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Abstract: The OH addition to ethene has been modeled using ab initio quantum chemical calculations and
classical transition state theory (CTST). The results agree with the hypothesis of Singleton and Cvetanovic
(Singleton, D. L.; Cvetanovic, R. J. J. Am. Chem. Soc. 1976, 98, 6812) that the reaction is not elemental, and
that it consists of a reversible first step involving the formation of a prereactive complex, followed by the
irreversible formation of an addition adduct. The overall rate depends on the rates of two competitive reactions,
i.e., the reverse of the first step and the second step, the former being more favored by an increase in temperature
than the latter. Applying CTST to the proposed mechanism, we obtain an overall rate constant of 11.7
10-12 cm3 molecule-1 s-1, which agrees very well with the experimental results. New results for the activation
energies of the OH addition to a series of substituted ethenes have also been obtained assuming that the above
mechanism holds. The activation energies were calculated from projected second-order Moller-Plesset total
energies obtained with the 6-311G** basis set. We find that a plot of these data vs the logarithm of the
experimental rate constants has a correlation coefficient of 0.996. This seems to imply that the preexponential
factor for the series should be approximately constant, in contradiction with the reported values for A. Moreover,
a plot of our effective activation energies for OH addition vs the activation energies of a similar reaction, the
addition of atomic oxygen to the same series of alkenes, also yields a good correlation. Indeed, for this reaction,
the reported A factors are similar to each other. We suggest that the experimental Arrhenius parameters of the
OH addition reaction need to be revised.
1. Introduction
In the troposphere, alkenes participate in a sequence of
reactions which ultimately lead to their breakdown into highly
toxic aldehydes, at the same time altering the equilibrium ratio
of nitrogen oxides and indirectly producing ozone.1 Alkenes
are known to enter the tropospheric reactants pool mainly
through one reaction,1 the addition of an OH radical to the
double bond:
R1R2CdCR3R4 + OH f
R1R2C(OH)-CR3R4 + R1R2C-CR3R4(OH) (1)
Rate constants for the OH addition to a large variety of
alkenes have been measured.2 Theoretical work on these
reactions has been reported for ethene,3-5 propene,6,7 and
Universidad de La Habana.
Dalhousie University.
Universidad Auto
noma Metropolitana.
(1) Finlayson-Pitts, B. J.; Pitts, N. Atmospheric Chemistry: Fundamentals
and Experimental Techniques; Wiley-Interscience: New York, 1986.
(2) Atkinson, R. J. Phys. Chem. Ref. Data 1997, 26, 215.
(3) Sosa, C.; Schlegel, H. B. J. Am. Chem. Soc. 1987, 109, 4193.
(4) Villa`, J.; Gonzalez-Lafont, A.; Lluch, J. M.; Corchado, J. C.;
Espinosa-Garca, J. J. Chem. Phys. 1997, 107, 7266.
(5) Sekusak, S.; Liedl, K. R.; Sabljic, A. J. Phys. Chem. A 1998, 102,
1583.
(6) Alvarez-Idaboy, J. R.; Diaz-Acosta, I.; Vivier-Bunge, A. J. Comput.
Chem. 1998, 88, 811.
AlVarez-Idaboy et al.
1012k (cm3
1012A (cm3
Ea
molecule-1 s-1) molecule-1 s-1) (kcal/mol)
ethene
propene
methylpropene
cis-2-butene
2-methyl-2-butene
2,3-dimethyl-2-butene
trichloroethene
tetrachloroethene
Alkene + OH
8.52
26.3
51.4
56.4
86.9
110
2.36
0.17
ethene
propene
methylpropene
cis-2-butene
2-methyl-2-butene
2,3-dimethyl-2-butene
Alkene + O(3P)
0.73
4.00
16.9
17.6
51.0
76.9
1.96
4.85
9.47
11.0
19.2
-0.87
-1.00
-1.00
-0.97
-0.89
0.56
9.64
-0.85
+2.40
10.6
10.1
15.9
11.0
28.2
24.9
+1.59
0.56
-0.03
-0.28
-0.40
-0.60
R1R2CdCR3R4 + OH h [R1R2CdCR3R4]OH f
products (2)
If k1 and k-1 are the rate constants for the first step and k2
corresponds to the second step, a steady-state analysis leads to
a rate constant for the overall reaction which can be written as
k)
k1k2
k-1 + k2
(3)
Even though the energy barrier for k-1 is about the same size
as that for k2,6 the entropy change is much larger in the reverse
reaction than in the formation of the products. Thus, one can
expect that k-1 be considerably larger than k2. With this
assumption, first considered in ref 12, one obtains
k)
( )
k1k2
A1A2 -(E1+E2-E-1)/RT
)
e
k-1
A-1
(4)
Since E1 is zero, the net activation energy for the overall reaction
is
method
Ea
PMP2/6-311G++(d,p)
PMP4(SDTQ)/6-311G++(d,p)
CCSD(T)/6-311G++(d,p)
-1.50
-0.92
0.51
1.35
1.92*
3.35*
PMP2/6-311G++(3df,2p)
PMP2/aug-cc-pVTZ
-2.70
-3.13
-0.11
-0.54*
a
For each method, the uncorrected Ea is given first, and the Ecorr
a ,
calculated including the ZPE corrections, is indicated in the third
column. The asterisk indicates that the ZPE was taken from the closest
lower level calculation.
k)
k1k2
) Keqk2
k-1
(6)
k)
QP-R
kBT QTS
expE-1/RT
exp-E2/RT
QR
h QP-R
(7)
AlVarez-Idaboy et al.
Table 4. Activation Energies (in kcal/mol) of the Alkenes + OH
Addition Reaction, Calculated using eq (5)
alkene
Ea
ethene
propene
methylpropene
cis-2-butene
2-methyl-2-butene
2,3-dimethyl-2-butene
trichlorethene
tetrachloroethene
-1.08
-2.06
-2.93
-3.41
-3.92
-4.45
+0.64
+3.37
Keq ) 0.00396
k2 ) 2.94 10-9 cm3 molecule-1 s-1
k ) 11.7 10-12 cm3 molecule-1 s-1
A ) 3.82 1012 cm3 molecule-1 s-1
kexp ) 8.52 10-12 cm3 molecule-1 s-1
The transition state partition function has been corrected for internal
rotations (see text).
From the above discussion we conclude that, when the OHalkene reaction occurs at atmospheric pressure, the following
hold:
(i) The reaction is not elemental.
(ii) The overall addition of OH is irreversible, due to the large
thermal effect of reaction 1 (H is usually larger than -30 kcal/
mol).
(iii) The overall rate depends on the rates of two competitive
reactions (the reverse of the first step and the second step in
reaction 1), the former being more affected by temperature than
the latter.
We claim that only Singleton and Cvetanovics hypothesis12
is compatible with the above three points, i.e., the existence of
a relatively stable prereactive complex, in equilibrium with the
reactants, and from which the addition adduct is formed
irreversibly. However, the activation energy of the OH-alkene
reactions at high pressures can be calculated as the difference
between the energy of the TS and that of the reactants, without
having to obtain the prereactive complex.
The proposed mechanism provides a clear explanation of the
experimental behavior. If E-1 is larger than E2, the former will
be relatively more favored by an increase in temperature and
the overall rate will decrease. This explanation was predicted
by Singleton and Cvetanovic a long time ago.12 It is also
interesting to note that, although mathematically the effective
rate constant may be written as that of an elemental reaction,
albeit with a negative activation energy, the latter has no physical
meaning. In particular, in reactions in which the tunnel effect
is important (as is the case in the hydrogen abstraction from
alkanes17 and small aldehydes, for example18), only E2 must be
considered.
In the global rate equation, eq 7, the temperature is present
both in the preexponential term and in the exponent, but in the
case of very small barriers, the latter are relatively less important
than usual, which may explain why, in this type of reaction, a
non-Arrhenius behavior is observed over a large temperature
range.
Finally, we would like to point out that, according to
Singleton and Cvetanovics hypothesis, k2 is expected to be
much smaller than k-1. When methyl groups are added to the
double bond, however, comparative results for ethene and
propene7 indicate that the prereactive complex becomes more
stable, meaning that E-1 increases. At the same time, experimental results indicate that the overall rate increases, implying
that E2 must decrease. Thus, the k2 , k-1 condition may not
be true any more, and the temperature dependence of the rate
constant may become more complex.
The fact that the methyl substitution at the double bond
increases the reaction rate appears to be due to the stabilization
of the transition state structure, due to inductive and dipoledipole effects.
A discrepancy is observed when the experimental data for
the Arrhenius parameters of a series of alkene + OH reactions
are compared with those reported for the alkene + O reaction.
Although these two reactions are expected to have similar
mechanisms, their reported Arrhenius parameters obey very
different trends. The results obtained in this work for the OH
+ alkene reaction agree with the trends observed by the O +
alkene parameters (Figure 3). When our activation energies,
calculated using eq 5, are compared directly with the experi(17) Sekusak, S.; Sabljic, A. J. Chem. Phys. Lett. 1997, 272, 353.
(18) Alvarez-Idaboy, J. R.; Mora-Diez, N.; Vivier-Bunge, A. Unpublished.
AlVarez-Idaboy et al.
R. Atkinson and to Professor P. D. Pacey for their valuable
comments.
Supporting Information Available: Tables of total energies
and zero point correction energies, in hartrees (PDF). This
material is available free of charge via the Internet at
http://pubs.acs.org.
JA993693W