Discussion
Electrochemical Half-cell
The half-cells constructed in this experiment consist of a piece of metal in
contact with an aqueous solution containing ions of the same metal. StandardState Conditions for such a half-cell require that the metal-ion concentration be
2+
1.0 M. Thus, a piece of pure zinc in a 1.0-M solution of Zn ions constitutes a
2+
Electrochemical Cell
If two half-cells are connected by placing a wire between the pieces of metal and by adding a salt bridge
between the two solutions, a direct electric current can flow through the circuit. The electric current is
generated because metal atoms in the more reducing metal convert to ions and leave one electrode to
enter the solution and ions of the less reducing metal accept electrons and plate out on the other electrode.
The electrons left behind when positive ions are formed at one electrode pass through the external circuit
and into the other electrode. There the electrons combine with ions from the solution to form metal
atoms. By measuring the direction of current flow, and the voltage generated in the cell, you can
determine which is the more reducing metal (stronger reducing agent), and by how much.
This experiment was designed and written by Joe March and revised by Gordon Bain. Further revision by Chad C. Wilkinson and John W.
Moore. Adapted by Julie C. Schlenker for use at Harvard. Copyright 2011 by the Department of Chemistry, University of Wisconsin.
Experiment 7
Salt Bridge
In order for current to flow, there must be a complete
electric circuit. The wire is part of the circuit and the salt
bridge completes the circuit. In this experiment, the salt
bridge is a porous cylinder soaked with 1.0 M aqueous
potassium nitrate. Remember that solutions of salts, such
as potassium nitrate, are electrolytesthey conduct
electrical current by movement of positive and negative
ions in the solution. Thus the porous cylinder provides a
path for conduction of electricity, just as the wire does,
completing the electrical circuit. Because diffusion of
the solutions through the porous cylinder is slow, there will be no mixing of the solution of one half-cell
with the solution of another on the time scale of the experiment. Thus the half-cells are connected
electrically, but not chemically, by the salt bridge.
Without a salt bridge a cell will not produce an electric current and you will not be able to measure the
electrical potential difference between the two electrodes.
Experiment 7
Because oxidation is defined as loss of electrons (increase in oxidation number), the half-cell where
oxidation is taking place generates electrons and causes the piece of metal to become more negative.
Thus, when the leads are connected so that the meter reading is positive, the anode (where oxidation is
occurring) is the electrode connected to the negative lead of the meter and the cathode is the electrode
connected to the positive lead. The meter reads the difference in potential between the positive lead and
the negative lead, so, when the meter reading is positive:
Ecell = Ecathode Eanode
Experimental Procedure
Safety in the Laboratory
Safety glasses or safety goggles and lab coats must be worn at all times while in the laboratory.
Nitrile gloves must be worn at all times while performing this experiment or handling chemicals.
Long sleeves must be worn as students will be working with 1 M silver nitrate that will stain your
skin. Do not lean on the lab surface.
The aqueous metal salt solutions may irritate your skin. In case of contact with the skin, wash the
affected area with water for 15 minutes.
Make sure you wash your hands before leaving the laboratory.
All solutions should be poured into the waste collection bucket provided.
Metal wire or foil must be washed thoroughly with distilled water, dried, and then returned to the
center bench. Do not put any solid metal in the trash!
Plastic pipettes can be tossed into solid trash after rinsing with distilled water
Multi-EChem module
multimeter with leads
alligator clips
copper strip, Cu (s)
zinc strip, Zn (s)
nickel, Ni (s)
iron nail, Fe (s)
silver strip, Ag (s)
sandpaper
1 M solution
Copper (II) nitrate
Zinc nitrate
Nickel (II) nitrate
Iron (II) chloride
Silver nitrate
2. Gently dispense 5 mL of KNO3(aq) into the center well of the Multi-EChem Module.
3. Obtain one strip of each type of metal (the electrode) from the center bench. If necessary, use
sandpaper to clean the surface of the metal and remove any oxide coating.
4. Place a metal electrode in each corresponding solution (e.g., Zn in the Zn(NO3)2(aq) solution, etc.).
5. All half-cells can be prepared in the Multi-EChem Module at the same time.
Thoroughly rinse all metal strips with distilled water over the Used Chemicals beaker. Dry the
metal strips with a paper towel and return them to the appropriate location at the center bench.
Thoroughly rinse your EChem module with distilled water, making sure that all rinse water goes
into the Used Chemicals beaker. Place your clean EChem module back at the center bench.
Rinse out the 10 mL flasks and the pipet with distilled water and put them back at the center
bench.
Pour all aqueous waste and the contents of your Used Chemicals beaker into the proper waste
container in the hood.
Put the multimeters and alligator clips back at the center bench.
Wipe down your lab bench with a paper towel when you are done.
TF:
Name:
Read the entire lab report, including the previous introduction and discussion, and the entire
procedure.
Complete the Prelab, which is the last page of the lab report, and turn the prelab into your TF as
you enter the lab.
Safety glasses or safety goggles and lab coats must be worn at all times while in the laboratory.
Nitrile gloves must be worn at all times while performing this experiment or handling chemicals.
Long sleeves must be worn as students will be working with 1 M silver nitrate that will stain your
skin. Do not lean on the lab surface.
The aqueous metal salt solutions may irritate your skin. In case of contact with the skin, wash the
affected area with water for 15 minutes.
Make sure you wash your hands before leaving the laboratory.
All solutions and aqueous waste should be disposed of in the waste bucket in the back hood.
Metal wire or foil must be washed thoroughly with distilled water, dried, and then returned to the
center bench. Do not put any solid metal in the trash!!
The EChem module must be rinsed with distilled water and returned to the center bench.
Wipe down your lab bench with a paper towel when you are done.
Submit your data and lab report to your TF. This page and all subsequent pages must be stapled
and turned in.
Wash your hands before leaving the lab.
Grading:
Prelab:
/10
Lab Report:
/20
Safety:
/3
Cleanup:
/2
Total:
/35
Negative lead
potential (V)
Cu|Cu
Cu|Cu
2+
Zn|Zn
2+
2+
Fe|Fe
2+
Ag|Ag
2+
2+
Zn|Zn
Ni|Ni
2+
Fe|Fe
2+
Ag|Ag
Metals are often listed as an electromotive (or electrochemical) series. Such a series places metals that
are most easily oxidized at the top. For example, sodium metal is very easily oxidized to sodium ions
so easily that it reacts with water to produce sodium ionsso sodium is near the top of the
electrochemical series. Consider the metals you worked with in this experiment. When a metal is
oxidized, ions of another metal are reduced at the same time. Since oxidation occurs at the anode, think
about your results for observed cell potentials, and list the metals in order of their ability to be oxidized.
Use your data from the table above to place each metal in the correct position in the electromotive series
below. Put the most easily oxidized metal at the left of the list and the least easily oxidized metal at the
right end.
Electromotive Series:
>
>
>
>
2+
2+
Conc. of Cu (aq)
(M)
(M)
(V)
(V)
1M
0.1 M
0.01 M
0.001 M
0.0001 M
3. On the axes below, plot your data from the previous table( i.e. plot Ecell vs. the log of the copper-ion
+
concentration). You
should plot the data collected using the Ag|Ag half-cell and the data collected
2+
using the Zn|Zn half-cell on the same axes.
Using a calculator or software, fit a line to each data set
2
and determine its slope, y-intercept, and R value.
y-int. =
R =
y-int. =
R =
2+
Lab Report
1. Discuss the graphs you obtained for cell potential as a function of the log of the copper (II)-ion
concentrations in Part B. How are the graphs of data from the silver half-cell and from the zinc
half-cell similar, and how are they different?
2. Oxidation occurs at the anode () and reduction occurs at the cathode (+). Using this information
and your data from Part A of the lab, write a complete balanced equation for the reaction that
2+
2+
occurs when the half cells are Cu|Cu and Zn|Zn , and then write a complete balanced equation
2+
+
for the reaction that occurs when the half-cells are Cu|Cu and Ag|Ag . Explain how you knew
which substance was being oxidized and reduced in each case.
3. Using your answers from problem 2, write out the Nernst equation for the reaction when the half2+
2+
cells are Cu|Cu and Zn|Zn , and write out the Nernst equation for the reaction when the half2+
+
cells are Cu|Cu and Ag|Ag . Using these equations, explain the reason for the differences in the
graphs that you noted in problem 1.
Experiment 7
2+
2+
2+
4. In the reaction that occurs when the half-cells are Cu|Cu and Zn|Zn , is Cu a reactant or a
product? Without referencing the Nernst equation, can you use concepts of equilibrium and
2+
LeChateliers principle to explain the relationship between Cu concentration and voltage? Note
that the greater (more positive) the value of Ecell, the greater the tendency of the reaction to run in
the forward direction and produce products.
5. Describe three possible sources of error in your measurements of cell potentials and how the
potentials would be affected by the error.
6. Predict the effect of replacing the 1 M copper (II) nitrate solution used in this experiment with a
1 M copper (II) chloride solution. Explain the basis for your prediction.
7. Suppose that before you began your experiments the supply of potassium nitrate for the salt
bridge solution had run out. The only substitute you could find was zinc nitrate solution. Will
using the zinc nitrate solution in the salt bridge compartment affect the cell potential you
measure? Why or why not
Experiment 7
Prelab
To be completed and handed in as you enter the lab.
2+
1. Suppose you connect the positive lead to a Zn|Zn half-cell and the negative lead to an Mg|Mg
half-cell and obtain a reading of +0.656 V from the multimeter.
2+
Draw a diagram of this electrochemical cell. Label the metals and corresponding solutions and
indicate the direction of electron flow. Which metal is the anode and which metal is the cathode?
Explain how you know.
2. You will have two 10 mL volumetric flasks and a 1 mL volumetric pipet to use for part B.
Explain how you will make solutions with copper-ion concentrations ranging from 0.1 M to
0.0001 M, starting with 1 M copper (II) nitrate.
Experiment 7