Nonlinear Kinetic Models with Chemical Reactions

Author(s):  
Cecil P. Grünfeld
Author(s):  
Maikel Ballester

Rate coefficients of bi-molecular chemical reactions are fundamental for kinetic models. The rate coefficient dependence on temperature is commonly extracted from the analyses of the reaction minimum energy path. However, a full dimension study of the same reaction may suggest a different asymptotic low-temperature limit in the rate constant than the obtained from the energetic profile.


1978 ◽  
Vol 9 (3) ◽  
pp. 330-348 ◽  
Author(s):  
John F. Wehmiller ◽  
Daniel F. Belknap

Alternative kinetic models for amino acid racemization in Pleistocene molluscan samples are compared by examination of results for samples from marine Pleistocene deposits in California, Washington, and Florida. Linear kinetic models previously have been applied to the Florida samples [ Mitterer, R.M. (1975). Earth and Planetary Science Letters 28 , 275–282.] because these kinetics were observed in laboratory pyrolysis experiments with the particular genus involved (Mercenaria). Nonlinear kinetic models, extrapolated from deep-sea foraminifera racemization kinetics, are applied to samples of Protothaca and Saxidomus from California and Washington and seem more consistent with their local chronologic and stratigraphic control. Average or effective diagenetic temperatures can be estimated by each of these models if reliably dated samples are available. Linear models applied to such samples from California and Florida suggest average diagenetic temperatures that are cooler (by as much as 10°C) than would be inferred from available paleoclimatic records. Nonlinear kinetic models yield estimates of average diagenetic temperatures that are more consistent with these records: full-glacial (i.e., approximately 18,000 yr BP) temperature reductions of between 2 and 6°C are inferred for coastal California and southern Florida. The nonlinear kinetic model is used to expand (by a factor of 2.5 to 3.0) the time scale proposed by Mitterer (1975) for five marine Pleistocene units of Florida.


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