Reductive fixation of carbonate in aqueous solution by nitrogen plasma

Article abstract of DOI:10.14233/ajchem.2013.14412

A jet of nitrogen plasma blown into a sodium carbonate solution produced reductive fixation of carbonate to formate. The reaction is explained by the nitrogen-mediated oxidation-reduction of water.

Full text of DOI:10.14233/ajchem.2013.14412

Asian Journal of Chemistry; Vol. 25, No. 9 (2013), 5059-5062
http://dx.doi.org/10.14233/ajchem.2013.14412
Reductive Fixation of Carbonate in Aqueous Solution by Nitrogen Plasma
1
,2,*
3
T. MUNEGUMI
and K. HARADA
1
2
3
Department of Science Education, Naruto University of Education, Naruto, Tokushima 772-8502, Japan
Oyama National College of Technology, Oyama, Tochigi 323-0806, Japan
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
*
Corresponding author: Fax: +81 88 6876022; Tel: +81 88 6876418; E-mail: tmunegumi@naruto-u.ac.jp; toramune@gmail.com
Received: 8 August 2012; Accepted: 20 March 2013) AJC-13137
(
A jet of nitrogen plasma blown into a sodium carbonate solution produced reductive fixation of carbonate to formate. The reaction is
explained by the nitrogen-mediated oxidation-reduction of water.
Key Words: Reductive fixation, Carbonate, Formate.
-
4
0
.14 %; formaldehyde, 2.8 × 10 %) of ferrous sulphate. The
INTRODUCTION
yield of formate in the absence of ferrous sulphate was much
lower, even though the reaction was conducted using higher
energy radiation. The observation suggests the importance of
the combination of carbon dioxide, water vapour, energy
sources and/or agents for reducing carbon dioxide. Chemical
evolution on primitive earth and extra terrestrial formation of
organic compounds is highlighted by these findings.
The atmospheric composition of primitive earth has been
discussed for many years. Many chemists had believed that
the primitive atmosphere of the earth was "reducing" (NH
3
,
1
CH
that the atmosphere was "nonreducing" (N
The production of organic compounds from N
is difficult because of the thermodynamic disadvantage
4 2 2
, H and H O) , while most geochemists have emphasized
2
-6
2
, CO
2
and H
2
O) .
2
, CO
2
and H O
2
11
In contrast, Folsome et al. examined electric discharge
in molecular nitrogen over an aqueous solution of calcium
2+
carbonate in the presence of Fe . Nitric acid, nitrous acid,
7
(
Scheme-I). Stribling and Miller examined the effect of electric
1
discharge (Miller discharge ) into gas mixtures possessing diffe-
rent concentrations of carbon dioxide, methane and hydrogen
and plotted the relationship between the initial gaseous ratio
and carbon yield of organic compounds produced. The carbon
yield became lower with higher concentrations of carbon
dioxide without hydrogen. These results demonstrate that under
discharge electrolysis, the reduction of organic compounds is
difficult without hydrogen.
ammonia and carbonate hydrazine were obtained, but formate
was not. They commented that molecular nitrogen served as
the primary oxidant scavenger, leading to the formation of
nitrite and nitrate.
If an aqueous solution is irradiated with nitrogen plasma
containing nitrogen radicals, the high energy conditions will
dissociate water molecules into hydroxyl (OH) and hydrogen
(
H) radicals (Scheme-II) and these radicals will react with
CO2
+
2H O
CH4
+
2O2
∆
Go
= 802 kJ/mol
298
2
nitrogen radicals in the plasma. The dissociation of water
molecules by glow discharge electrolysis (Harada discharge)
onto aqueous solutions and blowing a jet of argon plasma into
Scheme-I
8
Nevertheless, in early years of the last century, Löb and
9
Groth et al. confirmed the production of formate aldehydes
12,13
water has already been proven by Hase and Harada
Reductive fixation of carbon dioxide or carbonate has not been
.
from carbon dioxide and water vapor without hydrogen by
8
silent discharge or irradiation by ultraviolet light . The
14-17
reported, although reductive fixation of nitrogen by nitro-
18
gen-argon plasma and reduction of carbon-carbon double
9
formation of formate and formaldehyde by irradiation of
bonds in maleic acid by hydrogen-argon plasma have been
14-18
2+
aqueous solutions of carbon dioxide with a He beam (40
reported
.
10
MeV) is also possible . Aqueous solutions containing carbon
dioxide were irradiated in the presence (yield of formate, 22 %;
formaldehyde, 0.34 %) or in the absence (yield of formate,
Go
= 475 kJ/mol
298
H O
H
+
OH
∆
2
Scheme-II

5
060 Munegumi et al.
Asian J. Chem.
In this paper, we describe the formation of formate from
sodium carbonate in an aqueous solution induced by nitrogen
plasma as a model reaction for nonreducing atmospheric condi-
tions. Under nonreducing conditions, higher energy plasma
could be generated by the action of lightning, atmospheric
entry of meteors and meteorites or by radiation of solar winds
2
-4
or cosmic rays on the primitive ocean .
EXPERIMENTAL
Sodium carbonate and ammonium phosphate were
purchased from Wako Pure Chemical Industries Ltd. (Tokyo).
Chemicals for making buffer solutions: potassium gluconate,
pyroborate, acetonitrile and glycerin were purchased from
Tokyo Chemical Industry Co. Ltd. (Tokyo).
Fig. 2. Ion chromatograms of nitrate and nitrite. A Jasco HPLC system
was used for the analyses. Analytical column: TSK IC-Anion-PW
(50 mm × 4.6 mm I.D.). Eluent: 30 mM borate buffer (pH 3.0)
containing 1.3 mM potassium gluconate, 1.3 mM pyroborate, 10
Reaction apparatus and method: The apparatus for the
reaction induced by nitrogen plasma is shown in Fig. 1. A
plasma jet generated by electric discharge through a stream of
nitrogen-argon gas mixture was used as an energy and nitrogen
source for the reactions. A Well Pen PLA-J (Nippon Welding
Co. Ltd.) was used as a plasma generator. The flow of nitrogen-
argon was controlled at 2.0 L/min. A sample was removed
from the reaction mixture for analysis every 10 min. Nitrogen-
argon arc plasma (the nitrogen-argon flow rate: 0.0, 2.0; 0.5,
% acetonitrile and 0.5 % glycerin. Flow: 1.2 mL/min. Detection:
absorption at 210 nm
(a)
1
.5; 1.0, 1.0; 2.0, 0.0 L/min) was blown into a 20 mM sodium
carbonate aqueous solution (350 mL, pH 11.3) from the 20A,
0 V plasma torch. The reaction vessel was cooled using a
2
water jacket to maintain the reaction at 25-40 ºC.
Fig. 3. Chromatograms of formate or carbonate by using a reversed column
a) and an anion exchange column (b). (a) A Jasco HPLC system
(
was used for analyses. Column: GL Sciences Inc. Inertsil-ODS (250
mm × 4.6 mm I.D.). Eluent: 5 mM ammonium phosphate (pH 2.5).
Detection: absorption at 210 nm. Flow rate: 0.5 mL /min. (b) A
Dionex ion chromatography 2000i was used for analyses. Column:
HPICE-AS1 (250 mm × 4 mm I.D.) equipped with an AFS2 anion
fiber suppresser. Eluent: 0.125 mM octane sulfonic acid. Ion removal
agent: 5.0 mM tetrabutyl-ammonium hydroxide. Flow: 0.7 mL/min.
Detection: conductivity
Fig. 1. Apparatus for producing the plasma jet. A jet of nitrogen-argon
plasma produced from a mixture of nitrogen and argon gas was
blown out of a plasma torch into an aqueous solution containing 20
mM sodium carbonate. The reaction vessel was cooled by water
flowing in an outer cooling jacket to maintain the reaction at 25-
A Dionex ion chromatography 2000i was used for analyses
of formate and carbonate. Column: HPICE-AS1 (250 mm × 4
mm I.D.) equipped with an AFS2 anion fiber suppresser.
Eluent: 0.125 mM octanesulfonic acid. Ion removal agent: 5.0
mM tetrabutyl-ammonium hydroxide. Flow: 0.7 mL/min.
Detection: electric conductivity.
4
0 ºC
Analytical method: Resulting concentrations of nitrate
and nitrite were determined by an ion chromatography
equipped with an analytical column: TSK IC-Anion-PW (50
mm × 4.6 mm I.D.). Eluent: 30 mM borate buffer (pH 3.0)
containing 1.3 mM potassium gluconate, 1.3 mM pyroborate,
RESULTS AND DISCUSSION
A jet of nitrogen plasma was blown into a sodium
carbonate solution (20 mM) using different nitrogen-to-argon
flow ratios. Table-1 shows the concentration of products after
1
Detection: absorption at 210 nm (Fig. 2).
0 % acetonitrile and 0.5 % glycerin. Flow: 1.2 mL/min.
A Jasco HPLC system was used for analyses of formate.
Column: GL Sciences Inc. Inertsil-ODS (250 mm × 4.6 mm
I.D.). Eluent: 5 mM ammonium phosphate (pH 2.5). Detection:
absorption at 210 nm. Flow rate: 0.5 mL/min (Fig. 3).
9
0 min. Formate and ammonia and oxidative products such
as nitrite and nitrate were obtained in the reaction mixture.
Formate and other compounds increased with higher ratios of

Vol. 25, No. 9 (2013)
Reductive Fixation of Carbonate in Aqueous Solution by Nitrogen Plasma 5061
N
+
H
O
+
(7/2) H
CO
(1/2)
HNO
+ (3/2) HNO2 + (7/2)
HCOOH
Gº298 = 976 kJ/mol
TABLE-1
2
2
2
3
3
FORMATION OF NITRIC ACID, NITROUS ACID,
AMMONIA AND FORMATE BY BLOWING A JET OF
NITROGEN–ARGON PLASMA INTO AN AQUEOUS
∆
Scheme-III
SOLUTION OF SODIUM CARBONATE FOR 90 min
a
Flow rate (L/min)
N2
2N
∆
Gº298 = 911 kJ/mol
Yield (mM)
Entry
N -Ar
2
HNO3
0
NHO2
NH3
0
HCOOH
0
Scheme-IV
1
2
3
4
0.0-2.0
0.5-1.5
1.0-1.0
2.0-0.0
2.0-0.0
0
1.69
5.35
4.95
2.00
8.89
23.2
35.7
14.3
0.043
0.064
0.089
1.82
4.03
6.97
+
(7/2)
(1/2)HNO + (3/2)HNO
2
+ (7/2)HCOOH
2N
H
+
OH +
H
2
CO
3
3
∆
Gº298 = -410 kJ/mol
b
5
Scheme-V
0.200
b
–
a
17
Flow rate of each gas used for plasma jet generator. A plasma jet
blowing in a sodium borate buffer at pH 12.7.
Fig. 5 shows the decrease of carbonate and yield of
formate in the solution after reaction with the nitrogen plasma
for a longer time. The decrease in carbonate is similar to the
increase of formate. After 420 min (7 h), formate reached a
more than 80-90 % yield. When argon gas alone (2.0 L/min)
was used for the reaction, formate was not detected on the ion
chromatograms. These findings suggest the strong possibility
of formation of formate from carbonate in the primitive ocean
by nitrogen plasma in nature. The reductive reactions could
have produced various reducing organic compounds and
nitrogen to argon (0.0, 2.0; 0.5, 1.5; 1.0, 1.0; 2.0, 0.0 L/min),
while the compounds were not obtained when the jet did not
contain nitrogen.
To our best of knowledge, this is the first reported finding
of formate formation after blowing a jet of nitrogen containing
plasma into a sodium carbonate solution, although research
14,15
16,17
by Takasaki et al. and our research showed that ammonia,
nitric acid and nitrous acid formed after using a jet of nitrogen-
argon plasma and contact glow discharge electrolysis. This is
a typical disproportionation reaction between carbonate, water
and nitrogen under high energy conditions. These results
indicate that the nitrogen radical in plasma might trap OH
radicals and that the remaining H radical reduced carbonate
ammonia in the primitive ocean under a nonreducing atmos-
9
O) . The effectiveness of nitrogen and
phere (N
2
, CO
2
and H
2
1
9,20
carbon dioxide was also discussed by Rode and coworkers
after they found organic compounds such as simple amino
acids in the electric discharge on the junction between the
gaseous and aqueous phases of water when sparging with
nitrogen and carbon dioxide. Although the mechanism was
not discussed in detail, their results support the effectiveness
of an active nitrogen species derived from molecular nitrogen
in the primitive water sphere.
17
to give formate. Entry 5 shows the cited data in a sodium
borate buffer solution at pH 12.7. Yields of nitrite and nitrate
are rather lower and yield of ammonia is higher than the results
in entry 1-4. Comparison of these data suggests that carbonate
in the reaction mixture could accelerate the formation of nitrite
and nitrate and depress the formation of ammonia.
Fig. 4 shows the time course of formate production using
different nitrogen-to-argon flow ratios. The concentration of
formate increased with time. Nitrogen clearly plays an essential
role in formate production. And also nitrogen plasma gives a
thermodynamically advantage to the reactions. The formation
of formate from molecular nitrogen, water and carbonate is
thermodynamically difficult because of the thermal disadvan-
tage (Scheme-III). However, the high energy of nitrogen plasma
activates molecular nitrogen to nitrogen radicals to result in
the reductive fixation of carbonate to formate with a little
exothermal energy formation (Schemes IV and V).
Fig. 5. Formation of formate by blowing a jet of nitrogen-argon plasma
into 20 mM sodium carbonate. Plasma jet conditions: nitrogen-
argon flow, 2.0-0.0 L/min. Current and voltage: 20 A and 20 V;
reaction temperature 25-40 ºC
2
1,22
However, Tiang et al.
of hydrogen from primitive earth was much slower than that
recently showed that the escape
23
previously assumed. Chyba discussed the effect of a higher
concentration of hydrogen on the formation of carbon com-
pounds. They proposed a more reducing atmosphere containing
a higher concentration of hydrogen than that believed by many
Fig. 4. Formation of formate by blowing a jet of nitrogen-argon plasma
into 20 mM sodium carbonate. Plasma jet conditions: nitrogen-
argon flow: 0.0-2.0; 0.5-1.5; 1.0-1.0; 2.0-0.0 L/min. Current and
voltage: 20 A and 20 V; reaction temperature 25-40 ºC

5
062 Munegumi et al.
Asian J. Chem.
4
5
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7
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24
effect of nitrogen in relation to organic compound formation
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9
1
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The results shown here demonstrate that formate could
be produced from carbonate anions by the action of nitrogen
plasma in the primitive ocean under nonreducing conditions.
To our best of knowledge, this study is the first clear example
of organic compound formation in high yield from inorganic
compounds without iron under a nonreducing atmosphere. The
chemical action of nitrogen plasma in aqueous solution is now
under further investigation.
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