Department of Mechanical Engineering, Stanford University, Stanford, California 94305, USA.
J Phys Chem A. 2010 May 13;114(18):5718-27. doi: 10.1021/jp100204z.
The rate constants of the reactions: (1) H2O2+M-->2OH+M, (2) OH+H2O2-->H2O+HO2 were measured in shock-heated H(2)O(2)/Ar mixtures using laser absorption diagnostics for H(2)O and OH. Time-histories of H(2)O were monitored using tunable diode laser absorption at 2550.96 nm, and time-histories of OH were achieved using ring dye laser absorption at 306 nm. Initial H(2)O(2) concentrations were also determined utilizing the H(2)O diagnostic. On the basis of simultaneous time-history measurements of OH and H(2)O, k(2) was found to be 4.6 x 10(13) exp(-2630 K/T) [cm(3) mol(-1) s(-1)] over the temperature range 1020-1460 K at 1.8 atm; additional measurements of k(2) near 1 atm showed no significant pressure dependence. Similarly, k(1) was found to be 9.5 x 10(15) exp(-21 250 K/T) [cm(3) mol(-1) s(-1)] over the same temperature and pressure range.
反应（1）H2O2+M→2OH+M 和（2）OH+H2O2→H2O+HO2 的速率常数在使用激光吸收诊断法测量的 H2O2/Ar 混合物中的激波加热下进行了测量，该方法用于 H2O 和 OH 的激光吸收。使用可调谐二极管激光吸收在 2550.96nm 处监测 H2O 的时间历程，使用环形染料激光吸收在 306nm 处监测 OH 的时间历程。还利用 H2O 诊断法确定了初始 H2O2 浓度。基于 OH 和 H2O 的同时时间历程测量，在 1.8atm 下，温度范围为 1020-1460K 时，k2 被发现为 4.6×10(13)exp(-2630K/T)[cm3mol-1s-1]；在 1atm 附近进行的 k2 的附加测量表明其没有明显的压力依赖性。同样，在相同的温度和压力范围内，k1 被发现为 9.5×10(15)exp(-21250K/T)[cm3mol-1s-1]。
