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de Guzman, Emyli Ruth A.

Macapagal, Diana Marie V.


Yorobe, Marian Justine H.

Chem 157.1 | FEJ


May 11, 2015

Results
A. Determination of Electrode Potentials
Cathode: Cu2+ + 2e- Cu (s) cell=0.34 V

A
B
C
D

Test
electrode
Zn l Zn2+

Reduction Half-Reaction
Zn2+ + 2e- Zn (s)
Pb2+ + 2e- Pb (s)

2+

Pb l Pb
C l Fe2+,
Fe3+
Pb l
PbSO4(s),
SO42-

Fe3+ + e- Fe2+
PbSO4(s) + 2e- Pb (s) +
SO42-

Table 1 Reduction Half-Reactions of Test Electrodes

Test
electrode
A
B
C
D

cell
(V)
1.072
0.423
-0.413
0.562

anode
(V)
-0.732
-0.083
0.753
-0.222

Theoretical
Value
-0.7618 V
-0.1265 V
0.771 V
-0.3546 V

Table 2 Computed theoretical values of test electrodes

Sample computation:
cell = cathode - anode

B. Electromotive Force of Galvanic Cells

Zn l Zn2+
C l Fe2+, Fe3+
C l Fe2+, Fe3+
Pb l
PbSO4(s),
SO42-

Anode
Pb l
Pb2+
Zn l
Zn2+
Pb l
Pb2+
Zn l
Zn2+

Cell B: Zn l Zn2+ ll Fe2+ l Fe3+ l C


Anode: Zn (s) Zn2+ + 2e= -0.7618 V
Cathode: 2(Fe3+ + e- Fe2+)
= -0.771 V
Cell: Zn (s) + 2 Fe3+ 2Fe2+ + Zn2+
theo = -0.771 V (-0.7618 V) = 9.2 x 10-3 V
obs= 1.454 V
Cell C: Pb l Pb2+ ll Fe2+ l Fe3+ l C
Anode: Pb (s) Pb2+ + 2e= -0.1265 V
Cathode: 2(Fe3+ + e- Fe2+)
= -0.771 V
Cell: Pb (s) + 2Fe3+ Pb2+ + 2 Fe2+
theo = -0.771 V (-0.1265 V) = -0.6445 V
obs= 0.805 V
Cell D: Zn l Zn2+ ll PbSO4(s), SO42- l Pb
Anode: Zn (s) Zn2+ + 2e= -0.7618 V
Cathode: PbSO4(s) + 2e- Pb (s) + SO42- =
0.3546 V
Cell:PbSO4(s) +Zn(s) Pb (s) + SO42- + Zn2+
theo = 0.3546 V(-0.7618V) = 1.1164 V
obs= 0.497 V

For Zn l Zn2+ ll Cu2+ l Cu


1.072 V =0.34 V - anode
anode = -0.732 V

Cathode

theo = 0.7618 V (-0.1265 V) = 0.8883 V


obs = 0.621 V

theoretical
(V)

observed
(V)

0.8883

0.621

9.2 x 103

1.454

-0.6445

0.805

1.1164

0.497

Table 3 Theoretical and Observed cell values for coupled


electrodes

Cell A: Pb l Pb2+ ll Zn2+l Zn


Anode: Pb (s) Pb2+ + 2e= -0.1265 V
Cathode: Zn2+ + 2e- Zn (s) = 0.7618 V
Cell: Pb (s) + Zn2+ Zn (s) + Pb2+

C. Variation of Electrode Potential with


Concentration
[MnO [Mn2+ Log([MnO
mixture
cell
44]
]
]/[Mn2+])
5.0 x
1.0 x
0.87
1
0.69897
10-4
10-4
7V
5.0 x
2.0 x
0.87
2
0.39794
10-4
10-4
9V
1.0 x
3.0 x
0.94
3
-0.47712
10-4
10-4
8V
1.0 x
4.0 x
0.97
4
-0.60205
10-4
10-4
8V
Table 4 Computed Values of Concentrations and cell for
mixtures

7.5 x 10 mol MnS O4


Thus, NaC2O4 is the limiting reactant.
Final concentrations:
[MnO4-] = 7.0 x 10-4 - 2.0 x 10-4 = 5.0 x 10-4 / Vsoln
[Mn2+] = 2.0 x 10-4/ Vsoln
log([MnO4-]/[Mn2+]) = log (5.0 x 10-4/2.0 x 10-4) =
0.39794
MnO4- + 8H+ + 5e- Mn2+ + 4H2O
Nernst Equation:
cell = - (0.05916/n) log[Mn2+]/[MnO4-][ H+]8

Figure 1 Plot for cell vs. log([MnO4-]/[Mn2+])

Sample Computation:
5(C2O42- 2CO2 + 2e-)
2(MnO4- + 8H+ + 5e- Mn2+ + 4H2O)
5C2O42- + 2MnO4- + 16H+ + 10e- 10CO2+ 2Mn2+
+ 8H2O + 10e5 NaC2O4 + 2KMnO4 + 8H2SO4 12MnSO4 +
K2SO4 + 5NaSO4 + 8 H2O +10CO2

cell = - (0.05916/n) {(log[Mn2+]/[MnO4-])


-log[ H+]8}
= - (0.05916/n) {log([MnO4-] /[Mn2+])-1 +
8pH}
= + (0.05916/n) log([MnO4-] /[Mn2+]) (8)
(0.05916/n) pH
y = cell
m= (0.05916/n)
x = log ([MnO4-] /[Mn2+])
b = - (8)(0.05916/n) pH
Through linear regression of Figure 1:

For Mixture 2:
First, the limiting reactant is determined by
computing the number of moles for the product,
MnSO4.

0.035 L x 0.02

mol KMn O4 2 mol MnS O4


x
1L
2 mol KMn O4

7.0 x 104 mol MnS O4

0.010 L x 0.05

mol Na C2 O4 2 mol MnS O4


x
1L
5 mol Na C2 O 4

slope = -0.076526 = (0.05916/n)


y-intercept = 0.920839 = - (8)(0.05916/n) pH
cell = -0.076526 log ([MnO4-] /[Mn2+]) + 0.920839
D. Determination of Solubility Product Constant
Pb I Pb2+ II PbSO4(s), SO42- I Pb
Anode: Pb(s) Pb2+ + 2e= -0.1265 V
Cathode: PbSO4(s) + 2e- Pb(s) + SO42- =
0.3546 V
Cell Reaction: PbSO4(s) = Pb2+ + SO42cell= 0.3546 V-( -0.1265 V) = 0.4811 V

2.0 x 104 mol MnS O4

0.005 L x 6

mol H 2 S O4 2 mol MnS O 4


x
1L
8 mol H 2 S O4

Ksp = [Pb2+][ SO42-] = 1.6 x 10-8


Ksp from cell= 1.84 x1016
Measured cell potential: -0.104 V
Ksp from experimental data = 3.049 x 10-4

Sample Computations:
G = - RT ln K
ln K = (G/ -RT) = (-nF cell/ -RT) = (-n 96485
cell/ -8.314 x 298.15)
log K = (ncell/0.05916)
K = 10 ^ (ncell/0.05916)
Ksp = 10 ^ (2 x (-0.104)/0.05916)
Ksp= 3.049 x 10-4
Discussion

At the standard condition, Equation 1 becomes:


G = -RT ln Keq

Reactions such as oxidation and reduction are


characterized by a transfer of electrons. These
reactions can be carried in two ways: (1) the
oxidizing specie and the reducing specie are put
in contact with each other and (2) the species are
separated into two electrode compartments.
These are called electrochemical cells which are
typically comprised of the following: two
electrodes, or metallic conductors, and two
electrolytes which may be a solution, a liquid or a
solid. When they are physically separated in
different cells as in the second type, a salt bridge
is used to complete the circuit. The salt bridge is
a tube containing a concentrated electrolyte
solution such as KCl in agar jelly which enables
the circuit to function. The electrodes, the anode
and the cathode, are connected to or dipped into
the respective electrolyte (Atkins).
The reaction involved in electrochemical cells
occurs in the cathode and the anode where the
process of reduction and oxidation occurs,
respectively. Redox reaction happens as the
electrons travel from one cathode to another. This
reaction can be expressed and represented by
two reduction half-reactions, as seen in Table 1,
which show the transfer of electrons (Atkins).
There are two types of electrochemical cells: an
electrolytic cell and a galvanic cell.
The
electrolytic cell uses an external source of current
to drive a non-spontaneous reaction. On the
other hand, a galvanic cell is able to produce
electricity spontaneously (Atkins). Electrons
flowing from the anode into the cathode react
with the oxidized specie to form the reduced
specie. As the electrons travel, the potential
difference can be measured between the two
electrodes and is given by the cell, a measure of
spontaneity of the reaction as in:
G = -nFcell

In measuring the potential of any cell, it is


important to measure its electrode potential
against a standard hydrogen electrode or SHE at
a standard thermodynamic condition whereas the
pressure and temperature correspond to STP, 1
atm and 298 K, and the solute concentration is 1
M.

(Equation 1)

(Equation 2)

When
such
conditions
occur,
several
thermodynamic
quantities
can
now
be
determined such as free energy, activity, entropy
and enthalpy (Standard Electrode Potentials).
Galvanic cells, as the focus the experiment, could
be further classified into electrolyte concentration
cells and electrode concentration cells. In an
electrolyte concentration cell, the concentration of
the electrolytes is different but their electrode
compartments are identical. In an electrode
concentration cell, the electrodes differ in
concentrations since they may be gas electrodes
operating at different pressures or amalgams,
solutions in mercury, with varying concentrations.
Another difference between the two types is that
a liquid junction, to be further explained later, is
always present in an electrolyte concentration cell
and the electrode concentration cell has none
(Atkins).
The simplest setup for a cell has only one
electrolyte common to
both the anode and the
cathode. Other setups
require the use of two
different
electrolytes
with
electrodes
immersed
in
both
solutions. The Daniel
cell is an example of
such
wherein
one
electrode is Cu2+/Cu and
the other is Zn2+/Zn
Figure 2 Cell with one
(Atkins).
electrolyte for both
anodes

equilibrium lie to the left of the reduction reaction.


Electrons are more readily released from the
electrode as compared to hydrogen and thus, a
stronger reducing agent. A more positive value
results in the opposite, the equilibrium lies to the
right and a less likely donation of electrons
making it a comparably stronger oxidizing agent
("Making Predictions using Redox Potentials
(Electrode Potentials)", n.d.).

Figure 3 Daniel Cell

The setup in the experiment involved the use of


two compartments with two different electrolytes
with their corresponding electrodes immersed in
them. In part A, the measurement of the electrode
potentials of the test electrodes were carried out
appropriately at the standard state using a
reference solution of Cu|Cu2+. The cathode of the
voltmeter is attached to the reference and the
anode to the respective test electrode. At the
absence of a liquid junction, as in the setup
described, the cell potential is measured as the
difference of the cathode half-cell potential and
the anode half-cell potential.
cell = cathode - anode

(Equation 3)

These values are expressed in terms of standard


reduction potentials. The absolute electrode
potentials are impossible to determine because
oxidation and reduction occur simultaneously.
The potential difference is the main interest for
this part of the experiment and since a reference
of known potential was used, the potential
measured by the voltmeter is due to the
electrode's potential alone. As seen in Table 2,
there is a difference in the computed values of
the electrode potentials as compared to their
theoretical values. This discrepancy can be
accounted for by the fact that the standard
electrode may not have properly achieved the
standard state.
The standard electrode potential is an extensive
property and no change in the amount of matter
will affect its value but altering the temperature or
concentration may affect it. Two things may be
known of the electrolytes involved. One of which
is its ability to lose its electrons and the other, the
relative position of equilibrium in their respective
reduction reactions. Relative to the hydrogen
equilibrium, the more negative the value of the
electrode potential the further does the

In the second part of the experiment, the test


electrodes measured from the previous part are
coupled with each other to measure the
electromotive force of each coupled cell. In this
case, two different electrolytes are involved and a
liquid junction is used as an additional source of
potential difference across the two electrolytes
where the liquid potential, Eij, will move across. A
physical example of a liquid junction is the salt
bridge, as in the experiment done. It is necessary
to use a salt bridge especially when the two
electrolytes in contact with each other react. The
two solutions in contact with each other are
placed in individual containers and diffusion of
ions occurs between them. The potential
eventually settles down to a certain value when
the ions diffuse at the same rate but this
equilibrium is not completely achieved since
diffusion always occurs at the liquid junctions and
contributes to the potential or electromotive force,
emf. This unknown amount of contribution is often
small. Cells with liquid junctions are dependent
on the activities of ions and thus ions are used to
represent these cells (Alberty).
Electromotive force (EMF) is defined as the
maximum potential difference between two
galvanic or voltaic cells which demonstrates the
propensity of a metal, compound or ion to release
electrons. Galvanic cells are composed of two
different metals as electrodes where the half-cells
are connected by a salt bridge, in this experiment
a filter paper soaked in KNO 3. The emf is used to
describe the spontaneity of reversible reactions
while the potential differences are for irreversible
reactions. EMF can be measured using a
voltmeter while the theoretical standard cell
potential, E can be measured through the
subtraction of the established standard reduction
potential values of the two half cells, E. In this
experiment, only the theoretical value of the
standard cell potential for cell C showed a
negative value which indicates that the forward
reaction is not spontaneous; a positive sign
indicates a spontaneous reaction (Electromotive
Force, n.d.).

The solubility product, Kc, for the reaction can be


derived from the Nernst equation,

(Equation 4)
where Qc = Kc and at equilibrium E=0,

rearranging,

however, be compared with the theoretical value


of the y-intercept without identifying the pH of the
solution (The Nernst equation, n.d.).
References
Alberty, A. et al. (2005). Physical Chemistry. US:
John Wiley & Sons, Inc.
Atkins, P. and De Paula, J. (2006). Physical
chemistry. US: WH Freman
Electromotive Force (n.d.) Retrieved from:
http://www.science.uwaterloo.ca/~cchieh/cact/c12
3/emf.html

(Equation 5)
The Nernst equation is also used to describe the
effect of the variation of electrolyte concentration
in the electrode potential. The resulting plot in
Figure 1 follows the Nernst equation since when
the plotted points are substituted to the line
equation formulated from linear regression, the
results only differed a little at the hundredths unit
as compared to the values measured in the
experiment.
On the other hand, the y-intercept, b = - (8)
(0.05916/n) pH, depends on the pH of the
solution or the concentration of H + ions. It cannot,

"Making Predictions using Redox Potentials


(Electrode Potentials)". (2013) Retrieved from:
http://www.chemguide.co.uk/physical/redoxeqia/p
redict.html
Standard Electrode Potentials. (n.d.) Retrieved
from:
http://hyperphysics.phyastr.gsu.edu/hbase/chemical/electrode.html
The Nernst equation (n.d.) Retrieved from:
http://www.bris.ac.uk/physpharm/media/plangton/ugteach/ugindex/m1_inde
x/med_memb/file/Nernst1.htm