Experiment 9: Electrochemistry – Voltaic Cells

John To

4 December 2017

Fullerton College - Chemistry 111B Lab Manual

Objective

This experiment will investigate redox reactions, both, qualitatively and quantitatively. Different voltaic
cells will be constructed in order to measure experimental standard cell potentials, E°cell. The Nernst
equation will be used to find the concentration of Cu 2+ in an unknown solution.

Introduction

Redox, or oxidation-reduction, reactions involve the transfer of electrons from one species to another.
These reactions can be split into two half-reactions which are classified as oxidation and reduction. In the
oxidation half-reaction, one reactant donates electrons whereas in the reduction half-reaction, one
reactant accepts electrons. In the following example, copper (II) ions are reduced by a metal, zinc. Here,
zinc is a reducing agent because it donates electrons to the copper (II) ions. As a result, the copper (II)
ions are reduced to copper metal. At the same time, the copper (II) ions oxidize the zinc and is referred
to as the oxidizing agent.

Oxidation Half-Reaction: Zn(s) → Zn2+ (aq) + 2e-

Reduction Half-Reaction: Cu 2+(aq) + 2e- → Cu(s)

Net Redox Reaction: Zn(s) + Cu 2+(aq) → Zn2+(aq) + Cu(s)

Each half-reaction has a measure of spontaneity given by respective standard potential values measured
in volts, E°. By convention, these half-reactions are reported as reductions and the standard reduction
potentials are tabulated. The tabulated potential values are used to compare the relative oxidizing
strengths or various species. An example of this can be seen in the following standard reduction
potentials based on the half-reactions of zinc and copper:

Cu2+(aq) + 2e- ⇋ Cu(s) E° = + 0.34 V

Zn 2+(aq) + 2e- ⇋ Zn(s) E° = - 0.76 V

1
These reduction potential values indicate that Cu 2+ is more likely to be reduced when compared to Zn 2+.
The opposite is true for oxidation as the values indicate that zinc is more likely to be oxidized when
compared to copper.

A voltaic, or galvanic, cell uses a spontaneous redox reaction to produce an electric current. In such a
cell, the half-reactions are split into two different compartments called half-cells. Each compartment
contains a metal (the electrode), which is immersed in an electrolyte containing cations of the metal. The
electrode at which oxidation occurs is referred to as the anode and the electrode at which reduction
occurs is referred to as the cathode. Upon connection of the electrodes, electrons flow through a wire
from the anode to the cathode while ions are allowed to flow between the two half-cells through a salt
bridge.

The theoretical voltage provided by the cell (with 1.0 M solutions) can be calculated from the standard
half-fell reduction potentials:

E°cell = E°cathode - E°anode

Using this equation, the standard cell potential, E° cell, of a Zn/Cu voltaic cell is +1.10 V. A positive value for
E°cell indicates that the redox reaction will be spontaneous when connected in a voltaic cell, resulting in
an electric current.

It is often necessary to find the cell potential when the solutions are not the standard, 1.0 M,
concentrations. Under non-standard conditions, the cell potential, E cell, can be calculated using the Nernst
equation:

Ecell =E ° cell− ( RTnF ) ln Q

R: Ideal Gas Constant, 8.314 J mol-1 K-1
T : Temperature in kelvin
n : number of electrons transferred
F : Faraday Constant, 9.65 ∙ 104 J V-1 (mol e-)-1

Using the Zn/Cu redox reaction as an example: Zn(s) + Cu 2+(aq) → Zn2+(aq) + Cu(s)

2+¿
Zn¿
¿
2+¿
Cu¿
¿
¿
Q=¿

2
 ↓

2+¿
¿
Zn
¿
2+¿
Cu ¿
¿
¿
ln Q=ln¿

If [Zn2+] is held constant at 1.0 M while [Cu 2+] is varied, the Nernst equation reduces to:

2+¿
Cu¿
¿
¿
RT
Ecell = ( )
nF
ln ¿

This form of the equation follows that of a line (y = mx + b) and shows that Ecell will vary linearly with

ln[Cu2+] where Ecell is y and ln[Cu2+] is x. The slope ( RTnF ) and the y-intercept (E°cell) will be constant as

long as the temperature does not change over the course of the experiment.

The equation of the best-fit line, resulting from linear regression, can be used to determine the
concentration of Cu2+ in an unknown solution. This involves measuring the value of Ecell under the same
conditions as before, substituting the unknown Cu 2+ solution for the standard Cu2+ solutions that were
used to construct the pot. The cell potential increases with increasing concentrations of Cu 2+.

Chemicals and Equipment

24-well plate 1.0 M copper (II) nitrate, Cu(NO 3)2

1 mL graduated pipet and bulb Unknown copper (II) nitrate solution

Forceps 1.0 M lead (II) nitrate, Pb(NO 3)2

LabQuest 2 with voltage probe 1.0 M zinc nitrate, Zn(NO 3)2

Sand paper 1.0 M acidified* iron (II) sulfate, FeSO 4

3
Folded filter paper strips 1.0 M silver nitrate, AgNO 3

50 mL volumetric flasks (3) Small strips of copper, lead, zinc, and silver

Nitrile gloves 1.0 M potassium nitrate, KNO 3

Iron nails

*NOTE: Iron (II) sulfate solution must be acidified to help prevent the oxidation of iron (II) to iron (III). A
freshly prepared iron (II) sulfate solution should appear light green in color.

Safety

Most solutions used in this lab are skin and eye irritants. Wear gloves at all times when handling
solutions. Once wearing gloves, do not touch anything except lab equipment.

Be especially cautious when using silver nitrate and lead (II) nitrate solutions as they are toxic if ingested
or absorbed through the skin or eyes. Silver nitrate is light sensitive and will stain the skin and lead (II)
nitrate is a known carcinogen when ingested.

None of the solutions are safe to pour down the drain. Dispose of all waste in appropriate containers.

Procedure

NOTE: If concentrations of aqueous solutions are not stated, assume molarity to be 1.0M.

Part I: Redox Reactions

Place a 24-well plate on a paper towel and label it according to the diagram below (Figure 1).

1M 1M 1M
Cu(NO3)2 Pb(NO3)2 Zn(NO3)2

#1effff
Cu(s) #2
ffffffff
fffff

4
 PB(s) #3 #4

#6
Zn(s) #5

Figure 1. Part I well plate setup

Fill the wells in each column (about ¾ full) with the indicated, appropriate aqueous solutions. Wells that
are shaded grey in the diagram are unused wells and no solutions should go in these wells. Obtain about
two small strips of each metal and partially submerge them in the rows as indicated. Note that the
solutions are added by columns and that the solid strips are added by rows. Wait five minutes to allow
for any redox reactions to occur. Record observations for each well. Be specific about any change that
signifies and gives evidence of a chemical change. If not change is observed write “no reaction”. Once
observations have been made discard the waste in appropriate waste containers, separating the solid
waste from the liquid waste

Part II: Reduction Potentials

Several voltaic cells will be constructed in the well plate. Start by rinsing the well plate thoroughly with
deionized water and then by drying it with a Kimwipe. Obtain a LabQuest 2 and a voltage probe. While
touching the alligator clips together, click on the red area of the LabQuest 2 and choose “Zero” from the
dropdown menu. The sensor is now ready to use.

This is the first voltaic cell that will be constructed: Zn(s) | Zn(NO 3)2(aq) || Cu(NO3)2(aq) | Cu(s)

Fill one well ¾ full with 1.0 M Zn(NO3)2 and fill an adjacent well ¾ full with 1.0M Cu(NO 3)2 while making
sure not to splash one solution into the other. Wet a pre-folded strip of filter paper with 1.0 M KNO 3. If
necessary, remove excess solution by blotting with a Kimwipe. This paper will serve as the salt bridge.
Place this salt bridge so that the ends are immersed in the two solutions. Be careful as the wet paper
tears easily when wet. Obtain and lightly sand one strip of zinc. Do not sand the metal directly on top of
the lab bench as this will scratch the surface of the lab bench. Obtain a piece of copper and decide which
metal is more likely to become oxidized. This is the anode, so connect the black alligator clip to this metal
strip and the red clip to the other. In order to obtain a positive voltage, the black lead connects to the
anode and the red lead connects to the cathode. The recorded voltage will be commonly be less than
what was calculated from the standard reduction potentials. This is partly due to oxidation that occurs
very rapidly on the surface of most metals when exposed to air.

5
Following the same steps, prepare the following voltaic cells using two adjacent, dry and clean wells for
each while making the appropriate substitutions for the solutions and metals:

Zn(s) | Zn(NO3)2(aq) || Pb(NO3)2(aq) | Pb(s)

Zn(s) | Zn(NO3)2(aq) || Fe(NO3)2(aq) | Fe(s)

Zn(s) | Zn(NO3)2(aq) || AgNO3(aq) | Ag(s)*

*Obtain the silver metal from the instructor and do not dispose of the silver metal strip. Return the silver
metal strip in its original vial after it has been rinsed with deionized water and dried with a Kimwipe.

Again, make sure discard of solid and liquid waste appropriately.

Part III: Nernst Equation – Varying Cu2+ Concentrations

Using zinc and copper electrodes, voltaic cells will be prepared again with the concentration of Cu(NO 3)2
varying and the concentration of Zn(NO3)2 remaining at 1.0 M throughout. Using the Nernst equation, a
plot of Ecell against ln[Cu2+] will be used to find the concentration of Cu 2+ in an unknown solution.

Prepare 1.0 ∙10-2 M Cu2+

Using 1 mL of stock 1.0 M Cu(NO3)2 solution, prepare 100 mL of diluted solution. Do this by pipetting,
after conditioning, 1mL of stock Cu(NO3)2 solution to a 100 mL volumetric flask and then filling the flask
to the calibration mark with deionized water.

Prepare 1.0 ∙10-4 M Cu2+

Using 1 mL of 1.0 ∙10-2 M Cu2+ solution, perform a second dilution. After conditioning, pipet 1mL of
1.0 ∙10-2 M Cu2+ solution to a 100 mL volumetric flask and then fill the flask to the calibration mark with
deionized water.

Prepare 1.0 ∙10-6 M Cu2+

Using 1 mL of 1.0 ∙10-4 M Cu2+ solution, perform a third dilution. After conditioning, pipet 1mL of
1.0 ∙10-4 M Cu2+ solution to a 100 mL volumetric flask and then fill the flask to the calibration mark with
deionized water.

After the serial dilutions, rinse the well plate thoroughly with deionized water and dry with a Kimwipe.
Fill a well about ¾ full with Zn(NO3)2 solution and an adjacent well with 1.0∙10 -6 M Cu(NO3)2, the least
concentrated Cu2+ solution.

6
As done in Part II, prepare a new salt bridge using a folded strip of filter paper and KNO 3. Connect the
two half-cells by immersing one end of the salt bridge in one half-cell and the other end in the other
half-cell. Set up the rest of the well plate with solutions (Table 1) according to the diagram (Figure 2).

Table 1. Voltaic Cell Solutions

Solution # [Cu2+], M
1 1.0 ∙10-6
2 1.0 ∙10-4
3 1.0 ∙10-2
4 1.0

Voltaic Cell # 1 Voltaic Cell # 2

Zn2+ Zn2+ #2
#1

Zn2+ #3 Zn2+ #4

Voltaic Cell # 3 Voltaic Cell # 4

Figure 2. Well plate diagram for voltaic cells

7
Once the well plate has been filled, obtain one strip, each, of copper and zinc. Lightly sand both sides of
the zinc. Attach the black alligator clip to the appropriate metal (the anode). This will be the same metal
as in Part II. Attach the red alligator clip to the other metal (the cathode).

As in Part II, hold the copper strip in the Cu(NO 3)2 solution and the zinc strip in the Zn(NO 3)2 solution
while making sure that the alligator clips do not touch the solutions and that the metal strips do not
touch the salt bridge. Keep the strips in the solutions for about 5 – 10 seconds or until the reading
becomes relatively stable and record the non-standard cell potential, E cell. If a negative potential is read,
switch the metals that the alligator clips are attached to, making sure to wipe off and sand the zinc
beforehand.

Once a potential value is obtained, wipe off the metals. Continuing in the same manner as above, obtain
potential values for remaining voltaic cells prepared in the order of increasing concentration of Cu(NO 3)2.

Lastly, choose two clean, dry and adjacent wells and prepare a voltaic cell, as above, using Zn(NO 3)2 in
one well and the unknown copper solution in the other. As done for the previous four voltaic cells,
obtain and record the cell potential for this cell. Once this data has been obtained, dispose of waste in
appropriate containers and rinse and dry the well plate before putting it away.

Data

Table 2. Part I – Redox Reactions

Well # Observations
1 No Reaction

2 No Reaction

3 Color change (blue to green), metal dissolved

4 No Reaction

5 Color change (blue to green), black precipitate formed on metal

6 Black precipitate formed on metal

Table 3. Part II – Reduction Potentials

Voltaic Cell (Shorthand Notation) Measured E°cell, V

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) 0.993
Zn(s) | Zn2+(aq) || Pb2+(aq) | Pb(s) 0.485

8
 Zn(s) | Zn2+(aq) || Fe2+(aq) | Fe(s) 0.376
Zn(s) | Zn2+(aq) || Ag+(aq) | Ag(s) 1.427

Table 4. Part III – Nernst Equation (Varying Cu 2+ Concentration)

[Cu2+], M Measured E°cell, V

1.0 ∙10-6 0.808
1.0 ∙10-4 0.867
1.0 ∙10-2 0.938
1.0 0.986
Unknown 0.968

Calculations and Results

The molarity of the unknown copper solution was found to be 0.180 M.

Part I : Redox Reactions

Table 5. Theoretical E°cell Values and Spontaneity

Well # Net Reaction Theoretical E°cell, V Spontaneous?

2+¿(aq)+ Pb (s)
1 2+¿ ( aq ) → Cu¿ - 0.13 - (+ 0.34) = - 0.47 No
Cu ( s ) + Pb¿
2+¿( aq)+ Zn( s)
2 2+¿ ( aq ) →Cu¿ - 0.76 - (+ 0.34) = - 1.10 No
Cu ( s ) + Zn¿
2+¿(aq)+ Cu(s)
3 2+¿ ( aq ) → Pb¿ + 0.34 - (- 0.13) = 0.47 Yes
Pb ( s ) +Cu ¿
2+¿( aq)+ Zn( s)
4 2+¿ ( aq ) → Pb¿ - 0.76 - (- 0.13) = - 0.63 No
Pb ( s ) + Zn¿
2+¿(aq)+ Cu(s)
5 2+ ¿ ( aq ) → Zn¿ + 0.34 - (- 0.76) = 1.10 Yes
Zn ( s )+ Cu¿

9
 2+¿(aq)+ Pb (s)
6 2+ ¿ ( aq ) → Zn¿ - 0.13 - (- 0.76) = 0.63 Yes
Zn ( s )+ Pb ¿

Part II : Reduction Potentials

Using the known value for the standard half-cell potential of zinc, the anode, the potential of the
cathode (the different metals) half-cell can be calculated for each voltaic cell. The following is the half-
reaction that occurs at the anode for each voltaic cell along with the standard reduction potential, which
will be E°anode:

Zn2+(aq) + 2e- ⇋ Zn(s) E° = - 0.76 V

The equation for the standard potential of the voltaic cell can then be manipulated to solve for the
experimental E° of the cathode, E°cathode:

E°cell = E°cathode - E°anode

E°cathode = E°cell + E°anode

E°cathode = E°cell + ( - 0.76 V)

E°cathode = E°cell – 0.76 V

Voltaic Cell: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s); E°cell = + 0.993 V

E°cathode = + 0.993 V – 0.76 V

E°cathode = + 0.233 V,

Voltaic Cell: Zn(s) | Zn2+(aq) || Pb2+(aq) | Pb(s); E°cell = + 0.485 V

E°cathode = + 0.993 V – 0.76 V

E°cathode = - 0.275 V

Voltaic Cell: Zn(s) | Zn2+(aq) || Fe2+(aq) | Fe(s); E°cell = + 0.376 V

E°cathode = + 0.376 V – 0.76 V

10
 E°cathode = - 0.384 V

Voltaic Cell: Zn(s) | Zn2+(aq) || Ag+(aq) | Ag(s); E°cell = + 1.427 V

E°cathode = + 1.427 V – 0.76 V

E°cathode = + 0.667 V

The percent errors were calculated using the following formula:

¿ Theoretical−Experimental∨ ¿ × 100
Theoretical
error =¿

As an example, percent error in E° for Ag is calculated as follows:

¿ 0.80 V −0.67 V ∨ ¿ × 100

0.80 V
error =¿

% error = 16.25 %

Table 8. Reduction Potentials of Half-Reactions

Half-Reaction (Reduction) Theoretical E°, V Experimental E°, V Percent Error, %

Ag+(aq) + e- ⇋ Ag(s) + 0.80 + 0.67 16
Cu2+(aq) + 2e- ⇋ Cu(s) + 0.34 + 0.23 32
Pb2+(aq) + 2e- ⇋ Pb(s) - 0.13 - 0.28 110
Fe2+(aq) + 2e- ⇋ Fe(s) - 0.44 - 0.38 14
Zn2+(aq) + 2e- ⇋ Zn(s) - 0.76

11
 Part III: Nernst Equation (Varying Cu2+ Concentrations)

Table 9. Data for Nernst Plot

[Cu2+],
ln [Cu2+] E°cell, V
M
0.00000
-13.8155 0.808
1
0.0001 -9.21034 0.867
0.01 -4.60517 0.938
1 0 0.986

Graph 1. Nernst Plot

Nernst Plot: Zn(s) | Zn2+(aq) (1.0 M) || Cu2+ (aq) | Cu(s)

1
f(x) = 0.01x + 0.99
R² = 1
0.95
Ecell, V

0.9

0.85

0.8
-14 -12 -10 -8 -6 -4 -2 0
ln [Cu2+]

To find the molar concentration of Cu2+in the unknown solution the equation of the best-fit line was used
(Graph 1).

y=0.0131 x+ 0.9905

12
 2+¿
Cu¿
¿
¿
RT
Ecell =( )
nF
ln ¿

2+¿
Cu¿
¿
¿
Ecell =( 0.0131 ) ln ¿

2+¿
¿
Cu
¿
¿
ln ¿

2+¿
E −0.9905
(
Cu =e 0.0131
¿
cell
)
¿
↓

2+¿
Cu ¿
¿
¿
where Ecell = 0.968 V

Discussion

In first part of the experiment, different redox reactions were observed. The observations matched with
what was guess prior to the experiment. The theoretical potentials that were found to be negative were
linked to the wells in which there was no reaction. Positive theoretical potentials were linked to the wells
in which there was a reaction. This means that a positive theoretical potential of a cell indicates a
spontaneous reaction.

13
In the second part of this experiment, four voltaic cells were constructed and standard potentials were
measured. In all of these cells, zinc was the anode while different metals were used as the cathode. From
the measured potential values of the cells and the known reduction potential of the zinc half-reaction,
the reduction potentials of the metals were found. From the calculated potential values, the oxidizing
agents, in increasing strength, can be listed in the following order: Fe 2+, Pb2+, Cu2+, and Ag+. Also, the
metals, in increasing strength as reducing agents can be listed as follows: Ag, Cu, Pb, and Fe.

In the third part of the experiment, three serial dilutions beginning with the stock Cu(NO 3)2 were
produced and all four of the copper (II) nitrate solutions were used to create voltaic cells. The copper
solutions were used in the cathode half-cells and all the anode half cells consisted of 1.0 M Zn(NO 3)2. The
cell potentials were measured and used, along with the concentrations, to produce a Nernst Plot (Graph
1). The cell potential between the stock zinc solution and an unknown Cu 2+ solution was also measured.
This potential allowed for the calculation of the molarity of the unknown solution and this molarity was
found to be 0.180 M Cu2+.

Error Analysis

One of the main sources of error in this experiment is due to the nature of metals to oxidize
spontaneously and also very quickly. This is why, for example, the zinc was sanded down. As a
precaution, the other metals were also lightly sanded. If the metals used were in oxidized states, errors
would arise from this. In Part II, there was a wide range in the errors calculated. As the magnitudes of
values increased, there was less error which also meant that as the magnitudes of the values decreased,
there was more error. This can be seen in the example of Ag which had 16 % error versus Pb which had a
110 % error. Another factor that could affect the errors could be temperature. While, it was assumed
that the temperature would stay constant, it is possible that the temperature may have changed.
However, no noticeable temperature changes were noted.

14