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

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 NO-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 to 10 cm molecule s).

High-accuracy and high-sensitivity spectroscopic measurement of dinitrogen pentoxide (NO) in an atmospheric simulation chamber using a quantum cascade laser.

A spectroscopic instrument based on a mid-infrared external cavity quantum cascade laser (EC-QCL) was developed for high-accuracy measurements of dinitrogen pentoxide (NO) at the ppbv-level. A specific concentration retrieval algorithm was developed to remove, from the broadband absorption spectrum of NO, both etalon fringes resulting from the EC-QCL intrinsic structure and spectral interference lines of HO vapour absorption, which led to a significant improvement in measurement accuracy and detection sensitivity (by a factor of 10), compared to using a traditional algorithm for gas concentration retrieval. The developed EC-QCL-based NO sensing platform was evaluated by real-time tracking NO concentration in its most important nocturnal tropospheric chemical reaction of NO + NO ↔ NO in an atmospheric simulation chamber.

Kinetic Study of the Gas-Phase Reactions of Nitrate Radicals with Methoxyphenol Compounds: Experimental and Theoretical Approaches.

The gas-phase reactions of five methoxyphenols (three disubstituted and two trisubstituted) with nitrate radicals were studied in an 8000 L atmospheric simulation chamber at atmospheric pressure and 294 ± 2 K. The NO3 rate constants were investigated with the relative kinetic method using PTR-ToF-MS and GC-FID to measure the concentrations of the organic compounds. The rate constants (in units of cm(3) molecule(-1) s(-1)) determined were: 2-methoxyphenol (guaiacol; 2-MP), k(2-MP) = (2.

Reaction Kinetics of Catechol (1,2-Benzenediol) and Guaiacol (2-Methoxyphenol) with Ozone.

The kinetic reactions of 1,2-benzenediol (catechol) and 2-methoxyphenol (guaiacol) with ozone were studied in a simulation chamber (8 m(3)) under dark conditions. The rate coefficients were measured at 294 ± 2 K, atmospheric pressure and dry conditions (relative humidity, RH < 1%), except for 1,2-benzenediol where they were also measured as a function of relative humidity (RH = 1-80%). The concentrations of organic compounds were followed by a PTR-ToF-MS for a continuous monitoring of gas-phase species.

Rate Coefficients for the Gas-Phase Reactions of Hydroxyl Radicals with a Series of Methoxylated Aromatic Compounds.

Rate coefficients for the reactions of hydroxyl radicals (OH) with a series of oxygenated aromatics (two methoxybenzene and five methoxyphenol isomers) have been obtained using the relative kinetic method in 1080 and 480 L photoreactors at the University of Wuppertal, Germany. The experiments were realized at 295 ± 2 K and 1 bar total pressure of synthetic air using in situ Fourier transform infrared spectroscopy for the chemical analysis. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) were determined: methoxybenzene (anisole), (2.

Rate coefficients for the gas-phase reaction of chlorine atoms with a series of methoxylated aromatic compounds.

The reaction of a series of oxygenated aromatics (two methoxybenzene and six methoxyphenol isomers) with chlorine atoms has been studied in two simulation chambers with volumes of 1080 and 480 L at the University of Wuppertal. Experiments were performed at 295 ± 2 K and a total pressure of synthetic air of 1 bar using the relative kinetic method with in situ Fourier transform infrared spectroscopy for chemical analysis. The following rate coefficients (in units of cubic centimeter per molecule per second) were determined: (1.