ELECTROCHEMISTRY

KEY CONCEPT
1. Indroduction anode and pulls them towards the cathode is an
electrical potential called electromotive force also
Batteries are everywhere in modern societies. They known as cell potential or the cell voltage. Its unit is
provide the electric current to start our automobiles volt.
and to power a host of products such as pocket
calculator, digital watches, heart pacemaker, radio,
and tape recorders. Oxidation Potential (O.P.) Reduction Potential (R.P.)
 The electrode potential for  The electrode potential for
Electrochemistry is the area of chemistry concerned oxidation half reaction reduction half reaction
with the interconversion of chemical and electrical.  Tendency to get oxidised.  Tendency to get reduced.
 Greater the O.P. than greater  Greater the R.P. greater will be
A battery is a an electrochemical cell, a device for tendency to get reduced.
will be tendency to get oxidised.
interconverting chemical and electrical energy. A
battery takes the energy relased by a spontaneous
chemical reaction and uses it to produce electricity.
4. Concentration cell
Electrochemical cell :
It is device for converting chemical energy into  A concentration cell consists of two electrodes
electrical energy. of the same material, each electrode dipping in
Electrochemical cell are of two types a solution of its own ions and the solution being
at different concentrations.
Galvanic cells or Voltaic cell Electrolytic cell.  The two solutions are separated by a salt
 A spontaneous chemical reaction  An electric current drives a bridge. e.g. Ag(s) |Ag+ (a1) || Ag+(a2)| Ag(s)
Generates an electric current nonspontaneous reaction
(a1 < a2)a1, a2 are concentrations of each half cell
2. Construction of cell At L.H.S. electrode Anode :
Ag(s)  Ag+(a1) + e–
 It has two half-cells, each having a beaker
At R.H.S. electrode Cathode :
containing a metal strip that dips in its aqueous
solution. Ag+(a2) + e–  Ag(s)
 The metal strips are called electrodes and are The net cell reaction is :
connected by an conducting wire. Ag+(a2)  Ag+(a1)
 Two solutions are connected by a salt bridge. The nernst eq. is
 The oxidation and reduction half reactions E cell  
0.059 a
log 1
occur at a separate electrodes and electric n a2
current flows through the wire. (Here n = 1, Temp, 298 K)
 Likewise, the e.m.f. of the cell consisting
e e of two hydrogen electrodes operating at
different pressure P1 and P2 (P1 > P2) and
Zinc (anode) + Copper (cathode)
SO4 2Na dipping into a solution HCl is :
Salt bridge
0.059 P
E cell   log 1
2e 2e n P2
SO4
Zn+2 Cu+2 Work done by a cell :
(i) Let ‘n’ faraday charge be taken out of a cell of
Zn(s)  Zn+2(aq.) + 2e Cu+2(aq.) + 2e  Cu(s)
EMF ‘E’; then work done by the cell will be
calculated as :
3. Electrode Potential Work = Charge × Potential = nFE
(ii) Work done by cell = Decreases in free energy
The driving force that pushes the negative charge
So – G = nFE
electrons away from the anode and pulls them the
 or Wmax. = nFEº where Eº is standard EMF of IIst Law : When equal charge is passed through
the cell 2 electrolytic cells and this cells are connected
in series then mass deposited at electrode will
5. Thermodynamics of cell Potential be in the ratio of their electrochemical
equivalents or in the ratio of their equivalent
We know that : masses.
Gº  nFEcell
º
EQ
W  ZQ 
G º  nFEcell 96500
E cell W1 Z1 E 1
 
S  nF (Q = same)
T W2 Z 2 E 2
E cell
H  nFEcell  nFT
T 7. Electrolytic conductance
 E cell
2
Cp  nFE
T 2 Conductors

6. Electrolysis & Electrolytic cell Metallic Conductors Electrolytic Conductors

1. Charge carries are e– 1. Charge carries ions (cations/anions)
Electrolysis : 2. No chemical changes 2. Decomposition of electrolyte takes
3. No transfer of mass place.
 Electrolyte is a combination of cations and 4. Resistance is because of 3. Transfer of mass
anions which in fused state can conduct collision of e– s with fixed 4. Resistance is because of collision of
metal atoms ions with solvent molecules & because
electricity. 5. Temp.R of interionic force of attraction
 This is possible due to the movement of 6. Low resistance generally 5. Temp.R
good conductor. 6. Hight resistance generally
ions from which it is made of and
electrolyte.
 The process of using an electric current to 8. Resistance
bring about chemical change is called
electrolysis V
 Electrolysis is a process of oxidation and R (Ohm' s law ())
I
readuction due to current in the electrolyte. 
R
 The product obtained during electrolysis A
depends on following factors. -resistivity/specific resistance
 The nature of the electrolyte - resistance of unit length wire of unit area of
 The concentration of electrolyte cross section = constant = (m)
 The charge density flowing during 
RA
electrolysis 
 The nature of the electrode Resistivity of a solution is defined as the
resistance of the solution between two
 Faraday's Law of Electrolysis :
electrodes of 1 cm2 area of cross section and
 Ist Law : The mass deposited/released/produced 1 cm apart.
of any substance during electrolysis is or
proportional to the amount of charge passed Resistance of 1 cm3 of solution will be it's
into the electrolyte. resistivity.
W  Q  W = ZQ
Z-electrochemical equivalent of the substance. 9. Conductance
mass
Unit of Z =  Kg / C or g / C
coulomb
1
Z = Mass deposited when 1C of charge is   mho   1 = S (Siemens)
R
passed into the solution. Conductivity/specific conductance
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 1   molar conductivity and is represented by
K  
 RA A the symbol º.
Unit –1 cm–1 = conductivity of 1 cm3 of
solution  concentration of ions 10. Strong Electrolytes
1 1
K G
 R (A) For strong electrolytes.  increases slowly with
K  (no. of ions) no. of charge carries dilution and can be represented by the equation
 Since conductivity or resistivity of the  = º – AC1/2.
solution is dependent on it's concentration, (B) The value of the constant ‘A’ for a given
so two more type of conductivities are solvent and temperature depends on the type of
defined for the solution electrolyte i.e. the charges on the cations and
 Molar conductivity/molar conductance(m) : anion produced on the dissociation of the
  Conductance of a solution containing 1 mole of electrolyte in the solution.
an electrolyte between 2 electrodes which are Example : Thus NaCl, CaCl2, MgSO4 are
1 cm apart. known as 1-1, 2-1 and 2-2 electrolyte
K 1000 K  1000 respectively.
 m  KV m   m  (C) All electrolytes of a particular type have the
C molarity
same value for ‘A’
Its units are Ohm–1 cm2 mol–1.
 Equivalent conductance :
Conductivity of a solution containing 1 g 149.8

(S cm2 mol–1)

149.4
equivalent of the electrolyte.
149.0
eq – equivalent conductivity/conduction.
148.6
K  1000
eq  148.2
Normality 147.8
 Its units are Ohm–1 cm2 eq–1 147.4
  Ionic Mobility : 147.0
   Ionic Mobility = speed of the ion per unit 0
electrical field .005.010.015 .020 .025 .030 .035
speed speed c1/2(mol/L)1/2
    
electrical field potentialgradient Variation of  against c1/2
 Its units are v–1 cm2 sec–1
0M 0
Kohlarausch's Law :
Ionic mobility = u =  M
96500 F
(A) ‘‘At infinite dilution, when dissociations
  Variation of conductivity and molar complete, each ion makes a definite
conductivity with concentration : contribution towards equivalent conductance of
   Conductivity always decreases with the the electrolyte irrespective of the nature of the
decreases in concentration both for weak ions with which it is associated and the value of
and strong electrolytes. equivalent conductance at infinite dilution for
 The number of ions per unit volume that any electrolyte is the sum of contribution of its
carry the current in a solution decreases on constituent ions.’’
dilution. i.e.,  = + + –
   Molar conductivity increases with (B) At infinite dilution or near zero concentration
decreases in concentration. This is because when dissociation is 100%, each ion makes a
the total volume, v of solution containing definite contribution towards molar
one mole of electrolyte also increases. conductivity of electrolyte irrespective of the
   Molar conductivity is the conductance of nature of the other ion. (because interionic
solution forces of attraction are zero)
   When concentration approaches zero, the 0m electroly te  v  0m  v  0m 
molar conductivity is known as limiting a

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 v+ = no. of cations in one formula unit of 2e– + 4H+ + PbO2(s)  Pb2+(aq.) + 2H2O()
electrolyte
v– = no. of anions in one formula unit of Pb2+(aq.) + SO 24 (aq.) + 4H+ + 2e– 
electrolyte PbSO4(s) + 2H2O()
11. Weak electrolytes PbSO4(s) sticks to cathode rod.
Pb(s) + PbO2+ 4H+ + 2 SO 24 (aq.) 
(A) Weak electrolytes like acetic acid have lower
degree of dissociation at higher concentration         2PbSO4(s) + 2H2O()
and hence for such electrolytes, the change in  ECell = 2.05 V
with dilution is due to increases in the number Nickel-cadmium battery
of ions in total volume of solution that contains Ecell = constant as cell reaction has pure
1 mol of electrolyte. solide/liquids only
(B) At infinite dilution Anode : Cd/(s)
(i.e. concentration c  zero) electrolyte Cathode : NiO2(s)
dissociates completely ( = 1), but at such low Electrolyte: KOH
concentration the conductivity of the solution is Cd = 2OH–  Cd(OH)2 + 2e–
so low that it cannot be measured accurately.
2e– + NiO2 + 2H2O  Ni(OH)2(s) + 2OH–
(C) Molar conductivity versus c1/2 for acetic acid
(weak electrolyte) and potassium chloride Cd(s) + NiO2(s) + 2H2O() 
(strong electrolyte) in aqueous solutions.       Cd(OH)2(s) + Ni(OH)2(s)
Fuel cells (H2–O2 cell) :
400 CH3COOH Anode : H2  2H+ + 2e– × 2
/S cm2mol–1

Cathod : 4e– + 4H+ + O2  2H2O

200 2H 2  O2  2H2O()
KCl
CH4–O2 fuel cells :
Anode : 2H2O + CH4  CO2 + 8H+ + 8e–
0 0.2 0.4 Cathod : 4e– + 4H+ + O2  2H2O
c1/2/(mol/L)1/2 CH4  2O2  CO2  2H2O()

12. Some Cells

13. Mechanisum of corrosion

(A) Primary cells : These cells can not be recharge

Rust (Fe2O3. x H2O)
dry cell (lechlanche cell) mercury cells
water
(miniature cell used in these electronic devices)
Ecell = constant Fe2+ Fe2+
As all substances used are either pure solids or Cathode
pure liquids. Iron –
Anode e
(B) Secondary cells : Lead storage batteries used is
automobiles (Cars/bikes) Oxidation : Fe(s) Fe2+(aq.) + 2e–
Anode : Pb(s)
Cathode : PbO2(s) Reduction : 2O2–(g) + 4H+(aq.)  2H2O()
H2SO4(conc.) about 38% solution of H2SO4 is Atomospheric
taken. Oxidation : 2Fe2+(aq.) + 2H2O() + 1/2 O2 
Pb2+(aq.) + SO 24 (aq.)  PbSO4(s)         Fe2O3(s) + 4H+ (aq.)
Pb(s) + SO 24
(aq.)  PbSO4 + 2e–
most of the PbSO4(s) ppt sticks to the lead rod.
Cathode:

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 Electrochemistry

relates

Chemical energy Electrical energy

Batteries Electrore fining and
electroplating

used in Interconverted in used in

Represented Galvanic cells Process

Shorthand notation Electrolytic cells Shorthand notation
using (voltaic cells) called

reaction are reaction are

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

Anode Cathode
Interconverted in
calculate from used in

Standard reduction
Nernst equation
potentials

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