The ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy

Abstract

We have developed a method to quantify reaction product ratios using high resolution microwave spectroscopy in a cryogenic buffer gas cell. We demonstrate the power of this method with the study of the ozonolysis of isoprene, CH2[double bond, length as m-dash]C(CH3)-CH[double bond, length as m-dash]CH2, the most abundant, non-methane hydrocarbon emitted into the atmosphere by vegetation. Isoprene is an asymmetric diene, and reacts with O3 at the 1,2 position to produce methyl vinyl ketone (MVK), formaldehyde, and a pair of carbonyl oxides: [CH3CO-CH[double bond, length as m-dash]CH2 + CH2[double bond, length as m-dash]OO] + [CH2[double bond, length as m-dash]O + CH3COO-CH[double bond, length as m-dash]CH2]. Alternatively, O3 could attack at the 3,4 position to produce methacrolein (MACR), formaldehyde, and two carbonyl oxides [CH2[double bond, length as m-dash]C(CH3)-CHO + CH2[double bond, length as m-dash]OO] + [CH2[double bond, length as m-dash]O + CH2[double bond, length as m-dash]C(CH3)-CHOO]. Purified O3 and isoprene were mixed for approximately 10 seconds under dilute (1.5-4% in argon) continuous flow conditions in an alumina tube held at 298 K and 5 Torr. Products exiting the tube were rapidly slowed and cooled within the buffer gas cell by collisions with cryogenic (4-7 K) He. High resolution chirped pulse microwave detection between 12 and 26 GHz was used to achieve highly sensitive (ppb scale), isomer-specific product quantification. We observed a ratio of MACR to MVK of 2.1 ± 0.4 under 1 : 1 ozone to isoprene conditions and 2.1 ± 0.2 under 2 : 1 ozone to isoprene conditions, a finding which is consistent with previous experimental results. Additionally, we discuss relative quantities of formic acid (HCOOH), an isomer of CH2[double bond, length as m-dash]OO, and formaldehyde (CH2[double bond, length as m-dash]O) under varying experimental conditions, and characterize the spectroscopic parameters of the singly-substituted 13C trans-isoprene and 13C anti-periplanar-methacrolein species. This work has the potential to be extended towards a complete branching ratio analysis, as well towards the ability to isolate, identify, and quantify new reactive intermediates in the ozonolysis of alkenes.

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