Criegee intermediate is a short-lived intermediate, leading to a small steady-state
concentration in the atmosphere.60,61 This small concentration makes it difficult for direct field measurement. Although kinetic studies have established some basic properties of small Crigee intermediates, 81,96 the implication of Criegee intermediates in the
troposphere is still unclear due to the lack of knowledge on large Criegee intermediates.
New reaction pathway may exist when the number of carbon in a Criegee intermediate increases. For example, a recent theoretical study95 suggested that vinyl substituted Criegee intermediates has large unimolecular reaction rate, ~9000 s1, due to a new ring closure channel. The structures of small Criegee intermediates affects the reactivity towards water vapor and the thermal decomposition; it is reasonable to expect that new chemistry appears with Criegee intermediates with more complex structures.
Substitution effect on Crigee intermediate helps us to evaluate and predict the impact of Criegee intermediates in the atmosphere.
Due to the difficulties in synthesing complicated diiodoalkanes, preparing Criegee intermediate through photolysis method is limited. Theory is needed for predicting possible reactions of large Criegee intermediate with the theoretical prediction, experimental can focus more on the potentially important reactions.
In principle, there is no limitation on the type of Criegee intermediate to be studies with theoretical calculations; but the computation time becomes longer when the number of atom increases; calculation of large Criegee intermediates (number of atom > 10) might be difficult and less accurate due to more simplifications and approximations. To understand the reactivity of large Criegee intermediate, ozonolysis study is more
efficiency and closer to the real world.
Nonetheless, some puzzles remain even in the simple ozonolysis system.92 Kinetic study of small Criegee intermediate confirms some early speculations but some problems still unsolved. For example, reactivity of Cirgee intermediate with water vapor has been confirmed to have strong structure dependence. On the other hand, OH formation rate in TME ozonolysis system cannot be explained while both (CH3)2COO and VHP
decompose fast. 92
Notably, reaction of Criegee intermediates with ozone is still unclear. This reaction is important because ozone is always present when a Criegee intermediate is produced.
Knowledge of small Criegee intermediates reaction with alkene is limited to CH2OO and some small olefins.53,54 For the reaction with ozone, a few theoretical works 99,101
predicted a wide range of rate coefficient from 1017 to 1012 cm3 s1. This is an important problem to be solved by experiment.
We hope that the kinetic results of small Criegee intermediates can lead to new design of experiment for studying ozonolysis system in a well-controlled situation; so that, the ozonolysis reaction of simple olefins can be understood completely. With the improved model based on these results, modelers can better estimate the implications of Criegee intermediates and ozonolysis reaction in the troposphere.
Summary
In this thesis work, we have studied the reaction kinetics of two Criegee intermediates, CH2OO and (CH3)2COO, because they have the simplest structures of anti and syn types Criegee intermediates. An experimental setup based on UV absorption spectroscopy was built to study the kinetics of these two Criegee intermediates, including reactions with water vapor, alkenes, and thermal decomposition. We found the reactivity of CH2OO and (CH3)2COO is dramatically affected by their structures.
For example, CH2OO reacts rapidly with water dimer. By varying the reaction temperature, we have obtained k(H2O)2(298 K) = 7.4x1012 cm3 s1 and an activation energy of 8.1±0.6) kcal mol1,45 a rather strong negative temperature dependence.
Reaction of CH2OO with water monomer is much slower and cannot compete with the water dimer under ambient conditions, water monomer reaction can be observed only at high temperature (>349K)46 or under extremely low humidity level (HR<0.15%).80 On the other hand, we found the reaction of (CH3)2COO with water vapor is too slow to measure.48 However, (CH3)2COO has a fast thermal decomposition rate, ca. 361 s1 at 298 K and reveals an activation energy of 5.8 kcal mol1.42 A strong isotope effect was observed by measuring the decomposition rate of (CD3)2COO.42 Due to tunneling, intramolecular H atom transfer is still fast even with a high barrier (16.2 kcal mol1).37 In contrast, the thermal decomposition of CH2OO is slower than our detection limit. But Berndt et al have successfully measured it, ~0.2 s1, 80 in the ozonolysis study.
Theoretical calculations indicate a dioxirane formation channel with a barrier similar to that of the hydrogen transfer of (CH3)2COO, but the tunneling efficiency of O atom is much smaller.42
For the reaction of CH2OO with C2H4, we have measured the rate coefficients to be (6.8±0.7)x1016 cm3 s1 at 298 K with negligible pressure dependence from 50 to 760 Torr; this small reaction rate coefficient suggests that it cannot compete with other reactions in typical ambient and laboratory conditions. We don’t have a conclusion on the reaction rate coefficient for CH2OO reaction with TME because of some unknown factors to causing the scattering of experimental results. Our experimental results indicate an upper bound for this reaction to be 1.6x1015 cm3 s1 if the experiment is influenced by impurity in TME.
The structure dependence of reactions of small Criegee intermediates with alkenes has not been studied yet. Observed decay rate of (CH3)2COO shows a saturation behavior when [C2H4] > 1016 cm3; a gap in the decay rate of (CH3)2COO was also observed when TME was present. We don’t have good explanation for this strange behavior, thus no conclusion was made on (CH3)2COO reactions with small alkenes.
Based on our experimental results, anti-type Criegee intermediate will be scavenged by water vapor while syn-type Criegee intermediates will decompose into OH radical but still has a potential to oxidize atmospheric trace gases in a highly polluted area. The implication of Criegee intermediates is still an open issue due to lack of understanding on Criegee intermediate with more complicated structures.
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