Kinetics and thermochemistry of ClCO formation from the Cl+CO association reaction
Kinetics and thermochemistry of ClCO formation from the Cl+CO association reaction
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DOI：
10.1063/1.457862
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发表时间：
1990-03
影响因子：
4.4
通讯作者：
J. Nicovich;K. Kreutter;P. Wine
中科院分区：
文献类型：
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作者：
J. Nicovich;K. Kreutter;P. Wine
激光闪光光解的Cl 2/CO/M混合物（M=N2，CO，Ar，CO2）已被用于与Cl（2 PJ）的时间分辨共振荧光光谱检测相结合，以研究反应中的平衡动力学Cl（2 PJ）+CO ParticClCO作为温度（185-260 K）和压力（14-200 Torr）的函数。发现缔合和解离反应在所研究的实验条件范围内处于低压极限。在N2和/或CO缓冲气体中，ClCO生成和解离反应速率常数的温度依赖性由阿雷尼乌斯表达式k1=（1.05±0.36）×10−34 exp[（810±70）/T] cm 6 molecule−2 s−1和k−1=（4.1±3.1）×10−10 exp[（−2960±160）/T] cm 3 molecule−1 s−1描述（误差为2σ）。第二和第三定律分析了平衡常数（k1/k−1）与温度的关系，得出了缔合反应的热力学参数：Δ H 0298 =−7.7±0.6 kcal mol−1，Δ H 00 =−6.9±0.7 kcal mol−1，Δ S 0298 =−23.8±2.0 cal mol −1 K−1，Δ H 00 =− 6.9 ± 0.7 kcal mol − 1。
Laser flash photolysis of Cl2/CO/M mixtures (M=N2, CO, Ar, CO2) has been employed in conjunction with Cl(2PJ) detection by time‐resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl(2PJ) +CO↔ClCO as a function of temperature (185–260 K) and pressure (14–200 Torr). The association and dissociation reactions are found to be in the low‐pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k1=(1.05±0.36)×10−34 exp[(810±70)/T] cm6 molecule−2 s−1 and k−1=(4.1±3.1)×10−10 exp[(−2960±160)/T] cm3 molecule−1 s−1 (errors are 2σ). Second‐ and third‐law analyses of the temperature dependence of the equilibrium constant (k1/k−1) lead to the following thermodynamic parameters for the association reaction: ΔH0298 =−7.7±0.6 kcal mol−1, ΔH00 =−6.9±0.7 kcal mol−1, ΔS0298 =−23.8±2.0 cal mole−1 K−1, Δ...