Kinetics study of the reaction of OH radicals with C5-C8 cycloalkanes at 240-340 K using the relative rate/discharge flow/mass spectrometry technique.
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.
Department of Chemistry and Biochemistry, California State University Fullerton , Fullerton, California 92834, United States.
Sumitpal
S
Singh
Maria Fatima
MF
de Leon
Zhuangjie
Z
Li