DETERMINATION OF ELECTRODE POTENTIALS

J.G.K.B. CORTEZ1
1

COLLEGE OF PUBLIC HEALTH

UNIVERSITY OF THE PHILIPPINES, ERMITA, CITY OF MANILA 1000, PHILIPPINES
DATE SUBMITTED: JULY 7, 2015
DATE PERFORMED: JULY 14, 2015

ANSWERS TO QUESTIONS
1. Discuss the differences between galvanic and electrolytic cells.
Galvanic cells (also known as voltaic), is a type of electrochemical cell that stores
electrical energy. The most common type of these is batteries. The distinguishing
characteristic of galvanic cells is that the reaction occurring in the electrodes does
not need any external force to happen. Thus, it is spontaneous (Skoog, West, Holler,
& Crouch, 2004). Apart from this, the flow of electrons is observed to be from the
anode, where oxidation occurs, to the cathode, where reduction occurs, thru an
external conductor (Chang, 2010). This means that the negative electrode (anode),
when the cell is discharged, will be the potential source of electrons to the circuit of
the system. It can be noted that due to the spontaneous nature of the cell, the net
reaction during discharged is called spontaneous cell reaction (Skoog, West, Holler, &
Crouch, 2004).
On the other hand, there also exists another type of cell called an electrolytic cell.
This particular type of cell needs an external source of electrical energy to produce
the required reaction between the cells (Skoog, West, Holler, & Crouch, 2004). Apart
from this, the electron flow of electrolytic cells is the opposite of voltaic ones. The
electrons will start from the cathode, and then transfer to the anodes. This is due to
the reversal of reaction in each electrode (Chang, 2010). A good example for this
type of cell would be the process of metal plating (Skoog, West, Holler, & Crouch,
2004).
2. What is the measured value of E cell for each cell and its relevance to the E ored for the
iron half-cell and halogen half-cells?
Table1. Ecell values of each cell
Electrochemical Cell
Ecell
Zinc-Copper Cell
1.08 V
Iron-Copper Cell
0.30 V
Bromine Cell
0.18 V
Iodine Cell
0.007 V
The Ecell will be the used in determining the Ered of the substance being observed
through substitution with equation 1 for standard state conditions and 2 for halide
group cell calculations. Through substitution and manipulation of data and units, E red
has been calculated for the cells (Chang, 2010).

(1)

Ecell =Ecathode E anode

(2)

Ecell =Ecell

RT
ln Q
nF

3. Compare the calculated Eored for each half-cell with their literature value.
Table2.Calculated EOred for each half-cell and their theoretical values
Half Cell

Experimental (V)

Theoretical (V)

2+

Zn |Zn
-0.74
-0.763
Fe3+|Fe2|C
0.64
+0.771
Br-|Br2|C
+1.087
I-|I2|C
+0.536
As the researchers have computed for Zinc and Iron, there are certain discrepancies
with the experimental and theoretical values of the reduction potential. As seen in
table 2, Zinc has a 3.01% error for the experimental value while Iron has 16.99%
error. As the researchers have failed to gather accurate data with respect to Bromine
and Iodine, it has been decided that the theoretical data shall still be put in the table
for reference. It can be seen that Bromine has a high reduction potential. Its half-cell
reaction is readily reduced; therefore it is a good oxidizing agent (Chang, 2010).
Apart from this, Iodine has also shown a positive reduction potential meaning it also
is a good oxidizing agent though not as good as bromine.
4. Based on your observations, what are the most effective reactions which occur at the
anode and cathode during electrolysis?
The most effective reactions are supposed to be with Bromine and Iodine at the
anode which will both show, theoretically, a yellowish color once the current is
passed through. These halides are easily reduced and are seen as good oxidizing
agents. Once electrolysis is done, Bromine and Iodine are readily reduced and will
gain electrons in the process (Blaber, 2010).
5. Based on the calculated values, what are the most effective reducing and oxidizing
agents?
Based on Table 2 in question number 3, we can see that the biggest reduction
potential present in the experiment is from the Br -|Br2|C half cell reaction. Although
the value is theoretical, it is believed to have a reduction potential of +1.087 (Skoog,
West, Holler, & Crouch, 2004). This means that it is the most powerful oxidizing agent
in the group of substances being observed. On the other hand, the table also showed
that Zn2+|Zn half cell reaction has the most negative reduction potential. This shows
that it has a biggest oxidation potential in the group with an experimental value of
0.74 V. Zinc is the best reducing agent among the substances being observed.
6. Are values of standard reduction potentials helpful in determining the spontaneity of
a reaction?
As Skoog, et al. has stated (2004), a positive electrode potential of an
electrochemical cell exhibits a spontaneous reaction with respect to its comparison to
the standard hydrogen electrode half-reaction. A positive electrode potential is
essentially the value of a reduction potential (Chang, 2010). It has the ability to
indicate if the substance has a great tendency to be reduced. As the case of Gibbs
free energy, a positive Eo means the redox reaction will favor the formation of

products at equilibrium. That is, the reaction will display a negative Go

spontaneity (Blaber, 2010).

for

7. What are the possible sources of errors and their effect on the calculated
parameters? Rationalize.
Apart from personal errors during solution preparation, it can be noted that other
factors might affect the calculated parameters of the experiment. One of this is the
possible contamination of another metal to the ion being observed. Contamination
may come from unclean specimen containers or from reusing spatula while
transferring metals. The presence of other metals cans lower or higher the reading
depending on the ions identity (Jenkins, 2007).
The failure of the multimeter can also influence the results of the experiment. This
may stem from the simplest of causes such as the battery shortage. It should be
noted that batteries for digital devices used in the laboratory should be monitored
and safely stored in temperature-stable environments. Apart from battery issues,
product defect may also be considered. Issues regarding knobs, the LED screen, and
open wires should always be taken into account when using the multimeter (Jenkins,
2007).
Also, the researchers should be wary of the placement of cathode and anodes
depending on the cell being used. Electrodes should always be placed in the beaker
in such a manner that it will be submerged in the solution without touching the salt
bridge. Touching the salt bridge may increase the reading due to the interaction with
electrons in the area (Jenkins, 2007).

REFERENCES
Blaber, M. (2010). Sponteneity of Redox Reactions. Retrieved July 8, 2015, from
mikeblaber.org:
http://www.mikeblaber.org/oldwine/chm1046/notes/Electro/Spontan/Spontan.htm
Chang, R. (2010). Chemistry, 10th Edition. In R. Chang, Chemistry, 10th Edition (p.
842). McGraw-Hill.
Jenkins, F. (2007). Nelson Chemistry. Toronto: Thomson Nelson.
Skoog, D., West, D., Holler, J., & Crouch, S. (2004). Fundamentals of Analytic
Chemistry. In S. Kiselica (Ed.). Thomson Learning Academic Resource Center.

COMPUTATIONS
Zn2+|Zn
O

Ecell =Ecathode E anode

O

1.08 V =0.34E anode

EOanode =0.74

Due to the absence of data, the researcher have just decided to put the formula for
halide group EOcell computations in this part of the ATQ.

Ecell =EOcell

RT
ln Q
nF

It can be transformed to this form

HA

0.0592
O
Ecell =Ecell
log
n
wherein

HA

moles

HA
L of sample solution
Total HA

molesunreacted

and

1 mole HA 2
e
2 moles e
1 mole

96500 C L of sample solution

C
Amperes
Time( s)
s
[ HA 2 ]=

( )