dorsal/arxiv
View SchemaAn energy interconversion principle applied in reaction dynamics for the determination of equilibrium standard states
| Authors | Christopher G. Jesudason |
|---|---|
| Categories | |
| ArXiv ID | physics/0505209 |
| URL | https://arxiv.org/abs/physics/0505209 |
Abstract
Chemical theories involving thermodynamical equilibrium states invariably utilize statistical mechanical equilibrium density distributions. Here, a definition of heat-work transformation termed thermo mechanical coherence is first made, and it is conjectured that most molecular bonds have the above heat-work transformation property, which models a chemical bond as a "`centrifugal heat engine"' . Expressions are derived for the standard Gibbs free energy, enthalpy, and entropy where the bond coordinates need not conform to a non degenerate Boltzmann state, since bond breakdown and formation are processes that have direction, whereas equilibrium distributions are derived when the Hamiltonian is of fixed form, which is not the case for chemical reactions using localized Hamiltonians. The empirically determined Gibbs free energy from a known molecular dynamics simulation of a dimer reaction 2A--> A_2, accords rather well with the theoretical estimate. A relation connecting the rate of reaction with the equilibrium constant and other kinetic parameters is derived and could place the commonly observed linear relationship between the logarithms of the rate constant and equilibrium constant on a firmer theoretical footing. These relationships could include analogues of the Hammett correlations used extensively in physical organic chemistry, as well as others which are temperature dependent.
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"abstract": "Chemical theories involving thermodynamical equilibrium states invariably\nutilize statistical mechanical equilibrium density distributions. Here, a\ndefinition of heat-work transformation termed thermo mechanical coherence is\nfirst made, and it is conjectured that most molecular bonds have the above\nheat-work transformation property, which models a chemical bond as a\n\"`centrifugal heat engine\"\u0027 . Expressions are derived for the standard Gibbs\nfree energy, enthalpy, and entropy where the bond coordinates need not conform\nto a non degenerate Boltzmann state, since bond breakdown and formation are\nprocesses that have direction, whereas equilibrium distributions are derived\nwhen the Hamiltonian is of fixed form, which is not the case for chemical\nreactions using localized Hamiltonians. The empirically determined Gibbs free\nenergy from a known molecular dynamics simulation of a dimer reaction 2A--\u003e\nA_2, accords rather well with the theoretical estimate. A relation connecting\nthe rate of reaction with the equilibrium constant and other kinetic parameters\nis derived and could place the commonly observed linear relationship between\nthe logarithms of the rate constant and equilibrium constant on a firmer\ntheoretical footing. These relationships could include analogues of the Hammett\ncorrelations used extensively in physical organic chemistry, as well as others\nwhich are temperature dependent.",
"arxiv_id": "physics/0505209",
"authors": [
"Christopher G. Jesudason"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"title": "An energy interconversion principle applied in reaction dynamics for the determination of equilibrium standard states",
"url": "https://arxiv.org/abs/physics/0505209"
},
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