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Electrolytic Cell:
Contrary to a voltaic cell that produces electricity from a spontaneous chemical reaction, an
electrolytic cell uses electricity to drive a non-spontaneous chemical reaction (positive Go). A power
source, usually a battery, causes oxidation, still at the anode (now assigned a + sign), and reduction, still
at the cathode (now assigned a - sign), where as the overall reaction is non-spontaneous. Note the reversal
in the signs for the electrodes as compared to voltaic cells.
Electrolysis (electro means electricity, lysis means breaking up) has great industrial importance as
this is the main process used in recovering metals from their ores. Electrolysis of brine (NaCl solution) is
extensively used to produce chlorine gas, sodium hydroxide and hydrogen gas. In electrolysis of aqueous
salt solutions, two oxidation reactions and two reduction reactions are possible.
At the cathode (-): The metal cation itself can be reduced or water can be reduced based on the following
reduction half reactions.
M+ (aq) + e- M (s)
2H2O (l) + 2e- H2 (g) + 2 OH- (aq) E = -0.83 V
In general, water gets reduced at the cathode.
At the anode (+): The non-metal anion can be oxidized or water can be oxidized based on the following
two half reactions:
X- (aq) X (s) + e-
2H2O (l) O2 (g) + 4H+ (aq) + 4 e- E = -1.23 V
The non-metal normally gets oxidized at the anode.
However, these results depend on the individual half cell potentials. The reaction with less negative
reduction potential will be reduced (for the most part it is water) at the cathode and the reaction with less
positive reduction potential will be oxidized (which is normally the metal) at the anode (M. Silberberg
2007).
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Copyright 2011 Sudha Madhugiri
From the reactions at the anode and cathode, it can be deduced that more the # of moles of electrons
transferred, greater will be the product formed at a given electrode. This relationship was first put forth
by Michael Faraday and is known as Faradays law of electrolysis. This law states that "the amount of
substance produced at each electrode is directly proportional to the quantity of charge flowing through the
cell. 1
Using Faradays law, the current transferred in amperes (amps) can also be calculated:
1 amp = 1 coulomb/second
This simple relationship combined with a balanced half reaction can be used to calculate the required
parameters involving stoichiometry of electrolysis.
Electroplating:
Electrolysis has a variety of applications as mentioned earlier and one is electroplating. Electroplating is
a technique that uses electric current to coat a layer of a desired metal by reducing cations of that metal
from a solution. This process is performed to bestow properties that are not intrinsic to the material being
coated. For example, chrome plating is done on a variety of materials including parts of automobiles to
provide corrosion resistance, ease of cleaning, and aesthetic appeal. Gold or silver plating can be done on
pieces of jewelry and to keep expensive electronic material from tarnishing. The material that needs to be
coated can be made a cathode and using an electroplating solution, the cathode can be coated with the
desired metal using electrochemical reduction.
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Copyright 2011 Sudha Madhugiri
Objective:
You are trying to design a voltaic cell with the maximum voltage to be used as a power source for your
experiment. Use Figure 1 as a guide to construct 4 different voltaic cells using the above materials.
Cathode (+)
Anode (-)
Porous cup acting as a
cathode compartment
Anode
compartment
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Copyright 2011 Sudha Madhugiri
Prelab Questions for Part I:
2. Is it possible to create a cell that would follow the following cell reaction?
Fe2+ (aq) + Ni(s) Fe(s) + Ni2+ (aq)
If yes, calculate Eocell at 25oC.
If it is not possible, explain why.
Objective:
Construct an electrolytic cell based on the schematic provided in Figure 2 and coat a piece of copper strip
with nickel metal to understand the process of electroplating. Using the data collected by electroplating
nickel, calculate the current supplied in amperes (amps) in this process.
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Copyright 2011 Sudha Madhugiri
Battery
Anode (+)
Cathode (-)
Electroplating
Solution
1. Calculate the amount of copper produced in 1.0 h when aqueous CuBr 2 solution was electrolyzed
by using a current of 4.50 A.
2. In another electroplating experiment, if electric current was passed for 3 hours and 2.00 g of silver
was deposited from a AgNO3 solution, what was the current used in amperes?
Bibliography:
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Copyright 2011 Sudha Madhugiri