Gas-phase oxidation of CH2-=-C(CH3)CH2Cl initiated by OH radicals and Cl atoms: Kinetics and fate of the alcoxy radical formed

Article abstract of DOI:10.1002/poc.3439

Relative kinetics of the reactions of OH radicals and Cl atoms with 3-chloro-2-methyl-1-propene has been studied for the first time at 298-K and 1-atm by GC-FID. Rate coefficients are found to be (in cm³-molecule^-1-s^-1): k₁ (OH-+-CH₂-=-C(CH₃)CH₂Cl)-=-(3.23-±-0.35)-×-10^-11, k₂ (Cl-+-CH₂-=-C(CH₃)CH₂Cl)-=-(2.10-±-0.78)-×-10^-10 with uncertainties representing-±-2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC-MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2-hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed.

Full text of DOI:10.1002/poc.3439

Research Article
Received: 3 November 2014,
Revised: 4 February 2015,
Accepted: 16 February 2015,
Published online in Wiley Online Library: 6 April 2015
(wileyonlinelibrary.com) DOI: 10.1002/poc.3439
Gas-phase oxidation of CH =C(CH )CH Cl
2
3
2
initiated by OH radicals and Cl atoms: kinetics
and fate of the alcoxy radical formed
a
a
a
Cynthia Rivela , Rodrigo G. Gibilisco and Mariano A. Teruel *
Relative kinetics of the reactions of OH radicals and Cl atoms with 3-chloro-2-methyl-1-propene has been studied for
3
ꢀ1 ꢀ1
the first time at 298 K and 1 atm by GC-FID. Rate coefficients are found to be (in cm molecule
s
): k
with uncertainties representing
2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC-MS for
1 2
(OH + CH = C
ꢀ
11
ꢀ10
(
CH )CH Cl) = (3.23 ± 0.35) × 10 , k2 (Cl + CH = C(CH )CH Cl) = (2.10 ± 0.78) × 10
3 2 2 3 2
±
OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition
of the 1,2-hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed.
Copyright © 2015 John Wiley & Sons, Ltd.
Keywords: atmosphere; gas-phase mechanisms; relative kinetics; VOCs degradation
INTRODUCTION
CH2 ¼ CðCH3ÞCH2Cl þ Cl→Products
(2)
Volatile organic compounds (VOCs) are used as halogenated
solvents, fuel additives, or alternative fuels. Therefore, substantial
amounts of these compounds are emitted into the atmosphere
and will be able to suffer chemical transformations. The main
degradation pathway of these compounds in the troposphere
To the best of our knowledge, this is the first determina-
tion of the rate coefficients of the reactions (1) and (2) under
atmospheric conditions. Kinetics results are rationalized in
terms of reactivity trends by comparison with other haloge-
nated alkenes. In addition, product studies using gas
chromatography–mass spectrometry (GC-MS) technique
under atmospheric conditions were carried out for the first
time for the reaction of OH radicals with CH = C(CH )CH Cl.
2 3 2
Consequently, degradation pathways in the atmosphere are
discussed.
[
1]
is reaction with OH radicals or solar photolysis.
-Chloro-2-methyl-1-propene is used as an intermediate for
3
the synthesis of organic compounds and pesticides or as an
additive in the textile industry and perfumery. In some coun-
tries, 3-chloro-2-methyl-1-propene is used as an insecticide
[
2]
for grain plagues, snuff plagues, and soil.
Furthermore,
3
-chloro-2-methyl-1-propene can be dissolved in droplets and
aerosols, hydrolyze, and undergo further oxidation in the liquid
phase.
Atmospheric lifetimes of the VOC studied in this work were
calculated taking into account the experimental rate coefficients
obtained in this work and compared with other homogeneous
sinks in the troposphere.
It is known that the atmospheric degradation of halogenated
unsaturated compounds is controlled mainly by chemical reac-
tion with OH radicals, contributing to tropospheric ozone pro-
duction and formation of other secondary photooxidants in
[3]
polluted areas.
EXPERIMENTAL
The reaction of chlorine atoms with VOCs is considered of
potential relevance in the marine troposphere where significant
All the experiments were performed in an 80-liter Teflon bag located
in a wooden box with the internal walls covered with aluminum foil.
Measured amounts of the organic reactants were flushed from cali-
brated bulbs into the bag through a stream of nitrogen or synthetic
air. The bag was then filled to its full capacity at atmospheric pressure
[
4,5]
chlorine atoms concentration could be present.
In addition,
the detection of these species in midcontinental areas has
expanded the potential impact of Cl to tropospheric oxidation
[6,7]
chemistry.
Knowledge of the rate coefficients for the reac-
tions with tropospheric oxidants like OH radicals and Cl atoms,
as well as the degradation pathways are required to estimate
the persistence, fate, and harmful effects of the chloroalkenes
in the atmosphere.
*
Correspondence to: Mariano A. Teruel, INFIQC (CONICET), Departamento de
Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de
Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.
E-mail: mteruel@fcq.unc.edu.ar
In this work, we report the rate coefficient of the reaction of
3
2 3 2
-chloro-2-methyl-1-propene (CH =C(CH )CH Cl) with OH radicals
and Cl atoms at 298 K and 760 Torr:
a C. Rivela, R. G. Gibilisco, M. A. Teruel
INFIQC (CONICET), Departamento de Fisicoquímica, Facultad de Ciencias
Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000,
Córdoba, Argentina
CH2 ¼ CðCH3ÞCH2Cl þ OH→Products
J. Phys. Org. Chem. 2015, 28 480–484
(1)
Copyright © 2015 John Wiley & Sons, Ltd.

GAS-PHASE OXIDATION OF CH2 = C(CH3)CH2CL
with nitrogen or air. Chlorine atoms were generated by photolysis at
The initial concentrations used in the experiments were in the range
1
3
ꢀ3
254 nm of oxalyl chloride (ClC(O)C(O)Cl) :
of 224–262 ppm (1 ppm = 2.46 × 10 molecule cm
60 Torr of total pressure) for 3-ClMP. The concentration of Cl
from 190 to 220 ppm in around 750 Torr of N or air.
at 298 K and
7
2
ranged
2
CICðOÞCðOÞCl→2Cl þ 2CO
(3)
The analytical technique employed for qualitative identification of
the products formed after irradiation was GC-MS on a Shimadzu
GC-MS QP 5050 spectrometer equipped with a capillary column
VF-5MS (5% phenyl, 95% dimethylpolysiloxane) of 30 m × 0.25 mm.
Gas samples were removed from the Teflon bag using solid phase
OH radicals were generated by ultraviolet (UV) irradiation at 254 nm
of H
2 2
O :
microextraction (SPME) as
a preconcentration technique of the
H2O2 þ hv→2OH
(4)
analytes. The SPME technique is based on the extraction of analytes
from the sample matrix using a fused silica fiber generally cover with
an absorbent polymer, followed by desorption of analytes by temper-
ature on the injection port. In this work a [divinylbenzene/Carboxen/
polydimethylsiloxane (DVB/CAR/PDMS)]fiber was used for all
compounds. The exposure time was 15 and 3 min of desorption in
the injection port.
Reaction mixtures consisting of a reference organic compound and
the sample organic reactant, diluted in N , were prepared in the
reaction chamber and left to mix, prior to photolysis, for approximately
h. Measured amounts of the reagents were flushed from calibrated
Pyrex bulbs into the collapsible reaction chamber by a stream of zero
grade N , and the bag was then filled with the zero grade N . Before
each set of experiments, the bag was cleaned by filling it with a mixture
of O and N which was photolyzed for 15–25 min using six germicidal
lamps (Philips 30 W; Koninklijke Philips N.V., Amsterdam, Netherlands)
with a UV emission at 254 nm, to produce O . After this procedure,
the bag was cleaned again by repeated flushing with N and
2
1
2
2
MATERIALS
2
2
The following chemicals, with purities as stated by the
supplier, were used without further purification: N2 (AGA,
3
2
9
9.999%; American Gas Corporation, Washington, DC, USA),
checked before performing the experiments by GC that there were
no observable impurities.
synthetic air (Air Liquide, 99.999%; Paris, France), 3-chloro-2-
methyl-1-propene (Merck, 97%; Kenilworth, NJ, USA), methyl
methacrylate (Aldrich, 99%; Sigma-Aldrich, St. Louis, MO,
USA), allyl acetate (Aldrich, 99%), vinyl propionate (Aldrich,
Periodically, gas samples were removed from the Teflon bag using
calibrated gas syringes. The organics were monitored by GC (Shimadzu
GC-14B; Shimadzu Corp., Kyoto, Japan) coupled with flame ionization
detection, using a Porapak Q column held at a temperature of 160 °C
for this compound.
9
8%), oxalyl chloride (Aldrich, 99%), and oxygen peroxide
(
Ciccarelli, 60 wt.%; Farmaceutici Dottor Ciccarelli, Milano,
Italy).
In the presence of the oxidant X (Cl atom or OH radical), 3-chloro-
2
-methyl-1-propene (3-ClMP) and the references decay through the
following reactions:
RESULTS AND DISCUSSION
Relative rate coefficients for the reactions of OH radicals and Cl
atoms with 3-ClMP were determined by comparing the OH or
Cl reaction with the chloroalkene studied with the reference
compounds from Eqn (7). The data were fitted to a straight line
by the linear least-squares procedure.
X þ 3-ClMP
(5)
(6)
X þ Reference→products
The losses of 3-ClMP by OH radicals or Cl atoms are shown
with different reference compounds in Figures 1 and 2. For each
reaction studied, four runs were performed for the rate coeffi-
cient determination; however, for the sake of clarity, only one
example is displayed in Figures 1 and 2.
Provided that the reference compound and the reactant are lost only
by reactions (5) and (6), then it can be shown that
ꢀ½
3-ClMPꢁ0
ꢁ
k5
k6
ꢀ
½Referenceꢁ0
ꢁ
ln
¼
ln
(7)
½
3-ClMPꢁt
½Referenceꢁt
The data on relative rate coefficients k3-ClMP/kReference and
absolute rate coefficients k3-ClMP at room temperature (298 K)
are presented in Table 1. It is gratifying to note the agreement
between the experiments conducted with different reference
compounds. The rate coefficients obtained by averaging the
values from different experiments were the following:
where [3-ClMP]
0
, [Reference]
0
, [3-ClMP]
t
, and [Reference]
t
are the concen-
trations of the 3-ClMP and the reference compound at times t = 0 and t,
respectively, and k and k are the rate coefficients of reactions (5) and
6), respectively.
The relative rate technique relies on the assumption that both 3-ClMP
5
6
(
and the reference organics are removed solely by reaction with the ox-
idant species X (Cl or OH). To verify this assumption, mixtures of oxalyl
kOH ¼ ð3:23±0:35Þꢂ10ꢀ11cm3 moleculeꢀ1
s
ꢀ1
2
chloride or hydrogen peroxide with N or air with both organics were
prepared and allowed to stand in the dark for 2 h. In all cases, the
reaction of the organic species with the precursor of X (ClC(O)C(O)Cl
or H
2
O
2
), in the absence of UV light, was of negligible importance over
kC1 ¼ ð2:10±0:78Þꢂ10ꢀ10cm3molecule
ꢀ1 ꢀ1
s
the typical time periods used in this work. Additionally, to test for
possible photolysis of the reactants used, mixtures of 3-ClMP in nitro-
gen or air, in the absence of oxalyl chloride or hydrogen peroxide,
were irradiated using the output of all germicidal lamps surrounding
the chamber for 30 min. No photolysis of any of the reactants was
observed.
The errors quoted are twice the standard deviation arising
from the least-squares fit of the straight lines, to which we have
considered also the corresponding error on the reference rate
coefficients.The following compounds were used as reference
J. Phys. Org. Chem. 2015, 28 480–484
Copyright © 2015 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/poc

C. RIVELA, R. G. GIBILISCO AND M. A. TERUEL
0
0
0
0
0
,8
,6
,4
,2
,0
OH þ CH2 ¼ CðCH3ÞCðOÞOCH3→products
OH þ CH2 ¼ CHCH2OCðOÞCH3→products
Cl þ CH2CðCH3ÞCðOÞOCH3→products
Cl þ CH2 ¼ CHOCðOÞCH2CH3→products
(8)
(9)
(10)
(11)
ꢀ
11 [8]
ꢀ11 [9]
where k = (4.15 ± 0.32) × 10
,
k9 = (2.46 ± 0.02) × 10
,
8
ꢀ
10 [10]
ꢀ10.[11]
k10 = (2.82 ± 0.93) × 10
,
and k = (2.06 ± 0.36) × 10
All
11
3
ꢀ1 ꢀ1
the k values are in units of cm molecule
s
.
To the best of our knowledge, there are no other prior reported
values of the rate coefficients for the reactions (1) and (2) of OH
radicals and Cl atoms with 3-chloro-2-methyl-1-propene. Thus,
the present study is the first kinetic study of these reactions,
and therefore, no direct comparison with the literature can be
made. However, it is interesting to estimate and compare the rate
coefficient for the reaction of OH with 3-ClMP using the US EPA
0
,0
0,2
0,4
0,6
0,8
ln[(Reference) /(Reference) ]
0
t
Figure 1. Relative kinetic plot of the reaction of OH radical with 3-
chloro-2-methyl-1-propene using methyl methacrylate (●) and allyl
acetate (▼) as references at atmospheric conditions and 298 K
[
12]
AOPWIN program, which is based upon the structure–activity
[
13]
relationship (SAR) method described by Kwok and Atkinson.
The estimated OH rate coefficient by this method was
1
1
0
0
0
0
0
,2
,0
,8
,6
,4
,2
,0
ꢀ
11
3
ꢀ1 ꢀ1
3
.95 × 10
cm molecule
s . The SAR rate prediction for this
reaction is in a reasonable agreement, within the experimental
ꢀ
11
3
ꢀ1 ꢀ1
error, with the value of (3.23 ± 0.35) × 10
determined in this study.
cm molecule
s
Reactivity trends
Table 2 shows a comparison between the rate coefficients of the
reactions of OH radicals and Cl atoms with a series of haloge-
nated alkenes and the kinetic data obtained in this study for 3-
ClMP. It is possible to observe that the presence of different sub-
stituents produces significant variations on the rate coefficient
values. For example, comparing the rate k
of 3-ClMP
OH
ꢀ
ꢀ
11
11
3
ꢀ1 ꢀ1
0
,0
0,2
0,4
0,6
0,8
1,0
1,2
(3.23 × 10
(1.69 × 10
cm molecule
s
)
and
3-chloropropene
3
ꢀ1 ꢀ1 [16]
ln[(Reference) /(Reference) ]
cm molecule
s ),
it is possible to observe a
0
t
significant increase in the rate coefficient of 3-ClMP respect to
-chloropropene. This difference can be attributed to the pres-
ence of the -CH group as a H substituent attached to the olefinic
carbon. Both molecules are influenced by a negative inductive
effect on to the double bond induced by the chlorine substitu-
ent, but in the case of 3-ClMP, this effect appears to be overrid-
den by the methyl group attached at C2, generating a positive
inductive effect over the >C = C<.
Figure 2. Relative kinetic plot of the reaction of Cl atoms with 3-chloro-
-methyl-1-propene using methyl methacrylate (●) and vinyl propionate
♦) as references at atmospheric conditions
3
2
(
3
reactions: methyl methacrylate, allyl acetate, and vinyl propio-
nate to determine the rate coefficient of the reactions (1) and (2):
Table 1. Reference compound, measured rate coefficient ratios, k3-ClMP/kReference, and the obtained rate coefficients for the reac-
tions of OH radicals and Cl atoms with 3-chloro-2-methyl-1-propene at 298 K in 760 Torr of nitrogen
3
ꢀ1 ꢀ
Reaction
Reference
k
3-ClMP/kReference
k3-ClMP (cm molecule s )
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
11
11
11
11
11
10
10
10
10
10
CH = C(CH )CH Cl + OH
Methyl methacrylate
Methyl methacrylate
Allyl acetate
0.72 ± 0.03
0.85 ± 0.02
1.25 ± 0.05
1.34 ± 0.06
Average
0.81 ± 0.01
0.79 ± 0.02
1.01 ± 0.08
0.91 ± 0.02
Average
(3.00 ± 0.35) × 10
(3.52 ± 0.34) × 10
(3.08 ± 0.14) × 10
(3.30 ± 0.18) × 10
(3.23 ± 0.35) × 10
(2.26 ± 0.77) × 10
(2.20 ± 0.78) × 10
(2.08 ± 0.52) × 10
(1.85 ± 0.37) × 10
(2.10 ± 0.78) × 10
2
3
2
Allyl acetate
CH
2
= C(CH
3
)CH
2
Cl + Cl
Methyl methacrylate
Methyl methacrylate
Vinyl propionate
Vinyl propionate
wileyonlinelibrary.com/journal/poc
Copyright © 2015 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2015, 28 480–484

GAS-PHASE OXIDATION OF CH2 = C(CH3)CH2CL
Table 2. Rate coefficients of the reactions of OH radicals and
Cl atoms with a series of halogenated alkenes compared with
the kinetic data obtained in this study
A
1
1
10
Volatile organic
compound
kOH × 10
kCl × 10
3
ꢀ1 ꢀ1
3
ꢀ1 ꢀ1
(cm molecule
s
) (cm molecule
s )
a
b
CH = CHCH
3.01
3.23
2.64
2.10
2.40
2
3
c
c
CH = C(CH )CH Cl
2
3
2
d
e
CH = CHCH Cl
1.69f
2
2
g
CH = CHCH Br
1.66
1.64
1.23g
2
2
f
CH = CHCH F
0.49
2
a[14]
b[15]
2
c
This work.
B
d[16]
e[17]
f[18]
g[19]
Moreover, Table 2 shows the influence of the nature of the
halogen attached to the double bond of the alkenes. It is possible
to observe that the rate coefficient diminishes with the electro-
negativity of the halogen atom attached to the haloalkene. This
trend could be observed in reactions initiated with both oxidants,
OH radical and Cl atoms. However, the trend observed on the OH
rate coefficients are too small to affirm a real tendency influenced
by the electronegativity character of the substituents in the
molecule as it is in the case of the significant variation observed
in the rate coefficients of the Cl atoms initiated reactions
C
Figure 3. Gas chromatography–mass spectrometry chromatogram be-
fore (A) and after photolysis (B) of a mixture of 3-ClMP with H O in air
2 2
ꢀ
10
3
ꢀ1 ꢀ1
(
in 10
cm molecule
s ) :
at 298 K and atmospheric pressure. Chloropropanone was identified as
the unique product reaction by comparing the m/z mass fragmentation
[17–19]
kCH2 = CHCH2Cl =2.40> kCH2 = CHCH2Br =1.23> kCH2 = CHCH2F = 0.49.
Product identification
(
panel C) of the product peak centered at 4.2 min of retention time
In addition to the kinetic studies, the products of the reaction of
-ClMP with OH radicals were identified, as it is shown in Fig. 3. A
3
Consequently, the main fate of the 1-2-hydroxyalcoxy radicals
formed seems to be the decomposition channel, where the OH
preferably attacks the terminal carbon of the double bond. In
our experimental conditions, at NOx-free air, there are negligible
contributions of other molecular reaction channels such as isom-
first approach reveals that the main path of reaction is the elec-
trophilic addition of the OH radical to the double bond in either
carbon (C1 or C2) of the double bond, preferably to the terminal
[
20]
carbon of the double bond to generate a more stable radical.
The main reaction pathway of 3-ClMP toward OH radicals is
shown in Scheme 1:The reaction proceeds via an addition
mechanism of the OH radical to the double bond. The 1-2-
hydroxyalcoxy radical formed in the OH addition step decom-
2
erization or H abstraction by O molecules.
ATMOSPHERIC IMPLICATIONS
2
poses in the presence of O and in the absence of NO, leading
mainly to the corresponding carbonyl compound.
Chloropropanone was identified as the major product formed
from reaction (1). Fragments with m/e 43, 49, 77, 92, and 94
Atmospheric lifetimes, τ
calculated through the expression: τ
NO , and O . Table 3 lists the atmospheric lifetimes with respect
to the reaction with OH radicals, Cl atoms, NO radicals, and O
molecules for the chloroalkene studied in this work.
Tropospheric lifetimes are calculated assuming a 12 h aver-
x
, of the 3-ClMP studied in this work were
x
= 1/k [X] with X = OH, Cl,
x
3
3
(Fig. 3, panel C), characteristic of this compound were found in
3
3
[
21,22]
the mass spectrum of the 4.2 min retention time peak obtained
after irradiation of OH/3-ClMP/air mixture (Fig. 3, panel B). In
addition, an experiment was performed by GC-MS with a pure
standard of chloropropanone to confirm the identity of the peak
obtained at 4.2 min of retention time.
The reaction product found, together with the observed reac-
tivity trends, suggests that the reaction proceeds via an addition
mechanism of the OH radical to the double bond similar to that
6
ꢀ3 [23]
age concentration of OH of 2 × 10 molecule cm
.
The
lifetime of the reaction with OH radicals is 9 h, and the corre-
sponding lifetimes of the reaction with chlorine is around
5 days, considering a global average chlorine concentration of
4
ꢀ3 [24]
1 × 10 atoms cm
,
while the concentration of O molecules
3
11
ꢀ3[25]
and NO3 radicals are 7 × 10 molecule cm
and
[
5,6]
8
ꢀ3 [26]
proposed by Atkinson for the OH radical addition to alkenes.
5 × 10 radical cm
,
respectively.
J. Phys. Org. Chem. 2015, 28 480–484
Copyright © 2015 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/poc

C. RIVELA, R. G. GIBILISCO AND M. A. TERUEL
NOx, pressure and temperature ranges to be included in more
realistic atmospheric models.
Acknowledgements
The authors wish to acknowledge MINCYT (Argentina)-PICT
2012-1740, CONICET(PIP)- GI 2010-2012-cod: 11220090100623
(Argentina), and SECyT-UNC-14306/24 (Córdoba, Argentina) for
financial support of this research. C. R. and R. G. G. wish to
acknowledge the CONICET, CONACYT, and PRI UNC-AUGM for
fellowships and support.
REFERENCES
[
[
[
1] G. Moortgat , Chemical, Physical and Biogenic Processes in the Atmo-
sphere Max-Planck-Institut fur Chemie (Otto-Hahn-Institut), Obernai,
France, 2001.
2] U.S. Department of Health and Human Services Secretary Kathleen
Sebelius released the 12th Report on Carcinogens, http://ntp.
niehs.nih.gov/ntp/roc/twelfth/roc12, 2011.
3] A. Mellouki , G. Le Bras , H. Sidebottom , Chem. Rev. 2003, 103,
5
077–5096.
[4] B. Finlayson-Pitts , J. Res. Chem. Intermed. 1993, 19, 235–249.
[5] W. C. Keene , D. J. Jacob , S. M. Fan , Atmos. Environ. 1996, 30, 1–3.
[6] J. A. Thornton , J. P. Kercher , T. P. Riedel , N. L. Wagner , J. Cozic , S.
Holloway , W. P. Dube , G. M. Wolfe , P. K. Quinn , A. M. Middlebrook ,
B. Alexander , S. Brown , Nature. 2010, 464, 271–274.
[
7] L. H. Mielke , A. Furgeson , H. D. Osthoff , Environ Sci. Technol. 2011,
45, 8889–8896.
Scheme 1. Reaction mechanism proposed for the main pathway of re-
action of 3-ClMP with OH radicals
[8] M. B. Blanco , R. A. Taccone , S. I. Lane , M. A. Teruel , Chem. Phys. Lett.
006, 429, 389–394.
2
[
9] C. Ferrari , A. Roche , V. Jacob , P. Foster , P. Baussand , Int. J. Chem.
Kin. 1996, 28, 609–614.
Table 3. Estimated tropospheric lifetimes of the 3-chloro-2-
methyl-1-propene with different tropospheric oxidants
[
[
[
10] M. B. Blanco , I. Bejan , I. Barnes , P. Wiesen , M. A. Teruel , Atmos.
Environ. 2009, 43, 5996–6002.
11] M. A. Teruel , M. Achad , M. B. Blanco , Phys. Chem. Lett. 2009, 479,
25–29.
a
a
Cl
b
c
Volatile organic compound
τ
OH
τ
τ
NO3
τ
O3
12] W. M. Meylan , P. H. Howard , Chemosphere. 1993, 26, 2293–2299.
3
-Chloro-2-methyl-1-propene
9 h 5 days 1 day 4 days
[13] E. C. Kwok , R. Atkinson , Atmos. Environ. 1995, 29, 1685–1695.
[
[
[
[
[
14] R. Atkinson , D. L. Baulch , R. A. Cox , Hampson Jr, , R. F. Kerr ,
a
This work.
J. A. Troe , Phys. Chem. 1989, 18, 881–1097.
15] M. J. Ezell , W. Wang , A. A. Ezell , G. Soskin , B. J. Finlayson-Pitts ,
Phys. Chem. Chem. Phys. 2002b, 4, 5813–5820.
b[21]
c[22]
16] E. C. Tuazon , R. Atkinson , S. M. Aschmann , Int. J. Chem. Kinet. 1990,
2
2, 591–602.
17] D. Grosjean, E. L. Williams, Atmos. Environ. Part A 26. 1992,
395–1405.
1
In light of these results, the atmospheric lifetime of 3-ClMP is
determined by the OH-initiated degradation during day time
and at night time; when the concentration of OH decay and
the NO radical will not be affected by photolysis, the nitrate rad-
3
ical is the main sink of this halogenated compound. Moreover, in
marine areas where the chlorine concentration can reach a peak
18] J. Albaladejo , B. Ballesteros , E. Jimenez , D. de Mera , E. Martínez ,
Atmos. Environ. 2003, 37, 2919–2926.
[19] J. Albaladejo , A. Notario , C. A. Cuevas , B. Ballesteros , E. J. Martinez ,
Atmos. Chem. 2003, 45, 35–50.
[
20] M. B. Smith , J. March , March’s Advanced Organic Chemistry: Reac-
tions, Mechanisms, and Structure John Wiley & Sons, Hoboken,
New Jersey, 2007.
5
ꢀ3 [27,28]
as high as 1 × 10 atoms cm
,
Cl chemistry could compete
[21] R. W. S. Aird , C. E. Canosa-Mas , D. J. Cook , G. Marston , P. S. Monks ,
or dominate the OH radical chemistry.
R. P. Wayne , E. J. Ljungstrom , Chem. Soc. Faraday Trans. 1992, 88,
1
093–1099.
The short lifetimes estimated, in order of hours, indicate that
the compound is likely to be rapidly removed in the gas phase,
being the reaction with OH radicals, the major loss process.
Losses of 3-chloro-2-methyl-1-propene by photolysis can be
considered negligible because it is expected, by the UV–Vis spec-
trum of halogenated alkenes, to be photolytically stable in the
actinic region of the electromagnetic spectrum.
[
[
[
22] D. Johnson , A. R. Rickard , C. D. McGill , G. Marston , Phys. Chem.
Chem. Phys. 2000, 2, 323–328.
23] R. Hein , P. J. Crutzen , M. Heimann , Global Biogeochem. Cycles.
1997, 11, 43–76.
24] O. W. Wingenter , M. K. Kubo , N. J. Blake , T. W. Smith , D. R. Blake ,
F. S. Rowland , J. Geophys. Res. 1996, 101, 4331–4340.
25] J. A. Logan , J. Geophys. Res. 1985, 90, 463.
[
[
26] Y. Shu , R. Atkinson , J. Geophys. Res. 1995, 100, 7275.
Because kinetics and product distribution data are consider-
ably scarce, further experiments should be performed to obtain
product yields of the different channels of the alcoxy radical
formed. This information could contribute to elucidate and to
give confidence on the atmospheric degradation mechanism of
this chloroalkene and their derivatives in different scenarios of
[27] T. P. Riedel , N. L. Wagner , W. P. Dubé , A. M. Middlebrook , C. J.
Young , F. Öztürk , R. Bahreini , T. C. VandenBoer , D. E. Wolfe ,
E. J. Williams , J. M. Roberts , S. S. Brown , J. A. Thornton ,
J. Geophys. Res. Atmos. 2013, 118, 8702–8715.
[
28] H. B. Singh , G. L. Gregory , B. Anderson , E. Browell , G. W. Sachse , D. D.
Davis , J. Crawford , J. D. Bradshaw , R. Talbot , D. R. Blake , D. Thornton ,
R. Newell , J. Merrill , J. Geophys. Res. 1996, 101, 1907–1917.
wileyonlinelibrary.com/journal/poc
Copyright © 2015 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2015, 28 480–484