Daniell Cell and Faradays Law of Electrolysis

Glyzel G. Dizon
Chemical Engineering Department, College of Engineering and Technology, Pamantasan ng Lungsod ng Maynila
Intramuros, Manila, Philippines
dizonglyzel@gmail.com

Abstract This article discusses the determination of the
standard potential of the Daniell cell. Test tubes served as the
reaction chamber, together with the electrodes submerged in the
medium where alligator clips from a multimeter are attached.
Throughout the experiment, the multimeter was used to
determine the necessary data needed such as the voltage, current
and charge. The determination of the standard potential of the
Daniell cell used the concept of the Faradays law of electrolysis
and the Nernst equation. An 56.65 equivalent weight of copper
was obtained having a percent error of 10.86%.
Keywords Standard potential, Daniell cell, multimeter, alligator
clips, Faradays law of electrolysis, Nernst equation, equivalent
weight of copper
I. INTRODUCTION
The Daniel cell is a type of electrochemical cell,
where copper and zinc electrodes are immersed in a solution
of copper (II) sulfate and zinc sulphate, respectively. At the
anode, zinc is oxidized, and at the cathode, copper ions are
reduced. The reactions involved in the cell are:
Anode: Zn(s) Zn2+(aq) + 2e- Eo = -0.7618 V
Cathode: Cu (aq) + 2e Cu(s)
2+ -
Eo = +0.340 V
The total reaction is:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Eocell = +1.1018 V
The positive Eocell means that the redox reaction is
spontaneous. It can be determined using the Nernst equation.
For each half-cell reaction, (Ox + ze = Reduc)
RT aOx
Ered = Eored + ln
zF aRed
The total cell potential
RT
Ecell = Eocell - ln Qt
zF
Where F = 96485.34 C mol-1, R = 8.314 J K-1 mol-1, Qt is the
reaction quotient, z is the number of moles electrons, a Red is
the reductant and aOx is the oxidant. The molal concentrations
of the ions can be converted to activities using ax = yxcx. The
activity coefficient yx can be calculated from the extended
Debye-Huckel law.
In contrast, electrolytic cells require external source
to drive the redox reaction. Michael Faraday established the
relationship between the mass of the substance deposited to or
liberated from the electrodes to the charge used for the redox
reaction, and the equivalent weight. It is known as Faradays
law of electrolysis.
The Faradays 1st law of Electrolysis states that, The
mass of a substance altered at an electrode during the
electrolysis is directly proportional to the quantity of
electricity (charge) transferred at that electrode.
The Faradays 2nd law of Electrolysis states that, For
a given quantity of electric charge, the mass of an elemental
material altered at an electrode is directly proportional to the
elements equivalent weight.
The equivalent weight of a substance is equal to its
molar mass divided by the change in oxidation state it
undergoes upon electrolysis. The Faradays law of electrolysis
can be expressed as:
Q M
m=( )( )
F z
where m is the mass deposited; Q is the charge in Coulomb;
M is the molecular weight or atomic weight; z is the number
of electron transferred; and F is the Faradays constant. The
charge is the product of the current in Ampere and time in
seconds.
The objectives of this experiment are to construct a
Daniell cell, to determine the Eocell using different
concentrations of copper (II) and zinc (III) ions, and to
perform electrodeposition of copper.
The following figure below shows the set-up for this
experiment:
Fig. 1 Typical Experimental Set-up
 II. METHODOLOGY
The experiment was divided into four parts.
In the first part, 1 molal of zinc (II) sulfate and 1
molal copper sulfate solutions were used as the medium. The
electrodes were cleaned using sand papers removing the
oxides, coatings and contamination on the surfaces. The
solutions were then poured in the test tubes, and the electrodes
were submerged. A drinking straw with rolled filter paper at
both ends filled with NaCl solutions acted as the salt bridge
for the cell. The set-up is show below.
Fig. 2 Experimental Set-up for Daniell Cell
Cleaning the electrodes before submerging in the test tubes is
a must and necessary. The negative side of the multimeter was
connected to the copper electrode and the positive side was
connected to the zinc electrode. The potential was determined.
This potential is relative to copper. To determine the potential
relative to the standard hydrogen electrode (SHE), +0.34 V of
the Cu2+ was added to the measured potential. The values
were compared to the theoretical values.
And for the last part, the copper electrodes were
weighed and recorded as the initial weight. The set-up is
shown below, where the test tube served as the
electrochemical cell. The test tubes were filled with 0.5 molal
copper (II) sulfate. The electrodes must not touch each other
in the chamber. With a timer, the current flowing to the
solution was recorded. After 3 minutes, the copper electrode
at the cathode was removed, dried, weighed and recorded as
the final mass of copper. The electrode was then placed again
in the test tubes. The process was repeated for 6, 9 and 12
minutes. The charge for each time interval was calculated.
The mass of the copper deposited was then plotted against the
charge calculated, as the 1st law stated. The slope, number of
electrons transferred and the equivalent weight of copper were
also determined.

The molal concentration was converted to the acitivity of the

ions. The temperature of the solutions and the potential of the
cell was then determined, comparing it to the theoretical
values. This was done for three different concentrations such
as 1 molal, 0.5 molal and 0.25 molal.
In the second part, the zinc electrode was replaced
with another copper electrode. The reaction chamber was
filled with copper (II) sulfate. Always convert first the molal
concentration to activity of the ions before calculating. The
temperature of the chamber and the potential of the cell were
again determined. Remember, the Ecell should be positive. Fig. 4 Experimental Set-up for Electrocoagulation process
In the third part, using the same set-up, the test tube
with copper electrode was filled with 1 molal copper sulfate
solution, and the other test tube with zinc (II) sulfate was III. RESULTS and DISCUSSION
filled with 1 molal zinc sulfate solution.
Table 1 Experimental Potential of Daniell Cell
1.00 0.50 0.25
Concentration
molal molal molal
Zn (activity) 0.330 0.384 0.433
Cu (activity) 0.405 0.407 0.4295
Ecell (V) 0.708 0.636 0.433
Theoretical Ecell (V) 1.100 0.550 0.367
Percent Error 35.64% 15.63% 17.98%

The measured potential of the Daniell cell in

different concentrations obtained percent error less than 40%.
Fig. 4 Experimental Set-up for Measuring the Potential Relative to Copper
 Table 2 Experimental Potential of Concentration Cell Table 6 Values of Slope, Pearson R,
1.00 0.50 0.25 Equivalent and Theoretical weight of Copper
Concentration
molal molal molal Slope 0.00069
Zn (activity) 0.294 0.397 0.433 Pearson R 0.8536
Cu (activity) 0.433 0.401 0.4295 Number of electrons
0.9612
Ecell (V) 0.713 0.662 0.440 transferred
Theoretical Ecell (V) 1.100 0.550 0.367 Equivalent weight of Cu 56.65
Percent Error 35.18% 20.34% 19.87% Theoretical weight of Cu 63.35
Percent Error 10.86%
The measured potential of the cell with two copper
The slope obtained from the plot was 0.0069. The
electrodes in different concentrations obtained percent error
number of electrons transferred obtained was 0.9612 having
less than 40%, obtaining almost the same results as in part (a).
the equivalent weight of 56.65. A 10.86% error was obtained.
Table 3 Potential of Reduction with respect to Copper
Sample Zn Fe
Ecell 0.340 V 0.340 V IV. CONCLUSION
Eo of sample 1 -0.952 V -0.420 V
Eo of sample 2 -0.994 V -0.407 V
The plot of ln P against 1/T produced a small value
Average -0.948 V -0.4135 V
Standard Deviation 0.0462 0.0092 of slope such as 0.0069 and a correlation coefficient of R =
0.8536. The equivalent weight of copper computed was 56.65,
Table 4 Theoretical Values and Percent Error of Zinc a value close enough to the theoretical weight of copper such
and Iron Potentials relative to Copper as 63.55. The obtained result has a 10.86% error.
Eo of Zn 0.7618 V
Percent Error 24.44%
Eo of Fe 0.441 V
Percent Error 6.24% ACKNOWLEDGEMENT

Relative to copper, the potential of the zinc and iron The author would like to express his sincerest
gratitude to all group members for cooperating in the success
electrons measured resulted to less than 25% error.
of this experiment. Likewise, Mr. Tardaguilla for imparting
his knowledge that leads to the development of this
Table 5 Mass deposited, Charge and Current of Copper experiment. And above all, Glory to God Almighty for
Time (min) 3 6 9 12 continuance blessings of wisdom and power.
Initial mass
1.0369 0.3610 0.3207 0.3416
of Cu (g)
Final mass of
1.0391 0.3689 0.3272 0.3624 REFERENCE
Cu (g)
Mass of Cu
0.0022 0.0079 0.0065 0.0208
deposited (g) [1] Activity Coefficients. (n.d.). Retrieved from
Current (A) 0.0698 0.044 0.0488 0.047 http://www.kayelaby.npl.co.uk/chemistry/3_9/3_9_6.html
Charge (C) 12.564 15.84 26.352 34.056

Mass deposited of Cu vs. Charge

0.025
0.02
0.015
0.01
0.005
0
0 10 20 30 40
Fig. 5 Plot of Mass deposited of Cu (g) vs. Charge (C)