Radical concentration, effect

The propagation of polymer chains is easy to consider under stationary-state conditions. As the preceding example illustrates, the stationary state is reached very rapidly, so we lose only a brief period at the start of the reaction by restricting ourselves to the stationary state. Of course, the stationary-state approximation breaks down at the end of the reaction also, when the radical concentration drops toward zero. We shall restrict our attention to relatively low conversion to polymer, however, to avoid the complications of the Tromms-dorff effect. Therefore deviations from the stationary state at long times need not concern us. 

The superpositioning of experimental and theoretical curves to evaluate a characteristic time is reminiscent of the time-tefnperature superpositioning described in Sec. 4.10. This parallel is even more apparent if the theoretical curve is drawn on a logarithmic scale, in which case the distance by which the curve has to be shifted measures log r. Note that the limiting values of the ordinate in Fig. 6.6 correspond to the limits described in Eqs. (6.46) and (6.47). Because this method effectively averages over both the buildup and the decay phases of radical concentration, it affords an experimentally less demanding method for the determination of r than alternative methods which utilize either the buildup or the decay portions of the non-stationary-state free-radical concentration. 

Control of addition vs substitution by free radicals can be effected by the reaction conditions, ie, radical concentration, temperature, and phase. Using halogens as propylene reactants, high temperatures and the gas phase favor high radical concentrations and substitution reactions cold, Hquid-phase conditions favor addition reactions. 

On the other hand, the limiting conversion in a reactor of fixed size is dependent on the temperature and the radical concentration in the reactor and results from a predominating radical-radical interaction precipitated by an increased initiator concentration and the accompanying temperature excursion. At this point the solvent concentrations have little effect on the molecular... 

It has long been recognized that ascorbate levels are low in patients with RA (Lunec and Blake, 1985) and ascorbate is predominantly found in the dehydro form. The presence of increased dehydroascorbate has been suggested to indicate its rapid oxidation by stimulated PMNs (Halliwell and Gutteridge, 1990). When ascorbate concentrations are lower than about 20 /tmol/1, as can occur in rheumatoid synovial fluid, the Fe(III) reducing effects of ascorbate outweigh its radical-scavenging effects. Ascorbate then causes increased OH formation and promotes lipid peroxidation (Blake et al., 1981). 

With this setup a series of measurements was taken in which the power was varied from 5 to 30 W. The pressure was low, 0.06 Torr, while the temperature was 250°C. The SiH (0 < jr < 3) radical densities near the surface were measured as a function of effective power delivered to the discharge. It was found that the SiH3 radical is the most abundant one, with a concentration varying between 1.8 x 10" and 3.2 x lO cm. The SiH2 radical concentration was about a factor of 20 lower. Both radical concentrations increase with increasing power. 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

When the flow through the CNC was exhausted outside of the laboratory, we observed particle formation at higher SOp concentrations as expected (Table II). To prove that the radical scavenger effect is reproducible, another radical scavenger (92 ppb nitric oxide) was used in the presence of 110 ppb SOp concentration and 2% humidity, and the supression in particle formation was observed. Another possible mechanism that supressed the particle formation is that more neutralization of polonium ions occurred at the higher humidities and thus ion-induced nucleation would be suppressed. 

Such reactions have only been investigated on their role in the processes of ageing and carcinogenesis to a large extent (Dizdaroglu 1991), their effects on environmental contaminants and organisms have not been fully realized. Because of the short time and difficulties in chemical analyses for transitory presence of free radicals, relationship between free radical concentrations and effects on pollutants or natural microorganisms has not been fully established. It is clear that further... 

The formed hydroxyperoxide decomposes into free radicals much more rapidly than alkyl hydroperoxide [128]. So, the equilibrium addition of the hydroperoxide to the ketone changes the rate of formation of the radicals. This effect was first observed for cyclohexanone and 1,1-dimethylethyl hydroperoxide [128]. In this system, the rate of radical formation increases with an increase in the ketone concentration. The mechanism of radical formation is described by the following scheme ... 

Acceptors of alkyl radicals are known to be very weak inhibitors of liquid-phase hydrocarbon oxidation because they compete with dioxygen, which reacts very rapidly with alkyl radicals. The situation dramatically changes in polymers where an alkyl radical acceptor effectively terminates the chains [3,49], The study of the inhibiting action of p-benzoquinone [50], nitroxyl radicals [51-53], and nitro compounds [54] in oxidizing PP showed that these alkyl radical acceptors effectively retard the oxidation of the solid polymer at concentrations ( 10-3 mol L 1) at which they have no retarding effect on liquid hydrocarbon oxidation. It was proved from experiments on initiated PP oxidation at different p02 that these inhibitors terminate chains by the reaction with alkyl macroradicals. The general scheme of such inhibitors action on chain oxidation includes the following steps ... 

It can be observed that the initial rate of polymerization decreases and the autoacceleration peak is suppressed as the TED concentration is increased. The TED molecules generate dithiocarbamyl (DTC) radicals upon initiation. As a result, termination may occur by carbon-carbon combination which leads to a dead polymer and by carbon-DTC radical reaction which produces a reinitiatable ( living ) polymer. The cross-termination of carbon-DTC radicals occurs early in the reaction (with the carbon-carbon radical termination), and this feature is observed by the suppression of the initial rate of polymerization. As the conversion increases, the viscosity of the system poses mass transfer limitations to the bimolecular termination of carbon radicals. As has been observed in Figure 3, this effect results in a decrease in the ktCC. However, as the DTC radicals are small and mobile, the crosstermination does not become diffusion limited, i.e., the kinetic constant for termination of carbon-DTC radicals, ktCS, does not decrease. Therefore, the crosstermination becomes the dominant reaction pathway. This leads to a suppression of the autoacceleration peak as the carbon-DTC radical termination limits the carbon radical concentration to a low value, thus limiting the rate of polymerization. This observation is in accordance with results of previous studies (10) with XDT and TED, where it was found that when there was an excess of DTC radicals, the carbon radical concentration was lower and the cross-termination reaction was the dominant termination pathway. 

From these experimental and modeling studies, the mechanism of the living free radical polymerizations initiated by a combination of TED and DMPA have been elucidated. The TED produces DTC radicals that preferentially cross-terminate with the propagating carbon radicals. By this cross-termination reaction, the carbon radical concentration is kept low (as was shown in figure 6) and the rate of polymerization is decreased, as is the autoacceleration effect. This suppression of the autoacceleration peak in HEM A polymerizations and, interestingly, in DEGDMA polymerization has been observed to increase as the TED concentrations are increased. This behavior has been predicted successfully by the model as well. 

At high pressures the presence of the H02 radical also contributes via HCO + H02 — H202 + CO, but H02 is the least effective of OH, O, and H, as the rate constants in Appendix C will confirm. The formyl radical reacts very rapidly with the OH, O, and H radicals. However, radical concentrations are much lower than those of stable reactants and intermediates, and thus formyl reactions with these radicals are considered insignificant relative to the other formyl reactions. As will be seen when the oxidation of large hydrocarbon molecules is discussed (Section H), R is most likely a methyl radical, and the highest-order aldehydes to arise in high-temperature combustion are acetaldehyde and propionaldehyde. The acetaldehyde is the dominant form. Essentially, then, the sequence above was developed with the consideration that R was a methyl group. 

These are radical-radical reactions or reactions of methyl radicals with a product of a radical-radical reaction (owing to concentration effects) and are considered less important than reactions (3.72) and (3.86). However, reactions (3.72) and (3.86) are slow, and reaction (3.92) can become competitive to form the important methoxy radical, particularly at high pressures and in the lower-temperature region of flames (see Chapter 4). 

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