Kinetics of deuterium exchange on resorcinol in D2O at high pressure and high temperature
Kinetics of deuterium exchange on resorcinol in D2O at high pressure and high temperature
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DOI：
10.1021/jp991192r
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发表时间：
2000-01-13
影响因子：
2.9
通讯作者：
Yonker, CR
中科院分区：
文献类型：
--
作者：
Bai, S;Palmer, BJ;Yonker, CR
首次在高温高压条件下，采用流通式毛细管式反应器，在线检测了间苯二酚在纯D2O中的氢、氢、氢核磁共振反应动力学。在接近400bar的压力下(水的临界温度和压力分别为374.2摄氏度和218.3巴)，在200C-450K(723K)的温度下确定了氢/氢(H/D)交换的全球速率常数。用质子核磁共振技术测定了间苯二酚(1，3-二酚)在这些极端条件下的H/D交换率随间苯二酚在毛细管式反应器中的停留时间的变化，该反应器也用作高压核磁共振池。H-1和H-2核磁共振结果表明，在200℃下，环状质子在间苯二酚中发生了H/D交换。从H-1核磁共振实验数据中提取了间苯二酚的H/D交换动力学和活化能。
The kinetics of deuteration of resorcinol in pure D2O were studied for the first time using a flow-through capillary tubular reactor with on-line, proton, and deuterium NMR detection at high temperatures and high pressure. The global rate constants for hydrogen/deuterium (H/D) exchange were determined from temperatures of 200-450 degrees C (723 K) at a pressure of similar to 400 bar (the critical temperature and pressure of water are 374.2 degrees C and 218.3 bar, respectively). The H/D exchange rate in resorcinol (1,3-dihydroxybenzene) under these extreme conditions was determined using proton NMR as a function of the resorcinol residence time in a capillary tubular reactor, which also served as a high-pressure NMR cell. The H-1 and H-2 NMR results indicate that H/D exchange in resorcinol for the ring protons was observed at temperatures as low as 200 degrees C. The kinetics of H/D exchange in resorcinol and the activation energy was extracted from the experimental H-1 NMR data.