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Conor Linehan

Phillip Cox
2-10-15
Lab 3: Electrochemistry

Introduction:
The concepts that we focused on during this lab were mostly related to electrical half-cell
reactions and the new topic of overpotential. By creating our own half-cells and
measuring the different combinations of cell potentials, my lab partner and I reinforced
our understanding of basic electrochemistry. This lab also provided an inside look into
the topic of overpotential, which is defined as the loss of thermodynamic potential
necessary for a certain reaction to occur at a finite rate. The main equations that we used
for the lab/write up include the Nernst Equation: E cell = Ecell (.0592/ne-)log(Q) which
defines reduction potential of a half cell, and the Overpotential Equation: = - rev
( variables referring to the potential difference across an electrode during a flowing
current vs no flowing current respectively).

Procedure:
The lab began by completing step 3A of the procedure. A Cobalt Phosphate water
oxidation catalyst was grown by placing an FTO glass slide in a growth solution along
with a platinum wire. The growth solution included 19.5 mL of pH 7 buffer added with .5

mL of Cobalt solution. Electrolysis of this cell was then carried out at 1.49 V for
approximately one hour.
During the growth of the catalyst, the next part of the experiment was carried out.
Five pieces of dialysis film were cut and soaked in water. Then, using these squares of
dialysis film, along with glass tubes and rubber bands, five electrochemical cells were
created. These cells included metal nitrate solutions along with metal electrodes that
corresponded to each type of metal nitrate. The metal nitrates used were: 1M Ag(NO3)2,
1M Zn(NO3)2, 1M Pb(NO3)2, 1M Cu(NO3)2, and 0.1M Cu(NO3)2. The bottoms of the
five half-cells were then placed in a 1M KNO3 solution which was used as a salt bridge.
Cell potentials for each pair of half-cells were then measured using a fluke multimeter.
Then, using our results from the half-cell measurements, part 2 of the lab was completed.
This was done by using the Nernst Equation to determine the proper reaction quotient of
half-cells 4 and 5 that would yield a cell potential of .5V.
Part 3 of the lab was done by measuring the potential required to drive water
oxidation. The data for the control FTO slide was measured first. The control slide and a
platinum wire were inserted in a pH 7 buffer solution and the cell was prepared for
electrolysis. The voltage was then slowly increased until bubbles were seen forming on
the glass slide. These steps were repeated for the slide containing the pre-grown catalyst
and the slide containing the catalyst that was created at the beginning of the experiment.

Results:
Table 1 below shows the measured cell potentials from part one with respect to the AgCl
reference electrode and also with respect to the NHE (since all of the reactions were
spontaneous, a few of the reactions needed the electrodes switched to get positive
Cell
Connecte
d to the
Black
Electrod
e

Cell
Potenti
al: Trial
1 (vs
AgCl)
(V)

Cell
Potenti
al: Trial
2 (vs
AgCl)
(V)

Trial 1
Value
s (vs
NHE)
(V)

1 Reference

0.53

0.545

0.727

0.742

0.741

0.742

0.544

0.545

3
4 Reference
cell potential) :

0.377
0.133

0.378
0.133

0.180
0.330

0.181
0.330

Cell
Connecte
d to the
Red
Electrode

Reference
Reference

Trial 2
Values
(vs
NHE)
(V)

Averag
e (vs
NHE)
(V)

Standard
Deviation
(vs NHE
data)
0.005303
0.7345
0
0.000353
0.5445
5
0.000353
0.1805
5
0.330

The standard half-cell reactions are the following (not included in table above due to spacing):

1)
2)
3)
4)

Ag+ + e- -------> Ag(s) (Ecell = .7996 V) -------> % error = 8.14%


2: Zn(s) -------> Zn2+ + 2e- (Ecell = .7628 V) -------> % error = 28.6%
Pb(s) -------> Pb2+ + 2e- (Ecell = .1263 V) -------> % error = 42.9%
Cu+2 + 2e- -------> Cu(s) (Ecell = .3402 V) -------> % error = 3.0%

Cell Connected
to the Red
Electrode

Cell Connected
to the Black
Electrode
3
1

Cell
Cell
Potential:
Potential:
Trial 1(V)
Trial 2 (V)
2
0.291
0.31
2
1.284
1.273

1
3
0.453
0.436
1
4
0.411
0.413
4
2
0.868
0.871
4
3
0.513
0.514
4
5
0.046
0.047
Table 2 shows the results of our combination of half cells in part 2 in order to determine
which pair of half-cells had a potential that was closest to .50 V (This was determined to
be between half-cells 3 and 4):

Trial 1
Voltage
Applied
(vs Pt)
(V)

Trial
3
Trial 2 Volta
Volta
ge
ge
Appli
Applie ed
d (vs
(vs
Pt)(V) Pt)(V)

Avera
ge
Voltag
e (vs
NHE)
(V)

Average
Standard
Voltage
Deviatio
Electrode
(vs Pt)
n (vs
Used
(V)
NHE)
Bare FTO
3.232333
0.020404
Electrode
3.21
3.25 3.237
333
3.651
248
Pre-grown
2.602666
0.107150
Electrode
2.678
2.65
2.48
667
3.022
984
After carrying out the dilution process using the results of my Nernst Equation
calculations (see calculation page), we measured the potential between half-cells 3 and 4
to be .484V.

Table 3 dictates the data from the third part of the lab in which a voltage was applied to
each certain type of electrode until bubbles were seen forming on the glass slide (includes
raw data and average converted to NHE). We were not able to measure the data for our
grown catalyst because of an electrical problem related to our alligator clips:

Avera
Overp
ntial
NHE)

The class averages of the overpotential for each kind of electrode are shown bellow:

Electrode
Type
FTO
Grown in
Lab
Pre-grown

Standar
d
Average
Deviatio
Voltage
n of
Average
Applied
Ave.
Overpoten
(V)
Voltage
tial (V)
3.082
0.446
2.272
2.665
2.606

0.431
0.617

1.854
1.796

Standard
Deviation of
Overpotenti
al
0.446
0.431
0.617

The following graph plots the class average for overpotential along with my own
recorded overpotentials on the pre-made plot given in the Kannan and Nocera paper:

0
-0.5

0.5

1.5

2.5

-1
-1.5
-2
log(A/cm2)

-2.5

-3

-3

-3

Nocera Values
Class Average Values
Our Group's Values

-3.5
-4
-4.5
-5
Overpotential (V)

Discussion:
For part 1 of the lab, my data can be compared to the standard half-reactions with respect
to the NHE. All of my results excluding zinc were less than .1 V away from the standard
values. This shows that my results for Ag, Pb, and Cu were moderately close to the
accepted values (even though the percent error for Pb seemed high since the cell potential
is a small number). However, my value for the zinc reaction was significantly different
from the standard value (difference of .25 V). This could be due to the fact that one of our
half-cells was leaking during the lab and we never were able to figure out which one was
leaking. Otherwise, it could be due to experimental error in our measurements or our
execution of the procedure.
For part 2 of the lab, we tested several pairs of half-cells for the spontaneous reactions
between them in order to determine which pair of half-cells that had a cell potential
closest to .50 V. After determining that the reaction between Pb and Cu would be best, my

lab partner and I used the Nernst Equation to calculate the proper dilution of the Cu
solution in order to yield a cell potential of .5 V. However, after completing this process,
the cell we constructed had a cell potential reading of .484 V. This value was lower than
we expected. The deviation from the expected value of .50 V could have come from a
possible leak in the half cells that we were using. It also could have been because of
experimental error in the dilution process since we were using a relatively small quantity
of solution.
For part 3 of the lab, our lab group was only able to measure data for the bare FTO slide
and the pre-grown slide because of an electrical problem with the alligator clips. Due to
this complication, we were not able to grow our own catalyst. The data that we were able
to collect, along with the class averages that have been taken from the online posting
board, seemed to show less effective results than the Nocera paper. Essentially, our
catalysts were proven to be not as effective. This is because the catalysts used in the
Nocera paper had much more time to grow (7-8 hours). In addition, many of our pregrown catalysts had already been used by other groups in our lab section due to time
constraints. Since the effectiveness of the catalysts slowly decrease after each time they
are used, by the time we were able to collect our own data, the efficiency of the pregrown catalysts had decreased. However, our data in general makes sense because the
overpotential needed by the slide with the catalyst was less than the overpotential needed
for the bare FTO slide. This shows that the catalyst reduced the activation energy needed
for the electrolysis of water. A final factor to consider with regards to error is the fact that

we were basing our calculations off of when we saw bubbles forming, which can be very
hard to see.
The additional calculations required are shown on the calculations page and are discussed
in the conclusion.

Conclusion:
In conclusion, we found that the addition of a catalyst to an electrochemical reaction can
greatly decrease the activation energy needed to start the reaction. Our data supports this
claim, even though our catalysts were proven to be not as effective as the catalysts in the
Nocera paper. These results correspond to the first additional problem since we calculated
that the slide with a catalyst showed a 15.44% increase in efficiency in terms of the
activation energy needed to start the electrolysis reaction. This kind of electrochemistry is
used in real world situations similar to the second extra problem. This lab also confirmed
the claim that the Nernst Equation can be manipulated to yield a desired cell potential (as
seen in part 2).

Calculations page:

Converting AgCl values to NHE values:


.545 + .197 = .742 V (since the reduction potential of AgCl is .197 and it
was at the cathode for this situation)

Percent error:
(.7996-.7345) / .7996 = 8.14% error

Nernst Equation calculation used in part 2 for dilution:


Ecell = Ecell (.0592 / n) log(Q)
.5 = .513 [(8.3145 273) / (2 96485)] log(Q)
Q = [Oxidized] / [Reduced] = 2.77
1 / 2.77 = .361
1M .001L = .001n
.001 / .361 = final volume of Cu solution using 1 mL of solution and the
rest being water
1 mL of 1M Cu added to 1.77 mL water

Calculation of Pt Potential at pH 7:
Ecathode = 0.00 (.0592V / 2) log(1 / (107)2)
Ecathode = -.414V So we subtract this value from our electrolysis data to
convert to NHE data since the reaction is flipped (at the anode)
Extra Problem 1: Efficiency
(3.082 / 2.606) / 3.082 = 15.44% improvement

Extra Problem 2: Solar Power


(40.5 mA / 1 cm2) (10,000 cm2 / 1 m2) 5 m2 = 2025 A
(1 cm2 / .001A) 2025 A (1 m2 / 10,000 cm2) = 202.5 m2