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A computational evaluation of the gas‐phase ClO dimerization thermodynamics
Author(s) -
Slanina Zdeněk,
Uhlík Filip
Publication year - 1991
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/91gl02140
Subject(s) - thermodynamics , enthalpy , heat capacity , entropy (arrow of time) , standard enthalpy of formation , standard molar entropy , chemistry , equilibrium constant , thermochemistry , partition function (quantum field theory) , physics , quantum mechanics
The equilibrium constant K P and the standard enthalpy, entropy and heat capacity at constant pressure changes for the ClO ( g ) dimerization are calculated from partition functions. The Cl 2 O 2 partition functions are constructed using recent quantum‐chemical data while in the ClO case spectroscopic information is applied. A due attention is given to the Cl 2 O 2 isomerism, viz. to the individual species ClOOCl ( C 2 symmetry), ClClO 2 ( C 3 ), and ClOClO ( C 1 ). The available observed standard thermodynamic terms are reproduced within their estimated experimental errors, entropy terms yielding a better theory‐experiment agreement (comparing to enthalpy case). The thermodynamic terms are evaluated in a wide temperature interval, pointing out some features not amenable from the observations. The data can be useful in concentration evaluations as an intermediate for elucidating ozone‐depleting mechanisms.