EXPERIMENT 9: DETERMINATION OF ELECTRODE

POTENTIALS

B.F. SOSA and G.P. FORTU

1 1

INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE

1

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES

DATE SUBMITTED: 27 APRIL 2016
DATE PERFORMED: 22 APRIL 2016

ANSWERS TO QUESTIONS ! ( "#$$ 0 ! ( "*+,(&# = ! ( *.(&# ' (3)'

1.! Discuss the differences between
galvanic and electrolytic cells.
Both galvanic and electrolytic cells are
electrochemical cells but there are differences
between these two cells and these are the
following: In a galvanic or voltaic cell which
batteries are made of, stores electrical energy. It
has a reaction between an anode to a cathode
through a spontaneous flow of electrons. It has a
negative electrochemical reaction in Gibbs free
energy but a positive cell potential. While in an
electrolytic cell, which is the reverse of the
galvanic cell, is in need of an outside source of
electrical energy for it to operate. Electricity is
3.! Compare the calculated !%#&
for each
half-cell with their literature value.
The calculated !%#& for zinc half-cell is -1.04V.
Comparing it from the literature value which is -
0.763V, it gave a percentage error of 36.304%. For
the iron half-cell, the computed value is 0.32V
that gave a percentage error of 58.50% comparing
it to its literature value which is 0.771V. For Br#
|Br2|C' half#cell' the' computed' value' is' 0.3273V,'
comparing' it' to' the' literature' value' which' is'
1.09V,' it' gave' a' percentage' error' 69.97%.' Lastly'
for' I |I |C half-cell, the calculated value is
-
2

consumed by the system. It has an endothermic
chemical reaction which is not spontaneous.
2.! What is the measured value of !"#$$ for
each cell and its relevance to the !%#& for
the iron half-cell and halogen half-cells?
0.3027V. Comparing it to its literature value
which is 0.54V, it gave a percentage error equal to
43.96%.
4.! Based on your observations, what are the
half reactions which occur at the anode
and cathode during the electrolysis?

The measured !"#$$ for Fe |Fe half-cell is 0.66V;

3+ 2+
During electrolysis the the half-cell that occurred
for Br#|Br2|C'it'is'0.33'V'and'for'I |I |C it is
-
2 in the anode is the oxidation of halides, this
reaction is between bromine and iodine. This
0.30V. From these data, with the given !%#& of

Cu |Cu, !%#& of for the iron half-cell that works
2+
resulted in a change from a colorless solution to
as a cathode and halogen half-cell that works as a brown colored solution while in the cathode,
an anode, can be calculated with the use of the reduction of water happened showing
equation 1. bubbles that means effervescence.

5.! Based on the calculated values, what are

! ( "#$$ = ! ( "*+,(&# ! ( *.(&# ' (1)' the most effective reducing and
' oxidizing agents?
For'iron'half#cell,'! ( %#& 'can'be'computed'using'
equation'2.' When a reduction potential of a species is more
positive then it is more reduced in the reaction
' that makes it a more effective oxidizing agent
! ( "#$$ + 0 ! ( *.(&# = ! ( "*+,(&# ' (2)' while if the species has a more negative reduction
' potential then it is more oxidized in the reaction
For'halogen'half#cell,'! ( %#& 'can'be'computed' that makes it a more effective reducing agent.
Based on the calculated values from this
using'equation'3.'
experiment, the most effective reducing agent is
Br because it gave a reduction potential equal to
2 a negative standard potential reduction value
0.3273V that is the most positive of the four
values while the most effective oxidizing agent is
zinc which is the only half-cell that gave a
negative reduction potential which is -1.04V.
6.! Are the values of standard reduction
potentials helpful in determining the
spontaneity of a reaction?
In a reaction that gives a more positive standard
reduction potential, it favors the direction of the
formation of products while in a more negative
standard reaction potential, it favors the direction
of the reactants which is the reverse reaction of
the first. Relating the spontaneity of a reaction,
the Gibbs free energy equation is essential.
12 = 0 34! (4)
Relating equation 4, a positive standard
reduction potential means that the electrode on
the right is positive with respect to the electrode
on the left. This results to a negative value of 12
that corresponds to a spontaneous reaction while
if the standard reduction potential gives a
negative value, it indicates that the electrode on
the right is negative with respect to the electrode
on the left. Therefore this reaction states that
oxidation happens on the left and reduction
happens on the right that states a non-
spontaneous reaction. This is the reverse of the
first reaction. Relating this to Gibbs free energy,
results to a positive 12 that indicates a non-
spontaneous reaction.
7.! What are the possible sources of errors
and their effect on the calculated
parameters? Rationalize.
Possible errors in the experiment can be in the
solution preparation. The molarity of the
solutions should be equal to 1M because if not,
the equation E = E will not be valid for
cell
0
cell
calculating the !%#& of the electrodes. This is
(
because ! "#$$ is concentration dependent.
Another is when the multimeter is not checked
before performing the experiment and it gives a
wrong voltage reading that will affect the
calculations since all !%#& is based from the
measured voltage reading of the ! ( "#$$ .
REFERENCES
[1] Skoog, D. (2014). Fundamentals of Analytical
Chemistry. (p. 448-449). Belmont, CA: Brooks
Cole, A Part of Cengage Learning.
[2] Zumdahl, S.S., & Zumdahl S.A. (2012).
Chemistry. (pp.840-841, p.845). Belmont, CA:
Brooks Cole, A Part of Cengage Learning.
[3] Silbeberg, M. (2010). Principles of General
Chemistry. (p.709, p.716). New York, NY: The
McGraw- Hill Companies, Inc.
APPENDIX A: SAMPLE CALCULATIONS

Galvanic cell

Concentrations are 1.0M

0.0592 1.0>
! ( "#$$ = !"#$$ + log '
3 1.0>
(
! "#$$ = !"#$$

Half-cell: Zn2+|Zn&
?@AC1D?: FG HI (*K) + 2M N FG(P) '
@3C1D?:0Q3(P) Q3HI (*K) + 2M N '
FMRR0SM@?ADC3:0Q3(P) + FG HI (*K) Q3HI (*K) + FG(P) '
( ( (
! "#$$ = ! "*+,(&# ! *.(&# '
! ( "*+,(&# 0 ! ( "#$$ = 0 ! ( *.(&# '
0.340 01.38 = XY. Z[\'
|^_`a^b00`cdefd`g_^b0|
Percent'error'=' 0i0100'
+,#(%#+h"*$
(1.04) (0.763)
= 100% = no. nZ[%'
0.763
'
Half+cell:&Fe3+|Fe2+|C&
'
?@AC1D?: 20(4M pI (*K) + M N 04M HI )'
(*K)
@3C1D?:00FG(P) 0FG HI N
+ 2M '
(*K)
FMRR0SM@?ADC3:024M pI (*K) + FG(P) 4M HI (*K) + FG HI (*K) '

! ( "#$$ = ! ( "*+,(&# ! ( *.(&# '

! ( "#$$ + 0 ! ( *.(&# = ! ( "*+,(&# '
0.66q + (0.34q) = Z. nr\'
|^_`a^b00`cdefd`g_^b0|
Percent'error'=' 0i0100'
+,#(%#+h"*$
(0.32) (0.771)
= 100% = st. sZ%'
0.771
'
uvwxyz{v|y}x0~wvv&
&
Half+cell:&Br+|Br2|C&
'
mA'measured'='261'mA'='0.261'A'
Since'Br2(l)'+'2e*' 2S '*(aq),'then'
A 10CRM0H
( N)
H = 0 4 20CRM0M '
q
(.)() 00
( )
() 00
SH = 0 '='8.160010Xp 0>'
.
.H
Ecell0=0Eocell00 log0Q00
.
.H [ ][% ] .H [.]
Ecell0=00.330X0 0log0 00=0000.330X0 0log 00=00.32730V0
H 0% H 0.H00
 |^_`a^b00`cdefd`g_^b0|
Percent'error'=' 0i0100'
+,#(%#+h"*$
(0.3273) (1.09)
= 100% = o. %'
1.09
0
Half-cell: I |I |C
-
2

(.)() 00
( )
( 0 ) 00
SH = 0 '='0.0123>&
.
.H
Ecell0=0Eocell00 log0Q00
.
.H [ ][% ] .H [.]
Ecell0=00.300X0 0log0 00=0000.300X0 0log 00=00.30270V0
H 0% H 0.HpHp
|^_`a^b00`cdefd`g_^b0|
Percent'error'=' 0i0100'
+,#(%#+h"*$
(0.3026) (0.54)
= 100% = [n. o%'
0.54

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