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Chapter 19 Electrochemistry Semester 1/2011. Ref: http://www.mhhe.com/chemistry/chang. 19.2 Galvanic Cells 19.3 Standard Reduction Potentials 19.4 Spontaneity of Redox Reactions 19.5 The Effect of Concentration on Emf 19.8 Electrolysis. 19.2 Galvanic Cells. anode oxidation. cathode
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Electrochemistry
Semester 1/2011
Ref: http://www.mhhe.com/chemistry/chang
19.2 Galvanic Cells
19.3 Standard Reduction Potentials
19.4 Spontaneity of Redox Reactions
19.5 The Effect of Concentration on Emf
19.8 Electrolysis
Cu2+ is reduced to Cu
Cu electrode is Cathode (Oxidizing Agent)
Galvanic Cells
Cell Diagram
[Cu2+] = 1 M & [Zn2+] = 1 M
Cell Notation Zn (s)  Zn2+ (1 M)  Cu2+ (1 M)  Cu (s)
anode
cathode
Zn (s) Zn2+ (1 M) + 2e
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)
Standard Electrode Potentials
Zn (s)  Zn2+ (1 M)  H+ (1 M)  H2 (1 atm)  Pt (s)
Anode (oxidation):
Cathode (reduction):
19.3 Standard Reduction Potentials
Standard reduction potential (E0) is the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm.
Reduction Reaction
E0= 0 V
Standard hydrogen electrode (SHE)
E0 = Ecathode  Eanode
E0 = EH /H  EZn /Zn
cell
cell
cell
Standard emf (E0 )
cell
0
0
0
0
2+
+
2
0.76 V = 0  EZn /Zn
0
2+
EZn /Zn = 0.76 V
0
2+
Zn2+ (1 M) + 2e ZnE0 = 0.76 V
Standard Electrode Potentials
Zn (s)  Zn2+ (1 M)  H+ (1 M)  H2 (1 atm)  Pt (s)
0
0
Ecell = ECu /Cu–EH /H
2+
+
2
0.34 = ECu /Cu  0
0
2+
0
ECu /Cu = 0.34 V
2+
E0 = Ecathode  Eanode
E0 = 0.34 V
cell
cell
0
0
H2 (1 atm) 2H+ (1 M) + 2e
2e + Cu2+ (1 M) Cu (s)
H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M)
Standard Electrode Potentials
Pt (s)  H2 (1 atm)  H+ (1 M)  Cu2+ (1 M)  Cu (s)
Anode (oxidation):
Cathode (reduction):
0
0
0
0
0
= nFEcell
Ecell
Ecell
Ecell
F = 96,500
J
RT
V • mol
ln K
nF
(8.314 J/K•mol)(298 K)
ln K
=
0.0592 V
0.0257 V
log K
ln K
n (96,500 J/V•mol)
=
n
n
=
=
19.4 Spontaneity of Redox Reactions
DG = nFEcell
n = number of moles of electrons in reaction
= 96,500 C/mol
DG0 = RT ln K
E0cell > 0 spontaneous reaction
0
RT
nF
E = E0 
ln Q
0
0
E =
E =
E
E
0.0257 V
0.0592 V
log Q
ln Q
n
n


19.5 The Effect of Concentration on Cell Emf
DG = DG0 + RT ln Q
DG = nFE
nFE = nFE0+ RT ln Q
Nernst equation
At 298 K
ln = 2.303log
Quantitative Aspects
Case (i) Na + + 1e Na
1 mol. of electron produces 1 mol of Na Atom (22g)
1 F (96500 C)
Case (ii) Mg 2+ + 2e Mg
2 mol. of electron produces 1 mol of Mg Atom(24g)
2 F (2x 96500C)
Case (iii) Al 3+ + 3e Al
3 mol. of electron produces 1 mol of Al Atom(26g)
3 F (3 x 96500 C)
1 mole of electron = 96500 coulomb
1 mol. of Na atom = 22 g
1 mol. of Mg atom = 24 g
1 mol. of Al atom = 26 g