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Grace Wang

TA: Lucas Flagg


Due Tuesday, February 7th, 2017

Electrochemistry
Introduction

Redox (oxidation-reduction) reactions involve two half-cell reactions where one species

is reduced (gains electrons at the cathode) while the other one is oxidized (gives up electrons at

the anode). The overall cell potential is the sum of the potentials in either half-cell; we subtract

the standard reduction potential of the anode from that of the cathode as shown in Equation 1

because it occurs backwards, as an oxidation. When a redox reaction occurs spontaneously, the

cell is referred to as galvanic; a nonspontaneous reaction must be provided with external energy

in order to occur, and is referred to as an electrolytic cell. Cell potentials of galvanic cells are

always positive. In this lab, we began by investigating the potential between half cells in order to

determine which oxidation states of certain species reacted together spontaneously.

The standard reduction potentials listed in the Oxtoby Principles of Modern Chemistry

textbook assume standard statemeaning all aqueous solutions must be at 1 M concentration,

the partial pressures of gases must be at 1 atm, and the temperature must be at 298.15 K. When

conditions deviate from these standards, the Nernst equation (Equation 2) allows us to calculate

the new expected cell potential. In the equation, Q represents a reaction quotient where

concentrations and partial pressures of products are multiplied, and divided by the product of

those of the reactants, taking care to use reaction coefficients as exponents and omitting any pure

liquids or solids. Not only did the Nernst equation help us predict new cell potentials, but it also

allowed us determine desired solution molarities needed to obtain a certain voltage.

Equation 1: Ecell = Ecathode -Eanode


RT
Equation 2: E = E - nF ln (Q)
The electrolysis of water, which involves an electrolytic cell reaction, is a way to store

electrical energy generated by a renewable source in that it leads to the overall production of

oxygen and hydrogen gas as shown in Equation 3. The overpotential, as shown in Equation 4, is

the difference between the potential difference across an electrode solution interface when

current flows versus when no current flows. In other words, it is the difference between the

voltage needed to drive a nonspontaneous redox reaction (measured experimentally) and the

voltage needed calculated theoretically.

Equation 3: H2O (l) H2 (g) + O2 (g)

Cathode: 2H3O+ (aq) + 2e- H2 (g) + 2H2O (l)


Anode: 3H2O (l) O2 (g) + 2H3O+ (aq) + 2e-

Equation 4: = - rev

The electrolysis of water has a relatively high overpotential, making it possible for some salts

such as NaCl to be electrolyzed to produce chlorine gas in aqueous solutions even though the

formation of oxygen gas by oxidizing water is more thermodynamically favorablethe

electrolysis of water is much less kinetically favorable. Thus, it was practical for us to examine

the effect of catalysts that may reduce the overpotential involved in electrolyzing water;

specifically we worked with the CoPi catalyst. Although high temperatures or concentrations can

also speed up reactions, neither condition is practical for large-scale use in industrial processes,

and so catalysts are an important area of study not only for the reaction we considered.

Methods

Note: the growth of the CoPi catalyst should be prepared and started before all other

steps; a catalyst of sufficient thickness takes at least 1-2 hours to grow. See Part III.
Part I: Cell Potentials

In Part I, we measured the standard potentials of four electrodes against the standard

Ag/AgCl electrode. Five separate electrodes were constructed by attaching approximately 1.5 cm

square pieces of cellulose dialysis film rinsed in 1 M KNO3 solution to the smooth end of a glass

tube with a small rubber band. Leaks were tested for, and the dialysis film was stretched smooth.

The metal electrodes we worked with and their corresponding metal ion solutions are

summarized in the table below.

Table A.
Half Cell # Metal Electrode Metal Ion Solution
1 Ag 1M Ag(NO3)
2 Zn 1M Zn(NO3)2
3 Pb 1M Pb(NO3)2
4 Cu 1M Cu(NO3)2
5 Cu .1 M Cu(NO3)2
Table A: Summary of electrodes and corresponding metal ion solutions constructed and tested

Approximately 3 cm of the metal ion solutions were transferred into the appropriate half-cells,

and the cells were stored in a wide specimen jar and immersed in 1M KNO3 solution; cloudiness

of the salt solution indicated leaks, and half-cells were reconstructed as needed. For each metal

electrode, the ends were sanded until shiny and the top was bended to rest against the top of the

glass tube so that the metal electrode extended into the metal ion solution but did not make

contact with the cellulose film. A specimen jar was then filled with 1M KNO3 (about 3 cm deep),

and the standard Ag/AgCl electrode was rinsed and placed within the jar along with one

constructed half-cell. With the fluke multimeter set to read DC volts, we used alligator clips to

connect the wires to the standard and constructed half cellsfor conveniences sake when

recording data, we kept the standard Ag/AgCl electrode connected to the cathode, and made note

of this in our calculations. Cell voltage was recorded, and we cycled through half-cells 1-4

(repeatedly in the same order) until we had 3 recorded data values for each. The same procedure
was used to measure the potential between the constructed zinc and lead half cells, and data was

collected for 3 trials as before. Lastly, we wrote the spontaneous overall cell reactions for each

half-cell pair tested by looking at the recorded voltages and referencing which cell has been

connected to the cathode and anode.

Part II: Concentration Effects

Following a similar method as before, we measured the cell potential between half cells 4

and 5, which corresponded to two copper electrodes immersed in different concentrations of

copper nitrate. The sign as well as which probe was connected to each cell was recorded as

before, and trials were repeated to ensure accuracy. Next, from the data we collected in Part I we

determined that the pair of cells that could yield an overall cell potential closest to .5 V. In our

experiment, we considered the cell constructed with the lead and copper half cells, and used the

Nernst equation to adjust ion solution concentrations in order to bring the net cell voltage as

close to .5V as possible.

Part III: Overpotentials

In order to grow our CoPi catalyst for the electrolysis of water, we referenced the Kannan

and Nocera paper. To grow the catalyst, we used 9.75 mL of a .1M K3PO4 solution and .25 mL

of a .2 M Co2+ solution in order to obtain an overall (approximately) .1M potassium phosphate

and .5 mM cobalt solution. An FTO slide was connected to the anode, and a platinum wire was

used as the cathode; the CoPi catalyst was then plated onto the FTO slide when a voltage of 1.5

V was applied to the electrochemical cell. We allowed this reaction to proceed for 1-2 hours until

a dark coating could be seen on the FTO anode.

In this section, we tested our grown CoPi catalyst slide as well as two other slides: one

bare FTO control slide, and one with a pre-grown CoPi catalyst. The setup was similar to that of
growing the catalyst in that we again used a platinum wire as the cathode, but we used a pH 7

buffer solution. We also used a fluke multimeter to monitor the voltage (this gave a finer reading

than the display on the power supply), and rotated four times through using the three different

FTO slides as the anode. For each trial, we slowly applied ~100 mV of current, and recorded the

voltage at which we first observed O2 bubbles forming at the anode.

After collecting our results, we rinsed the slides with deionized water. All metal ion

solution waste was collected and disposed of into a biohazard container.

Results

Table B.
Trial Measured Voltage (DC)
Ag/Ag(NO3) (1 M) as anode
Trial 1 -.560 V
Trial 2 -.558 V
Trial 3 -.562 V
Zn/Zn(NO3)2 (1M) as anode
Trial 1 .768 V
Trial 2 .758 V
Trial 3 .759 V
Pb/Pb(NO3)2 (1M) as anode
Trial 1 .372 V
Trial 2 .372 V
Trial 3 .373 V
Cu/Cu(NO3)2 (1M) as anode
Trial 1 -.138 V
Trial 2 -.137 V
Trial 3 -.137 V
Table B: Data collected from Part I. The Ag/AgCl electrode was always connected to the cathode.
Table C.
Half Cell Average Standard Half Cell Actual Half Percent Error
Reduction Deviation Reduction Cell
Potential Potential Reduction
Measured vs. Potential
Ag/AgCl*
Ag/Ag(NO3) .560 V .002 .7823 V .7996 V 2.16 %
Zn/Zn(NO3)2 -.762 V .006 -.5397 V -.7628 V 29.25 %
Pb/Pb(NO3)2 -.372 V .001 -.1047 V -.1263 V 17.1 %
Cu/Cu(NO3)2 .137 V .001 .3593 V .3402 V 5.61 %
Table C: This table shows the comparison of measured half-cell reduction potentials with respect to both
the standard Ag/AgCl and SHE electrodes. The reduction potential in reference to the SHE electrode was
obtained by adding the reduction potential of AgCl (s) (.2223 V), as that of water is 0V. Real half-cell
reduction potentials listed in the textbook are also displayed, as well as the experimental percent error.
*The signs on this column have been adjusted from the raw data to measured reduction potential.

Table D.
Electrode Spontaneous Equation
Ag/Ag(NO3) Ag (s) + Ag2+ (aq) + Cl- (aq) AgCl (s) + Ag (s)
Ag/Ag(NO3) Zn (s) + 2AgCl (s) 2Ag (s) + 2Cl- (aq) + 2Zn2+ (aq)
Pb/Pb(NO3)2 Pb (s) + 2AgCl (s) 2Ag (s) + 2Cl- (aq) + Pb2+ (aq)
Cu/Cu(NO3)2 2Ag (s) + Cu2+ (aq) + 2Cl- (aq) 2AgCl (s) + Cu (s)
Table D: Spontaneous reactions as observed in the lab between the indicated electrode and the standard
Ag/AgCl electrode. The reactions with the cathode and anode configured as written led to experimentally
positive Ecell values, indicating a spontaneous reaction.

Table E.
Trial Voltage
Trial 1 .382 V
Trial 2 .376 V
Trial 3 .376 V
Average .567 V
Table E. Potential in volts between the Zn/Zn(NO3)2 (1M) and Pb/Pb(NO3)2 (1M) electrodes; the lead
electrode was connected to the cathode and the zinc to the anode.

Equation 5: Pb2+ (aq) + Zn (s) Zn2+ (sq) + Pb (s)

Equation 5: Displays the spontaneous reaction between the zinc and lead electrodes we constructed as
observed in the lab.
Table F.
Measured Cell Standard Calculated Actual Cell Percent Percent error
Potential Deviation Cell Potential Potential Difference
(Average) Measured and
Calculated
.567 V .003 .435 V .637 V 26.35% 10.99%
Table F: Here the measured cell potential is compared to that predicted by our half-cell measurements
and the standard value as listed in the textbook.
Table G.
Trial Voltage
Cu/Cu(NO3)2 (.1M) as anode Cu/Cu(NO3)2 (1M) as cathode
Trial 1 .045 V
Trial 2 .042 V
Trial 3 .043 V
Average .043 V
Standard Deviation .001
Pb/Pb(NO3)2 (1M) as anode Cu/Cu(NO3)2 (XM) as cathode
Trial 1 (1M copper nitrate) .514 V
Trial 2 (.333 M copper nitrate) .477 V
Trial 3 (.5 M copper nitrate) .490 V
Table G: Concentration effects. The bottom three trials were conducted to obtain a voltage as close to .5
V as possible. Calculations shown below following the Nernst equation (Equation 2 in the Introduction
section) in the Calculations section below.

Table H.
Trial Voltage
Blank
Trial 1 2.834 V
Trial 2 2.729 V
Trial 3 2.760 V
Trial 4 2.746 V
Average 2.768 V
Standard Deviation .046
Grown CoPi Catalyst
Trial 1 2.469 V
Trial 2 2.364 V
Trial 3 2.353 V
Trial 4 2.343 V
Average 2.382 V
Standard Deviation .246
Prepared CoPi Catalyst
Trial 1 2.166 V
Trial 2 2.350 V
Trial 3 2.362 V
Trial 4 2.266 V
Average 2.286 V
Standard Deviation .091
Table H: In each trial, the FTO slide indicated was connected at the anode, and a platinum metal
electrode was connected to the cathode. The voltage at which oxygen bubbles were first seen at the anode
was recorded and is displayed for each trial.
Table I.
Anode Average Voltage Average Class Average Class Average
vs. NHE Overpotential Voltage vs. NHE Overpotential
Blank FTO 2.354 V 1.125 V 2.673 V 1.444 V
Grown CoPi 1.968 V .739 V 2.242 V 1.023 V
Pregrown CoPi 1.872 V .643 V 2.182 V .9527 V
Table I: The voltage vs. NHE was found by accounting for the cells being electrolytic, and the cathode
(reduction of water) in pH 7 being -.4144 V. To obtain overpotential, the theoretical voltage needed
(1.229 V) to electrolyze water was subtracted by the experimental value.

Figure 1.

Figure 1: This Tafel plot shows our experimental overpotential data (as well as the class averages) in
comparison to the Nocera paper values; we assumed the current density we passed through our samples
was 1mA per cm2.
Table J.
FTO slide Percent Class Average Percent Improvement Percent
Efficiency Percent from Blank Improvement
Efficiency from Blank,
Class Average
Blank FTO 52.21% 45.98% X X
Grown 62.45% 54.82% 19.61% 19.23%
Catalyst
Pre-Grown 65.65% 56.32% 25.74% 22.49%
Catalyst
Table J: This table shows the efficiency of each of the FTO slides, as well as the percent improvement
when comparing each of the catalysts to the bare FTO slide.

Discussion

In Part I, it was important for us to keep in mind that our goal was to look at the overall

potential of galvanic cells, although our raw data reading gave a positive or negative charge

based on which electrode was connected to the cathode and anode. In comparing our

experimental values for half-cell reduction potentials (after converting to NHE), we found that

our most accurate measurements were for the silver electrode (approximately 2% error), and the

least accurate were for zinc (approximately 30% error). This was probably a completely random

error that a certain cell yielded much more accurate experimental values. Potential sources of

error include grease from our fingers being coated onto the metal electrodes, as well as non-

standard solutions of metal ions. We shared the same solutions with all groups in the lab, and so

both contamination and small human errors (for example, test tubes having residue solution or

water before usage) would have led to concentrations that were not perfectly 1M.

In Part II, we found that cell potential does depend on the concentration of the metal ion

solutions at each electrode. In working with solutions of copper nitrate that were 1 and .1 M, we

expected the half-cell with a higher concentration of metal ions solution to be reduced. Since we

are examining reduction potentials, we know that Q of the Nernst equation for this specific

reaction is inversely proportional to the metal ion solution concentration. High values of Q
would mean smaller values are subtracted from the standard reduction potential; the more

positive reduction potential always occurs as written. Our results confirm this expectation, as

connecting the 1M solution to the cathode yielded a positive cell potential of approximately .04

V, this positive value indicated a spontaneous reaction. Thus, over time we would expect the

concentration of copper ions at the cathode (higher starting concentration) to decrease as ions are

reduced and plated out as copper solid, and that at the anode to increase until the two are in a sort

of equilibrium. In trying to construct a cell with a voltage of exactly .5V, we struggled because

our calculated dilutions led to larger changes in voltage than desired. This may have been caused

by a number of factors. For instance, our starting molarities of metal ion solutions were not

exact, and our dilutions of tiny amounts of solutions were by no means exact. Additionally, we

rounded many figures in our calculations to make the desired concentration relatively easy to

make. Overall, we also knew that many of our half-cells leaked a little bit; this was indicated by

a murkiness that developed in our KNO3 solution in which we stored our half cells.

In Part III, we calculated cell potential and overpotential of the electrolytic cell where we

reduced water at the cathode (platinum wire) and oxidized it at the anode (rotating FTO slide).

The values recorded were always positive, as these corresponded to the voltage applied. Thus,

the negative of this value was the Ecell, which we converted to the standard reduction potential at

the anode by considering the reduction potential of water at pH 7 as Ecathode (calculated to be

-.4144 V with the Nernst equation). When calculating overpotential, we used 1.229 V as the

theoretical voltage needed to electrolyze water. We noticed that this value remained unchanged

at different levels of pH, simply because if the Nernst equation Q expressions are considered, the

change in the concentration of hydronium ions has an equal effect on the half-cell potentials at

the anode and cathode for reducing water, shifting both so the overall difference does not
change. In Figure 1, our data is plotted alongside Noceras. We ignored the iR correction factor,

and also assumed that the current density passed through every square centimeter was

approximately .001A. The overpotentials that we calculated from our data are clearly higher than

that of Noceras, but the data points do lie near the line that Noceras data (that is adjusted for

pH) approaches asymptotically. In addition to the assumption about current density, a small

amount of resistance probably contributed to our margin of error, as did the fact that we only had

1-2 hours to grow our catalyst. In comparing the efficiency of the slides with and without

catalysts, we noticed that both our grown catalyst and the pre-grown catalyst (looking at

individual and class data) increased the efficiency from that of the blank FTO slide by about 20-

25%. As we hypothesized, the pre-grown slide was the most efficient out of the three, lowering

the overpotential by a few percent more than our grown catalyst. This is probably due to the fact

that our catalyst only had about an hour to grow. Although the CoPi catalyst is a solid meaning

its effectiveness should depend mainly on its surface area, our catalyst was visibly thinner

(lighter color) and so may have had areas where the catalyst was too thin to function properly. In

comparing our data to the class data, our overpotential values were all lower than the class

average. The significant difference in each groups data was mainly due to the fact that we

determined the voltage needed to electrolyze water by merely looking for oxygen bubble

formation at the anode, which is not a very error-proof method. The bubbles were hard to see,

even though we were very careful with slowly applying more voltage.

Conclusion

Further investigation into the effect of catalysts on the cell potential of various reactions,

especially the electrolysis of water, is extremely important especially for the renewable power

industry. The energy harvested in the form of solar power must be stored in some manner, and
using it to drive the production of oxygen and hydrogen gas is a potential method to look further

into. In a sense, this would resemble artificial photosynthesis; industrial replication of a natural

process this fundamental leads to many avenues of research. We found in this lab that the

presence of the CoPi catalyst could lower the voltage required to power an electrolytic reaction,

lowering the overpotential by approximately 20%. However, its overall efficiency was found to

not exceed 66%, and even with SunPowers best modules, a huge electrode area larger than

2,400 m2 would be needed. Thus, other catalysts or modifications of the CoPi catalyst must be

explored. We also found that manipulating the concentrations of solutions at either electrode

could affect the overall cell potential, but this is not always a practical approach especially if it

leads to the need for extremely high or low concentrations, which are either expensive and

difficult to achieve or lead to high margins of error. Still, the relationship between different

electrodes, their concentrations, and their standard reduction potentials is highly interesting and

practical to investigate. For example, zinc can be used as a sacrificial anode to protect iron for

rusting. In relationship to this particular lab, recommendations for future investigation include

using different samples of the same metal in individually constructed half-cells between trials of

the same electrode in order to be able to distinguish outliers of data more easily. We were able to

successfully measure half-cell potentials and correctly predict spontaneous redox reactions

between different metal electrodes, but many of our margins of error exceeded 10%.
Calculations

Note: all additional calculations except the Nernst equation concentration calculations not
shown here were repetitive basic division or addition expressions that were completed in Excel.
Calculations done in lab and for the Nernst equation are attached.

Average Value
Calculating the average value for reduction potentials of Ag/Ag(NO3) vs. Ag/AgCl
Measured values: -.560, -.558, -.562 V
Average: (-.560 + -.558 + -.562)/3 = -.560 V

Percent Error
Comparing the measured and actual reduction potentials for the Ag/Ag(NO3) electrode
Actual: .7996 V
Experimental: .7823 V
Percent error: (.7996-.7823)/.7996 = 2.16% error

Standard Deviation
Calculating the standard deviation for the measurements made for the reduction potential of the
blank FTO slides; values recorded were: 2.834, 2.729, 2.760, 2.746 V; average 2.768 V
Square the difference between the average and each value
For first data point: (2.768-2.834)2 = .004356
Sum all of these values, and take the square root:
(.004356 + .001521 + .000064 + ,000484)1/2 = .046

Half-cell Reduction Potential vs. NHE


Example: the reduction potential vs. Ag/AgCl measured for the Ag/AgNO3 electrode was
measured to be .560 V.
Reduction potential vs. NHE = .560 + .2223 V = .7833 V
Given that .2223 V = reduction potential for AgCl (s)

Zinc, Lead Cell Expected Voltage


After converting raw data to standard reduction potentials vs. NHE, our measured reduction
potentials for Zinc and Lead were:
Zinc (s): -.5397 V
Lead (s): -.1047 V
The cell was observed to be Galvanic when zinc functioned as the anode. This makes sense,
because lead has the more positive reduction potential, and thus occurs as written
Ecell = Ecathode -Eanode = Elead -Ezinc = -.1047 (-.5397) = .453 V

Lead, Copper (expected .5V) and Nernst Equation Calculations


Measured cell potential between the lead and copper electrodes: .514 V
Using the Nernst equation, using .5 as the desired voltage
.5 = .514 - .0592/2 log(Q)
Solving the log, Q = 2.97
Since copper is reduced to solid, the quotient Q has [Pb2+] on top and [Cu2+] on the bottom
Thus, we need to dilute [Cu2+] to 1/3 the molarity of that of [Pb2+], both began at 1 M
Dilute 1 mL [Cu2+] to 3 mL to obtain a .333 M solution of copper nitrate

Applied Voltage vs. NHE


The measured voltages were Ecell vs. the Ag/AgCl electrode. However, we must remember that
these are electrolytic cells. The cathode, which involved the reduction of water at pH 7, was
calculated in the prelab to have a reduction potential of -.4144 V.
Ecell = Ecathode Eanode
-(voltage applied) = -.4144 V Eanode
Example with the blank FTO slide; the measured voltage was 2.768 V.
-(2.768 V) = -.4144 V -Eanode
Eanode = 2.354 V (standard reduction potential of the blank FTO vs. NHE)

Overpotential
Overpotential = (potential applied) V (pH 7)
Example for blank FTO slide (our data), average voltage applied measured = 2.354 V
Overpotential = 2.354 V 1.229 V = 1.125 V

Percent and Comparative Efficiency


Percent efficiency is calculated as the output over the input voltage. In other words, to split
water, we are realizing 1.229 V of potential, but we have to apply more than 1.229 V.
Example with average blank FTO slide, measured potential = 2.354 V
(1.229 V/2.354 V) * 100 = 52.21% efficiency
Improvement of efficiency from our blank FTO (52.21%) to our grown catalyst slide (62.45 %)
Percent improvement:
((62.45-52.21)/52.21) * 100 = 19.61% improvement with grown catalyst

Solar Power Question


Calculate the electrode area needed if operating at a current density operating at 1 mA/cm2 if you
wanted to run the output from a small rooftop solar panel (5 m2) using SunPowers best Si
photovoltaic modules.
The best ones operate at a current density of 72.9 mA/cm2, and are 23% efficient
(72.9 mA/cm2) * (100000 cm2/m2) * 5 m2 = 3645 A
* 1/.23 efficiency = 15847.83 A
15847.83 A * (1 cm2/.001 A) * (1 m2/10000 cm2) * 1/.66 efficiency
= 2401.19 m2

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