Propagation kinetics

A more accurate, but also more complex form, will be discussed later in the section on Path Integral Monte Carlo. Note that we have S3mimetrized the primitive form in order to reduce the systematic error of the factorization [19]. The explicit form of the kinetic propagator is the Green s function of the Bloch equation of a system of free particles [19,21], i.e. a diffusion equation in configurational space... 

Other Derivatives. The structures of the nitromethane derivatives C(N02)4 and HC(N02)3, C1C(N02)3, and BrC(N02)3 have been determined by electron diffraction. Both the thermal and photochemical decompositions of methyldi-imide in the gaseous phase have been studied. Both decompositions yield CHt and N2 in equal amounts, and proceed by a radical chain mechanism with -order kinetics, propagated by the reactions CH3 + CH3N2H —> CH4+CH3N2 and CH3N2 CH3+N,. ""... 

J. Liklema, Kinetically Propagating Self-Avoiding Random Walls Fractals in Physics, Myr, Moscow, Russia, 1988, 131-137. [In Russian]... 

In-situ Raman spectroscopy experiments were used to determine effective kinetic propagation constants for a series of unsteady-state divinyl ether polymerisations at different isothermal temperatures and light intensities. A series of Raman experiments were performed on cationic photopolymerisations of a divinyl ether initiated with a diaryliodonium salt of hexafluoroantimonate photosensitised by anthracene. Isothermal Raman experiments were performed for a series of reaction temperatures and were used to determine the overall activation energy of the polymerisation reaction. 20 refs. USA... 

The kinetic propagation reaction equations for radical copolymerization of two monomers, Mj and M2, are written in Fig. 3.45. The complications due to additional, different monomers, as well as transfer, reverse, and termination reactions increase the numbers of equations and rate constants, so that the resulting reaction equations are unhandy, and it needs much experimental work to establish the rate constants. Also, the computational effort to solve the many equations becomes excessive. 

Polymerization kinetics propagation, transfer, LCB formation, site activation and deactivation Microstructure formation MWD, CCD, LCB Chain crystallization... 

As reactants transfonn to products in a chemical reaction, reactant bonds are broken and refomied for the products. Different theoretical models are used to describe this process ranging from time-dependent classical or quantum dynamics [1,2], in which the motions of individual atoms are propagated, to models based on the postidates of statistical mechanics [3], The validity of the latter models depends on whether statistical mechanical treatments represent the actual nature of the atomic motions during the chemical reaction. Such a statistical mechanical description has been widely used in imimolecular kinetics [4] and appears to be an accurate model for many reactions. It is particularly instructive to discuss statistical models for unimolecular reactions, since the model may be fomuilated at the elementary microcanonical level and then averaged to obtain the canonical model. 

Once the grid (or two grids) are prepared, there are two similar types of approaches to propagate the initial wavefiinction forward with time. One approach is split-operator methods, [59] where the short-time propagator is divided into a kinetic and potential parts so that... 

A kinetics text with a strong theoreticai bent that overviews transient kinetic methods and discusses data anaiysis issues such as error propagation and sensitivity anaiysis. 

Excitable media are some of tire most commonly observed reaction-diffusion systems in nature. An excitable system possesses a stable fixed point which responds to perturbations in a characteristic way small perturbations return quickly to tire fixed point, while larger perturbations tliat exceed a certain tlireshold value make a long excursion in concentration phase space before tire system returns to tire stable state. In many physical systems tliis behaviour is captured by tire dynamics of two concentration fields, a fast activator variable u witli cubic nullcline and a slow inhibitor variable u witli linear nullcline [31]. The FitzHugh-Nagumo equation [34], derived as a simple model for nerve impulse propagation but which can also apply to a chemical reaction scheme [35], is one of tire best known equations witli such activator-inlribitor kinetics ... 

The kinetic energy operator evaluation and then the propagation of the 0, <]) degrees of freedom have been performed using the FFT [69] method followed... 

The mechanism of these reactions places addition polymerizations in the kinetic category of chain reactions, with either free radicals or ionic groups responsible for propagating the chain reaction. 

Elsewhere in this chapter we shall see that other reactions-notably, chain transfer and chain inhibition-also need to be considered to give a more fully developed picture of chain-growth polymerization, but we shall omit these for the time being. Much of the argumentation of this chapter is based on the kinetics of these three mechanistic steps. We shall describe the rates of the three general kinds of reactions by the notation Rj, Rp, and R for initiation, propagation, and termination, respectively. 

The kinetic chain length has a slightly different definition in the presence of chain transfer. Instead of being simply the ratio Rp/R, it is redefined to be the rate of propagation relative to the rates of all other steps that compete with propagation specifically, termination and transfer (subscript tr) ... 

We shall consider these points below. The mechanism for cationic polymerization continues to include initiation, propagation, transfer, and termination steps, and the rate of polymerization and the kinetic chain length are the principal quantities of interest. 

In writing Eqs. (7.1)-(7.4) we make the customary assumption that the kinetic constants are independent of the size of the radical and we indicate the concentration of all radicals, whatever their chain length, ending with the Mj repeat unit by the notation [Mj ], This formalism therefore assumes that only the nature of the radical chain end influences the rate constant for propagation. We refer to this as the terminal control mechanism. If we wished to consider the effect of the next-to-last repeat unit in the radical, each of these reactions and the associated rate laws would be replaced by two alternatives. Thus reaction (7. A) becomes... 

An important descriptor of a chain reaction is the kinetic chain length, ie, the number of cycles of the propagation steps (eqs. 2 and 3) for each new radical introduced into the system. The chain length for a hydroperoxide reaction is given by equation (10) where HPE = efficiency to hydroperoxide, %, and 2/ = number of effective radicals generated per mol of hydroperoxide decomposed. For 100% radical generation efficiency, / = 1. For 90% efficiency to hydroperoxide, the minimum chain length (/ = 1) is 14. 

Autooxidation. Liquid-phase oxidation of hydrocarbons, alcohols, and aldehydes by oxygen produces chemiluminescence in quantum yields of 10 to 10 ° ein/mol (128—130). Although the efficiency is low, the chemiluminescent reaction is important because it provides an easy tool for study of the kinetics and properties of autooxidation reactions including industrially important processes (128,131). The light is derived from combination of peroxyl radicals (132), which are primarily responsible for the propagation and termination of the autooxidation chain reaction. The chemiluminescent termination step for secondary peroxy radicals is as follows ... 

Kinetics. Details of the kinetics of polymerization of THF have been reviewed (6,148). There are five main conclusions. (/) Macroions are the principal propagating species in all systems. (2) With stable complex anions, such as PF , SbF , and AsF , the polymerization is living under normal polymerization conditions. When initia tion is fast, kinetics of polymerizations in bulk can be closely approximated by equation 2, where/ is the specific rate constant of propagation /is time [I q is the initiator concentration at t = 0 and [M q, [M and [M are the monomer concentrations at t = 0, at equiHbrium, and at time /, respectively. 

For counterions that can form esters with the growing oxonium ions, the kinetics of propagation are dominated by the rate of propagation of the macroions. For any given counterion, the proportion of macroions compared to macroesters varies with the solvent—monomer mixture and must be deterrnined independentiy before a kinetic analysis can be made. The macroesters can be considered to be in a state of temporary termination. When the proportion of macroions is known and initiation is sufftcientiy fast, equation 2 is satisfied. 

The mechanism of anionic polymerization of cyclosiloxanes has been the subject of several studies (96,97). The first kinetic analysis in this area was carried out in the early 1950s (98). In the general scheme of this process, the propagation/depropagation step involves the nucleophilic attack of the silanolate anion on the sUicon, which results in the cleavage of the siloxane bond and formation of the new silanolate active center (eq. 17). 

Emulsion Polymerization. Emulsion SBR was commercialised and produced in quantity while the theory of the mechanism was being debated. Harkins was among the earliest researchers to describe the mechanism (16) others were Mark (17) and Elory (18). The theory of emulsion polymerisation kinetics by Smith and Ewart is still vaUd, for the most part, within the framework of monomers of limited solubiUty (19). There is general agreement in the modem theory of emulsion polymerisation that the process proceeds in three distinct phases, as elucidated by Harkins (20) nucleation (initiation), growth (propagation), and completion (termination). 

Copolymers with butadiene, ie, those containing at least 60 wt % butadiene, are an important family of mbbers. In addition to synthetic mbber, these compositions have extensive uses as paper coatings, water-based paints, and carpet backing. Because of unfavorable reaction kinetics in a mass system, these copolymers are made in an emulsion polymerization system, which favors chain propagation but not termination (199). The result is economically acceptable rates with desirable chain lengths. Usually such processes are mn batchwise in order to achieve satisfactory particle size distribution. 

Termination. The conversion of peroxy and alkyl radicals to nonradical species terminates the propagation reactions, thus decreasing the kinetic chain length. Termination reactions (eqs. 7 and 8) are significant when the oxygen concentration is very low, as in polymers with thick cross-sections where the oxidation rate is controlled by the diffusion of oxygen, or in a closed extmder. The combination of alkyl radicals (eq. 7) leads to cross-linking, which causes an undesirable increase in melt viscosity. 

Radical Scavengers Hydrogen-donating antioxidants (AH), such as hindered phenols and secondary aromatic amines, inhibit oxidation by competing with the organic substrate (RH) for peroxy radicals. This shortens the kinetic chain length of the propagation reactions. 

Impact and Erosion. Impact involves the rapid appHcation of a substantial load to a relatively small area. Most of the kinetic energy from the impacting object is transformed into strain energy for crack propagation. Impact can produce immediate failure if there is complete penetration of the impacted body or if the impact induces a macrostress in the piece, causing it to deflect and then crack catastrophically. Failure can also occur if erosion reduces the cross section and load-bearing capacity of the component, causes a loss of dimensional tolerance, or causes the loss of a protective coating. Detailed information on impact and erosion is available (49). 

The balanced equation for turbulent kinetic energy in a reacting turbulent flow contains the terms that represent production as a result of mean flow shear, which can be influenced by combustion, and the terms that represent mean flow dilations, which can remove turbulent energy as a result of combustion. Some of the discrepancies between turbulent flame propagation speeds might be explained in terms of the balance between these competing effects. 

---