CHAPTER

3 Electrochemistry

Galvanic Cell E cell = 0.0591 log P1 ; (P = Pressure)

For a cell reaction in an electrochemical cell 2 P2
Zn(s) + CuSO 4 (aq) 
 Cu(s) + ZnSO 4 (aq) ™For Electrolyte Concentration Cell
Cell representation ⇒ Zn | Zn (aq.) | | Cu (aq.) |Cu
2+ 2+ (Cu | Cu 2 + (C1 ) || Cu 2 + (C2 ) | Cu)
anode( − ) Cathode( + )
Anode( − ) Cathode( + )
0.0591 C
For half cell reaction E cell = log 2
n+ − o o 2 C1
M → M (aq.) + ne ; E OX E
= M / Mn+
For concentration cells, E 0cell = 0
n+ − o o
M (aq) + ne → M; E E
=
red Mn+ / M ™ At Equilibrium
0 0 0 0 0
Emf of cell, E
= E cell right −E left = E cathode −E anode Ecell = 0 (as DG = 0)
R.P. R.P
(R.P. = Reduction potential)
Thermodynamics for the Cell
™ Oxidation potential for half cell reaction:
™ Temperature Coefficient (T.C.)
M → M+n + ne–
 ∂E cell 
2.303RT (T.C.) =  
E= OX
0
E OX − log[M n + ]  ∂T ρ
nF
™ Change in Entropy
™ Reduction potential for half-cell reaction:
2.303RT  ∂E 
Mn+ + ne– → M, E= E 0red + log[M n + ] DS = nF  
red
nF  ∂T p
Nernst's Equation ™ Relation Between ECell & (T.C.)
™ ∆G = −nFE cell =− W  −∆H   ∂E 
=
E cell   + T 
∆G = ∆G ° + 2.303RT log Q  nF   ∂T  p
∆G° = −nFE οcell {∆H =Heat of cell reaction}
2.303RT
E= E οcell − log Q  ∂E 
cell nF   > 0 ⇒ Cell reaction is endothermic and vice versa.
DG = Change in free energy  ∂T p
W = Useful work done Quantitative Analysis
n = Number of electrons exchanged
™ Faraday’s 1st Law of Electrolysis
F = Faraday constant (96500 coulomb)
m = ZIt
Q = Reaction quotient
m = mass of substance deposited
At room temperature (25°C)
Z = electrochemical equivalent
⇒ Nernst’s equation
I = current
0 0.0591
⇒ E= cell E cell − log Q t = time
n
Atomic mass
Z =
Concentration Cell n×F
™For Electrode Concentration Cell ™ Faraday’s 2nd Law of Electrolysis (Q = constant)

Pt | H 2 (P1 ) | H + (c M) || H + (c M)|H 2 (P2 )|Pt

 m E {N = Normality}
1 = 1 (E = equivalent weight)
m2 E2 ΛM
Λ eq =
(n − factor)
Conductance
Λ = lim Λ
0 C →0 C
™ Ohm’s Law
{Λ0 = equivalent conductance at infinite dilution
V = RI
(or zero concentration)}
R = ρ
a ™ For Weak Electrolyte

V = Potential difference 1
Λ C ∝
C
R = Resistance
1/ 2
I = Current For strong electrolyte, Λ C =Λ 0 − B(C) (B = constant)
™ At Infinite Dilution, for an Electrolyte AxBy
ρ = Specific resistance (resistivity)
y+ x−
l = length of conductor A x By  xA + yB
a = cross-section area of conductor Λ 0A x By = xλ 0A y+ + yλ 0Bx −
0 0
™ Conductance { λ A y+ , λ Bx − = equivalent conductance at infinite dilution of
1 cation and anion}
G =
R ™ Ionic Mobility
™ Specific Conductance (Conductivity) Ionic Velocity
µ =
1 Potential gradient
κ =
ρ
Degree of Dissociation
™ Cell Constant
™For a Weak Electrolyte

G =
*
(CH 3 COOH  CH 3 COO − + H + )
a
Λm C(Λ m / Λ 0 ) 2
κ= G × G * =
α = , Ka
Λ0 1 − (Λ m / Λ 0 )
™ Molar Conductance
Solubility Product
1000 × κ
Λ m =  Ag + (aq) + Cl− (aq))
For solubility of salt (AgCl(s) 
C( or M)
2
{C = concentration of electrolyte in terms of molarity}  1000 κ 
K sp =  
 Λ0 
™ Equivalent Conductance
1000 × κ
Λ eq =
N

6 JEE (XII) Module-1 PW

 Electrochemistry

relates

Chemical energy Electrical energy

Batter ies Electrorefining
and electroplating

used in
interconverted i n used in

Shorthand represented Galvanic cells Electroytic cells

notation using (Voltaic cells)

reactions are reactions are

having

Spontaneous Non spontaneous

Standard oxidation-reduction oxidation-reduction
cell potential, Eº
producing requiring
related to
∆G = – ∆G = (+)
Electric current
Ecell= (+) Ecell= (–)
(1) Free energy change, ∆Gº
(2) Equilibrium constant, K
oxidation half-reaction Reduction half-reaction
occurring at the occurring at the

calculate from used in Anode Cathode

Standard reduction Nernst

potentials equation

P
W Electrochemistry 7