Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols

Article abstract of DOI:10.1002/1097-4601(200102)33:2<142::AID-KIN1007>3.0.CO;2-F

Using a relative rate method, rate constants for the gas-phase reactions of OH radicals with allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol have been measured at 296±2 K and atmospheric pressure of air. Using 1,3,5-trimethylbenzene as the reference compound, the rate constants (in units of 10^-11 cm³ molecule^-1 s^-1) were: allyl alcohol, 5.46±0.35; 3-buten-1-ol, 5.50±0.20; 3-buten-2-ol, 5.93±0.23; and 2-methyl-3-buten-2-ol, 5.67±0.13; where the indicated errors are two least-squares standard deviations and do not include the uncertainty in the rate constant for 1,3,5-trimethylbenzene. The H-atom abstraction products acrolein and methyl vinyl ketone were observed from the allyl alcohol and 3-buten-2-ol reactions, respectively, with respective yields of 5.5±0.7 and 4.9±1.4%. No evidence for formation of acrolein from 3-buten-1-ol or 3-buten-2-ol was obtained, with upper limits to the acrolein yields of ≤1.2 and ≤0.5%, respectively, being determined. Reaction mechanisms are discussed.

Full text of DOI:10.1002/1097-4601(200102)33:2<142::AID-KIN1007>3.0.CO;2-F

Rate Constants for the
Gas-Phase Reactions of OH
Radicals with a Series of
Unsaturated Alcohols
CHRISTINE PAPAGNI,1,2 JANET AREY,1,3 ROGER ATKINSON1,3,4
Air Pollution Research Center, University of California, Riverside, CA 92521
Received 19 May 2000; accepted 11 September 2000
ABSTRACT: Using a relative rate method, rate constants for the gas-phase reactions of OH
radicals with allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol have been
measured at 296 Ϯ 2 K and atmospheric pressure of air. Using 1,3,5-trimethylbenzene as the
11
1
reference compound, the rate constants (in units of 10Ϫ cm3 moleculeϪ sϪ1) were: allyl
alcohol, 5.46 Ϯ 0.35; 3-buten-1-ol, 5.50 Ϯ 0.20; 3-buten-2-ol, 5.93 Ϯ 0.23; and 2-methyl-3-
buten-2-ol, 5.67 Ϯ 0.13; where the indicated errors are two least-squares standard deviations
and do not include the uncertainty in the rate constant for 1,3,5-trimethylbenzene. The H-
atom abstraction products acrolein and methyl vinyl ketone were observed from the allyl
alcohol and 3-buten-2-ol reactions, respectively, with respective yields of 5.5 Ϯ 0.7 and 4.9 Ϯ
1.4%. No evidence for formation of acrolein from 3-buten-1-ol or 3-buten-2-ol was obtained,
with upper limits to the acrolein yields of Յ1.2 and Յ0.5%, respectively, being determined.
Reaction mechanisms are discussed. ᭧ 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 142–147,
2001
INTRODUCTION
loss processes for 2-methyl-3-buten-2-ol [14]. To date,
rate constants for the OH radical reactions with un-
saturated alcohols are available only for allyl alcohol
[5] and 2-methyl-3-buten-2-ol [6–8], with the avail-
able rate constant for allyl alcohol being at 440 K. In
this work, we have used a relative rate method to mea-
sure rate constants at 296 Ϯ 2 K for allyl alcohol, 3-
buten-1-ol [CH2 "CHCH2CH2OH], 3-buten-2-ol
[CH2 "CHCH(OH)CH3], and 2-methyl-3-buten-2-ol.
In addition, we have investigated the formation of
products that arise after initial H-atom abstraction
from the allylic C9H bonds in these alcohols.
2-Methyl-3-buten-2-ol [(CH3)2C(OH)CH"CH2] is
emitted into the atmosphere in large quantities from
vegetation [1–3], and allyl alcohol [CH2 "
CHCH2OH] is used as an intermediate in the manu-
facture of a number of chemicals [4]. In the tropo-
sphere, these and other unsaturated alcohols react with
OH radicals [5–8], NO3 radicals [7,9,10], and O3
[7,11–13], with the O3 and daytime OH radical reac-
tions being calculated to dominate as the tropospheric
Correspondence to: R. Atkinson (ratkins@mail.ucr.edu)
1 Environmental Toxicology Interdepartmental Graduate Pro-
gram
EXPERIMENTAL
2 Present address: Agricultural and Environmental Chemistry
Graduate Program, University of California, Davis, CA 95616
3 Also Department of Environmental Sciences
4 Also Department of Chemistry
The experimental methods were similar to those used
previously [15]. Experiments were carried out in a
7000-l Teflon chamber at 296 Ϯ 2 K and 740 Torr
᭧ 2001 John Wiley & Sons, Inc.

RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF OH RADICALS
143
total pressure of purified air at ϳ5% relative humidity.
The chamber is equipped with two parallel banks of
black lamps for irradiation and a Teflon-coated fan to
ensure rapid mixing of reactants during their introduc-
tion into the chamber. Rate constants were measured
using a relative rate method in which the relative dis-
appearance rates of the alcohols and a reference com-
pound, whose OH radical reaction rate constant is re-
liably known, were measured in the presence of OH
radicals [15]. Providing that the alcohols and the ref-
erence compound reacted only with OH radicals, then
[15],
diations, a mixture containing the alcohols (ϳ2.4 ϫ
3
1013 molecule cmϪ each) and n-octane (1.0 ϫ 1016
3
molecule cmϪ ) in air was irradiated for up to 40 min
at the same light intensity as used in the rate constant
determinations. The excess of n-octane was present to
scavenge any OH radicals formed during the irradia-
tion. To investigate the formation of selected products
and to ascertain that reaction products did not interfere
with the analysis of the other reactants, irradiations of
CH3ONO9NO9individual alcohol–air mixtures
were also carried out using similar initial concentra-
tions as in the rate constant determinations.
The concentrations of the alcohols and reference
compounds were measured using gas chromatography
with flame ionization detection (GC-FID). Gas sam-
ples of 100 cm3 volume were collected from the cham-
ber onto Tenax-TA solid adsorbent with subsequent
thermal desorption at ϳ225ЊC onto a 30-m DB-1701
megabore column held at Ϫ40ЊC and then temperature
[alcohol]t
0
ln
ͩ ͪ
[alcohol]t
k1
k2
[reference compound]t
0
ͩ ͪ
ϭ
ln
(I)
[reference compound]t
1
programmed to 240ЊC at 8ЊC minϪ . Based on repli-
where [alcohol]t and [reference organic] are the con-
t0
0
centrations of the alcohol and the reference compound,
respectively, at time t0, [alcohol]t and [reference or-
ganic]t are the corresponding concentrations at time t,
and k1 and k2 are the rate constants for reactions (1)
and (2), respectively:
cate analyses in the dark, the GC-FID measurement
uncertainties for the alcohols and reference com-
pounds were typically 1–2%. GC-FID response fac-
tors for the alcohols and selected potential products
were determined by introducing measured amounts of
the compounds into the chamber and conducting sev-
eral replicate analyses [21]. Products were confirmed
by combined gas chromatography–mass spectrometry
(GC–MS) analyses, with collection of pre- and post-
reaction samples onto Tenax-TA solid adsorbent with
subsequent thermal desorption onto a DB-1701 col-
umn in a Hewlett-Packard (HP) 5890 GC interfaced
to an HP 5971A Mass Selective Detector. Confirma-
tion of products involved matching of GC retention
times and mass spectra with those of authentic stan-
dards. The NO and initial NO2 concentrations were
measured using a Thermo Environmental Instruments,
Inc. Model 42 chemiluminescence NO–NO2 –NOx
analyzer.
OH ϩ alcohol !: products
(1)
(2)
OH ϩ reference organic !: products
Therefore, plots of ln([alcohol]t /[alcohol]t) against
0
ln([reference organic]t /[reference organic]t) should be
0
straight lines with slope k1/k2 and zero intercept.
OH radicals were generated by the photolysis of
methyl nitrite (CH3ONO) in air at wavelengths Ͼ300
nm [16], and NO was added to the reactant mixtures
to suppress the formation of O3 and hence of NO3
radicals [16]. The initial reactant concentrations (in
3
molecule cmϪ units) were: CH3ONO, ϳ2.4 ϫ 1014
;
NO, ϳ2.4 ϫ 1014 ; and alcohols and reference com-
pound, ϳ2.4 ϫ 1013 each. 1,3,5-Trimethylbenzene and
m-xylene were used as reference compounds because
their OH radical reaction rate constants [17–20] are
similar to those reported for allyl alcohol (at 440 K)
[5] and 2-methyl-3-buten-2-ol [6–8], and they could
be analyzed by gas chromatography using the same
sampling procedure and gas chromatographic column
as the alcohols. Irradiations were carried out for 7–33
min, resulting in up to 45–84% reaction of the initially
present alcohols, m-xylene and 1,3,5-trimethylben-
zene.
The chemicals used, and their stated purities, were:
allyl alcohol (99ϩ%), AcrosOrganic; acrolein (90%),
3-buten-1-ol (98ϩ%), 3-buten-2-ol (97%), 2-methyl-
3-buten-2-ol (98%), methyl vinyl ketone (99%), n-oc-
tane (99ϩ%), and m-xylene (99ϩ%), Aldrich Chem-
ical Company; 1,3,5-trimethylbenzene, Eastman
Chemical Company; and NO (Ն99%), Matheson Gas
Products. Methyl nitrite was prepared and stored as
described previously [16].
RESULTS
To check on the importance of photolysis of the
unsaturated alcohols during the CH3ONO9NO9
alcohol–1,3,5-trimethylbenzene–m-xylene–air irra-
Irradiation of an alcohols–n-octane–air mixture for
up to 40 min showed Ͻ5% loss of any of the alcohols,

144
PAPAGNI ET AL.
indicating that photolysis of the alcohols during the
OH radical rate constant determinations was of no im-
portance. Furthermore, over the ϳ6-h duration of the
photolysis experiment the concentrations of the alco-
hols changed by Ͻ5%, showing that wall losses of the
alcohols were also negligible. The lack of photolysis
of these alcohols at wavelengths Ͼ300 nm is consis-
tent with the measured, very weak absorption of
2-methyl-3-buten-2-ol above 290 nm [6]. A series of
CH3ONO –NO –alcohol-1,3,5-trimethylbenzene-m-
xylene-air irradiations was carried out, and the exper-
imental data obtained are plotted in accordance with
Eq. (I) in Figure 1. Straight-line plots are observed,
and the rate constant ratios k1/k2 obtained by least-
squares analyses of the data are given in Table I. These
rate constant ratios k1/k2 are placed on an absolute ba-
sis by use of a rate constant k2 for the reaction of the
OH radical with 1,3,5-trimethylbenzene of k2 ϭ 5.70
Figure 1 Plots of Eq. (I) for the gas-phase reactions of the
OH radical with allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 2-
methyl-3-buten-2-ol, and m-xylene, with 1,3,5-trimethyl-
benzene (1,3,5-TMB) as the reference compound. The data
for 3-buten-1-ol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol
have been displaced vertically by 0.4, 0.8, and 1.2 units,
respectively, for clarity.
ϫ 10Ϫ cm3 moleculeϪ sϪ at 296 K (with an esti-
mated overall uncertainty of Ϯ10%), this being an av-
erage of the rate constants obtained from the relative
rate studies of Atkinson and Aschmann [18] (5.75 ϫ
11
1
1
11
1
1
10Ϫ cm3 moleculeϪ sϪ at 296 Ϯ 2 K) and Kramp
and Paulson [20] (5.64 ϫ 10Ϫ11 cm3 moleculeϪ1 sϪ1 at
296 Ϯ 2 K, after reevaluation using the most recent
recommendations [19,22] for the rate constants of the
reference compounds used). 1,3,5-Trimethylbenzene
Table I Rate Constant Ratios k1/k2 and Rate Constants k1 for the Gas-Phase Reactions of OH Radicals
with Unsaturated Alcohols at 296 Ϯ 2 K and Atmospheric Pressure of Air
Ϫ1
Ϫ1
1011 ϫ k1 (cm3 molecule
s )
This Workb
Literature
Reference
a
Alcohol
k1/k2
Allyl alcohol
3-Buten-1-ol
3-Buten-2-ol
0.958 Ϯ 0.060 5.46 Ϯ 0.35 2.59 Ϯ 0.34 (at 440 K) Gordon and Mulac [5]
0.965 Ϯ 0.035 5.50 Ϯ 0.20
1.04 Ϯ 0.04
5.93 Ϯ 0.23
2-Methyl-3-buten-2-ol 0.995 Ϯ 0.022 5.67 Ϯ 0.136.4
Ϯ 0.6
Rudich et al. [6]
Fantechi et al. [7]
Fantechi et al. [7]
Ferronato et al. [8]
4.27 Ϯ 1.80c
3.85 Ϯ 0.80d
7.35 Ϯ 0.79e
6.43 Ϯ 0.54f
Ferronato et al. [8]
m-Xylene
0.347 Ϯ 0.027 1.98 Ϯ 0.16 2.30 Ϯ 0.06g
Atkinson and Aschmann [18]
Kramp and Paulson [20]
Aschmann and Atkinson [39]
2.18 Ϯ 0.19g
2.09 Ϯ 0.14g
a Indicated errors are two least-squares standard deviations.
b Placed on an absolute basis using a rate constant for the reaction of the OH radical with 1,3,5-trimethylbenzene of k2 ϭ
5.70 ϫ 10Ϫ11 cm3 moleculeϪ1 sϪ1 at 296 K [18,20]. The indicated errors are two least-squares standard deviations and do not take
into account uncertainties in the rate constant k2 (estimated to be approximately Ϯ10% [20]).
1
1
c At 298 Ϯ 2 K, relative to k2(isoprene) ϭ 1.01 ϫ 10Ϫ10 cm3 moleculeϪ sϪ [22].
1
1
d At 298 Ϯ 2 K, relative to k2(propene) ϭ 2.63 ϫ 10Ϫ11 cm3 moleculeϪ sϪ [22].
1
e At 295 Ϯ 1 K, relative to k2(ethene) ϭ 8.65 ϫ 10Ϫ12 cm3 moleculeϪ sϪ1 [22].
1
1
f At 295 Ϯ 1 K, relative to k2(propene) ϭ 2.68 ϫ 10Ϫ11 cm3 moleculeϪ sϪ [22].
g Relative rate studies at 296 Ϯ 2 K. The rate constant of Kramp and Paulson [20] has been reevaluated to be consistent with
the most recent recommendations [17,19,22] for the reference compounds used.

RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF OH RADICALS
145
was used as the reference compound rather than m-
xylene because the alcohols studied here are very sim-
ilar to 1,3,5-trimethylbenzene in their reactivity to-
wards the OH radical, but are a factor of ϳ3more
reactive than is m-xylene. The resulting rate constants
k1 are given in Table I.
the literature values in Table I. Our rate constant for
2-methyl-3-buten-2-ol agrees to within 11% with the
absolute room-temperature rate constant reported by
Rudich et al. [6] and is between the rate constants ob-
tained in the relative rate studies of Fantechi et al. [7]
and Ferronato et al. [8]. Rudich et al. [6] observed
formation of OH radicals from 2-methyl-3-buten-2-ol
in the absence of O2, presumably from elimination of
the hydroxyl group at the 2-position. The rate constant
of Rudich et al. [6] cited in Table I was obtained from
experiments using OH radicals in the presence of O2
and from experiments using OD radicals [6].
The only rate constant available for allyl alcohol
was obtained by Gordon and Mulac [5] at 440 K (Ta-
ble I). The rate constant for reaction of the OH radical
with 2-methyl-3-buten-2-ol has a temperature depen-
dence of B (in k ϭ AeϪB/T) ϭ Ϫ610 K [6] (similar to
the temperature dependencies for reactions of the OH
radical with alkenes [17,19], which typically have B
ϳ Ϫ500 K). Hence, a 296 K rate constant for allyl
alcohol of ϳ(4.5–5.0) ϫ 10Ϫ11 cm3 moleculeϪ1 sϪ1 is
anticipated from the 440 K rate constant measured by
Gordon and Mulac [5], in reasonable agreement with
our measured value (Table I). No rate constants have
been reported to date for the reactions of the OH rad-
ical with 3-buten-1-ol or 3-buten-2-ol. The rate con-
stant measured here for m-xylene is in reasonable
agreement with the literature values [17–20,28–40]
and especially with the more recent relative rate stud-
ies [18,20,39].
GC-FID analyses of irradiated CH3ONO–NO–al-
cohol–air mixtures suggested the formation of acro-
lein from allyl alcohol and methyl vinyl ketone from
3-buten-2-ol, and these products were confirmed by
GC-MS analyses. There was no evidence for the for-
mation of acrolein from 3-buten-1-ol or from 3-buten-
2-ol (products of the OH radical reaction with 2-
methyl-3-buten-2-ol have previously been studied by
Fantechi et al. [23], Ferronato et al. [8], and Alvarado
et al. [24] and were hence not studied here). Acrolein
and methyl vinyl ketone also react with the OH radical
[17,19], and in the product yield determinations sec-
ondary reactions with the OH radical were taken into
account as described previously [25]. Corrections to
account for secondary reactions with OH radicals in-
crease with the rate constant ratio k(OH ϩ product)/
k(OH ϩ alcohol) and with the extent of reaction [25]
and are expressed as multiplicative correction factors
F [25]. For each experimental data point the multi-
plicative factor F was calculated using the analytical
expression given by Atkinson et al. [25], using rate
constants for reactions of OH radicals with acrolein
and methyl vinyl ketone at 296 K of 1.99 ϫ 10Ϫ11 cm3
1
moleculeϪ1 sϪ1 [19] and 2.06 ϫ 10Ϫ11 cm3 moleculeϪ
sϪ [26,27], respectively. The maximum values of F
The reactions of the OH radical with the four un-
saturated alcohols studied here are expected
[17,19,24,41] to proceed mainly by initial addition of
1
were 1.25 for formation of acrolein from allyl alcohol,
1.45 for the potential formation of acrolein from 3-
buten-1-ol, 1.48 for formation of methyl vinyl ketone
from 3-buten-2-ol, and 1.20 for the potential formation
of acrolein from 3-buten-2-ol. Least-squares analyses
of the amounts of product formed, corrected for re-
action with the OH radical, against the amounts of
alcohol reacted lead to formation yields of acrolein
from allyl alcohol of 5.5 Ϯ 0.7%, of acrolein from 3-
buten-1-ol of Յ1.2%, and of methyl vinyl ketone and
acrolein from 3-buten-2-ol of 4.9 Ϯ 1.4% and Ͻ0.5%,
respectively, where the indicated errors are two least-
squares standard deviations combined with estimated
overall uncertainties in the GC-FID response factors
for the products and alcohols of Ϯ5% each.
the OH radical to the carbon atoms of the
C"C
bond. The first-generation products anticipated to be
formed from OH radical addition to allyl alcohol, 3-
buten-1-ol, and 3-buten-2-ol in the presence of NO are
HOCH2CHO
HOCH2CH2CHO ϩ HCHO from 3-buten-1-ol, and
HOCH2CHO CH3CHO and HCHO
ϩ
HCHO from allyl alcohol,
ϩ
ϩ
CH3CH(OH)CHO from 3-buten-2-ol [19,22]. Unfor-
tunately, apart from acetaldehyde, these products are
not expected to be amenable to analysis by gas chro-
matography without prior derivatization [24,42,43]
and were not observed in the present study.
H-atom abstraction from the C9H bonds of the
substituent groups is anticipated to be relatively minor
compared to OH radical addition to the
C"C
bonds [17,19] (note that H-atom abstraction from vi-
nylic C9H bonds and from O9H bonds is of neg-
ligible importance [17,19,41]). H-atom abstraction
from the allylic C9H bonds of allyl alcohol leads to
DISCUSSION
The rate constants measured here for reaction of OH
radicals with unsaturated alcohols are compared with
и
the ␣-hydroxy radical CH2 "CHC HOH,

146
PAPAGNI ET AL.
OH ϩ CH2 "CHCH2OH !:
CH "CHCH(Oи)CH OH !:
2
2
и
H2O ϩ CH2 "CHC HOH (3)
CH "CHCHO ϩ иCH OH
2
(8)
2
Our upper limit to the formation yield of acrolein
from 3-buten-1-ol of Յ1.2% is consistent with the ex-
which is expected to react with O2 [19] to form acro-
lein:
и
pectation that CH2CH"CHCH2OH is the dominant
radical after H-atom abstraction from the allylic C9
H bonds of 3-buten-1-ol. H-atom abstraction from the
C9H bonds of the CH2OH group in 3-buten-1-ol is
expected to result in the formation of CH2 "
CHCH2CHO, which was not observed in this work
(note, however, that no standard of this product was
available).
и
CH2 "CHC HOH ϩ O2 !:
CH2 "CHCHO ϩ HO2 (4)
This is the only route to acrolein formation from allyl
alcohol, and our measured formation yield of acrolein
from allyl alcohol of 5.5 Ϯ 0.7% therefore refers to
the fraction of the reaction proceeding via initial H-
atom abstraction from the allylic C9H bonds in the
CH2OH group.
H-atom abstraction from the allylic C9H bond of
3-buten-2-ol results in the formation of methyl vinyl
ketone by analogous reactions:
The 296 K rate constants for reaction of OH radi-
cals with allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, and
2-methyl-3-buten-2-ol are all similar at (5.5–5.9) ϫ
10Ϫ cm3 moleculeϪ1 sϪ1 and are a factor of 2.1–2.2
11
higher than the 296 K rate constant for propene (2.66
11
1
1
ϫ 10Ϫ cm3 moleculeϪ sϪ [17,19,22]). Because H-
atom abstraction from the reactions of 2-methyl-3-bu-
ten-2-ol [24] (which contains no allylic C9H bonds),
allyl alcohol, and 3-buten-2-ol is predicted [17,41] and
observed to be of minor or negligible importance, then
the substituent C(OH)(CH3)2, CH2OH, and
CH(OH)CH3 groups must activate the CH2 "CH9
bond by a factor of ϳ2 towards OH radical addition,
relative to propene. While it is possible that H-atom
abstraction from the CH2 and CH2OH groups in 3-
buten-1-ol is significantly higher than that observed
from allyl alcohol and 3-buten-2-ol (i.e., Ͼ5%), the
observed OH radical reaction rate constant for 3-bu-
ten-1-ol suggests that the CH2CH2OH group also ac-
tivates the CH2 "CH9 bond towards OH radical ad-
dition by a factor of ϳ2.
OH ϩ CH2 "CHCH(OH)CH3 !:
и
H2O ϩ CH2 "CHC (OH)CH3 (5)
и
CH2 "CHC (OH)CH3 ϩ O !:
2
CH2 "CHC(O)CH3 ϩ HO
(6)
2
while H-atom abstraction from the CH3 group
is expected to lead to formation of acrolein because
the
intermediate
alkoxy
radical
CH2 "
и
CHCH(OH)CH2O will undergo decomposition [22]:
и
CH2 "CHCH(OH)CH2O !:
и
CH2 "CHC HOH ϩ HCHO (7)
и
CH2 "CHC HOH ϩ O2 !:
Finally, all four of the unsaturated alcohols studied
here are calculated to have tropospheric lifetimes due
to gas-phase reaction with the OH radical of 2.5 h for
a 12-h average daytime OH radical concentration of
2.0 ϫ 106 molecule cmϪ3 [44,45].
CH2 "CHCHO ϩ HO2 (4)
Therefore, our measured formation yield of methyl vi-
nyl ketone from 3-buten-2-ol of 4.9 Ϯ 1.4% refers to
the fraction of the reaction proceeding via initial H-
atom abstraction from the allylic C9H bond of 3-
buten-2-ol. The upper limit to the acrolein yield from
3-buten-2-ol places an upper limit of 0.5% for the con-
tribution of H-atom abstraction from the methyl group
to the overall OH radical reaction.
The authors gratefully thank the National Science Founda-
tion for supporting this research through Grant No. ATM-
9809852, and thank Ms. Sara M. Aschmann for conducting
the GC-MS analyses. RA and JA also thank the University
of California Agricultural Experiment Station for partial sal-
ary support.
For 3-buten-1-ol, H-atom abstraction from the al-
lylic C9H bonds leads initially to the CH2 "
и
CHC HCH2OH radical, which is expected to exist
и
mainly as CH2CH"CHCH2OH and ultimately form
и
HC(O)CH"CHCH2OH [22]. The CH2 "CHC
HCH2OH radical would lead to formation of acrolein
BIBLIOGRAPHY
through the intermediary of the CH2 "
1. Goldan, P. D.; Kuster, W. C.; Fehsenfeld, F. C.;
Montzka, S. A. Geophys Res Lett 1993, 20, 1039.
и
CHCH(O )CH2OH radical:

RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF OH RADICALS
147
2. Harley, P.; Fridd-Stroud, V.; Greenberg, J.; Guenther,
A.; Vasconcellos, P. J Geophys Res 1998, 103, 25479.
3. Guenther, A.; Geron, C.; Pierce, T.; Lamb, B.; Harley,
P.; Fall, R. Atmos Environ 2000, 34, 2205.
4. Handbook of Environmental Fate and Exposure Data for
Organic Chemicals, Vol. 1, Large Production and Pri-
ority Pollutants; Howard, P. H., Ed.; Lewis Publishers:
Chelsea, MI, 1989.
5. Gordon, S.; Mulac, W. A. Int J Chem Kinet 1975, Symp.
1, 289.
6. Rudich, Y.; Talukdar, R.; Burkholder, J. B.; Ravishan-
kara, A. R. J Phys Chem 1995, 99, 12188.
7. Fantechi, G.; Jensen, N. R.; Hjorth, J.; Peeters, J. Int J
Chem Kinet 1998, 30, 589.
8. Ferronato, C.; Orlando, J. J.; Tyndall, G. S. J Geophys
Res 1998, 103, 25579.
9. Rudich, Y.; Talukdar, R. K.; Fox, R. W.; Ravishankara,
A. R. J Phys Chem 1996, 100, 5374.
10. Hallquist, M.; Langer, S.; Ljungstro¨m, E.; Wa¨ngberg, I.
Int J Chem Kinet 1996, 28, 467.
11. Grosjean, D.; Grosjean, E.; Williams, E. L., II. Int J
Chem Kinet 1993, 25, 783.
12. Grosjean, E.; Grosjean, D. Int J Chem Kinet 1994, 26,
1185.
13. Grosjean, E.; Grosjean, D. J Atmos Chem 1999, 32,
205.
14. Atkinson, R.; Arey, J. Acc Chem Res 1998, 31, 574.
15. Papagni, C.; Arey, J.; Atkinson, R. Int J Chem Kinet
2000, 32, 79.
16. Atkinson, R.; Carter, W. P. L.; Winer, A. M.; Pitts, J.
N., Jr. J Air Pollut Control Assoc 1981, 31, 1090.
17. Atkinson, R. J Phys Chem Ref Data 1989, Monograph
1, 1.
18. Atkinson, R.; Aschmann, S. M. Int J Chem Kinet 1989,
21, 355.
19. Atkinson, R. J Phys Chem Ref Data 1994, Monograph
2, 1.
20. Kramp, F.; Paulson, S. E. J Phys Chem A 1998, 102,
2685.
21. Atkinson, R.; Tuazon, E. C.; Aschmann, S. M. Environ
Sci Technol 1995, 29, 1674.
25. Atkinson, R.; Aschmann, S. M.; Carter, W. P. L.; Winer,
A. M.; Pitts, J. N., Jr. J Phys Chem 1982, 86, 4563.
26. Atkinson, R.; Aschmann, S. M.; Pitts, J. N., Jr. Int J
Chem Kinet 1983, 15, 75.
27. Gierczak, T.; Burkholder, J. B.; Talukdar, R. K.; Mel-
louki, A.; Barone, S. B.; Ravishankara, A. R. J Photo-
chem Photobiol A: Chem 1997, 110, 1.
28. Doyle, G. J.; Lloyd, A. C.; Darnall, K. R.; Winer, A.
M.; Pitts, J. N., Jr. Environ Sci Technol 1975, 9, 237.
29. Hansen, D. A.; Atkinson, R.; Pitts, J. N., Jr. J Phys
Chem 1975, 79, 1763.
30. Lloyd, A. C.; Darnall, K. R.; Winer, A. M.; Pitts, J. N.,
Jr. J Phys Chem 1976, 80, 789.
31. Perry, R. A.; Atkinson, R.; Pitts, J. N., Jr. J Phys Chem
1977, 81, 296.
32. Ravishankara, A. R.; Wagner, S.; Fischer, S.; Smith, G.;
Schiff, R.; Watson, R. T.; Tesi, G.; Davis, D. D. Int J
Chem Kinet 1978, 10, 783.
33. Cox, R. A.; Derwent, R. G.; Williams, M. R. Environ
Sci Technol 1980, 14, 57.
34. Nicovich, J. M.; Thompson, R. L.; Ravishankara, A. R.
J Phys Chem 1981, 85, 2913.
35. Atkinson, R.; Aschmann, S. M.; Carter, W. P. L. Int J
Chem Kinet 1983, 15, 37.
36. Ohta, T.; Ohyama, T. Bull Chem Soc Jpn 1985, 58,
3029.
37. Edney, E. O.; Kleindienst, T. E.; Corse, E. W. Int J
Chem Kinet 1986, 18, 1355.
38. Sommerlade, R.; Parlar, H.; Wrobel, D.; Kochs, P. En-
viron Sci Technol 1993, 27, 2435.
39. Aschmann, S. M.; Atkinson, R. Int J Chem Kinet 1998,
30, 533.
40. Alvarado, A.; Arey, J.; Atkinson, R. Atmos Chem 1998,
31, 281.
41. Kwok, E. S. C.; Atkinson, R.Atmos Environ 1995, 29,
1685.
42. Aschmann, S. M.; Shu, Y.; Arey, J.; Atkinson, R. Atmos
Environ 1997, 31, 3551.
43. Bethel, H.; Atkinson, R.; Arey, J. Int J Chem Kinet
2000, submitted for publication.
44. Prinn, R. G.; Weiss, R. F.; Miller, B. R.; Huang, J.;
Alyea, F. N.; Cunnold, D. M.; Fraser, P. J.; Hartley, D.
E.; Simmonds, P. G. Science 1995, 269, 187.
45. Hein, R.; Crutzen, P. J.; Heimann, M. Global Biogeo-
chem Cycles 1997, 11, 43.
22. Atkinson, R. J Phys Chem Ref Data 1997, 26, 215.
23. Fantechi, G.; Jensen, N. R.; Hjorth, J.; Peeters, J. Atmos
Environ 1998, 32, 3547.
24. Alvarado, A.; Tuazon, E. C.; Aschmann, S. M.; Arey,
J.; Atkinson, R. Atmos Environ 1999, 33, 2893.