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KINETICS IN SOLIDS (1997)

Vyazovkin, S. ; Wight, C. A.

Palo Alto, Calif. : Annual Reviews

Annual Review of Physical Chemistry 48 (1997), S. 125-149

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ISSN: 0066-426X

Source: Annual Reviews Electronic Back Volume Collection 1932-2001ff

Topics: Chemistry and Pharmacology , Physics

Notes: Abstract The kinetics of solid state reactions generally cannot be assumed to follow simple rate laws that are applicable to gas-phase reactions. Nevertheless, a widely practiced method for extracting Arrhenius parameters from thermal analysis experiments involves force fitting of experimental data to simple reaction-order kinetic models. This method can produce significant errors in predicted rates outside the experimental range of temperatures, and it is of limited utility for drawing mechanistic conclusions about reactions. In this review, we discuss how an alternative "model-free" approach to kinetic analysis, which is based on the isoconversional method, can overcome some of these limitations.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1146/annurev.physchem.48.1.125

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Tunneling dynamics and spatial correlations of long chain growth in solid-state photochlorination of ethylene at low temperatures (1993)

Misochko, E. Ya. ; Wight, C. A. ; Vetoshkin, E. V. ; [et al.]

Springer

Russian chemical bulletin 42 (1993), S. 648-662

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ISSN: 1573-9171

Keywords: cryochemistry ; solid-state reactions ; photochlorination ; chlorine ethylene

Source: Springer Online Journal Archives 1860-2000

Topics: Chemistry and Pharmacology

Notes: Abstract A novel method is described for preparing reactive cryocrystals by deposition of argondiluted reactant beams and subsequent crystallization during evaporation of the inert gas. Photochlorination of equimolecular ethylene—chlorine mixtures obtained by this method and studied by means of kinetic UV- and IR-spectroscopy reveals activationless chain growth with mean length 300 units in the temperature range 17–45 K. Mean chain lengths greater than 100 are observed up to the conversion degree of 0.6–0.7. Comparison of the experimental data with computer simulations shows that the tunneling reaction is due to the formation of a closely packed reaction complex with high amplitudes of zero-point vibrations which lower the reaction barrier. The commensurability of reactant and product crystal lattices results in linear propagation of chains without accumulation of deformation strain. The chain termination mechanism associated with the spatial correlations of chains is discussed.