RICE 2 Experimental theory

Sigmundsson K., Masson G., Rice R., Beauchemin N., and Obrink B. (2002), Determination of active concentrations and association and dissociation rate constants of interacting biomolecules an analytical solution to the theory for kinetic and mass transport limitations in biosensor technology and its experimental verification, Biochemistry 41, 8263-8276. 

D.W. Rice, CombstnFlame 8(1), 21-8 (1964) CA 60, 14325 (1964) (Effect of compositional variables upon oscillatory combustion of solid rocket propellants) N ) R.W. Hart F.T. McClure, "Theory of Acoustic Instability in Solid Propellant Rocket Combustion , lOthSympCombstn (1965), pp 1047-65 N2) E.W. Price, "Experimental Solid Rocket Combustion Instability , Ibid, pp 1067-82 Qi) R.S. Levine, "Experimental Status of High Frequency Liquid Rocket Combustion Instability , Ibid, pp 1083-99 O2) L. Crocco,... 

A thermal explosion theory as developed by D.A. Frank-Kamenetskil (Ref 5) led to the equation AT = -[Pg.565]

In Sect. 2, a few experimental results were mentioned which strongly indicate that some molecular reactions are limited by the rate of approach of reactants to form an encounter pair. There have been many hundreds of studies of the rates of reaction in solution. Some studies are discussed in books and reviews by Grunwald et al. [19], Pilling [35], Sutin [15], Rice and Pilling [39], Hart and Anbar [17], Birks [6] and Lorand [22]. As it is not the purpose of this article to consider all these studies but to select some of the more recent, detailed and interesting studies to compare theory and experiment, the reader is encouraged to consult these articles as well as this review. 

Rabinovitch et al. (85) studied the reaction of H atoms with trans-ethylene-d2 as a function of ethylene pressure in the temperature range — 78 to 160°C. They were able to account for all secondary reactions of the hot ethyl radicals and to determine the rates of their decomposition (relative to stablization). Simultaneously they calculated the theoretical rates on the basis of the Rice-Ramsperger-Kassel theory of uni-molecular reactions, using expressions derived by Marcus (71), and found a reasonable agreement with the experimental values. Similar satisfactory agreements had been found previously by Rabinovitch and Die-sen (84) for hot sec-butyl radicals. Extensive studies of hot radicals produced by H or D atom additions to various olefins have been carried... 

On the basis of the theory of free radical chains one can often predict not only reaction rates, chain lengths and orders of reaction, but nature of products and the influence of temperature and walls. In the experimental studies Rice adopts a simplifying procedure which, although somewhat unsatisfactory, is justified by its simplicity. The reaction is allowed to proceed only partially to completion—perhaps ten per cent. If it goes nearly to completion the decomposition products themselves will decompose and react so that the original reaction will be largely obscured. 

The development of a theory of unimolecular reactions proceeded rapidly in the mid-1920s, initiated by Hinshelwood with an A whose collision-free lifetime for reaction was approximated by an energy-independent one. The analysis was much elaborated by Rice and Ramsperger [60] and Kassel [61], known later as the RRK theory, where now the lifetime was, as it is in modern times, energy-dependent [62]. These theoretical works of the 1920s stimulated many measurements of the unimolecular rates of dissociation of organic compounds as a function of the gas pressure. Within a few years, however, this entire field collapsed or, more precisely, evolved into a new field It was shown experimentally that the unimolecular reactions , assumed originally to consist of only one chemical step, in-... 

Forst treated the decomposition of azomethane with the quantum harmonic version of the Marcus-Rice theory of unimolecular reactions. He used different models which comprised three dimensional free rotations of the two methyls and of the central nitrogen molecule and adjusted the overall moments of inertia to give the correct total entropy. For planar or tetrahedral methyls calculations gave an increase of six in the number of active rotations in going from the molecule to the complex. With a minimum of assumption it was also possible to reproduce the pressure fall-off curve of the experimental first order rate coefficient for planar and tetrahedral complexes. A further result of the computations is the conclusion that the vibrational frequency pattern of the complex is so much less important than the number of active rotations that both tetrahedral and planar complexes lead to identical fall-off behaviour. 

In the review we discuss the recent developments which have led to a unified quantum mechanical theory of all of the diverse phenomena which are classified as involving radiationless processes. Since the recent developments and the resultant description of the radiationless processes are the main interest, reference to the older work is made only insofar as it is necessary for the sake of clarity and completeness. Except for some (very interesting) recent developments, the experimental basis for our understanding of radiationless processes is reviewed by Jortner, Rice, and Hochstrasser 0, so it need not be repeated here, except to illustrate some typical behavior. 

In the case of pure liquids numerical computations for the transport coefficients in argon, krypton, and xenon have been carried out by Palyvos et al. using a modified Lennard-Jones potential and the radial distribution function of Kirkwood, Lewinson, and Alder. The results, for instance for argon, represent percentages betw een 60 and 90% of the experimental values in a wide range of temperatures and densities. Besides, they agree with experiment better than the results derived from the Kirkwood of Rice-AIInatt types of theories. 

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