The

Determination of Thermodynamic Functions of the Reactions in Commercial

Alkaline-manganese Dioxide Galvanic Cell (Duracell)

September 14, 2016

Nur Nadzirah B. Mohd Jaafar

Partners: Colin Mahon, Brianna Haglan, Blaise Pfaff

Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802
CHEM 457, Section 5, Fall 2016

Results and Discussion

In this experiment, a commercial alkaline-manganese dioxide galvanic cell which is AA
Duracell battery (mass of battery = 24.650.01 g) was used to study the thermodynamic
functions of the chemical reactions. The mass of the casing is determined to be 40% of the
overall mass. The predicted maximum electromotive force of this battery was calculated
using this equation:
!"# =

! (0.6)
!" !"#!

(1)

Where ! is the Gibbs free energy of reaction at 298K, m is the mass of the battery, !" is
the number of moles of zinc and !"#! is the number of moles of manganese oxide. The
initial temperature recorded at the beginning of the experiment is 22.3 0.1C. The voltage
recorded at this temperature is 1.5989 0.0001 V.

The performance of the battery was observed from by changing six different temperatures
and the results from the experiment were tabulated in the Table 1 as shown below:

Tm (C)
22.5 0.1
18.5 0.1
14.5 0.1
10.5 0.1
6.5 0.1
2.5 0.1

Tr (C)
22.5 0.1
22.6 0.1
22.7 0.1
22.8 0.1
22.8 0.1
22.8 0.1

E (mV)
24.745 0.001
25.078 0.001
25.426 0.001
25.780 0.001
26.166 0.001
26.519 0.001

Table 1: The measured voltage (E) at measured temperature (Tm) and reference
temperature (Tr)

From the results above, the reference temperatures are observed to have a slight increase.
The temperatures are adjusted by using equation 2 to account the change in reference
temperature.
!,!"#$%&'" = ! !! !!

These adjustments were made to create a consistent result based on only one reference so
that a linear plot can be achieved. This is because the slope from the plot will provide an
important information that will be discussed later. Since the precision of the multimeter
used in this experiment is 0.001mv, the conversion has to be accounted in the calculation.
The new values for the results are shown in the table below:

Tm, adjusted (C)
E (V)

22.5 0.1
0.0247 0.001

18.4 0.1
0.0251 0.001

14.3 0.1
0.0254 0.001

10.2 0.1
0.0258 0.001

6.2 0.1
0.0262 0.001

2.2 0.1
0.0265 0.001


Table 2: Adjusted temperature (Tm,adjusted) and the relative electromotive force (E)

From the results collected, we managed to calculate the Gibbs free energy based on this
equation:
= ! G

(3)

where v is the number of electron involved in the redox reaction which in this case is 2, F is
the Faraday constant (F = 9.6 x 104 C mol-1), and E is the electromotive force which is in
voltage,V. The Gibbs free energy calculated is -306988.8 19200 J mol-1. This negative
value of Gibbs free energy indicates that the reaction is spontaneous and favorable. By
having Gibbs free energy, we can determine the equilibrium constant, K for the reaction. It
is calculated using Nernst equation as shown below:

ln =

!
=

(4)

Equilibrium constant, K will provide some information on the favorable products when the
reaction is at equilibrium. If K is larger than 1, the equilibrium favors the products which is
it will shift to the left and it is opposite for K lesser than 1 where the equilibrium favors the
reactants. From the calculation, the equilibrium constant is determined to be 1.7374 x 1054.
This value is extremely bigger than 1 which provide us that the reaction is most favorable
to the product and shift to the right.
These values of Gibbs free energy and equilibrium constant show that the
commercial battery will produce current resulted from the spontaneous chemical reaction
at equilibrium in the galvanic cell.

A graph of electromotive force, E versus temperature is plotted as shown in figure 1 below:

Electromotive force,E vs Temperature,T

0.0268

Electromotive force,E (mV)

0.0266
0.0264

y = -9E-05x + 0.0507
R = 1

0.0262
0.026
0.0258
0.0256
0.0254
0.0252
0.025
0.0248
0.0246
270

275

280

285

290

295

300

Temperature (K)

Figure 1: Electromotive force, E versus temperature, T

From the graph above, it shows that the R2 value is 1. This means that the results were
consistent and no significant error. It also shows that the emf is inversely proportional to
the temperature. This is reasonable, as lower temperature will need more energy to
produce the current.
The value of the slope of this graph is -9E-5 2.03 E-5. The slope from the graph can be
used to calculate the entropy of the reaction based on this equation:

!
=

(5)

! = (6)

From the calculation, the value of ! is -17.28 1.0807 J mol-1. The negative entropy
means that it violated the second law of thermodynamic. But, that is applicable for an
isolated system. Since the system in this experiment is influences by lots of outside factors,

the second law of thermodynamic is not violated. By having the entropy of reaction value,
the enthalpy of reaction can be determined using the equation below:

! = ! + ! =

(7)

From the calculation, the experimental value of enthalpy of the cell reaction is 312097.63 19518 J mol-1. The literature value of the enthalpy is -279280 J mol-1. The
error to the literature value is only 11.75% which indicates that the deviation from the
experimental is still acceptable. The experimental enthalpy is higher than the literature
value. This means that higher energy is needed for during the experimental procedure.
This deviation can be explained by some error that could be happened during the
experiment. One possibility is that the inconsistent temperature throughout the
experiment would cause an affect to the results. This could be happened by both ways,
whether from the way the temperature was measured and how the temperature was set.
First, the temperature was measured from outside of the battery. The reaction takes place
inside the battery makes it hard to find the exact temperature for the reaction. Lower
temperature compared to the real temperature might be collected during the experiment.
This will cause the energy needed become higher. Secondly, the temperature was set by
adding dry ice into the dewar. An inconsistent addition might slightly affect the result.
Some improvement that can be done is to put the thermocouple inside the battery.
This could improve the change in temperature of the inside where the reaction occurs.
Other than that, the dewar could be properly insulated so that the temperature does not
fluctuates too much.

Reference:

1. Milosavljevic, B.H. Lab Packet for CHEM 457: Experimental Physical Chemistry, The
Determination of Thermodynamic Functions of the Reactions in Commercial
Alkaline-manganese dioxide galvanic cell (Duracell). University Press: University
Park, 2016.
2. Atkins, P. and de Paula, J., Physical Chemistry, Seventh Edition. (2002) W.H Freeman
and Company: New York City, New York.
3. Reynolds, W. C. (1968). Thermodynamics. New York: McGraw-Hill.

Supporting information

Sample Calculations

Calculating Gibbs Free Energy, G

= ! G
=
=
= ,
! G = 2 9.610! !! 1.5989 = 306988.8 !!
Uncertainty of Gibbs Energy , G

! G =

! G

!

!

, = 0.0001
! G =

306988.88 !

0.0001!
= 19200
(1.598910!! )!

Calculating equilibrium constant, K

ln =

!
=

306988.8 !!
= exp
= 1.737410!"
8.134 !! !! 295.65
Uncertainty of equilibrium,
=

= 1.737410!" 0.0001 = 1.737410!"

Calculating entropy of reaction, !

!
=

! =

! = (910!! ) 2 9.610! !!
! = 17.28 !!
Uncertainty of entropy of reaction, ! S

!
! S !

!

! S =

! S =

17.28 !

0.0001!
= 1.0807
(1.598910!! )!

Calculating enthalpy of reaction, !

! = ! + ! =

! = 306988.8 !! + 295.65 17.28 !!

! = 312097.63 !!
Uncertainty of enthalpy of reaction, !
! H =

! H =

! H

312097.63 !

! !
+
! !
1.0807!
306988.8

! H

+
!

! !

! !

312097.63

! H = 19519
Calculating literature enthalpy of reaction, !
! = ! !"#$%&' ! !"#$%#&%
! = 348.28 971 !! 2520 !!
! = 279.28 !!
Error in literature value of enthalpy


=
100%

1.0807!

17.28 !

312097.63 + 279280
100 = 11.75%
279280

Linear Regression of emf, E versus temperature,T