Experiment 8: GALVANIC CELLS

Group 1
Lamayan, Ivy B. 2004-20483
Sison, Kevin Anthony S. 2005-73193

Chem. 157.1 DE
Mr. Leo Yambot

Department of Physical Sciences and Mathematics

College of Arts and Sciences
University of the Philippines Manila

I. Introduction

Oxidation and reduction reactions involve the transfer of electrons. These types
of reactions can be carried in to two ways, one is both the oxidizing specie and reducing
specie are put into contact and the other with both species separated into two connected
compartments. The latter, involves the use of an electrochemical cell. In this cell, the
oxidant and reductant are physically separated but has electrical contact by means of a
salt bridge, it also consists of two conductors called electrodes, and each of them is
immersed in an electrolyte solution. Of the two electrodes, the cathode is the part where
reduction occurs, while oxidation occurs at the anode.
There are two types of electrochemical cells; they are either galvanic or
electrolytic. A galvanic cell converts chemical energy to electrical energy. On the other
hand, an electrolytic cell requires an external source of electrical energy to make a non-
spontaneous reaction to proceed. In a galvanic cell, at the left hand electrode “active”
metals are oxidized to their respective cation and releases at the same time electrons.
This electron travels through the conductor then to the right-hand side electrode where it
is gained by the cations in the solution, thereby reducing it. The prolonged build-up of
the charges due to oxidation and reduction is avoided by the migration of the cations and
anions from the salt bridge. As electrons travel, a potential difference is made between
the two electrodes and is given by εcell. ε cell is also a measure of the spontaneity of the
reaction, as stated by :
∆G = -nFε cell
if in the standard state:
∆G° = -nFε° cell = -RT lnKeq
by measuring the electrode potentials, thermodynamic quantities such as the Gibbs free
energy can be measured. Equilibrium constants as well as activity coefficient for ions in
solutions can be computed from ε cell measurements.

II. Methodology

A. Preparation of Cu l Cu2+ Reference Electrode

Tightly pack the tip of a 4-5 cm long pipet with cotton.

Immerse the tip in a solution of KCL or KNO3 until fully soaked.

Fill the pipet with 0.1 M CuSO4 solution.

Coil a copper wire in a metal rod with the diameter smaller than the pipet’s. Leave some
wire uncoiled.

Insert the coiled wire into the pipet. Fix the position of the wire and seal the pipet using
clay.

Alternate procedure A:
Secure a 4-5 inch long copper wire and dip in a solution of 0.1 M CuSO4 solution

Preparation of salt bridge: cut 1 x8 cm of filter paper and dip in a saturated solution of
KCL or KNO3. Always prepare a fresh one for every solution.

B. Determination of Electrode Potentials

Assemble the following test half-cells:
2+
a. Zn l Zn electrode: dip metal zinc (1 x 5 cm) in a 50 ml beaker with 25 ml 0.1 M
ZnSO4.

b. Pb l Pb2+ electrode: dip Pb wire (10 cm long) in a 50 ml beaker with 0.1 M Pb(NO3)2.
c. C l Fe2+, Fe3+ electrode: dip graphite rod in a 50 ml beaker with 12.5 ml 0.2 M
Fe(NH4)2(SO4)2 + 12.5 ml 0.2 M FeNH4(SO4)2
d. Pb l PbSO4(s), SO42- electrode dip lead wire coated with PbSO4 in 50 ml beaker with
25 ml 0.1 M K2SO4 (to prepare lead wire coated with PbSO4: dip Pb wire in conc.
H2SO4 until coated with white powdery substance )
Each of the prepared test electrode were coupled with the Cu l Cu2+ reference
electrode. Having Cu l Cu2+ as the cathode (red terminal) and the test electrode as the
anode. Respective voltages of the test electrodes were measured, with the reference
electrode having a standard reduction potential of 0.34 V.

C. Electromotive Force of Galvanic Cells

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

D. Variation of Electrode Potential with Electrolyte Concentration

Mixtures of varying concentrations of MnO4- and Mn2+ were prepared according to

the following formulations:

Mixture mL of 0.02 M mL of 0.05 M mL of 6M H2SO4

KMnO4 Na2C2O4
1 30 5 15
2 35 10 15
3 20 15 15
4 25 20 15

Reduction potentials of each mixture was then measured by pairing it with the
Cu l Cu2+ reference electrode as the cathode.
E. Determination of Solubility Product Constant
A Pb I Pb2+ II PbSO4(s), SO42- I Pb cell was prepared and its voltage was
measured using a voltmeter.
 F. Determination of Activity Coefficient
Solutions of 0.100 M, 0.080 M, 0.060 M, 0.040 M and 0.020 M FeSO4 were
prepared. After which each solution was paired with a Pb l PbSO4(s) as a cathode
forming the cell:
Fe l FeSO4 (aq) (a), PbSO4(s) l Pb

III. Results

A. Determination of Electrode Potentials

Cathode: Cu2+ + 2e-  Cu (s) ε°cell=0.34 V
Test Reduction Half Reaction εcell εanode Theoretical
electrode
Zn l Zn2+ Zn2+ + 2e-  Zn (s) 0.468 V -0.128 V -0.7618 V
Pb l Pb2+ Pb2+ + 2e-  Pb (s) 0.3888 -0.0488 -0.1265 V
V V
C l Fe2+, Fe3+ Fe3+ + e-  Fe2+ -0.408 V 0.748 V 0.771 V
Pb l PbSO4(s), PbSO4(s) + 2e-  Pb (s) + SO42- 0.456 V -0.116 V -0.3546 V
SO42-

Sample computation:
ε°cell = ε°cathode - ε°anode
For Zn l Zn2+ ll Cu2+ l Cu
0.468V =0.34 V - ε°anode

ε°anode = -0.128 V
% error =l{[-0.128 – (-0.7618)]/-0.7618}l *100 = 83.20 %
B. Electromotive Force of Galvanic Cells
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
 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
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
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. Variation of Electrode Potential with Concentration

mixture [MnO4-] [Mn2+] Log([MnO4-]/[Mn2+]) εcell

1 5.0 x 10-4 1.0 x 10-4 0.69897 -1.153 V
2 5.0 x 10-4 2.0 x 10-4 0.39794 0.438 V
3 1.0 x 10-4 3.0 x 10-4 -0.477121 0.433 V
4 1.0 x 10-4 4.0 x 10-4 -0.6020599913 -0.402 V
 Variation of Electrode Potential with
Electrolyte Concentration

1 Electrode
y = 0.2248x - 0.733 Potential of
0.5 [MnO4-] and
[Mn2+]
0 mixtures
εcell

0 2 4 6
-0.5
Linear
(Electrode
-1
Potential of
[MnO4-] and
-1.5
[Mn2+]
log([MnO4-] /[Mn2+] mixtures)

Sample computation:
5(C2O42-  2CO2 + 2e-)
2(MnO4- + 8H+ + 5e-  Mn2+ + 4H2O)
5C2O42- + 2MnO4- + 16H+ + 10e-  10CO2+ 2Mn2+ + 8H2O + 10e-
5 NaC2O4 + 2KMnO4 + 8H2SO4  12MnSO4 + K2SO4 + 5NaSO4 + 8 H2O +10CO2
For mixture 1:
Determining the limiting reactant:
Considering KMnO4
0.030 L (0.02 mol KMnO4/ 1L) x (2mol MnSO4/2 mol KMnO4) = 6.0 x 10-4 mol MnSO4
Considering H2SO4
0.015 L(6mol H2SO4/1L) x (2mol MnSO4/8 mol H2SO4) = 0.0225 mol MnSO4
Considering NaC2O4
0.005L(0.05 molNaC2O4/1L) x (2mol MnSO4/5 mol NaC2O4)= 1.0 x 10-4 NaC2O4
Therefore NaC2O4 is the limiting reactant.
Final concentrations:
[MnO4-] = 6.0 x 10-4 - 1.0 x 10-4 = 5.0 x 10-4 / Vsoln
[Mn2+] = 1.0 x 10-4/ Vsoln
log([MnO4-]/[Mn2+]) = log (5.0 x 10-4/1.0 x 10-4) = 0.6989700042
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
Writing the Nerns’t Equation,
 εcell = ε° - (0.05916/n) log[Mn2+]/[MnO4-][ H+]8
εcell = ε° - (0.05916/n) {(log[Mn2+]/[MnO4-]) -log[ H+]8}
=ε° - (0.05916/n) {log([MnO4-] /[Mn2+])-1 + 8pH}

=ε° + (0.05916/n) {log([MnO4-] /[Mn2+]) – (8)(0.05916/n) pH }

εcell = (0.05916/n) {log([MnO4-] /[Mn2+]) + ε° – (8)(0.05916/n) pH }

y m x +b
Using linear regression,
Slope = 0.2248 = (0.05916/n)
Y-intercept = -0.733 = ε° – (8)(0.05916/n) pH
D. Determination of Solubility Product Constant

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
Sample Computation:
∆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
F. Determination of the Activity Coefficient

[FeSO4] εcell° ε°cell + √I Activity

0.05916 Coefficient, γ
log[FeSO4]
0.100 M 0.0155 V -0.04366 0.63245532 8.77 x 10-3
0.080 M 0.0698 V 4.91 x 10-3 0.5656854249 1.32 x 10-3
0.060 M 0.0202 V -0.052 0.4898979486 0.012
0.040 M 0.0292 V -0.054 0.4 0.013
0.020 M -0.012 V -0.11 0.2828427125 0.13

ε°cell + 0.05916 log[FeSO4] 2.5

y = 0.1207x + 1.895 Experimental
2 Results

1.5 Theoretical values

1
Linear
(Experimental
0.5 Results)
y = -0.0491x - 0.0066 Linear
0 (Theoretical
0 0.5 1 values)
-0.5
√I

Fe l FeSO4 (aq) (a), PbSO4(s) l Pb

Anode: Fe2+ (a Fe2+) + 2e-  Fe (s) ε°= -0.440 V

Cathode: PbSO4(s) + 2e-  Pb (s) + SO42- (aSO42-) ε°= 1.455 V
Cell Rxn: Fe (s) + PbSO4(s)  Fe2+ (a Fe2+) + Pb (s) + SO42- (aSO42-) ε°= 1.895 V
Since there is no liquid boundary: (a Fe2+)=(aSO42-), therefore
Fe (s) + PbSO4(s)  FeSO4(aq) (a)+ Pb (s)
εcell = ε° - (0.05916/2) log a
a= (a Fe2+) 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°cell= ε°- (0.05916/2)log(γm ) 2
ε°cell= ε°- 0.05916log(γm )
ε°cell + 0.05916 logm = ε°- 0.05916 logγ
recall DHLL:
logγ = -0.51 lZ+Z-l I1/2
I= ½ ΣCiZi2
ε°cell + 0.05916 log[FeSO4] = ε°- 0.05916(-0.51 lZ+Z-l I1/2)
y b m x
logγ= ε - ε° + 0.05916 logm
-0.05916 -0.05916

ε°- ε - log m
γ= 10
-0.05916

Sample Computations

For [FeSO4] = 0.100 M

εcell (observed)= 0.0155 V
ε°cell + 0.05916 log[FeSO4] = 0.0155 V + 0.05916 log0.100 M = -
0.04366
I = ½Σcizi2 = ½{(0.1)(+2)2 + (0.1)(-2)2} = 0.4

√I = 0.63245532

Using Linear Regression,

r = 0.79254755
slope = 0.2403598409
y-intercept = -0.1653431285 V = ε°

ε°- ε - log m - log

γ= 10 γ= 10 -0.1653431285 –(-0.0155) 0.1 = 8.77 x 10-3
-0.05916 -0.05916

Theoretical Values

ε°cell + 0.05916 √I γ
log[FeSO4]
1.971328781 0.632455532 0.05126143034
1.963270538 0.5656854249 0.07014580933
1.95412402 0.4898979486 0.1001401371
1.94327456 0.4 0.1527566053
1.929135269 0.2828427125 0.2648505443

r=1
slope = 0.1207
y-intercept = 1.895 =ε°

IV. Discussion
A. Determination of Electrode Potentials
The cell’s potential when it is connected at the cathode and the
standard hydrogen electrode (SHE), a reference electrode is connected
at the anode is called an electrode potential. According to IUPAC sign
conventions, when there is no liquid junction the cell potential can be
expressed as the difference of the cathode half-cell potential and the
anode half-cell potential, that is
ε°cell = ε°cathode- ε°anode
Take note that the values ε°cathode and ε°anode are expressed in
standard reduction potentials to avoid any confusion. It is impossible to
measure absolute electrode potentials, since neither oxidation nor
reduction occurs alone. Also, what is of interest is the potential difference;
this and not the absolute potential are measured by voltage measuring
devices. To circumvent this problem a reference electrode is assigned at
the anode having a half-cell potential of 0.000 V, for this purpose a
standard hydrogen electrode is used. Using the equation above, when we
pair our electrode in question with the SHE at the anode, the potential
read by the meter is solely due to the potential of the electrode in
question.
In the experiment we paired electrodes of “unknown” electrode
potentials with a Cu l Cu2+ reference electrode. The reference electrode is
connected at the positive terminal or the cathode such that when the
voltmeter gives the cell potential, the half-cell potential/ electrode potential
of the electrode in question by subtraction following the equation given
above. The standard electrode potential or ε° is defined as the electrode
potential when the activities of all reactants and products are all unity, and
that the pressure of any gas involved is 1 atm. Having a standard state
allows us to obtain relative values of free energy, activity, entropy, and
enthalpy. Take note that the electrode potential is an intensive property,
i.e. it is not affected by the amount of matter but may vary when
temperature and or concentration is changed, as what we will see in
Nernst equation.

B. Electromotive Force of Galvanic Cells

 For current to move along a circuit, an electromotive force must be
present. An emf causes differences of potential to exist between points in
the circuit causing charges to move. An emf is associated only with
reversible conversions of energy, whereas potential differences exist not
only in sources of emf but also in resistors, which convert energy to heat
irreversibly.
In this part of the experiment, the equation given in part A is still
applied to get the theoretical cell potential. The 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. A positive electrode potential, gives a negative free energy, this
means that this reaction is spontaneous relative to the SHE. The more
positive the electrode potential, the greater is its tendency to be reduced;
therefore it is a stronger oxidizing agent/ oxidant compared to that of the
reference electrode. Electrons lost during oxidation at the anode flows
from the anode to the cathode where it is gained by cations during
reduction. When an external load such as a bulb, is added to Galvanic
cell instead of a voltmeter, electrons would then through the bulb’s
filament causing it to light. In addition all Galvanic cells have a positive
cell potential; otherwise such cell is known to be electrolytic.

C. Variation of Electrode Potential with Electrolyte Concentration

When the concentration of the active species is other than unity, the
Nernst equation is applied. This equation expresses emf in terms of the
composition.
ΔrG = ΔrG° + RT ln Q, where Q is the reaction quotient. Dividing
both sides by –nF,
ε = -( ΔrG°)/nF – {(RT)/nF} ln Q
ε° = -( ΔrG°)/nF
ε = ε° – {(RT)/nF} ln Q
If the system is at equilibrium, Q = K, then
ε = ε° – {(RT)/nF} ln K
 D. Determination of Solubility Product Constant
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.

E. Determination of Activity coefficient

The cell constructed is an example of a galvanic chemical cell

without transference. This chemical cell, is composed only of one
compartment containing only one solution, such that the activities of the
cation is equal to that of the anion.

Fe l FeSO4 (aq) (a), PbSO4(s) l Pb

Anode: Fe2+ (a Fe2+) + 2e-  Fe (s) ε°= -0.440 V

Cathode: PbSO4(s) + 2e-  Pb (s) + SO42- (aSO42-) ε°= 1.455 V
Cell Rxn: Fe (s) + PbSO4(s)  Fe2+ (a Fe2+) + Pb (s) + SO42- (aSO42-) ε°= 1.895 V
Since there is no liquid boundary: (a Fe2+)=(aSO42-), therefore
Fe (s) + PbSO4(s)  FeSO4(aq) (a)+ Pb (s)
εcell = ε° - (0.05916/2) log a
a= (a Fe2+) x (aSO42-) = (γm )Fe2+(γm)SO42-
if m=conc. of FeSO4 = M FeSO4
m = mFe2+ = mSO42-
a= (γ+m ) (γ+m )= γ2m2 =(γm ) 2
εcell= ε°- (0.05916/2)log(γm ) 2
εcell= ε°- 0.05916log(γm )
εcell + 0.05916 logm = ε°- 0.05916 logγ
recall DHLL:
logγ = -0.51 lZ+Z-l I1/2
I= ½ ΣCiZi2
εcell + 0.05916 log[FeSO4] = ε°- 0.05916(-0.51 lZ+Z-l I1/2)
y b m x
logγ= ε - ε° + 0.05916 logm
-0.05916 -0.05916

ε°- ε - log m
γ= 10
-0.05916

The activities calculated on the basis of the equation just above is

tabulated in the results. Experimental activity coefficients agree with the trend
that is followed by their theoretical counterparts. Recall that in a concentrated
solution counter ions surround ions thereby decreasing their activity. This results
to a lower activity coefficient. By plotting εcell + 0.05916 log[FeSO4] vs (I1/2) we
obtained a straight line, which when extrapolated to the y-axis gives a y-intercept
equal to ε°, this constant would then be used to calculate the activity coefficient.
The activity coefficient could also be obtained from the colligative properties.

V. Answers to Questions

1. Does the plot obtained conform to the Nernst equation? Why Support
your answer.
The plot obtained does not conform to the Nernst equation, but
theoretically it should. Plotted points did not correspond to a line as
predicted by the equation
2. What is the significance of the slope of the line? How does it compare
with the theoretical value?
 Theoretically, the slope of the line corresponds to 2.303RT/nF. The
obtained slope was much higher about 38 times as large as that of the
expected.

3. What is the significance of the value of the y-intercept obtained in your

plot? How does it compare with the theoretical value?
The y-intercept is equal to ε° – (8)(0.05916/n) pH. The theoretical value
cannot be obtained because it requires knowing the pH of the solution
which was not obtained during the experiment.

VI. Reference(s)
Fundamentals of Analytical Chemistry 8th ed. Skoog, West, and Holler
Physical Chemistry 3rd ed. Laidler and Meiser
Physical Chemistry 7th ed. Atkins and de Paula
College Physics 5th ed. Weber, Manning, White, and Weygand
Learning modules in Gen. Chemistry 2 2002 ed. Engle and Ilao