Experiment 3: Equilibrium Constant of a Redox Reaction

Objectives:

a) To experimentally determine the equilibrium constant of a redox reaction.

b) To compare the experimental equilibrium constant with the theoretical value obtained using
Nernst Equation.

Introduction:

The Nernst equation is used to calculate the cell voltage under the non – standard conditions
where the formula of the equation is:

𝑅𝑇
𝐸 = 𝐸˚ − (ln 𝑄)
𝑛𝐹

where Q is the reaction quotient. At 298 K, the equation can be written as:

0.02257 𝑉
𝐸 = 𝐸˚ − (ln 𝑄)
𝑛

And also can be expressed as:

0.0592 𝑉
𝐸 = 𝐸˚ − (ln 𝑄)
𝑛

During the experiment of galvanic cell, anode is the negative terminal while cathode is a positive
terminal. Electron will flow from anode to cathode resulting of product formation and cause the
reactant concentration decreased. At equilibrium, there is no electron transfer which is Ecell = 0 and Q =
K where K is the equilibrium constant. So, the equation when in equilibrium state is:

0.0592 𝑉
0 = 𝐸˚ − (ln 𝐾)
𝑛

The Nernst equation helped in calculating E as a function of reactant and product concentration
in a redox reaction. In this experiment, Zn – Cu cell is used for study. The concentration of Zn half – cell
is at 1.0 M and varying the Cu half – cell concentration where the value is from 0.00010 to 1.0 M.
Procedures:

1. The metal strips of Zn and Cu is cleaned using sandpaper then rinsed in distilled water and then
dried.
2. In 1st beaker, the solution of 1.0 M Zn2+ solution is filled in until the electrode of Zn is covered.
3. For the next beaker, proper dilutions is done to get the following Cu2+ solutions of 0.00010 M,
0.0010 M, 0.010 M, 0.1 M and 1.0 M.
4. 0.00010 M is placed into the 2nd beaker until covered the Cu electrode. The circuit is connected
the voltage reading is measured.
5. The Cu2+ solution is replaced with the next higher concentration (0.0010 M) and the voltage
reading is measured.
6. This process is continued until the concentration of Cu 2+ is 1.0 M.

Data and Results:

Zinc half – cell Copper half – cell 1⁄

Cell [Cu2+ ] Ln 1⁄[Cu2+ ] Emf of cell (V)
(M) (M)
1 1.0 0.00010 10000 9.2103 + 0.990
2 1.0 0.0010 1000 6.9078 + 1.018
3 1.0 0.010 100 4.6052 + 1.026
4 1.0 0.1 10 2.3026 + 1.061
5 1.0 1.0 1 0 + 1.092

Ecell vs ln 1/[Cu2+]
1.12

1.08

1.04

0.96

0.92
0 2.3 4.6 6.9 9.2
Calculations:

From the graph, concentration of Cu2+ at equilibrium:

Ln 1⁄[𝐶𝑢2+] = 7.60

1⁄
[𝐶𝑢2+] = 1998

[Cu2+] = 0.0035 M

Anode: Zn → Zn2+ + 2e¯ E˚ = - 0.76 v

Cathode: Cu2+ + 2e¯ → Cu E˚ = + 0.34 v
E˚cell = E˚cathode - E˚anode
Overall equation: Zn + Cu2+ → Zn2+ + Cu = +0.34 v - -0.76 v
E˚cell = 1.10 v

0.0592 𝑉
𝐸 = 𝐸˚ − (ln 𝐾)
𝑛

0.0592 𝑉
0 = 1.10 − (ln 𝐾)
2

ln 𝐾 = 37.162

Experimental equilibrium constant, K = 1.38 x 1016

Using Nernst equation to calculate theoretical value of equilibrium constant:

𝑅𝑇
𝐸 = 𝐸˚ − (ln 𝐾)
𝑛𝐹

(8.314)(298)
0 = 1.10 − (ln 𝐾)
2(96500)

ln 𝐾 = 8.46

Theoretical equilibrium constant, K = 4.72 x 103

Discussion:

In this experiment, we used the Nernst equation to calculate the equilibrium constant of a redox
reaction between Zinc and Copper. At anode, oxidation reaction occur which involving zinc electrode
where Zn → Zn2+ + 2e¯ while at cathode, reduction reaction occur which involving copper electrode
where Cu2+ + 2e¯ → Cu. The overall equation for this reaction is Zn + Cu2+ → Zn2+ + Cu. At equilibrium, Ecell
= 0 while the K is the equilibrium constant. The formula used to calculate the equilibrium constant is:

0.0592 𝑉
𝐸 = 𝐸˚ − (ln 𝐾)
𝑛

The concentration used for Zinc electrode is constant which is 1.0 M while for Copper, the
concentration is varying from 0.00010 M to 1.0 M. The equilibrium constant for different concentration
of Cu is determined. E˚cell for this experiment is + 1.10 v. To calculate the theoretical value of K, we used
formula of:

𝑅𝑇
𝐸 = 𝐸˚ − (ln 𝐾)
𝑛𝐹

The experimental value of K is 1.38 x 1016. From the graph, the concentration of Cu2+ is 0.0035
M. Meanwhile the theoretical equilibrium constant, K is 4.72 x 103. The value is different because there
might be slightly mistake when doing the dilution. As well, frequently, non – standard conditions may be
used in a lab. The standard cells are for 1 M solutions. They are measured at 25 degrees Celsius.
Differences in these conditions will cause changes.

Conclusion:

The equilibrium constant is determined where K is 1.38 x 1016 and the experimental constant is
compared by theoretical value obtained by Nernst equation.
References:

1. Nernst Equation. Retrieved October 17, 2017 from

http://en.wikipedia.org/wiki/Nernst_equation

2. Nernst Equation. Retrieved October 17, 2017 from

http://www.science.uwaterloo.ca/~cchieh/cact/c123/nernsteq.html
3. Equilibrium Constant of a Redox Reaction. Retrieved October 17, 2017 from
https://s3.amazonaws.com/academia.edu.documents/37330501/Equilibrium_constant_of_a_re
dox_reaction.pdf?AWSAccessKeyId=AKIAIWOWYYGZ2Y53UL3A&Expires=1508688918&Signatur
e=zeV1nS9qhaEo0eXNe0k4bGJXtuI%3D&response-content-
disposition=attachment%3B%20filename%3DEquilibrium_constant_of_a_redox_reaction.pdf