Development of a kinetic analysis to elucidate the dynamics chemical reactions

开发动力学分析来阐明动力学化学反应

• 批准号: 08454181
• 负责人: YAMASAKI Katsuyoshi
• 金额: $ 4.35万
• 依托单位: Niigata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454181/
• 关键词: Reaction rate constant; Vibrational relaxation; Laser-induced fluorescence; Linear analysis; レーザ励起蛍光; 振動分布

A new method has been developed to determine the branching ratios between reactive removal and vibrational relaxation. The method needs information on neither photochemical parameters nor relative detectivities of vibrational levels of interest. We applied the method to analyze the time-dependent profiles of the laser-induced fluorescence (LIF) signals of OH (X^2PI_i, upsiron=OMICRON -4) produced in the reactions O (^1D) +CH_4 and O (^1D) +NH_3. The OH (upsiron) were deteced by LIF excited via A^2SIGMA^+-X^2PI_i transitions of the sequences DELTAupsiron=OMICRON (upsiron^"=0,1, and 2) and DELTAupsiron=-3 (upsiron^"=3 and 4). The rate constants for the reactive removal of OH by CH_4 were determined to be kappa (upsiron=1) =1.8*10^<-13> and kappa (upsiron=2) =1.0*10^<-12> cm^3 molecule^<-1> s^<-1>, and those of OH (upsiron) by NH_3 were kappa upsiron=1) =8.4*10^<-12> and kappa (upsiron=2) =6.4*10^<-11> cm^3 molecule^<-1> s^<-1>. Rate constants for vibrational relaxation of OH (upsiron) +CH_4 * OH (upsiron-1) +CH_4 were kappa (upsiron=1) =4.2*10^<-13> and kappa (upsiron=2) =1.3*10^<-12> cm^3 molecule^<-1> s^<-1>, and those of OH (upsiron) +NH_3 were kappa (upsiron=1) =2.5*10^<-11> and kappa (upsiron=2) =6.4*10^<-11> cm^3 molecule^<-1> s^<-1>. Reactive removal of OH (upsiron=1) by CH_4 was 29 times faster than that for OH (upsiron=OMICRON) ; that of OH (upsiron=1) by NH_3 was accelerated by a factor of 52. The ratio of the reactive removal OH (upsiron=2) /OH (upsiron=1) was 5.6 for the reaction with CH_4, and 7.6 for that with NH_3. It has also been found that reactive processes (reactions) are more enhanced than physical processes (relaxation) by a vibrational excitation. This is the first report on the determination of the branching ratios between chemical reaction and vibrational relaxation.

发展了一种新的方法来确定反应去除和振动弛豫之间的分支比。该方法既不需要光化学参数的信息，也不需要感兴趣的振动能级的相对探测率的信息。我们用这种方法分析了O(^1D)+CH4和O(^1D)+NH_3反应中产生的OH(X^2pi，upsiron=Omicron-4)的激光诱导荧光(LIF)信号随时间的分布。通过序列DELTAupsiron=Omicron(upsiron^“=0，1和2)和DELTAupsiron=-3(upsiron^”=3和4)的A^2SIGMA^+-X^2pi跃迁激发LIF探测到了OH(Upsiron)。测得CH4反应脱除OH的速率常数kappa(upsiron=1)=1.8×10^-13；-13；kappa(upsiron=2)=1.0*10；-12；-12；cm^3分子^-1；-1；S；-1；-1；NH_3对OH(Upsiron)的反应速率常数为kappa upsiron=1)=8.4×10^&lt；-12&gt；和kappa(upsiron=2)=6.4*10^lt；-11&gt；cm^3分子^1；-1&gt；S^1；-1&gt；其振动弛豫速率常数分别为kappa(upsiron=1)=4.2×10^-lt；-13和kappa(upsiron=2)=1.3*10^-lt；-12&gt；cm^3分子^-1&gt；S^-1；-1&gt；和OH(upsiron=1)+NH_3分别为kappa(upsiron=1)=2.5*10^&lt；-11&gt；和kappa(upsiron=2)=6.4*10^&lt；-11&gt；-1&gt；S^&lt；CH4对OH(upsiron=1)的反应脱除速度是OH(upsiron=Omicron)的29倍，NH3对OH(upsiron=1)的反应速度提高了52倍。CH_4和NH_3反应的反应脱除OH(upsiron=2)/OH(upsiron=1)之比分别为5.6和7.6。实验还发现，振动激发对反应过程(反应)的促进作用大于物理过程(松弛)。这是首次报道了化学反应和振动弛豫之间支化比的测定。

项目成果

Katsuyoshi Yamasaki: "Application of a new method to the determination of rate constants : Examination of the effect of noise an the data" International Journal of Chemical Kinetics. 30. 47-54 (1998)

Katsuyoshi Yamasaki：“应用新方法测定速率常数：检查噪声和数据的影响”国际化学动力学杂志。

Katsuyoshi Yamasaki: "Application of a new method to the determination of the rate constants : Examination of the effect of noise the data" International Journal of Chemical Kinetics. 30. 47-54 (1998)

Katsuyoshi Yamasaki：“应用新方法测定速率常数：检查噪声数据的影响”国际化学动力学杂志。

山さき勝義: "A new method of determining the rate constants for state-to-state vibrational relaxation : an integrated profiles method" Bulletin of the Chemical Society of Japan. 70・1. 89-95 (1997)

Katsuyoshi Yamasaki：“确定状态间振动弛豫速率常数的新方法：综合轮廓方法”日本化学会通报70・1（1997）。

Katsuyoshi Yamasaki: "Application of a new method to the determination of rate constants: Examination of the effect of noise on the data" Interrational Journal of Chemical Kinetics. 30. 47-54 (1998)

Katsuyoshi Yamasaki：“应用一种新方法来确定速率常数：检查噪声对数据的影响”Interrational Journal of Chemical Kinetics。

Katsuyoshi Yamasaki: "A new method of determining the rate constants for stateto - state vibrational relaxation : an integrated profiles method" Bulletin of the Chemical Society of Japan. 70・1. 89-95 (1997)

Katsuyoshi Yamasaki：“确定状态振动弛豫速率常数的新方法：综合轮廓方法”日本化学会通报70・1（1997）。