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Identification of two-step chemical mechanisms and determination of thermokinetic parameters using frequency responses to small temperature oscillations
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10.1063/1.4811288
/content/aip/journal/jcp/138/24/10.1063/1.4811288
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/24/10.1063/1.4811288

Figures

Image of FIG. 1.
FIG. 1.

Protocol to be followed to determine a chemical mechanism from the frequency responses of the considered reactive system submitted to a temperature modulation. This method also provides all the rate constants and enthalpies of reaction without need of fitting.

Image of FIG. 2.
FIG. 2.

Frequency behavior of the (ω) function. The color lines correspond to the responses issued from the various chemical systems described in Table I and modeled by Eq. (1) : the and concentrations have been computed for all possible (, , ) triplets and introduced in Eq. (7) . The values for the different kinetic parameters are s, s, s, s, ε = 10, ε = 13, ε = 12, and ε = 6. The total concentration is chosen as a unit reference concentration. The unit of (ω) and ω is s.

Image of FIG. 3.
FIG. 3.

Frequency behavior of the two (ω) functions built when the stoichiometry of the mechanism described in Eq. (1) is assumed to obey (, , ) = (2, 0, 1). The various color lines correspond to the responses issued from the various chemical systems described in Table I : the , , and concentrations have been computed for all possible (, , ) triplets and introduced in Eqs. (20) and (21) . The values for the different kinetic parameters are identical to the ones used in Fig. 2 . The (ω) functions have the same unit as and the unit of ω is s.

Image of FIG. 4.
FIG. 4.

Frequency behavior of the two (ω) functions built when the stoichiometry of the mechanism described in Eq. (1) is assumed to obey (, , ) = (2, 0, 1). The various color lines correspond to the responses issued from the various chemical systems described in Table I : the , , and concentrations have been computed for all possible (, , ) triplets and introduced in Eqs. (22) and (23) . The values for the different kinetic parameters are identical to the ones used in Fig. 2 . The function (ω) is dimensionless and the unit of ω is s.

Tables

Generic image for table
Table I.

Examples of proteins where folding obeys the various mechanisms that can be depicted by Eq. (1) . Considering a given set of stoichiometric coefficients (, , ), the intermediate I is an -mer and the product P is an ( + )-mer. The assumed dynamical process used to illustrate our method, (2, 0, 1), is emphasized in bold. We could not find any relevant example for the (1, 1, 1) case.

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/content/aip/journal/jcp/138/24/10.1063/1.4811288
2013-06-27
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Identification of two-step chemical mechanisms and determination of thermokinetic parameters using frequency responses to small temperature oscillations
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/24/10.1063/1.4811288
10.1063/1.4811288
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