ntroducing Electrolysis
• Electrical Conductivity can be used to divide matter into 3 distinct groups:
Electrical Conductors
Non-conductors and
Semi-conductors
Can you give examples and descriptions of each?
• Electrical conductors can be divided into:
Metals
Graphite &
Electrolytes
How are the above groups able to conduct electricity?
• Solid ionic compounds like sodium chloride, NaCl, do not conduct an electrical current. Why is this so
and how may they be able to conduct electricity?
• Electrolytes are divided into two groups based on their extent of ionization:
Strong Electrolytes and
Weak Electrolytes
How would you define both types of electrolytes.
• The following points should be noted about conduction in metals:
1. There is no net gain or loss of electrons
2. Electrons leave one end at the same rate as they enter the other
3. No chemical reactions occur
4. Conduction is instantaneous and takes place at the speed of light
What is the speed of light?
• Can you present a definition for electrolysis?
• Molten and aqueous ionic compounds, as well as aqueous solutions of some polar compounds, conduct electricity
and are decomposed by the current. This decomposition of an electrolyte by an electric current is known as
electrolysis.
• An electrolytic cell is the apparatus used to carry out electrolysis. Can you draw a standard one for me please?
• The electrodes are the points at which the current enters and leaves the electrolyte and are made of either
graphite or metal. What are the names of the positive and negative electrode?
• Electrons from the battery are supplied to the cathode and are removed from the anode. During electrolysis
cations move towards the cathode and anions move towards the anode.
• Electrodes may be inert or active. What does this mean?
• During electrolysis cations move towards the cathode and accept electrons whereas anions move towards the
anode and give up electrons.
• Using the above statement as a guide at which electrode does oxidation and reduction take place.
• Remember, oxidation is the loss of electrons :: Xn+ - ne- X
and reduction is the gain of electrons:: Mn- + ne- M
• The electrons lost at the anode enter the external circuit and re-enter the electrolytic cell at the cathode; so that
the number or electrons lost at the anode must be the same as the number gained at the cathode – otherwise we
would be creating and destroying electrons!
• The electric current can produce the following types of chemical change:
Deposition of metals at the cathode – Why?
Evolution of hydrogen at the cathode
Discharge of non-metals at the anode – Why?
Metal atoms leaving the anode and entering the solution as metal ions
• Electrolyte solutions are aqueous solutions of dissociated ions. When a molten salt like sodium chloride, NaCl, is
electrolysed it becomes dissociated into Na+ ions and Cl- ions. However, because it is dissolved within water, H2O, to
make it into an electrolyte it has other ions present within its aqueous solution as water becomes partially ionized.
Can you tell me what these ions are?
• Owing to the above note concerning electrolytes containing multiple ions each of the ions have preferential value
based on their position within the electrochemical series or reactivity series which determines which set of ions will
be distributed mainly to which electrode.
• When more than one cation is present at the cathode, the one which is prefentially discharged is the one lower in
the reactivity series
• When more than one anion is present at the anode the one which is preferentially discharged is the one lower in
the reactivity series
• However there are exceptions to these general rules, particularly when the electrolyte solution is concentrated.
Reactivity Series
Reactivity Series for Cations Reactivity Series for Anions
K SO42-
Na NO3-
Ca OH-
Mg Cl-
Al Br-
Zn I-
Fe
Pb
H
Cu
Hg
Ag
Au
• Much of the early work on electrolysis was done by the British scientist named Michael Faraday (1791-1867).
In 1834, Faraday discovered that the mass of substance discharged at an electrode during electrolysis is
directly proportional to the quantity of electricity passing through the electrolytic cell. Where::
m α C
mass α Coulomb where one mole of electrons was experimentally found to have a charge of 96 500
Coulombs
also
1 Coulomb = 1 Ampere * 1 Second
where C = quantity of electricity in coulombs
I = current strength in amperes
t = time in seconds
• Do you see the how everything is related here?
• Check this out!
When one mole of a singly-charged ion is discharged at an electrode this happens::
M+ + e- M (reduction)
Or
X- e- + X (oxidation)
The above process requires the passage of 96 500C, or the additon or removal of 1 mole of electrons.
• In general to discharge 1 mole of an ion, Mn+ or Xn-, at an electrode :: n * 96 500 C of electricity must be passed
through the electrolyte where n stands for the number of electrons.
• Look at these two reactions below::
Pb2+ + 2e- Pb at the cathode (reduction)
2Br- - 2e- Br2 at the anode (oxidation)
In the case of n * 96 500 C what does n equal for both reactions? ____ * 96 500 C
• So let’s recap::
a. mass of 1 mole of the element 96 500 C
b. actual mass of element C = (Amperes * Time in seconds)
Remember you must always write out your half equations to complete ratio a.
• Try this question::
What mass of magnesium is deposited at the cathode by the passage of 2.00 amperes through molten
magnesium chloride, MgCl2, for 30 minutes? Remember there are stipulations for the calculations of this and
when in doubt follow the ratios above. Life made easy!
• Show me your understanding now by calculating these following equations:::
How many moles of chlorine molecules are liberated by the passage of 4.32 * 10 4 C? What mass of chlorine is
liberated by this charge? Hint – relate to the ratio fepicted on the previous page.
• Find (a) the number of moles of sodium atoms and (b) the mass of sodium liberated when a current of 4 A
flows through a cell containing molten sodium chloride for 2 hours. Na = 23 u.
• What cell current will liberate 0.5 kg of copper in 1 hour?
