Article

pubs.acs.org/IECR

Preparation of Nitroform from Isopropanol and Study of the

Reaction Mechanism
Peng Ding, Liang Wen, Huiying Wang, Guangbin Cheng, Chunxu Lu, and Hongwei Yang*
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

ABSTRACT: The mechanism of the oxidation, nitration, and hydrolysis process of isopropanol with fuming nitric acid (98%,
white) was studied by 13C NMR spectroscopy. The effect of the nitronium (NO2+) on the preparation of nitroform from
isopropanol was investigated by using fuming nitric acid and H2SO4−HNO3 as nitrating agents. The results indicated that fuming
nitric acid showed a better efficiency for the studied reaction. Furthermore, the effect of specific factors, such as reaction
temperature, reaction time, and molar ratio of nitrating agent to isopropanol, on the yield of nitroform was investigated. Pure
nitroform can be obtained under optimized condition with excellent yield of 51.3%, about 26% higher than that reported in
literature. Orthogonal experiments were also carried out to further support the effectiveness.

1. INTRODUCTION not accepted due to the difficulty of obtaining pure nitroform.

Hydrazine nitroformate (HNF) is of interest as a potential
oxidizer for energetic solid rocket propellants with environ-
mentally combustion products.1,2 As the crucial raw material of
hydrazinium nitroformate (HNF), nitroform (NF) has
attracted considerable attention in the search for new energetic
materials3 since it was first synthesized by Shishkov.4 Synthetic
methods for NF have been explored by nitration of various
substrates including acetylene, acetic anhydride, pyrimidine-4,6-
diol, and isopropanol,5−9 as shown in Scheme 1. However,
Scheme 1. Synthetic Routes for the Synthesis of Nitroform
Using Different Substrates
industrial production of nitroform lags far behind laboratory
research because of the inevitable problems exist in these
synthetic procedures, such as poor safety for synthetic route
using acetylene, high costs for synthetic route using pyrimidine-
4,6-diol, and environmentally unfriendly synthesis for synthetic
route using acetic anhydride as substrate. Isopropanol shows
certain advantages over the substrates used in synthesis of
nitroform, for example, safety, low costs, and environmentally
friendly synthesis. Accordingly, the synthetic route from
isopropanol is potentially interesting for industrial scale
production. Synthesis of nitroform from isopropanol was
reported by Frankel et al.10 first in 1978 by using concentrated
nitric acid as the nitrating agent, but further study on optimal
reaction condition to improve the yield of NF from isopropanol
seemed to be balky.11 And the quantification for nitroform was
In addition, although mechanism has always been the crucial
part in the promotion of yield of target compounds, the
mechanism for the preparation of nitroform from isopropanol
has never been referred to in related literatures. Herein, we
reported syntheses of pure nitroform from isopropanol using
different nitrating agents and optimized conditions in fuming
nitric acid. The reaction mechanism was studied using 13C
NMR spectroscopy.
2. EXPERIMENTAL SECTION
2.1. General Information. All reagents were commercially
available. 1H NMR and 13C NMR spectra were recorded on a
Bruker Avance 300 spectrometer operating at 300.13 and 75.48
MHz, respectively, using DMSO-d6 or CDCl3 as solvent.
Although no explosion or detonation happened in the course of
the research, the intermediate KC(NO2)3 should be handled
with care since it may be subject to detonation by heat or
friction. KC(NO2)3 and NF should be stored at low
temperature (0 °C) to preclude the decomposition.
2.2. General Procedure for the Synthesis of Nitroform
from Isopropanol. To a vigorously stirred nitrating system
was added isopropanol (1.56 g, 0.026 mol) at room
temperature, and temperature was strictly controlled below
35 °C during the feeding course. Then the system was heated
up to setted temperature and reacted for specific time (Tables
1−6). The reaction was quenched by lowering the temperature
of the reaction system with ice−water bath and was extracted
with dichloromethane (30 mL × 4). The organic phase was
isolated, and the organic solutions were combined, washed with
saturated sodium carbonate aqueous solution, and dried over
MgSO4. To the purified organic solution was added a solution
of potassium hydroxide (KOH) in methanol until no yellow
precipitate was formed, and then crude KC(NO2)3 was
Received: April 21, 2014
Revised: June 19, 2014
Accepted: June 19, 2014
Published: June 19, 2014

© 2014 American Chemical Society 10886 dx.doi.org/10.1021/ie5011993 | Ind. Eng. Chem. Res. 2014, 53, 10886−10891
Industrial & Engineering Chemistry Research Article

Table 1. Yield of Nitroform Produced from Isopropanol in (300 MHz, CDCl3), 7.49 (s, 1H); 13C NMR (75 MHz,
H2SO4−HNO3a CDCl3), 113.3.
2.3. General Procedure for the Mechanistic Studies
Using 13C NMR. 2.3.1. Procedure for Taking Samples at the
End of the Feeding Course and the End of the Reaction of
Isopropanol. Isopropanol (2 mL) was added dropwise into
entry time (h) n(H2SO4)/n(HNO3) KC(NO2)3 (g)b yield (%)c
fuming nitric acid (14 mL). During the feeding course,
temperature was controlled below 35 °C. And then the
1 2 0:1 2.23 41.8
reaction system was heated to 60 °C and refluxed for 3 h. The
2 4 0:1 2.40 44.1
mixed liquid (0.5 mL) was sampled at the end of the feeding
3 6 0:1 1.08 19.1
course and at the end of the reaction, respectively, following by
4 2 1:10 1.12 23.0
mixing with 1 mL of DMSO-d6. The 13C NMR spectra were
5 4 1:10 1.21 20.7
recorded to afford Figure 1a and 1c. 13C NMR (75 MHz,
6 6 1:10 1.09 18.6
7 2 1:5 0.92 15.3
DMSO-d6): 22.9, 27.3, 32.6, 153.1, 166.0, 175.9, 189.5, 211.2
8 4 1:5 0.73 12.2
ppm (Figure 1a, for NMR sample at the end of the feeding
9 6 1:5 0.67 10.2
course). 13C NMR (75 MHz, DMSO-d6): 181.7, 119.0, 23.8
10 2 1:1 − −
ppm (Figure 1c, for NMR sample at end of the reaction).
11 6 1:1 − −
2.3.2. Procedure for Taking Samples at the End of the
12 2 3.5:1 − − Reaction of Acetone. The sample was taking at the end of the
13 6 3.5:1 − − feeding course of acetone following same procedure with
isopropanol. Two milliliters of acetone was used and the 13C
a
Isopropanol (1.56 g, 26.0 mmol); reaction temperature was 60 °C;
molar ratio of anhydrous nitric acid to isopropanol was 12:1. NMR spectra was recorded to afford Figure 1b. 13C NMR (75
b
KC(NO2)3 was obtained after recrystallization. cThe yield was MHz, DMSO-d6): 23.0, 27.3, 32.6, 91.4, 153.2, 175.4, 189.5,
calculated by the equation: yield% = n(NF)/n(isopropanol). 210.2 ppm.

3. RESULTS AND DISCUSSION

obtained by filtration and purified by recrystallization from 3.1. Mechanism Study of Synthesis of Nitroform from
methanol. And pure nitroform as white crystals prepared by the Isopropanol in Fuming Nitric Acid. The reaction
acidification of KC(NO2)3 with concentrated sulfuric acid in mechanism involved three elementary steps (Scheme 2). At
bromoethane and then extracted with bromoethane. 1H NMR the first step, hydroxy (OH) in isopropanol could be oxidized

Figure 1. (a) 13C NMR spectrum recorded at the end of the feeding course of isopropanol into fuming nitric acid. (b) 13C NMR spectrum recorded
at the end of the feeding course of acetone into fuming nitric acid. (c) 13C NMR spectrum recorded at the end of the reaction of isopropanol in
fuming nitric acid.

10887 dx.doi.org/10.1021/ie5011993 | Ind. Eng. Chem. Res. 2014, 53, 10886−10891

Industrial & Engineering Chemistry Research
Scheme 2. Mechanism of the Synthesis of Nitroform from Isopropanol in Fuming Nitric Acid
Scheme 3. Formation of Nitronium (NO2+) in HNO3−H2SO4 and HNO3
to generate carbonyl (CO), thus acetone would be formed
by the oxidation of isopropanol in fuming nitric acid. The
second step would involve the formation of series of polynitro
compounds. The generation of acetone made the nitration of
C−H single-bond possible because of the strong electron
withdrawing ability of the carbonyl (CO). 1,1,1-trinitroace-
tone (intermediate A) was formed by the substitution of three
hydrogen atoms in acetone with NO2+ step by step. At the last
step, nitroform would be generated by hydrolysis of
intermediate A. The strong electron withdrawing ability of
trinitromethyl (-C(NO2)3) in A contribute to be hydrolyzed by
H2O to generate nitroform and acetic acid.
Considering the great differences in the “carbon chemical
environment” of varied intermediates, 13C NMR spectral tests
were conducted to support the proposed mechanism above.
Because of the formation of acetone in the possible oxidation
step of isopropanol, we took the sample to record 13C NMR
spectral during the feeding course and end of reaction with
isopropanol and acetone as substrate, respectively. As shown in
Figure 1a,1b, obviously, carbon atoms observed at 189.5 and
211.2 ppm was assigned to the carbonyl (CO), while the
carbon atoms observed at 153.1, 166.0, 175.9 ppm could be
assigned to the derivatives derived from the nitration process of
acetone, which presented a direct testimony to the oxidation of
isopropanol into acetone (step 1). 13C NMR spectral during
the feeding course in acetone as substrate shows great similarity
with that of isopropanol. The only difference in the two 13C
NMR spectra is located at the carbon atoms observed at 91.4
ppm for acetone system and 166.0 ppm for isopropanol system,
which could be attributed to nitration process accelerated by
heat released from the oxidation step involved in isopropanol
system. The carbon atom observed at 91.4 ppm might be
assigned to mononitroacetone and corresponding carbon atom
at 166.0 ppm would be assigned to trinitroacetone. This great
similarity proved further the formation of acetone (step 1) in
the proposed mechanism.
10888
Article
13
C NMR spectrum recorded at the end of the reaction of
isopropanol in fuming nitric acid is shown in Figure 1c. The
carbon signal of nitroform was found at 119.1 ppm, while other
signals observed at 23.9 and 181.9 ppm were in good
agreement with that of acetic acid. The generation of nitroform
and acetic acid presented a direct testimony to the formation
(step 2) and hydrolysis (step 3) of intermediate A.
3.2. Preparation of Nitroform from Isopropanol in
Fuming Nitric Acid. 3.2.1. Preparation of Nitroform from
Isopropanol in H2SO4−HNO3 Nitrating System: Selection of
the Nitrating Agents. The oxidation capacity and the nitration
capacity of nitrating agents would effect on the yield of
nitroform from isopropanol according to the reaction
mechanism. Therefore, the effect of the nitronium (NO2+) on
the preparation of nitroform from isopropanol was investigated
by using fuming nitric acid and H2SO4−HNO3 as nitrating
agents. The formation of NO2+ in fuming nitric acid and
H2SO4−HNO3 is shown in Scheme 3. Compared to the fuming
nitric acid without addition of concentrated sulfuric acid, the
ionization process was greatly promoted in nitrating system
because of the strong dehydration of concentrated sulfuric
acid.12,13 Thus, the nitration capacity for H2SO4−HNO3 was
strengthened. However, the oxidation capacity for HNO3 was
weakened when concentrated sulfuric acid was added to fuming
nitric acid.14−16 The results are shown in Table 1.
In our preliminary investigation, we carried out the nitration
of isopropanol with fuming nitric acid only with reaction
temperature of 60 °C when the molar ratio of fuming nitric acid
to isopropanol was 12:1. The hydrazine nitroformate (KC-
(NO2)3) stood as an important intermediate in preparation
process of NF. The output of KC(NO2)3 in the synthetic
strategy directly symbolized extremum of yield of NF. Yield of
nitroform experienced an increase and a decrease when reaction
time changed from 2 to 4 h (entries 1−3). Lengthen of reaction
time to 6 h will cut down yield of nitroform, which was
probably because of a side reaction accompanying the nitration
reaction. In comparison, H2SO4−HNO3 nitrating system with
dx.doi.org/10.1021/ie5011993 | Ind. Eng. Chem. Res. 2014, 53, 10886−10891
Industrial & Engineering Chemistry Research Article

the settled molar ratio was adopted as the nitrating system, and Table 3. Effect of Reaction Time on the Yield of Nitroform
the results are shown in Table 1. Yields of nitroform went down in Fuming HNO3a
when concentrated sulfuric acid was added to the fuming nitric
entry reaction time (h) KC(NO2)3 (g)b yield (%)c
acid nitrating agent. The yields of nitroform decreased from
23.0% to 10.2% as molar ratio of concentrated sulfuric acid to 1 2 2.23 41.8
fuming nitric acid increased from 1:10 to 1:5 (entries 4−9). 2 3 2.65 49.5
Furthermore, nitroform can scarcely be obtained when the 3 4 2.40 44.1
molar ratio increased to 1:1 or 3.5:1 (entries 10−13). The 4 5 1.73 32.1
decrease of the yield could be attributed to the characteristic of 5 6 1.08 19.1
sulfuric acid in the nitrating system. Although the nitration a
Isopropanol (1.56 g, 26.0 mmol); reaction temperature was 60 °C;
capacity was strengthened, the capacity for oxidation of the molar ratio of anhydrous nitric acid to isopropanol was 12:1.
b
nitrating system was weakened when concentrated sulfuric acid KC(NO2)3 was obtained after recrystallization. cThe yield was
was added to the fuming nitric acid. Moreover, the hydrolysis of calculated by the equation: yield% = n(NF)/n(isopropanol).
intermediate A would be greatly inhibited because of
dehydration of concentrated sulfuric acid. Thus, we conclude The effect of molar ratio of fuming nitric acid to isopropanol
that fuming nitric acid has higher efficiency than H2SO4− on the yield of nitroform in fuming nitric acid was investigated
HNO3 nitrating system for preparation of nitroform from with different molar ratio values, and the results are shown in
isopropanol. Table 4. Yield of nitroform was improved continuously with the
3.2.2. Preparation of Nitroform from Isopropanol in
Fuming HNO3: Conditions Screening. On the basis of nitrating Table 4. Effect of Molar Ratio of Fuming Nitric Acid to
agents we investigated, we studied the effect of reaction Isopropanol on the Yield of Nitroform in Fuming HNO3a
temperature in the range of 40−90 °C on the yield of nitroform entry molar ratio KC(NO2)3 (g)b yield (%)c
produced by isopropanol in fuming nitric acid. As shown in 1 3:1 0.29 2.8
Table 2, nitration of isopropanol with fuming nitric acid 2 6:1 0.59 8.7
3 9:1 1.76 32.4
Table 2. Effect of Temperature on the Yield of Nitroform in 4 12:1 2.66 50.5
Fuming HNO3a 5 15:1 2.70 51.3
entry temperature (°C) KC(NO2)3 (g)b yield (%)c 6 18:1 2.77 53.0
7 21:1 2.87 54.1
1 40 1.08 19.1
8 24:1 2.92 54.8
2 50 2.47 45.1
3 60 2.65 49.5
a
Isopropanol (1.56 g, 26.0 mmol); reaction temperature was 60 °C;
4 70 2.26 41.8 and reaction time was 3 h. bKC(NO2)3 was obtained after
recrystallization. cThe yield was calculated by the equation: yield% =
5 80 1.09 18.6
n(NF)/n(isopropanol).
6 90 0.50 7.4
a
Isopropanol (1.56 g, 26.0 mmol); reaction time was 3 h; molar ratio increase of the molar ratio of fuming nitric acid to isopropanol
of anhydrous nitric acid to isopropanol was 12:1. bKC(NO2)3 was in the range of 3:1 to 24:1. The reaction rarely proceeded with
obtained after recrystallization. cThe yield was calculated by the
equation: yield% = n(NF)/n(isopropanol).
yield of nitroform 2.81% when molar ratio of fuming nitric acid
to isopropanol was 3:1 (entry 1). When the value of molar ratio
increased to 6:1, which was the theoretical amount of fuming
nitric acid, the yield of nitroform was only 8.7% (entry 2). This
nitrating system afford nitroform in good yields of 49.5% was probably due to the dilution of the fuming nitric acid in the
(entries 2 and 3) with an excess amount of fuming nitric acid nitration procedure. By further increasing the ratio to 9:1 or
(12 equiv), 60 °C of reaction temperature and 3 h of reaction 12:1, the yield of nitroform was improved dramatically and
time. Yield of nitroform goes up when reaction temperature reached up 50.5%(entries 1−4). Only 4% of yield improvement
changed from 40 to 60 °C (entries 1−3), which could be was achieved when the molar ratio of fuming nitric acid to
attributed to the low reactivity of fuming nitric acid when the isopropanol increased from 12:1 to 24:1 (entries 4−8). The
reaction system was under relative low temperatures. And continuous enhancement of yield is attributed to improvement
further increase of the reaction temperature witnessed a sharp of the nitration capacity and the oxidative capacity with an
decrease for the yield of nitroform (entries 3−6). When increasing concentration of fuming nitric acid in isopropanol. It
reaction temperature was 90 °C, nitroform was obtained with also could be seen that 12:1 was optimized ratio in
only 7.4% of yield. This was probably because of losses of target consideration of economical efficiency and effectiveness.
compound derived from its high volatility and instability. 3.2.3. Orthogonal Experiments. To further confirm the high
The effect of reaction time on the yield of nitroform in efficiency under optimized condition, orthogonal experiments
fuming nitric acid was investigated with time in the range of 2− L9(34) were designed to define the factors such as reaction
6 h, and the results are shown in Table 3. It could be seen from temperature, reaction time and molar ratio of fuming HNO3 to
the table that the yield of nitroform was as high as 49.5% when isopropanol. For “L9(34)”, “9” represents the number of
reaction time was 3 h (entry 2). If the reaction time was shorter experiments, “3” is the number of factor levels, and “4” is the
or longer, yields of nitroform decreased. The conclusion is number of factors. Value of the selected factors in L9(34)
drawn that enough time is needed for the completion of orthogonal table are shown in Table 5, and results are shown in
nitration procedure and that increase of the reaction time could Table 6. Kij, kij, and Rj (i = 1, 2, 3; j = A, B, C) in the table were
bring about the losses of nitroform synthesized in the reaction obtained from the experimental data with respect to the yield
system because of side reaction. (%) of NF (kij = Kij/3). The value for Rj displayed the effect of
10889 dx.doi.org/10.1021/ie5011993 | Ind. Eng. Chem. Res. 2014, 53, 10886−10891
Industrial & Engineering Chemistry Research Article

Table 5. Factor-Level Table nitric acid and H2SO4−HNO3 as nitrating agents. The fuming
nitric acid showed good efficiency in the synthesis of nitroform
factor
with mild, efficient and time saving nitration procedure.
A B C Furthermore, the effect of specific factors such as reaction
level temperature (°C) time (h) molar ratio temperature, reaction time, and molar ratio of nitrating agent to
1 50 2 9:1 isopropanol, on the yield of nitroform was investigated. Pure
2 60 3 12:1 nitroform can be obtained under optimized condition with
3 70 4 15:1 excellent yield of 51.3%, 26% higher than that reported in
literature.10 Also, the orthogonal experiments were carried out
Table 6. L9(34) Orthogonal Factor-Level Tablea to confirm the efficiency and practicality of the synthetic route
for nitroform. In addition, a relatively convenient after-
treatment method to afford pure nitroform which involved
the intermediate potassium nitroformate (KC(NO2)3) was
utilized. In a word, the synthetic methodology and mechanistic
A B C studies will provide the basis for further studies on the
industrial production of nitroform.

■
temperature molar KC(NO2)3 yield
entry (°C) time (h) ratio (g)b (%)c
1 50 2 9:1 1.59 29.1 AUTHOR INFORMATION
2 50 3 12:1 2.47 45.1 Corresponding Author
3 50 4 15:1 2.56 47.7 *Tel.: +0086-25-84303286. E-mail: hyang@mail.njust.edu.cn.
4 60 2 12:1 2.23 41.8
Notes
5 60 3 15:1 2.70 51.3
The authors declare no competing financial interest.

■
6 60 4 9:1 2.03 36.7
7 70 2 15:1 2.28 41.3
8 70 3 9:1 1.90 34.4 ACKNOWLEDGMENTS
9 70 4 12:1 2.23 40.0 This work was supported by the Natural Science Foundation of
K1j 121.9 112.2 100.2 Jiangsu Province (BK2011696) and the National Natural
K2j 129.8 130.8 126.9 Science Foundation of China (No. 21376121).
K3j
K1j
K2j
115.7
40.63
43.27
124.4
37.40
43.60
140.3
33.40
42.30
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10891 dx.doi.org/10.1021/ie5011993 | Ind. Eng. Chem. Res. 2014, 53, 10886−10891