Absolute determination of chemical kinetic rate constants by optical tracking the reaction on the second timescale using cavity-enhanced absorption spectroscopy

Literature Information

Publication Date 2022-02-28
DOI 10.1039/D2CP00206J
Impact Factor 3.676
Authors

Hongming Yi, Tao Wu, Amélie Lauraguais, Cecile Coeur, Alexandre Tomas, Hongbo Fu, Xiaoming Gao, Weidong Chen


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Abstract

We report a new spectroscopic platform coupled to an atmospheric simulation chamber for the direct determination of chemical rate constants with high accuracy at a second time-scale resolution. These developed analytical instruments consist of an incoherent broadband cavity enhanced absorption spectrometer using a red light emitting diode (LED) emitting at ∼662 nm (LED-IBBCEAS) associated with a multipass cell direct absorption spectrometer (MPC-DAS) coupled to an external cavity quantum cascade laser (EC-QCL) operating in the mid-infrared region at approximately 8 μm (EC-QCL-MPC-DAS). Spectrometers were employed to investigate the NO3-initiated oxidation of four selected volatile organic compounds (VOCs) for the determination of the corresponding rate constants with a dynamic range of 5 orders of magnitude (from 10−11 to 10−16 cm3 molecule−1 s−1). Rate constants of (6.5 ± 0.5) × 10−15, (7.0 ± 0.4) × 10−13, and (5.8 ± 0.5) × 10−16 cm3 molecule−1 s−1 for propanal, isoprene and formaldehyde, respectively, were directly determined by fitting the measured concentration–time profiles of NO3 and VOCs (measured using a proton transfer reaction time-of-flight mass spectrometer, PTR-ToF-MS) to chemical models based on the FACSIMILE simulation software (version 4.2.50) at 760 torr and 293 ± 2 K. The obtained rate constants are in good agreement with the most recent recommendations of the IUPAC (International Union of Pure and Applied Chemistry). In addition, a rate constant of (2.60 ± 0.30) × 10−11 cm3 molecule−1 s−1 for the oxidation of 2-methoxyphenol by NO3 radicals was first determined using the absolute kinetic method. Compared to the mostly used indirect relative rate method, the rate constant uncertainty is reduced from ∼20% to ∼12%. The results demonstrated the high potential of using modern spectroscopic techniques to directly determine the chemical reaction rate constants.

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Contents list

Front/Back Matter

DOI: 10.1039/C4CP90154A

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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