Experiment 9: Determination of Electrode Potentials
C. Grefaldia1, C. Hernia2
1
College of Home Economics, University of the Philippines, Diliman, Quezon City 1101
2
National Institute of Geological Sciences, College of Science, University of the Philippines, Diliman, Quezon City 1101
Performed 30 June 2017; Submitted 4 July 2017
Answers to Questions
1. Discuss the differences between galvanic and
electrolytic cells.
One main difference between the two cells is that galvanic
cell converts chemical energy into electrical energy
whereas an electrolytic cell converts electrical energy into
chemical energy. The redox reaction in galvanic cell is
spontaneous whereas in electrolytic cell, it is non-
spontaneous therefore an electrical energy has to be
supplied in order to start a reaction. Galvanic cell uses two
different containers, one for each half-cell and a salt bridge
containing ions connect both containers. On the other
hand, in an electrolytic cell, both electrodes are placed in
the same container containing the solution of the
electrolyte. In galvanic cell, the anode is negative
(oxidation) and cathode (reduction) is positive while in
electrolytic cell, its the other way around. Because the
reaction in the galvanic cell is spontaneous, electrons are
supplied by the species getting oxidized whereas in an
electrolytic cell, the battery supplies the electrons, entering
through the cathode and coming out through the anode. [1]
Figure 1. Electrolytic cell vs. Galvanic cell Diagram
2. What is the measured value of Ecell for each cell and
its relevance to the E red for the iron half-cell and
halogen half-cells?
The measured value of E cell is the total voltage of the whole
cell which is made up of two half-cells, which both have
different electric potential. The conditions during the
experiment were standard (1M solutions, 1 atm, 25C) so it
is safe to assume that Ecell is equal to the Ecell so the
equation is:
Ecell = Eredcathode - Eredanode [2]
The measured value for Ecell indicates that for copper and
zinc reaction, the reaction is spontaneous when the copper
is the cathode and zinc is the anode. In the copper and iron
reaction, iron undergoes reduction and gains electron
whereas copper undergoes oxidation and loses electrons. A
positive Ecell means that the reaction will proceed
spontaneously whereas a negative value means that the
reverse reaction is going to take place. The higher the value
of Ecell, the more it will undergo reduction. [2]
3. Compare the calculated E red for each half-cell with
their literature value.
The experimental values of Ecell were different from their
literature value, mostly lower than their book values. The
calculated percent error ranges from 12.8-44.5%.
4. Based on your observations, what are the half
reactions which occur at the anode and cathode during
the electrolysis?
The half reactions that occur in electrolysis are
respectively: i. Anode 1. 2A - A2 + 2e- wherein A is either
Bromine or Iodine, in the experiment ii. Cathode 1. 2e - +
2H2O 2OH- + H2 as no other species are present. [3]
5. Based on the calculated values, what are the most
effective reducing and and oxidizing agents?
Using the theoretical values, the increasing trend of the
oxidizing property is Br2>I2>Fe3+>Zn2+, Bromine being the
most effective oxidizing agent whereas Zn is the most
effective reducing agent. In the experimental values, Zinc is
still the most reducing, but between the other 3 ions,
Fe3+>Br2>I2 is the increasing trend of their oxidizing
property which is very different from the theoretical trend.
This indicates error in the experiment.
6. Are values of standard reduction potentials helpful
in determining the spontaneity of a reaction?
The spontaneity of a reaction is given by the negative
change in Gibbs Free energy, the Ecell should be positive.
Because the standard reduction potential are elements of
the Ecell computation, i.e. Ecell = Ecathode- Eanode, so
the values of the standard reduction potential determine
whether a reaction is spontaneous or not.
7. What are the possible sources of errors and their
effect on the calculated parameters? Rationalize.
Errors during the solution preparation may be one possible
error which affects the data collected. Another one is the
conditions in which the experiment was done, it was only
assumed that the standard conditions of 1M, 1 atm and 25
degree Celsius, so these factors can contribute to the
errors. Errors in the multimeter can result in error in the
calculated parameters.
References
[1] Skoog,, Fundamentals of Analytical Chemistry, 8th ed.;
Brooks/Cole-Thomson Learning: California, 2004. Print
[2] UPD Chem 26.1 Analytical Chemistry Laboratory
Manual, Institute of Chemistry, University of the
Philippines, 2017 edition. Print.
[3] Electrolytic Cell (Retrieved July 4, 2017)
http://chemed.chem.purdue.edu/genchem/topicreview/b
p/ch20/faraday.ph Web.