Коэффициенты скорости обменных реакций в воздухе и углекислом газе


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Rate Coefficients of Exchange Reactions in Air and Carbon Dioxide

A simple theoretical Treanor-Marrone model is generalized to calculate state-resolved ex-change reaction rate coefficients in air and carbon dioxide. An analytical dependence of the activation energy on the vibrational energy of the reactants and products is obtained for the Zeldovich reactions. This allows taking into account the vibrational excitation of NO molecules formed as a result of exchange reactions. The state-resolved reaction rate coefficients calculated using the proposed model are in good agreement with the latest data of quasi-classical trajectory calculations. The developed approach is applied to calculate the state-resolved exchange reaction rate coefficients in carbon dioxide. The effect of the model parameter on the reaction rate coefficients is estimated. Multi-temperature rate coefficients of exchange reactions in CO2 are calculated under conditions characteristic for shock waves on the basis of vibrational distributions taking into account fast intermode VV exchange between symmetric and bending modes and slow VT relaxation in bending and antisymmetric modes. The effect of vibrational excitation of various modes on the reaction rate is discussed.

vibrational-chemical kinetics, state-to-state model, exchange reactions.

DOI: http://doi.org/10.33257/PhChGD.19.3.759


Том 19, выпуск 3, 2018 год



Проведено обобщение простой теоретической модели Тринора-Маррона для расчета поуровневых коэффициентов скорости обменных реакций в воздухе и углекислом газе. Для реакций Зельдовича получена аналитическая зависимость энергии активации от колебательной энергии реагентов и продуктов. Это позволило учесть колебательное возбуждение молекулы NO, образующейся в результате обменных реакций. Коэффициенты скорости реакций, рассчитанные по предложенной модели, хорошо согласуются с последними данными квазиклассических траекторных расчетов. Разработанный подход применен для вычисления поуровневых коэффициентов скорости обменных реакций в углекислом газе, оценено влияние параметра модели на скорость реакции. Проведен расчет многотемпературных коэффициентов скорости обменных реакций в CO2 в условиях, характерных для течений за ударными волнами. При этом использованы колебательные распределения, учитывающие быстрый межмодовый VV обмен между симметричной и деформационной модами и замедленную VT релаксацию в деформационной и антисимметричной модах. Обсуждается влияние колебательного возбуждения различных мод на скорость реакции.

колебательно-химическая кинетика, поуровневая модель, обменные реакции.

DOI: http://doi.org/10.33257/PhChGD.19.3.759


Том 19, выпуск 3, 2018 год



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