Thermodynamics of electrochemical cells- Lab report
Electrochemistry studies the relationship between electrical energy
and chemical conversions. Electron transfers in the spontaneous redox
reactions occurring at the electrodes is at the root of energy changes,
and is reflected in the enthalpy changes. The Gibbs free energy
measures the amount of useful work that could be extracted from an
electrochemical cell, while entropy change indicates the change in
randomness of the system. The purpose of this experiment is to study
the behavior of EMF of a galvanic cell at changing temperatures and
calculating thermodynamic parameters there from.
Primary Data:
The experiment was performed as outlined in the lab manual. Two
2+/Cu
+/ Ag
electrodes,
(anode) and
(cathode) were prepared by
C u
A g
dipping the metallic electrodes into a solution of their soluble sulfate
salts. Coupling the two electrodes through a salt bridge affords a
0
complete electrochemical cell, having E value of 0.46 V. Keeping
the electrolyte concentrations and other physical factors nearly
constant, the EMF of this cell was measured and studied at three
different temperatures. Resulting electrode potential values are listed
as a function of time and temperature. The change in free energy,
enthalpy and entropy were calculated from these data utilizing the
following thermodynamic relations:
G=nFE
S=nF
( ET )
H= G+T S
( ET )
value was calculated from the slope of the potential vs.
temperature graph.
Table 1: Cell potential vs. time
Temperature
Cold = 5.10
Med = 25.1
Hot = 68.6
Time (min)
0
5
10
15
16
17
18
19
20
21
22
Potential (V)
0.3586
0.3722
0.3751
0.37623
0.37647
0.3766
0.3767
0.37676
0.3768
0.37686
0.3769
Potential (V)
0.358
0.35655
0.3534
0.35023
0.35065
0.3510
0.3506
0.34995
0.35045
0.3502
0.35025
Potential (V)
0.323
0.300
0.294
0.28451
0.28094
0.27737
0.27466
0.27219
0.2709
0.26943
0.26807
Table 2: Cell potential vs. temperature
E (V)
Absolute Temp
(K)
0.3765
0.3508
0.2769
278.25
298.15
341.75
Theoretical Values at 25C for the reaction, from literature values:
T (K)
298.15
G(J /mol)
E(V )
S(J /mol . K )
H ( J /mol)
88766
0.46 00
192.5
146131
Results:
From the experimental results, the following graphs were obtained:
Figure 1: Plot of EMF vs. Time at three temperature values
EMF vs. time
0.4
0.35
0.3
EMF (V)
0.25
potential(5.1)
0.2
potential(25.1)
0.15
potential(68.6)
0.1
0.05
0
0
10
15
Time (min)
20
25
Figure 2: Plot of EMF vs. Temperature
EMF vs. Temperature
0.40000
0.35000
f(x) = - 0x + 0.82
R = 1
0.30000
0.25000
EMF (V)
0.20000
0.15000
0.10000
0.05000
0.00000
270
280
290
300
310
320
Temperature (K)
Calculations:
From the graph of variation of EMF with temperature,
E0298 =0.00159 298.15+0.821 3=0.347 2 V
G=nF E0=2 96485 0.34 72V =6 7007 J /mol
330
340
350
S=nF
( ET ) =2 96485 0.00159=307 K .Jmol
P
H= G+T S=67007
% Absolute error in
calculations
calculations
307192.5
100 =59.5
192.5
% Absolute error in
887666 7007
100 =24.5
88766
% Absolute error in
(307 ) J
J
J
+298.15
=158539
mol
mol
mol
calculations
158 539146131
100 =8. 5
146131
Discussion:
The equilibrium values of EMF were used. So, the average potential data after about 10
minutes from the beginning of the experiment, when the EMF values stabilized, were
considered for relevant calculations. The literature values of G , S
and H
were taken from Table of Constants, Physical Chemistry, 8e by Atkins, P. ;
De Paula, J. Oxford University Press, Oxford (2006).
The EMF of an electrochemical cell varies with temperature since the cell reaction
involves a change in entropy, S. A rise in temperature causes a rise in S. Assuming H
to remain constant, it lowers the G, and hence the potential value. Addition of heat near
lower temperatures increased the entropy to a greater degree than at higher temperatures.
The purpose of this experiment was to study how changes of temperature affect
electromotive force of the electrochemical cell. The variation was nicely demonstrated
from the results of this experiment. Sources of errors could be from insufficient
stabilization of EMF, error in the assumption that the electrolyte concentration was
constant throughout and from the electronic measuring devices. In addition, the errors
could also have come from inadequate cleansing of the voltmeter that read the cell.
Conclusion
The experiment demonstrated the variation of EMF of a
Cu/CuSO 4 A g2 S O4 / Ag
galvanic cell, with variation in temperature and established that as temperature increases,
the cell potential decreases. The percent error in the final results of G , H S
based on the experimental data was determined. The absolute error values ranged from
8.5% in H
measurement to a huge 59% in S measurement. This may be due to
insufficient homogenization of the electrolyte chambers during heating, or due to some
procedural error.
