.

MOLAR MASS OF COPPER BY ELECTROLYSIS

Electrolysis is the general term for reactions in which chemical changes occur at electrodes under
the influence of an electrical current. A diagram of a generalized electrochemical cell is shown in
Figure 9.

Figure 9. Generalized electrochemical cell

Notice that the positively charged cations migrate to the cathode for subsequent reduction and
the anions migrate to the anode at which they are oxidized. Power to support the overall reaction
is supplied in this case by an external battery. When the switch is closed, electrons flow through
the external circuit from the anode to the cathode. Simultaneously, ions migrate toward the
electrodes and chemical reactions occur at the electrodes to complete the circuit. These reactions
result in the plating out or dissolution of substances on the electrode surfaces or the evolution of
gases from the electrode surfaces. In both processes, the ionic substances either lose or gain
electrons; and such reactions are called oxidation or reduction reactions, respectively. The entire
process of current flow and chemical reaction is called electrolysis.

Quantitative measurements of the changes that occur at the electrode surfaces reveal that a
relationship exists between the amount of charge passed through the cell and the amount of
chemical change at the electrodes. Michael Faraday first studied these phenomena early in the
nineteenth century and his observations laid a basis for the development of the atomic theory.
From Faraday's work, two fundamental laws can be formulated:

1. The mass of a substance produced by an electrode reaction in electrolysis is directly

proportional to the quantity of electricity passed through the cell.
2. The masses of different substances produced by the same quantity of electricity are
proportional to the equivalent weights of the substances.

The second statement introduces the term "equivalent weight", and this exercise is directed
toward the determination of the equivalent weight of one substance, copper.
We may say that the extent of reaction is proportional to the number of moles of electrons lost or
gained in an oxidation or reduction reaction. For example, in the reduction of silver cations to
silver metal as described by the reaction

Ag+(aq) + e- Ag(s) [1]

one mole of electrons "react" with one mole of silver ions to produce one mole (i.e., 107.8 g) of
solid silver. Thus in this case, when 107.8 g of silver are deposited on the cathode, we know that
one mole of electrons must have passed through the cell. For convenience, the amount of
electricity that must pass through an electrolysis cell in order to deliver one mole of electrons is
known as a Faraday (F). A Faraday is then simply another way of saying "a mole of electrons."

Experimentally it has been determined that the amount of charge on one single electron is 1.602
x 10-19 coulombs. One mole of electrons (i.e., a Faraday) would then be:

(1.602 x10-19 C/electron) X (6.022 x 1023 electrons/mole) = 96,500 C/mole

This quantity of charge, 96,500 coulombs, is then the Faraday, the amount of electricity that
must pass through an electrochemical cell in order to deliver one mole of electrons.

One Faraday must be supplied to produce 107.8 g of silver. Two would deposit 215.6 g of silver,
and so on. For a reaction in which three electrons were needed for each cation, such as the
reduction of aluminum,

Al3+(aq) + 3 e- Al (s) [2]

three Faradays would be required to deposit one mole (27 g) of aluminum metal. One Faraday
would only have deposited one third of a mole (9 g) of aluminum. This relationship is implied by
the second statement. The equivalent weight of a substance participating in these types of
processes (oxidation-reduction reactions) is then defined as the mass in grams of that substance
that consumes or produces one mole of electrons. This mass of the substance is considered equal
to, or equivalent in charge to, the charge present in one mole of electrons.

As Faraday concluded in 1832, the number of charges, either positive or negative, that exist on
individual ions is always a small whole number. An ion may have a charge of +1, +2, +3 or -1, -
2, -3; but never will an ion have a charge such as +1.25 or -2.33. Thus another way of
considering the equivalent weight of ionic substances in these processes would be to define it as
the molar mass divided by the charge on the ion. For example, the equivalent weight of sodium
would be 23.0 g/equiv, which is the atomic weight divided by 1. The equivalent weight of
magnesium would be 12.2 g/equiv because the molar mass is 24.3 and the charge on the ion is
+2. Aluminum would have an equivalent weight of 9.0 g/equiv, this value being calculated from
the molar mass of 27 g/mole and the charge of +3.

In this experiment, you will determine the molar mass of copper found in a solution of copper
(II) sulfate. The formula of copper (II) sulfate is CuSO4. When this ionic substance dissolves in
water, it dissociates into the Cu2+ cation and the SO42- anion. A current, supplied by a dry cell
battery, will be passed through the CuSO4 solution. At the cathode, copper cation will be
reduced to copper metal:

Cu+2(aq) + 2e- Cu(s) [3]

At the anode, two processes may occur. Water molecules may lose electrons with oxygen being
evolved, or the copper in the anode may lose electrons and dissolve:

2 H2O(l) O2(g) + 4 H+(aq) + 4 e- [4]

Cu(s) Cu2+(aq) + 2 e- [5]

One final point needs to be made about how the quantity of electricity may be measured. The
System Internationale (SI) unit of charge is the coulomb (C). The unit for the measurement of the
rate of flow of charge (a.k.a. current) is the ampere (A) and so the ampere is defined as one
coulomb per second (C/sec). The quantity of electricity passed through a solution may then be
determined by keeping the current constant at some value (0.5 amps, for example) and recording
the total time that the electrolysis is conducted. The net number of coulombs delivered is then
calculated by multiplying the current (in amps, a.k.a. coulombs/sec) by the total elapsed time (in
seconds).