Chapter 2
Chapter 2
Chapter 2
Outline
1.
2.
3.
4.
5.
6.
2+ 2-
2Mg
O2 + 4e4
2MgO (s)
2Mg2+ + 4e-
2O2-
Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.
1.
In monatomic ions, the oxidation number is equal to the charge on the ion.
4.
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
Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72-
2.
Fe3+ + Cr3+
Fe2+
Oxidation:
+6
Reduction:
3.
Cr2O7
Cr3+
Cr2O727
2-
Fe3+
2Cr3+
+3
+3
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-
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-
2Cr3+ + 7H2O
Add the two half-reactions together and balance the final equation by inspection. The number of
electrons on both sides must cancel.
6Fe2+
Oxidation:
Reduction:
14H+ + Cr2O72- + 6Fe2+
8.
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
anode
salt bridge
cathode
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)
Reduction Reaction
2e- + 2H+ (1 M)
E0 = 0 V
13
H2 (1 atm)
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
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
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
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?
Cd (s) E0 = -0.40 V
Cr (s) E0 = -0.74 V
Cd will oxidize Cr
Anode (oxidation):
2e- + Cd2+ (1 M)
Cathode (reduction):
2Cr (s) + 3Cd2+ (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
= -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
DG0 = -RT ln K
19
= -nFE0cell
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
0.0257 V
=e
x2
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)
+
Batteries
Mercury Battery
Anode:
Cathode:
25
Batteries
Lead storage
battery
Anode:
Cathode:
Batteries
27
Batteries
Anode:
Cathode:
28
4OH- (aq)
2H2O (l)
CH3COO- + 2O2 + H+
29
2CO2 + 2H2O
Corrosion
Corrosion is the term usually applied to the deterioration of metals by an electrochemical process.
30
31
Electrolysis is the process in which electrical energy is used to cause a nonspontaneous chemical
reaction to occur.
32
Electrolysis of Water
33
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:
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-
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