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Nov 8, 2012 · PDF Focus.Net - How to convert PDF to Word using C#. SautinSoft.Duration: 4:17 Posted: Nov 8, 2012

The brackets around any species indicate the presence of a solvent cage, which traps the radicals for some short period before they defuse apart Equation 3-67 represents the primary step of initiator decomposition into two radicals, which are held within the solvent cage The radicals in the solvent cage may undergo recombination (the reverse of Eq 3-67), reaction with each other (Eq 3-68), or reaction with monomer (Eq 3-69), or may diffuse out of the solvent cage (Eq 3-70) Once outside the solvent cage, the radicals may react with monomer (Eq 3-71) or decompose according to Eq 3-72 to yield a radical that may undergo various reactions (Eqs 3-73 to 3-75) Reaction 3-72 probably also occurs within the solvent cage followed by diffusion of the two species Recombination of the primary radicals (Eq 3-67) has no effect on the initiator ef ciency Initiation of polymerization occurs by Eqs.



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!!.- P(t) =

3-69, 3-71, and 3-73 The initiator ef ciency is decreased by the reactions indicated by Eqs 3-68, 3-74, and 3-75, since their products are stable and cannot give rise to radicals Of these reactions the decomposition within the solvent cage (Eq 3-68) is usually much more signi cant than the others in decreasing the value of f That this reaction is competitive with those leading to initiation of polymerization can be seen by considering the timescale of the various events [Koenig and Fischer, 1973; Noyes, 1961] The average life of neighboring radicals is perhaps 10 10 10 9 s Since rate constants for radical radical reactions are in the range 107 L mol 1 s 1 and higher, and the concentration of radicals in the solvent cage is about 10 M, there is a reasonable probability that Reaction 3-68 will occur.





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You can use PowerPoint s views to change how your presentation appears on-screen. By default, PowerPoint displays your presentation in Normal view, with the Slides tab showing the order of slides in your presentation. You can view the Outline tab to see your presentation in an outline format or switch to Slide Sorter view to see all the slides at the same time. In addition to changing PowerPoint views, you can use the PowerPoint zoom settings to change the magnification of a slide. You can also change the size of the panes in the PowerPoint window, making them larger or smaller as needed.

(6.68)

Reaction 3-69 cannot compete effectively with Reaction 3-68, since radical addition reactions have much lower rate constants (10 105 L mol 1 s 1 )..

(6.69)

where the presence or absence of the subscript s indicates the presence or absence, respectively, of a substituent that is capable of resonance stabilization. Vinyl acetate and styrene

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Fig. 6-11 Reaction coordination diagram for the reaction of a polymer radical wth a monomer. The dependence of the potential energy of the system (radical monomer) on the separation between the radical and the unsaturated carbon atom of the monomer is shown. The subscript s indicates the presence of a substituent that is capable of resonance stabilization. Activation energies are represented by the solid-line arrows; heats of reaction, by the broken-line arrows. After Walling [1957] (by permission of Wiley, New York).

We are now ready to look into how the cavity changes spontaneous emission. The system starts from the product state 1l) 10) with the atom in the excited state and the cavity field in the vacuum. Then there are only three states [34, 273] involved in the time evolution described by (6.69):

monomers are examples of M and Ms, respectively; vinyl acetate and styrene radicals are examples of R and Rs , respectively. There are two sets of potential energy plots in Fig. 6-11. One set of four repulsion plots represents the energetics of the approach of a radical to a monomer; the other set of two Morse plots represents the stability of the bond (or of the polymer radical) nally formed. The intersections of the plots represent the transition states for the monomer-radical reactions (Eqs. 6-51a to 6-51d) where the unbonded and bonded states have the same energies. The various activation energies and heats of reaction are represented by the solid-line and broken-line arrows, respectively. The separation between the two Morse plots is signi cantly larger than that between either the top or bottom two repulsion plots, since substituents are much more effective in decreasing radical reactivity than in increasing monomer reactivity. Figure 6-11 shows that the order of reaction rate constants for the various monomer radical reactions is

1 1 )=1l)10), 12) = 11)11), 13) = 11)10).

since the order of activation energies is the exact opposite (This assumes that there are no appreciable differences in the entropies of activation a reasonable assumption for sterically

(6.70) (6.71)

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