Oxidation of molecular nitrogen with hydrogen peroxide [1]

Full text of DOI:10.1023/A:1023956100890

768
Russian Chemical Bulletin, International Edition, Vol. 52, No. 3, pp. 768—770, March, 2003
Letters to the Editor
Oxidation of molecular nitrogen with hydrogen peroxide*
a
b
b
a
A. E. Gekhman,а I. P. Stolyarov, A. F. Shestakov, A. E. Shilov, and I. I. Moiseev
ꢀ
aKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 954 1279. Eꢀmail: iimois@igic.ras.ru
bEmanuel´ Institute of Biochemical Physics, Russian Academy of Sciences,
4 ul. Kosygina, 117977 Moscow, Russian Federation.
Eꢀmail: shilov@icp.ac.ru
Molecular nitrogen is among the most inert to oxidaꢀ
For instance, N2O formation has been detected in the
highꢀtemperature decomposition of hydrogen peroxide in
a nitrogen atmosphere,2—4 which fact is in accord to the
thermodynamic data.
In the work5 theoretical aspects of molecular nitrogen
oxidation have been considered in the relation to bioꢀ
mimetic processes.
tion substrates. Under close to standard conditions, the
oxidation of molecular nitrogen to nitrogen(I or II) oxides
with dioxygen in its ground (3O2) and excited 1O2(1∆g)
states is thermodynamically unfavourable. However, the
oxidation of molecular nitrogen with hydrogen peroxide
is allowed thermodynamically**:
The data6 showed that vanadium(V) complexes in the
catalytic VV/H2O2/CF3COOH system are capable of
transferring to various substrates not only such oxygenꢀ
containing active species as 1O2(1∆g)6—8 but also an О(1Р)
atom or [О•+] radical cation.9 Two latter species are strong
acids in terms of the Usanovich theory10,11 and therefore
should exhibit acidic properties even toward such a weak
base as N2 to oxidize this substrate.
2 H2O2(l) + N2(g) = 2 NO(g) + 2 H2O(l)
,
(1)
(2)
(3)
∆G°298 = –58.3 kJ mol–1
,
H2O2(l) + N2(g) = N2O(g) + H2O(l)
,
∆G° = –13.1 kJ mol–1
,
298
In our study we found the first example of involving
molecular nitrogen in the hydroperoxideꢀcatalyzed oxiꢀ
dation.
3 H2O2(l) + N2(g) = N2O(g) + 3 H2O(l)
+ ,
3O2(g)
∆G°298 = –185.5 kJ mol–1
.
The oxidation of N2 (special purity grade) was carried out in
a gas flow reactor passing N2 flow (30—60 mL min–1) through a
solution of H2O2 (1 mol L–1) and VO(acac)2 (10–2 mol L–1) in
trifluoroacetic acid at 0—20 °C. The outgoing gas was collected
above an aqueous solution of NaCl or NaOH during 5—20 min
and then analyzed by chromatoꢀmass spectrometry (Automass
* Dedicated to Academician I. P. Beletskaya on occasion of her
anniversary.
** Thermodynamic parameters for compounds in reacꢀ
tions (1)—(3) are taken from the Handbook.1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 733—735, March, 2003.
1066ꢀ5285/03/5203ꢀ768 $25.00 © 2003 Plenum Publishing Corporation

Oxidation of molecular nitrogen
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
769
I
The chromatogram of the collected gas contains the
unseparated N2—O2 peak (retention time 57 s) and the
CO2 peak (retention time 63 s) (Fig. 1, a), along with a
lowꢀintensity chromatographic peak with a retention time
of 67 s (Fig. 1, b). The mass spectrum of the component
corresponding to the latter chromatographic peak, which
was obtained by subtraction of the averaged background
before and after the chromatographic peak, contains ions
with masses (intensities are in parentheses) 44 (100),
30 (27), and 28 (14) m/z (Fig. 2, a). This spectrum is in
good agreement with the literature mass spectrum of N2O,
m/z: 44 (100), 30 (31), and 28 (13) (Fig. 2, b), as follows
from a close to zero intensity of the lines in the difference
spectrum (Fig. 2, c). The concentration of N2O estimated
from the ratio of the ionic currents of the components is
at most 0.1%. The chromatograms of gaseous nitogen
used in the runs and those of the gaseous products of
hydrogen peroxide decomposition in the presence of
VO(acac)2 in a solution of trifluoroacetic acid in helium
atmosphere contain no peaks close in the retention time
and shape to the chromatographic signals found in the
spectrum of the products of nitrogen oxidation. In the
runs performed in the absence of VO(acac)2, no chroꢀ
matographic peaks corresponding to N2O were found.
The data obtained give evidence that molecular nitroꢀ
gen is oxidized in the VV/H2O2/CF3COOH catalytic sysꢀ
tem to form N2O. Analysis of the reaction solutions for
the presence of other products of nitrogen oxidation was
not carried out.
a
50
60
70
τ/s
I
b
1
2
60
70
τ/s
Fig. 1. Chtomatogram of gaseous products of N2 oxidation in
the VV/H2O2/CF3COOH system: a, chromatogram of total ionic
current; and b, part of the chromatogram (1) and fragmentoꢀ
gram (2) for m/z = 30.
The data available does not allow for definite concluꢀ
sions on the nature of the active intermediate responsible
for dinitrogen oxidation and the mechanism of formation
of nitrogen(I) oxide. However, the above thermodynamic
150 (DelsiꢀNermag) chromatoꢀmass spectrometer, column
SupelꢀQPlot (Supelco), 30 m×0.32 mm, –10 °C, Рinj = 0.5 bar,
flow splitting 1 : 40, probe volume 100 L, electron impact 70 eV,
mass interval 25—100 amu, spectrum sweep time 50 ms).
I/rel. units
44
a
28
30
45
27
44
b
30
28
c
30
40
M/amu
Fig. 2. Oxidation of molecular nitrogen: a, massꢀspectrum of the component with a retention time of 67 s in the chromatogram of
gaseous products of N2 oxidation in the VV/H2O2/CF3COOH system; b, the literature electron impact (70 eV) mass spectrum of
nitrogen(I) oxide; and c, difference between mass spectra a and b.

770
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Gekhman et al.
data unambiguously rule out the participation of free ozone
and singlet dioxygen in the reaction under question.
References
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Studies of the oxidation of perfluoroalkenes, alkanes,
and arenes with hydrogen peroxide showed6—8 that the
intermediate vanadium (V) complexes like 1 and 2 can be
formed in a solution of trifluoroacetic acid containing
vanadium compounds. These complexes can transfer an
oxygen atom and/or radical cation O•+ to a substrate, in
our case to the N2 molecule, to form nitrogen(I) oxide or
its radical cation. However, the formation of N2O•+
,
which could be expected in the N2 + O•+ reaction, is
improbable because of a rather high N2O ionization poꢀ
tential. It seems that the found product of N2 oxidation is
formed through a transfer of the oxygen atom to the niꢀ
trogen molecule, for example
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and Bases], Goskhimizdat, Moscow, 1949 (in Russian).
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kislot i osnovanii [Study in the Theory of Solutions and the
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1970 (in Russian).
This work was financially supported by the Governꢀ
ment of Russian Federation (Program for State Support
for Leading Scientific Schools, Grant 00ꢀ15ꢀ97429).
Received January 24, 2003