Determination of Electrode Potentials

Nathalie D. Dagmang
Institute of Chemistry, University of the Philippines, Diliman, Quezon City, 1101 Philippines

Department of Food Sciences, College of Home Economics, University of the Philippines, Diliman, Quezon City 1101 Philippines

ABSTRACT

The two main objectives of the experiment are to (1) relate and apply the concepts of electrochemistry to actual
experiments, (2) understand the processes and elements of an electrochemical cell and (3) determine the
spontaneity of reduction-oxidation (redox) reactions based on standard reduction potential.

Different half-cells were prepared and connected to copper, which served as the reference electrode, to set up a
voltaic cell. The volt-meter readings of the set-ups were then used to calculate for the standard reduction potentials of
the variable half-cells. The results obtained from the experiment indicated the spontaneity of the redox reactions
investigated, showing that the least spontaneous system is that connected to another copper half- while the most
spontaneous system is that connected to the Zinc half-cell.

Introduction
−¿¿

Zn(s ) → Zn2+ ¿+2 e ¿

( aq ) [2]
In a redox reaction, an electron is being −¿→Cu (s ) ¿

Cu2+¿+2 e ¿
[3]
transferred from one reactant to another. This (aq )

process is shown in the equation below, with the

In equation [2], zinc with the less affinity for
example of the redox reaction between Zinc and
electrons undergoes oxidation wherein it losses
Copper:
electrons and causes copper to undergo reduction.
2+ ¿¿
2 +¿→Cu (s) +Zn(aq) ¿ This makes zinc the reducing agent, while the copper
Zn(s )+Cu(aq) [1]
is the oxidizing agent.
An electrochemical process occurs when a This set-up, where the anode and cathode
spontaneous redox (or reduction-oxidation) reaction are separated, is called an electrochemical cell. There
produces energy or a non-spontaneous reaction uses are two types of electrochemical cell: the voltaic cell,
up energy. wherein work is done by the system, and the
This reaction can be prompted by directly electrolytic cell, wherein work is needed to set off the
immersing a Zinc solid in a CuSO4 solution. This reaction. The voltaic cell (also called galvanic cell), is
reaction can also be set off even when the two shown in Figure 1.
reactants were separated, and their electrons are
transferred not by direct contact but through a wire. In 3
this case, a certain amount of work is done or used by
the system. In equation [1], the anode, where the Figure 1. Voltaic cell
oxidation occurs (equation [2]), is zinc while the
cathode, where the reduction occurs (equation [3]), is This can also be representation through a shorthand
copper. These two components can be separated into notation. In this case, the cell notation is:
what are called half-cells:
Zn¿ [4]

1
wherein the reactant on the left is always the anode E ⁰cell =E ⁰cathode −E ⁰ anode[5]
and the one on the right is always the cathode. The
single vertical line represents a phase boundary while However, this standard potential only applies
the double vertical line represents the two phase to solutions with the concentration of 1 M. In the
boundaries at both ends of the salt bridge. experiment, it was assumed that the concentration of
the halide ion did not significantly change with the
In this set-up, a salt bridge provides ions to electrolysis of the solution. But if the concentration
the two solutions to neutralize its charges by adding was not 1 M, and other conditions such as the
negative ions to the positive half-cell (Zinc) and temperature and nature of the reactant were altered,
positive ions to the negative half-cell (Copper). This the cell potential will be different from the standard
prevents the reactants to react directly with one potential. The effects of these factors are shown in
another but still maintains electrical contact between the Nernst equation:
the two half cells.
RT
The electrons produced from the Zinc rod E=E °− lnQ [5]
nF
passes through the wire, enter the copper rod and
interact with the copper ions in solution. As the Where R is the gas constant with a value of
electrons travel through the wire, energy is produced 8.314 J/molK, T is the temperature in Kelvin, n=
and the bulb is lighted. In the experiment, a load like number of moles of electrons that appear in the half
the light bulb was not connected to the wire, but a cell reaction, and F is Faraday which is equal to 96,
volt-meter. A volt-meter measures the voltage/ 485 Coulombs. The Q in the equation is the reaction
electric potential difference or the measure of quotient, given by the formula
electromotive force, the amount that can be extracted
from the system. While doing this, the volt-meter does [ products]m
Q= [6]
not consume the energy produced as it has an infinite [r eactants ]n
resistance. The voltage also serves as a parameter
for the tendency of the reaction to proceed to an where m e the coefficients of the products and n are
equilibrium state. As the reaction proceeds, the the coefficients of the reactants in the balanced
potential continues to decrease until it reaches 0.000 equation. The values enclosed in brackets are the
V. concentrations of the reactants and products.

However, absolute electrode potentials Simplifying the Nernst equation by

cannot be measured. This is because all volt-meters substituting the constant values and indicating that
measure only differences in potential between two the temperature is at 25⁰C, the cell potential can be
half cells. Thus, the values of electrode potential used calculated from the formula:
in calculations are only those of the half cells when
O . O592
these are reacted with a standard hydrogen electrode E=E °− logQ [7]
n
which has an assigned value of potential of 0.00 V. In
this reaction, the standard hydrogen electrode serves According to Faraday’s law, the mass of the
as the anode while the electrode to be tested is the product formed or the reactant used is proportional to
cathode. From this reaction, the standard reduction the amount of electricity that passes through the
potential ( E ° ) is measured. This value can then be system. This relationship is shown in the equation:
used to compute for the standard potential of the
whole electrochemical cell using the equation: C= At [8]

2
where C is the amount of electricity passing through Figure 2. Voltaic Cell Set-up
the circuit, 1 coulumb being transported every second
by each ampere. A is the current in ampere and t is For the second part of the experiment,
time in seconds. 96,500 Coulomb per mole of another 3 half cells were prepared with cell notations
electron is equivalent to 1 Faraday, which is the Cl-(1 M), Cl2| C, Br-(1 M), Br2| C, I-(1 M), I2| C. Like in
electrical charge contained in 1 mole electron. Using the third half cell, a graphite electrode was used.
this formula, the concentration of the half-cell can be Potassium halide (KX) solutions were electrolyzed by
calculated and substituted to the Nernst equation. immersing two graphite electrodes into the solution
and connecting these to a 1.5 V dry cell which serves
The purpose of this experiment is to further as its energy source as shown in Figure 3. This was
understand and apply the concepts of done for 1 minute, until the halide ions were oxidized
electrochemistry and the processes and elements of to halogens, X2.
an electrochemical cell to actual experiments and to
determine the spontaneity of reduction-oxidation
reactions based on standard reduction potential.
batt
Experimental Detail Figure 3. Electrolytic Cell Set-up

For the first part of the experiment, three half The prepared mixture of halogens and halide
cells were prepared, with cell notations of Cu2+(1M)| solutions were then connected to the copper half-cell
Cu, Zn2+(1M)|Zn and Fe3+(1M),Fe2+(1M)|C. The first like the set-up in Figure 2.
electrode was prepared by immersing a copper
The volt-meter reading for the six voltaic
electrode in 1 M CuSO4. The second half cell was
cells prepared were recorded and used in
prepared by immersing a zinc electrode in 1 M
calculations.
ZnSO4. Lastly the third half cell was a mix of equal
volumes of 2 M FeSO4 and 2 M FeCl3 with graphite as Results and Discussion
its electrode. An iron nail was not used due to the
side reaction that might cause rust to form on the The measured voltages of the prepared
nail’s surface: voltaic cells are tabulated in Table 1.

Fe3 +¿→ Fe
2+ ¿→ FeO ¿
¿
[9] Table 1. Volt-meter Readings

Instead, a graphite electrode, which is a semi- Set-up Cell Notation Volts

#
conductor, was used. This is made of the electrically
1 Cu|Cu2+||Cu2+|Cu 0.0896
inert carbon that would not participate in the reaction.
2 Zn|Zn2+||Cu2+|Cu 1.08
These half cells were then connected with
the wires of the volt-meter to a copper half cell 3 Cu|Cu2+||Fe3+|Fe 0.414
prepared in the same manner. A salt bridge was
4 C|Cl-,Cl2||Cu2+|Cu 0.468
made out of rolled filter paper soaked in saturated
potassium nitrate and then each of its ends was 5 C|Br-,Br2||Cu2+|Cu 0.269
soaked in one of the two half-cells. The set-ups for
the first part of the experiment is shown in Figure 2. 6 C|I-,I2||Cu2+|Cu 0.121

X-
3
 The potentials measured from the Table 2. Calculated standard potential
experiment are the potentials of the whole voltaic cell
set-ups while the given potential of the reference Set-up Variable Half- Calculated Book % Error
# Cell Notation Volts Value
electrode, Cu2+/Cu, is 0.34 volts. From these data, the
experimental value of potential of the different half 1 Cu|Cu2+ 0.2504 0.00 26 %
cells connected to the copper half-cell can be
calculated using equation [5]. 2 Zn|Zn2+ - 0.74 - 0.763 3.01 %

3 Fe3+|Fe 0.754 0.771 2.2 %

If the copper served as the anode in the
voltaic cell, the formula for the potential of the variable 4 C|Cl-,Cl2 0.808 1.359 40.54 %
half-cell is calculated from:
5 C|Br-,Br2 0.609 1.087 43.97 %
Ecathode =E cell +0.34 [10]
6 C|I-,I2 0.461 0.615 25.04 %
Otherwise, the potential of the half cell will
be
These values were compared to the book
Eanode =0.34−Ecell [11]
value and yielded percentages of error within the
For set-ups 1, 2, 4, 5 and 6, the reference range of 2.2%-43.97%.
electrode, Cu, served as the anode. Thus, given the The percent error were highest for the last
E⁰red of Cu as 0.34, the standard potential of the three set-ups for these were calculated without taking
cathode was calculated from equation [10]. The first into account the changes in concentration due to the
set-up should have yielded a voltage reading of 0.00 electrolysis done prior to setting up the voltaic cell.
V because both half-cells supposedly have the same
content and concentration. Because of this, the Eanode If the change in concentration was taken into
and Ecathode should have the same value and the Ecell account, the current (in Amperes) and time length of
should be equal to 0.00 V. However, a difference in the electrolysis should be measured. For example, in
concentration can also add to the potential difference, the experiment, Cl- is converted into Cl2. which follows
so even a slight error in the volume measurements the reaction:ly
can add to the error of the results. −¿+ Cl2( s) ¿
e
2 Cl−¿→2
(aq)
¿
[12]
Set-ups 4, 5 and 6 were affected by the
concentration. However, in the experiment, it was The Cl- solution was electrolyzed for 4
assumed that the change in concentration due to the minutes and 30 seconds and the measured current
hydrolysis was negligible and was not taken into was 0.065 Amperes. Substituting these values to
account in the calculations. equation 8, the calculated amount of electricity is
17.55 Coulombs. This is then converted to mole e- by
Because in set-up 3, copper served as the dividing 17.55 by 96,500. Using stoichiometry, the
cathode, the value calculated for was the standard number of moles of Cl- is calculated, hence, also the
potential of the anode. This was computed from concentration of Cl- in the solution. This new
equation [11]. concentration can be substituted to equation [7] and
Using these equations, the resulting [Cl 2 ]
since Q= and the activity of Cl2 is taken as 1,
experimental value for the standard reduction ¿¿¿
potentials of the variable half-cells are as follows: Q is only equal to
1 .
¿¿¿
4
 The measured voltage of the voltaic cell, potential, or the potential of the electrode with respect
which is 0.468 V, was then used to calculate the to the solution, can be calculated from the Nernst
potential of the Chloride half-cell: equation:

Ecathode =0.468+0.34=0.808 V O .O 592

Eeq =E °− log ¿ ¿ [14]
n
The n, calculated Q, and potential of the
cathode was substituted in the Nernst equation to get If the given potential of the electrode, E’,
the standard reduction potential of the cathode: exceeds the Eeq, the wire is not in equilibrium, thus
electrons are still exchanged between the
0.0592 1 components of the solution until the potentials of the
E=E °− log
2 [0.00364]2 solution and the electrode are equal. The value of the
ratio ¿ ¿ increases to lessen the value of E’ and the
0.808=E °−0.1444 ferric iron tends to be reduced (reaction [13]). On the
other hand, if E’ is less than Eeq, the ratio decreases
E °=0.9524 V
and reverse reaction predominates.
By using this method of calculation, the
Consider the electrolysis of a Chloride
percent error will decrease from 40.54% to 29.92%.
solution in part B:
These calculated reduction potentials can −¿¿

2 Cl−¿→Cl +2 e [15]
2 ¿
serve as a parameter for the spontaneity of a
reaction. In the electrolytic cell, voltage is applied to
If the calculated values for the potentials of the two chemically inert graphite electrodes, one of
the half-cells are more positive than 0.34, the which serves as the cathode, the other, the anode.
reactants of that half-cell are stronger oxidizing The voltage applied can be calculated from the
agents. If the potential difference is positive, the formula:
reaction follows a forward direction. Otherwise, the V applied =Eanode −E cat h ode [16]
backward reaction is favored and work is needed to
stimulate the forward reaction. An electrolytic cell set- If a potential applied to the cathode, Ecathode,
up is used in this experiment to initiate a reaction like is less than Eanode, the system is not in equilibrium.
this, namely the halide half-cells. This causes the Ecathode to increase and the Eanode to
decrease until Ecell = 0, producing work instead of
Consider the cathode iron half-cell in set-up
consuming it from the energy input (dry cell). So if the
3 where the following reduction reaction occurred:
passage of current or electrolysis is aimed to occur,
the Eanode should be greater than Ecathode.
2+ ¿¿
−¿→Fe ¿

Fe3 +¿+ e [13]

¿

The potential at the anode of the cell and the

When the chemically inert electrode,
reduction potential of the cathode can also be
graphite, was inserted to the solution, a continuous
calculated from the Nernst equation:
exchange in electrons occurs between the electrode
and the oxidizing and reducing substances that came
O .O 592 [Cl2 ]
in contact with it. At equilibrium, when Q = Keq, Ecat h ode=E ° − log ¿¿ ¿ [17]
n
reaction [13] and its reverse reaction occur at the
same rate, making the composition of the solution O . O592
near the electrode, constant. The equilibrium Eanode = E° − log ¿ ¿ ¿ [18]
n

5
 Referring to the aforementioned concept, as concentration due to electrolysis is taken into
the produced Cl2 increases, the oxidation potential account. This can be done by measuring the amperes
decreases. Conversely, the reduction potential of the and recording the time of the duration of electrolysis.
cathode increases with the increase of Cl2. This
causes the potential needed by the system to Also, the effect of concentration differences
decrease until it reaches equilibrium and making the between the half-cells can also be investigated by
reaction more spontaneous. After the electrolysis of setting up two half-cells containing the same solutions
the system, it can already be connected to the copper but in different concentrations.
half-cell to produce a galvanic cell. It now acts as the References
cathode because of the high amount of Cl2 which tend
to be reduced to Cl-. [1] Belcher, R. Quantitative Inorganic Analysis, 1970

Conclusions [2] Christian, G.D. Analytical Chemistry, 1986

The three main objectives of the experiment, [3] Day, Underwood, et al. Quantitative Analysis,
namely to (1) relate and apply the concepts of 1967
electrochemistry to actual experiments, (2)
understand the processes and elements of an [4] Haenisch, Pierce, et al. Quantitative Analysis,
electrochemical cell and (3) determine the 1958
spontaneity of reduction-oxidation (redox) reactions
[5] Skoog, et al., Fundamentals of Analytical
based on standard reduction potential, were all
Chemistry, Eighth edition, 2004
achieved in the experiment.
[6]
From the read voltages, the spontaneity of
http://academic.pgcc.edu/psc/chm103/103_manual.p
the reactions was measured. It can be concluded
df
based on the data gathered and values calculated
that the spontaneity of the reactions with respect to a
copper half-cell in decreasing order is:

Set-up # 2 > # 4 > # 3 > # 5 > # 6 > # 1

This was concluded using the knowledge

that a higher potential difference or Ecell produces a
more spontaneous reaction and more work that can
be done by the system. This means that the farther
the value of the standard reduction potential (SRP) of
the half-cell is from the SRP of copper, the more
spontaneous the reaction would be. Individually, the
standard reduction potentials of the half-cells, when at
a higher value, also indicate a higher tendency to be
reduced and serve as a cathode in the voltaic cell and
as an anode in an electrolytic cell.

To further understand the concepts of

electrochemistry, it is recommended that in the
second part of the experiment, the change in