Determination of Avogadros Number by Electrolysis

Preliminary Reading: Chang, section 19.8 Electrolysis reactions are nonspontaneous oxidation-reduction reactions that take place when an external voltage source 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 ores or other compounds. In this experiment we will use the electrolysis of copper to experimentally determine Avogadros number. Two copper plates are immersed in a beaker containing copper sulfate solution. The copper anode undergoes oxidation according to: Cu(s) g Cu2+(aq) + 2 eG While another copper plate electrode, the cathode, undergoes reduction: Cu2+(aq) + 2eG g Cu(s) [2] [1]

The electrode to be plated (the cathode) is weighed before and after the experiment. The difference in these masses represents the mass of plated metal. Electrical current, I, is defined as the time rate of passage of electrical charge, q. I=q/t Units: 1 ampere (A) = 1 coulomb (C) /sec (s) [3]

The electrical charge that flows through the system during electrolysis can be calculated by measuring the current with an ammeter and the time period over which current is allowed to pass through the cell. Avogadros number, NA, can be calculated if we know the number of Cu atoms plated out, N(Cu), and the number of moles of Cu plated out, n(Cu). NA = N(Cu) / n(Cu) atoms/mol [4]

The number of moles is determined from the mass, m, of Cu plated and the molar mass M, 63.55 g/mol. n(Cu) = m / M [5] The number of atoms of Cu plated, N(Cu), is related to the number of electrons that has passed through the circuit, N(e-), taking note of the stoichiometry of equation [2]. N(Cu) = N(eG) But how do we find the number of electrons? You will recall that Robert Millikan measured the charge on one electron in the oil-drop experiment and found it to be 1.602 x 10-19 C/e-; this value is commonly symbolized e. Thus, if we know the total charge in coulombs that has passed through the cell, we can calculate the number of electrons that have passed through the cell. N(eG) = q / e [7] [6]

Now, the combination of equations 4-7 allows the calculation of NA. The electrical unit one faraday, F, is defined as the amount of electrical charge on one mole of electrons. Interpreting equations 1 and 2 in terms of moles rather than atoms, we can calculate the number of moles of electrons by first determining the number of moles of copper plated (equation 5), and then taking the stoichiometry of equation 2 into account (2 mol eG / 1 mol Cu). If we divide the total charge passed through the cell (equation 3) by the number of moles of electrons passed through the cell, the result is the value of the faraday.: F = q / n(eG) C/mol [8]

PROCEDURE 1. Assemble the cell as shown in Figures 2 and 3. Make certain that the connections make good electrical contact. Note that an AC-DC converter is used in place of the dry cell. Be sure that the converter is set for the lowest voltage and observe the proper polarity. 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 0.001 g and reattach it to the cell. 4. Fill the glass beaker about 3/4 full with the copper sulfate solution. 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 while simultaneously starting the timer, then quickly adjust the resistor so that one half amp (0.50A) flows through the cell. 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 0.001 g. 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. 2

13. From the net change in mass of the electrode and the total quantity of charge consumed in the electrolysis, calculate Avogadros number and the Faraday constant. Note that you may not use the known values of either NA or F in these calculations.

Figure 2. Electrolysis apparatus

Figure 3. Electrolysis Circuit Diagram