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A reduction half-reaction occurs at the electrode (cathode) attached to the
negative terminal of the battery.
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Electrolysis in aqueous solution
To be continued…... 24-5
Oxidations? Reductions?
2H2O(R) 6 4H+(aq) + O2(g) + 4e-, EE -1.23V 2H2O(R) + 2e- 6 H2(g) + 2OH-(aq), EE -0.83 V
2F-(aq) 6 F2(g) + 2e-, EE -2.87 V Na+(aq) + e- 6 Na(s), EE -2.71 V
The most easily oxidized species is the one with the most positive potential 6 this
means that in this case water will be oxidized to O2(g) (EE -1.23 V), rather than
fluoride ion be oxidized to fluorine gas (-2.87 V).
The most easily reduced species is the one with the most positive potential
6 this means that in this case water ( EE -0.83 V ) will be much more easily
reduced (to H2(g)) than Na+ (EE -2.71 V) (to solid sodium, Na(s))
Shortcut to remember
The reaction with the most positive E “wins”
Water is converted to hydrogen gas and oxygen gas and the Na+(aq)
and F-(aq) stay in solution.
Add
6H2O(R) 6 4H+(aq) + O2(g) + 2H2(g) + 4OH-(aq)
but:
4H+(aq) + 4OH-(aq) 6 4H2O(R) What is E0 ?
-does it make sense
hint: +ve or -ve
So overall we simply have:
2H2O(R) 6 O2(g) + 2H2(g)
and the sodium fluoride undergoes no chemical change - it simply
provides ions to carry the current
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Another example
The electrolysis of brine is used to make Chlorine (and Hydrogen) gas and
Sodium Hydroxide solution.
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Example:a 1M aq. soln of ZnBr was electrolyzed using inert electrodes.
What are the products? There was a 0.5V overpotential for both oxidation
and reduction of water.
Remember to only consider reactions to things that are already in solution
Possible reductions
Zn2+ + 2e Zn E0 = - 0.67
versus
2H2O(R) + 2e- 6 H2(g) + 2OH-(aq), E0 = -0.83 V = - 1.33 with o.p
Possible oxidations
m = (ItM)/Fn
i.e. Mass deposited or evolved =
(mole of e) x (mass produced per mole of e)
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example
What mass of Cu is deposited when a current of
10.0 A is passed for 30.0 minutes through 1.00 L of a 0.100 M CuSO4 solution?
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example: work through by yourselves:
How many grams of Al(s) and Cl2(g) are produced if a cell of molten AlCl3 is
electrolyzed with 0.452 amps for 1.5 hours?
m= MIT/Fn
Al Cl2
m = (27 x 0.452 x 1.5 x 60 x 60)/ 96485 x 3 m = (70.9 x 0.452 x 1.5 x 60 x 60)/ 96485 x 2
= 0.896 g
= 0.228 g
(0.309 L)
note well: "n" is different for the processes at the anode and cathode
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homework
1. How long would it take to produce a solution of pH
2.00 by electrolysis of 500 mL of 0.100 M AgNO3(aq) by
using a constant current of 0.240 Amperes?
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