Experiment 8: GALVANIC

CELLS
C. Electromotive Force of Galvanic
Cells
 Methodology
 Two test electrodes were coupled and connected
through a salt bridge. Cells A to D were prepared
and their respective potential differences measured
by means of a voltmeter. Below is the schematic
diagram for cells A to B:
 Cell A: Zn l Zn2+ ll Pb2+ l Pb

 Cell B: Zn l Zn2+ ll Fe2+ l Fe3+ l C

 Cell C: Pb l Pb2+ ll Fe2+ l Fe3+ l C

 Cell D: Zn l Zn2+ ll PbSO4(s), SO42- l Pb

C. Electromotive Force of Galvanic
Cells
 Results

Cell A: Zn l Zn2+ ll Pb2+ l Pb

Anode: Zn (s)  Zn2+ + 2e- ε°= -0.7618 V
Cathode: Pb2+ + 2e-  Pb (s) ε°= -0.1265 V
Cell: Zn (s) + Pb2+ Pb (s) + Zn2+ ε°theo =
-0.1265 V – (-0.7618 V) = ε°theo = 0.6353 V
ε°obs= 0.1092 V
C. Electromotive Force of Galvanic
Cells
 Results

Cell B: Zn l Zn2+ ll Fe2+ l Fe3+ l C

Anode: Zn (s)  Zn2+ + 2e- ε°= -0.7618 V
Cathode: 2(Fe3+ + e-  Fe2+) ε°= 0.771 V
Cell: Zn (s) + 2 Fe3+ 2Fe2+ + Zn2+ ε°theo
= 0.771 V –(-0.7618 V) ε°theo = 1.5328 V
ε°obs= 9.33 x 10-4 V
C. Electromotive Force of Galvanic
Cells
 Results

Cell C: Pb l Pb2+ ll Fe2+ l Fe3+ l C

Anode: Pb (s)  Pb2+ + 2e- ε°= -0.1265 V
Cathode: 2(Fe3+ + e-  Fe2+) ε°= 0.771 V
Cell: Pb (s) + 2Fe3+  Pb2+ + 2 Fe2+ ε°theo =
0.771 V – (-0.1265 V) ε°theo = 0.8975V
ε°obs= 8.02 x 10-4 V
C. Electromotive Force of Galvanic
Cells
 Results
Cell D: Zn l Zn2+ ll PbSO4(s), SO42- l Pb
Anode: Zn (s)  Zn2+ + 2e- ε°= -0.7618 V
Cathode: PbSO4(s) + 2e-  Pb (s) + SO42- ε°=-0.3546 V
Cell:PbSO4(s) +Zn(s) Pb (s) + SO42- + Zn2+ ε°theo = -0.3546
V–(-0.7618V) ε°theo = 0.4072V
ε°obs= 0.385 V
C. Electromotive Force of Galvanic
Cells
 Discussions
 For current to flow, an emf is required.
 Emf causes differences of potential to exist between points in
the circuit causing charges to move.
 Standard electrode potential measures the relative force
tending to drive the half reaction from a state in which the
reactants and products are at unit activity to a state in which
the reactants and products are at their equilibrium activities .
 The more positive the electrode potential, the greater is its
tendency to be reduced; therefore it is a stronger oxidizing
agent/ oxidant
 The electrical work done on the external load is equal to
 ∆G = -nFε cell
E. Determination of Solubility
Product Constant
 Methodology
A Pb I Pb2+ II PbSO4(s), SO42- I Pb cell
was prepared and its voltage was measured
using a voltmeter.
E. Determination of Solubility
Product Constant
 Results and Computations
Pb I Pb2+ II PbSO4(s), SO42- I Pb
Anode Half Reaction: -( Pb2+ + 2e-  Pb(s) ) ε°= -0.126 V
Cathode Half Reaction: PbSO4(s) + 2e-  Pb(s) + SO42- ε°= -0.350
V
Cell Reaction: PbSO4(s) = Pb2+ + SO42-
εcell°= -0.350 V-( -0.126 V) = -0.224 V
Ksp = [Pb2+][ SO42-] = 1.6 x 10-8
Ksp from εcell°= 2.70665207 x 10-8
Ksp from experiment = 0.9618516805
E. Determination of Solubility
Product Constant
 Computations
∆G° = - RT ln K
ln K = (∆G°/ -RT) = (-nF εcell°/ -RT) = (-n
96485 εcell°/ -8.314 x 298.15)
log K = (nεcell°/0.05916)
K = 10 ^ (nεcell°/0.05916)
Ksp = 10 ^ (2 x (-0.5 x10-3)/0.05916) =
0.9618516805
E. Determination of Solubility
Product Constant
 Discussion
Equilibrium constants can be evaluated from the standard cell potential
by applying the Nernst equation. Since our system is at equilibrium ε
= 0, therefore
0 = εcell° – {(RT)/nF} ln K
{(RT)/nF} ln K = εcell°
ln K = (nF εcell°)/RT
K = exp((nF εcell°)/RT)
Consider a saturated solution of a slightly soluble solute which is in
contact with the undissolved solid.
Cell reaction : AxBy (s) = x Ay+(aq) + yBx-(aq)
Ka = a(Ay+)x a(Bx-)y , in very dilute solutions, the activity coefficient
is almost equal to 1.00 and activity is taken to be equal to molar
concentration
Ksp = [Ay+]^x[Bx-]^y
The Ksp can be solved from the cell potential of the cell reaction given
above.
Determination of Activity Coefficient

 Know the half reactions and overall

reaction process
 Measure εcell

 Compute ε° cell
 Obtainionic strength at different
concentrations
 Compute activity coefficient using Nernst
law
 AHR: Fe(s) → Fe2+ + 2e-
 CHR: PbSO4(s) + 2e- → Pb (s) + SO42-

 Overallrxn: PbSO4(s) + Fe(s) → Pb (s) +

Fe2+ + SO42-
OR
PbSO4(s) + Fe(s) → Pb (s) + Fe2+ (aFe2+ )+
SO42-(aSO42-)
 The general emf equation follows as:

ε = ε° - (RT/nF) ln aFe2+ + aSO4-

OR
ε = ε° - (RT/nF) ln aFeSO4
[FeSO4], M Εcell (V)

0.100 15.5 x 10-3

0.080 69.8 x 10-3

0.060 20.0 x 10-3

0.040 29.2 x 10-3

0.020 -12 x 10-3

 Εcell +
[FeSO4], M
(RT/nF)ln[FeSO4]
0.100 -0.01406

0.080 0.03737

0.060 -0.01592

0.040 -0.01213

0.020 -0.06223
[FeSO4], M Ionic Strength, μ
0.100 0.400
0.080 0.320
0.060 0.240
0.040 0.160
0.020 0.080

Ionic strength, μ = ½[ΣCiZi2]

 ε° = ε + RT/nF ln [FeSO4]
ε° = ε + RT/nF ln aFeSO4
a= (aFe2+)x(aSO42-) = (γm)Fe2+(γm)SO42-
if m=conc. of FeSO4=M FeSO4
m = mFe2+ = mSO42-
a= (γ+m )●(γ+m )= γ2m2 =(γm ) - 2
ε = ε° - 2(RT/nF) ln γm
ε + (2RT/nF)lnm= ε°- (2RT/nF)lnγ
 0.06

ε + (2RT/nF)lnm 0.04 y = 0.1814x - 0.0994

0.02
Series1
0
0 0.2 0.4 0.6 0.8 Linear
-0.02
(Series1)
-0.04

-0.06

-0.08
μ^(1/2)

R = 0.708 b = ε° = -0.0994
 Final Equation:

lnγ = [(ε°- ε)/ (2RT/nF)] - lnm

 εcell + (RT/nF) Activity
[FeSO4] εcell (Volts) Ionic Strength, µ
ln[FeSO4] Coefficient,γ

0.100 M 15.5 x 10-3 -0.01406 0.40 0.01725

0.800 M 69.8 x 10-3 0.03737 0.32 0.15852

0.600 M 20.2 x 10-3 -0.01592 0.24 0.11751

0.400 M 29.2 x 10-3 -0.01213 0.16 0.6650

0.200 M -12 x 10-3 -0.06223 0.08