dorsal/arxiv
View SchemaThe form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics
| Authors | Christopher G. Jesudason |
|---|---|
| Categories | |
| ArXiv ID | physics/0608073 |
| URL | https://arxiv.org/abs/physics/0608073 |
Abstract
The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association as a n-meric process, ion activity coefficients may in principle be determined under varying applicable assumptions.
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"abstract": "The rates or formation and concentration distributions of a dimer reaction\nshowing hysteresis behavior are examined in an ab initio chemical reaction\ndesigned as elementary and where the hysteresis structure precludes the\nformation of transition states (TS) with pre-equilibrium and internal\nsub-reactions. It was discovered that the the reactivity coefficients, defined\nas a measure of departure from the zero density rate constant for the forward\nand backward steps had a ratio that was equal to the activity coefficient ratio\nfor the product and reactant species. From the above observations, a theory is\ndeveloped with the aid of some proven elementary theorems in thermodynamics,\nand expressions are derived whereby a feasible experimental and computational\nmethod for determining the activity coefficients from the rate constants may be\nobtained The theory developed is applied to ionic reactions where the standard\nBronsted-Bjerrum rate equation and exceptions to this are rationalized, and by\nviewing ion association as a n-meric process, ion activity coefficients may in\nprinciple be determined under varying applicable assumptions.",
"arxiv_id": "physics/0608073",
"authors": [
"Christopher G. Jesudason"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"title": "The form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics",
"url": "https://arxiv.org/abs/physics/0608073"
},
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