Arabian Journal of Chemistry (2017) 10, S665–S670

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

A new look at the b-pinene–ozone reaction using

the atmospheric pressure reactor
Fadel Alwedian *

Department of Chemistry, Faculty of Science, Tafila Technical University, P.O. Box 179, Tafila 66110, Jordan

Received 8 April 2012; accepted 13 November 2012

Available online 23 November 2012

KEYWORDS Abstract b-Pinene–ozone reaction without a scavenger was performed for the first time, in the sta-
Static bag reactor; tic bag atmospheric pressure reactor coupled into ion trap mass spectrometer. The diffusion coef-
Gas-phase reactions; ficients and evolution times (t10–90%) of multiple fragments were used to characterize their neutral
Ozone; parent ions. Mainly identified products (yields in parentheses) of the reaction such as nopinone
b-Pinene; (0.58 ± 0.05), formaldehyde (0.19 ± 0.05), HCOOH, CH3COOH, and acetone were successfully
Evolution time associated with their fragment ions. While, 3-hydroxy-nopinone and cis-pinic acid were unsuccess-
fully associated with their fragments because of the lack of available standard reference mass spec-
tra of these compounds for comparison. Meanwhile, two short-lived intermediates were detected
with tentative contributions of products of masses 70 and 97.
ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction leading to the formation of photochemical air pollution in

Alkenes are an important fraction of nonmethane hydrocar-
bons which are introduced in the atmosphere from anthropo-
genic and biogenic sources (Atkinson, 1997; Seinfeld and
Pandis, 1998). They are the major components in gasoline
fuels, automobile exhaust emission, and ambient air in the
highly urbanized areas. In troposphere, they react with O3,
OH, and NO3 which result in a complex series of chemical
transformations and physical sink reactions in the atmosphere
* Mobile: +962 03 22 50 326; fax: +962 03 22 50 002.
E-mail address: alwedfad@yahoo.com.
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
http://dx.doi.org/10.1016/j.arabjc.2012.11.006
1878-5352 ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
urban and rural areas (Atkinson and Arey, 1998; Seinfeld
and Pandis, 1998).
The kinetics and products of the gas phase reaction of ozone
with alkene have been extensively studied. The ozone–alkene
reaction proceeds via the addition of ozone to the alkene dou-
ble bond, followed by the decomposition of resulting molozo-
nide to yield carbonyl compounds (primary products) and
initially energy-rich Criegee biradical, the Criegee biradical
can undergo unimolecular decomposition or isomerization to
yield the secondary products (Atkinson and Arey, 1998;
Seinfeld and Pandis, 1998). The kinetics for large ozone/alkene
reactions are well understood, while there are less available
data concerning mechanism and product of small alkenes under
atmospheric conditions (Atkinson, 1997; Atkinson and Arey,
1998; Guenther et al., 1995; Hasson et al., 2001; Seinfeld and
Pandis, 1998; Tuazon et al., 1998).
An important fraction of nonmethane hydrocarbons are
the monoterpenes (C10H16), a-pinene and b-pinene which
S666
are among the most abundant terpenes emitted into the
atmosphere by vegetation (Atkinson and Arey, 1998; Atkin-
son and Aschmann, 1993; CalogIrou et al., 1999; Grosjean
et al., 1993; Hakola et al., 1994; Guenther et al., 1995;
Hatakeyama et al., 1991; Librando and Tringali, 2005).
The gas-phase oxidation reactions of terpenes have been
the subject of several investigations. Major products that re-
sulted from a-pinene oxidation (Hatakeyama et al.,1989;
Hatakeyama et al., 1991; Librando and Tringali, 2005;
Venkatachari and Hopke, 2008) are pinonaldehyde, norpi-
nonaldehyde, formaldehyde, CO, and CO2; and nopinone
and formaldehyde from the oxidation of b-pinene (CalogI-
rou et al., 1999; Hatakeyama et al., 1989; Hatakeyama
et al., 1989; Jay and Stieglitz, 1987; Hakola et al., 1994;
Winterhalter et al., 2000). However, very little is known
about the atmospheric fate of these terpene oxidation prod-
ucts (Atkinson, 1997; CalogIrou et al., 1999; Librando and
Tringali, 2005; Seinfeld and Pandis, 1998; Winterhalter
et al., 2000). Scheme 1 shows the chemical structures of a-
pinene, b-pinene, nopinone, pinonaldehyde, and
norpinonaldehyde.
The static bag atmospheric pressure reactor coupled into
ion trap mass spectrometer (ITMS) (Wedian and Atkinson,
2010) is convenient to use because it permits continuous, sen-
sitive, and specific monitoring of the gas-phase reactions by
the ITMS. The ITMS is potentially valuable as a detector
since it provides various clean chemical ionization modes
and Tandem MS/MS experiments which can be used for
structure determinations. In addition, the ITMS is an inex-
pensive bench top instrument. The static bag atmospheric
pressure reactor can provide kinetic measurements in the
range of 10–200 s, as well as calibration of product yield mea-
surements (Wedian and Atkinson, 2010).
The objective of this work is to demonstrate the use of the
static pressure reactor to study the gas phase b-pinene–ozone
reaction in order to validate the detection of the primary and
secondary products and to detect new stable intermediates
and then identify their chemical formulae. The time evolutions
(t10–90%) of fragment ions of products in the static bag atmo-
spheric pressure reactor coupled into ion trap mass spectrom-
eter were determined and used to correlate the ions to their
distinct neutral species.
(a) (b)
(d) (e)
Scheme 1 The chemical structures of a-Pinene and b-pinene and their major oxidation products: (a) a-pinene (b) b-pinene (c) nopinone
(d) pinonaldehyde (e) pinic acid (f) norpinonaldehyde.
F. Alwedian
2. Experimental
2.1. The ion trap mass spectrometer
The reactor used in this work contained a flowing reacting
atmospheric pressure gas mixture that was admitted to an ion
trap mass spectrometer through a flow restrictor for analysis.
The custom reactor was coupled to a Varian Saturn 2000 ion
trap mass spectrometer via the 35.6 mm outer diameter direct
insertion probe interface. The reactor interface was inserted into
the vacuum adaptor installed in the GC transfer line inlet port.
The experiments reported here were conducted using the
methane chemical ionization. The mass spectra (m/z 30–250)
were collected using the ion trap control software in the GC
mode. The WSearch reduction program was used to convert
the measured mass spectra to the ASCII form for further
analysis.
2.2. Static reactor setup
The reactor setup was described in a previously published work
(Wedian and Atkinson 2010). Briefly, all reactions were carried
out in a 12 L Teflon bag. One side of the bag was connected to
mass spectrometer via a custom made interface while the other
side was connected to a 3-way valve. In one valve position, the
valve admitted a He flow sufficient to supply the mass spec-
trometer interface and to maintain the bag shape. He served
as the gas medium for reactions as well as the carrier gas that
delivered the reactants and products into the mass spectrome-
ter. In the second valve position, the bag was connected to a
diaphragm pump to evacuate the bag’s contents between suc-
cessive experiments. The vapor phase of b-pinene and ozone,
was injected with a syringe through a hole in the side of the bag.
2.3. Static reactor operation
The reactions were performed in this experiment by filling with
He then taking the background of the bag, after few minutes,
the b-pinene (initial calculated concentration of 6 ppmv) was
injected into the bag using a 25 ml syringe until the signal
reached the steady state, and then finally, excess amount of
(c)
(f)
A new look at the b-pinene–ozone reaction usingthe atmospheric pressure reactor S667

purified ozone in nitrogen was introduced into the bag using a
50 mL syringe to complete the reaction. It is expected that the
primary and secondary products of ozonation are formed in
few seconds. Moreover, it is expected all reactants and prod-
ucts were exposed to similar conditions of wall reactions, dilu-
tion, and transport of all products (Wedian and Atkinson
2010). Between experiments, the reactor bag was flushed and
filled several times with He to remove the contents from the
previous experiment. The ozone concentration in the reactor
was determined in separate experiments by exhausting the
reactor through a Dasibi ozone instrument.
2.4. Chemicals
Chemicals and gases used in these experiments were: b-pinene
(Fluka, 99.5%), acetone (Aldrich, 99%), nopinone (Aldrich,
98%), formaldehyde (Aldrich, 36.5–38.0%), He (commercial
grade 99.998, Airgas Inc.), Methane (UHP 99.9995, Airgas
Inc.), N2 (UHP 99.9995, Airgas Inc.), and O2 (UHP 99.9995,
Airgas Inc.).
3. Results and discussion
3.1. b-pinene–ozone reaction
Fig. 1A shows the mass spectrum of the reaction mixture at
long reaction time, after subtracting the pre-reaction back-
ground. The mass spectrum is dominated by ions of unreacted
b-pinene and nopinone which produce strong peaks at m/z 57,
59, 69, 83, 97, and 107 and a few weaker fragments. Fig. 1B
shows the mass spectrum of b-pinene which is dominated by
major fragments (m/z = 67, 81, 93, 107, and 121), Fig. 1C is
chemical ionization mass spectrum of pure Nopinone which
is dominated by the fragments (m/z = 55, 69, 81, 93, 97,
107, 135 and 137). The CI mass spectrum of pure pinene and
nopinone was measured in separate experiments. Multiplying
the reference b-pinene and nopinone CI spectra by an appro-
priate weighting factor, and then subtracting them from the
b-pinene–ozone reaction mixture (Fig. 1A) allowed the contri-
bution of nopinone and un-reacted b-pinene to be removed
and Fig. 1D shows the resulting mass spectrum. The other

69
100
57
59
A
83
Relative Intensity

80
60 45
40 31 97
107
20 177
0

81
100
93
B
Relative Intensity

80
60
40
107
121 136
20
0

81
100 C
Relative Intensity

80
93
60
40 109
57 138
20

350 69
300
57 D
250 59 83
Intensity

200 31
45
150
100 97 100
50
0
40 60 80 100 120 140 160 180
m/z

Figure 1 (A) The mass spectrum of the b-pinene–ozone reaction mixture after subtraction of the ozone background. The spectrum is
dominated by b-pinene and nopinone. (B) The mass spectrum of b-pinene. (C) The mass spectrum of nopinone. (D) The net mass
spectrum of the b-pinene–ozone mixture after subtracting contributions of ozone, pure b-pinene, and pure nopinone.
S668 F. Alwedian

200 80
A B
150 60

Intensity
m/z 57
100 40

m/z 61
m/z 93
50 20

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
160 150
C D
120 m/z 57
100
Intensity

80 m/z 55
m/z 83
50
40 m/z 60
m/z 96

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
m/z m/z

Figure 2 Function (1 exp ( a1t)) a2, with adjustable coefficients, used to fit the initial growth of product ions of b-pinene /O3 in the
static bag reactor: (A) the growth ion profile of m/z 57 and 93 of nopinone. (B) The growth ion profile of m/z 61. (C) The growth ion
profile of m/z 55 and 60. (D) The growth ion profiles of m/z 57, 83, and 96.

Table 1 Major ions of the b-pinene–ozone reaction observed Table 2 The molar masses of the reported primary and
by the ion trap using CH4 chemical ionization, from Fig. 1A secondary products of the b-pinene–ozone reaction Winterhal-
and D, listed in order of decreasing rise coefficients. ter et al. (2000).
m/z Rise Tentative assignment Compound name Molar mass (g/mol) Chemical formula
coefficient a, s 1
of neutral parent
Carbon monoxide 28 CO
31 0.01639 HCHO Formaldehyde 30 HCHO
93, 81, 107, 138 0.01512 Nopinoneb Carbon dioxide 44 CO2
70 0.01213 C4H5O Formic acid 46 HCOOH
45, 55, 56,60, 69, 99 0.01113 – Nopinone 138 C9H14O
47 0.01012 HCOOH 3-Hydroxy-nopinone 154 C9H14O2
97 0.009211 C5H4O2 cis-Pinic acid 186 C9H14O4
57, 71, 72, 82, 83, 96, 98 0.009013 –
59 0.009009 Acetone
61 0.008013 CH3COOH
characterize the ions as a primary product by showing a short
a
Obtained by fitting (1 exp ( a1t)) a2 to measured signals vs. revolution time or as a secondary product by showing a
time after injection of excess O3 (with O2) in He into an unstirred relatively long revolution time (Table 1).
bag reactor containing b-pinene. It was concluded from the differences in the fitted rise
b
Data from Fig. 1C.
coefficients in Table 1 that an ion with a unique rise coefficient
corresponds to a distinct neutral species in the atmospheric-
pressure reactor, moreover, the multiple ions with the same
products of the b-pinene–ozone reaction are now more easily rise coefficient in Fig. 1 also belong to a single species and
recognized (m/z 31, 45, 47, 57, 59, 69, 83, and 97). those fragments are produced by the low-pressure chemical
The logistic growth function (1 exp ( a1t))a2, where a1 is ionization of the single species inside the ion source of the
the rise coefficient adjustable in (s 1), and a2 (the upper limit of ITMS.
the growth), was used to fit the initial growth of product ions The ions in Fig. 1A with (m/z 57, 81, 93, 109, 135 and 137)
vs. time after injection of excess ozone into the unstirred reac- are associated with nopinone (scheme 1C) which is one of the
tor (Fig. 2). This experiment was carried out by injecting excess two primary products of the b-pinene–ozone reaction. Of the
ozone into the reactor containing b-pinene in order to monitor ions in Fig. 1D, the growth of m/z = 31, was satisfactorily fit-
the behavior of the unreacted b-pinene and the products of ted with the logistic growth function, with an evolution time of
b-pinene–ozone reaction (Fig. 1A). The measured growth coef- 21 ± 7 s, and is associated with protonated formaldehyde
ficients and evolution times of all ions (Fig. 1D) were used to which is the other primary product identified by Winterhalter
A new look at the b-pinene–ozone reaction usingthe atmospheric pressure reactor
Table 3 Yields of the primary products from the reaction of ozone with b-pinene.
Static bag reactor Winterhalter et al. (2000)
Formaldehyde 0.58 ± 0.05 0.65 ± 0.04
Nopinone 0.19 ± 0.05 0.16 ± 0.04
et al. (2000), Atkinson (1997), and Grosjean et al. (1996). This
conclusion was supported by MS/MS data.
The growth of m/z = 47, is tentatively associated with
HCOOH, which showed a slow evolution time, diagnostic of
a secondary product. The MS/MS experiments confirmed this
conclusion. Winterhalter et al. (2000) showed that HCOOH is
a secondary product resulting from the decomposition of the
C9-Criegee intermediate and other radicals. The growth of
m/z = 59 is associated with presumably protonated acetone,
which is probably present as an impurity in the reactor or as
a product of the reaction of ozone with an olefinic impurity
(Grosjean et al., 1993). The MS/MS experiments supported
this conclusion.
The ion at m/z = 61 showed a slow evolution time, charac-
teristic of a secondary product which is a contribution of a
protonation product of mass 60 such as CH3COOH. This con-
clusion was confirmed by the MS/MS data. Winterhalter et al.
(2000) who used ion chromatograms were able to identify
traces of CH3COOH as a result of the decomposition of unsta-
ble intermediates such as acetaldehyde monopeacetate.
Fig. 1D showed the presence of overlapped multiple frag-
ments which may result from at least two unidentified second-
ary products. The mathematical fitting was used to correlate
the fragments in clusters, Table 1; the first cluster of ions at
m/z 45, 55, 56, 60, 69 and 99 showed a slow evolution time
of 55 ± 19 s which is a characteristic of a secondary product;
and another cluster of ions at m/z 57, 71, 72, 82, 83, 96 and 98
are fragments of the other secondary product of the
b-pinene–ozone reaction with an induction delay of
48 ± 14 s. Based on Winterhalter et al. (2000) work, these
fragments are associated with two detected secondary prod-
ucts: 3-hydroxy-nopinone and the cis-pinic acid. The MS/MS
experiments for selected m/z from each cluster showed severe
fragmentation and produced no unique ion fragment in the
daughter mass spectra making it difficult to correlate them
to either possible compound. Up to the time of doing these
experiments, standard mass spectra of pure 3-hydroxy-nopi-
none and the cis-pinic acid were not available in our research
group which limited the ability to get a positive correlation of
ions to their neutral compound.
The main products of the b-pinene–ozone reaction
identified by Winterhalter et al. (2000) are HCHO, nopinone,
3-hydroxy-nopinone, CO2, CO, HCOOH, the secondary
ozonide of b-pinene, and cis-pinic acid. There were two
primary products of the b-pinene–ozone reaction identified
by Winterhalter et al. (2000), Atkinson (1997), and Grosjean
et al. (1996): formaldehyde and nopinone. Table 2 lists all
primary and secondary products of the b-pinene–ozone
reaction and their molar masses identified in the literature.
3.2. New short-lived intermediates
This reactor was able to detect new ions with unique rise
coefficients which could have possibly resulted from contribu-
tions of thermalized neutral intermediates:
S669
Grosjean et al. (1993) Hakola et al. (1994)
0.42 –
0.22 0.23 ± 0.05
The ion at m/z = 70 showed a slow evolution time,
diagnostic for a secondary product which may associate with
a neutral parent ion or a short-lived neutral intermediate
yielding m/z = 70 on protonation. The MS/MS spectrum of
m/z = 70 dominated with (m/z 70, 52 (base peak), and 30)
which did not provide enough information to reach a definite
conclusion regarding the nature of this ion. The tentative
chemical formula of m/z = 70 is C4H5O.
The ion at m/z = 97 is associated with a secondary
component with an induction delay of 42 ± 19 s; The
MS/MS spectrum of m/z = 97 dominated with (m/z 97, 79,
69 (base peak), and 44), these data did not provide more infor-
mation to support whether the m/z = 97 is an unidentified new
secondary product or a contribution of short-lived intermedi-
ate. It is believed that m/z = 97 may have a tentative chemical
formula of C5H4O2.
3.3. Calibrations and yields of the primary products
The calibrations of the primary products and their yields were
performed without a scavenger in a similar procedure that was
described in detail in previous work (Wedian and Atkinson
2010). The yields of formaldehyde and nopinone were 0.58
(±0.05), and 0.19 (±0.05), respectively. Table 3 shows a
comparison of the yields of this work and other previous
b-pinene–ozone studies.
The limitations of this reactor in its present state of devel-
opment lie mainly with the lack of accurate identification of
the parent ion mass of fragments; Moreover, the system does
not exclude any possible contribution of thermalized neutral
fragments. Those limitations could be overcome when a stan-
dard mass spectra library of the ion trap mass spectrometer is
available for most detected compounds.
4. Conclusion
The b-pinene–ozone reaction was studied without scavenger in
a atmospheric bag reactor coupled into ITMS. The detected
ions of the products showed different rise coefficients in the
static reactor. The observed differences in rise coefficients were
used to distinguish the ions and then associated with their
possible parent ions. In this system, at least two secondary
product fragments were failed to be correlated to their possible
parent ions. The reactor showed a potential advantage in the
gas phase studies by the detection of short-lived intermediates
at m/z = 70 and 97.
Acknowledgments
The author would like to acknowledge the financial support of
the Tafila Technical University (Grand number 176/2008), and
the author would like to thank the Portland State University’s
atmospheric research group for their inspiration.
S670
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