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Chapter 18 Electrochemistry
Chapter 18 Electrochemistry
• Half–Reactions Method:
• The overall reaction is split into two half–
reactions, one involving oxidation and one
reduction.
8H+ + MnO4 + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O
Example:
• Cr2O72-(aq) 2Cr3+(aq)
• HSO3-(aq) HSO4-(aq)
• Adding electrons:
• 6e- + Cr2O72-(aq) 2Cr3+(aq)
• HSO3-(aq) HSO4-(aq) + 2e-
• Half-Reactions:
Fe3+ + e– Fe2+ E° = 0.77 V
Cu2+ + 2e– Cu E° = 0.34 V
• To balance the cell reaction and calculate the
cell potential, we must reverse reaction 2.
Cu Cu2+ + 2e– – E° = – 0.34 V
• Each Cu atom produces two electrons but each
Fe3+ ion accepts only one electron, therefore
reaction 1 must be multiplied by 2.
2Fe3+ + 2e– 2Fe2+ E° = 0.77 V
Standard Cell Potential
• Cell Potential: E
E°cell = E°(cathode) – E°(anode)
E°cell = 0.77 V – 0.34 V = 0.43 V
Calculating Standard Cell Potential
o 2.303RT
Ecell E cell log Q
nF
o 0.0592
Ecell Ecell log Q at 25oC
n
– F = 96,485 C/mol e–
– R = 8.314 JK– mol–
32
o 0.0592
Ecell Ecell log Q
n
• Basically, second half of equation is correcting factor
for not being std conc. If at std conc (1M each), Q=1
and log 1 = 0. Could use even at std and get correct
answer.
34
2 2
Zn(s ) Cu (aq ) Zn (aq ) Cu(s ) Eocell = 1.10V
o 0.0592
Ecell E cell log Q
n
2
o 0.0592 [ Zn ]
Ecell E cell log 2
n [Cu ]
5
0.0592 1.0 10
Ecell 1.10 V log
2 0.100
Ecell 1.10 V ( 0.12) 1.22 V
voltaic, spon 35
Nernst Equation
• At 25oC.
0.0591
E = E log Q
n
0.0591
E= log K
n
Cell Potential for Concentration Cells
• Production of aluminum
• Purification of metals
• Metal plating
• Electrolysis of sodium chloride
• Production of chlorine and sodium hydroxide
The Hall-Heroult Process for Al Production
Electroplating/Silver Plating a Spoon
The Downs Cell for the Electrolysis of Molten
Sodium Chloride
The Mercury Cell for Production of
Chlorine and Sodium Hydroxide