Kinetics and Mechanism of

the Reaction of Propylene

Oxide with Chlorine Atoms
and Hydroxy Radicals
SRIKAR MIDDALA, SEAN CAMPBELL, CATALINA OLEA, AUSTEN SCRUGGS, ALAM S. HASSON
Department of Chemistry, California State University, Fresno, Fresno, CA 93740
Received 20 April 2011; revised 2 June 2011; accepted 9 June 2011
DOI 10.1002/kin.20580
Published online 21 July 2011 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: The kinetics and mechanism of gas-phase propylene oxide (PPO) reactions were
studied in a 142-L reaction chamber by long-path Fourier transform infrared spectroscopy
at atmospheric pressure and 298 K. Rate coefficients for the reaction of PPO with ozone
(O3 ), chlorine atoms (Cl), and hydroxyl radicals (OH) were measured using the relative rate
technique. Product yields of acetic acid, acetic formic anhydride, formic acid, and carbon
monoxide were determined for the following reactions: PPO with Cl both in the presence and
absence of NO, PPO with OH and NO, methyl acetate with Cl both in the presence and absence
of NO, and ethyl formate with Cl both in the presence and absence of NO. The measured rate
coefficients for PPO with O3 , Cl, and OH are <3.5 1021 cm3 molecule1 s1 , (3.0 0.7)
1011 cm3 molecule1 s1 , and (3.0 1.0) 1013 cm3 molecule1 s1 , respectively. The
carbon balance for the products measured ranged from 10% (for OH + PPO) to 100% (for Cl +
methyl acetate in the absence of NO). The mechanistic and atmospheric implications of these
measurements are discussed.  C 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 507521, 2011

INTRODUCTION proposed as a candidate for use in some postharvest fu-

Methyl bromide has been used for many years as a po-
tent pesticide with a wide variety of applications. How-
ever, owing to its impact on the stratospheric ozone
layer [1], its use has been phased out for most appli-
cations. The agricultural industry has, therefore, been
searching for effective methyl bromide alternatives.
Propylene oxide (PPO) is a pesticide that has been
Correspondence to: Alam S. Hasson; e-mail: ahasson@
csufresno.edu.
Contract grant sponsor: National Oceanic and Atmospheric
Administration.
Contract grant number: NA06OAR4810187.
c 2011 Wiley Periodicals, Inc.
migation processes [2]. Widespread use of PPO would
lead to a significant release of this chemical into the
atmosphere. However, little is known about its atmo-
spheric chemistry.
The potential removal processes for PPO from the
atmosphere are washout/rainout, photolysis, and chem-
ical reaction. The predominant daytime chemical sinks
for organics in the atmosphere are reaction with the
hydroxyl radical (OH), ozone (O3 ), and under certain
conditions, reaction with Cl atoms. The Henrys law
constant for PPO is 14 M atm1 at 275 K [3], and so
the lifetime with respect to wet deposition is expected
to be of the order of several years. There are two mea-
surements of the rate coefficient for OH + PPO in
the literature. Wallington et al. [4] determined the rate
508 MIDDALA ET AL.

coefficient to be 4.95 1013 cm3 molecule1 s1

using a flash photolysis system with fluorescence de-
tection. In contrast, Edney et al. [5] reported a rate co-
efficient more than two times faster (1.11 1012 cm3
molecule1 s1 ) using the relative rate technique, with
n-butane as the reference compound. Given that the
typical OH radical concentration in the troposphere is
of the order of 106 molecules cm3 , the lower of the
two reported rate coefficient is consistent with a life-
time of PPO of about 3 weeks.
Estimates of the average global Cl atom con-
centration are typically in the range 103 104
molecules cm3 , for example [68], with concentra-
tions in the marine boundary layer potentially as high as
106 molecules cm3 [9]. Since organics typically react
faster with Cl atoms compared to OH radicals, the re-
action with Cl atoms is potentially a significant sink for
PPO. We are unaware of any previous measurements of
the rate coefficient for the reaction of PPO with either
Cl atoms or ozone. The reaction of PPO with ozone,
O .O 2 O
O
(+ O2) O
(R3)
The peroxy radical formed in reaction (R3) can react
further to form the major products observed.
The reaction of PPO with both Cl atoms and OH
radicals is expected to follow a similar mechanism
to that of ethylene oxide. A hydrogen atom may be
abstracted from any of the three carbon atoms in the
molecule, leading to the formation of three different
organic peroxy radicals.
O O
.O
+ Cl/OH (+ O2) 2

however, is expected to be unimportant in the atmo-

(R4a)
sphere because the reaction with ozone is typically
slow for compounds that do not contain double bonds.
O
There are no prior measurements of product yields .O
for the reaction of Cl or OH with PPO under at- 2
mospherically relevant conditions. However, a study
of the mechanism for the reaction of ethylene ox- (R4b)
ide with Cl atoms in air using Fourier transform in-
O
frared (FTIR) spectroscopy has been reported [10].
The reaction products measured were formic anhy-
O2
.
dride, hydroxymethyl formate, formaldehyde, formic
acid, carbon monoxide, and carbon dioxide. The prod-
ucts observed are consistent with H-atom abstraction, (R4c)
followed by oxygen addition to form a peroxy radi-
cal (reaction (R1)). Subsequent reaction of the peroxy
radicals results in the formation of an alkoxy radical The peroxy radicals formed in reaction (R4) may react
(reaction (R2)), that preferentially ring opens via C C with NO, when present, to form alkoxy radicals
bond scission (reaction (R3)).
O O
.O O
2
+ NO + NO2
(R5a)
O
O
O . .O O

+ Cl (+ O2) O2 + HCl
2
+ NO O + NO2

(R1) (R5b)
O O
O
O
. O
O .
O2
2 2
2 + O2 + NO O + NO2

(R2) (R5c)

International Journal of Chemical Kinetics DOI 10.1002/kin

 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS 509

The alkoxy radical formed in reaction (R5a) may react EXPERIMENTAL

with oxygen to form an aldehyde.
Experiments were carried out in a 142-L Teflon-lined
O photochemical reactor, described in previous work
O [11]. In brief, the evacuable chamber is interfaced to a
O
+ O2
O
+ HO2 . Nicolet Nexus 470 FTIR spectrometer and is equipped
with Hanst-type multipass optics. Internally mounted
blacklight lamps are used to initiate the photochemi-
(R6)
cal reactions. The chamber was configured such that
the path length of the infrared beam was 38 m during
Alternatively, the radical may decompose to produce the experiments. Infrared spectra were collected at a
formaldehyde and the same peroxy radical as that pro- resolution of 1 cm1 by averaging 200 scans. Concen-
duced from ethylene oxide via reaction (R1). trations of reactants and products within the chamber
were determined by subtraction of reference spectra,
O which were generated by evaporating calibrated vol-
O
O .
O2
umes of pure liquid standards into the chamber.
(+ O2) CH2O +
(R7)
Kinetics Measurements
By analogy to the chemistry of ethylene oxide, the Rate coefficients for the reaction of PPO with chlorine
alkoxy radicals formed in reactions (R5b) and (R5c) atoms and hydroxyl radicals were determined using the
are expected to ring open via C C bond cleavage, relative rate technique. Mixtures of the radical precur-
resulting in the formation of peroxy radicals sor, (25) 1014 molecules cm3 of PPO (Matheson;
99%) and (25) 1014 molecules cm3 of a refer-
O ence compound were photolyzed in these experiments,
and decreases in the concentrations of PPO and the
O .O O
reference compound were monitored by FTIR. Exper-
O (+ O2) 2 iments measuring the Cl + PPO rate coefficient used
(49) 1014 molecules cm3 chlorine gas (Matheson;
(R8) 99.5%) to generate the radicals and were performed
in both synthetic air mixtures of nitrogen and oxygen

O2
. (Praxair; UHP grade) and in nitrogen. Methanol and
O
O (+ O2) O O
(R9)
which then undergo further reactions to form products
including acetic formic anhydride (AFAN), acetic acid,
and formic acid, as discussed below. Thus, the chemical
fate of PPO depends on the site of H-atom abstraction
in reaction (R4).
In this work, the rate coefficients for the reaction
between PPO and Cl atoms, OH radicals, and ozone
were measured using the relative rate technique. This
study also provides some information on the potential
for PPO to degrade photolytically in the troposphere.
Product yields for the reaction of PPO with Cl atoms
and with OH radicals were also investigated. Collec-
tively, these measurements provide information on the
chemical fate of PPO in the atmosphere.
acetaldehyde were used as the reference compounds.
OH radicals were generated by photolyzing mixtures
of commercially available isobutyl nitrite or butyl ni-
trite (Aldrich; 95%, (25) 1014 molecules cm3 )
and nitric oxide (Matheson; 99.5%, (0.52) 1014
molecules cm3 ) in air (reactions (R10)(R12); R =
(CH3 )2 CH for isobutyl nitrite and CH3 (CH2 )2 for
butyl nitrite).
RCH2 ONO + hv RCH2 O + NO (R10)
RCH2 O + O2 RCHO + HO2 (R11)
HO2 + NO OH + NO2 (R12)
Acetone (SigmaAldrich; 99.5%) and methanol
(SigmaAldrich; 99.8%) were used as the reference
compounds in these experiments. The rate coefficients
for the reaction of PPO were then determined from
linear least-squares fits to the relative rate expression

International Journal of Chemical Kinetics DOI 10.1002/kin

510 MIDDALA ET AL.
   
[PPO]0 kPPO [Reference]0
ln = ln
[PPO]t kReference [Reference]t
where [X]0 and [X]t are the concentrations of X at the
beginning of the reaction and at time t, respectively.
Reported uncertainties in the relative rate coefficients
are 95% confidence limits for the slopes of these plots.
The kinetics of the reaction between ozone and PPO
was investigated by mixing the reagents within the
chamber in the presence of 1 atm of air. Ozone was
generated as a mixture in oxygen by flowing pure oxy-
gen over a mercury lamp (Jelight). The concentration
of ozone produced by the ozone generator was deter-
mined by measuring the consumption of ethene (Math-
eson; 99.995%) in the chamber following the addition
of calibrated volumes of the ozone/oxygen mixture.
It is well established that the reaction of ethene with
ozone generates a significant fraction of OH radicals
[1216] that may subsequently react with ethene, and
so the amount of ethene consumed is greater than the
amount of ozone added. Here, the ozone concentration
was calculated using an OH radical yield for the ozone
+ ethene reaction of 18% [14].
Product Yield Measurements
The mechanism for the reaction between PPO and Cl
atoms was investigated by measuring yields of reac-
tion products from the photolysis of PPO/chlorine/air
mixtures, defined as [Product]/[Reactant]. Exper-
iments were carried out in both the presence and ab-
sence of nitric oxide. The reaction of PPO with OH
radicals was investigated by measuring product yields
from the photolysis of mixtures of PPO/isobutyl ni-
trite/NO/air. Additional insight into the reaction mech-
anisms was gained by examining the products formed
from the photolysis of methyl acetate (SigmaAldrich;
99%)/chlorine/air and ethyl formate (SigmaAldrich;
97%)/chlorine/air mixtures. In all experiments, the re-
action products monitored were AFAN, acetic acid,
formic acid, and carbon monoxide. Uncertainties in
the measured product yields are reported as one stan-
dard deviation of the slopes of linear least-square fits
to the product yield plots.
RESULTS AND DISCUSSION
Kinetics Measurements
In preliminary experiments, (25) 1014 molecules
cm3 PPO was introduced into the chamber in 760
Torr air. Over the course of 2 h, which is longer than
the typical experimental run time, the concentration of
PPO decreased by less than 5%. The photolysis lamps
(1) were then illuminated for an additional 30 min. No ad-
ditional loss of PPO was observed during this period.
While the experiments are not designed to determine
the photolysis rate of PPO, the fact that it does not
photolyze on the timescale of these experiments in-
dicates that the atmospheric lifetime with respect to
photolysis will be long compared to reaction with OH.
Acetaldehyde and acetone are known to be photochem-
ically labile, and photolysis of these reference com-
pounds may potentially bias the kinetic measurements.
However, previous measurements (unpublished work)
indicate that these species do not degrade photolyti-
cally within the chamber on the timescales of these
experiments.
PPO + Ozone
Mixtures of ozone in oxygen were added to PPO in
air and were allowed to mix for 110 min. Within this
time period, no detectable decrease in the PPO concen-
tration was observed. Given that a >5% loss of PPO
can be measured and that the concentration of ozone
in the experiment was 2 1015 molecules cm3 , the
upper limit for the reaction rate coefficient is 3.5
1021 cm3 molecule1 s1 . There are no previous mea-
surements of this rate coefficient for comparison, but
given that the molecule is saturated, the reaction of
PPO with ozone is expected to be slow.
PPO + Cl
Relative rate plots for PPO/chlorine/reference com-
pound mixtures in both nitrogen and in air are shown
in Fig. 1 using acetaldehyde and methanol as the ref-
erence compounds. A potential problem with the tech-
nique used is that an IR absorption band for a reaction
product may overlap with that of a reactant, leading to
systematic errors in the rate coefficient measured. The
reaction products formed in the presence and absence
of oxygen typically have different spectral features, and
so a comparison of the slopes of relative rate plots from
experiments in air and in nitrogen provide a check on
potential interferences between reactant and product
IR bands. For both reference compounds, the relative
rates of reaction with and without oxygen present are
indistinguishable within the mutual uncertainties of the
data, indicating that systematic errors arising from such
interferences are unlikely in these experiments.
Since the slopes of individual relative rate exper-
iments in the presence and absence of oxygen were
identical for a given reference compound within the
International Journal of Chemical Kinetics DOI 10.1002/kin
 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS
0.6
ln([PPO]0/[PPO]t )
0.4
ln([PPO]0/[PPO]t)
0.2
0.0
0.0 0.5 1.0
ln([Acetaldehyde]0/[Acetaldehyde]t)
Figure 1 Relative rate plots for the reaction of chlorine atoms with reference compounds (acetaldehyde and methanol) and
PPO in the presence (filled symbols) and absence (open symbols) of oxygen at 298 K and 1 atm.
mutual uncertainties, a least-squares linear fit to the
entire data set was carried out, as shown in Fig. 1.
kPPO kMethanol is 0.45 0.02 with O2 present and
0.50 0.03 in the absence of O2 , and kPPO kAcetaldehyde
is 0.37 0.02 with O2 present and 0.38 0.03
 absence of O2 . The relative rate of reaction
in the
kPPO kReference for the entire data set is 0.49 0.02
and 0.38 0.02 for methanol and acetaldehyde as the
reference compounds, respectively. Literature values
for the rate coefficients of the reference compounds are
(5.5 1) 1011 cm3 molecule1 s1 for kMethanol and
(8.0 1.2) 1011 cm3 molecule1 s1 for kAcetaldehyde
[17]. Combining these with the slopes of the relative
rate plots shown in Fig. 1 leads to rate coefficients for
PPO + Cl of (2.8 0.5) 1011 cm3 molecule1 s1
and (3.2 0.5) 1011 cm3 molecule1 s1 us-
ing methanol and acetaldehyde as the reference com-
pounds, respectively. Since the two values lie within
the mutual uncertainties of the measurements, the
rate coefficient is reported as (3.0 0.7) 1011
cm3 molecule1 s1 , the average of the two values.
There are no previous measurements of this rate
coefficient for comparison. However, there are two lit-
erature values for the reaction of ethylene oxide with
Cl atoms. Bartels and coworkers [18] measured the rate
coefficient using the relative rate technique with ethane
as the reference compound, reporting a value of 2.82
International Journal of Chemical Kinetics DOI 10.1002/kin
511
0.6
0.4
0.2
0.0
1.5 0.0 0.5 1.0 1.5
ln([Methanol]0/[Methanol]t)
1011 cm3 molecule s1 . In contrast, Ponomarev et al.
[19] determined the rate coefficient to be 5.0 1012
cm3 molecule s1 using ethyl chloride and methyl for-
mate as the reference. While the origin of this large
difference is unclear, Ponomarev et al. have suggested
that heterogeneous reaction between ethylene oxide
and Cl2 may have been significant in the Bartels et
al. experiments, and that this may have resulted in an
anomalously high rate coefficient in their study. The
reaction rate coefficient with chlorine atoms typically
increases along a homologous series of organics, with
a substantial increase between the C2 and C3 species.
The measurements reported here for PPO are, there-
fore, more consistent with the results of Ponomarev et
al. rather than with those of Bartels et al.
PPO + OH
Relative rate plots for the reaction of OH with PPO and
the reference compounds are shown in Fig. 2. Since the
OH generation scheme requires oxygen to be present,
these experiments were all carried out in air. Linear
least-squares
 fits to the data lead to relative rates for
kPPO kReference of 1.34 0.06 and 0.43 0.06 for
acetone and methanol as the reference compounds, re-
spectively. Combining these slopes with the literature
512 MIDDALA ET AL.
0.16
0.12
ln([PPO]0/[PPO]t )
0.08
0.04
0.00
0.00 0.04
ln([Acetone]0/[Acetone]t )
Figure 2 Relative rate plots for the reaction of OH radicals with reference compounds (acetone and methanol) and PPO in air
at 298 K and 1 atm.
values for the rate coefficients for acetone and methanol
[17] [(1.8 0.3) 1013 cm3 molecule1 s1 and
(9.0 2.0) 1013 cm3 molecule1 s1 ] gives values
for kPPO of (2.4 0.4) 1013 cm3 molecule1 s1
and (3.6 0.9) 1013 cm3 molecule1 s1 , respec-
tively. The average of these two values is reported here,
i.e., (3.0 1.0) 1013 cm3 molecule1 s1 .
As discussed above, there are two literature val-
ues for this rate coefficient, which are in poor agree-
ment with each other. The rate coefficient measured
here is more consistent with the lower value reported
by Wallington and coworkers [4], which was deter-
mined in flash photolysisresonance fluorescence ex-
periments. The faster rate coefficient reported by Edney
et al. [5] was measured using the relative rate technique,
with butane as the reference compound. While butane
was not available to us in this study, several experi-
ments were conducted using pentane as the reference
compound. The rate coefficient obtained in these exper-
iments was systematically higher than that measured
using acetone and methanol. Since the rate coefficient
for OH with pentane is much faster than the corre-
sponding reaction between OH and the other reference
compounds used, the fraction of PPO consumed in the
pentane experiments is smaller than in the other rela-
tive rate experiments. Wall losses of PPO are slow, but
on the timescale of the experiments, a few percent of
0.15
0.10
ln([PPO]0/[PPO]t )
0.05
0.00
0.08 0.12 0.0 0.1 0.2 0.3
ln([Methanol]0/[Methanol]t )
the initial PPO concentration are lost in the dark. In the
case of the pentane tracer experiments, this additional
loss process results in a systematically high measured
rate coefficient for OH + PPO. Since the rate coeffi-
cient for hydroxyl radicals with butane is also signif-
icantly higher than the corresponding rate coefficient
reported here and by Wallington and coworkers, it is
possible that wall losses may have contributed to the
larger rate coefficient reported by Edney et al.
Product Yield Measurements
Product yields were not corrected for secondary chem-
istry. Kinetic simulations using ACUCHEM indicated
that the effects of secondary reactions on the measured
product yields are relatively small (less than 20% and
usually less than 10%) under the reaction conditions
in these experiments unless stated otherwise. Further-
more, product yield plots were found to be linear within
the experimental uncertainties.
As described above, H-atom abstraction from either
of the carbon atoms in the epoxide group may result
in the formation of a peroxy ester (reactions (4b) and
(4c) followed by reactions (R8) and (R9)). These per-
oxy radicals are also formed more directly via H-atom
abstraction from methyl acetate and ethyl formate in
air. To provide more insight into the chemical behavior
International Journal of Chemical Kinetics DOI 10.1002/kin
 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS 513

Table I Summary of Product Yields Measured

Measured Yielda

Methyl Methyl Ethyl Ethyl Formate PPO + PPO +

Product Acetate + Cl Acetate + Cl + NO Formate + Cl + Cl + NO PPO + Cl Cl + NO OH + NO
Formic acid 0.44 0.10 0.76 0.15 0.20 0.02 0.19 0.01 0.04 0.01
Acetic acid 0.40 0.05 0.39 0.05 0.12 0.01 0.16 0.01 0.03 0.01
AFAN 0.72 0.20 0.24 0.03 0.13 0.02 0.05 0.02 0.22 0.01 0.08 0.01 0.01 0.01
CO 0.50 0.13 0.49 0.02 0.31 0.03 0.30 0.05 0.20 0.05
Acetaldehyde <0.02 <0.02
All experiments were performed at 298 K and in 1 atm air.
a
Reported uncertainties are one standard deviation. See the text for details.

of PPO, the reactions of both of these esters with chlo- O

rine atoms were also investigated. The product yields
measured from all of the reactions investigated in this
study are summarized in Table I. O O + R-OH
(R14b)
Cl + Methyl Acetate O
Yields of acetic acid, carbon monoxide, and AFAN
were measured from the photolysis of methyl ac- O O + RO + O2
etate/chlorine/air mixtures both in the presence and
absence of nitric oxide. Typical product yield plots are (R14c)
shown in Fig. 3. With no nitric oxide present, the yields
of acetic acid, AFAN, and CO are 0.40 0.05, 0.72 The methoxy acetate radical formed in reaction (R14c)
0.20, and 0.50 0.13, respectively. With NO also either may react with oxygen to form AFAN (reac-
present, the measured product yields are 0.39 0.05, tion (R15)) or may undergo an -ester rearrangement
0.24 0.03, and 0.49 0.02 for acetic acid, AFAN, [2023] to produce acetic acid and carbon monoxide
and CO, respectively. (reaction (R16)).
It is well established that H-atom abstraction by Cl
atoms occurs almost exclusively from the methyl group O O O
in the ester [20,21] (reaction (R13)).
O O + O2 O + HO2
O O
(R15)
.O O O
O + Cl (+ O2) 2

(R13) O O CH3C(O)OH + HCO

In the absence of NO, this peroxy radical may react (R16)
with HO2 to form a hydroperoxide, or with a peroxy
radical to generate hydroxymethyl acetate, AFAN, or HCO + O2 CO + HO2
an alkoxy radical (reactions (R14a)(R14c)). (R17)

O O The relative rates of reactions (R15) and (R16) are

.O O .
dependent on the oxygen concentration, and previous
studies [20,21,23] have shown that under atmospheric
2 + RO 2 HO O + R=O
conditions (PO2 = 140 Torr), the relative yield of acetic
(R14a) acid/AFAN is about 1:2, consistent with this work. The

International Journal of Chemical Kinetics DOI 10.1002/kin

514 MIDDALA ET AL.

a) b)

13 13
3.0 10 3.0 10
3
[Product]/molecules cm

13 13
2.0 10 2.0 10

13 13
1.0 10 1.0 10

0.0 0.0
13 13 13 13 13 13
0.0 2.0 10 4.0 10 6.0 10 0.0 2.0 10 4.0 10 6.0 10
3 3
[Methyl acetate]/molecules cm [Methyl acetate]/molecules cm

Acetic acid
AFAN
Figure 3 Typical product yield plots for the reaction of methyl acetate with Cl atoms at 298 K in 1 atm air (a) in the absence
of NO and (b) in the presence of NO.

absolute yields depend somewhat on the relative con- erature [20,21]. Absolute product yields are also likely
centrations of RO2 and HO2 radicals present, which to be affected by NO2 , which is unavoidably present in
are determined by the concentrations of the reactants these experiments, via reaction (R19).
present and the output of the photolysis source. Given
the differences in experimental design, the product O O
yields reported here are again largely consistent with
the literature. O O + NO2 O2NO O
When nitric oxide is present, the peroxy radicals will
react with NO to produce methoxy acetate radicals. (R19)

O O The nitrate product may account for a significant frac-

. and could explain why the acetic acid yield does not
O2 O + NO
Because reaction (R18) is more exothermic than re-
action (R14c), the alkoxy radicals formed from reac-
tion with NO have greater internal energy than those
formed via reaction with RO2 , which increases that rate
of the -ester rearrangement [20,21]. Thus the acetic
acid/AFAN yield is significantly increased due to both
an enhancement of acetic acid formation via reaction
(R16) and the suppression of reaction (R14b) by NO.
The relative yields measured in this work are consistent
with the 2:1 acetic acid/AFAN ratio reported in the lit-
tion of the missing carbon balance in these experiments
O O + NO2
increase significantly in our experiments when NO is
(R18) added. Nitrate formation depends on the relative rates
of reactions (R15), (R16), and (R19). The rate con-
stants for these reactions are not known, but literature
values for other alkoxy radical reactions indicate that
reaction with NO2 is of the order of 34 orders of
magnitude larger than reaction with O2 (e.g., Malanca
et al. [24] and references therein). Given that [NO2 ]
may reach 1014 molecules cm3 , and 140 Torr of oxy-
gen (4.6 1018 molecules cm3 ), it is therefore fea-
sible that nitrate formation via reaction (R19) may be
competitive with AFAN formation via reaction with
oxygen (reaction (R15)).

International Journal of Chemical Kinetics DOI 10.1002/kin

 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS 515

a) b)
14 14
1.0 10 1.0 10

13 13
7.5 10 7.5 10
3
[Product]/molecules cm

13 13
5.0 10 5.0 10

13 13
2.5 10 2.5 10

0.0 0.0
13 14 14 13 14 14
0.0 5.0 10 1.0 10 1.5 10 0.0 5.0 10 1.0 10 1.5 10
3 3
[Ethyl formate]/molecules cm [Ethyl formate]/molecules cm

Formic acid
AFAN
Figure 4 Typical product yield plots for the reaction of ethyl formate with Cl atoms at 298 K in 1 atm air (a) in the absence of
NO and (b) in the presence of NO.

The methyl acetate experiments show that under the
typical conditions employed in our reaction chamber,
methyl peroxy acetate radicals form acetic acid with a
yield of 40% both in the presence and absence of NO.
Since these peroxy radicals are also formed from PPO
via H-atom abstraction from the central carbon atom
(reaction (R4b)), this means that the acetic acid yield
can potentially be used as a marker for the branching
ratio for this reaction.
Cl + Ethyl Formate
tween Cl and ethyl formate is H-atom abstraction from
the CH2 group of the ethyl moiety (reaction (R20a)),
with a significant contribution from H-atom abstrac-
tion from the carbonyl group (reaction (R20b)). This
result is qualitatively consistent with mechanistic mea-
surements of the Cl + ethyl formate reaction reported
by Tyndall and Orlando [25].
.
O2

Typical product yield plots from the photolysis of chlo- O O + Cl (+ O2) O O + HCl
rine/ethyl formate/air mixtures are shown in Fig. 4. The
yields of AFAN, formic acid, and acetaldehyde from (R20a)
the photolysis of Cl2 /ethyl formate mixtures are 0.13
0.02, 0.44 0.10, and <0.02, respectively. In the pres-
ence of NO, the measured yields of AFAN, formic
.
O2
acid, and acetaldehyde are 0.05 0.02, 0.76 0.15,
and <0.02, respectively.
A recent study investigated the branching ratios O O + HCl (R20b)
for the reaction of Cl atoms with ethyl formate by
measuring product distributions from the photolysis of
chlorine/ethyl formate/NO2 mixtures [24]. This work The peroxy radical formed in reaction (R20a) may react
indicates that the major pathway for the reaction be- with an organic peroxy radical to form hydroxyethyl

International Journal of Chemical Kinetics DOI 10.1002/kin

516 MIDDALA ET AL.

formate, AFAN, or an alkoxy radical.

.
CH3CH2O + O2 CH3CHO + HO2 (R26)
.
O2 OH
Thus, AFAN and formic acid are formed via reac-
tion (R20a) whereas acetaldehyde is formed in reac-
O O .
+ RO 2 O O + R=O tion (R20b). Acetaldehyde has a large rate coefficient
for reaction with Cl atoms compared with ethyl for-
(R21a) mate, and so is rapidly removed upon formation and
O does not build up to sufficient levels to be observed
in these experiments. Tyndall and Orlando measured
product yields from the reaction of ethyl formate and
O O + R-OH (R21b) Cl atoms as a function of temperature and oxygen par-
tial pressure [25]. At room temperature and an oxygen
O partial pressure of 150 Torr, Tyndall and Orlando report
yields of formic acid and AFAN of 0.39 and 0.19, re-
spectively, in good agreement with the values reported
O O + RO. + O 2 (R21c) here. The sum of the yields of AFAN and formic acid in
this work (0.57) and reported by Tyndall and Orlando
The alkoxy radical formed in reaction (R21c) may (0.58) are also in good agreement with the branching
either react with oxygen to form AFAN (reaction ratio for reaction (R20a) reported by Malanca et al. of
(R22)) or react via the -ester rearrangement, produc- 0.62 [24].
ing formic acid (reaction (R23)). The reactions occurring in the presence of NO are
similar to the NOx-free mechanism, but the peroxy
O O radicals formed in reactions (R20a) and (R20b) will
react with NO to form alkoxy radicals.
O O + O2 O O + HO2
(R22) O2
. O

O
O O + NO O O + NO2
O O HCO2H + CH3C(O). (R27)

(R23)
O2
. O
The peroxy radical formed in reaction (R20b) is ex-
pected to react with a peroxy radical to form an alkoxy O O + NO O O + NO2
radical (reaction (R24)), which will subsequently de-
compose to produce carbon dioxide and acetaldehyde (R28)
(reactions (R25) and (R26)).
Because the alkoxy radicals are formed with greater
internal energy in reaction (24) than via reaction with
.
O2 O RO2 (reaction (R21c)), the rate of the -ester rearrange-
ment is expected to be faster in the presence of NO.
O O .
+ RO 2 O O
.
+ RO + O2 Thus, the yield of formic acid relative to AFAN (via re-
actions (R22) and (R23)) is expected to be higher under
(R24) these conditions. The observed increase in formic acid
yield (from 0.44 to 0.76) and the decrease in AFAN
O
yield (from 0.13 to 0.05) in the presence of NO in
these experiments are consistent with this. The mea-
O O CO2 + CH3CH2O
. surements indicate that the peroxy radical formed in
reaction (R20a) is almost quantitatively converted into
(R25) formic acid in the presence of NO in these experiments.

International Journal of Chemical Kinetics DOI 10.1002/kin

 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS
a)
13
1.5 10
3
[Product]/molecules cm
13
1.0 10
12
5.0 10
0.0
13
0.0 2.5 10 5.0 10
[PPO]/molecules cm
Figure 5 Typical product yield plots for the reaction of PPO with Cl atoms at 298 K in 1 atm air (a) in the absence of NO and
(b) in the presence of NO.
Cl + PPO
Product yield plots from the Cl + PPO reaction in
the absence of NO are shown in Fig. 5. The yields
of formic acid, acetic acid, AFAN, and CO are 0.20
0.02, 0.12 0.01, 0.22 0.01, and 0.31 0.03. As out-
lined above, acetic acid and formic acid can be used as
markers to determine the branching ratios for reactions
(R4b) and (R4c), respectively. If H-atom abstraction
occurred exclusively from the secondary carbon center
of PPO (reaction (R4b)), the acetic acid yield would be
40%. The measured yield of 12% therefore implies that
the branching ratio for reaction (R4b) is 0.12/0.40 =
0.30 0.05. Likewise, H-atom abstraction from the
terminal carbon atom of the epoxide moiety (reaction
(R4c)) results in a formic acid yield of effectively unity.
The measured formic acid yield in these experiments
is thus consistent with a branching ratio for reaction
(R4c) of 0.2 0.03.
No evidence is found for the formation of either
formaldehyde or formic acid anhydride, which are the
expected products of reaction (R4a) via reaction (R7).
In the absence of NO, the peroxy radical formed in
(R4a) is expected to react with organic peroxy rad-
International Journal of Chemical Kinetics DOI 10.1002/kin
517
b)
13
1.5 10
13
1.0 10
12
5.0 10
0.0
13 13 13 13 13
7.5 10 0.0 2.5 10 5.0 10 7.5 10
3 3
[PPO]/molecules cm
Acetic acid
AFAN
Formic acid
icals and hydroperoxy radicals to form alcohol, car-
bonyl, and hydroperoxide products. However, a sig-
nificant fraction of the reactions between organic per-
oxy radicals should yield the same alkoxy radical as
that formed in reaction (R5a). This implies that ei-
ther the branching ratio for reaction (R4a) is small,
or that the peroxy radical generated in this reaction
primarily forms an aldehyde via reaction (R6). There
is evidence in the literature that leads us to expect
that the alkoxy radical formed via reaction (R4a) will
preferentially react with O2 to form an aldehyde (re-
action (R6)) rather than undergoing unimolecular de-
composition (reaction (R7)). For example, in mech-
anistic investigations the CH2 (OH) CH2 O radical,
which shows structural similarities to the alkoxy radi-
cal formed from PPO via reaction (R4a) (both can be
written as O CHR CH2 O , where R = H or CH2 ),
primarily reacts with O2 to form CH2 (OH)CH(O) at
298 K and in 1 atm of air [26].
The aldehyde generated in reaction (R6) is expected
to react faster with Cl atoms than the parent PPO
[27], and its subsequent reaction is expected to lead
to several reaction products, including formic anhy-
dride. The steady-state concentration of the compound
518 MIDDALA ET AL.
is therefore likely to be low. Since the compound is not
commercially available, it was not possible to deter-
mine the yield of this aldehyde in these experiments,
and as noted above, no evidence for the formation of
formic anhydride was found. However, if the branch-
ing ratios for reactions (R4b) and (R4c) are correct,
the branching ratio for reaction (R4a) should be 1
(YR4b + YR4c ), implying that YR4a is 0.50 0.08.
To further investigate the branching ratio for reac-
tion (R4a), mixtures of chlorine, PPO, and nitrogen
were irradiated. In the absence of oxygen, H-atom ab-
straction from each carbon atom results in the for-
mation of an alkyl radical that may react with Cl2 to
produce an organic chloride. H-atom abstraction from
the methyl group (reaction (R29)) leads to the forma-
tion of epichlorohydrin via reaction (R30), which is
commercially available.
O molecular reaction with O2 , and so reaction with NO2
O (reactions (R31) and (R32)) should also be too slow to
+ Cl H2C
(R29)
O the analysis of the product yields from the OH-initiated
O
H2C Cl
+ Cl2 + Cl
(R30)
The yield of epichlorohydrin measured in these exper-
iments is 0.08 0.02. This is a lower limit for the
branching ratio for reaction (R4a) since trace amounts
of oxygen present within the chamber may still result
in the majority of alkyl radicals formed via reaction
(R29) producing peroxy radicals (via reaction (R4a)).
Previous studies of Cl + organic reactions in N2 have
shown that product yields can be significantly altered
due to trace levels of oxygen as a contaminant since
the reaction of alkyl radicals with Cl2 can be slow [28].
This result is therefore not inconsistent with a branch-
ing ratio for YR4a of 0.50. However, the large missing
carbon balance means that the branching ratios deter-
mined here must be treated with some caution.
When NO is added to the reaction mixture, the
yields of formic acid, acetic acid, CO, and AFAN from
the Cl + PPO reaction are 0.19 0.01, 0.16 0.01,
0.30 0.05, and 0.08 0.01, respectively. Based on
the experiments carried out with methyl acetate and
ethyl formate, the yields of acetic acid and formic acid
from reactions (R23) and (R16) are not expected to
change significantly when NO is added to the reaction.
The yields of these products from PPO are potentially
affected by the presence of NO2 in the chamber via
reactions (R31) and (R32).
O O
O + NO2 O 2NO (R31)
O
O
O + NO2 ONO2
(R32)
As discussed above, the reaction of alkoxy radicals
with NO2 may be competitive with the alkoxy + O2
reaction under the experimental conditions used in this
study. However, the observed products indicate that
the unimolecular ring opening of these alkoxy radicals
(reactions (R8) and (R9)) is much faster than the bi-
compete with the unimolecular reactions. The yields of
acetic acid and formic acid do not change appreciably
when NO is present, which is consistent with this anal-
ysis. This observation has important implications for
oxidation of PPO, where both NO and NO2 are always
present.
OH + PPO
Product yield plots from the photolysis of isobutyl ni-
trite/PPO/NO/air mixtures are shown in Fig. 6. The
measured product yields for the OH-initiated oxida-
tion of PPO are 0.04 0.01, 0.03 0.01, 0.20
0.05, and 0.01 0.01 for formic acid, acetic acid, CO,
and AFAN, respectively. Based on Atkinsons struc-
ture activity relationship (SAR) approach [29], AFAN
is expected to react with OH about 30 times faster than
PPO. Thus, the steady-state concentrations of AFAN
are low and cannot be used to infer branching ratios. As
discussed above, the yields of formic acid and acetic
acid can be used to determine the branching ratios
for H-abstraction from the terminal (R4c) and central
(R4b) carbon atoms in the epoxide group, respectively.
Combining the yields measured from OH + PPO with
the results from the methyl acetate and ethyl formate
experiments discussed above gives branching ratios of
0.08 0.03 and 0.04 0.01 for YR4b and YR4c , respec-
tively. There is no direct way to measure the branching
ratio for YR4a in these experiments since a standard
for the expected reaction product is not available, and
ACUCHEM simulations indicate that about 80% of
the aldehyde produced would react with OH under
the reaction conditions used. Nonetheless, an upper
International Journal of Chemical Kinetics DOI 10.1002/kin
 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS 519

12
5.0 10

12
4.0 10
3
[Product]/molecuels cm

12
3.0 10

12
2.0 10

12
1.0 10

0.0
13 13 13
0.0 2.5 10 5.0 10 7.5 10
3
[PPO]/molecules cm

Acetic acid
AFAN
Formic acid
Figure 6 Typical product yield plots for the reaction of PPO with OH radicals at 298 K in 1 atm air. Acetic acid concentrations
have been shifted vertically for clarity.

limit for YR4a can be estimated as 1 (YR4b + YR4c ).
This leads to the branching ratios YR4a :YR4b :YR4c of
0.88:0.08:0.04. As with the PPO + Cl measurements,
the very low carbon balance and the fact that no chem-
ical marker is available for reaction (R4a) means that
the large branching ratio for YR4a inferred here should
be treated as tentative.
While the low carbon balance makes it difficult to
evaluate the apparent result that the reaction between
OH and PPO occurs predominantly via reaction (R4a),
the kinetic measurements do provide some support for
this conclusion. Atkinson and Kwok have developed a
widely used SAR to estimate the rate coefficients for
the reaction of OH radicals with a wide range of organic
compounds [29]. Rate coefficients are calculated as
the sum of partial rate coefficients for reaction at each
carbon atom within the organic molecule
 constants for cyclic hydrocarbons. The presence of
k= kPartial
The partial rate coefficients are calculated as the prod-
uct of an incremental rate coefficient (k o ) for the carbon
center (primary, secondary, and tertiary) and a sub-
stituent factor F for the groups attached to the carbon
center. The values for the incremental rate coefficients
and the substituent factors are determined from fits to
existing experimental rate data.
kPartial,Primary = kPrimary F (X)
kPartial,Secondary = kSecondary F (X) F (Y )
kPartial,Tertiary = kTertiary F (X) F (Y ) F (Z)
Following this approach leads to an overall
rate coefficient for OH + PPO of 5.4 1013
molecules cm3 s1 , significantly higher than the rate
coefficient measured here. The calculation of the rate
coefficients includes a factor of 0.017 that accounts
for the ring strain in the three-membered epoxide ring.
However, this value was determined from fits to rate
the oxygen atom in the three-membered ring may sig-
nificantly affect this factor and may partially explain
the discrepancy between the predicted and measured
rate coefficients and branching ratios. Reducing the

International Journal of Chemical Kinetics DOI 10.1002/kin

520 MIDDALA ET AL.
ring strain factor to 0.0055 reduces the SAR rate co-
efficient to 3.0 1013 cm3 molecule1 s1 , as re-
ported in this work. The SAR rate coefficient for ethy-
lene oxide + OH using the literature value of 0.017
for the three-membered ring factor is 2.2 1013
cm3 molecule1 s1 . However, when this value is
changed to 0.0055, the predicted rate coefficient de-
creases to 7.3 1014 cm3 molecule1 s1 , which sistent with the literature.
is in better agreement with the experimental literature
value for this rate coefficient [4,30,31]. Thus, the lit-
erature is consistent with the use of this lower three-
membered ring strain factor for epoxides. Furthermore,
the partial rate coefficients for OH + PPO using a ring
strain factor of 0.017 imply that the branching ratios
YR4a , YR4b , and YR4c are 0.34, 0.45, and 0.20, respec-
tively, in relatively poor agreement with the branching
ratios inferred above. Reducing the ring strain factor to
0.0055 changes the predicted branching ratios for YR4a ,
YR4b , and YR4c to 0.62, 0.26, and 0.12, respectively,
in better agreement with the measurements reported
here.
CONCLUSIONS
The rate coefficients for the reaction of PPO with
Cl atoms, OH radicals, and ozone are (3.0
0.7) 1011 cm3 molecule1 s1 , (3.0 1.0)
1013 cm3 molecule1 s1 , and <3.5 1021
cm3 molecule1 s1 , respectively. Using estimated at-
mospheric concentrations of Cl [68], OH, and O3 of
3 103 , 1 106 , and 6 1011 molecules cm3 ,
the lifetime of PPO with respect to these oxidants is
150 days, 24 days, and >15 years, respectively. Thus,
reaction with OH is expected be the dominant chemical
sink for this species in the troposphere. However, in the
marine boundary layer, where Cl atom concentrations
may reach 105 molecules cm3 or higher, reaction with
Cl may be the primary chemical sink.
For the Cl + PPO and the OH + PPO reactions, the
observed product yields and the measured rate coef-
ficients are consistent with H-atom abstraction occur-
ring primarily from the methyl group (reaction (R4a)).
Since formic anhydride is not observed in these experi-
ments, the major product expected from these reactions
is formyl ethylene oxide. However, the branching ratio
for reaction (R4a) could not be directly measured in
this work due to the lack of an available standard and
because of the low concentrations that are expected due
to its high reactivity compared to PPO. Further work is
therefore needed to test this conclusion. Formyl ethy-
lene oxide generated in reaction (R6) would be ex-
pected to react in the atmosphere to form a mixture of
products including a peracid (under low NOx condi-
tions), formic anhydride, and formic acid as the major
products. The larger yields of formic acid, acetic acid,
and AFAN from the Cl + PPO reaction compared to
the OH + PPO reaction imply that Cl atoms are less se-
lective and a greater fraction of them abstract H-atoms
from one of the carbons on the epoxide ring. This lower
selectivity for Cl- versus OH-initiated reactions is con-
C.O. and S.M. thank the National Science Foundation (award
#0914718) and the Division of Graduate Studies at California
State University, Fresno, respectively, for support.
BIBLIOGRAPHY
1. Ko, M. K. W.; Sze, N. D.; Scott, C.; Rodriguez, J. M.;
Weisenstein, D. K.; Sander, S. P. J Geophys Res 1998,
103, 2818728195.
2. Isikber, A. A.; Navarro, S.; Finkelman, S.; Rindner, M.
Phytoparasitica 2006, 34, 412419.
3. Sander, R. Compilation of Henrys Law Constants for In-
organic and Organic Species of Potential Importance in
Environmental Chemistry (Version 3), 1999. Retrieved
from http://www.henrys-law.org.
4. Wallington, T. J.; Liu, R.; Dagaut, P.; Kurylo, M. J. Int J
Chem Kinet 1988, 20, 177186.
5. Edney, E. O.; Kleindienst, T. E.; Corse, E. W. Int J Chem
Kinet 1986, 18, 13551371.
6. Singh, H. B.; Thakur, A. N.; Chen, Y. E.; Kanakidou,
M. Geophys Res Lett 1996, 23, 15291532.
7. Rudolph, J.; Koppmann, R.; PlassDulmer, C. Atmos En-
viron 1996, 30, 18871894.
8. Wingenter, O. W.; Kubo, M. K.; Blake, N. J.; Smith,
T. W., Jr.; Blake, D. R.; Rowland, F. S. J Geophys Res
D 1996, 101, 43314340.
9. Spicer, C. W.; Chapman, E. G.; Finlayson-Pitts, B. J.;
Plastridge, R. A.; Hubbe, J. M.; Fast, J. D.; Berkowitz,
C. M. Nature 1998, 394, 353356.
10. Chen, J.; Young, V.; Hooshiyar, P. A.; Niki, H.; Hurley,
M. D. J Phys Chem 1995, 99, 40714077.
11. Singh, S.; Hernandez, S.; Ibarra, Y.; Hasson, A. S. Int J
Chem Kinet 2009, 41, 133141.
12. Hasson, A. S.; Chung, M. Y.; Kuwata, K. T.; Converse,
A. D.; Krohn, D.; Paulson, S. E. J Phys Chem A 2003,
107, 61766182.
13. Kroll, J. H.; Clarke, J. S.; Donahue, N. M.; Anderson,
J. G. J Phys Chem A 2000, 105, 15541560.
14. Paulson, S. E.; Fenske, J. D.; Sen, A. D.; Callahan,
T. W. J Phys Chem A 1999, 103, 20502059.
15. Rickard, A. R.; Johnson, D.; McGill, C. D.; Marston,
G. J Phys Chem A 1999, 103, 76567664.
16. Atkinson, R.; Aschmann, S. M.; Arey, J.; Shorees,
B. J Geophys Res D 1992, 97, 60656073.
International Journal of Chemical Kinetics DOI 10.1002/kin
 REACTION OF PROPYLENE OXIDE WITH CHLORINE ATOMS AND HYDROXY RADICALS
17. Atkinson, R.; Baulch, D. L.; Cox, R. A.; Crowley, J.
N.; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; Rossi,
M. J.; Troe, J. Atmos Chem Phys 2004, 4, 14611738.
18. Bartels, M.; Hoyermann, K.; Lange, U. Ber Bunsen-Ges
Phys Chem 1989, 93, 423427.
19. Ponomarev, D.; Hurley, M. D.; Wallington, T. J. Int J
Chem Kinet 2002, 34, 122125.
20. Christensen, L. K.; Ball, J. C.; Wallington, T. J. J Phys
Chem A 2000, 104, 345351.
21. Andersen, V. F.; Nilsson, E. J. K.; Jorgensen, S.; Nielsen,
O. J.; Johnson, M. S. Chem Phys Lett 2009, 472, 2329.
22. Tuazon, E. C.; Aschmann, S. M.; Atkinson, R.; Carter,
W. P. L. J Phys Chem A 1998, 102, 23162321.
23. Tyndall, G. S.; Pimentel, A. S.; Orlando, J. J. J Phys
Chem A 2004, 108, 68506856.
24. Malanca, F. E.; Fraire, J. C.; Arguello, G. A. J Photochem
Photobiol A: Chem 2009, 204, 7581.
International Journal of Chemical Kinetics DOI 10.1002/kin
521
25. Orlando, J. J.; Tyndall, G. S. Inter J Chem Kinet 2010,
42, 397413.
26. Orlando, J. J.; Tyndall, G. S.; Bilde, M.; Ferronato, C.;
Wallington, T. J.; Vereecken, L.; Peeters, J. J Phys Chem
A 1998, 102, 81168123.
27. Atkinson, R. Atmos Environ 2007, 41, S200S240.
28. Iwasaki, E.; Taketani, F.; Takahashi, K.; Matsumi, Y.;
Wallington, T. J.; Hurley, M. D. Chem Phys Lett 2007,
439, 274279.
29. Kwok, E. S. C.; Atkinson, R. Atmos Environ 1995, 29,
16851695.
30. Baldwin, R. R.; Keen, A.; Walker, R. W. J Chem Soc
Faraday Trans 1: Phys Chem Condens Phases 1984, 80,
435456.
31. Fritz, B.; Lorenz, K.; Steinert, W.; Zellner, R. In Proceed-
ings of the European Symposium on Physico-Chemical
Behavior of Atmospheric Pollutants, 1982.