Evidence initial

Effect of Solvent Polarity. Quasiliving polymerization of IBVE was also attempted in a nonpolar solvent, n-heptane, ap -50 and -70°C. Figure 5 gives results obtained at -70°C. The Mn versus Wj ve plots obtained at this temperature are strongly curved. Importantly, the N values were less than unity at the beginning of the reactions and they increased beyond unity with increasing WibVE Evidently initiation is slow in nonpolar media due to incomplete ionization of the initiator (i.e., N >1). 

In fact the mechanism of the reaction is more complex and is evidently initiated by addition of a nucleophile Y, such as OH or bisulfite, followed by elimination of the thiazole (Eq. 14-18). 

Phenylpropiolic thioanilide and bromonitromethane in presence of triethylamine give the 2-nitrothiophene 24.22 Evidently, initial 5-alkylation is followed by addition of the acidic methylene to the triple bond as in Eq. (5). 

After racking off gross lees, two different phases of M3G disappearance were evident Initially, the M3G concentration declined rapidly by proximately 30% (100 mg/L) within 60 days, followed by a second period of slower anthocyanin disappearance with the loss of a further 100 mg/L M3G over the subsequent 14 months. In total, approximately 70% of M3G was lost after. 16... 

The sequence of steps in Scheme 39 (X = Cl) is evidently initiated by association (in molecular and ionic species) of the halogen with the ester later NMR signals were linked with the presence of several quaternary phosphonium salts, some with only one, but others with two phosphorus centres. The main product of the reaction sequence is tert-butylphenylphosphinic chloride, accompanied by trace amounts of the corresponding phosphinothioic chloride which presumably arise through the collapse of structure 147 the latter is probably reached by the alternative manner of breakdown of structure 146. 

Colin Pitchfork, the first criminal convicted of murder based on DNA fingerprinting evidence, initially evaded arrest by telling a friend that he was terrified of needles and paying that friend to submit a blood sample for him. 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

Different types of chemisorption sites may be observed, each with a characteristic A value. Several adsorbed states appear to exist for CO chemisorbed on tungsten, as noted. These states of chemisorption probably have to do with different types of chemisorption bonding, maybe involving different types of surface sites. Much of the evidence has come initially from desorption studies, discussed immediately following. 

The first finite element schemes for differential viscoelastic models that yielded numerically stable results for non-zero Weissenberg numbers appeared less than two decades ago. These schemes were later improved and shown that for some benchmark viscoelastic problems, such as flow through a two-dimensional section with an abrupt contraction (usually a width reduction of four to one), they can generate simulations that were qualitatively comparable with the experimental evidence. A notable example was the coupled scheme developed by Marchal and Crochet (1987) for the solution of Maxwell and Oldroyd constitutive equations. To achieve stability they used element subdivision for the stress approximations and applied inconsistent streamline upwinding to the stress terms in the discretized equations. In another attempt, Luo and Tanner (1989) developed a typical decoupled scheme that started with the solution of the constitutive equation for a fixed-flow field (e.g. obtained by initially assuming non-elastic fluid behaviour). The extra stress found at this step was subsequently inserted into the equation of motion as a pseudo-body force and the flow field was updated. These authors also used inconsistent streamline upwinding to maintain the stability of the scheme. 

Acid-catalyzed isomerization reactions of alkanes as well as alkylation and condensation reactions are initiated by protolytic ionization. Available evidence indicates nonlinear but not necessarily triangular... 

Evidence from the viscosities, densities, refractive indices and measurements of the vapour pressure of these mixtures also supports the above conclusions. Acetyl nitrate has been prepared from a mixture of acetic anhydride and dinitrogen pentoxide, and characterised, showing that the equilibria discussed do lead to the formation of that compound. The initial reaction between nitric acid and acetic anhydride is rapid at room temperature nitric acid (0-05 mol 1 ) is reported to be converted into acetyl nitrate with a half-life of about i minute. This observation is consistent with the results of some preparative experiments, in which it was found that nitric acid could be precipitated quantitatively with urea from solutions of it in acetic anhydride at —10 °C, whereas similar solutions prepared at room temperature and cooled rapidly to — 10 °C yielded only a part of their nitric acid ( 5.3.2). The following equilibrium has been investigated in detail ... 

The evidence outlined strongly suggests that nitration via nitrosation accompanies the general mechanism of nitration in these media in the reactions of very reactive compounds.i Proof that phenol, even in solutions prepared from pure nitric acid, underwent nitration by a special mechanism came from examining rates of reaction of phenol and mesi-tylene under zeroth-order conditions. The variation in the initial rates with the concentration of aromatic (fig. 5.2) shows that mesitylene (o-2-0 4 mol 1 ) reacts at the zeroth-order rate, whereas phenol is nitrated considerably faster by a process which is first order in the concentration of aromatic. It is noteworthy that in these solutions the concentration of nitrous acid was below the level of detection (< c. 5 X mol... 

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

Azobisnittiles are efficient sources of free radicals for vinyl polymerizations and chain reactions, eg, chlorinations (see Initiators). These compounds decompose in a variety of solvents at nearly first-order rates to give free radicals with no evidence of induced chain decomposition. They can be used in bulk, solution, and suspension polymerizations, and because no oxygenated residues are produced, they are suitable for use in pigmented or dyed systems that may be susceptible to oxidative degradation. 

Aldehydes are important products at all pressures, but at low pressures, acids are not. Carbon monoxide is an important low pressure product and declines with increasing pressure as acids increase. This is evidence for competition between reaction sequence 18—20 and reaction 21. Increasing pressure favors retention of the parent carbon skeleton, in concordance with the reversibiUty of reaction 2. Propylene becomes an insignificant product as the pressure is increased and the temperature is lowered. Both acetone and isopropyl alcohol initially increase as pressure is raised, but acetone passes through a maximum. This increase in the alcohoLcarbonyl ratio is similar to the response of the methanoLformaldehyde ratio when pressure is increased in methane oxidation. 

The mechanism of initiation in cationic polymerization using Friedel-Crafts acids appeared to be clarified by the discovery that most Friedel-Crafts acids, particularly haUdes of boron, titanium, and tin, require an additional cation source to initiate polymerization. Evidence has been accumulating, however, that in many systems Friedel-Crafts acids alone are able to initiate cationic polymerization. The polymerization of isobutylene for instance can be initiated, reportedly even in the absence of an added initiator, by AlBr or AlCl (19), TiCl ( )- Three fundamentally different... 

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