Autocatalytic

In the bromate-iron clock reaction, there is an autocatalytic cycle involvmg the species intennediate species HBrO. This cycle is comprised of the following non-elementary steps ... 

The Landolt reaction (iodate + reductant) is prototypical of an autocatalytic clock reaction. During the induction period, the absence of the feedback species (Irere iodide ion, assumed to have virtually zero initial concentration and fomred from the reactant iodate only via very slow initiation steps) causes the reaction mixture to become kinetically frozen . There is reaction, but the intemiediate species evolve on concentration scales many orders of magnitude less than those of the reactant. The induction period depends on the initial concentrations of the major reactants in a maimer predicted by integrating the overall rate cubic autocatalytic rate law, given in section A3.14.1.1. 

The bromate-ferroin reaction has a quadratic autocatalytic sequence, but in this case the induction period is detennined primarily by the time required for the concentration of the hiliibitor bromide ion to fall to a critical low value tlirough the reactions... 

Bromide ion acts as an inliibitor through step (9) which competes for HBr02 with the rate detennining step for the autocatalytic process described previously, step (4) and step (5). Step (8) and Step (9) constitute a pseudo-first-order removal of Br with HBr02 maintained in a low steady-state concentration. Only once [Br ] < [Br ] = /fo[Br07]//r2 does step (3) become effective, initiating the autocatalytic growth and oxidation. 

Figure A3.14.17. Self-replicating spots in the FIS reaction in a CFUR, comparing an experimental time sequence with numerical simulation based on a simple autocatalytic scheme. (Reprmted with pennission from Lee etal [M], Macmillan Magazines Ltd. 1994.)...

Hansen L D, Eatough D J, Lewis E A and Bergstrom R G 1990 Calorimetric measurements on materials undergoing autocatalytic decomposition Can. J. Chem. 68 2111-14... 

A particularly interesting type of micellar catalysis is the autocatalytic self-replication of micelles [58]. Various examples have been described, but a particularly interesting case is the biphasic self-reproduction of aqueous caprylate micelles [59]. In this system ethyl caprylate undergoes hydroxyl catalysed hydrolysis to produce the free carboxylate anion, caprylate. Caprylate micelles then fonn. As these micelles fonn, they solubilize ethylcaprylate and catalyse further production of caprylate anion and caprylate micelles. 

Pitting occurs witli many metals in halide containing solutions. Typical examples of metallic materials prone to pitting corrosion are Fe, stainless steels and Al. The process is autocatalytic, i.e., by initial dissolution, conditions are established which furtlier stimulate dissolution inside tire pit tire metal (Fe in tire example of figure C2.8.6 dissolves. 

As an example of chemical front instability consider a simple cubic autocatalytic reaction, A + 2B 3B, occurring in... 

C3.6.13 where large diffusion fluxes are indicated by —> and smaller diffusion fluxes by —+. For tire part of tire B front tliat protmdes into tire A region, fast diffusion of B leads to dispersal of B and suppresses tire autocatalytic reaction tliat requires two molecules of B. The front will have difficulty advancing here. In tire region where A protmdes into B, A will react leading to advancement of tire front. The net effect is to remove any initial nonplanarity and give rise to a planar front. 

In addition to flame fronts, which have been extensively studied experimentally, front instabilities have been investigated for the isothennal cubic autocatalytic iodate arsenous acid system [70] as well as for polymerization... 

At relatively low temperatures, the effect of added nitric acid was to catalyse the reaction strongly, and to modify it to the autocatalytic form. At higher temperatures the effect of this additive was much weaker, as was the induced autocatalysis. Under these circumstances the catalysis was second-order in the concentration of nitric acid, and the presence of 0-25 mol l i of it brought about a sixfold change in the rate. 

The effect of temperature on the non-catalysed reaction was difficult to disentangle, for at lower temperatures the autocatalytic reaction intervened. However, from a limited range of results, the reaction appeared to have an experimental activation energy of c. +71 kj moh. ... 

The catalysed reaction was considered to arise from the heterolysis of dinitrogen pentoxide induced by aggregates of molecules of nitric acid, to yield nitronium ions and nitrate ions. The reaction is autocatalytic because water produced in the nitration reacts with the pentoxide to form nitric acid. This explanation of the mechanism is supported by the fact that carbon tetrachloride is not a polar solvent, and in it molecules of nitric acid may form clusters rather than be solvated by the solvent ( 2.2). The observation that increasing the temperature, which will tend to break up the clusters, diminishes the importance of the catalysed reaction relative to that of the uncatalysed one is also consistent with this explanation. The effect of temperature is reminiscent of the corresponding effect on nitration in solutions of nitric acid in carbon tetrachloride ( 3.2) in which, for the same reason, an increase in the temperature decreases the rate. 

Under the same conditions the even more reactive compounds 1,6-dimethylnaphthalene, phenol, and wt-cresol were nitrated very rapidly by an autocatalytic process [nitrous acid being generated in the way already discussed ( 4.3.3)]. However, by adding urea to the solutions the autocatalytic reaction could be suppressed, and 1,6-dimethyl-naphthalene and phenol were found to be nitrated about 700 times faster than benzene. Again, the barrier of the encounter rate of reaction with nitronium ions was broken, and the occurrence of nitration by the special mechanism, via nitrosation, demonstrated. 

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

Pentaeiythritol Tetranitrate. Specification-grade pentaerythritol tetranitrate (PETN) can be stored up to 18 months at 65°C without significant deterioration. However, many materials have been found to be incompatible with PETN and the presence of as Htfle as 0.01% occluded acid or alkah greatly accelerates decomposition. The decomposition of PETN is autocatalytic with reported kinetic constants oi E = 196.6 kJ/mol (47 kcal/mol) and Z = 6.31 x 10 . The decomposition products of PETN at 210°C in wt % are 47.7 NO, 21.0 CO, 11.8 NO2, 9.5 N2O, 6.3 CO2, 2.0 H2, and 1.6... 

Acrylonitrile and its comonomers can be polymerized by any of the weU-known free-radical methods. Bulk polymerization is the most fundamental of these, but its commercial use is limited by its autocatalytic nature. Aqueous dispersion polymerization is the most common commercial method, whereas solution polymerization is used ia cases where the spinning dope can be prepared directly from the polymerization reaction product. Emulsion polymerization is used primarily for modacryhc compositions where a high level of a water-iasoluble monomer is used or where the monomer mixture is relatively slow reacting. 

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

Although bulk polymerization of acrylonitrile seems adaptable, it is rarely used commercially because the autocatalytic nature of the reaction makes it difficult to control. This, combined with the fact that the rate of heat generated per unit volume is very high, makes large-scale commercial operations difficult to engineer. Lastiy, the viscosity of the medium becomes very high at conversion levels above 40 to 50%. Therefore commercial operation at low conversion requires an extensive monomer recovery operation. 

The problems of monomer recovery, reaction medium viscosity, and control of reaction heat are effectively dealt with by the process design of Montedison Fibre (53). This process produces polymer of exceptionally high density, so although the polymer is stiU swollen with monomer, the medium viscosity remains low because the amount of monomer absorbed in the porous areas of the polymer particles is greatly reduced. The process is carried out in a CSTR with a residence time, such that the product k jd x. Q is greater than or equal to 1. is the initiator decomposition rate constant. This condition controls the autocatalytic nature of the reaction because the catalyst and residence time combination assures that the catalyst is almost totally expended in the reactor. 

Under normal processing conditions at 300—350°C, Tefzel resins are not subject to autocatalytic degradation. However, extended overheating can result in "blow-backs" through extmder feed hopper or barrel front. 

Formaldehyde condenses with itself in an aldol-type reaction to yield lower hydroxy aldehydes, hydroxy ketones, and other hydroxy compounds the reaction is autocatalytic and is favored by alkaline conditions. Condensation with various compounds gives methylol (—CH2OH) and methylene (=CH2) derivatives. The former are usually produced under alkaline or neutral conditions, the latter under acidic conditions or in the vapor phase. In the presence of alkahes, aldehydes and ketones containing a-hydrogen atoms undergo aldol reactions with formaldehyde to form mono- and polymethylol derivatives. Acetaldehyde and 4 moles of formaldehyde give pentaerythritol (PE) ... 

The mechanism of oxidative dyeing involves a complex system of consecutive, competing, and autocatalytic reactions in which the final color depends on the efficiency with which the various couplers compete with one another for the available diimine. In addition, hydrolysis, oxidation, or polymerization of diimine may take place. Therefore, the color of a mixture caimot readily be predicted and involves trial and error. Though oxidation dyes produce fast colors, some off-shade fading does occur, particularly the development of a red tinge by the slow transformation of the blue indamine dye to a red phenazine dye. 

Hydrolysis is a significant threat to phosphate ester stabiHty as moisture tends to cause reversion first to a monoacid of the phosphate ester ia an autocatalytic reaction. In turn, the fluid acidity can lead to corrosion, fluid gelation, and clogged filters. Moisture control and filtration with Fuller s earth, activated alumina, and ion-exchange resias are commonly used to minimise hydrolysis. Toxicity questions have been minimised ia current fluids by avoiding triorthocresyl phosphate which was present ia earlier natural fluids (38). 

The potassium permanganate crystals are dried at atmospheric pressure below 150°C, cooled, and packaged. Care is taken to prevent heating the product above 200°C during drying to avoid autocatalytic exothermic decomposition of the product. 

Thermal stabihty of the foaming agent in the presence of high temperature steam is essential. Alkylaromatic sulfonates possess superior chemical stabihty at elevated temperatures (205,206). However, alpha-olefin sulfonates have sufficient chemical stabihty to justify their use at steam temperatures characteristic of most U.S. steamflood operations. Decomposition is a desulfonation process which is first order in both surfactant and acid concentrations (206). Because acid is generated in the decomposition, the process is autocatalytic. However, reservoir rock has a substantial buffering effect. 

Kinetics are slow and many hours are requited for a 95% conversion of the reactants. In the case of the subject compound, there is evidence that the reaction is autocatalytic but only when approximately 30% conversion to the product has occurred (19). Reaction kinetics are heavily dependent on the species of halogen ia the alkyl haHde and decrease ia the order I >Br >C1. Tetrabutylphosphonium chloride exhibits a high solubiHty ia a variety of solvents, for example, >80% ia water, >70% ia 2-propanol, and >50% ia toluene at 25°C. Its analogues show similar properties. One of the latest appHcations for this phosphonium salt is the manufacture of readily dyeable polyester yams (20,21). 

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