UNIT - II

APPLICATION OF ELECTROMOTIVE FORCE

Application of measurements of EMF in the determination of
(1) Solubility product and solubility of sparingly soluble salts
(2) Ionic product of water by galvanic cell
(3) Transport number of ions
(4) Equilibrium constant
(5) pH by Hydrogen, Glass and Quinhydrone electrodes
(6) Energy sources Ni-Cd Cell and Li- ion Cell, Lithium Polymer Cell
Numerical problems.
 Applications of EMF
(1) Determination of Solubility and Solubility product
The solubility of sparingly soluble salts such as AgCl , PbSO4,BaSO4 ,, AgCNO etc. can be
determined by emf measurements.
To determine the solubility of AgCl , the following cell is set up
Ag |0.01 M KCl (a1) |Saturated NH4NO3 | 0.01M AgNO3(a2) | Ag
saturated with AgCl
It consists of two silver electrodes- one is Ag rod dipped in 0.01M KCl solution saturated with AgCl
and other is Ag rod dipped in 0.01MAgNO3 solution. The saturated solution is prepared by adding a
drop of AgNO3 solution in 0.01M KCl solution in first electrode. The salt bridge consists of saturated
solution of NH4NO3
The cell so assembled is a concentration cell reversible with respect to silver ions. One silver
electrode is in contact with solution of sliver ions of known concentration,0.01M. It may be assumed
that 0.01 M AgNO3 is completely ionized. While the other electrode is in contact with a solution of
much lower concentration of Ag+ ions(furnished by the ionization of sparingly soluble AgCl) which is
unknown. The emf of this cell is determined potentiometrically at 25°C. The cell reaction is
Anode Ag → Ag+ (a1) + e-
Cathode Ag+(a2) + e- → Ag
Net reaction Ag+(a2) → Ag+(a1)
Nernst equation for this reaction is written as

2.303RT 𝐴𝑔 + (𝑎 1 )
E cell = E°cell ‒ 𝑛𝐹
𝑙𝑜𝑔 𝐴𝑔 + (𝑎 2 )
----(1)
For dilute solution activity is equal to concentration and both the electrodes are same
therefore, a1 = C1 = unknown, a2 = C2 = 0.01M and E°cell =0. Thus the above equation
becomes
2.303RT 𝐶
E cell = ‒ log 1 ----(2)
𝑛𝐹 𝐶2
2.303RT 𝐶2
or E cell = 𝑛𝐹
log 𝐶1
----(3)

If we substitute n =1 , R = 8.314JK-1mol-1 , F = 96500Coulombs mol-1, T =298K then

The above equation becomes
𝐶
E cell = 0.0591 log 𝐶2 ---(4)
1
0.01
or E cell = 0.0591 log 𝐶1
---(5)
where C1 is the unknown concentration of Ag+ ions furnished by silver chloride in KCl
solution .Activities in terms of a± = m±γ± can be used for better accuracy.

After putting the value of Ecell(obtained from potentiometer) in equation (5) we get the
value of C1(i.e. the unknown concentration of Ag+ of AgCl).
If it is assumed that KCl is completely ionized then Cl- ions concentration will be 0.01M.
Now Ksp can be determined as
Ksp = C1 x CCl-
or Ksp = C1 x (0.01) M2
EX-1 The cell given below has EMF 0.814 Volt at 18°C
Ag | AgI(s),0.1MKI (C1) |Saturated NH4NO3| 0.1M AgNO3(C2) |
Ag
If KI and AgNO3 are completely ionized then calculate solubility and
2.303RT
solubility product of AgI.(At 18°C = 0.058)
𝐹
EX-2 The cell given below has EMF 0.45 Volt at 25°C
Ag | AgCl(s),0.1MKCl (C1) |Saturated NH4NO3| 0.1M AgNO3(C2) | Ag
If 0.1M KCl and 0.1M AgNO3 are ionized 85 % and 82 % respectively then
2.303RT
calculate solubility and solubility product of AgCl.(At 25°C 𝐹
= 0.0591)
EX-3 The cell given below has EMF 0.4298 Volt at 25°C
Ag | AgCl(s),KCl (m =0.05,γ = 0.821) ||AgNO3(m =0.1, γ = 0.725) | Ag
a1 a2
2.303RT
Calculate solubility and solubility product of AgCl.(At 25°C 𝐹
=
0.0591)
Ex-4 Calculate Ksp of Fe(OH)3 Given
Fe(OH)3 + 3 e- → Fe + 3 OH- E° = -0.77 V
Fe3+ + 3 e- → Fe E° = -0.036 V
(2) Determination of Ionic Product of Water
Ist Method- We know the dissociation of water in hydronium ions
(for convenience H+ ions) and hydroxide ions in very small amount.
Therefore the following equilibrium exists.
H2O ⇌ H+ + OH-

and ionic product of water Kw is give as

Kw = 𝑎𝐻 + x 𝑎𝑂𝐻 − ----(1)
The ionic product of water can be determined using the following
concentration cell
Pt| H2(g,1atm)| KOH(m1)|| HCl(m2)| H2(g,1atm)| Pt
In this concentration cell both the electrodes are hydrogen
electrodes and both are reversible to H+
ions. The EMF of this cell at 25 °C is given as
(𝑎 𝐻 + )2
E cell = 0.0591 𝑙𝑜𝑔 ----(2)
(𝑎 𝐻 + )1
Where (𝑎𝐻 + )2 is the hydrogen activity in RHS half cell and (𝑎𝐻 + )1
is the hydrogen ion activity in LHS half cell.
In LHS half cell (𝑎𝐻 + )1 can be determined using Kw equation
Kw = 𝑎𝐻 + 1 x 𝑎𝑂𝐻 − 1
𝐾𝑤
and 𝑎𝐻 + 1 = ---(3)
−𝑎 𝑂𝐻 1
substitute this value of 𝑎𝐻 + 1 in eq(2) we get
(𝑎 𝐻 + )2 𝑎𝐻+ x 𝑎 𝑂𝐻 − 1
2
E cell = 0.0591 log 𝐾𝑤 = 0.0591 log
𝐾𝑤
𝑎 𝑂𝐻 − 1
 𝑎𝐻+ x 𝑎 𝑂𝐻 − 1 𝐸𝑐𝑒𝑙𝑙
2
log =
𝐾𝑤 0.0591
Take antilog of both sides
𝑎𝐻 + x 𝑎 𝑂𝐻 − 1 𝐸𝑐𝑒𝑙𝑙
2
= Antilog
𝐾𝑤 0.0591
𝑎𝐻+ x 𝑎 𝑂𝐻 − 1
2
Kw = 𝐸 𝑐𝑒𝑙𝑙
Antilog
0.0591
By putting the value of Ecell , 𝑎𝐻 + 2 and 𝑎𝑂𝐻 − 1 , the value of Kw
can be determined
IInd Method- The ionic product of water can also be determined
using the following type of cell
H2(g,1atm) | MOH(m1), MCl(m2),AgCl(s) | Ag(s)
Where M = Li, K,or Na type metals
For this cell anode and cathode reaction can be written as
Anode reaction ½ H2(g,1atm) → H+ + e-
Cathode Reaction AgCl(s) + e – → Ag(s) + Cl-
Net reaction ½ H2(g,1atm) + AgCl(s) → H+ + Ag(s) + Cl-
𝑎𝐻2 = 1 , n = 1 therefore Nernst equation for the above cell reaction is
 2.303𝑅𝑇
Ecell = E°cell ‒ log 𝑎𝐻 + (𝑎𝐶𝑙 − ) ----(1)
𝐹
But Kw = 𝑎𝐻 + x 𝑎𝑂𝐻 −
𝐾
and 𝑎𝐻 + = 𝑤 − ---(2)
𝑎 𝑂𝐻
substitute this value of 𝑎𝐻 + fro eq(2) into eq(1) we get

2.303𝑅𝑇 𝐾𝑤
Ecell = E°cell ‒ log (𝑎𝐶𝑙 − ) ----(3)
𝐹 𝑎 𝑂𝐻 −
2.303𝑅𝑇 (𝑎 𝐶𝑙 − )
Ecell = E°cell ‒ [log Kw + log ]
𝐹 𝑎 𝑂𝐻 −
As we know a = mγ , put the value of a = mγ in eq(3) we get
2.303𝑅𝑇 𝑚 − 𝛾 𝐶𝑙 −
Ecell = E°cell ‒ [log Kw + log 𝐶𝑙 ]
𝐹 𝑚 𝑂𝐻 − 𝛾 𝑂𝐻 −
2.303𝑅𝑇 𝑚 𝐶𝑙 − 𝛾 𝐶𝑙 −
Ecell ‒ E°cell = [ ‒ log Kw ‒ log ]
𝐹 𝑚 𝑂𝐻 − 𝛾 𝑂𝐻 −
°
𝐹(𝐸𝑐𝑒𝑙𝑙 −𝐸𝑐𝑒𝑙𝑙 ) 𝑚 − 𝛾 −
= ‒ log Kw ‒ log 𝐶𝑙 − ‒ log 𝐶𝑙 − ------(4)
2.303𝑅𝑇 𝑚 𝑂𝐻 𝛾 𝑂𝐻
 𝛾 𝐶𝑙 − 𝛾 𝐶𝑙 −
At infinite dilution the value of =1 and log =0,
𝛾 𝑂𝐻 − 𝛾 𝑂𝐻 −
therefore eq(4) becomes
°
𝐹(𝐸𝑐𝑒𝑙𝑙 −𝐸𝑐𝑒𝑙𝑙 ) 𝑚 𝐶𝑙 − 1
= - log - log Kw ----(5) [ μ = 𝑚𝑖 𝑧𝑖2 ; μ∝m]
2.303𝑅𝑇 𝑚 𝑂𝐻 − 2

The EMF of the cell is measured using various dilutions of alkali

chloride and alkali hydroxide. The left hand side of eq(5) is plotted
against ionic strength. The curve is then extrapolated to zero
concentration, the intercept will be equal to ‒ log Kw
The value of E°cell = 0.2224volt at 25°C and MOH and MCl are
completely ionized at infinite dilution then mOH- and mCl- are equal to
m1 and m2. The value of ‒log Kw = 13.9965 is obtained and the value
of Kw = 1.008 x 10-14 is obtained.
Ex-1 Pt | H2(g, 1atm), KOH(0.01m) || HCl(0.01m) |
H2(g,1atm) | Pt
The EMF of this cell at 25°C is 0.5860 volt. If average activity
constant of the solution is 0.9 then calculate Kw.
Sol. aH+ = 0.01x0.9 = 0.009 ; aOH_ = 0.01 x 0.9 = 0.009 ; Ecell
= 0.5860V
𝑎𝐻+ x 𝑎 𝑂𝐻 − 1
2
Kw = 𝐸
𝑐𝑒𝑙𝑙
Antilog 0.0591
0.009 x 0.009 8.1 x 10 −5
Kw = 0.5860 =
𝐴𝑛𝑡𝑖𝑙𝑜𝑔 𝐴𝑛𝑡𝑖𝑙𝑜𝑔 9.9154
0.0591
8.1 x 10 −5
Kw = = 9.84 x 10-15
8.23 𝑥 10 9
Or Kw = 0.984 x 10-14
Ex-2 The EMF of the cell given below is 0.725 V at 25°C
Pt | H2(g, 1atm), NaOH(0.1N) || HCl(0.5N) | H2(g,1atm) | Pt
If degree of dissociation of 0.5N HCl and 0.1N NaOH are 0.87 and
0.9 respectively then calculate Kw
𝐾𝑤 𝐾𝑤
Anode reaction ½ H2 (g,1atm) → H+( = )
𝑂𝐻 − 0.1 𝑥0.9
Cathode reaction H+ (0.5 x 0.87) → ½ H2 (g,1atm)
𝐾𝑤 𝐾𝑤
Net Reaction H+( 0.5 x0.87 ) → H+( − = )
𝑂𝐻 0.1 𝑥0.9
𝐾𝑤
2.303 RT
Nernst equation for this reaction isE cell=E°cell ‒ 𝑙𝑜𝑔 0.1 𝑥 0.9
𝑛𝐹 0.5𝑥0.87
As both the electrodes are hydrogen electrode E°cell = 0 and
2.303 RT
= 0.0591
𝑛𝐹
𝐾𝑤
𝐾𝑤
Then 0.725 = ‒ 0.0591 log 0.1 𝑥 0.9
= ‒ 0.0591 log
0.5𝑥0.87 0.5𝑥0.87𝑥0.1 𝑥 0.9
𝐾𝑤 0.725
log = ‒ = ‒ 12.2673
0.5𝑥0.87𝑥0.1 𝑥 0.9 0.0591
Take antilog of both sides
𝐾𝑤
= 5.40 x 10-13
0.5𝑥0.87𝑥0.1 𝑥 0.9
Kw = 5.4 x 10-13x0.5 x 0.87x0.1x0.9
Kw = 0.211 x 10-13 =2.11 x 10-14
(3) Determination of Equilibrium Constant
The equilibrium constant of reaction taking place in a cell can be
determined from the EMF of the cell.
The standard free energy change of a reaction in terms of equilibrium
constant can be written as
ΔG° = ‒ RT ln K
and
ΔG° = ‒ nFE°
From these two equations, we get
‒ RT ln K = ‒ nFE°
𝑛𝐹 𝐸 °
ln K =
𝑅𝑇
here E° means E°cell
°
𝑛𝐹 𝐸𝑐𝑒𝑙𝑙
ln K =
𝑅𝑇
°
𝑛𝐹 𝐸𝑐𝑒𝑙𝑙 E °cell
log K = = 2.303 𝑅𝑇
2.303 𝑅𝑇
𝑛𝐹
𝑛 E °cell
log K =
0.0591
log K = 16.92 nE°cell
Take antilog of both sides we get
K = Antilog 16.92 nE°cell
where E°cell = [E°red(cathode) - E°red(anode)] or [E°oxi(anode) -
E°oxi(cathode)]
Ex-1 Calculate EMF and equilibrium constant at 25°C for the
following cell
Pt | H2(0.9atm)|H+(0.1M) || KCl(0.1M) , AgCl| Ag
Anode reaction ½ H2(0.9atm) → H+(0.1M) + e- E°red = 0.000 V
Cathode Reaction AgCl + e- → Ag + Cl- E°red = 0.220 V
Net Reaction AgCl+½ H2(0.9atm) → Ag + Cl- (0.1M) + H+(0.1M)
E°cell = [E°red(cathode) - E°red(anode)] = 0.220 ‒ 0.000 = + 0.220 V
[𝐻 + ][𝐶𝑙 − ]
Nernst equation for this cell is Ecell = E°cell ‒ 0.0591 log
[𝐻2 ]1/2
0.1𝑥0.1
Ecell = 0.220 ‒ 0.0591 log
[0.9]1/2
0.1𝑥0.1
Ecell = 0.220 ‒ 0.0591 log
0.9486
Ecell = 0.220 ‒ 0.0591 (- 1.977) = 0.220 + 0.1168
Ecell = 0.3368 V
Net reaction AgCl + ½ H2(0.9atm) → Ag + Cl- (0.1M) + H+(0.1M)
or 2AgCl + H2(0.9atm) → 2Ag +2 Cl- (0.1M) +2 H+(0.1M)
for this reaction n = 2
log K = 16.92 x2x 0.22 =7.44
K = Antilog 7.44 = 2.75 x 107
Ex-2 Calculate the equilibrium constant of the reaction between Fe2+
and Ce4+ at 25°C
Anode Fe2+ → Fe3+ + e- E°oxi = - 0.771 V
Cathode Ce4+ + e- → Ce3+ E°red = 1.700 V
Net reaction Fe2+ + Ce4+ →Fe3+ + Ce3+

E°cell = [E°red(cathode) - E°red(anode)] = 1.70 – 0.771 = 0.929 V

𝐶𝑒 3+ [𝐹𝑒 3+ ]
K= 𝐶𝑒 4+ [ 𝐹𝑒 2+ ]
𝑛 E °cell 1 𝑥 0.929
log K = = 0.0591
== 0.0591
1 𝑥 0.929
log K = 0.0591
=15.72
Take antilog of both sides
K = 5.25 x 1015
Ex-3 Calculate the voltage and equilibrium constant for the
following cell at 25°C
Fe | Fe+2(a =0.1) || Cd2+ (a=0.01)| Cd
Cathode Cd2+ + 2 e- → Cd E°red = - 0.40 V
Anode Fe → Fe2+ + 2 e- E°oxi = + 0.44 V
+2 +2
Net reaction Fe + Cd →Fe + Cd

E°cell = [E°red(cathode) - E°red(anode)] = - 0.40 – (- 0.44) = 0.04 V

0.0591 𝑎 𝐹𝑒 2+
E cell = E°cell ‒ 𝑙𝑜𝑔
2 𝑎 𝐶𝑑 2+
0.0591 0.1
E cell = 0.04 ‒ 𝑙𝑜𝑔
2 0.01
Ecell = 0.04 – 0.03 = 0.01 V
𝑛 E °cell 2 𝑥 0.04
log K = = == = 1.35
0.0591 0.0591
Take antilog of both sides
K = 22.38
APRIL-2018
Q. Calculate Cell potential and the equilibrium constant of a Daniell Cell having 0.01M
CuSO4 and 0.20 M ZnSO4 ( E° Zn2+/Zn = - 0.76 V , E° Cu2+/Cu = 0.34 V ) at 25°C

APRIL-2019
Q. Calculate the equilibrium constant for an electrochemical reaction.
2Fe3+ + Sn2+ → 2Fe2+ + Sn4+
E° Fe3+/ Fe2+ = 0.75 V , E° Sn4+/Sn2+ = 0.15 V )
APRIL-2020
Q. Calculate the equilibrium constant for an electrochemical reaction.
2Cu+ ⇌ Cu2+ + Cu
E°R(Red) = 0.52 V , E° L(Red) = 0.34 V )
 April-2017
1.Calculate the emf of the following cell at 298 K
Pt,H2(g)(1atm) / H+ (pH= 7.50) // H+(pH = 3.10)/H2(g)(1atm) , Pt Ans 0.260V
April-2016
2.The value of measured emf is 0.385 V. Calculate pH of HCl solution for the following
cell. Pt/H2(1atm) /HCl // AgCl /Ag Eref = 0.3034 V Ans pH = 1.38
3. The emf of the following cell is 0.1182 V. Calculate pH of the solution
Pt,H2(g)(1atm) / H+ (aH+= x) // H+(aH+ = 0.1)/H2(g)(1atm) , Pt Ans 2.98
4.The emf of the following cell at 298 K is 0.480V. The electrode potential of reference
electrode is 0.280 V Calculate pH of the solution.
Pt,H2(g)(740 Torr) / Solution of Unknown pH) // 1M KCl,Hg2Cl2/Hg/Pt
Ans . 3.38
(4) Determination of Transport number
The EMF of the concentration cell with transference is represented by
Et in which the end electrodes are reversible with respect to cation, is
given by
Pt| H2(g, 1atm) | HCl(a1) | HCl(a2) |H2(g,1atm) | Pt
For this cell
t- HCl(a2) = t- HCl(a1) and
𝑅𝑇 𝑎
Et = t - ln 2 ---- (1)
𝐹 𝑎1
The EMF of the same concentration cell with same solutions but
without transference is represented by E
Pt| H2(g, 1atm) | HCl(a1)| AgCl(s)| Ag |AgCl(s)| HCl(a2) |H2(g,1atm) |
Pt
For this cell
HCl(a2) = HCl(a1) and
𝑅𝑇 𝑎
E= ln 2 ---- (2)
𝐹 𝑎1
Divide Eq(1) by (2)
𝐸𝑡
= t-
𝐸
and t+ = 1 – t-
Thus the ratio of the EMF of the two concentrations cells , one with
transference and other without transference , gives the transport number
of anion, if the end electrodes are reversible with respect to the cation.
If the end electrodes are reversible with respect to the anion, then the
ratio of two EMF will give the transference number of the cation of the
electrolyte.
Ex-1 The EMF of the following cell
Ag | AgCl(s),0.1m HCl| Ag0.01M HCl,AgCl(s) |Ag
is 0.0925volt at 298 K . The EMF of the same cell but without transference
is 0.1116 Volt at 298 K . Calculate the mean transference number of the
hydrogen and chloride ion in the given range of concentrations.
Sol. The given cell is a concentration cell with transference in which the
end electrodes are reversible to anions.
𝐸 0.0925
 t+ = 𝑡 = = 0.8289
𝐸 0.1116
tH+ = 0.8289 ; tCl- = 1 – 0.8289 = 0.1711
5. Determination of pH
 April-2017
1.Calculate the emf of the following cell at 298 K
Pt,H2(g)(1atm) / H+ (pH= 7.50) // H+(pH = 3.10)/H2(g)(1atm) , Pt
April-2016
2.The value of measured emf is 0.385 V. Calculate pH of HCl solution for the following
cell. Pt/H2(1atm) /HCl // AgCl /Ag Eref = 0.3034 V
3. The emf of the following cell is 0.1182 V. Calculate pH of the solution
Pt,H2(g)(1atm) / H+ (aH+= x) // H+(aH+ = 0.1)/H2(g)(1atm) , Pt
4.The emf of the following cell at 298 K is 0.480V. The electrode potential of reference
electrode is 0.280 V Calculate pH of the solution.
Pt,H2(g)(740 Torr) / Solution of Unknown pH) // 1M KCl,Hg2Cl2/Hg/Pt
5. The emf of the following cell is 0.6372 V . Calculate pH.
Pt/H2(g,1atm) / Sol.(pH=?) /SCE ESCE =0.242 V Ans 6.68
6. The emf of Hydrogen and NCE is 0.435 V. Calculate pH and activity of H+ ion
Ans 2.62 , 2.39 x 10-3
OCT-2015 -- The EMF of the following cell is 714 mV at 25°C
Pt /H2(g)(1atm) /Unknown pH sol // Hg2Cl2 / Hg
Sat. KCl
Calculate pH of Unknown solution Ecalomel = 0.2415 V
APRIL-2017 The EMF of the following cell is 0.3014 V at 25°C
Pt / Buffer Solution // Saturated KCl / Hg
H2Q + Q Hg2Cl2
Calculate pH of the buffer solution. [Ecalomel = 0.2415 V and E H2Q + Q = 0.699 V
April-2018 -- The EMF of the following cell is 0.215 V at 25°C
Hg / Hg2Cl2, 1N KCl // Unknown pH sol / H2(g)(1atm) /Pt
Calculate pH of Unknown solution Ecalomel = 0.2800V
OH O

+ -
+ 2H + 2e

OH O

QH Q
 For the cell Pt/H2(g)(1atm) Buffer sol.(unknown pH)// 1N HCl,H2Q+Q / H+ at 25°C value of
emf is 1.1024 V. Find out pH
EH2Q + Q = 0.6992 V [ Electrodes are wrongly written]
Ans . 6.82
Why the Quinhydrone electrode is not used if pH is greater than 8 ?
Hydroquinone is weak acid but when pH is greater than 8 it dissociates completely which
disturbs the normal equilibrium. Moreover it is oxidized in the atmosphere in presence of
oxygen
QH ⇌ Q + 2H+ + 2e-

OH O

+ -
+ 2H + 2e

OH O
April 2017
1.Calculate the emf of the following cell at 298 K
Pt,H2(g)(1atm) / H+ (pH= 7.50) // H+(pH = 3.10)/H2(g)(1atm) , Pt Ans 0.260V
April-2016
2.The value of measured emf is 0.385 V. Calculate pH of HCl solution for the following
cell. Pt/H2(1atm) /HCl // AgCl /Ag Eref = 0.3034 V Ans pH = 1.38
3. The emf of the following cell is 0.1182 V. Calculate pH of the solution
Pt,H2(g)(1atm) / H+ (aH+= x) // H+(aH+ = 0.1)/H2(g)(1atm) , Pt Ans 2.98
4.The emf of the following cell at 298 K is 0.480V. The electrode potential of reference electrode is
0.280 V Calculate pH of the solution.
Pt,H2(g)(740 Torr) / Solution of Unknown pH) // 1M KCl,Hg2Cl2/Hg/Pt
Ans . 3.38