Supriya Dublish

Jeremy Lehrer/Phil Cox (Section AB)

February 12, 2013
Electrochemistry and Overpotential of Electrolysis of Water
Introduction:
In this lab, we looked at both the properties of galvanic and electrolytic cells. For the first part,
we looked at the relative voltage created between various half cells, as well as looking at the
voltage in comparison to the Ag/AgCl standard electrode to get a sense of the absolute voltage.
The equation for the reduction is:
AgCl (s) + e-Ag (s) + ClThese values will be later converted to the NHE (normal hydrogen electrode, which is the
standard for electrochemical reactions) values with the use of this equation:
Ecell = Ecathode - Eanode
When Ecathode is the value of the reduction half-cell and Eanode is the value of the oxidation halfcell. In order to convert from the AgCl reference to NHE, the equations:
Ecell + .2223 = Ecathode
or
Eanode = .2223 - Ecell
Will be used, depending on whether AgCl is the cathode (first equation) or the anode (second
equation), since the standard reduction potential of AgCl in NHE is .192 V.
After testing all combinations of half cells and determining the electrochemical reaction which
has a voltage closest to .5 V, the Nernst equation:
Ecell =Ecell

.0592
logQ
n

When n represents the number of moles of electrons being transferred, Q represents the reaction
quotient for the cell reaction, and the reaction is happening at standard temperature and pressure,
can be used in order to determine what the molarities of the metal ion solution needs to be made
to get the above value.
The second part of the lab focuses on the overpotential of the electrolysis of water. The
electrolysis of water is governed by two equations:
2H3O+ + 2e- H2 (g) + 2H2O; Ecathode = 0 V
3H2O .5 O2 (g) + 2H3O+ + 2e- ; Eanode = 1.229 V

Overpotential is calculated with the equation:

= rev
When

represents the voltage needed experimentally (when current is flowing) and

rev represents the voltage calculated experimentally (when current is not flowing).
Overpotential is caused when more energy is required for a reaction than what would be
expected theoretically, which is usually because a reaction is hard to do on a kinetic level. This
lab examined the effects of using a cobalt catalyst on the overpotential of the electrolysis of
water, to see if it would be easier to electrolyze if the catalyst is present. A catalyst helps increase
the rate of reaction by providing another pathway for the reaction to occur, lowering the
activation energy and making it more likely for the reaction to happen.
Procedure:
Part 1: Growing Cobalt Catalyst
I took one FTO slide and submerged it in a .5 mM Co2+ solution which I diluted with pH
7 buffer from the provided 20 mM solution. Then, I added enough Co2+ solution so that it covered
both the platinum electrode and around 1 cm2 of the FTO slide. The FTO slide was connected to
the positive electrode while the platinum wire was connected to the negative electrode. The
voltage was set to 1.50 V and was let to run for around an hour. If the procedure worked, a dark
coat of cobalt catalyst will start to form on the slide.
Part 2: Determining Standard Potentials of Cells
We cut up 6-8 pieces of dialysis film and soaked them in 1 M KNO3 for around five
minutes. Then, I attached them to the bottom of open-bottomed tubes, stretched tightly, with
rubber bands. After testing for leaks, I assembled the tubes with the appropriate metal ion
solution and electrode according to the table below:
Half Cell
Metal Electrode
Metal Ion Solution
1
Ag
1.0 M AgNO3
2
Zn
1.0 M Zn(NO3)2
3
Pb
1.0 M Pb(NO3)2
4
Cu
1.0 M Cu(NO3)2
5
Cu
.1 M Cu(NO3)2
I made sure there was enough metal ion solution to cover the end of the electrode, and that the
electrode was not touching the bottom the film. I got one more tube, the Ag/AgCl reference
electrode, which was taken from class supplies. Then, I put all the tubes into a specimen jar and
added enough 1 M KNO3, which was serving as our salt bridge, so that it was around 2 cm deep
in the jar. Then I recorded the voltage using the multimeter between the five made half cells and
the reference electrode, as well as between all made half cells (1/2, 1/3, 1/4, etc). I recorded the
cathode and anode for each reaction as well as the positive voltage.

With the above data, I picked the reaction which was the closest to .50 V and used the Nernst
equation to figure out which of the solutions I needed to dilute in order to get the expected value.
I then measured then voltage between the two half-cells and recorded the data.
Part 3: Electrolysis of Water
After removing the FTO we attempted to create catalyst on, I placed the electrode and the
FTO slide with no catalyst into the pH 7 buffer, in the same formation as mentioned above (FTO
connected to electrode side and platinum wire connected to negative electrode). In addition, I
connected the Fluke multimeter to the set up in order to get a more accurate reading of the
voltage being run through the system. I slowly raised the voltage, waiting a minute or so in
between, until the first bubbles appeared, indicating that electrolysis was successful. I repeated
this a total of three times for the clear FTO slide, the pre-grown catalyst, and the catalyst made in
Part 1, recording the voltage on the Fluke multimeter each time.
Results:
Reduction Half Cell

Oxidation Half Cell

Trial 1

Trial 2

Ag/AgNO3
Ag/AgCl
Ag/AgCl
Cu/Cu(NO3)2 (1 M)
Cu/Cu(NO3)2 (.1 M)
Ag/AgNO3

Ag/AgCl
Zn/Zn(NO3)2
Pb/Pb(NO3)2
Ag/AgCl
Ag/AgCl
Zn/Zn(NO3)2

.540 V
.640 V
.352 V
.139 V
.098 V
1.165 V

.536 V
.637 V
.352 V
.136 V
.095 V
1.167 V

Reduction Half Cell

1
Ag/AgCl
Ag/AgCl
4
5
1

Oxidation Half Cell

Ag/AgCl
2
3
Ag/AgCl
Ag/AgCl
2

Trial 3

Average
(V)

Standard
Deviation
(V)
0.002
0.002
0.000
0.002
0.002
0.004

.537 V
0.538
.641 V
0.639
.352 V
0.352
.135 V
0.137
.096 V
0.096
1.172
1.168
V
Ag/AgNO3
Pb/Pb(NO3)2
.897 V
.896 V
.895 V
0.896
0.001
Ag/AgNO3
Cu/Cu(NO3)2 (1 M)
.394 V
.392 V
.392 V
0.393
0.001
Ag/AgNO3
Cu/Cu(NO3)2 (.1 M)
.433 V
.430 V
.430 V
0.431
0.002
Pb/Pb(NO3)2
Zn/Zn(NO3)2
.277 V
.272 V
.283 V
0.277
0.006
Cu/Cu(NO3)2 (1 M)
Zn/Zn(NO3)2
.726 V
.722 V
.727 V
0.725
0.003
Cu/Cu(NO3)2 (.1 M)
Zn/Zn(NO3)2
.724 V
.741 V
.744 V
0.736
0.011
Cu/Cu(NO3)2 (1 M)
Pb/Pb(NO3)2
.498 V
.498 V
.498 V
0.498
0.000
Cu/Cu(NO3)2 (.1 M)
Pb/Pb(NO3)2
.460 V
.460 V
.460 V
0.460
0.000
Cu/Cu(NO3)2 (1 M) Cu/Cu(NO3)2 (.1 M)
.031 V
.032 V
.031 V
0.031
0.001
Table 1: Calculated Ecell potentials for the various electrochemical reactions, along with their
standard deviations and averages. Because lack of space, the conversion of the Ag/AgCl
reduction potentials to NHE is in Table 3.
Overall Cell Equation
Ag+ + Cl- AgCl (s)
2 AgCl (s)+ Zn (s) 2 Ag (s) + 2 Cl- + Zn2+
2 AgCl (s)+ Pb (s) 2 Ag (s) + 2 Cl- + Pb2+
Ag (s) + Cu2+ + 2Cl- AgCl (s) + Cu (s)
Ag (s) + Cu2+ + 2Cl- AgCl (s) + Cu (s)
2 Ag+ + Zn (s) Zn2+ +Ag (s)

1
3
2 Ag+ + Pb (s) Pb2+ +Ag (s)
1
4
2 Ag+ + Cu (s) Cu2+ +Ag (s)
1
5
2 Ag+ + Cu (s) Cu2+ +Ag (s)
3
2
Pb2+ + Zn (s) Zn2+ + Pb (s)
4
2
Cu2+ + Zn (s) Cu2+ + Pb (s)
5
2
Cu2+ + Zn (s) Cu2+ + Pb (s)
4
3
Cu2+ + Pb (s) Pb2+ + Cu (s)
5
3
Cu2+ + Pb (s) Pb2+ + Cu (s)
5
4
Transfer of electrons to create charge
Table 2: Overall cell reaction for various electrochemical reactions. The ions only part of the
oxidation and reduction reaction are included. For the last equation, the same molecules are used
in both sides, with the molarities only differing; the only way the charges are created are by a
transfer of electrons not necessarily governed by a simple reaction law. See Procedure to see
what half-cell is represented by each number.
Half Cell

Potential based off

Reduction potential Standard reduction
AgCl (V)
based off NHE (V)
potential (V)
Ag/AgNO3
0.538
.760
.7996
Zn/Zn(NO3)2
0.639
-.417
-.7628
Pb/Pb(NO3)2
0.352
-.130
-.1263
Cu/Cu(NO3)2 (1 M)
0.137
.360
.3402
Cu/Cu(NO3)2 (.1 M)
0.096
.319
.3106
Table 3: Conversion of Ag/AgCl potential to NHE reduction potential. Standard reduction
potentials are based off Appendix E in Oxtoby. The average values of the AgCl/ metal ion
potential were used in this table for the conversion. It is not called the reduction potential is not
all metal ions were acting like a cathode in the given reaction. To determine the NHE reduction
potential of the fifth reaction (Cu/Cu(NO3)2 (.1 M) ), the Nernst equation was used.
Reaction closest to .5 V
Cu2+ + Pb (s) Pb2+ + Cu (s)
[Pb2+]
.856 M
[Cu2+]
1M
Voltage of Nernst Equation
.5 V
Table 4: The equation of the reaction used in Part II of the experiment, as well as the new
molarities calculated by the Nernst equation to get the correct value. The work for this table is in
Calculations
Type of FTO slide
No catalyst (group)

Trial 1
2.301 V

Pre-grown catalyst (group)

1.861 V

No catalyst (class)
Pre-grown catalyst (class)
Lab-grown catalyst (class)

----

Trial 2
2.191
V
1.667
V
----

Trial 3
2.257 V

Average
2.250 V

Standard Deviation
.055 V

1.810 V

1.779 V

.101 V

----

2.277 V
1.868 V
1.826 V

0.196 V
0.251 V
0.260 V

Table 5: Combination of class and group data about voltage needed for electrolysis to happen, as
well as standard deviation. During our experiment, the catalyst was unable to grow, and with the
approval of the TA, we only used the pre-grown catalyst.
Theoretical Voltage of Electrolysis at NHE
1.229 V
Theoretical Voltage of Electrolysis at pH=7
1.229 V
Overpotential without catalyst (group/class)
1.021 V
1.048 V
Overpotential with pre-grown catalyst (group/class)
.550 V
0.597 V
Overpotential with lab-grown catalyst (class)
0.639 V
Table 6: Voltage of electrolysis under standard conditions as well as pH = 7, as well as the
overpotentials based off the results in Table 5. To calculate the overpotential, the voltage at pH=7
was subtracted from the average voltage needed for electrolysis to happen.

Figure 1: The comparison of the data found in the Nocera paper (Science v.321 p.1072-1075)
with the class data. The Nocera paper was plugged in by hand, with the values determined by
visual analysis. The class data (FTO, Grown in Lab, and Pre-grown) of overpotentials was
determined by the average of the values posted on GoPost. The standard deviation was
calculated in a similar manner. The y-value was determined since the current density passing
through the electrode was assumed to be 1 mA/ cm2, which would be 10-3 A/cm2 for all
conditions, and the log of this value is -3.
Discussion:

The results of the cell potential section of the lab went pretty smoothly. By looking at
Table 1, a few trends can be seen. Firstly, it seems like out of all the metal solutions, silver is the
strongest oxidizing agent, always being the cathode in any reaction. This is followed by copper,
which is the cathode for all other reactions except when in the presence of silver. It is interesting
to note that the molarity of copper affects how good of an oxidizing agent it is; a 1 M solution is
stronger than a .1 M solution. This is supported by the Nernst equation; if all the molarities
1
remain the same at 1 M, the expression for Q would be .1 =10 , and the log 10 equals a
positive number, decreasing the reduction potential. It is also interesting to note how there is a
charge present for during the 1 M/ .1 M Cu mixture, even though the stoichiometry of the
reaction would indicate that there should be no change. This does make sense; since the
concentrations are different, the voltages are different, so subtracting the cathode from the anode
would not equal zero. The reason this happens could be because the electrons are still able to
move across to balance the difference in reduction potentials.
The reference electrode, AgCl, seems to separate the stronger oxidizing agents from the
weaker oxidizing agents. It is the anode when in the presence of copper and silver, but is the
cathode when in the presence of lead and zinc. Between lead and zinc, zinc is the weaker
oxidizing agent, since in a lead/zinc reaction, lead serves as the cathode and therefore would be
the stronger oxidizing agent. This is supported also by the fact that zinc is always the anode for
any reaction it is in.
All these trends are also supported by the calculated values of the reduction potential in
NHE. The values based off the reference electrode are not a good comparison since we attempted
to make all measured values positive, thereby preventing all the metals from acting as an
oxidizing agent, since some could be more easily oxidized by AgCl compared to its ability to
oxidize AgCl. Therefore, the values related to the reference electrode were not all reduction
potentials; some were oxidation potentials. When converting to NHE, however, they all became
reduction potentials, making the trend very obvious.
As seen in Table 3, most of the experimental values for the standard cell potentials of
each metal ion solution were close to the standard values, being off by a few hundredths for most
values. The only exception to this is the zinc ion, which was off by a large amount. Since the
standard deviation in Table 1 for the reactions which involved zinc are typically higher than the
other standard deviations calculated, indicating that the reactions which zinc have a higher
variability than other reactions, it is possible that the inconsistency of the reaction created an
unreliable result in the end. It is interesting to note that the calculated values of the reduction
potential, with the exception of silver and zinc, were always more than the standard reduction
potential. Copper and lead are the metals which are neither the strongest or weakest oxidizing
agents; the results could be linked to that, especially considering the possibility that AgCl, the
reference electrode, has a reduction potential pretty close to these metals, possibly making the
results less accurate. It does seem like the calculated values of NHE are in line with the
experimental results shown in Table 2; for example, the average voltage of the Pb/Zn reaction
was .277 V, which is pretty close to .287 V, the predicted value based off the calculated reduction
potentials in NHE, but is much lower than the .637 V, the expected value based off the standard

reduction potentials. Whatever mistake was made in the experiment was consistent, which would
indicate that either something more is going on with the experiment or the multimeter was faulty.
The results for the Nernst equation also made sense. With the calculated molarity values,
we were able to get the expected voltage, indicating that the Nernst equation can be a pretty
decent way of changing the voltage when needed.
As for the electrolysis of water, while the overpotential for the reaction was expected
because of prior knowledge that kinetically, the electrolysis of water is extremely hard, it was a
bit surprising to see how much it deviated from the expected value given the data in the Nocera
paper. Figure 1 easily illustrates the fact that adding a catalyst lowers the overpotential needed
for electrolysis to happen, and that the class values for overpotential were higher than expected,
though the difference between the pre-grown catalyst and catalyst grown in lab was negligible.
While there is some overlap with the expected value because of the standard deviation bars, it is
not enough to say that the difference between the expected and calculated was caused by random
chance. In addition, the standard deviation is pretty large for the given data set, indicating the
data in general was very variable and therefore not as accurate as it could be. There could be a
few reasons why the data did not come out as expected. Firstly, the experiment in the Nocera lab
had much different and probably more sophisticated equipment than we did. We did not have a
power supply which could deliver volts as accurately or display the volts to a high degree of
accuracy, which limited how fine of a control we had over determining the voltage passing
through the cell. In addition, we were unable to measure the current passing through the
electrode, using the appearance of bubbles as a way to estimate rather than measuring it directly.
Our setup was a bit different as well, since we had a two electrode system versus the three
electrodes used in the original experiment, which might have affected the results as well. All
these factors could have decreased the accuracy of the results.
One of the problems I faced in the lab was the creation of the catalyst. As far as I could
tell, the procedure was followed correctly, and since electrolysis of water occurred successfully
later on, the power supply was not broken. It is possible that there was something wrong with the
connection to the power supply, preventing enough voltage from going through in the beginning,
or there was not enough FTO on the slide for the catalyst to form, or some other variable which
has not been accounted for affected the formation of results.
Conclusion:
The metal which is the strongest oxidizing agent is Ag, followed by Cu (1 M), Cu (.1 M),
AgCl, Pb, and Zn. The experimental values based off the AgCl reference electrode were
generally close to the expected standard reduction potentials based off NHE, with the exception
of zinc, which was much smaller than expected. The calculated values of NHE based off
experimental data match the data provided in other reactions, indicating that the results are
consistent throughout the experiment. A current is able to flow between two solutions made of
the same ions as long as the concentrations vary, a result supported by the Nernst equation. The
Nernst equation is also a pretty accurate way of changing the cell potential by changing the
concentration of the metal ions. For the electrolysis of water, while adding a catalyst decreased
the overpotential needed for electrolysis to occur, the class average for the overpotential with the
catalyst, pre-grown or grown during the lab, was much higher than expected, which could have

been caused by the differences in equipment and experimental design between the class setup
and the Nocera paper.
By using the cobalt catalyst, the efficiency improves from approximately 55% with no
catalyst to 69% with a catalyst, a 14% increase. This is helpful if someone is attempting to create
a fuel cell based off the electrolysis of water; less energy is needed to break water into gases
which can be burned for energy, making this process more viable as a fuel cell.
If a solar cell of 5 m2 produces around 3.79 A, then in order for the current density to be 1
mA/cm2, the electrode area has to be 3790 cm2 or .379 m2. This also makes sense; since the
current passing through the electrode increased substantially, the area of the electrode has to
increase by a similar magnitude for the current density to be the same. This would make it hard
for solar cells to power the electrolysis of water, since it would require a huge electrode area for
the target current density to be hit, making the contraption take up more area and thus make it
harder for it to be applied in situations where space is limited, like in cars or apartments.

Calculations:
Calculation Average Voltage/Overpotential (same process)
.540 V +.536 V +.537 V
=.538 V
3
Calculation Standard Deviation Voltage/ Overpotential (same process)

(.540V .538 V )2 +(.536V .538 V )2 +(.537 V .538 V )2

=0.002 V
31

Conversion from AgCl reference to NHE

Ecell + .2223 V = Ecathode
Since Ecell = 0.538 V
Ecathode = .538 V + .2223 V = .760 V
Therefore, the NHE for Ag is around .760 V
Nernst Equation to Modify Concentration so Ecell = .5 V
Ecell =Ecell

.0592
logQ
n

2+
Pb

Cu
:
Since Ecell = .5 V, Ecell = 0.498 V, n = 2, and Q =
2+

2+
Pb

2+

Cu

.5 V =.498 V

.0592
log
2

Pb

2+

Cu

2+

.0592
.002V =
log
2
Pb

2+

Cu

2+

.0676=log
2+
Pb

Cu

2+

.856=

Since only one molarity needs to be changed, if [Cu2+] = 1 M, then [Pb2+] = .856 M
Conversion of Voltage at pH=7 to NHE
+
H 3 O

Ecathode =Ecathode

.0592
log
n

According to the introduction, Ecathode = 0 V, n = 2, and since pH =7, [H3O+] = 10-7:

Ecathode =0 V

.0592
1
log
2
[ 107 ]2

Ecathode =.414 V
Now
+
H 3 O

.0592

Eanode =E anode
log
e
According to the introduction, Eanode = 1.229, n = 2, and since pH = 7, [H3O+] = 10-7:
Eanode =1.229 V

.0592
1
log 7 2
2
[10 ]

Eanode =.815 V
Therefore, since Ecell = Ecathode - Eanode :
Ecell = -.414 V - .815 V = -1.229 V
Calculation Overpotential
= rev

 = experimental value = 2.250 V; rev = theoretical value = 1.229 V

=2.250V 1.229V =1.021V

Efficiency of Electrolysis
Efficiency=100(

Since

rev
)

= experimental value = 2.250 V; rev = theoretical value = 1.229 V

Efficiency=100

=55
( 1.229V
2.250V )

Electrode Area Needed for 1 mA/cm2 Current Density

According to Sunpower, for a 1.24 m2 solar panel, .94 A are released. Therefore, for a 5 m2 solar
panel:
.94 A
5 m2=3.79 A are created
2
1.24 m
Since the current density needs to be 1 mA/cm2 or 10-3 A/cm2:
103 A
x cm 2=3.79 A
2
cm
2

x cm =
2

3.79 A cm2
103 A

x cm =3790 cm

Therefore, for the current density to be around 1 mA/cm2, the electrode area should be 3790 cm2