Kinetic method*, classification

TTie classification of kinetic methods proposed by Pardue [18] is adopted in the software philosophy. TTie defined objective of measurement in the system is to obtain the best regression fit to a minimum of 10 data points, taken over either a fixed time (i.e. the maximum time for slow reactions) or variable time (for reactions complete in less than 34 min, which is the maximum practical observation time). In an analytical system generating information at the rate of SO datum points per second, with reactions being monitored for up to 2040 s, effective data-reduction is of prime importance. To reduce this large quantity of analytical data to more manageable proportions, an algorithm was devised to optimize the time-base of the measurements for each individual specimen. 

Pardue HL. A comprehensive classification of kinetic methods of analysis used in clinical chemistry. Clin Chem 1977 23 2189-201. 

H. L. Pardue, A Comprehensive Classification of Kinetic Methods of Analysis Used in Clinical Chemistry, Clin. Chem., 23 (1977) 2189. 

Kinetic methods have been classified according to a number of criteria. One classification distinguishes between catalytic and noncatalytic methods (see Table 1). The former are further divided according to the type of reaction involved, while the latter are categorized according to whether they are used to determine a single species or several components in mixtures (differential reaction-rate methods)... 

Table 3 Classification of kinetic methods according to data acquisition and processing...

Design and operation of chemical reactors in a chemical industry profoundly influence the impact that the industry may have on the surrounding environment. Understanding different types of reactions and characterising their kinetic behaviour are important for optimal design and operation of chemical reactors. This chapter outlines the basic principles of chemical kinetics, methods of obtaining rate equations for different types of reactions, principles of catalysis and kinetics of catalytic reactions. A brief introduction on the types and classification of reactors is presented in this chapter. 

We will conclude this section on theory with such a case. In Section 8.3 it was shown that the influence of substituents on the rate of dediazoniation of arenediazonium ions can be treated by dual substituent parameter (DSP) methods, and that kinetic evidence is consistent with a side-on addition of N2. We will now discuss these experimental conclusion with the help of schematic orbital correlation diagrams for the diazonium ion, the aryl cation, and the side-on ion-molecule pair (Fig. 8-5, from Zollinger, 1990). We use the same orbital classification as Vincent and Radom (1978) (C2v symmetry). 

The grouping of ammonium salts in a separate section serves to emphasize the similarities of behaviour which are apparent in reactions yielding the volatile NH3 molecule, following removal of a proton from the NH4 cation. This property is not unique indeed, many cations are volatile and numerous salts leave no residue on completion of decomposition. Few kinetic investigations have, however, been reported for other compounds, in contrast to the extensive and detailed rate measurements which have been published for solid phase decompositions of many ammonium salts. Comparisons with the metal salts containing the same anion are sometimes productive, so that no single method of classification is altogether satisfactory. 

This account of the kinetics of reactions between (inorganic) solids commences with a consideration of the reactant mixture (Sect. 1), since composition, particle sizes, method of mixing and other pretreatments exert important influences on rate characteristics. Some comments on experimental methods are included here. Section 2 is concerned with reaction mechanisms formulated to account for observed behaviour, including references to rate processes which involve diffusion across a barrier layer. This section also includes a consideration of the application of mechanistic criteria to the classification of the kinetic characteristics of solid-solid reactions. Section 3 surveys rate processes identified as the decomposition of a solid catalyzed by a solid. Section 4 reviews other types of solid + solid reactions, which may be conveniently subdivided further into the classes... 

The classification of methods for studying electrode kinetics is based on the criterion of whether the electrical potential or the current density is controlled. The other variable, which is then a function of time, is determined by the electrode process. Obviously, for a steady-state process, these two quantities are interdependent and further classification is unnecessary. Techniques employing a small periodic perturbation of the system by current or potential oscillations with a small amplitude will be classified separately. 

The different theoretical models for analyzing particle deposition kinetics from suspensions can be classified as either deterministic or stochastic. The deterministic methods are based on the formulation and solution of the equations arising from the application of Newton s second law to a particle whose trajectory is followed in time, until it makes contact with the collector or leaves the system. In the stochastic methods, forces are freed of their classic duty of determining directly the motion of particles and instead the probability of finding a particle in a certain place at a certain time is determined. A more detailed classification scheme can be found in an overview article [72]. 

Many classifications of spectra exist those describing the spectral region involved (ultraviolet, infrared) the appearance of the spectra (line, band) the method of observation (absorption, emission) or the species producing the spectra (atoms, molecules). With respect to processes and properties of expls and proplnts, classification by species is most appropriate since information concerning reaction kinetics is frequently provided by spectroscopic techniques, From a spectroscopic viewpoint, it is convenient to divide the electromagnetic spectrum into a number of sections (see Fig 1). 

Our book is about the emerging field of Superelectrophiles and Their Reactions. It deals first with the differentiation of usual electrophiles from superelectrophiles, which show substantially increased reactivity. Ways to increase electrophilic strength, the classification into gitionic, vicinal, and distonic superelectrophiles, as well as the differentiation of superelec-trophilic solvation from involvement of de facto dicationic doubly electron deficient intermediates are discussed. Methods of study including substituent and solvent effects as well as the role of electrophilic solvation in chemical reactions as studied by kinetic investigations, spectroscopic and gas-phase studies, and theoretical calculations are subsequently reviewed. Subsequently, studied superelectrophilic systems and their reactions are discussed with specific emphasis on involved gitionic, vicinal, and distonic superelectrophiles. A brief consideration of the significance of superelectrophilic chemistry and its future outlook concludes this book. 

The most common classification scheme in electrophoresis focuses on the nature of electrolyte system. Using this scheme, electrophoretic modes are classified as continuous or discontinuous systems. Within these groupings the methods may be further divided on the basis of constancy of the electrolyte if the composition of the background electrolyte is constant as in capillary zone electrophoresis, the result is a kinetic process. If the composition of the electrolyte is not constant, as in isoelectric focusing, the result is a steady-state process. 

An interesting classification of reactions in solution has been made by Moelwyn-Hughes2 on the basis of equation (2). This author, who has published many researches on the theory of kinetics of reactions in solution, has examined many bimolecular reactions in solutions and calculated z by equation (2) and E by the standard method of plotting log k against /T from the experimental data at different temperatures. He then calculates k by equation (2) and compares it with the experimentally observed rate constant. If the two agree within a factor of ten or so, the reac-... 

It can be inferred from the above descriptions that chemical reactions may involve processes characteristic of one or all of. these categories in such fashion as to become almost impossible of simple description or classification. Because of this near infinity of possible behaviors of reacting systems, we shall restrict our discussion in the present chapter to the most general methods for the mathematical description of such systems. At the present stage, this is all that can be done to provide a basis for their study. As the experimenter will easily discover, kinetic systems when investigated in detail display an anarchistic tendency to become unique laws unto themselves. 

An alternative method that enables the classification of geometrical and optical isomers is accomplished by substituting the Fe + ion with kinetically more inert d Cr + or... 

In Section 6 we have attempted to demonstrate the possible ways of using the various aspects of graph-theoretical classification and coding of the chemical reaction mechanisms in solving various problems in chemical kinetics, as well as in the development of computer simulation methods. 

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