d 9-Butanol or 1-butan-d 9-ol (D9B) is often used as an OH radical tracer in atmospheric chemistry studies to determine OH exposure, a useful universal metric that describes the extent of OH radical oxidation chemistry. Despite its frequent application, there is only one study that reports the rate coefficient of D9B with OH radicals, k 1(295 K), which limits its usefulness as an OH tracer for studying processes at temperatures lower or higher than room temperature. In this study, two complementary experimental techniques were used to measure the rate coefficient of D9B with OH radicals, k 1(T), at temperatures between 240 and 750 K and at pressures within 2–760 Torr. A thermally regulated atmospheric simulation chamber was used to determine k 1(T) in the temperature range of 263–353 K and at atmospheric pressure using the relative rate method. A low-pressure (2–10 Torr) discharge flow tube reactor coupled with a mass spectrometer was used to measure k 1(T) at temperatures within 240–750 K, using both the absolute and relative rate methods. The agreement between the two experimental aproaches followed in this study was very good, within 6%, in the overlapping temperature range, and k 1(295 ± 3 K) was 3.42 ± 0.26 × 10–12 cm3 molecule–1 s–1, where the quoted error is the overall uncertainty of the measurements. The temperature dependence of the rate coefficient is well described by the modified Arrhenius expression, k 1 = (1.57 ± 0.88) × 10–14 × (T/293)4.60±0.4 × exp(1606 ± 164/T) cm3 molecule–1 s–1 in the range of 240–750 K, where the quoted error represents the 2σ standard deviation of the fit. The results of the current study enable an accurate estimation of OH exposure in atmospheric simulation experiments and expand the applicability of D9B as an OH radical tracer at temperatures other than room temperature.
In the current study, the temperature dependence of the Cl atom rate coefficient with 2‐methyl‐3‐butene‐2‐ol (MBO) is re‐assessed. Relative rate kinetic measurements were performed inside THALAMOS (thermally regulated atmospheric simulation chamber) facility under atmospheric pressure (760 Torr) of zero air in the temperature range of 256–353 K. The rate coefficient of the title reaction was found to be independent of temperature with a value of kMBO = (3.20 ± 0.10) × 10−10 cm3 molecule–1 s–1, where the quoted error corresponds to 2σ standard error of the mean value and includes the overall uncertainty of the measurements. Besides the kinetic study we have also determined the yields of the major products formed, in the temperature range of 273–353 K. Acetone and chloroacetaldehyde were identified as primary oxidation products with almost identical yields, ranging between 60% and 80%. Formaldehyde and methyl vinyl ketone were also observed with yields below 10% and 0.5%, respectively. Our experimental results indicate that the dominant reaction pathway is the addition of Cl atoms to the terminal carbon atom of MBO.
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