Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India.
Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India; Centre for Atmospheric and Climate Sciences, Indian Institute of Technology Madras, Chennai, 600036, India.
Chemosphere. 2023 Oct;339:139664. doi: 10.1016/j.chemosphere.2023.139664. Epub 2023 Jul 26.
The relative rate method was employed to investigate the kinetics of the Cl-initiated reactions of 1-chlorobutane (1-CB) and 2-chlorobutane (2-CB) over 263-363 K, and the measured rate coefficients at room temperature are (1.04 ± 0.24) × 10 and (5.84 ± 0.27) × 10 cm molecule s, respectively. The Arrhenius equations for the title reactions were derived to be k (T = 263-363 K) = (2.77 ± 0.72) × 10 exp [(422 ± 79)/T] and k (T = 263-363 K) = (1.40 ± 0.32) × 10 exp [(415 ± 70)/T] cm molecule s, respectively. The products were analysed qualitatively using gas chromatography-mass spectrometry (GC-MS), and the reaction mechanism was proposed for the reactions. The rate coefficients for the title reactions were calculated computationally over the temperature range of 200-400 K using canonical variational transition state theory with appropriate tunnelling corrections at CCSD(T)/6-311++G(2d,2p)//BHandHLYP/6-311++G(2d,2p) level of theory to complement our experimentally measured kinetic parameters. The experimental and theoretical data obtained were used to evaluate the impact of the studied molecules in the troposphere.
相对速率法被用于研究 1-氯丁烷（1-CB）和 2-氯丁烷（2-CB）在 263-363 K 下的 Cl 引发反应动力学，在室温下测量的速率系数分别为(1.04 ± 0.24)×10 和 (5.84 ± 0.27)×10 cm 分子 s。推导出了标题反应的阿仑尼乌斯方程，分别为 k（T = 263-363 K）=(2.77 ± 0.72)×10 exp[(422 ± 79)/T]和 k（T = 263-363 K）=(1.40 ± 0.32)×10 exp[(415 ± 70)/T]cm 分子 s。使用气相色谱-质谱联用仪（GC-MS）对产物进行了定性分析，并提出了反应机制。在 200-400 K 的温度范围内，使用正则变分过渡态理论并结合适当的隧道校正，在 CCSD(T)/6-311++G(2d,2p)//BHandHLYP/6-311++G(2d,2p)理论水平上计算了标题反应的速率系数，以补充我们实验测量的动力学参数。利用实验和理论数据评估了研究分子在对流层中的影响。
