122 19 Review

Electrochemistry
Chapter 19
Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)
2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)
O2 + 4e- 2O2- Reduction half-reaction (gain e-)
19.1
Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.
1. Free elements (uncombined state) have an oxidation

number of zero.
Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
4.4
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.
5. Group IA metals are +1, IIA metals are +2 and fluorine

is always –1.
6. The sum of the oxidation numbers of all the atoms in

a molecule or ion is equal to the charge on the
molecule or ion.
HCO3-
Oxidation numbers of all O = -2 H = +1
the atoms in HCO3- ?
3x(-2) + 1 + ? = -1
C = +4
4.4
Galvanic Cells
anode cathode
oxidation reduction
spontaneous
redox reaction
19.2
Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
Cell Diagram
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode cathode
19.2
Standard Electrode 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
2e- + 2H+ (1 M) H2 (1 atm)
E0 = 0 V
Standard hydrogen electrode (SHE) 19.3

Ecell
0
= 0.76 V
Standard emf (Ecell

0
)
Ecell
0
= E0cathode - Eanode
0
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Ecell
0
= E0H+/H2 - EZn
0 2+
/Zn
0.76 V = 0 - E0Zn2+/Zn
E0Zn2+/Zn = -0.76 V
Zn2+ (1 M) + 2e- Zn E0 = -0.76 V
19.3
Ecell
0
= 0.34 V
Ecell
0
0
E0cell = E0Cu2+/Cu – EH0 +/H 2
0.34 = E0Cu2+ /Cu - 0

E0Cu2+/Cu = 0.34 V
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M)
19.3
• E0 is for the reaction as
written
• The more positive E0 the
greater the tendency for the
substance to be reduced
• The half-cell reactions are
reversible
• The sign of E0 changes
when the reaction is
reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change
the value of E0
19.3
What is the standard emf of an electrochemical cell made
of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?
Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer

Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V Cd will oxidize Cr
Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2

Cathode (reduction): 2e- + Cd2+ (1 M) Cd (s) x3
2Cr (s) + 3Cd2+ (1 M) 3Cd (s) + 2Cr3+ (1 M)
Ecell
0
0
Ecell
0
= -0.40 – (-0.74)
Ecell
0
= 0.34 V
19.3
Spontaneity of Redox Reactions
G = -nFEcell n = number of moles of electrons in reaction
J
G = 0
-nFE 0
cell F = 96,500 = 96,500 C/mol
V • mol
0
G0 = -RT ln K = -nFEcell
RT (8.314 J/K•mol)(298 K)
0
Ecell = ln K = ln K
nF n (96,500 J/V•mol)
0 0.0257 V
Ecell = ln K
n
0.0592 V
0
Ecell = log K
n
19.4
Spontaneity of Redox Reactions
19.4
What is the equilibrium constant for the following reaction
at 250C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)
0 0.0257 V
Ecell = ln K
n
Oxidation: 2Ag 2Ag+ + 2e-

n=2
Reduction: 2e- + Fe2+ Fe
E0 = E0Fe2+ /Fe – EAg
0
+/Ag
E0 = -0.44 – (0.80)
E0 = -1.24 V Ecell
0
xn -1.24 V x 2
K = exp = exp
0.0257 V 0.0257 V
K = 1.23 x 10-42
19.4
The Effect of Concentration on Cell Emf
G = G0 + RT ln Q G = -nFE G0 = -nFE 0
-nFE = -nFE0 + RT ln Q
Nernst equation
RT
E = E0 - ln Q
nF
At 298
0.0257 V 0.0592 V
E = E0 - ln Q E = E0 - log Q
n n
19.5
Will the following reaction occur spontaneously at 250C if
[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)
Oxidation: Cd Cd2+ + 2e-

n=2
Reduction: 2e- + Fe2+ 2Fe
E0 = E0Fe2+ /Fe – ECd
0
2+/Cd
E0 = -0.44 – (-0.40) 0.0257 V

E = E0 - ln Q
n
E0 = -0.04 V
0.0257 V 0.010
E = -0.04 V - ln
2 0.60
E = 0.013
E>0 Spontaneous
19.5
Electrolysis is the process in which electrical energy is used
to cause a nonspontaneous chemical reaction to occur.
19.8
Electrolysis of Water
19.8
Electrolysis and Mass Changes
charge (C) = current (A) x time (s)
1 mole e- = 96,500 C
19.8
How much Ca will be produced in an electrolytic cell of
molten CaCl2 if a current of 0.452 A is passed through the
cell for 1.5 hours?
Anode: 2Cl- (l) Cl2 (g) + 2e-
Cathode: Ca2+ (l) + 2e- Ca (s)
Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)
2 mole e- = 1 mole Ca
C s 1 mol e- 1 mol Ca
mol Ca = 0.452 x 1.5 hr x 3600 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca
= 0.50 g Ca
19.8
Chemistry In Action: Dental Filling Discomfort
2+
Hg2 /Ag2Hg3 0.85 V
2+
Sn /Ag3Sn -0.05 V
2+
Sn /Ag3Sn -0.05 V

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Electrochemistry

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

1. Free elements (uncombined state) have an oxidation

Na, Be, K, Pb, H2, O2, P4 = 0

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

5. Group IA metals are +1, IIA metals are +2 and fluorine

6. The sum of the oxidation numbers of all the atoms in

Standard reduction potential (E0) is the voltage associated

2e- + 2H+ (1 M) H2 (1 atm)

Standard hydrogen electrode (SHE) 19.3

Standard emf (Ecell

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

E0cell = E0Cu2+/Cu – EH0 +/H 2

0.34 = E0Cu2+ /Cu - 0

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer

Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2

Oxidation: 2Ag 2Ag+ + 2e-

Oxidation: Cd Cd2+ + 2e-

E0 = -0.44 – (-0.40) 0.0257 V

charge (C) = current (A) x time (s)

Anode: 2Cl- (l) Cl2 (g) + 2e-

Cathode: Ca2+ (l) + 2e- Ca (s)

Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

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