Electrochemistry

Cell Notation :Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s) ; LOAN : Left / Oxidation /Anode / Negative
Nernst Eqn
Store CuSO4 in Zn pot? No. because the following reaction takes place Zn(s) + CuSO4(aq) → ZnSO4 (aq) + Cu(s) ;
F2(g) + 2e– → 2F– ; E0 = 2.87 F2(g) is the strongest oxidizing element
Electrochemical Series Li+ + e– → Li(s) ; E0 = –3.05 Li is the strongest reducing element
A negative E0 means that the redox couple is a stronger reducing agent(Itself will be oxidized)
Relation between
E0 / Kc & ΔG
R, G, κ, G*

Molar Conductivity (Λm)

Kohlrausch Limiting molar conductivity of an electrolyte can be represented as the sum of the individual
law contributions of the anion and cation of the electrolyte.
α & Ka
The amount of chemical reaction which occurs at any electrode during electrolysis is
Faraday’s 1st Laws
proportional to the quantity of electricity passed through the electrolyte (solution or melt).
The amounts of different substances liberated by the same quantity of electricity passing
Faraday’s 2nd Laws through the electrolytic solution are proportional to their chemical equivalent weights (Atomic
Mass of Metal ÷ Number of electrons required to reduce the cation).
Electrolysis of
NaCl (molten) Cathode : Na+(l) + e– → Na(s) Anode : Cl–→ ½Cl2+e–
NaCl (aq) Cathode : H2O (l ) + e– → ½H2(g) + OH– Anode : Cl–→ ½Cl2+e–
+ -
H2SO4(dil) Cathode : H + e  ½ H2 Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
+ -
H2SO4(conc) Cathode : H + e  ½ H2 Anode: 2SO4 2– (aq) → S2O8 2– (aq) + 2e–
AgNO3(aq)-Ag electrodes Cathode : Ag+(aq) + e-  Ag(s) Anode: Ag(s)  Ag+(aq) + e-
+ -
AgNO3(aq)- Pt electrodes Cathode : Ag (aq) + e  Ag(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
+ -
CuCl(aq)- Pt electrodes Cathode : Cu (aq) + e  Cu(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
Pri & Sec Batteries In the primary batteries, the reaction occurs only once, and cannot be reused again
Anode(Zn) : Zn(s) → Zn2+ + 2e–
Dry Cell
Cathode(Graphite) : MnO2 + NH4+ + e– → MnO(OH) + NH3 The emf = 1.5 V.
Anode(Zn-Hg) : Zn(Hg) + 2OH– → ZnO(s) + H2O + 2e–
Cathode(HgO-C) : HgO + H2O + 2e– → Hg(l ) + 2OH–
Mercury Cell
EMF= 1.35 V and remains constant during its life as the overall reaction does not involve any
ion in solution whose concentration can change during its life time.
Anode : Pb Cathode : Pb packed with PbO2 Electrolyte : 38% H2SO4
Lead Storage Anode: Pb(s) + SO4 2–(aq) → PbSO4(s) + 2e–
Battery Cathode: PbO2(s) + SO4 2–(aq) + 4H+(aq) + 2e– → PbSO4 (s) + 2H2O (l )
On charging the battery the reaction is reversed
Anode&Cathode : Porous C Electrolyte : Aq NaOH
Cathode: O2(g) + 2H2O(l ) + 4e–  4OH–(aq)
Anode: 2H2 (g) + 4OH–(aq)  4H2O(l) + 4e–
Fuel Cells
The cell runs continuously as long as the reactants are supplied. Efficiency of about 70 %
Pollution free. The water vapours produced during the reaction were condensed and added to the
drinking water supply for the astronauts (Apollo space programme)
Oxidation: Fe (s)→ Fe2+ (aq) +2e–
Corrosion of Iron
Reduction: O2 (g) + 4H+(aq) +4e– → 2H2O(l)
(Rusting)
Atomospheric oxidation : 2Fe2+(aq) + 2H2O(l) + ½O2(g) → Fe2O3(s) + 4H+(aq)
By covering the surface with paint or by some chemicals (e.g. bisphenol). / Cover the surface
Prevention of Corrosion by other metals (Sn, Zn, etc.) that are inert or react to save the object. An electrochemical
method (sacrificial electrode like Mg, Zn, etc.) which corrodes itself but saves the object.