OH-INITIATED OXIDATION OF SMALL UNSATURATED ALCOHOLS
157
at low pressure and are not appropriate for atmospheric
pressure, and the results from Fantechi et al. [14] ap-
pear to be in error. The remaining absolute and relative
rate studies listed in Table I are in good agreement.
Taking averages of these data give values of k(OH +
OH
CH OH
HOH
2
C
CH OH
2
2
H
O2
−11
O
allyl alcohol) = 5.32 × 10 , k(OH + 3-buten-1-ol) =
11
NO
−
O
5.90 × 10 , and k(OH + 2-methyl-3-buten-2-ol) =
11 3
O
−
−1 −1
cm molecule s . Combining these
6
.39 × 10
6
−3
HOH
2
C
CH
2
OH
HOH C
CH OH
values with a daytime average [OH] = 2.5 × 10 cm
2
2
H
H
gives lifetimes of approximately 2 h for these small
unsaturated alcohols with respect to reaction with OH
radicals. Clearly, these are very reactive compounds,
which will be oxidized in the atmosphere close to their
sources.
NO2
O
O2
+
CH OH
HCHO + HO2
2
HOH
2
C
H
Figure 6 Mechanism showing the formation of glycolalde-
hyde (HOCH2CHO) and formaldehyde (HCHO) in the OH-
initiated oxidation of allyl alcohol.
This study was partly supported by Program for Improve-
ment of Research Environment for Young Researchers from
Special Coordination Funds for Promoting Science and Tech-
nology (SCF) commissioned by the Ministry of Education,
Culture, Sport, Science and Technology (MEXT) of Japan
radical initiated oxidation of allyl alcohol, as shown in
Fig. 2. Figure 5 shows a plot of the observed formation
of glycolaldehyde (corrected for secondary loss via re-
action with OH) versus the loss of allyl alcohol follow-
ing the UV irradiation of mixtures of 13.2–16.3 mTorr
allyl alcohol, 100–106 mTorr CH3ONO, and 13–25
mTorr NO in 700 Torr air. Linear least-squares analy-
sis of the data in Fig. 5 gives a glycolaldehyde yield of
(
K T.). This work was also supported by Grants-in-Aid from
the MEXT for ScientiÞc Research on Innovative Areas “Im-
pacts of Aerosols in East Asia on Plants and Human Health”
(K. T.)
BIBLIOGRAPHY
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The results presented here serve to increase the kinetic
database concerning the reactions of hydroxyl radicals
with small unsaturated alcohols. As discussed above,
the experiments of Upadhyayaet al. [9] wereconducted
International Journal of Chemical Kinetics DOI 10.1002/kin