Rate coefficients and product yields from reaction of OH with 1-penten-3-ol, (Z)-2-penten-1-ol, and allyl alcohol (2-propen-1-ol)

Article abstract of DOI:10.1021/jp0041712

The atmospheric chemistry of two recently discovered biogenic volatile organic compounds (VOCs), 1-penten-3-ol and (Z)-2-penten-1-ol, has been studied at 298 K using an environmental chamber/FTIR apparatus. Rate coefficients for their reaction with OH (determined by the relative rate technique) were found to be (6.7 ± 0.9) × 10^-11 cm³ molecule^-1 s^-1 and (10.6 ± 1.5) × 10^-11 cm³ molecule^-1 s^-1 for 1-penten-3-ol and (Z)-2-penten-1-ol, respectively. Products observed (with molar yields in brackets) from the OH-initiated oxidation of these species in 1 atm air at 298 K were glycolaldehyde (47 ± 6%) and formaldehyde (35 ± 4%) from 1-penten-3-ol; and propanal (91 ± 13%), glycolaldehyde (87 ± 11%) and formaldehyde (11 ± 2%) from (Z)-2-penten-1-ol. As a model for the more complex unsaturated alcohols, similar studies were also carried out on a simpler species, allyl alcohol (2-propen-1-ol, CH₂=CHCH₂OH). Reaction of this species with OH was found to proceed with a rate coefficient of (4.5 ± 0.6) × 10^-11 cm³ molecule^-1 s^-1. Products observed were formaldehyde (98 ± 12%), glycolaldehyde (90 ± 12%), and acrolein (5 ± 2%). Data obtained are used to assess the atmospheric fate and impact of the pentenols and to further develop structure-activity rules for the determination of OH rate coefficients with unsaturated species.

Full text of DOI:10.1021/jp0041712

3564
J. Phys. Chem. A 2001, 105, 3564-3569
Rate Coefficients and Product Yields from Reaction of OH with 1-Penten-3-ol,
(Z)-2-Penten-1-ol, and Allyl Alcohol (2-Propen-1-ol)
John J. Orlando,* Geoffrey S. Tyndall, and Noah Ceazan
Atmospheric Chemistry DiVision, National Center for Atmospheric Research, Boulder, Colorado 80303
ReceiVed: NoVember 10, 2000; In Final Form: January 17, 2001
The atmospheric chemistry of two recently discovered biogenic volatile organic compounds (VOCs), 1-penten-
3-ol and (Z)-2-penten-1-ol, has been studied at 298 K using an environmental chamber/FTIR apparatus. Rate
coefficients for their reaction with OH (determined by the relative rate technique) were found to be (6.7 (
0.9) × 10-11 cm3 molecule-1 s-1 and (10.6 ( 1.5) × 10-11 cm3 molecule-1 s-1 for 1-penten-3-ol and (Z)-
2-penten-1-ol, respectively. Products observed (with molar yields in brackets) from the OH-initiated oxidation
of these species in 1 atm air at 298 K were glycolaldehyde (47 ( 6%) and formaldehyde (35 ( 4%) from
1-penten-3-ol; and propanal (91 ( 13%), glycolaldehyde (87 ( 11%) and formaldehyde (11 ( 2%) from
(Z)-2-penten-1-ol. As a model for the more complex unsaturated alcohols, similar studies were also carried
out on a simpler species, allyl alcohol (2-propen-1-ol, CH2dCHCH2OH). Reaction of this species with OH
was found to proceed with a rate coefficient of (4.5 ( 0.6) × 10-11 cm3 molecule-1 s-1. Products observed
were formaldehyde (98 ( 12%), glycolaldehyde (90 ( 12%), and acrolein (5 ( 2%). Data obtained are used
to assess the atmospheric fate and impact of the pentenols and to further develop structure-activity rules for
the determination of OH rate coefficients with unsaturated species.
Introduction
Experimental Section
Emissions of volatile organic compounds (VOCs) from
vegetation exceed those from anthropogenic sources1,2 and are
known to exert a profound influence on tropospheric chemistry.3-5
In addition to emissions from healthy plants, release of VOCs
is known to occur as a result of leaf damage (for example, from
grazing, cutting, harvesting, freezing, and drying).6-9 The most
heavily documented wound-induced emissions are a series of
C6 compounds and their derivatives, (Z)-3-hexenal, (Z)-3-
hexenol, (E)-2-hexenal, (Z)-3-hexenyl acetate, n-hexanal, n-
hexanol, and hexyl acetate.7,8,10,11 However, in a recent study
using an in situ proton-transfer mass spectrometer system, Karl
et al.9 report the observation of C5 oxygenated species, including
1-penten-3-ol and (Z)-2-penten-1-ol, in ambient air in the
Austrian Alps. The origins of these pentenol species, which
reached concentrations of a few ppbv, are believed to be from
freeze-damaged leaves as a result of peroxidation of fatty
acids.9,12
At present, insufficient information is available to assess the
atmospheric fate of these pentenol species. As with other
unsaturated alcohols (and unsaturated species in general13), these
compounds will be rather short-lived in the atmosphere (lifetime
of a few hours), with reaction with OH, O3, and NO3 all playing
a role in their atmospheric destruction. While rate coefficients
for reaction of O3 with 1-penten-3-ol and (Z)-2-penten-1-ol have
been reported,14 the OH- and NO3-initiated oxidation of these
species has yet to be studied.
All experiments discussed here were carried out at 298 K in
a stainless steel environmental chamber that has been described
previously.15,16 The cell is 2 m in length and has a volume of
47 L. It is interfaced to a Bomem DA3.01 Fourier transform
spectrometer (operating in the infrared) via a set of Hanst-type
multipass optics, which provided an optical path length of 32.6
m. Quantitative analysis of the chamber contents was ac-
complished by recording infrared spectra over the range 800-
3900 cm-1 at a spectral resolution of 1 cm-1. Typically, spectra
were obtained from the coaddition of 200 interferograms, which
required about 4 min of acquisition time.
Rate coefficients for the reaction of OH with the three
unsaturated alcohols (1-penten-3-ol, (Z)-2-penten-1-ol, and allyl
alcohol) were obtained using standard relative rate techniques,
using propene as the reference compound and ethyl nitrite
photolysis as the OH source. Photolyses were carried out using
a Xe-arc lamp, filtered to provide radiation over the range 240-
400 nm. Mixtures containing ethyl nitrite ((0.7-1.1) × 1015
molecule cm-3), the alcohol under study ((0.6-1.4) × 1015
molecule cm-3), propene ((4-7) × 1014 molecule cm-3), and
NO ((4-9) × 1014 molecule cm-3) in synthetic air (700 Torr)
were irradiated three to five times (for periods of 3-5 min),
with an infrared spectrum being recorded following each
irradiation. The minor components of the mixture were added
to the reaction chamber via expansion from smaller calibrated
volumes, while N2 (boil-off from a liquid N2 dewar) and O2
(UHP Grade, U. S. Welding) were added directly to the
chamber. Relative rate coefficients were obtained from the
relative rate of disappearance of the unsaturated alcohol versus
that of propene:
In this paper, rate coefficients for the reaction of OH radicals
with 1-penten-3-ol and (Z)-2-penten-1-ol are determined, as are
the products of the OH-initiated oxidation of these species in
air. The data are used to assess the atmospheric lifetime and
fate of the pentenols. Complementary studies on a simpler model
compound, allyl alcohol (2-propen-1-ol), are also reported.
ln{[alcohol]o/[alcohol]t} )
kalcohol/kpropene ln{[propene]o/[propene]t}
* To whom correspondence should be addressed.
10.1021/jp0041712 CCC: $20.00 © 2001 American Chemical Society
Published on Web 03/13/2001

Reaction of OH with Alcohols
J. Phys. Chem. A, Vol. 105, No. 14, 2001 3565
Figure 2. Plots of the decay of (Z)-2-penten-1-ol versus that of
1-penten-3-ol in the photolysis of CH3ONO/1-penten-3-ol/(Z)-2-penten-
1-ol/NO/air mixtures at 700 Torr total pressure, 298 K.
Figure 1. Plots of the decay of allyl alcohol (open squares), 1-penten-
3-ol (filled circles), or (Z)-2-penten-1-ol (open circles) versus that of
propene in the photolysis of CH3ONO/unsaturated alcohol/propene/
NO/air mixtures at 700 Torr total pressure, 298 K.
For completeness, rate coefficient ratios for the reaction of OH
with 1-penten-3-ol and (Z)-2-penten-1-ol were determined using
analogous procedures. Control experiments showed that propene
and the unsaturated alcohols were not lost to any significant
extent via heterogeneous processes over the time scale of a
relative rate experiment.
Product studies involved the photolysis of mixtures containing
ethyl nitrite ((0.7-1.2) × 1015 molecule cm-3), the alcohol under
study ((0.5-1.5) × 1015 molecule cm-3), and NO ((5-10) ×
1014 molecule cm-3) in 700 Torr of synthetic air. Each fill of
the chamber was irradiated three to five times (each photolysis
5 min), and an infrared spectrum was recorded following each
irradiation. Concentrations of starting materials and products
(formaldehyde, CH2O; glycolaldehyde, HOCH2CHO; propanal,
CH3CH2CHO; acrolein, CH2dCHCHO) were quantified by
spectral stripping routines, using standard spectra recorded in
our laboratory. Absorption cross sections for glycolaldehyde
obtained in our lab agree favorably with those from Niki et
al.17 and Tuazon et al.18 Small corrections (typically 5%) to
observed product concentrations were made for secondary
chemistry (reaction with OH19,20 and, in the case of glycol-
aldehyde, a slow heterogeneous loss to the chamber walls, which
occurs with a rate coefficient of 1.5 × 10-5 s-1).20
Figure 3. Observed product concentrations (corrected for secondary
chemistry) as a function of unsaturated alcohol consumption, in the
photolysis of CH3ONO/unsaturated alcohol/NO/air mixtures at 700 Torr
total pressure, 298 K: open squares, glycolaldehyde from allyl alcohol;
filled squares, formaldehyde from allyl alcohol; open circles, glycol-
aldehyde from 1-penten-3-ol; filled circles, formaldehyde from 1-penten-
3-ol.
Relative rate data are shown in Figure 1. Standard linear least-
squares analysis of these data yields the following rate coef-
ficient ratios: k1/k4 ) 1.72 ( 0.12, k2/k4 ) 2.56 ( 0.16, k3/k4
) 4.04 ( 0.45. Using the accepted value13 for k4 at 700 Torr
and 298 K, 2.63 × 10-11 cm3 molecule-1 s-1, yields the
following values for k1 through k3 under these conditions: k1
) (4.5 ( 0.6) × 10-11 cm3 molecule-1 s-1, k2 ) (6.7 ( 0.9) ×
10-11 cm3 molecule-1 s-1, and k3 ) (10.6 ( 1.5) × 10-11 cm3
molecule-1 s-1. Quoted uncertainties in the values for k1-k3
include 2σ precision errors and uncertainties in the reference
rate coefficient (estimated at 10%). As a consistency check, the
rate coefficient ratio k3/k2 was also determined at 298 K from
the photolysis of CH3CH2ONO/1-penten-3-ol/(Z)-2-penten-1-
ol/NO mixtures in 700 Torr synthetic air. As shown in Figure
2, a value of k3/k2 ) 1.44 ( 0.12 was obtained, consistent
(within experimental uncertainty) with the ratio determined from
the measurements made relative to k4, k3/k2 ) 1.58 ( 0.22.
Product Yield Data. Products of the OH-initiated oxidation
of allyl alcohol, 1-penten-3-ol, and (Z)-2-penten-1-ol were also
determined in the environmental chamber system. As shown in
Figure 3, products observed following reaction of OH with allyl
alcohol were formaldehyde and glycolaldehyde, with molar
Chemicals were obtained from the following sources: allyl
alcohol (Aldrich, 99+%), 1-penten-3-ol (Aldrich, 99+%), (Z)-
2-penten-1-ol (Aldrich, 95%), propene (Matheson, UHP), NO
(Linde, UHP). Ethyl nitrite (CH3CH2ONO) was synthesized
from the dropwise addition of concentrated H2SO4 to an ethanol/
sodium nitrite slurry21 and stored in dry ice. The alcohols and
ethyl nitrite were purified/degassed by several freeze-pump-
thaw cycles before use.
Results
OH Rate Coefficients. Rate coefficients for the reaction of
OH with allyl alcohol (k1), 1-penten-3-ol (k2), and (Z)-2-penten-
1-ol (k3) were obtained relative to propene (k4):
OH + HOCH2CHdCH2 f products
(R1)
OH + CH2dCHCH(OH)CH2CH3 f products (R2)
OH + HOCH2CHdCHCH2CH3 f products (R3)
OH + CH3CHdCH2 f products
(R4)

3566 J. Phys. Chem. A, Vol. 105, No. 14, 2001
Orlando et al.
Figure 4. Chemistry occurring in the OH-initiated oxidation of allyl alcohol.
TABLE 1: Rate Coefficients for Alkenes and Their 1-Hydroxy-Substituted Counterparts at 1 atm Total Pressure, 298 Ka
parent alkene
OH rate coefficient
2.6
corresponding unsaturated alcohol
OH rate coefficient
enhancement factor
1.9
propene
CH3CHdCH2
1-butene
CH3CH2CHdCH2
3-methyl-1-butene
(CH3)2CHCHdCH2
1-pentene
CH3CH2CH2CHdCH2
(Z)-2-pentene
allyl alcohol
HOCH2CHdCH2
1-buten-3-ol
CH3CH(OH)CHdCH2
2-methyl-3-buten-2-ol
(CH3)2C(OH)CHdCH2
1-penten-3-ol
CH3CH2CH(OH)CHdCH2
(Z)-2-penten-1-ol
4.5b
5.5c
5.9c
3.1
3.2
3.1
6.6
1.9
2.0
2.2
1.6
6.3d
6.7b
10.6b
CH3CH2CHdCHCH3
CH3CH2CHdCHCH2OH
a Rate coefficients are given in units of 10-11 cm3 molecule-1 s-1. Data for the parent alkenes are from ref 13. b This work. c From ref 24.
d Average of data from refs 16, 24, 26.
TABLE 2: Rate Coefficients and Estimated Atmospheric Lifetimes for 1-Penten-3-ol and (Z)-2-Penten-1-ol with Respect to
a
Reaction with OH, O3, and NO3
lifetime vs
OH, h
lifetime vs
O3, h
lifetime vs
NO3, h
b
c
d
pentenol
kOH
kO
kNO
3
1-penten-3-ol
(Z)-2-penten-1-ol
6.7 × 10-11
2.1
1.3
1.8 × 310-17
11
1.2
1.4 × 10-14
20
20
10.6 × 10-11
1.7 × 10-16
1.4 × 10-14
a All rate coefficients in cm3 molecule-1 s-1. Lifetimes estimated using [OH] ) 2 × 106 molecule cm-3 (daytime only), [O3] ) 1.4 × 1012
molecule cm-3, and [NO3] ) 1 × 109 molecule cm-3 (nighttime only).1 b This work. c From ref 14. d Estimates are based on measurements of refs
29 and 30.
yields of 98 ( 12% and 90 ( 12%, respectively. Acrolein was
also identified in the product spectra but, due to the small yield,
could only be quantified at large allyl alcohol conversion. The
yield of acrolein is estimated to be 5 ( 2%. The identified
products account for 98 ( 12% of the reacted carbon. As shown
in Figure 4, glycolaldehyde and formaldehyde are the expected
coproducts obtained following OH-addition to either end of the
double bond in allyl alcohol, while the presence of acrolein is
evidence for a minor abstraction channel. The near-100%
identification of products in the allyl alcohol oxidation experi-
ments gives us confidence in our ability to quantify glycol-
aldehyde and other products obtained in the pentenol oxidation
experiments discussed below.
The OH-initiated oxidation of 1-penten-3-ol resulted in the
formation of glycolaldehyde and formaldehyde, as shown in
Figure 3, with molar yields of 47 ( 6% and 35 ( 4%,
respectively. The chemistry occurring following addition of OH
to the 1-penten-3-ol double bond is shown in Figure 5. As seen
from the figure, the formation of glycolaldehyde is expected to
be accompanied by propanal formation, while CH2O should
occur along with 2-hydroxybutanal. Propanal was clearly present
in the product spectra. Though difficult to quantify accurately
due to spectral overlap with the various other carbonyl species,
its concentration was found to be within (30% of that of
glycolaldehyde. Assuming the two coproducts to be present,
82 ( 8% of the reacted carbon is accounted for. The lack of
100% carbon balance suggests that other channels play a role
in the chemistry. One possibility is isomerization of the 2,3-
dihydroxy-1-pentoxy radical, which would likely lead to 2,3,4-
trihydroxypentanal or 2,3-dihydroxypropanal (see Figure 5). The
isomerization (rate coefficient ≈ 3 × 106 s-1 22
) is likely to be
a minor but nonnegligible fate of the 2,3-dihydroxy-1-pentoxy
radical (rate coefficient for dissociation ≈107 s-1 by analogy
to 2-hydroxy-1-propoxy radical23). Also, a small contribution
from H-abstraction at the C3 carbon24 to produce ethyl vinyl
ketone (EVK) is a possibility. By analogy to methyl vinyl ketone
(MVK), relatively strong absorption features for EVK are
expected near 950 and 1710 cm-1. Weak, unidentified features
in these regions are evident in the product spectra; however,
based on the assumption that MVK and EVK have similar
absorption cross sections, the EVK yield is unlikely to be greater
than 7%.
Products obtained in the OH-initiated oxidation of (Z)-2-
penten-1-ol were glycolaldehyde, propanal, and formaldehyde,
with molar yields of 87 ( 11%, 91 ( 13%, and 11 ( 2%,
respectively (see Figure 6). The observed products account for
100 ( 14% of the reacted carbon. Furthermore, the equal yields
of glycolaldehyde and propanal are consistent with the expected

Figure 5. Chemistry occurring following the addition of OH to 1-penten-3-ol and (Z)-2-penten-1-ol.

3568 J. Phys. Chem. A, Vol. 105, No. 14, 2001
Orlando et al.
in the oxidation of both 1-penten-3-ol and 2-methyl-3-buten-
2-ol (MBO)16 may indicate that OH addition to the side of the
CdC double bond adjacent to the hydroxy group is being
activated.
Measured and estimated rate coefficient data for reaction of
OH (this work), O3,14 and NO3 with 1-penten-3-ol and (Z)-2-
penten-1-ol are collected in Table 2. As no NO3 data are
available, these rate coefficients were based on data29,30 for NO3
reaction with 2-methyl-3-buten-2-ol, but-1-en-3-ol, and allyl
alcohol. It is clear from the lifetime estimates in Table 2 that
reaction with OH will play a major role in the atmospheric
destruction of the pentenols (lifetimes 1-2 h), though reaction
with O3 will be competitive, particularly in the case of (Z)-2-
penten-1-ol. Reaction with NO3 may also play a significant role
in the nighttime chemistry of the pentenols. The major products
obtained in the OH-initiated oxidation of the pentenols are
all aldehydes (formaldehyde, glycolaldehyde, propanal, and
2-hydroxybutanal), and they will react with OH and photolyze
in the atmosphere with overall time constants of less than 1
day. The high reactivity of the parent pentenols and of their
major reaction products implies that large emissions of these
species will play a significant role in boundary layer ozone
production. Finally, we note that further oxidation of propanal
and possibly 2-hydroxybutanal will, in part, generate peroxy-
propionyl nitrate (PPN). The production of PPN from the
pentenols and hexenyl-type wound compounds8,31,32 may con-
tribute to recent observations of elevated PPN/PAN ratios in
rural air.32
Figure 6. Observed product concentrations (corrected for secondary
chemistry) as a function of (Z)-2-penten-1-ol consumption, in the
photolysis of CH3ONO/(Z)-2-penten-1-ol/NO/air mixtures at 700 Torr
total pressure, 298 K: open circles, glycolaldehyde; filled circles,
formaldehyde; filled triangles, propanal.
mechanism. As shown in Figure 5, OH addition to the C3 carbon
in (Z)-2-penten-1-ol could lead to either propanal and glycol-
aldehyde, or formaldehyde and 2-hydroxybutanal, while addition
at the C2 site would likely lead exclusively to the formation of
propanal and glycolaldehyde. As was the case for 1-penten-3-
ol, a minor contribution from abstraction (at the C1 site, leading
to 2-pentenal) cannot be excluded. Note that no isomerizations
via transition states containing six-membered rings are possible
from the oxy radicals generated in the (Z)-2-penten-1-ol system.
Acknowledgment. The National Center for Atmospheric
Research is operated by the University Corporation for Atmo-
spheric Research under the sponsorship of the National Science
Foundation. The authors would like to thank Ray Fall for many
helpful discussions regarding this work. We are also indebted
to Ray Fall, Thomas Karl, Roger Atkinson, and their co-workers
for communicating results prior to publication. Finally, thanks
are due to Julia Lee-Taylor and Chris Cantrell (NCAR) for their
comments on the manuscript.
Discussion and Conclusions
The atmospheric chemistry of allyl alcohol has recently been
studied by Papagni et al.24 Their value for the rate coefficient
of OH with allyl alcohol, k1 ) (5.5 ( 0.5) × 10-11 cm3
molecule-1 s-1, is consistent (within experimental uncertainties)
with our value, (4.5 ( 0.6) × 10-11 cm3 molecule-1 s-1
.
Although a full product study was not conducted by Papagni et
al.,24 they did observe acrolein in 5% yield, thus confirming
the existence of a minor abstraction channel. Previous studies
of k1 at elevated temperature conducted by Gordon and Mulac25
(k1 ) 2.6 × 10-11 cm3 molecule-1 s-1 at 440 K) are broadly
consistent with the room-temperature data (assuming a weak
negative temperature dependence for k1). However, we note that
Gordon and Mulac25 reported a positive temperature dependence
for the OH rate coefficient with a number of alkenes (albeit
over a limited temperature range). We are unaware of any
previous studies of the reaction of OH with either 1-penten-3-
ol or (Z)-2-penten-1-ol.
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