Determination of Avogadro’s Number by Electrolysis

In an electrolytic cell, a power supply is used to drive chemical changes at the electrodes. Electrolysis
can be used in many ways, including plating of metals onto surfaces and production of various pure
elements from ore or other compounds.

For this experiment, we will use the electrolysis of copper to experimentally determine Avogadro’s
number. Two copper plates are immersed in a beaker containing copper sulfate solution. The copper
anode undergoes oxidation according to:

Cu(s) Cu2+(aq) + 2 e- [1]

While another copper plate electrode, the cathode, undergoes reduction:

Cu2+(aq) + 2e- Cu(s) [2]

The electrode to be plated is weighed before (mi = initial mass) and after the experiment (mf = final
mass). The difference in these masses represents the mass of plated metal:

m = mf – mi [3]

The electrical charge that flows through the system during electrolysis, q, can be calculated using the
following equation:

q=It [4]

where I is the current and t is the total running time.

Avogadro’s number, NA, can then be calculated using equation 5:

qM
NA = [5]
n m qe

where M is the atomic mass of the metal, n is the number of electrons in the half-reaction and qe is the
charge on one electron.

Faraday’s constant, F, can be calculated using equation 6:

qM
F = [6]
n m
 Electrolysis and Avogadro’s Number
PROCEDURE

1. Assemble the cell as shown in Figures 2 and 3. Make certain that the connections make good
electrical contact.

2. Remove the center plate, which is

the cathode, and clean it with
sandpaper. Hold it by the edges
or with a tissue when it is clean.

3. Weigh the cathode to the nearest

milligram and reattach it to the
cell.

4. Fill the glass beaker about ¾ full

with the copper sulfate solution. Figure 2. Electrolysis apparatus
Have the lab instructor check
your apparatus to insure that all connections are correct. CAUTION: The copper sulfate
electrolysis solution contains sulfuric acid and is corrosive to tissue; use appropriate procedures
in handling this solution.

5. At "zero time", immerse the electrodes in the solution, start the timer, and adjust the resistor so
that one half amp (0.50A) flows through the cell. These steps should be done in a few seconds.
Record the precise value of the current to as many significant figures as possible.

6. Periodically check the ammeter, and adjust the resistor to keep the current constant.

7. After 20 minutes, terminate the electrolysis by removing the cell top with the electrodes from the
solution. Stop the timer as you remove the electrodes.

8. Disconnect the wire leads from the top and rinse the center electrode with deionized water.
Follow the water rinse with an acetone rinse.

9. Carefully remove the center electrode, prop it against a

beaker, and allow it to dry completely.

10. Weigh the dry cathode to the nearest milligram.

11. Carry out a second trial and third trial.

12. Return the copper sulfate solution to the storage

bottles. Disassemble the apparatus and rinse all
glassware with deionized water.

13. From the net change in mass of the electrode and the
total quantity of charge consumed in the electrolysis,
calculate Avogadro’s number and the Faraday
constant.
Figure 3. Electrolysis Circuit Diagram

2
 Electrolysis and Avogadro’s Number

Name:
___________________________________________________________________________

1. A constant current of 500 mA is delivered over 16.0 minutes. Calculate the electrical charge
delivered.

2. Given the values in question 1, calculate how many grams of copper are expected to plate.

3. The instructions are clear that the center electrode should be connected to the negative terminal
of the battery and thus should serve as the cathode. What would be the outcome if just the
opposite were done? What effect would this have upon the procedure and the final results?

4. The electrolysis could conceivably be conducted at either higher or lower current levels. What
would be the effect(s) of such modification to the experiment?

5. The electrolyte in this experiment is returned to the storage bottle for re-use. Why is this
possible?

3
 Electrolysis and Avogadro’s Number
Data:

Mass of cathode, g Avogadro’s Faraday’s

Trial Initial Final Change Time, s Current, Charge, Number Constant
A C
1

Average

6. Compare your experimental values for Avogadro’s number and the Faraday constant to the
accepted values. Calculate the absolute and relative error.

http://chemistry.about.com/cs/generalchemistry/a/aa121903a_2.htm

http://chemistry.about.com/cs/generalchemistry/a/aa121903a.htm

http://www.westminster.edu/acad/sim/pdf/SDeterminingAvogadro_001.pdf

http://web.cocc.edu/zziegler/G_CHM_Spring/LABS/Labwk5_AvogadrosNO.pdf