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Kinetics of elementary reactions

OthSympCombstn (1965), pp 245-52 19) N.I. Yushchenkova 8c S.I. Kosterin, "On the Effect of Kinetics of Elementary Reactions on Ionization in stationary and Nonstationary Supersonic.Expansion and Compression of Gases , Ibid, pp 721-30 20) E.A. Fletcher,... [Pg.581]

In our recently published paper on kinetics of elementary reactions in polymerization of BPL, initiated with acetate anion with potassium crowned with dibenzo--18-crown-6 ether (DBCK+) counterion in methylene... [Pg.274]

The kinetics of elementary reactions occurring in the gas phase are well represented by expressions of the form... [Pg.210]

The kinetics of elementary reactions occurring at a solid surface cannot be described with anything near the accuracy available for gas and liquid phase reactions, and, as a consequence, it is often necessary to describe the kinetics of an overall reaction using power-law or Langmuir-Hinshelwood-... [Pg.210]

Hall, D.G The relationship between thermodynamics and the kinetics of elementary reactions in non-ideal systems. Z. Phys. Chem. N. F. 129,109-117 (1982)... [Pg.276]

This reaction mechanism was first proposed by Halsted and Thrush (30) when studying the kinetics of elementary reactions involving the oxides of sulfur. Visible and UV spectroscopic studies (31) confirmed that the chemiluminescent emission was from SO2. Recently, it has also been confirmed that the sulfur- analyte molecule from the GC effluent is converted to SO in the flame of the SCD (32). Even though SO is a free radical, it can be sufficiently stabilized in a flow system under reduced pressure (33,34) to be sampled and transferred to a vessel to react with introduced O. Based on these operational principles. Burner and Stedman (33) concluded that SO produced in a flame could be easily detected. They modified a redox chemiluminescence detector (36) to produce what was termed a Universal Sulfur Detector (USD). A linear response between 0.4 ppb and l.S ppm (roughly equal to 3 to 13,000 pg of S/sec) was demonstrated with equal response to the five sulfur compounds tested. This detection scheme has been utilized as the basis for the commercially available GC detector. [Pg.26]

Figure 3 The "arrow of time" in chemistry and biology drawn to describe some strides in real-time studies [3]. For other developments, such as molecular beam and chemiluminescence studies in the kinetics of elementary reactions, see text. Figure 3 The "arrow of time" in chemistry and biology drawn to describe some strides in real-time studies [3]. For other developments, such as molecular beam and chemiluminescence studies in the kinetics of elementary reactions, see text.
This chapter considers the kinetics of elementary reactions. Unlike complex reactions, elementary reactions cannot be subdivided into processes of lesser molecular complexity, whereas complex reactions proceed through a network of elementary reactions. Elementary reactions necessarily involve the participation of a small integral number of atoms and/or molecules, and one can further define them by saying that the chemical change involves molecular processes which mimic the chemical equation that is used to represent the reaction. Thus, the reaction... [Pg.21]

The next chapter discusses, inter alia, chemical networks and the context in which research on the kinetics of elementary reactions is applied in the ISM. In particular it provides a rationale for the provision of rate coefficients, channel efficiencies and uncertainties in rate parameters. It provides the justification for many of the topics discussed in Chap. 3. [Pg.108]

Wamatz, J., Maas, U., Dibble, R.W. Combustion. Physical and Chemical Fundamentals, Modeling and Simulation, Experiments, Pollutant Formation, 4th edn. Springer, Berlin (2006) Zddor, J., Taatjes, C.A., Fernandes, R.X. Kinetics of elementary reactions in autoignition chemistry. Prog. Energy Combust. Sci. 37, 371 (2011)... [Pg.38]

Zador J, Taatjes CA, Fernandes RX. Kinetics of elementary reactions in low-temperature autoignition chemistry. Prog Energy Combust Sci. August 2011 37 371-421. [Pg.177]

At the limit of extremely low particle densities, for example under the conditions prevalent in interstellar space, ion-molecule reactions become important (see chapter A3.51. At very high pressures gas-phase kinetics approach the limit of condensed phase kinetics where elementary reactions are less clearly defined due to the large number of particles involved (see chapter A3.6). [Pg.759]

Flere, we shall concentrate on basic approaches which lie at the foundations of the most widely used models. Simplified collision theories for bimolecular reactions are frequently used for the interpretation of experimental gas-phase kinetic data. The general transition state theory of elementary reactions fomis the starting point of many more elaborate versions of quasi-equilibrium theories of chemical reaction kinetics [27, M, 37 and 38]. [Pg.774]

An important point about kinetics of cyclic reactions is tliat if an overall reaction proceeds via a sequence of elementary steps in a cycle (e.g., figure C2.7.2), some of tliese steps may be equilibrium limited so tliat tliey can proceed at most to only minute conversions. Nevertlieless, if a step subsequent to one tliat is so limited is characterized by a large enough rate constant, tlien tire equilibrium-limited step may still be fast enough for tire overall cycle to proceed rapidly. Thus, tire step following an equilibrium-limited step in tire cycle pulls tire cycle along—it drains tire intennediate tliat can fonn in only a low concentration because of an equilibrium limitation and allows tire overall reaction (tire cycle) to proceed rapidly. A good catalyst accelerates tire steps tliat most need a boost. [Pg.2700]

In Chapter 1 we distinguished between elementary (one-step) and complex (multistep reactions). The set of elementary reactions constituting a proposed mechanism is called a kinetic scheme. Chapter 2 treated differential rate equations of the form V = IccaCb -., which we called simple rate equations. Chapter 3 deals with many examples of complicated rate equations, namely, those that are not simple. Note that this distinction is being made on the basis of the form of the differential rate equation. [Pg.59]

Each of these variables will be considered in this book. We start with concentrations, because they determine the form of the rate law when other variables are held constant. The concentration dependences reveal possibilities for the reaction scheme the sequence of elementary reactions showing the progression of steps and intermediates. Some authors, particularly biochemists, term this a kinetic mechanism, as distinct from the chemical mechanism. The latter describes the stereochemistry, electron flow (commonly represented by curved arrows on the Lewis structure), etc. [Pg.9]

For most real systems, particularly those in solution, we must settle for less. The kinetic analysis will reveal the number of transition states. That is, from the rate equation one can count the number of elementary reactions participating in the reaction, discounting any very fast ones that may be needed for mass balance but not for the kinetic data. Each step in the reaction has its own transition state. The kinetic scheme will show whether these transition states occur in succession or in parallel and whether kinetically significant reaction intermediates arise at any stage. For a multistep process one sometimes refers to the transition state. Here the allusion is to the transition state for the rate-controlling step. [Pg.126]

In earlier chapters, we have seen how kinetic phenomena can be interpreted, for example, to provide a reaction scheme consisting of a set of elementary reactions. Over the years, several models have been devised to explain and sometimes to predict the rates of elementary reactions. It is these that we now wish to examine on a more fundamental basis in this chapter, plus Chapters 9 and 10. [Pg.155]

Chapter 1 treated single, elementary reactions in ideal reactors. Chapter 2 broadens the kinetics to include multiple and nonelementary reactions. Attention is restricted to batch reactors, but the method for formulating the kinetics of complex reactions will also be used for the flow reactors of Chapters 3 and 4 and for the nonisothermal reactors of Chapter 5. [Pg.35]

In this paper, we first briefly describe both the single-channel 1-D model and the more comprehensive 3-D model, with particular emphasis on the comparison of the features included and their capabilities/limitations. We then discuss some examples of model applications to illustrate how the monolith models can be used to provide guidance in emission control system design and implementation. This will be followed by brief discussion of future research needs and directions in catalytic converter modeling, including the development of elementary reaction step-based kinetic models. [Pg.13]

Unraveling catalytic mechanisms in terms of elementary reactions and determining the kinetic parameters of such steps is at the heart of understanding catalytic reactions at the molecular level. As explained in Chapters 1 and 2, catalysis is a cyclic event that consists of elementary reaction steps. Hence, to determine the kinetics of a catalytic reaction mechanism, we need the kinetic parameters of these individual reaction steps. Unfortunately, these are rarely available. Here we discuss how sticking coefficients, activation energies and pre-exponential factors can be determined for elementary steps as adsorption, desorption, dissociation and recombination. [Pg.267]

Temperature-programmed reaction spectroscopy offers a straightforward way to monitor the kinetics of elementary surface reactions, provided that the desorption itself is not rate limiting. Figure 7.14 shows the the reaction CO -f O CO2 + 2. ... [Pg.285]

Table 10.4 lists the rate parameters for the elementary steps of the CO + NO reaction in the limit of zero coverage. Parameters such as those listed in Tab. 10.4 form the highly desirable input for modeling overall reaction mechanisms. In addition, elementary rate parameters can be compared to calculations on the basis of the theories outlined in Chapters 3 and 6. In this way the kinetic parameters of elementary reaction steps provide, through spectroscopy and computational chemistry, a link between the intramolecular properties of adsorbed reactants and their reactivity Statistical thermodynamics furnishes the theoretical framework to describe how equilibrium constants and reaction rate constants depend on the partition functions of vibration and rotation. Thus, spectroscopy studies of adsorbed reactants and intermediates provide the input for computing equilibrium constants, while calculations on the transition states of reaction pathways, starting from structurally, electronically and vibrationally well-characterized ground states, enable the prediction of kinetic parameters. [Pg.389]

Steady-state approximation. Fractional reaction orders may be obtained from kinetic data for complex reactions consisting of elementary steps, although none of these steps are of fractional order. The same applies to reactions taking place on a solid catalyst. The steady-state approximation is very useful for the analysis of the kinetics of such reactions and is illustrated by Example 5.4.2.2a for a solid-catalysed reaction. [Pg.277]

The Flory principle allows a simple relationship between the rate constants of macromolecular reactions (whose number is infinite) with the corresponding rate constants of elementary reactions. According to this principle all chemically identical reactive centers are kinetically indistinguishable, so that the rate constant of the reaction between any two molecules is proportional to that of the elementary reaction between their reactive centers and to the numbers of these centers in reacting molecules. Therefore, the material balance equations will comprise as kinetic parameters the rate constants of only elementary reactions whose number is normally rather small. [Pg.170]

This is the simplest of the models where violation of the Flory principle is permitted. The assumption behind this model stipulates that the reactivity of a polymer radical is predetermined by the type of bothjts ultimate and penultimate units [23]. Here, the pairs of terminal units MaM act, along with monomers M, as kinetically independent elements, so that there are m3 constants of the rate of elementary reactions of chain propagation ka ]r The stochastic process of conventional movement along macromolecules formed at fixed x will be Markovian, provided that monomeric units are differentiated by the type of preceding unit. In this case the number of transient states Sa of the extended Markov chain is m2 in accordance with the number of pairs of monomeric units. No special problems presents writing down the elements of the matrix of the transitions Q of such a chain [ 1,10,34,39] and deriving by means of the mathematical apparatus of the Markov chains the expressions for the instantaneous statistical characteristics of copolymers. By way of illustration this matrix will be presented for the case of binary copolymerization ... [Pg.180]

To the uninitiated student, the task of postulating a suitable mechanism for a complex chemical reaction often seems to be an exercise in extrasensory perception. Even students who have had some exposure to kinetics often cannot understand how the kineticist can write down a series of elementary reactions and avow that the mechanism is reasonable. Nonetheless, there is a set of guidelines within which the kineticist works in postulating a mechanism. Since these... [Pg.83]


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