Parandaman A, Rajakumar B
Department of chemistry, Indian Institute of Technology Madras , Chennai 600036, India.
J Phys Chem A. 2016 Oct 20;120(41):8024-8036. doi: 10.1021/acs.jpca.6b06386. Epub 2016 Oct 7.
A single pulse shock tube was used to study the thermal decomposition of 2-pentanol in the temperatures between 1110 and 1325 K. Three major decomposition products are methane, ethylene, and propylene. The minor products detected in lower concentration are ethane, acetylene, acetaldehyde, 1-pentene, and 2-pentene. The rate coefficient for the overall decomposition of 2-pentanol was found to be k(1110-1325 K) = (4.01 ± 0.51) × 10 exp(-(36.2 ± 4.7)/RT) s, where the activation energies are given in kcal mol. To simulate reactant and product distribution over the experimentally studied temperatures between 1110 and 1325 K, a reaction scheme was constructed with 34 species and 39 reactions. In addition to this, the temperature and pressure dependent rate coefficients were computed for various unimolecular dissociation pathways using RRKM theory. The high pressure limit rate coefficient for overall decomposition of 2-pentanol was obtained to be k(500-2500 K) = (9.67 ± 1.11) × 10 exp(-(67.7 ± 2.9)/RT) s. The calculated high pressure rate coefficients and experimentally measured rate constants are in good agreement with each other. The reaction is primarily governed by the unimolecular elimination of water.
使用单脉冲激波管研究了2-戊醇在1110至1325 K温度范围内的热分解。三种主要分解产物是甲烷、乙烯和丙烯。检测到的低浓度次要产物是乙烷、乙炔、乙醛、1-戊烯和2-戊烯。发现2-戊醇总体分解的速率系数为k(1110 - 1325 K) = (4.01 ± 0.51) × 10 exp(-(36.2 ± 4.7)/RT) s，其中活化能以kcal mol给出。为了模拟在1110至1325 K实验研究温度范围内的反应物和产物分布，构建了一个包含34种物质和39个反应的反应方案。除此之外，使用RRKM理论计算了各种单分子解离途径的温度和压力依赖性速率系数。2-戊醇总体分解的高压极限速率系数为k(500 - 2500 K) = (9.67 ± 1.11) × 10 exp(-(67.7 ± 2.9)/RT) s。计算得到的高压速率系数与实验测量的速率常数彼此吻合良好。该反应主要由水的单分子消除控制。
