Experimental study of the reaction of isopropyl nitrate with OH radicals: Kinetics and products

Article abstract of DOI:10.1002/kin.20891

The kinetics of the reaction of isopropyl nitrate (IPN) with OH radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + (CH₃)₂CHONO₂ → products (2). The rate constant of the title reaction was determined using both the absolute method, monitoring the kinetics of OH radicals consumption in excess of IPN, and the relative rate method using the reaction of OH with Br₂ as reference one and following HOBr formation. As a result of the absolute and relative measurements, the overall rate coefficients, k₂ = (6.6 ± 1.2) × 10^-13 exp(-(233 ± 56)/T) was determined at a pressure of 1 Torr of helium over the temperature range 268-355 K. Acetone, resulting from H-atom abstraction from the tertiary C-H bond of IPN followed by 2-nitroxy-2-propyl radical decomposition, was found to be a major reaction product with the yield of 0.82 ± 0.13, independent of temperature in the range 277-355 K.

Full text of DOI:10.1002/kin.20891

Experimental Study of the
Reaction of Isopropyl
Nitrate with OH Radicals:
Kinetics and Products
MANOLIS N. ROMANIAS, JULIEN MORIN, YURI BEDJANIAN
Institut de Combustion, A e´ rothermique, R e´ activit e´ et Environnement (ICARE), CNRS and Universit e´ d’Orl e´ ans, 45071,
Orl e´ ans, Cedex 2, France
Received 12 September 2014; revised 28 October 2014; accepted 29 October 2014
DOI 10.1002/kin.20891
Published online in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The kinetics of the reaction of isopropyl nitrate (IPN) with OH radicals has been
studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer:
OH + (CH3)2CHONO2 → products (2). The rate constant of the title reaction was determined
using both the absolute method, monitoring the kinetics of OH radicals consumption in
excess of IPN, and the relative rate method using the reaction of OH with Br2 as reference
one and following HOBr formation. As a result of the absolute and relative measurements,
−
13
the overall rate coefficients, k2 = (6.6 ± 1.2) × 10
exp(–(233 ± 56)/T) was determined
at a pressure of 1 Torr of helium over the temperature range 268–355 K. Acetone, resulting
from H-atom abstraction from the tertiary C–H bond of IPN followed by 2-nitroxy-2-propyl
radical decomposition, was found to be a major reaction product with the yield of 0.82 ± 0.13,
independent of temperature in the range 277–355 K. ꢀC 2014 Wiley Periodicals, Inc. Int J Chem
Kinet 1–8, 2014
INTRODUCTION
and also in the NO3-initiated oxidation of unsaturated
organic compounds [1]. Organic nitrates are temporary
reservoirs of NOx with a tropospheric lifetime from a
few days to a few weeks, depending on the reactiv-
ity of nitrates toward OH radicals and their photoly-
sis rate [2–5]. Photolysis of organic nitrates is known
to produce NO2 and alkoxy radicals. The products of
OH radical–initiated degradation of nitrates are not
so well characterized, in particular, with regard to the
Organic nitrates are the intermediates of the atmo-
spheric oxidation of volatile organic compounds in the
presence of nitrogen oxides. They are formed in the
minor channel (1b) of the reaction of peroxy radicals
with NO:
RO2 + NO → RO + NO2
RONO2
(1a)
(1b)
→
release of NO . The understanding of the complex
2
multistep mechanism of the atmospheric oxidation of
nitrates requires first of all the information on kinet-
ics and primary products of their initial reaction with
OH.
Correspondence to: Yuri Bedjanian; e-mail: yuri.bedjanian@
cnrs-orleans.fr.
ꢀ
C
2014 Wiley Periodicals, Inc.

2
ROMANIAS, MORIN, AND BEDJANIAN
Figure 1 Diagram of the flow reactor.
In the present work, we report the results of the
eter as the detection method [11–15]. The main reactor,
shown in Fig. 1 along with the movable injector of the
reactants, consisted of a Pyrex tube (45 cm length and
2.4 cm i.d.) with a jacket for the thermostated liquid
circulation (water or ethanol). The walls of the reactor
as well as of the injector were coated with halocar-
bon wax to minimize the heterogeneous loss of active
species.
experimental investigation of the reaction of isopropyl
nitrate (IPN) with OH radicals. This reaction is of spe-
cial kinetic and mechanistic interest, since it is ex-
pected to proceed to a great extent via tertiary H-atom
abstraction [6], followed by rapid decomposition of
the 2-nitroxy-2-propyl radical formed [7], leading to
recycling of NO2 (reaction (2a)):
Two different methods were used for the generation
of OH radicals. In the first one, the fast reaction of
hydrogen atoms with NO2 was used, H atoms being
•
OH + (CH ) CHONO2 → (CH ) C ONO2 + H2O
3
2
3 2
ꢀ
(CH ) CO + NO2
produced in a microwave discharge of a H /He mixture:
3
2
2
(2a)
H + NO2 → OH + NO
(3)
•
OH + (CH ) CHONO2 → (CH )(C H2)CHONO
3
2
3
2
(2b)
NO was always used in excess over H atoms. In
2
the second method, OH radicals were produced in the
reaction of F atoms with an excess of H2O, with F
atoms formed in the microwave discharge of F2/He
mixtures
Previously, the reaction rate constant was measured
in two relative rate kinetic studies, at room temper-
ature and 760 Torr total pressure [8,9], and with an
absolute rate method in the temperature range 233–
F + H2O → OH + HF
(4)
3
95 K [3]. There is roughly a factor of two spread in
the values of the rate coefficient reported in the three
studies at room temperature. The existing uncertainty
on the rate constant is also reflected by a difference
of factor 1.4 in the recommendations of Jet Propul-
sion Laboratory (JPL) [10] and International Union of
Pure and Applied Chemistry (IUPAC) [2] evaluations.
In the present paper, we report complementary results
on reaction (2), including temperature dependence of
k2, and the branching ratio for the acetone-forming
channel (2a) as a function of temperature.
To reduce F atom reactions with a glass surface in-
side the microwave cavity, a ceramic (Al2O3) tube was
inserted in this part of the injector. OH radicals were de-
+
tected as HOBr (m/z = 96/98) after scavenging by an
13
−3
,
excess of Br2 ([Br2] = (5–10) × 10 molecule cm
added at the end of the reactor, 5 cm upstream of the
sampling cone) via the reaction:
OH + Br2 → HOBr + Br
(5)
EXPERIMENTAL
This method for OH detection was preferred to the
+
Experiments were carried out in a discharge flow reac-
tor using a modulated molecular beam mass spectrom-
direct detection of these radicals at m/z = 17 (OH ) due
to significant contributions of water vapor (traces or
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

EXPERIMENTAL STUDY OF THE REACTION OF ISOPROPYL NITRATE WITH OH RADICALS
3
precursor of OH) at this mass. Similarly, the chemical
conversion of OH to HOBr was used for the measure-
ments of the absolute concentrations of the radicals:
[
OH] = [HOBr] = ꢀ[Br2], i.e., concentrations of OH
were determined from the consumed fraction of [Br2].
Br2] was determined from the measured flow rate of
[
known Br2/He mixtures. The possible influence of sec-
ondary chemistry on this method of HOBr detection
and their absolute calibration procedure was discussed
in detail in previous papers from this group [11,12].
IPN was introduced into the flow reactor by passing
helium through a thermostated glass bubbler contain-
ing liquid IPN and was detected by mass spectrometry
+
at its fragment peak at m/z = 90 (CH3CHONO2 ),
which was much more intensive than the parent one
(
m/z = 105). All other species were detected at their
+
+
parent peaks: m/z = 58 (acetone, C3H6O ), 160 (Br2 ),
+ + + +
9
6/98 (HOBr ), 46 (NO2 ), 30 (NO ), and 18 (H2O ).
The absolute concentrations of IPN as well as of other
stable species in the reactor were calculated from their
flow rates obtained from the measurements of the pres-
sure drop of mixtures of the species with helium in
calibrated volume flasks.
Figure 2 Examples of the exponential decay kinetics of
NO OH 2 i. n reaction (2): T = 293 K; OH source, reaction H +
The purities of the gases used were as fol-
lows: He >99.9995% (Alphagaz, France) was passed
through liquid nitrogen traps; H2 >99.998% (Al-
phagaz, France); Br2 >99.99% (Aldrich, France);
F2, 5% in helium (Alphagaz, France); NO2 >99%
(
Alphagaz, France). IPN >99.0% (Sigma-Aldrich,
France) was degassed before use; and acetone > 99.8
Sigma-Aldrich, France).
(
RESULTS AND DISCUSSION
Rate Constant of Reaction (2)
Absolute Measurements. The measurements of the rate
constant of reaction (2) were carried out under pseudo–
first-order conditions in high excess of IPN over OH
radicals. The initial concentration of OH radicals was
1
2
−3
(
0.3–0.8) × 10 molecule cm , and the initial con-
Figure 3 Example of pseudo–first-order plots obtained
f3 r 5o 5m Kt )h .e OH decay kinetics in excess of IPN (T = 300 and
centration of IPN was varied in the range (0.2–22.4)
14
−3
×
10 molecule cm . The flow velocity in the re-
−1
actor was (900–1400) cm s . The concentrations of
OH radical and IPN were simultaneously measured as
a function of reaction time. A consumption of IPN was
negligible as a result of the sufficient excess of IPN
over OH radicals. Examples of the exponential decay
kinetics of OH in reaction (2) are shown in Fig. 2.
Figure 3 shows the pseudo–first-order rate constant,
ꢁ
arate experiments. All the measured values of k2 were
corrected for axial and radial diffusion [16] of OH. The
diffusion coefficient of OH in He was calculated using
1
.85
the following expression: D0 = 640 × (T/298)
Torr
2
−1
cm s [17–19]. Corrections were generally less than
10%; however, for a few kinetic runs, they reached up
to 25%. The slopes of the straight lines in Fig. 3 give the
values of k2 at respective temperatures. The intercepts
ꢁ
k2 = k2[IPN] + kw, as a function of the concentra-
tion of IPN. kw represents the rate of OH decay in the
absence of IPN in the reactor and was measured in sep-
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

4
ROMANIAS, MORIN, AND BEDJANIAN
Table I Summary of the Measurements of the Rate
Constant of the Reaction OH + IPN
Considering the derived expression,
−13
3
−1 −1 a
Methodb
T (K) k2 (10
cm molecule
s
)
[
OH]0
k2 [IPN]
k [Br ]
−
[HOBr]
1 =
(I)
2
2
2
2
3
3
3
3
3
3
3
68
73
77
93
00
13
20
30
40
47
55
3.02
2.68
2.75
3.02
2.90
3.06
3.06
3.33
3.21
3.74
3.29
AM/H+NO2
AM/F + H2O
RM
AM/H+NO2
AM/F + H2O
RM
AM/F + H2O
AM/H+NO2
AM/F + H2O
RM
5
2
k2/k5, and hence k2, could be obtained by plotting
[OH]0/[HOBr] – 1) as a function of the [IPN]/[Br2]
(
ratio. It can be noted that this method did not need
absolute calibration of the mass-spectrometric signals
for OH radicals and HOBr because the initial concen-
tration of OH could be expressed as a HOBr signal in
the absence of IPN, when OH is titrated with an excess
of Br2. Thus, in the experiments, only the HOBr signal
was detected, first in the IPN-free system, correspond-
ing to [OH] , and then in the Br and IPN-containing
AM/F + H2O
a
Typical uncertainty on k
2
is nearly 15%.
b
AM/H+NO
with H + NO and F + H
RM is the relative rate method with OH + Br
2
and AM/F+H
O reactions as OH source, respectively;
as a reference reaction.
2
O: absolute rate measurements
0
2
2
2
system, corresponding to the fraction of [OH]0 reacted
with Br2. The initial concentration of OH radicals in
2
12
−3
.
these experiments was nearly 2 × 10 molecule cm
The concentration ranges of IPN and Br2 used in these
experiments are presented in Table II. The reaction
time was typically ࣈ 20 ms.
are in good agreement with the corresponding OH loss
rate measured in the absence of IPN in the reactor.
All the results obtained for k2 within the described
approach and at different temperatures are presented
in Table I. At negative temperatures in the reactor,
we have observed an abnormal increase in the reac-
tion rate constant, which was attributed to the het-
erogeneous reaction of OH with surface-adsorbed ni-
trate. For this reason, the measurements of the rate
constant were limited to relatively high temperatures
Figure 4 shows experimental data observed at T =
2
77 and 347 K. According to expression (I), the slopes
of the linear dependences in Fig. 4 give the k2/k5 ratios.
All the results obtained in this way for k2/k5 as well
as the final results obtained for k2 are presented in
Table II. The values of k5 used in the calculations of k2
were determined from the Arrhenius expression k5 =
−
11
3
−1 −1
1
.9 × 10
exp(235/T) cm molecule s . This last
(Table I).
expression is based on two previous studies of reaction
5) [12,20], where similar values were measured for
The possible impact on the measurements of k2 of
(
the secondary reactions of OH radicals with primary
products of reaction (2) was explored in a separate se-
ries of experiments at T = 300 K, where the rate of reac-
tion (2) was measured for a fixed concentration of IPN
the activation factor, E/R = 235 [12] and 238 K [20],
and the difference between the reported preexponential
factors was around 10%.
Temperature Dependence of k2. All the results ob-
tained for k2 in the present study are shown in Table I
and Fig. 5 (open symbols). The combined uncertainty
on the measurements of the rate constants was esti-
mated to be in the range of 15–20%, including sta-
tistical error (within a few percent) and those on the
measurements of the flows (5%), pressure (3%), tem-
perature (1%), and the absolute concentrations of the
relevant species (ࣘ10%). The unweighted exponen-
tial fit to the present data for k2 yields the following
Arrhenius expression:
14
−3
(
5.5 × 10 molecule cm ) with four different [OH]0
12
−3
.
varying in the range (0.3–2.5) × 10 molecule cm
ꢁ
−1
The measured reaction rate k2 = (180 ± 17) s was
found to be independent (within 10%) of the initial
concentration of OH, indicating the negligible contri-
bution of the secondary chemistry to the OH loss.
Relative Rate Measurements. The rate constant of
reactions (2) was measured using reference reaction of
OH with Br2. The experiments consisted of a fast titra-
tion of the initial concentration of OH radicals, [OH]0,
by a mixture of excess IPN and Br2 and the measure-
ments of HOBr yield as a function of the [IPN]/[Br2]
ratio. The concentration of HOBr formed was defined
by the fraction of [OH]0 reacting with Br2:
k2 = (6.6 ± 1.2) × 10−
13
3
−1 −1
s
×
exp(−(233 ± 56)/T) cm molecule
k5 [Br2]
[
HOBr] =
× [OH]0
k5 [Br2] + k2 [IPN]
where the cited uncertainties are 1σ statistical ones.
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

EXPERIMENTAL STUDY OF THE REACTION OF ISOPROPYL NITRATE WITH OH RADICALS
5
Table II Experimental Conditions and Results of the Relative Measurements of k2 Using OH + Br2 (k5) as the
Reference Reaction
Number of Data
[IPN]
[Br2]
k2
Points/Experiments T (K) (1014 molecule cm ) (1012 molecule cm ) [IPN]/[Br2] k2/k5 (10
−3
−3
−13
cm molecule s )
3
−1 −1 a
7
7
8
277
313
347
3.9–4.6
3.8–5.3
4.6–4.8
0.6–9.4
0.5–42.0
1.1–22.0
45–761 0.0062
9–1045 0.0076
21–407 0.0100
2.75
3.06
3.74
a
Estimated uncertainty on k
2
is nearly 20%.
ꢁ
−1
ꢁ
−1
ting parameter; k2 = 55 s and kw = 19 s (for the
data in Fig. 6) were determined from the exponential
fit of the OH decays in a reaction with IPN (Fig. 6,
open symbols) and on the wall of the reactor (not
shown), respectively. The value of α obtained from
the best fit to the acetone profile in Fig. 6 is 0.76. The
branching ratio for an acetone-forming reaction path-
way (2a) was measured at different temperatures in the
reactor. Experiments consisted of the monitoring of the
OH consumption and acetone formation in the reaction
of OH with IPN. Initial concentrations of the reactants
1
1
12
were largely varied: [OH] = 2.8 × 10 to 2.5 × 10
13
14
−3
.
and [IPN] = 2.0×10 to 3.7×10 molecule cm
The typical reaction time was ࣈ20 ms. The formation
of acetone at m/z = 58 was monitored by switching on
and off the OH source (microwave discharge). It can be
noted that the background signal at m/z = 58 (from IPN
fragmentation) was not changed upon switch on and
off of the microwave discharge, since no consumption
of IPN was observed in these experiments. The frac-
tion of [OH] consumed in a reaction with IPN (and
not on the wall of the reactor) was determined from
the reduction of the OH concentration upon addition
of IPN in the reactor. An example of the experimental
data observed at T = 300 K is shown in Fig. 7. One can
note good agreement between the results obtained with
different methods of the generation of the OH radical,
indicating that the possible reactions of the radical pre-
Figure 4 HOBr yield from OH titration with Br2 + IPN
mixtures at different temperatures (see Eq. (I) in the text).
Reaction Products
The formation of the reaction product was clearly ob-
served at m/z = 58 (and attributed to acetone) despite
the relatively high background signal at this mass due
to fragmentation of the IPN in the ion source of the
mass spectrometer. An example of the kinetics of the
product formation along with the kinetics of OH decay
is shown in Fig. 6. Solid lines in Fig. 6 represent the
results of simulation of the experimental data. A tem-
poral profile of acetone was fitted with the following
equation:
•
cursors, NO2 and H2O, with (CH3)2C ONO2 formed
in the first step of the reaction (2a) are not competitive
with its decomposition. The slope of the straight line
in Fig. 7 provides the branching ratio for the acetone-
forming channel of reaction (1): 0.77 at T = 300 K.
All the results obtained in this way for k2a/k2 at differ-
ent temperatures are presented in Table III. The k2a/k2
ratio can be considered as independent of temperature
between 277 and 355 K, and a mean value
ꢁ
ꢁ
ꢁ
[
acetone] = α×(k2 − kw )/k
2
ꢁ
×
[OH] ×(1 − exp(−k2 t),
0
k2a/k2 = 0.82 ± 0.13
ꢁ
ꢁ
where α is the acetone yield in reaction (2), k2 and kw
are the first-order rate constants of OH consumption in
the presence and in the absence (heterogeneous loss)
of IPN in the reactor, respectively. α was the only fit-
can be recommended from this study. The esti-
mated nearly 15% uncertainty on the measurements of
k2a/k2 arises mainly from the combined errors on the
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

6
ROMANIAS, MORIN, AND BEDJANIAN
Figure 5 Summary of the measurements of the rate constant of the reaction OH + IPN. For the data from this study: AM,
absolute measurements; RM, relative rate method.
Figure 6 Example of kinetics of OH consumption and ace-
tone formation in a reaction of OH radicals with IPN: T =
Figure 7 Concentration of acetone formed in reaction (2) as
a function of the consumed concentration of OH: T = 300 K.
Source of OH radicals: ◦, reaction H + NO2; ꢀ, reaction F
+ H2O.
14
−3
3
00 K; [IPN] = 1.3 × 10 molecule cm ; OH source,
reaction F + H2O.
measurements of the absolute concentrations of OH
impossible, because of the very strong contribution of
the IPN fragment on this mass. We have tried to mon-
(ࣘ10%) and acetone (a few percent).
+
An attempt was undertaken to detect the coprod-
itor the fragment peak of NO2 on m/z = 30 (NO ),
uct of acetone, NO2. Direct detection of NO2 by mass
where the contribution of IPN was much lower. In-
+
spectrometry on its parent peak m/z = 46 (NO2 ) was
deed, an increase in the signal at m/z = 30 was clearly
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

EXPERIMENTAL STUDY OF THE REACTION OF ISOPROPYL NITRATE WITH OH RADICALS
7
Table III Acetone Yield in the Reaction of OH with IPN
as a Function of Temperature
straction of an H atom from the alkyl group. Product
data from the present study also point in favor of this
mechanism.
Number of Experimental Runs T (K)
k2a/k2a
In a previous study of Aschmann et al [21], the
products of the OH-initiated degradation of IPN were
investigated in a smog chamber, at room temperature
and 740 Torr total pressure of air, and in the presence
of NO in the reactive system. Acetone was the only
reported quantified product with a yield of 58 ± 18%.
This value is in a satisfactory agreement with that from
the present study, 82 ± 13%, considering the reported
uncertainties. In a theoretical study of Vereecken [7],
α-nitroxy-substituted alkyl radicals were shown to be
unstable, dissociating spontaneously without an ener-
getic barrier to form a carbonyl compound and NO2.
In this respect, the measured acetone yield is in good
agreement with the value of 78% which can be pre-
dicted using the estimation method [6] for the extent
of H-atom abstraction from the tertiary C–H bond fol-
6
6
1
5
5
5
277
288
300
320
340
355
0.82
0.87
0.77
0.78
0.79
4
0.89
mean: 0.82 ± 0.05
a
Number of experimental runs.
2
Typical uncertainty on k2a/k is nearly 15%.
observed upon a reaction of OH with IPN. If this signal
is entirely attributed to the production of NO2, then the
calculated yield of NO2 is 1.7 ± 0.3, independent of
temperature in the temperature range 277–355 K. This
abnormal yield of NO2 indicates that, besides NO2,
other species—products of reaction (2)—contribute to
the signal at m/z = 30, preventing correct measurement
of the NO2 yield.
•
lowed by 2-nitroxy-2-propyl radical, (CH3)2C ONO2,
decomposition [7] to acetone and NO2. It should be
noted that the study of Aschmann et al [21] was car-
ried out at 1 atm total pressure of air, whereas the
data from the present work were obtained at nearly
1
Torr pressure of helium. The good agreement be-
Comparison with Previous Data
tween the results from the two studies indicates that
the rate of the prompt (CH3)2C ONO2 radical decom-
•
Previously, the rate constant of reaction (2) was mea-
sured in two relative rate kinetic studies, at room tem-
perature and 760 Torr total pressure, k2 = (5.3 ± 2.1) ×
position under atmospheric conditions is much higher
than the rate of its possible stabilization and/or a re-
action with O2 in agreement with the conclusion of
Vereecken [7] that the radical decomposition occurs on
timescales that are too short for any chemical process to
compete.
−
1
13
−13
3
−1
1
s
0
[8] and (3.83 ± 0.49) × 10
cm molecule
−
[9], and with an absolute rate method in the tem-
−
12
perature range 233–395 K: k2 = 4.3 × 10
exp(–
−
13
1
250/T) + 2.5 × 10
exp(–32/T) [3]. All these re-
sults are shown in Fig. 5 together with the data from
the present study. Also shown are the current recom-
−
12
mendations from the JPL [10], k2 = 1.2 × 10
exp(–
CONCLUSIONS
−13
3
3
20/T) and IUPAC [2], 6.2 × 10
exp(–230/T) cm
−1
s over the temperature range 230–300 K,
−1
molecule
In this work, we investigated the kinetics and products
of the reaction of OH radicals with IPN in the tempera-
ture range between 277 and 355 K. The temperature de-
pendence of the reaction rate constant, measured using
both absolute and relative rate methods, is in excellent
agreement with the data from the sole previous study.
Acetone was directly detected as a primary product of
the OH reaction with IPN for a first time. The measured
relatively high yield of acetone, 0.82 ± 0.13, indicates
that the main channel of the IPN reaction with OH
leads to NO2 (a coproduct of acetone) recycling from
the nitrate. In addition, the measured acetone yield
is in good quantitative agreement with the theoretical
predictions for the extent of H-atom abstraction from
the tertiary C–H bond followed by 2-nitroxy-2-propyl
evaluations, the first one being based on the mean of
the room temperature values from the three previous
studies and temperature dependence from Talukdar et
al [3] and the second one, essentially, on the data
of Talukdar et al [3]. The values of k2 measured in
the present study are in excellent agreement with the
data of Talukdar et al [3] and support the current rec-
ommendation of IUPAC [2]. It should be noted that
the experiments of Talukdar et al [3] were carried out
at total pressure of 50–300 Torr with different buffer
gases (He, O2, SF6), whereas the data from the present
study were obtained at nearly 1 Torr pressure of he-
lium. The good agreement between the results of two
studies supports the conclusion of Talukdar et al [3]
that addition of OH to the alkyl nitrate is unlikely;
the reaction is a bimolecular one and proceeds via ab-
•
radical, (CH3)2C ONO2, decomposition to acetone and
NO2.
International Journal of Chemical Kinetics DOI 10.1002/kin.20891

8
ROMANIAS, MORIN, AND BEDJANIAN
This study was supported by French National Research
Agency (ANR) from an ONCEM grant. J. M. is very grate-
ful for his Ph.D. grant from CAPRYSSES project (ANR-
10. Sander, S. P.; Abbatt, J.; Barker, J. R.; Burkholder, J.
B.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C.
E.; Kurylo, M. J.; Moortgat, G. K.; Orkin, V. L.; Wine,
P. H. Chemical Kinetics and Photochemical Data for
Use in Atmospheric Studies, Evaluation No. 17; JPL
Publication 10-6; Jet Propulsion Laboratory: Pasadena,
CA, 2011. Available at http://jpldataeval.jpl.nasa.gov.
Accessed September 1, 2014.
1
1-LABX-006–01) funded by ANR through the PIA (Pro-
gramme d’Investissement d’Avenir).
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International Journal of Chemical Kinetics DOI 10.1002/kin.20891