Lead-Acid

Batteries & Cells 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

Lithium Batteries
Li → Li+ + e
 Graphite

142 pm

341 pm
The Lithium-Ion Battery
( Electrolyte: LiClO4 dissolved in propylene Carbonate )
 Anode Reaction:

Cathode Reaction:

Thus, the overall discharge reaction is

Fuel Cells: H2 – O2 version
( cars running on water ! ! )
Cathode: 4e-+O2 (g) +2H2O (l)4OH-(aq)
Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

2H2 (g) + O2 (g) 2H2O (l)

(impregnated with Pt or Pd)

 Corrosion and its Prevention

Corrosion of metals & Alloys occurs through

spontaneous electrochemical reactions
Why do we call it reverse metallurgy ?
 Corrosion of Iron
Caused by Electrochemical Reactions
Oxidation and Reduction go together

→ Oxidation: Fe → Fe + 2 e ( Metal corrodes )

2+

→Reduction happens in the environment such as:

a. 2 H+ + 2 e → H2 ( acidic medium )
b. O2 + 4H+ + 4 e → 2 H2O ( acidic medium with dissolved O2 )
c. O2 + 2 H2O + 4 e → 4 OH -( Neutral / basic medium with
dissolved O2 )
d. Metal ion can also be reduced
Cu2+ + 2 Fe2+ → Cu + 2 Fe3+

H+, O2 , H2O and impurities are involved in rusting

1. Rusting of Iron in oxygen rich water: Rust Fe2O3.xH2O
2. Step I: Fe → Fe2+ + 2e
3. ½ O2 + H 2O + 2e → 2 OH-
4. Overall: Fe + 1/2 O2 + H2O → Fe2+ + 2 OH- ( Soluble )
5. Or 2 Fe + O2 + 2 H2 O → 2 Fe2+ + 4 OH-…(1)
6. Step II: 2 Fe2+ → 2 Fe3+ + 2e
7. ½ O2 + H2 O + 2 e → 2 OH-

8. Overall: 2 Fe2+ + ½ O2 + H2 O → 2 Fe3+ + 2 OH- ….(2)

9. Add reaction (1) and (2) to get
10. 2 Fe + 3/2 O2 + 3 H2O → 2 Fe ( OH )3
Fe ( OH )3 transforms into : Fe2O3.xH2O which is called rust
 The factors which speed up corrosion

1. Dissolved salts facilitate corrosion

2. Acidity favors corrosion. Acidity comes from

dissolved CO2, oxides of S & Fe3+ + 3H2O → Fe(OH)3 + 3H+ etc

3. Biocorrosion due to sulfate reducing bacteria

Iron pipes buried in clay soils or covered by polluted water corrode even in
the absence of O2. Under these conditions ions such as SO42- are reduced
by anaerobic bacteria thereby accelerating corrosion
 Inhibition of Corrosion

1. Coatings of paint or plastics protect the metal, but they can crack or suffer
other damage, thereby localizing and accentuating the process.

2. Passivation: in which a thin metal oxide layer forms on the surface and
prevents further electrochemical reactions. (Aluminum reacts with
oxygen to form a tightly bound thin protective layer of A12O3

3. Special paints designed for rust prevention contain potassium dichromate

(K2Cr2O7) and lead oxide (Pb3O4) which cause the surface of iron to be
oxidized and passivated.
4.The presence of small quantities of alloying materials can greatly influence
the amount of protection that a film provides.

Stainless steel is an alloy of iron + chromium in which the

chromium leads to passivation through Cr2O3
formation and prevents rusting
 Corrosion prevention

5. Use of a sacrificial anode such as Mg for protecting Fe:

According to the standard reduction potentials of iron and magnesium
Fe2+(aq)+ 2 e- → Fe(s) Eo = -0.41 V
Mg2+(aq)+ 2 e- → Mg(s) Eo = -2.39 V
Mg2+ (aq) is much harder to reduce than Fe2+ (aq). It follows that Mg (s)
is more easily oxidized than Fe(s)
Magnesium is the sacrificial anode

6. Galvanizing with Zn ( see next slide )

7. Tin coating on Steel
8. Silver coating on Steel ( Silver spoon )
Mg as sacrificial anode

Inert ( graphite )