Class 9.

2
Redox Chemistry III

Wednesday, October 20
CHEM 462
T. Hughbanks

Latimer diagrams: Nitrogen

acid solution (pH = 0)

+0.79 +1.07 +0.996 +1.59 +1.77 -1.87 +1.41 +1.275
HNO3 N2O 4 HNO2 NO N2O N2 NH3OH+ N2H 5+ NH4 +

-3.09
HN3

basic solution (pH =14)

-0.86 +0.88 -0.46 +0.76 +0.94 -3.04 +0.73 +0.1
NO3– N2O4 NO2– NO N2 O N2 NH2 OH N2H4 NH3

Frost diagrams: Nitrogen

Frost diagrams: aqueous Nitrogen species

7 HNO3

6 Cu2+ /Cu
N2 O4
H+/H2
5 Zn2+ /Zn
HNO2
4
nE˚/V NH2 OH NO
3 N2 H4
NH3 N2 O4
2 NH3OH+
N2 O NO
NO3 -
HN3
1 N2 O NO2 -
N2 H5 +
0
N2
-1 NH4 +

-3 -2 -1 0 1 2 3 4 5
oxidation number
 Some important N/O reactions

NH4+(aq) + NO3–(aq)  N2O(g) + H2O(l) spontaneous
N2O: Useful anesthetic (laughing gas)
Nearly “thermoneutral” rxns:

NO(g) + NO2(g) + H2O(l)  2 HNO2(aq) rapid

2 HNO2(aq)  HNO3(aq) + 2 NO(g) + H2O(l) rapid

2 NO2 + H2O(l)  2 HNO3(aq) + HNO2 (aq) slow
These or similar rxns important for nitric acid synthesis.

Example Problem

Write balanced half-reactions for the

reduction of NO to N2O and N2O to N2 in
basic solution.

Is N2 O thermodynamically stable with
respect to disproportionation to NO and N2
in basic solution? What is
Go?

Latimer diagrams: Manganese

acid solution (pH = 0)

+0.90 +1.28 +2.90 +0.95 +1.5 -1.18
MnO4– HMnO4– (H3MnO4 ) MnO2 Mn3+ Mn2+ Mn

basic solution (pH =14)

+0.56 +0.27 +0.93 +0.146 -0.234 -1.56
MnO4 – MnO42– MnO43– MnO2 Mn2 O3 Mn(OH)2 Mn
 Frost diagrams: Manganese

6 MnO4–
H2O2/H2O
5
O2/H2O HMnO4–
4
H+/H2
3 (H3MnO4)
2
nE˚/V 1 MnO2
0 Mn
Mn 3+
-1 MnO4–
Mn 2+ MnO42–
-2 MnO43–

-3 Mn2O3
Mn(OH)2 MnO2
-4
0 1 2 3 4 5 6 7
oxidation number

Manganese vs. Rhenium

Manganese vs Rhenium (acidic soln)

6 MnO 4–
5 –
HMnO4
4
ReO42–
3 (H3MnO4)

nE˚/V 2 ReO4–
Re3+ ReO 2 ReO 3
1
0 Mn, Re MnO 2
-1 Mn3+
-2
Mn 2+
-3
-4
0 1 2 3 4 5 6 7
oxidation number

Cyclic Voltammetry

Most common tool of

inorganic chemists to time
survey redox
properties of “new
molecules”.

Voltage at the
current
working electrode is
(i)
swept against time in
a “sawtooth” function. E0
E1/2
– +
V
Voltammogram
of a Cluster