Measurement of reaction rate constants using RCM: A case study of decomposition of dimethyl carbonate to dimethyl ether
Measurement of reaction rate constants using RCM: A case study of decomposition of dimethyl carbonate to dimethyl ether
复制标题
使用 RCM 测量反应速率常数：碳酸二甲酯分解为二甲醚的案例研究
DOI：
10.1016/j.combustflame.2017.05.006
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发表时间：
2017-09
影响因子：
4.4
通讯作者：
Feng Zhang
中科院分区：
文献类型：
--
作者：
Peng Zhang;Shuang Li;Yingdi Wang;Weiqi Ji;Wenyu Sun;Bin Yang;Xin He;Zhi Wang;Chuang K. Law;Feng Zhang
This paper proposes a method to measure the reaction rate constants in kinetically-simple pyrolysis systems using rapid compression machine (RCM) and fast sampling. The method involves first performing sensitivity analysis based on a reasonable kinetic model to identify the species dominated by a target reaction. Then the time-resolved species concentration profiles are measured in RCM experiments using fast sampling and gas chromatography. Finally, the pre-assigned pre-exponential factor and the activation energy are optimized by an iterative fitting procedure, in which the entire temperature profile derived from the pressure history is taken into account. In order to validate this method, the rate constant of the reaction CH 3 OCHO (methyl formate, MF)=> CH 3 OH+ CO (R1) was determined by measuring the CO concentration over 948–1112 K at 30 bar, obtaining the rate expression k R 1/s− 1= 3.04× 10 13 exp (− 30968 K/T), which is consistent with previous theoretical and experimental studies. The rate constant of the reaction CH 3 OCOOCH 3 (dimethyl carbonate, DMC)=> CH 3 OCH 3 (dimethyl ether, DME)+ CO 2 (R2) was then studied by measuring the time-resolved DME concentration over 994–1068 K at 30 bar. The measured rate expression of k R 2/s− 1= 2.02× 10 13 exp (− 34248 K/T) with an uncertainty of±30% agrees well with the RRKM/Master Equation calculation based on a high-level quantum chemical potential energy surface.
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影响因子：
4.4
作者：
L. Roblee
通讯作者：
L. Roblee
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影响因子：
4.4
作者：
Haisheng Di;Xin He;Peng Zhang;Zhi Wang;Margaret S. Wooldridge;Chung K. Law;Cuiping Wang;Shijin Shuai;Jianxin Wang
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影响因子：
4.4
作者：
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通讯作者：
Apurba K. Das;Apurba K. Das;M. Uddi;C. Sung
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
4.4
作者：
Wei Ren;E. Dames;Derrek Hyland;D. Davidson;R. Hanson
通讯作者：
Wei Ren;E. Dames;Derrek Hyland;D. Davidson;R. Hanson