Chapter 2: Electrochemistry
Outline
1.
2.
3.
4.
5.
6.
Redox Reaction: Reduction, Oxidation & Oxidation
Number
Redox Reaction: Balancing Redox using Half- Reaction
Method
Electrolysis & Electrolytic Cells
Voltaic Cells & Cells Potentials
Nernst Equation
Primary & Secondary cells.
What is Redox Reaction
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
2+ 2-
2Mg (s) + O2 (g)
2Mg
O2 + 4e4
2MgO (s)
2Mg2+ + 4e-
Oxidation half-reaction (lose e-)
2O2-
Reduction half-reaction (gain e-)
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.
5
The oxidation number of oxygen is usually 2. In H2O2 and O22- it is 1.
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
Identify the oxidation numbers of all the atoms in
HCO3 ?
O = 2
H = +1
3x(2) + 1 + ? = 1
6
C = +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-
2.
Fe3+ + Cr3+
Separate the equation into two half-reactions.
+2
Fe2+
Oxidation:
+6
Reduction:
3.
Cr2O7
Cr3+
Balance the atoms other than O and H in each half-reaction.
Cr2O727
2-
Fe3+
2Cr3+
+3
+3
Balancing Redox Equations
4.
For reactions in acid, add H2O to balance O atoms and H+ to balance H atoms.
Cr2O72-
2Cr3+ + 7H2O
14H+ + Cr2O725.
Add electrons to one side of each half-reaction to balance the charges on the half-reaction.
Fe2+
Fe3+ + 1e-
6e- + 14H+ + Cr2O72-
6.
2Cr3+ + 7H2O
If necessary, equalize the number of electrons in the two half-reactions by multiplying the halfreactions by appropriate coefficients.
6Fe2+
8
2Cr3+ + 7H2O
6Fe3+ + 6e-
6e- + 14H+ + Cr2O72-
2Cr3+ + 7H2O
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.
6Fe2+
Oxidation:
6e- + 14H+ + Cr2O72-
Reduction:
14H+ + Cr2O72- + 6Fe2+
8.
6Fe3+ + 6e2Cr3+ + 7H2O
6Fe3+ + 2Cr3+ + 7H2O
Verify that the number of atoms and the charges are balanced.
14x1 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3
9.
9
For reactions in basic solutions, add OH- to both sides of the equation for every H+ that appears in
the final equation.
Galvanic Cells
anode
oxidation
cathode
reduction
spontaneous
redox reaction
10
Galvanic Cells
The difference in electrical potential between the
anode and cathode is called:
cell voltage
electromotive force (emf)
cell potential
Zn (s) + Cu2+ (aq)
Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M and [Zn2+] = 1 M
Cell Diagram
phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
11
anode
salt bridge
cathode
Standard Reduction Potentials
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)
Anode (oxidation):
Zn (s)
2e- + 2H+ (1 M)
Cathode (reduction):
Zn (s) + 2H+ (1 M)
12
Zn2+ (1 M) + 2e-
Zn2+ + H2 (1 atm)
H2 (1 atm)
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)
E0 = 0 V
13
Standard hydrogen electrode (SHE)
H2 (1 atm)
Standard Reduction Potentials
E0 = 0.76 V
cell
Standard emf (E0 )
E0 = Ecathode 0- Eanode
cell
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)
E0 = EH /H -0E+Zn
cell
0.76 V = 0 - EZn
/Zn
/Zn
2
2+
2+
EZn0 /Zn
2+ = -0.76 V
2+ (1 M) + 2eZn
14
Zn
E0 = -0.76 V
cell
0
Standard Reduction Potentials
E0 = 0.34 V
cell
E0 = Ecathode 0- Eanode
cell
Ecell0 = ECu
0.34 = ECu
ECu0
2+ =
/Cu
0 2+
EH /H
/Cu
0 -2+
0
/Cu
0.34 V
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode (oxidation):
Cathode (reduction):
15
H2 (1 atm) + Cu2+ (1 M)
H2 (1 atm)
2H+ (1 M) + 2e-
2e- + Cu2+ (1 M)
Cu (s) + 2H+ (1 M)
Cu (s)
0
0+
16
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
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):
2e- + Cd2+ (1 M)
Cathode (reduction):
2Cr (s) + 3Cd2+ (1 M)
3Cd (s) + 2Cr3+ (1 M)
E0 = Ecathode 0- Eanode
cell
E0 = -0.40 (-0.74)
cell
E0 = 0.34 V
17
cell
x2
Cr3+ (1 M) + 3e-
Cr (s)
Cd (s)
x3
Spontaneity of Redox Reactions
DG = -nFEcell
DG0
n = number of moles of electrons in reaction
= -nFEcell 0
F = 96,500
DG0 = -RT ln K
E0cell =
RT
nF
V mol
= 96,500 C/mol
= -nFE0cell
ln K
(8.314 J/Kmol)(298 K)
E0cell =
0.0257 V
n
ln K
E0cell =
0.0592 V
n
log K
18
n (96,500 J/Vmol)
ln K
Spontaneity of Redox Reactions
DG0 = -RT ln K
19
= -nFE0cell
What is the equilibrium constant for the following reaction at 250C?
Fe (s) + 2Ag+ (aq)
E0cell =
0.0257 V
n
ln K
Oxidation:
E0 = EFe
2Ag+ + 2e-
2Ag
2e- + Fe2+
Reduction:
0 EAg
/Fe
2+ /Ag
n=2
Fe
E0 = -0.44 (0.80)
E0
E0 = -1.24 V
cell
xn
-1.24 V
0.0257 V
K= e
K = 1.23 x 10-42
20
Fe2+ (aq) + 2Ag (s)
0.0257 V
=e
x2
The Effect of Concentration on Cell Emf
DG = DG0 + RT ln Q
DG = -nFE
DG0 = -nFE
-nFE = -nFE0 + RT ln Q
Nernst equation
E = E0 -
RT
ln Q
nF
At 298 K
E=
21
E0 -
0.0257 V
n
ln Q
E=
E0 -
0.0592 V
n
log Q
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
2e- + Fe2+
Reduction:
E0 = EFe
ECd /Cd
/Fe 2+
E0 = -0.44 (-0.40)
Cd2+ + 2e-
n=2
2Fe
2+
E=
E0 -
E0 = -0.04 V
E=
0.0257 V
n
0.0257 V
-0.04 V 2
E = 0.013
E>0
22
ln Q
Spontaneous
ln
0.010
0.60
Concentration Cells
Galvanic cell from two half-cells composed of the same material but differing in ion concentrations.
23
Batteries
Dry cell
Leclanch cell
Anode:
Cathode:
Zn (s)
+
2NH4 (aq) + 2MnO2 (s) + 2e-
Zn (s) + 2NH4 (aq) + 2MnO2 (s)
24
Zn2+ (aq) + 2eMn2O3 (s) + 2NH3 (aq) + H2O (l)
Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)
Batteries
Mercury Battery
Anode:
Cathode:
Zn(Hg) + 2OH- (aq)
HgO (s) + H2O (l) + 2eZn(Hg) + HgO (s)
25
ZnO (s) + H2O (l) + 2e-
Hg (l) + 2OH- (aq)
ZnO (s) + Hg (l)
Batteries
Lead storage
battery
Anode:
Cathode:
Pb (s) 4+ SO2- (aq)
PbO2 (s) + 4H+ (aq)4 + SO2- (aq) + 2e-
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2- (aq) 4
26
PbSO4 (s) + 2ePbSO4 (s) + 2H2O (l)
2PbSO4 (s) + 2H2O (l)
Batteries
27
Solid State Lithium Battery
Batteries
A fuel cell is an electrochemical
cell that requires a continuous
supply of reactants to keep
functioning
Anode:
Cathode:
28
2H2 (g) + 4OH- (aq)
4H2O (l) + 4e-
O2 (g) + 2H2O (l) + 4e-
4OH- (aq)
2H2 (g) + O2 (g)
2H2O (l)
Chemistry In Action: Bacteria Power
CH3COO- + 2O2 + H+
29
2CO2 + 2H2O
Corrosion
Corrosion is the term usually applied to the deterioration of metals by an electrochemical process.
30
Cathodic Protection of an Iron Storage Tank
31
Electrolysis is the process in which electrical energy is used to cause a nonspontaneous chemical
reaction to occur.
Electrolysis of molten NaCl
32
Electrolysis of Water
33
Electrolysis and Mass Changes
charge (C) = current (A) x time (s)
1 mol e- = 96,500 C
34
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?
2Cl- (l)
Anode:
Cathode:
Ca2+ (l) + 2eCa2+ (l) + 2Cl- (l)
Cl2 (g) + 2eCa (s)
Ca (s) + Cl2 (g)
2 mole e- = 1 mole Ca
mol Ca = 0.452
C
s
= 0.0126 mol Ca
= 0.50 g Ca
35
x 1.5 hr x 3600
s
hr
1 mol e96,500 C
1 mol Ca
2 mol e-
Chemistry In Action: Dental Filling Discomfort
2+ Hg 0.85 V
Hg2 /Ag
2
3
2+ Sn -0.05 V
Sn /Ag
3
2+ Sn -0.05 V
Sn /Ag
3
36
