you need to construct (design) a Galvanic Cell ?
2. What is the function of each part which you need ?
3. Write the electrodes and overall reactions
4. Write the cell diagram
5. Where does the energy delivered by Galvanic cell come from ?
6. How is the energy of reactions in the cell related to cell voltage ?
7. Differentiate between electronic and ionic conductors

∆G = - 218 kJ / mol

∆G = - n . F . E
Why and How Cu – Zn cell works

Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)

Zn Cu
Sublimation +130 -340 in kJ/mol

Ionization +2641 -2704

Hydration - 2009 +2064

∆H = - 218 kJ / mol ( converted to electrical energy )

 How is electrode potential measured?
We use Standard Hydrogen Electrode ( SHE )

SHE as anode: Pt(s) H+(1M) ; (H2 1 atm) H2 (s)→ 2H+ (aq)+ 2 e, Oxidation
SHE as cathode: H+(1M) ; (H2 1 atm) Pt(S) 2H+ (aq) + 2e → H2 (s), Reduction
 Zn - SHE Cell

2H+ (aq.) + 2e → H2 (g) ; 0.00 V

Zn (s) → Zn2+ (aq.) + 2e ; 0.76 V

Zn(s) + 2H+ (aq.) → Zn2+ (aq.) + H2(g) ; Ecell = 0.76 V

Zn2+ (aq.) + 2 e → Zn (s) ; - 0.76 V

Cu - SHE CELL H2 (g, 1atm) + Cu2+ (aq, 1M)  Cu (s) + 2H+(aq, 1M)
Standard electrode reduction potentials and
their table

The convention is to report all electrode potentials in

the reduction form as given below ! !

The standard reduction potentials of electrodes

are tabulated along with reduction half-reactions.
 Predict the natural (spontaneous) direction of redox
reactions.
spontaneous ?

Zn + Cu2+  Zn2+ + Cu Cu+ Zn2+  Cu2++ Zn

Zn displaces Cu2+ or Cu displaces Zn2+ ? ?

l.Choose the appropriate half-reactions from the table

; Eº = - 0.763 v
; Eº = + 0.337 v

2.Choose the half reaction with the more +ve (or less - ve) Eo
as the spontaneous reaction on the cathode (reduction):

v
3.Reverse the other half-reaction and its potential to make it
oxidation

Zn  Zn2+ + 2 e ; +0.763 [notice sign of the potential]

4.Balance the number of electrons if necessary

Cu2+ + 2 e  Cu ; +0.337 Zn  Zn2+ + 2 e ; +0.763

5.Add the half-reactions and the associated potentials.

Cu2+ + 2 e  Cu +0.337 V (st. red. potential)
Zn  Zn2+ + 2 e +0.763 V (st. Ox. potential)
Zn +Cu2+ Zn2+ + Cu ; E0cell =+1.100 V (+ve means favoured)
Voltage depends
on concentration
NERNST EQUATION: Effect of concentration on Cell voltage

aA + bB ↔ cC + dD
Voltage:
Standard conditions Eᵒ
Non-standard conditions E

Concentrations are time dependent

Writing equilibrium constants for the chemical equations
Write the electrode and overall reaction for the Cell below
Write the equilibrium constant for the overall reaction

Zn(s) ZnO(s) NaOH(aq.) HgO(s) Hg(l)

What happens to Cell Voltage at equilibrium
when:

1. Concentration of Cu2+ is increased,

2. Concentration of Zn2+ is increased

Use the following equation to answer these questions:

Voltage of Galvanic Cell depends on concentrations
of reactants and products, their physical states, and Temperature

Write equilibrium constant and reaction quotient for the above chemical equation
 Calculating Cell voltage under
non-standard conditions) Qc =

aA + bB ↔ cC + dD

1. Calculate Q
2. Read Eᵒ from the table
3. Insert values of F, T, which are given
4. Find n from the chemical equation
What will happen to the value of
E when equilibrium is achieved ?
E will become zero !
At equilibrium Q = K and Ecell = 0, hence

At 25ᵒ C

= (0.02570 J.C-1) / ν. ln K = (0.02570 V)/ν ln K

E0 = (0.02570 V) / ν. ln K
Whare does E in Galvanic cell come from:

Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)

Zn Cu
Sublimation +130 -340 in kJ/mol

Ionization +2641 -2704

Hydration - 2009 +2064

∆H = - 218 kJ / mol ( converted to electrical energy )

Calculate Standard voltage at 25◦C if Ecell for the cell below is 1.13 V
Batteries & Cells
Lead-Acid
automobile
battery
 Lead-Storage Battery invented in 1859

Temperature range: - 35 to + 45⁰C

Typically delivers one Ampere current for 45 hours
Rechargeable, used for cranking, lighting, Igniting in ICE

PbO2 (s)+ Pb(s) + 2H+ (aq)+ 2HSO4 ↔ 2PbSO4 (s)+ 2H2O(l)

PbO2(s)
cathode 2V e
+ -
40wt% aq. H2SO4

Compressed
spongy Pb (s)
anode
 Lead storage battery ( 40 mass% aq. H2SO4)

Cathode Reactions (why):

PbO2(s) + 4H+(aq) + 2e  Pb2+ (aq) + 2H2O(l)

Pb2+(aq) + HSO4-(aq) → PbSO4(s) + H+(aq)

► PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e → PbSO4(s) + 2H2O(l):+ 1.685 V

Anode reactions (why):

Pb(s) → Pb2+(aq) + 2e
Pb2+(aq) + HSO4- (aq) → PbSO4(s) + H+ (aq)

► Pb(s) + HSO4- (aq)  PbSO4 (s) + H+(aq) + 2e- : + 0.3560V

Overall: PbO2(s) +Pb(s) + 2HSO4-(aq) + 2H+(aq)2PbSO4 (s) + 2H2O (l)

 Nickel-Cadmium Battery ( rechargeable )

NiOOH Cd(s)
(s) 1.4V anode
cathode + -

KOH

Electrode reactions
Anode: Cd(s)+2OH- (aq)  Cd(OH)2(s) + 2e
cathode: 2NiOOH(s)+2H2O(l)+2e-2Ni(OH)2(s)+2OH-(aq)

Overall: Cd(s) + 2NiOOH(s)+2H2O(l)2Ni(OH)2 (s) +Cd(OH)2 (s)

 Nickel Metal Hydride Battery (NMH)

First introduced in 1989

NiMH batteries have two to three times greater charge capacity and up to 40
percent longer service life than standard nickel-cadmium batteries.
→ Anode made from hydrogen - absorbing alloy.
→ Cathode made from nickel-oxide hydroxide, Ni(OOH)
→ Electrolyte is aq. KOH

Anode: MH + OH - → M + H2O + e +0.83 V

Cathode: NiOOH + H2O + e → Ni(OH)2 + OH - ; +0.52 V

Overall: MH + NiOOH → M + Ni(OOH); +1.35 V

The Lithium-Ion Battery
( Electrolyte: LiClO4 dissolved in propylene Carbonate )

3.7 V