Kinetic/thermodynamic

M. L. Davis, V. V. Vesselovsky, and H. L. Johnston, Kinetics, Thermodynamics, Physico-Chemical Properties and Manufacture ofHydra ne, Ohio State University, Wright-Patterson Air Eorce Base, Dayton, Ohio, Mar. 15, 1952. 

Rozengerk, v. A. Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy Oligomers with Amines. Vol. 75, pp. 113-166. 

In this chapter, the discussion has centred on the redox behaviour of the cyclic systems of a limited range of metal ions. Nevertheless, the examples are of sufficient breadth to illustrate that the redox behaviour of a particular system usually depends upon a fine balance between kinetic, thermodynamic and structural factors in which both the nature of the central metal ion and of the cyclic ligand are major influences. Of course, such considerations are not restricted to macrocyclic systems - however, the latter have provided convenient models for the elucidation of a variety of redox behaviour - much of which is of relevance to other areas and, for example, to many of the natural redox systems. 

Throughout the book I have tried to constrain the wonders of imagination inspired by the subject by using simple calculations. Can all of the water on the Earth have been delivered by comets if so, how many comets How do I use molecular spectroscopy to work out what is happening in a giant molecular cloud Calculations form part of the big hard-sell for astrochemistry and they provide a powerful control against myth. I have aimed the book at second-year undergraduates who have had some exposure to quantum mechanics, kinetics, thermodynamics and mathematics but the book could easily be adapted as an introduction to all of these areas for a minor course in chemistry to stand alone. 

On looking over this collection of new findings and insights, I count myself fortunate in having cultivated a modest competence in mathematics, kinetics, thermodynamics and, especially electrochemistry. Without those skills I would not have been able to do what I did. In other words, it was essential for success - and to avoid gross solecisms - to be multi-facetted, and polymer chemistry as usually understood would just not have been enough. 

Improvement in metal hydride hydrogen storage has been slow in achieving the targets needed for several applications. But slow, steady progress is foreseen as material processing in the nano-range improves the kinetics, thermodynamics, and capacity of the metal hydride systems so that they become acceptable for some applications perhaps for stationary systems. 

Belles [29] essentially established a pure chemical-kinetic-thermodynamic approach to estimating detonation limits. Questions have been raised about the approach, but the line of reasoning developed is worth considering. It is a fine example of coordinating various fundamental elements discussed to this point in order to obtain an estimate of a complex phenomenon. 

How to Cain Access to Kinetics, Thermodynamics, and Mechanisms of Electroorganic Reactions... 

Quantitative analysis relies on a highly probable mechanistic hypothesis and determines as many as possible kinetic, thermodynamic, and/or transport parameters for the various steps. This is often a complex problem, since the values of the parameters are usually correlated, their relation to experimental data is nonlinear, and the data contain artifacts and statistical errors [40, 41]. 

Because cryosolvents must be used in studies of biochemical reactions in water, it is important to recall that the dielectric constant of a solution increases with decreasing temperature. Fink and Geeves describe the following steps (1) preliminary tests to identify possible cryosolvent(s) (2) determination of the effect of cosolvent on the catalytic properties (3) determination of the effect of cosolvent on the structural properties (4) determination of the effect of subzero temperature on the catalytic properties (5) determination of the effect of subzero temperature on the structural properties (6) detection of intermediates by initiating catalytic reaction at subzero temperature (7) kinetic, thermodynamic, and spectral characterization of detected intermediates (8) correlation of low-temperature findings with those under normal conditions and (9) structural studies on trapped intermediates. 

Burbaum et al. considered how kinetic/thermodynamic features of present-day enzyme-catalyzed reactions suggest that enzyme evolution tends to maximize catalytic effectiveness. They analyzed Uni Uni enzymes in terms of reaction energetics. Catalytically optimized enzymes... 

A representation of all of the elementary reactions that lead to the overall chemical change being investigated. This representation would include a detailed analysis of the kinetics, thermodynamics, stereochemistry, solvent and electrostatic effects, and, when possible, the quantum mechanical considerations of the system under study. Among many items, this representation should be consistent with the reaction rate s dependence on concentration, the overall stoichiometry, the stereochemical course, presence and structure of intermediate, the structure of the transition state, effect of temperature and other variables, etc. See Chemical Kinetics... 

Chapter 1 reviews the concepts necessary for treating the problems associated with the design of industrial reactions. These include the essentials of kinetics, thermodynamics, and basic mass, heat and momentum transfer. Ideal reactor types are treated in Chapter 2 and the most important of these are the batch reactor, the tubular reactor and the continuous stirred tank. Reactor stability is considered. Chapter 3 describes the effect of complex homogeneous kinetics on reactor performance. The special case of gas—solid reactions is discussed in Chapter 4 and Chapter 5 deals with other heterogeneous systems namely those involving gas—liquid, liquid—solid and liquid—liquid interfaces. Finally, Chapter 6 considers how real reactors may differ from the ideal reactors considered in earlier chapters. 

We discuss kinetic, thermodynamic and transient data that indicate that the nature of the bonding of the intermediate is directly related to its further reaction via selective and unselective pathways. 

Kinetic-Thermodynamic Correlations. The ligand react on rate can vary greatly as the metal ion is changed, especially for redox reactions or those with very specific stereochemical demands. In cases where only the acidity of the metal ion is important one might expect more regularity. For very regular systems a Bron-sted Catalysis Law for metal ions should be valid. Thus,... 

Bruno, J., Casas, I., Cera, E., Swing, R. C., Finch, R. C. Werme, L. O. 1995. The assessment of the long-term evolution of the spent nuclear fuel matrix by kinetic, thermodynamic and spectroscopic studies of uranium minerals. Materials Research Society Symposium Proceedings, 353, 633-639. 

Turgeon, S.L., Beaulieu, M., Schmitt, C., Sanchez, C. (2003). Protein-polysaccharide interactions phase-ordering kinetics, thermodynamics and structural aspects. Current Opinion in Colloid and Interface Science, 8, 401 414. 

Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy Oligomers with Amines... 

In this review, modem interpretations of the kinetics, thermodynamics and mechanisms of curing of epoxy oligomers with primary, secondary, and tertiary amines and their mixtures, as well as the structure of the resulting polymers are discussed. The effect of the structure of the reagents on their reactivity is analyzed. Kinetic peculiarities of the deep stages of the curing process are emphasized Problems to be solved in the future are formulated. 

Low-molecular-weight model compounds such as phenylglycidyl or other mono-glycidyl ethers as well as primary, secondary and tertiary amines have been used for the study of the kinetics, thermodynamics and mechanism of curing. To reveal the kinetic features of network formation, results of studies of the real epoxy-amine systems have also been considered. Another problem under discussion is the effect of the kinetic peculiarities of formation of the epoxy-amine polymers on their structure and properties. 

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