Experiment #16

Thermodynamics of Electrochemical cells

Abstract

In this experiment, the electrochemistry of electrochemical cells was studied and in the process the values
of the thermodynamic functions ∆G, ∆H, and ∆S was determined. The electrochemical cells were
constructed by combining different metallic systems (silver and zinc electrodes) and their solutions. The
voltage of the prepared cells at various temperatures render the values of the thermodynamic functions
∆G, ∆H, and ∆S. The values computed for ∆G, ∆S, and ∆H are -208kJ/mol, 154.38 J/K and -254kJ
respectively. The theoretical value of ∆G was -301 kJ/mol. A percent error of 30% was found. Sources of
errors can be found in the preparation of the zinc amalgam electrode which was not completely immersed
in sulfuric acid until all layers and scales dissolve and then was not immediately immersed in saturated
Hg(NO3)2 solution. This affected the reading in the digital voltmeter which did not gave an accurate and
precise measurements of the voltage readings.

1. Introduction

Electrochemistry studies the relationship between electrical and chemical energy. In this
sense chemical energy is produced from electrical energy in a electrolytic cell and vice versa in a
voltaic cell. These energy transfers are in the form of electron transfers in a redox reaction where
one species loses electrons while the other gains electrons simultaneously. In the voltaic cell a
voltage is induced as the electrons move. This is called EMF (electromotive force) whose
magnitude is quantitative.[1]

The four laws of thermodynamics (from zeroth to third) govern the relation between the
equilibrium conditions and the temperature of the reaction to the thermodynamic functions of
enthalpy, entropy and free energy (Gibb’s).[1]

2. Experimental

The zinc amalgam was prepared as follows: the surface of a zinc rod was cleaned by
immersing it in 30% sulfuric acid until all surface layers and scales dissolve. This was rinsed
with distilled water and immersed immediately in saturated Hg(NO3)2 solution for 2-3 minutes.
This was rinsed with distilled water and then with 0.50 M ZnCl2 solution. Fifty to One-hundred
milliliter of 0.50M ZnCl2 solution was placed in a beaker or in a three-necked flask. A silver-
silver chloride electrode, a zinc amalgam electrode and a thermometer was immersed in this
solution. The flask was placed in a constant temperature water bath and the temperature was
recorded. The electrodes were connected to the terminals of a digital voltmeter such that a
positive voltage is obtained. The polarity of the electrodes was noted and the voltage was
recorded. The voltage of the cell was measured at the following temperatures: 20°C, 25°C, 30°C,
35°C, 40°C, 45°C and 50°C.

3. Results and Discussion

The three laws of thermodynamics are applied to chemical reactions, they relate the
equilibrium condition and the temperature of the reaction to the thermodynamic functions,
namely change in enthalpy (∆H), change in entropy (∆S), and change in free energy (∆G). By
studying the effect of temperature on the equilibrium condition for a chemical reaction, we can
calculate these thermodynamic functions. The reaction to be evaluated is:

Zn(s)+ 2AgCl(s) = Zn2+(aq) + 2Ag+(aq) + 2Cl-(aq)

Each electrode is connected to the voltmeter by alligator clips and metal wiring. The
voltmeter measures the voltage generated by the redox reaction. The voltage reading will be
positive when the electrodes are connected properly for spontaneous reaction. A spontaneous
redox reaction occurs when the species with higher reduction potential is connected as the
cathode. Otherwise, the voltage reading will be negative. The meter reading will be positive
when the cathode is connected to the (+) outlet and the anode is connected to the (-) outlet.
Physically, a negative voltage reading means that you have connected the wrong electrode as
cathode. The experiment determined that the Zinc amalgam electrode is the anode and the
Silver-sliver chloride electrode is the cathode. The standard reduction potential of Zn2+ is -0.76

and for Ag+ is 0.80. With this data, the Eocell can be computed:

E°net =E°ox + E°red

E°net=E°Zn + E°Ag
E°net =(+0.76 V) + ( +0.80 )=1.56 V

The computed Ecell is the theoretical potential of the cell. The voltage of the cell
was plotted against the temperature in Figure 1. The slope of the best straight line
was determined to be -0.0008. This gives the value of the temperature coefficient
of the cell potential (E/P. The cell electromotive force is measured as a
function of temperature. The plot in Figure 1 has a negative slope that implies a
negative ∆S. This means that entropy decreases. S depends on the temperature
dependence of the electromotive force of an electrochemical cell. [3]

TEMPERATURE VS VOLTAGE
voltage Linear (voltage) y = -0.0008x + 1.0998
R² = 0.965
1.09

1.085

1.08
VOLTAGE( V)

1.075

1.07

1.065

1.06

1.055
0 10 20 30 40 50 60
TEMPERATURE (°C)

Figure 1. Plot of the voltage of the cell against the temperature

The ∆G of a process at any concentration is given by:

G  Go  RT ln Q

Where ∆Go is the free energy of the reaction under the defined standard conditions of 1 atm and
1 M concentrations of reactants. ∆G is the observed change in free energy at conditions other
than standard. At equilibrium Q = Keq. The reaction favors neither products nor reactants at
equilibrium, and ∆G = 0. Under these conditions the previous equation becomes:
Go   RT ln Keq
In galvanic cell, a spontaneous reaction happens and the free energy of the electrochemical
system decreases. Electrical work is done at the expense of the free energy of the system. The
cell potential is related to the free-energy change as follows:

Go   nFEo

In this equation, F is Faraday’s constant, the electrical charge on 1 mol of electron 1F = 96,485

C/mol e- = 96,485 J/V-mol e- and n represents the number of moles of electrons transferred in
the reaction. [2] This equation relates thermodynamics and electrochemistry. Through this, the
emf of a cell can be predicted from the free energy change of the electrochemical system before
it is set up. The significance of this equation is to assess the feasibility of the production of
electricity through a given chemical reaction.

The G provides a criterion for spontaneity. Based on the relationship of G and E, the cell
emf can therefore be used a criterion for spontaneity.

If E>0 this means that G <0 and the cell reaction will occur spontaneously. The cell will
generate an electric current spontaneously and can function as a galvanic cell. If E < 0 this means
that G > 0 indicating that the cell reaction is non-spontaneous and the cell is not a galvanic cell.
To have a positive value for the potential of the cell, the reduction potential of the cathode has to
be more positive than that of the anode. The previous equation relates G and E allows the
evaluation of a non-measurable quantity G. It also enable the calculation of the entropy change
of the cell reaction through the equation:

S=nF(E/P

The equation shows that S can be determined by measuring the cell emf at different
temperatures at constant pressure.[4]

From the plot in Figure 1, the Ecell can be computed through the equation of the best fit line
substituting x with 25°C which serves as the standard condition.

Ecell = -0.0008 (25°C) + 1.0998 =1.0798

From the equation above, the value of ∆G, ∆H, and ∆S for the cell reaction at 25°C were
calculated using the following equations:

ΔG= −(n)(F)(E°cell) = -(2 mole )(96,485 J/ V· mol)(1.0798V)

=-2.08X105J

=-208kJ/mol

S=nF(E/P =-(2 mol e- )(96,485 J/ V-mole e-)(-0.0008V/K)

 =154.38 J/K

H=G-TS = -3.01X105J /mol – (25+273K)(154.38J/K)

=-2.54x105J

=-254kJ

Thus the values for ∆G, ∆S, and ∆H are -208kJ/mol, 154.38 J/K and -254kJ. Appendix 2 shows
the computation for the theoretical value of ∆G using the E°cell computed using the standard
reduction potential for Ag+ and Zn2+. The theoretical value was -301 kJ/mol. A percent error of
30% was found (Appendix 3). Sources of errors can be found in the preparation of the zinc
amalgam electrode which was not completely immersed in sulfuric acid until all layers and
scales dissolve and then was not immediately immersed in saturated Hg(NO3)2 solution. This
affected the reading in the digital voltmeter which did not gave an accurate and precise
measurements of the voltage readings.

4. Conclusion

By studying the effect of temperature on the equilibrium condition for a chemical

reaction, the values for the thermodynamic functions was calculated. The values computed for
∆G, ∆S, and ∆H are -208kJ/mol, 154.38 J/K and -254kJ respectively. The theoretical value of
∆G was -301 kJ/mol. A percent error of 30% was found. Sources of errors can be found in the
preparation of the zinc amalgam electrode and the immersion in saturated Hg(NO3)2 solution.
This affected the reading in the digital voltmeter which did not gave an accurate and precise
measurements of the voltage readings.

5. References

[1] S. Thermodynamics of Electrochemical Cells

https://www.scribd.com/doc/28541035/Thermodynamics-of-Electrochemical-Cells (accessed
May 5, 2017).

[2] Electrochemistry and Thermodynamics www.columbia.edu/itc/chemistry/chem-

c2507/navbar/Electrochem_2002.doc (accessed May 5, 2017).

[3] THERMODYNAMICS OF ELECTROCHEMICAL CELLS

http://www.chem.hope.edu/~polik/Chem345-1998/electrochem/Electrochemistry.html (accessed
May 5, 2017).

[4] Sevilla, Fortiunato, III. "Electrochemical cells." 11 May 2017. Reading.

Appendix

1.

Temperature Voltage
20°C 1.085V
25°C 1.080V
30°C 1.077V
35°C 1.069V
40°C 1.067V
45°C 1.064V
50°C 1.062V

2. ΔG= −(n)(F)(E°cell) = -(2 mole )(96,485 J/ V· mol)(1.56V) =-301kJ/mol

/−301kJ/mol−(−208kJ/mol)/
3. % error = =30%
301 𝑘𝐽/𝑚𝑜𝑙