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Titolo:
Applications of non-steady-state kinetics in physical organic chemistry: guidelines for the resolution of the kinetics of complex reaction mechanisms
Autore:
Parker, VD; Zhao, YX;
Indirizzi:
Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA Utah State UnivLogan UT USA 84322 pt Chem & Biochem, Logan, UT 84322 USA
Titolo Testata:
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
fascicolo: 9, volume: 14, anno: 2001,
pagine: 604 - 611
SICI:
0894-3230(200109)14:9<604:AONKIP>2.0.ZU;2-H
Fonte:
ISI
Lingua:
ENG
Soggetto:
TOLUENE SOLUTION; INTERNAL RETURN; AMINE BASES; (4-NITROPHENYL)NITROMETHANE; ABSENCE;
Keywords:
non-steady-state kinetics; complex mechanisms; reaction kinetics;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
18
Recensione:
Indirizzi per estratti:
Indirizzo: Parker, VD Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA Utah State Univ Logan UT USA 84322 iochem, Logan, UT 84322 USA
Citazione:
V.D. Parker e Y.X. Zhao, "Applications of non-steady-state kinetics in physical organic chemistry: guidelines for the resolution of the kinetics of complex reaction mechanisms", J PHYS ORG, 14(9), 2001, pp. 604-611

Abstract

The resolution of the kinetics of the reversible consecutive second-order reaction mechanismA + B reversible arrow (kf)(kb) I --> P-kpinvolving the formation of a kinetically significant intermediate, which does not reach steady state before late in the first half-life, followed by an irreversible product-forming reaction is discussed. It is shown that an apparent second-order rate constant k(app) and an extent of reaction-time profile are the only experimental data necessary for the evaluation of k(f) and k(b) (the forward and reverse rate constants) as well as k(p) (the microscopic rate constant for the product forming reaction), When the product-forming step involves the cleavage of a C-H bond, for which there is a deuterium kinetic isotope effect on kp, the resolution of the kinetics is enhanced. In this case, the experimental data include two apparent rate constants(k(app)(H) and k(app)(D)) and two extent of reaction-time profiles, one for normal reactants app and the other for isotopically substituted reactants. Under these circumstances, a unique highly resolved experimental to theoretical data fit is found that results in the evaluation of all four microscopic rate constants: k(f), k(b), k(p)(H) and k(p)(D). An alternative, when a kinetic isotope effect is not involved, is to fit the extent of reaction-time profiles for two or more concentrations of reactants concurrently. This procedure results in the resolution of the three microscopic rate constants for the reaction. Copyright (C) 2001 John Wiley & Sons, Ltd.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 29/11/20 alle ore 00:46:57