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Redox Chemistry: Nitrogen & Manganese

This document summarizes a class lecture on redox chemistry of nitrogen and manganese species. It includes: 1) Latimer and Frost diagrams depicting the redox chemistry of nitrogen and manganese species in acidic and basic solutions. 2) Key reactions of nitrogen oxides like the synthesis of nitric acid from NO and NO2. 3) An example problem on the redox of nitrogen oxide species in basic solution. 4) A comparison of the redox properties of manganese and rhenium in acidic solutions using Frost diagrams. 5) An overview of cyclic voltammetry as a tool to study redox properties of new molecules.

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15 views4 pages

Redox Chemistry: Nitrogen & Manganese

This document summarizes a class lecture on redox chemistry of nitrogen and manganese species. It includes: 1) Latimer and Frost diagrams depicting the redox chemistry of nitrogen and manganese species in acidic and basic solutions. 2) Key reactions of nitrogen oxides like the synthesis of nitric acid from NO and NO2. 3) An example problem on the redox of nitrogen oxide species in basic solution. 4) A comparison of the redox properties of manganese and rhenium in acidic solutions using Frost diagrams. 5) An overview of cyclic voltammetry as a tool to study redox properties of new molecules.

Uploaded by

Cao Thị Vân Giang
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

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

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