Rate for decomposition

TABLE 4. Arrhenius parameters and comparative rates for decomposition of chlorocyclohexenes at 360 °C... 

Annealing the formate-covered Ni(llO) surface to 340 K, the leading edge of formate decomposition produces scattered Ni islands of monatomic step height amidst the c(2 x 2)-formate domains and the small number of pits of monatomic step depth (Fig. 11.15) [21]. The Ni islands are apparently formed by Ni adatoms released during the decomposition of a small fraction of formate. The Ni islands were also observed when annealing the acetate-covered Ni(llO) surface to 360 K [21]. These observations provide a more detailed explanation for the kinetic explosion in the decomposition of formate and acetate. It appears that the released Ni atoms catalyzed the further decomposition of the carboxylates. The released Ni atoms can either catalyze the reaction before they nucleate into islands or provide unoccupied metal sites, which are produced exponentially due to desorption of the carboxylates with the exponential rate, for decomposition. This ultimately leads to a kinetic explosion in the decomposition of the carboxylates on Ni(llO). 

The parallelism of the linear plots indicates one value for the activation energy, 104.8 kcal mole , and an enhanced rate for decomposition in the presence of increased amounts of Oj. A plot of the observed rate coefficients at a temperature of 5000° K versus the mole fraction of oxygen supports the linearity assumption for Xq, < 0.10. The straight line drawn in Fig. 15 represents the linearity assumption. The deviations of the points at higher mole fractions which are outside the limits of experimental error can most probably be accounted for by the increased contributions of vibration-vibration processes which would lower the rate coefficients for > 0.10. 

The complete assembly for carrying out the catalytic decomposition of acids into ketones is shown in Fig. Ill, 72, 1. The main part of the apparatus consists of a device for dropping the acid at constant rate into a combustion tube containing the catalyst (manganous oxide deposited upon pumice) and heated electrically to about 350° the reaction products are condensed by a double surface condenser and coUected in a flask (which may be cooled in ice, if necessary) a glass bubbler at the end of the apparatus indicates the rate of decomposition (evolution of carbon dioxide). The furnace may be a commercial cylindrical furnace, about 70 cm. in length, but it is excellent practice, and certainly very much cheaper, to construct it from simple materials. 

The controlled thermal decomposition of dry aromatic diazonium fluoborates to yield an aromatic fluoride, boron trifluoride and nitrogen is known as the Schiemann reaction. Most diazonium fluoborates have definite decomposition temperatures and the rates of decomposition, with few exceptions, are easily controlled. Another procedure for preparing the diazonium fluoborate is to diazotise in the presence of the fluoborate ion. Fluoboric acid may be the only acid present, thus acting as acid and source of fluoborate ion. The insoluble fluoborate separates as it is formed side reactions, such as phenol formation and coupling, are held at a minimum temperature control is not usually critical and the temperature may rise to about 20° without ill effect efficient stirring is, however, necessary since a continuously thickening precipitate is formed as the reaction proceeds. The modified procedure is illustrated by the preparation of -fluoroanisole ... 

The type of initiator utilized for a solution polymerization depends on several factors, including the solubiUty of the initiator, the rate of decomposition of the initiator, and the intended use of the polymeric product. The amount of initiator used may vary from a few hundredths to several percent of the monomer weight. As the amount of initiator is decreased, the molecular weight of the polymer is increased as a result of initiating fewer polymer chains per unit weight of monomer, and thus the initiator concentration is often used to control molecular weight. Organic peroxides, hydroperoxides, and azo compounds are the initiators of choice for the preparations of most acryUc solution polymers and copolymers. 

Nitrocellulose is among the least stable of common explosives. At 125°C it decomposes autocatalyticaHy to CO, CO2, H2O, N2, and NO, primarily as a result of hydrolysis of the ester and intermolecular oxidation of the anhydroglucose rings. At 50°C the rate of decomposition of purified nitrocellulose is about 4.5 x 10 %/h, increasing by a factor of about 3.5 for each 10°C rise in temperature. Many values have been reported for the activation energy, E, and Arrhenius frequency factor, Z, of nitrocellulose. Typical values foiE and Z are 205 kj/mol (49 kcal/mol) and 10.21, respectively. The addition of... 

Either mechanism can be used to describe how antimony—halogen systems operate in both the condensed and vapor phases. In the condensed phase a chat that is formed during the reaction of the polymer, antimony trioxide, and the halogen reduces the rate of decomposition of the polymer therefore, less fuel is available for the flame (16). 

If a self-sustained oxidation is carried out under limiting rate conditions, the hydroperoxide provides the new radicals to the system (by reaction 4 or analogues) and is maintained at a low concentration (decomposition rate = generation rate). For these circumstances, the rate equation 9 holds, where n = average number of initiating radicals produced (by any means) per molecule of ROOH decomposed and / = fraction of RH consumed which disappears by ROO attack (25). 

AlkyUithium compounds are primarily used as initiators for polymerizations of styrenes and dienes (52). These initiators are too reactive for alkyl methacrylates and vinylpyridines. / -ButyUithium [109-72-8] is used commercially to initiate anionic homopolymerization and copolymerization of butadiene, isoprene, and styrene with linear and branched stmctures. Because of the high degree of association (hexameric), -butyIUthium-initiated polymerizations are often effected at elevated temperatures (>50° C) to increase the rate of initiation relative to propagation and thus to obtain polymers with narrower molecular weight distributions (53). Hydrocarbon solutions of this initiator are quite stable at room temperature for extended periods of time the rate of decomposition per month is 0.06% at 20°C (39). 

When a component at an austenitizing temperature is placed in a quenchant, eg, water or oil, the surface cools faster than the center. The formation of martensite is more favored for the surface. A main function of alloying elements, eg, Ni, Cr, and Mo, in steels is to retard the rate of decomposition of austenite to the relatively soft products. Whereas use of less expensive plain carbon steels is preferred, alloy steels may be requited for deep hardening. 

Therefore, first-order, decomposition rates for alkyl hydroperoxides, ie, from oxygen—oxygen bond homolysis, are vaUd only if induced decomposition reactions... 

At temperatures near the critical temperature, many organic degradation reactions are rapid. Halogenated hydrocarbons loose the halogen in minutes at 375°C (38). At temperatures typical of nuclear steam generators (271°C (520°F)), the decomposition of amines to alcohols and acids is well known (39). The pressure limits for the treatment of boiler waters using organic polymers reflect the rate of decomposition. 

It was found (32) that in the acid range (pH 4—6) the alkyl group does not influence the rate of decomposition, which is similar for all xanthates. In the alkaline range the rates are markedly influenced by the substitutional group, and the rates could be correlated with the Taft polar substituent constants estabhshed for the various groups. 

At room temperature bismuthine rapidly decomposes into its elements. The rate of decomposition increases markedly at higher temperatures (8). Bismuthine decomposes when bubbled through silver nitrate or alkafl solutions but is unaffected by light, hydrogen sulfide, or 4 sulfuric acid solution. There is no evidence for the formation of BiH, though the phenyl derivative, (C H BU, is known. The existence of BiH would not be anticipated on the basis of the trend found with other Group 15 (V) "onium" ions. 

Carbonates decompose at relatively high temperatures, 660 to 740°C (1,220 to 1,364°F) for CaCO,3. When large samples are used the rate of decomposition can be controlled by the rate of heat transfer or the rate of CO9 removal. 

The rate of decomposition in unmanaged landfills, as measured by gas production, reaches a peak within the first 2 years and then slowly tapers off, continuing in many cases for periods up to 25 years or more. The total volume of the gases released during anaerobic decomposition can be estimated in a number of ways. If all the organic constituents in the wastes (with the exception of plastics, rubber, and leather) are represented with a generahzed formula of the form QH O N, the total volume of gas can be estimated by using Eq. (25-27) with the assumption of completed conversion to carbon dioxide and methane. 

The overall rate for tire formation of ammonia must tlrerefore be a balance between the formation and tire decomposition of the product species. Experimental data suggest tlrat tlris balance can be represented by the equation... 

The chlorine present results in a self-extinguishing polymer. It also leads to a polymer which has a high rate of decomposition at the temperatures required for processing. 

The kinetics of the hydrolysis of some imines derived from benzophenone anc primary amines revealed the normal dependence of mechanism on pH with ratedetermining nucleophilic attack at high pH and rate-determining decomposition of the tetrahedral intermediate at low pH. The simple primary amines show a linear correlation between the rate of nucleophilic addition and the basicity of the amine Several diamines which were included in the study, in particular A, B, and C, al showed a positive (more reactive) deviation from the correlation line for the simple amines. Why might these amines be more reactive than predicted on the basis of thei ... 

Time to maximum rate (TMR) The time taken for a material to selfheat to tlie maximum rate of decomposition from a specific temperamre. 

It seems reasonable to assume that in regard to their formation and decomposition the derivatives of phenylpentazole correspond roughly to the unsubstituted compound (see Table V). The rate data for m-and p-substituted phenylpentazoles conform to the Hammett equation with p= -f-1.01. Finally, the high rate of decomposition and... 

The highest energy required in this new reaction path is only 18 kcal, much lower than the activation energy shown in Figure 8-10 for the uncatalyzed reaction. Hence the rate of decomposition is much faster when add is present. 

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