Treatment of Thermal Non-Equilibrium Dissociation Rates: Application to $\rm H_2$
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arXiv
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| Autores principales: | , , , , |
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| Formato: | Preprint |
| Publicado: |
2025
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| _version_ | 1866909447583956992 |
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| author | Carroll, Alex T. Wolmer, Jacob Blanquart, Guillaume Brandis, Aaron M. Cruden, Brett A. |
| author_facet | Carroll, Alex T. Wolmer, Jacob Blanquart, Guillaume Brandis, Aaron M. Cruden, Brett A. |
| contents | This work presents a detailed description of the thermochemical non-equilibrium dissociation of diatomic molecules, and applies this theory to the case of $\rm H_2$ dissociation. The master equations are used to derive corresponding aggregate rate constant expressions that hold for any degree of thermochemical non-equilibrium. These general expressions are analyzed in three key limits/ regimes: the thermal equilibrium limit, the quasi-steady-state (QSS) regime, and the pre-QSS regime. Under several simplifying assumptions, an analytical source term expression that holds in all of these regimes, and is only a function of the translational temperature, $T_{\rm t}$, and the fraction of dissociation, $ϕ_{\rm A}$, is proposed. This expression has two input parameters: the QSS dissociation rate constant in the absence of recombination, $k_{\rm d,nr}(T_{\rm t})$, and a pre-QSS correction factor, $η(T_{\rm t})$. The value of $η(T_{\rm t})$ is evaluated by comparing the predictions of the proposed expression against existing master equation simulations of a 0-D isothermal and isochoric reactor for the case of $\rm H_2$ dissociation with the third-bodies $\rm H_2$, $\rm H$, and $\rm He$. Despite its simple functional form, the proposed expression is able to reproduce the master equation results for the majority of the tested conditions. The best fit of $k_{\rm d,nr}(T_{\rm t})$ is then evaluated by conducting a detailed literature review. Data from a wide range of experimental and computational studies are considered for the third-bodies $\rm H_2$, $\rm H$, and inert gases, and fits that are valid from 200 to 20,000 K are proposed. From this review, the uncertainty of the proposed fits are estimated to be less than a factor of two. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2501_01626 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Treatment of Thermal Non-Equilibrium Dissociation Rates: Application to $\rm H_2$ Carroll, Alex T. Wolmer, Jacob Blanquart, Guillaume Brandis, Aaron M. Cruden, Brett A. Chemical Physics This work presents a detailed description of the thermochemical non-equilibrium dissociation of diatomic molecules, and applies this theory to the case of $\rm H_2$ dissociation. The master equations are used to derive corresponding aggregate rate constant expressions that hold for any degree of thermochemical non-equilibrium. These general expressions are analyzed in three key limits/ regimes: the thermal equilibrium limit, the quasi-steady-state (QSS) regime, and the pre-QSS regime. Under several simplifying assumptions, an analytical source term expression that holds in all of these regimes, and is only a function of the translational temperature, $T_{\rm t}$, and the fraction of dissociation, $ϕ_{\rm A}$, is proposed. This expression has two input parameters: the QSS dissociation rate constant in the absence of recombination, $k_{\rm d,nr}(T_{\rm t})$, and a pre-QSS correction factor, $η(T_{\rm t})$. The value of $η(T_{\rm t})$ is evaluated by comparing the predictions of the proposed expression against existing master equation simulations of a 0-D isothermal and isochoric reactor for the case of $\rm H_2$ dissociation with the third-bodies $\rm H_2$, $\rm H$, and $\rm He$. Despite its simple functional form, the proposed expression is able to reproduce the master equation results for the majority of the tested conditions. The best fit of $k_{\rm d,nr}(T_{\rm t})$ is then evaluated by conducting a detailed literature review. Data from a wide range of experimental and computational studies are considered for the third-bodies $\rm H_2$, $\rm H$, and inert gases, and fits that are valid from 200 to 20,000 K are proposed. From this review, the uncertainty of the proposed fits are estimated to be less than a factor of two. |
| title | Treatment of Thermal Non-Equilibrium Dissociation Rates: Application to $\rm H_2$ |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2501.01626 |