Determination of Thermodynamic Values using an Electrochemical System

Bracero, Jestoni L. February 24, 2020

Groupmates: Alcano, Jason C.
Bacus, Ma. Isabel
Esparrago, Moreen Roce C.

Abstract

Thermodynamic functions ΔG, ΔS and ΔH of the reaction inside an electrochemical cell were
determined by measuring the voltage at different temperatures. Through calculations and use of the
EMF vs. Temperature plot the Ecell values for the reactions were found to be 1.83V for T1and 1.74 V
for T2. Both Ecell values showed deviations from that of the theoretical values which 2.71. The
functions ΔG (-353.1 kJ/mol and -335.8 kJ/mol for respective trials) 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 ΔS (0.1158 and 0.3280 kJ/mol.K) and ΔH (-
318.6 and -238.0 kJ/mol) by using the slope of the graph in equations 3 and 4. The ΔG, ΔS and Δ H
value were quite far from the theoretical value which are 0.1674 kJ/mol.K, -522.9 kJ/mol, and -473.0
kJ/mol respectively.
I. Introduction

Thermodynamics is not unpretentiously an academic exercise focused on arcane pursuits like

determining equilibrium quantities or predicting the direction of some reaction. Formulating a
thermodynamic experiment without involving sophisticated thermal equipment like bomb
calorimeters is a bit hard to come by. But, in this experiment, electrochemical systems can be used to
derive the thermodynamic values at constant pressure that are ∆H, ∆G, and ∆S. the electromotive
force of the system recorded at varing temperature can be the basis of these calculations [1]. This
experiment utilizes the Cu2+/Mg2+ electrochemical system which is a spontaneous redox reaction that
is already used in some batteries nowadays.
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
energy[2].
The purpose of this experiment is to determine and explore the thermodynamics values of an
electrochemical cell of Cu2+/Mg2+ system. 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 equation.
(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 reaction.

(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.

(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.
(4)
II. Experimental Method

The method employed in this experiment was anchored to the designed method of Saieed and
Davies (1996) [4]. The modified method were as follows:

Preparation of Electrochemical System Set-up

Three clean, dry test tubes were prepared and labelled and an adhesive tape was used to hold
the testubes tightly together. Then the test tubes were clamped onto an iron stand. Thereafter, a 100-
mL beaker was filled with water halfway to prepare a water bath. Carefully, the salt solutions (1M
CuSO4, 1M MgSO4) were added to the designated test tubes in the assembly. The Cu and Mg
electrodes then were prepared to be used by softly scraping the surface with a small piece of steel
wool to clean the entire wire electrodes until it is shiny. Next, the said electrodes were rinsed wel with
distilled water. The assembly was submerged to the beaker with water and the elctrode was placed to
their corresponding salt solutions. The KCl salt bridge was put between the two half cells through a
sponge or filter paper. Then, the alligator clips were attached to the electrodes; with the black wire (-)
to the Mg electrode and the red (+) to the Cu electrode; and a thermometer was placed into the
assembly by suspending it in the distilled water filled in the test tube.

Measurement of EMF of the system at Varying Temperatures

The assembly was placed in the hot plate. (Do not turn on the hot plate first.) The current
temperature and voltage reading of the system were recorded. Heating the set-up until the following
temperature (0.0°C, 25.0°C, and 50.0°C) was achieved and the electric potential readings using a
voltmeter were recorded. Same steps for the trial T2. Therafter, the thermodynamic values, ∆H, ∆G,
and ∆S were calculated using the data collected.

III. Results

The results of this experiment were recapitulated in tables below (all tables presented display
all the data taken in different stages of the experiment).
Table 1. Voltage of Cell at Different Temperatures
TRIALS, V
TARGET TEMPERATURE, K ACTUAL TEMPERATURE, K
T1 T2
273.15 274.15 1.803 1.727
298.15 298.15 1.821 1.736
323.15 323.15 1.831 1.812

Table 2. Experimental and Accepted Thermodynamics Values

Experimental Value Accepted Value
T1 T2 T1 T2
E 1.83 V 1.74 V 2.71 V 2.71 V
ΔS 0.1158 kJ/mol.K 0.3280 kJ/mol.K 0.1674 kJ/mol.K 0.1674 kJ/mol.K
ΔG -353.1 kJ/mol -335.8 kJ/mol -522.9 kJ/mol -522.9 kJ/mol
ΔH -318.6 kJ/mol -238.0 kJ/mol -473.0 kJ/mol -473 kJ/mol
 Figure 1. Temperature vs. Electric Potential
1.835

Electric Potential, V
1.83 y = 0.0006x + 1.6481
1.825 R² = 0.9696
1.82
1.815
1.81
1.805
1.8
270.00 280.00 290.00 300.00 310.00 320.00 330.00
Temperature, K

Figure 2. Temperature vs. Electric Potential

1.82
y = 0.0017x + 1.2379
Electric Potential, V

1.8
R² = 0.8372
1.78
1.76
1.74
1.72
1.7
270.00 280.00 290.00 300.00 310.00 320.00 330.00
Temperature, K

IV. Discussion

The galvanic cell was first placed at an initial temperature about 0°C where the first voltage
was recorded. The temperature was then increased at intervals of about 25°C while recording the
results of voltage until the temperature reached close to 50°C. There were two sets of results obtained
at different temperatures that were graphed so that the slope can be used to calculate the
thermodynamic functions ΔS, ΔG, and ΔH.
The results of the experiment (two trials were made) 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 1 and 2 is considered to have a strong correlation since the R2 value of 0.9696 and
0.8372 for the trial 1 and trial 2 respectively were relatively a bit far to 1 showing that the results were
inconsistent and a bit little critical errors occurred.
 The EMF of an electrochemical cell varies with temperature since the cell reaction involves a
change in entropy, ∆S [5]. In this lab experiment, the following anode and cathode half-cell reactions
were noted respectively: Mg → Mg2+ + 2e; Cu2+ +2e → Cu, leading to an over equation of: Cu2+ +
Mg→ Mg2+ + Cu. Through calculations and use of the EMF vs. Temperature plot the Ecell values for
the reactions were found to be 1.83V for T1and 1.74 V for T2 . Both Ecell values showed deviations
from that of the theoretical values which 2.71. Following this values of ∆H, ∆G and ∆S were found.
The Gibbs free energy value of -353.1 and -335.8 kJ/mol were calculated and showed a difference in
value to that of the theoretical value of -522.9kJ/mol. This negative ΔG value indicated that the
reaction was spontaneous meaning that once a reaction began (after activation barrier is surmounted)
it continues without intervention, therefore overall the reaction is thermodynamically stable - but can
be kinetically slow.
The recordings of temperature and voltage obtained from the experiment were then plotted in
a graph that had a slope value of 0.0006 and 0.0018 for the T1 and T2 respectively. This value was
then used to calculate the thermodynamic function of entropy (ΔS) and enthalpy (H). Equation 3 was
first used in order to calculate the entropy (ΔS) of the electrochemical reaction in T1 and T2, which
was found to be 0.1158 kJ/mol.K and 0.3280 kJ/mol.K respectively. The value of ΔS along with the
value calculated for ΔG previously were then plugged into equation 4 that gave a ΔH of -318.6 kJ/mol
and -238.0 kJ/mol - which is quite far from the literature value of ΔH° -473.0 kJ/mol.
The ΔH value obtained from this experiment is considered to be reasonable from the literature
value which is caused from limitations that cannot 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 value of ΔH 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 [6]. The
experiment can be considered a success since a reasonable value for ΔH has been obtained that was a
bit far to the literature value due to experimental limitations. 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 electrochemical reactions taking place.

V. References

[1] Brown Theodore L. Chemistry The Central Science. 13TH edition.. 2015
[2] Clugston, M, Flemming, R. Advanced Chemistry; Oxford University Press: Oxford, 2000.
[3] Dean, John A. Lange’s Handbook of Chemistry, 11th ed.; McGraw-Hill: New York, New York,
1979; pp 9:4-9:128.
[4] Kotz, J, Treichel, P, Townsend, J. Chemistry and Chemical Reactivity, Seventh Edition; Thomson
Brooks/Cole: Belmont, 2009
[5] Lide, David R. CRC Handbook, 84th ed.; CRC Press: Boca Raton, Florida, 2003; pp 5:5-5:60,
5:85-5:86. http://chemistry-reference.com/standard%20thermodynamic%20values.pdf
[6] Milosavljevic, B.H. Lab Packet for CHEM 457: Experimental Physical Chemistry, Gravimetric
Determination of the Gas Constant. University Press: University Park, 2009.
VI. Appendices

From Graphs: Experimental; T1 and T2

Ecell = 0.0006 (298.15 K) + 1.6481
= 1.83 V
Ecell = 0.0017 (298.15 K) + 1.2379
= 1.74 V
Theoretical
Ecell = Ecathode – Eanode
= 0.34 – (-2.37) V
=2.71 V
From Graph: Experimental; T1 and T2
ΔG= -nFEcell
= -(2 mol x 96485 Cmol-1 x 1.83 V)
= -353.1 kJ/mol
ΔG= -nFEcell
= -(2 mol x 96485 Cmol-1 x 1.74 V)
= -335.8 kJ/mol

Theoretical
ΔG= -nFEcell
= - (2 mol x 96485 Cmol-1 x 2.71 V)
= -522.9 kJ/mol

Experimental; T1 and T2
ΔS = nF(Gradient)
= (2 mol x 96485Cmol-1 x 0.0006)
= 0.1158 kJ/mol.K
ΔS = nF(Gradient)
= (2 mol x 96485Cmol-1 x 0.0017)
= 0.3280 kJ/mol.K

Experimental; T1 and T2
ΔH at (298.15 K) = ΔG + TΔS
= -353.1 kJ/mol + (298.15 K) (0.1158 kJ/mol.K)
= -318.6 kJ/mol
ΔH at (298.15 K) = ΔG + TΔS
= -335.8 kJ/mol + (298.15 K) (0.3280 kJ/mol.K)
= -238.0 kJ/mol
Theoretical; Enthalpy of Reaction
Mg(s) + Cu2+(aq) → Mg2+(aq) + Cu(s)
ΔH = ΔHMg +ΔHCu= +407 -880 = -473 kJ/mol
= 0.1674 kJ/mol