Kinetics Study of the Reaction of OH Radicals with C₅–C₈Cycloalkanes at 240–340 K using the Relative Rate/Discharge Flow/Mass Spectrometry Technique

Abstract

Rate constants of reactions of hydroxyl radical with cyclopentane (k1), cyclohexane (k2), cycloheptane (k3), and cyclooctane (k4) have been acquired at 240-340 K and a total pressure of about 1 Torr using the technique of relative rate combined with discharge flow and mass spectrometry (RR/DF/MS). At 298 K, the rate constants are determined using two reference compounds, which are averaged to be k1 = (4.81 ± 0.88) × 10(-12), k2 = (6.41 ± 0.85) × 10(-12), k3 = (10.30 ± 1.44) × 10(-12), and k4 = (1.42 ± 0.27) × 10(-11) cm(3) molecule(-1) s(-1). The Arrhenius expressions at 240-340 K for these reactions are determined to be k1(T) = (2.43 ± 0.50) × 10(-11)exp[-(481 ± 58)/T], k2(T) = (3.96 ± 0.60) × 10(-11)exp[-554 ± 42)/T], k3(T) = (5.74 ± 0.66) × 10(-11)exp[-527 ± 33)/T], and k4(T) = (1.12 ± 0.21) × 10(-10)exp[-626 ± 53)/T]. Using the kcycloalkane+OH(277 K) values measured in the present work, the atmospheric lifetime for cyclopentane, cyclohexane, cycloheptane, and cyclooctane is estimated to be about 78, 64, 38, and 29 h, respectively.

Rate coefficients for the reactions of OH radical with C3-C11 alkanes determined by the relative rate technique

“…Singh et al, 2013) and the absolute value (5.02) of Droege et al(Droege and Tully, 1987). And the obtained KOH values for cyclohexane are highly consistent (3% or better) with the absolute values (7.14×10 -12 , 7.19×10 -12 ) obtained by Droege and Tully and Sprengnether et al (Droege and Tully, Comparison of Experimental in this work with the reported in the literature…”

“…The error, σ av , was given by: σ av = (1/σ ref1 +1/σ ref2 +…) -0.5 . b: (Demore and Bayes, 1999); c: (Mellouki et al, 1994); d: (Talukdar et al, 1994); e: (Atkinson and Arey, 2003); f: (Cox et al, 1980); g: (Morin et al, 2015); h: (Wilson et al, 2006); i: (Tully et al, 1986); j: (Edney et al, 1986); k: (Perry et al, 1976); m: (Greiner, 1970a) ; n: (Donahue et al, 1998); o: (Harris and Kerr, 1988); p: (Calvert et al, 2015); q: (Droege and Tully, 1987); r: (Singh et al, 2013); s: (Badra and Farooq, 2015) u: (Sprengnether et al, 2009); t: (Anderson et al, 2004); v: (Greiner, 1970b), y: (Crawford et al, 2011) ; z: (Li et al, 2006); L: (Shaw et al, 2020); w: (Atkinson et al, 1982); A: (Ferrari et al, 1996); B: (Sivaramakrishnan and Michael, 2009); D: (Bejan et al, 2018); F: (Ballesteros et al, 2015). 22% lower than the experimental value obtained in this study.…”

Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

“…The H-abstracting species that were taken into consideration are H, O, OH, O2, HO2, CH3, CH3O2, CH3O and C2H5 (referred to as X in Figures 1 and 2 [18,20,[34][35][36][37][38][39][40], most of them are limited to a narrow temperature range (< 500 K) [18,36,37,39,40] or even just to a single temperature [34,35,38]. In this work we used rate coefficients for the cyclopentane + OH reaction based on the work of Sivaramakrishnan and Michael, who investigated this reaction using shocktube experiments between 813 to 1341 K [20].…”

Thermolysis of 1,3-dioxin-4-ones: fast generation of kinetic data using in-line analysis under flow

“…In addition, rapid collection of data may be facilitated under flow conditions by in-line analysis, and examples employing UV, 2 IR, 3 Raman, 4 Fluorescence 5 and NMR spectroscopy, 6 as well as mass spectrometry 7 and HPLC, 8 have been reported for kinetic study of reactions conducted under steady-state continuous flow conditions. A drawback of using steady-state flow conditions for kinetic studies is that, except where it is feasible to vary the position of an analytical probe along the reactor pathway, 9 a separate experiment is needed for each time point.…”