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Mid-infrared quantum cascade laser spectroscopy probing of the kinetics of an atmospherically significant radical reaction, \(\hbox {CH}_{3}\hbox {O}_{2}+\hbox {NO}_{2}+\hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2}+\hbox {M}\), in the gas phase

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Abstract

The kinetic parameters of an important atmospheric reaction, \(\hbox {CH}_{3}\hbox {O}_{2} + \hbox {NO}_{2} + \hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2} + \hbox {M}\), have been recorded by monitoring directly the changes in concentrations of methylperoxy radicals \((\hbox {CH}_{3}\hbox {O}_{2})\) in the gas phase employing a new mid-infrared quantum cascade laser (QCL)-based apparatus. \(\hbox {CH}_{3}\hbox {O}_{2 }\) radicals in our apparatus have been generated by pulsed UV laser (266 nm) photolysis of \(\hbox {CH}_{3}\hbox {I}\) in a gaseous mixture with oxygen. The absorption band corresponding to the mid-infrared O-O stretching fundamental of the peroxy radical, within a narrow spectral range, 1070–1120 \(\hbox {cm}^{-1}\), has been recorded by tuning the wavelength of the QCL operated in CW mode. The kinetics of the aforementioned reaction of \(\hbox {CH}_{3}\hbox {O}_{2}\) with \(\hbox {NO}_{2}\) has been followed by analyzing the changes of the infrared (QCL) decay profile of \(\hbox {CH}_{3}\hbox {O}_{2}\) at \(9.1~\upmu \hbox {m}\) \((1098.9~\hbox {cm}^{-1})\) maintaining a pseudo first order reaction condition. We noticed that the rate constant of the reaction at 298 K varies in the range of (1.21–3.08) \(\times 10^{-12}\) \(\hbox {cm}^{3 }~\hbox {molecule}^{-1 }\,\hbox {s}^{-1 }\) for changing the total pressure in the range of 75–730 mbar. The absorption cross-section of \(\hbox {CH}_{3}\hbox {O}_{2}\) at the probe wavelength \((1098.9~\hbox {cm}^{-1})\), has been estimated for the first time to be \(8.3 \pm 0.4 \times 10^{-20}~\hbox {cm}^{2}\).

Graphical Abstract 

Kinetics measurement of an atmospherically important gas phase reaction, \(\hbox {CH}_{3}\hbox {O}_{2}+\hbox {NO}_{2}+\hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2}+\hbox {M}\), is studied using a newly developed apparatus based on pulsed UV laser photolysis time-resolved mid-infrared absorption spectroscopy. \(\hbox {CH}_{3}\hbox {O}_{2}\) radicals are probed in the mid-infrared by a CW quantum cascade laser (QCL).

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Acknowledgements

The authors sincerely acknowledge the financial support received from the Department of Science and Technology, Govt. of India, under the Scheme Number SB/S1/PC-027/2013. AC thanks CSIR, Govt. of India and IACS for the Senior Research Fellowship, MS and KM thank UGC, Govt. of India for Junior Research Fellowships.

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  1. Department of Physical Chemistry, Indian Association for the Cultivation of Science, 2A Raja S C Mullick Road, Jadavpur, Kolkata, West Bengal, 700 032, India

    Aparajeo Chattopadhyay, Monoj Samanta, Koushik Mondal & Tapas Chakraborty

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  1. Aparajeo Chattopadhyay
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Chattopadhyay, A., Samanta, M., Mondal, K. et al. Mid-infrared quantum cascade laser spectroscopy probing of the kinetics of an atmospherically significant radical reaction, \(\hbox {CH}_{3}\hbox {O}_{2}+\hbox {NO}_{2}+\hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2}+\hbox {M}\), in the gas phase. J Chem Sci 130, 54 (2018). https://doi.org/10.1007/s12039-018-1451-2

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