Electrochemistry

Chapter 12
 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
 Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?

1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72- Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O7 2- Cr3+

3. Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+
19.1
 Balancing Redox Equations
4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- 2Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
19.1
 Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation: 6Fe2+ 6Fe3+ + 6e-

Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.

14x1 – 2 + 6x2 = 24 = 6x3 + 2x3

9. For reactions in basic solutions, add OH- to both sides of the

equation for every H+ that appears in the final equation.
19.1
 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 Reduction Potentials

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

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)
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

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

E0 = 0 V

Standard hydrogen electrode (SHE) 19.3

 Standard Reduction Potentials
0 = 0.76 V
Ecell

0 )
Standard emf (Ecell
0 = E0
Ecell 0
cathode - Eanode

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

0 = E 0 + - E 0 2+
Ecell H /H2 Zn /Zn

0.76 V = 0 - EZn0 2+
/Zn
0 2+
EZn /Zn = -0.76 V

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V

19.3
 Standard Reduction Potentials

0 = 0.34 V
Ecell
0 = E0
Ecell 0
cathode - Eanode

Cu /Cu – EH +/H 2
0 = E 0 2+
Ecell 0

0 2+
0.34 = ECu /Cu - 0
0 2+
ECu /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)

0 = E0
Ecell 0
cathode - Eanode
0 = -0.40 – (-0.74)
Ecell
0 = 0.34 V
Ecell
19.3
 Spontaneity of Redox Reactions
DG = -nFEcell n = number of moles of electrons in reaction
J
DG0 = 0
-nFEcell F = 96,500 = 96,500 C/mol
V • mol
DG0 = -RT ln K = -nFEcell
0

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 0.0592 V
Ecell = log K
n

19.4
Spontaneity of Redox Reactions

DG0 = -RT ln K = -nFEcell

0

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

2+/Fe – EAg + /Ag

0
E0 = EFe 0

E0 = -0.44 – (0.80)
E0 = -1.24 V 0
Ecell 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
DG = DG0 + RT ln Q DG = -nFE DG0 = -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
2+/Fe – ECd2+/Cd
0
E0 = EFe 0

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
 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

19.6
 Batteries

Mercury Battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

19.6
 Batteries

Lead storage
battery

Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO2-

4 (aq) + 2e
- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-

4
(aq) 2PbSO4 (s) + 2H2O (l)

19.6
 Batteries

Solid State Lithium Battery 19.6

 Batteries

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)

19.6
Chemistry In Action: Bacteria Power

CH3COO- + 2O2 + H+ 2CO2 + 2H2O

Corrosion

19.7
Cathodic Protection of an Iron Storage Tank

19.7
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