Electrochemistry

Sreetha Sidharthan
Experiment #3Honors Chemistry 155 AC
Introduction Redox (or oxidation-reduction) reactions are chemical reactions in which one species gives up electrons to another species, resulting in changes in the oxidation states. The substance that gains electrons is said to be reduced while the substance that loses electrons is said to be oxidized. The overall net reaction can be separated into half reactions, which make it easier to track the transfer of electrons between the participating species. Redox reactions become especially important and useful when their two halfreactions are physically separated. Electrochemical cells, for instance, couple the oxidation-reduction reactions to external electric circuits. In electrochemical cells, two half-reactions are physically separated into compartments that prevent mixing but allow for ion flow, as seen in the figure to the right. The electrode at which oxidation takes place is called the anode, while the electrode at which reduction takes place is called the cathode. When the reaction takes place without any inputted source of energy, it does so spontaneously and thus its voltage will always be positive. Such electrochemical cells where electrical energy is provided to the external circuit are called galvanic cells.
http://www.saskschools.ca/curr_content/chem30_0 5/graphics/6_graphics/electrochem_cell_a_complet e_sm.gif

A half-cells reduction potential essentially measures the tendency for the half-cell to proceed as a reductionthe greater the standard half-cell potential, the more likely that half-cell will proceed as a reduction in an electrochemical cell. Because the tendency of a species to give up or accept electrons can only be measured by comparing it to other species, it has been decided internationally that the universal reference electrode is the standard hydrogen electrode (SHE) which is defined as having a standard reduction potential of 0 V. In this experiment, we chose to set aside an AgCl/Ag electrode as the reference electrode. The standard half-cell reduction potentials assume that the concentrations of ions are 1 M. However, at different concentrations the half-cell reduction potentials and cell voltage can be calculated using the Nernst Equation E = E

0.0591 V log Q where n is the number of n

electrons transferred and Q is the reaction quotient.

Understanding electrochemical cells is vital to understanding how batteries work as

wella battery is essentially a group of galvanic cells arranged in series that converts chemical energy into electrical energy to do work. As a result, half-cells and electrochemical cells can be arranged and connected in series to create batteries of a desired voltage. In this lab, we had several major aims. First of all, we attempted to measure the standard reduction potentials of Ag/Ag+, Pb/Pb2+, Cu/Cu2+ and Zn/Zn2+ as well as write the spontaneous reaction for each pair of half-cells that were connected. Another major goal was to better understand how batteries work by constructing a battery out of two electrochemical cells connected in series. We also wanted to examine the effect of concentration on cell voltage both by measuring the cell potential between two half cells (with different ion concentrations) and creating a galvanic cell with a cell potential of 0.50 V.

In the second part of this experiment, we measured the overpotential required for water oxidation on several different electrodes, which required growing a cobalt phosphate water catalyst. The electrolysis of water between inert electrodes such as platinum has the half reactions:

2 H 3O+ ( aq) + 2e H 2 ( g) + 2 H 2O( l) 1 3H 2O( l) O2 ( g) + 2 H 3O+ + 2e 2

And the overall reaction:

1 H 2O( l) H 2 ( g) + O2 ( g) 2

In pure water, the overall cell voltage comes out to be -1.299 V, meaning that it can only be

an external voltage sufficient to overcome the intrinsic negative made to occur by applying
voltage of the cell. According to Kanan and Nocera, the realization of artificial systems that perform water splitting requires catalysts that produce oxygen from water without the need for excessive driving potentials. In this experiment, we focus on the cobalt phosphate water catalyst. Overpotential ( ) is defined by the equation = rev where is the potential difference across an electrode/solution interface when a current is flowing, and rev is the
no current is flowing. It potential difference across the electrode/solution interface at which
the reaction occur at a essentially reflects the loss of thermodynamic potential necessary to make

finite rate.

Experimental Methods A. Electrochemical Half Cells Six to eight pieces of cellulose dialysis film approximately 2.5 cm in width and length were rinsed with deionized water and placed in a specimen jar of 1 M potassium nitrate solution. They were allowed to soak for at least five minutes before each piece of film was cut into two separate, single layer squares. To make an electrochemical half-cell, one square of dialysis film was centered over the end of a glass tube. The film was then securely wrapped onto the glass tube using a rubber band, and then checked for any leaks using water. In the same way, a total of five half-cells were produced. The appropriate metal ion solutions (see Figure 1) were placed into the half-cells to a depth of approximately 3 cm using a dropper bottle. These half-cells were labeled from one to five according to the respective solutions as indicated in Figure 1 and placed in a specimen jar. Next, the appropriate metal electrodes were carefully placed into the half-cellsthe electrodes were at least 1 cm into the metal ion solutions but were not touching the cellulose film. To make good electrical contact, their ends were polished using sandpaper and contact between the metal and our fingers were limited.
Half Cell # 1 2 3 4 Metal Electrode Ag Zn Pb Cu Metal Ion Solution 1.0 M AgNO3 1.0 M Zn(NO3)2 1.0 M Pb(NO3)2 1.0 M Cu(NO3)2

5 Cu 0.1 M Cu(NO3)2 Figure 1. Electrochemical half-cells and their components.

To account for any error in our Ag/AgCl reference electrode, we rinsed the electrode with water and measured its potential against a high quality Ag/AgCl electrode. The specimen jar containing the half-cells was filled with 1 M potassium nitrate solution to a depth of 2 cm.

Finally, the cell potentials were measured against the Ag/AgCl electrode. In order to do so, the Fluke multimeter was set to read DC volts, probe wires were inserted into the meter, and then, connections between the probe tips and the metal electrodes were made using the wires with alligator clips. Using the Ag/AgCl electrode as a reference, we measured and recorded the potential of half-cells #1-#4. During each trial, the Ag/AgCl electrode was consistently connected to the black lead. The potentials were measured two more times for each of the halfcells for a total of three trials. We made sure to rotate through our cells when repeating these measurements as well. The voltage for the spontaneous reaction between half-cell #2 (Zn/Zn2+) and half-cell #3 (Pb/Pb3+) was also measured and recorded for a total of three trials. During these trials, the black lead was connected to the Pb/Pb3+ half-cell. By examining the results of our standard half-cell potentials, we were able to hypothesize which two electrochemical cells can be constructed in series to make a battery that has a total voltage greater than 1.7 Volts. We constructed this battery by first setting up the two electrochemical cells, in much the same way described earlier. For each electrochemical cell, two pre-determined half-cells were placed in a solution of 1 M potassium nitrate. Using the wires with alligator clips, connections between the probe tips and metal electrodes were made in the respective electrochemical cells. Then, they were arranged and connected in series. The voltage of the battery was measured from the anode of the first electrochemical cell to the cathode of the second using the Fluke multimeter. To study concentration effects, the voltage between half-cell #4 (Cu/Cu2+ (1 M)) and half-cell #5 (Cu/Cu2+ (0.1 M)) was measured. Using the data we collected earlier on, the pair of half cells with a potential closes to 0.50 V when connected together--Pb(s)/Pb2+ and Cu(s)/Cu2+--

was determined. Then, using the Nernst equation, we determined which half-cells metal ion solution needs to be diluted to reach a potential of exactly 0.50 V. This cell was assembled using a 10 mL graduated cylinder to dilute the 1.0 M concentration of the metal-ion solutions.

B. Overpotentials To begin growing a cobalt phosphate water oxidation catalyst, three glass slides were first obtained that had one side coated with fluorine doped tin oxide (FTO). One of the slides was precoated with a layer of the CoPi catalyst. Another slide served as a control, on which no catalysts were grown. On the third slide, we grew our own CoPi catalyst film. 0.25 mL of buffer was first removed from the 10.0 mL of pH 7.0 phosphate buffer. Then 0.25 mL of stock 20 mM Co2+ was added to this buffer for a 5 mM Co2+ concentration. This solution was placed into a small specimen jar. Next, we carefully placed an FTO electrode (one without the pre-coated layer of CoPi catalyst) into this specimen jar along with a platinum wire. The FTO electrode was attached to the red lead while the platinum wire was attached to the black lead. Then a steady voltage of 1.324 V was applied for consistently for an hour. Once a good coating of CoPi had formed, the power supply was disconnected, and both the Pt wire and CoPi coated electrodes were carefully rinsed with distilled water. Some pH 7.0 buffer solution without Co was then added to a clean jar. The Pt wire and clean bare FTO electrode was placed into this solution with the Pt wire connected as the cathode and the FTO slide as the anode. We began by applying 1.23 V (the voltage required to electrolyze water). Every 30-60 seconds, we increased the applied potential by about 100 mV. The potential reading from the Fluke multimeter at which we first observed oxygen bubbles forming on the FTO electrode was recorded. The FTO and Pt were then rinsed with water.

These steps were repeated with the CoPi catalyst-coated slide we grew and the pre-grown CoPi catalyst slide. Three trials for each of the slides were performed.

Results
Half-Cell Ag(s)/Ag+(1 M) Zn(s)/Zn2+(1 M) Pb(s)/Pb2+(1 M) Cu(s)/Cu2+(1 M) Average Potential versus Ag/AgCl reference electrode (V) 0.556 -0.772 -0.369 0.138 Half-Cell Reduction Potential (V) 0.777 -0.551 -0.148 0.359 Actual HalfCell Reduction Potential 0.7996 -0.7628 -0.1263 0.3402 Percentage Error 2.82% 27.76% 17.18% 5.53%

Figure 2: Calculated Half-Cell Reduction Potentials. The above table shows the half-cell reduction potentials calculated from the measured cell potentials using the Ag/AgCl electrode that was itself found to have a half-cell potential of 0.2213 V. It also compares these values to the actual half-cell reduction potentials that were referenced from Oxtobys Principles of Modern Chemistry. The percent error between the literature values and the values derived from our results are also included.

Using the information compiled in Figure 2, the spontaneous reaction between each half-cell and the Ag/AgCl reference could be written:
2 Ag( s) + 2Cl + Cu 2 + 2 AgCl( s) + Cu( s) Ag( s) + Cl + Ag + AgCl( s) + Ag( s) 2 AgCl( s) + Zn ( s) 2 Ag( s) + 2Cl + Zn 2 + 2 AgCl( s) + Pb( s) 2 Ag( s) + 2Cl + Pbs 2 +
Average Calculated Cell Measured Cell Potential (V) Potential (V) 0.352 0.403 Actual Cell Potential (V) 0.6365 Percent Error Between Measured and Calculated 12.66% Percent Error Between Measured and Actual 44.70%

Figure 3: Cell Potential between half-cell #2 (Zn/Zn2+) and half-cell #3 (Pb/Pb2+). This table shows the cell potential between half-cells #2 and #3 determined through a number of different means. First, it shows the average measured cell potentialessentially, the average of the cell potentials we measured in three trials. The calculated cell potential used the values of the half-cell reduction potentials determined earlier in the experiment and as recorded in Figure 2. The actual cell potential was determined similarly except that instead of using the experimental values of half-cell reduction potential, we used literature values found in Oxtoby. Finally, the percent error between the measured and actual values is indicated.

Two electrochemical cells that could potentially be connected in series and have a total voltage greater than 1.7 V:

Zn( s) Zn 2 + , NO3 Ag + , NO3 Ag( s) Pb( S ) Pb 2 + , NO3 Cu 2 + , NO3 Cu( s) Total Voltage ( Experimental half cell reduction values) : 1.84 V Total Voltage ( Actual half cell reduction values) : 2.03 V Percent error : 9.6%

The calculated expected potential, V, for the copper concentration cell with half-cells #4 and #5
is 0.0294 V. Essentially the overall spontaneous reaction occurring is:

Cu 2 + (1 M ) Cu 2 + (0.1 M )
The pair of half-cells that have a cell potential close to 0.50 V (0.507 V) when connected

Cu(s)/Cu2+. In order to reach a potential of exactly 0.50 V, the together: Pb(s)/Pb2+ and
Cu(s)/Cu2+ needs to be diluted to a concentration of 0.58 M. This means dilution 1 mL of 1.0 M Cu2+ to a volume of 1.72 mL. The overall cell would then be:

Pb( s) Pb 2 + (1 M ) Cu 2 + (0.58 M ) Cu( s)

Average Potential at which Oxygen bubbles first appeared (V) 2.578 2.108 1.764 Standard Deviation (V) 0.051 0.141 0.172 Class Average Potential at which Oxygen bubbles first appeared (V) 2.682 2.17 2.023

Anode Bare FTO electrode CoPi catalyst coated electrode Pre-grown CoPi catalyst coated electrode

Figure 4. Averages of the potentials at which oxygen bubbles were first observed. This table shows the average potential at which oxygen bubbles first appeared, both in terms of our own data and the class data. The standard deviation of our data is also included to give an idea of the range of our values.

Anode Bare FTO electrode CoPi catalyst coated electrode Pre-grown CoPi catalyst coated electrode

Our Average Overpotential (V) 0.935 0.465 0.121

Class Average Overpotential (V) 1.039 0.527 0.38

Average Overpotential (V) 0.987 0.496 0.251

Figure 5. Average Overpotentials. This table displays the average overpotential required for each electrode to pass approximately 1 mA/cm2 (both for our data and class data and the averages compiled).

Figure 6. Overpotential data graphed beside Kanan and Noeras Tafel Plot. The above plot shows the overpotential data for the bare FTO electrode and the CoPi catalyst coated electrode. The x-axis is the ratio between the overpotential and the applied voltage while the y-axis is simply -3 (log(0.001 A/cm2)). The overpotential data for the pre-grown CoPi catalyst coated electrode does not fit in the graph because its n/V value is less than 0.25 (approximately 0.09). The point on the far right corresponds to the bare FTO electrode while the one on the left corresponds to the CoPi coated electrode.

Calculations

Half-Cell potential of Ag/AgCl reference electrode

E cathode E anode = E 0.2223 V E anode = 0.001 E anode = 0.2213 V

Average Potential versus Ag/AgCl reference electrode

(0.559 V ) + (0.554 V ) + (0.554 V ) = 0.556 V 3

Half-Cell Reduction Potential

If the average potential versus the Ag/AgCl reference electrode was positive, then the Ag/AgCl electrode was the anode. If the average potential was negative, then the Ag/AgCl electrode was the cathode. This is because the Ag/AgCl electrode was always connected to the black lead.

E = E cathode E anode 0.556 = E cathode 0.2213 C E cathode = 0.777 V

Percentage Error

Percent Error =

Measured Value Actual Value 100% Actual Value

Calculated Cell Potential Between Half Cell #2 and #3

E = E cathode E anode E = 0.148 V ( 0.551 V ) = 0.403 V

Total Voltage of Battery:

Total Voltage = ( E cathode E anode) + ( E cathode E anode) = (0.777 V ( 0.551 V )) + (0.359 V ( 0.148V )) = 1.84 V
Half-Cell Reduction Potential of Cu/Cu2+ (0.1 M) Half-cells:

E = E

0.0592 V log Qhc n hc 0.0592 V 1 = 0.3402 V log 2 0.1 M = 0.3106 V

Expected Potential of Copper Concentration Cell (half-cells #4 and #5):

E = E cathode E anode = (0.3402 V ) (0.3106 V ) = 0.0294 V

Dilution of Cu/Cu2+ half-cell to achieve 0.50 V with Pb/Pb2+ (1 M):

0.50 V = E cathode E anode 0.50 V = E cathode ( 0.148 V ) E cathode = 0.352 V 1 0.0592 V log 2 [Cu 2 + ]

0.352 V = 0.0359 V [Cu 2 + ] = 0.58 M

(1 mL)(1 M ) = (V )(0.58 M ) V = 1.72 mL

Applied Potentials

Potential of Pt Cathode = E E vs
SHE

= E anode = ( E cathode

0.0592 V 1 log 7 2 = 0.414 V 2 (10 ) E cell ) = ( 0.414 V ( 2.578 V )) = 2.164 V

The applied potential is therefore +2.164 V.

Overpotentials

= ( potential applied ) E ( pH 7) = (2.164 V ) 1.229 V = 0.935 V

Overpotential/ Applied Voltage

0.935 V = = 0.43 V 2.164 V

Improvement in Overall Efficiency of using the CoPi catalyst compared to a bare FTO

electrode:
our CoPi catalyst : (0.496 V ) (0.987 V ) 100% = 49.8% 0.987 V pre made CoPi catalyst : (0.251 V ) (0.987 V ) 100% = 74.6% 0.987 V

Electrode area needed to operate at this current density if we wanted to run the output from a small rooftop panel (5 m2) of SunPowers best Si modules (24.2% efficiency): Sunpowers Si modules are approximately 6000 times more efficient.
5 m 2 6000 = 30,000 m 2

Discussion

Figure 2 displays the calculated half-cell reduction potentials for the four half-cells that were studied in this experiment. It also compares these calculated values to the actual half-cell reduction potentials, referenced from Oxtobys Principles of Modern Chemistry. One important note to make is that although the measured and average potentials of these electrochemical cells could have been negative, in reality all the cell potentials are positive because they are galvanic cells. Since no energy is inputted into the system, they are spontaneous reactions. The measured negative values are dependent on which half-cell acts as the cathode and anode as well as where the black lead and red leads are attached during the experiment. For instance, when the meter shows a positive reading, the black lead is on the oxidation half-reaction and the red lead is on the reduction half-reaction. Some of the measured half-cell reaction voltages have a large error when compared to the actual half-cell reduction voltagefor instance, the Zn/Zn2+ half-cell potential has an error of about 28%. There are several possible causes of this error. For one, the handling of the metal (which was necessary when sharing between multiple groups carrying out the same experiment) may have led to greasy residues, which can limit or slow down the transfer of electrons. Another potential error is that there could have been a small unnoticeable leak in the cellulose film that held together the half-cells. Such leaks would result in metal ions leaking out into the potassium nitrate solution. The decrease in concentration of the metal ion solution would

thereby result in lower reduction potentials, as indicated by the Nernst equation. Inaccuracies in the original concentration of the ion solutions would also affect the half-cell reduction potentialsconcentrated solutions increase the reduction potential while dilute solution decrease the reduction potential. Figure 3 displays the cell potential between half-cell #2 (Zn/Zn2+) and half-cell #3 (Pb/Pb2+). The average measured cell potential is moderately close to the calculated cell potential (using the half-cell reduction values calculated and displayed in Figure 1) with an error of 12.66%. However, the average measured cell potential varies quite drastically from the actual cell potential, with an error of 44.7%. This makes sense as the calculated values for the individual half-cell reduction potentials were most off for these two half cells Zn/Zn2+ and Pb/Pb2+. Curiously, it is the half-cells with the most oxidizing potential that had the greatest error. We hypothesize that this is probably a random error. Although we never got the chance to actually build the battery (
Zn( s) Zn 2 + , NO3 Ag + , NO3 Ag( s) , Pb( S ) Pb 2 + , NO3 Cu 2 + , NO3 Cu( s) )we calculated

that the total voltage of the battery using both our experimental half-cell reduction values and our
The error was a negligible 9.6%. The reason why we can actual half-cell reduction values.

simply add the cell potentials to get the total voltage of the battery is because the electrochemical cells are arranged in series. Since the voltage in essentially a change or difference in electric potential energy, the change in voltage is relative to the voltage after a cell. Although the current stays constant, we can therefore add together the individual cell potentials to get the total voltage. The concentration of a solution affects the half-cell potentials because it influences the relative stability of the ions. Because of the dissolution-precipitation equilibria, concentrated

solutions slow down the formation of more ions and therefore increase the reduction potential of the half reaction. On the other hand, dilute solutions (solutions with concentrations less than the standard 1 M) favor oxidation reactions and decrease the reduction potential of the half-reaction. To decrease the overall cell potential from 0.507 V to 0.50 V, the concentration of the cathode Cu/Cu2+ was reduced to 0.58 M. Pb( s) Pb 2 + (1 M ) Cu 2 + (0.58 M ) Cu( s) . The decrease in the concentration of Cu2+ led to a decrease in its half-cell reduction potential, leading to an overall

decrease in the cell potential. It is important to note, however, that the cell potential will not be
exactly 0.50 V. For one, it is difficult to make a dilute concentration of exactly 0.58 M especially since even this concentration (0.58) is a rounded figure. Additionally, the actual cell potentials of Cu/Cu2+ and Pb/Pb2+ varied quite a lot from the actual values. Figure 4 presents the averages of the potentials at which oxygen bubbles were first observed. There is a clear pattern among the different anodes and these average potentials: the bare FTO electrode required much greater applied potentials than did the CoPi catalyst coated electrodes. Additionally, the pre-grown CoPi catalyst coated electrode required less applied potential for oxidation than did our CoPi coated catalyst. This is most likely due to the fact that our CoPi coated catalyst was only grown for about an hour, and therefore had less CoPi coating on it than did the pre-coated ones. From just these values, it seems clear that CoPi is an effective catalyst for the electrolysis of water. Data from Figure 5, which displays the average overpotentials further support this conclusion. The average overpotential, using both the class data as well as ours, for the bare FTO electrode was 0.987 V. However, the overpotential for the pre-grown CoPi coated catalyst was significantly less0.251 V. Because the presence of CoPi results in a decrease in overpotential, we conclude that it is an effective catalyst. Moreover, the pre-grown CoPi catalyst coated electrode had a lower overpotential than our CoPi catalyst coated

electrode (0.496) because of the presence of more catalyst surface. The approximately 50% improvement in overall efficiency using the CoPi catalyst compared to a bare FTO electrode also indicates the effectiveness of CoPi as a catalyst for water electrolysis. This conclusion is extremely important to the realization of artificial water splitting systemsit indicates that the catalyst can form oxygen from water without the need for excessive driving potentials. The discrepancies in the values of average potentials and overpotentials could be due to a number of errors. For one, it is difficult to notice when the oxygen is produced since it is indicated only by very tiny bubbles forming on the FTO electrode. Moreover, the applied potential was supposed to be increased very slowlythe lack of time caused some groups to rush leading to average potentials and overpotentials that were likely higher than in actuality.

Conclusion In this experiment we attempted to meet several major goals. In part I, we hoped to measure the standard reduction potentials of several half-cells, examine the effect of concentration on cell voltage, and construct a battery out of two electrochemical cells. Although some of the standard reduction potentials we calculated were close to the actual values, others differed quite greatly. Consequently, if this experiment were to be repeated in the future, we would perform more trials. More importantly, with each trial we would use a different samples of the same metal for the electrodein this way, if one of the electrodes were contaminated or corroding, they could be ignored as outliers. This change would lead to a more accurate data set. In this experiment, we were only able to study the concentration and batteries through

calculations because of the restrictions on time. We would like to check our calculations by doing these sections experimentally rather than theoretically. In the second part of this lab we studied the overpotential required for water oxidation on several different electrodes: a bare FTO electrode, a CoPi catalyst covered electrode, and a pregrown CoPi catalyst coated electrode. We found that the CoPi catalyst aid in the production of oxygen from water without the need for excessive driving potentials. This conclusion has major implications for the future. The utilization of solar energy on a large scale requires its storage and artificial photosynthesis is one viable option. Artificial photosynthesis like natural photosynthesis uses energy from the sunlight to produce oxygen and hydrogen from water. Understanding catalysts and water-splitting chemistry could potentially make this artificial photosynthesis possible on a large scale. Nonetheless, as of now, the CoPi catalyst method is not very efficientas we saw it would take an extremely large electrode area if we wanted to run the output from a small rooftop solar panel of Sunpowers best Si modules. With further research and study of catalysts in the electrolysis of water, we could improve this efficiency.