The determination of thermodynamic functions of the

reactions in commercial alkaline-manganese dioxide galvanic

cell (Duracell)
Ahmad Alhazeem, Roberto Hernandez, Christopher Rinschler and Danielle Baginsky
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Submitted: February 14, 2013 (CHEM 457, Section 5)

The thermodynamic functions rG, K, rS and rH of the reaction inside an alkaline cell
were determined by measuring the voltage at different temperatures. The functions rG (309100.8 J) and K (1.02x1054) were first found by recording the temperature and voltage
at standard conditions. The results obtained of voltage at diferent temperatures were then
graphed and used to calculate rS (-16.61.13 J) and rH (-314,077.221266.4 J) by
using the slope of the graph in equations 3 and 4. The rH value was 12.3% within the
literature value, which is reasonable despite the experimental limitations.

Introduction
The basis topic of this experiment, electrochemistry, is about the study of
reactions in which charged particles (ions or electrons) cross the interface between two
phases of matter, typically a metallic phase (the electrode) and a conductive solution (the
electrolyte). A galvanic cell is an electrochemical cell in which the free energy of a
chemical reaction is converted into electrical energy1. Redox reactions inside the cell
cause an electric current to flow in an external circuit, where useful work can be done. So
when batteries are being used like switching on an electric torch or staring a car engine
electrical energy is provided by the redox reactions happening inside electrochemical
cells2.

Galvanic cells are classified as either primary or secondary cells in which the
main difference is that a primary cell may be used only once and a secondary cell may be
recharged by passing an electric current through it in the opposite direction to the current
flow during discharge2. In these cells ions flow through the electrolyte and electrons flow
in the electrodes where the anode is the site of oxidation and the cathode is the site of
reduction. The cell is used in this experiment is an alkaline dry cell, shown in Figure 1,
where the anode is a paste of powdered zinc with an electrolyte of potassium hydroxide,
and the cathode is manganese dioxide in the same electrolyte. The electrode reactions that
occur are zinc is oxidized to zinc oxide at the anode and manganese dioxide is reduced to
manganese (III) oxide at the cathode. The alkaline cell battery can be used for a variety of
devices but it is commonly known as a torch battery2.
The purpose of this experiment is to determine the thermodynamic functions of
the electrochemistry happening inside the cell so equations are needed to relate those two
sections. The free energy change for the process shows the maximum amount of
electrical work that can be obtained and its relation to the cell potential (E) is shown in
equation 1 where F is the Faraday constant and v is the number of moles of electrons
involved in balance equation3.

vFE=r G

(1)

When a voltaic cell produces an electric current, reactants are converted to

products causing the cell potential to decrease and eventually reach zero where
equilibrium is achieved. This situation can be analyzed by the Nernst equation shown in

equation 2 relating the cell potential to the equilibrium constant (K) that shows the extent
of reaction3.

lnK =

vF E
RT

(2)

Using equation 1 and a thermodynamic relationship, equation 3 shows that the

standard cell potential can also be related to entropy, which is the measure of the
dispersal of the energy in the system.

dE r S
=
dT vF

(3)

Enthalpy, which is the amount of heat energy used or released in a system, can
then be obtained using the Gibbs free energy equation as shown in equation 4.

r H = r G+T r S

(4)

Figure 1. Diagram of a dry alkaline cell

Experimental
Details of the experiment are explained in the lab manual4, which is basically
about measuring the voltage of a commercial alkaline dry cell (AA 1.5 Volt Duarcell
PC1500 Procell alkaline battery) at different temperatures. The temperature in this
experiment is measured using a digital thermometer and the voltage is measured using a
digital multimeter (Hewlet Packard 34401A multimeter). The alkaline dry cell is placed
in a dewar filled with ethanol at an intitial temperature of 30C and then it is cooled down
to about 0C by adding dry ice to the ethanol while recording the temperature and voltage
at regular intervals of about 5C. The Varistat is also used to regulate the temperature to a
suitable value that can be recorded within the approximate intervals. The temperature and
voltage was also recorded at standard conditions in order to calculate rG. The setup of

this experiment also uses a reference battery with the measured battery increasing the
precision of the measurements.

Results and Discussion

The alkaline galvanic cell was first placed at an intitial temperature of 30C where
the first voltage was recorded. The temperature was then decreased at inertvals of about
5C while recording the results of voltage until the temperature reached close to 0C.
There were seven sets of results obtained at different temperatures that were graphed so
that the slope can be used to calculate the thermodynamic functions rS and rH.
The results of the experiment are shown in Table 1 that were then used to plot E
vs. T shown by the graph in Figure 2. The trend of the results show that as the
temperature increases the cell potential decreases which is proven by the Nernst equation
shown in equation 2 earlier in the introduction where reactants are converted to products
causing the cell potential to decrease and eventually reach zero achieving equilibrium.
The decrease of the cell potential however is not that much as the temperature increases
since the slope of the graph is quite small. The results graphed in Figure 2 is considered
to have a strong correlation since the R2 value of 0.97757 is very close to 1 showing that
the results were consistent and no critical errors occurred.

Table 1. Voltage of alkaline cell at different temperatures

T (C)

E (mV) (0.001)

30

8.957

25.7

9.481

20.2

10.059

15.2

10.542

11.2

10.875

6.2

11.198

1.5

11.391

E vs. T
0.01
0.01

f(x) = - 0x + 0.04
R = 0.98

0.01

E (V)

0.01
0
0
0
270

275

280

285

290

Temperature (K)

Figure 2. E vs. T of alkaline cell

295

300

305

During the experiment the temperature and voltage were recorded at standard
conditions by placing the appropriate leads of the voltmeter to the battery holder. This
was then used to calculate the Gibbs free energy (rG) and equilibrium constant (K) of
the reaction inside the cell. Equations 1 and 2 were used for the calculations that were
found to be -309100.8 J for rG and 1.02x1054 for K. Since the value of rG was negative
and K was much greater than 1, this shows that the reactions was product-favored at
equilibrium and spontaneous at standard conditions which is expected for a commercial
alkaline battery where reactants are converted to products when an electric current is
produced.
The recordings of temperature and voltage obtained from the experiment were
then plotted in a graph that had a slope value of -0.00008670.00000587. This value was
then used to calculate the thermodynamic function of entropy (rS) and enthalpy (rH).
Equation 3 was first used in order to calculate the entropy (rS) of the electrochemical
reaction, which was found to be -16.61.13 J. The value of rS along with the value
calculated for rG previously were then plugged into equation 4 that gave a rH of
-314,077.221266.4 J which is within 12.3 % of the literature value of fH -279.6 kJ.
This difference between those two values is due to the fact that the literature value is
obtained from bulk values whereas the result from the experiment is obtained from only
one alkaline cell.
The rH value obtained from this experiment is be considered to be reasonable
being only 12.3% from the literature value which is caused from limitations that can not
be controlled during the experiment. Most of the errors that occur in this experiment are
to due problems with the temperature of the system. The first error was that the

temperature that was being measured for this experiment was from the outside of the
alkaline cell whereas the reaction was occurring inside the cell. This means that the
temperature being measured is not the absolute actual temperature of the electrochemical
reaction. The second error was that the temperature fluctuates when adding dry ice to
cool it down and using the Varistat to heat it up which decreases the accuracy of the
results since the battery needs to thermally equilibrate at each cooling data point for 10
minutes before recording the temperature and voltage.
The value of rH is important since shows how much energy is contained inside
the galvanic cell before it is used or released in the system as heat when an electric
current is produced. The experiment can be considered a success since a reasonable value
for rH has been obtained that was close to the literature value despite the experimental
limitations. The experiment might be improved by using a more suitable method to
control the temperature of the system instead of dry ice and the Varistat, like having
temperature sensors inside the dewar that can be control the temperature inside digitally
from a screen on the outside. Also to improve the accuracy of the results the temperature
of the reaction inside the cell needs to be measured by possibly having a wire inside the
cell without interrupting the electro chemical reactions taking place.

Conclusion
So in conclusion the thermodynamic functions rG, K, rS and rH of the reaction
inside an alkaline cell were determined by measuring the voltage at different
temperatures. The functions rG (-309100.8 J) and K (1.02x1054) were first found by
recording the temperature and voltage at standard conditions then plugging the values

into equations 1 and 2. The results obtained of voltage at diferent temperatures were then
graphed and used to calculate rS (-16.61.13 J) and rH (-314,077.221266.4 J) by
using the slope of the graph in equations 3 and 4. The rH value was 12.3% within the
literature value, which is reasonable despite the experimental limitations. One of the main
sources of error on this experiment was the measurement and control of temperature of
the alkaline cell that might be solved by having a digital method of controlling the
temperature instead of using dry ice and the Varistat. This experiment shows how much
energy is contained inside a commercial alkaline cell and how the voltage is affected by
changes in temperature.

Acknowledgement

The author would like to acknowledge the group members mentioned in the first page,
Dr. Milosavljevic and our CHEM 457 teaching assistant for their assistant with the
completion of all aspects of this study including data collection and analysis.

References
(1) Patra, B. B., Samantray, B. Engineering Chemistry I (for BPUT); Dorling Kindersley:
India, 2011.
(2) Clugston, M, Flemming, R. Advanced Chemistry; Oxford University Press: Oxford,
2000.
(3) Kotz, J, Treichel, P, Townsend, J. Chemistry and Chemical Reactivity, Seventh Edition;
Thomson Brooks/Cole: Belmont, 2009.
(4) Milosavljevic, B.H. Lab Packet for CHEM 457: Experimental Physical Chemistry,
Gravimetric Determination of the Gas Constant. University Press: University Park, 2009.