Decomposition law

Composition Law The whole is more than the sum of its parts . Decomposition Law The part is more than a fraction of the whole . Are these two statements contradictory ... 

Cook (Ref 1), in describing thermal decomposition of some HE s conducted in the quartz spring apparatus (described in Ref 1, p 175 and shown there in Figs 8.1a 8.1b), stated that PETN, RDX, Tetryl and to a small extent TNT decomposed autocatalyti-cally. EDNA followed the first-order decomposition law only until about 5% of the explosive had decomposed and then the reaction stabilized. The term autostabilization was applied here on the supposition that one of the condensed decomposition products of EDNA which accumulated in the explosive apparently tended to stabilize the bulk of expl and thus slow down the decomposition. After about 10% of the expl had decompd, however, the "autocatalysis developed. 

If decomposition proceeds at the same rate over entire range until practically no sample remains (like with(AN),it is said that the explosive exhibits (ideal) first-order decomposition, and that no autocatalyzation takes place as in the decompn of.PETN,Tetryl or RDX. EDNA followed the first-order decomposition law only until ca 5% of the expl had decomposed. This was followed by autostabilization, the term applied here on the supposition that one of the condensed decompn products of EDNA which accumulated in the sample apparently tended to stabilize it, thus slowing down the decompn. After ca 10% of the expl had decomposed, however, autocatalysis developed... 

The Pt-catalyzed decomposition of NO (into N2 and O2) is found to obey the experimental rate law... 

Figure 6.1 Volume of nitrogen evolved from the decomposition of AIBN at 77°C plotted according to the first-order rate law as discussed in Example 6.1. [Reprinted with permission from L. M. Arnett, /. Am. Chem. Soc. 14 2021 (1952), copyright 1952 by the American Chemical Society.]...

Decompositions may be exothermic or endothermic. Solids that decompose without melting upon heating are mostly such that can give rise to gaseous products. When a gas is made, the rate can be affected by the diffusional resistance of the product zone. Particle size is a factor. Aging of a solid can result in crystallization of the surface that has been found to affect the rate of reaction. Annealing reduces strains and slows any decomposition rates. The decompositions of some fine powders follow a first-order law. In other cases, the decomposed fraction x is in accordance with the Avrami-Erofeyev equation (cited by Galwey, Chemistry of Solids, Chapman Hall, 1967)... 

Organic Solids A few organic compounds decompose before melting, mostly nitrogen compounds azides, diazo compounds, and nitramines. The processes are exothermic, classed as explosions, and may follow an autocatalytic law. Temperature ranges of decomposition are mostly 100 to 200°C (212 to 392°F). Only spotty results have been obtained, with no coherent pattern. The decomposition of malonic acid has been measured for both the solid and the supercooled liquid. The first-order specific rates at 126.3°C (259.3°F) were 0.00025/min for solid and 0.00207 for liquid, a ratio of 8 at II0.8°C (23I.4°F), the values were 0.000021 and 0.00047, a ratio of 39. The decomposition of oxalic acid (m.p. I89°C) obeyed a zero-order law at 130 to I70°C (266 to 338°F). 

If the decomposition reaction follows the general rate law, the activation energy, heat of decomposition, rate constant and half-life for any given temperature can be obtained on a few milligrams using the ASTM method. Hazard indicators include heats of decomposition in excess of 0.3 kcal/g, short half-lives, low activation energies and low exotherm onset temperatures, especially if heat of decomposition is considerable. 

A gas decomposition reaction with stoichiometry 2A —> 2B -i- C follows a second order rate law rj(mol / m s) = kC, where C is the reactant concentration in mol/m. The rate constant k varies with the reaction temperature according to the Arrhenius law ... 

Laws of Thermochemistry. Lavoisier and Laplace (1780) found that the heat required to decompose a chemical compound into its elements was numerically equal to the heat generated in its formation under the same conditions of T and P. That is, AHj = -AHp where the subscript d refers to decomposition reaction [52, p. 24 61, p. 303]. 

This ease with which we can control and vary the concentrations of H+(aq) and OH (aq) would be only a curiosity but for one fact. The ions H+(aq) and OH (aq) take part in many important reactions that occur in aqueous solution. Thus, if H+(aq) is a reactant or a product in a reaction, the variation of the concentration of hydrogen ion by a factor of 1012 can have an enormous effect. At equilibrium such a change causes reaction to occur, altering the concentrations of all of the other reactants and products until the equilibrium law relation again equals the equilibrium constant. Furthermore, there are many reactions for which either the hydrogen ion or the hydroxide ion is a catalyst. An example was discussed in Chapter 8, the catalysis of the decomposition of formic acid by sulfuric acid. Formic acid is reasonably stable until the hydrogen ion concentration is raised, then the rate of the decomposition reaction becomes very rapid. 

The numerator of the first term is the number of ways N white balls could appear in 6 draws, and the denominator N is the number of ways these same Ar white balls could be interchanged. (Division by N in the first term reflects the fact that the order in which any specific white ball is drawn is unimportant, since this division by Nl produces the effect of making individual white balls indistinguishable.) If the decomposition of radioactive atoms and the resultant emission of charged particles really follow the laws of chance that govern the drawing of balls from a bag, then radioactivity must be a random process. 

When the cell is in action, a definite chemical reaction occurs in its interior, and according to Faraday s laws the amount of chemical decomposition is proportional to the quantity of... 

Sometimes decomposition reactions can be avoided by carrying out diazotizations in concentrated sulfuric acid. By this method Law et al. (1991) obtained the 1,5-bisdiazonium salt (incorrectly called tetrazonium salt) of l,5-diamino-4,8-dihy-droxy-anthraquinone, which is deprotonated to 2.28. The structure was verified by cross-polarization magic angle spinning (CPMAS) 13C NMR spectroscopy. 

Gamer and Hailes [462] postulated a chain branching reaction in the decomposition of mercury fulminate, since the values of n( 10—20) were larger than could be considered consistent with power law equation [eqn. (2)] obedience. If the rate of nucleation is constant (0 = 1 for the generation of a new nuclei at a large number of sites, N0) and there is a constant rate of branching of existing nuclei (ftB), the nucleation law is... 

Kinetic expressions for appropriate models of nucleation and diffusion-controlled growth processes can be developed by the methods described in Sect. 3.1, with the necessary modification that, here, interface advance obeys the parabolic law [i.e. is proportional to (Dt),/2]. (This contrasts with the linear rate of interface advance characteristic of decomposition reactions.) Such an analysis has been provided by Hulbert [77], who considers the possibilities that nucleation is (i) instantaneous (0 = 0), (ii) constant (0 = 1) and (iii) deceleratory (0 < 0 < 1), for nuclei which grow in one, two or three dimensions (X = 1, 2 or 3, respectively). All expressions found are of the general form... 

This deceleratory reaction obeyed the parabolic law [eqn. (10)] attributed to diffusion control in one dimension, normal to the main crystal face. E and A values (92—145 kJ mole-1 and 109—10,s s-1, respectively) for reaction at 490—520 K varied significantly with prevailing water vapour pressure and a plot of rate coefficient against PH2o (most unusually) showed a double minimum. These workers [1269] also studied the decomposition of Pb2Cl2C03 at 565—615 K, which also obeyed the parabolic law at 565 K in nitrogen but at higher temperatures obeyed the Jander equation [eqn. (14)]. Values of E and A systematically increased... 

The decomposition kinetics of mercury fulminate [725] are significantly influenced by ageing, pre-irradiation and crushing these additional features of reaction facilitated interpretation of the observations and, in particular, the role of intergranular material in salt breakdown. Following a slow evolution of gas ( 0.1%) during the induction period, the accelerator process for the fresh salt obeyed the exponential law [eqn. (8)] when a < 0.35. The induction period for the aged salt was somewhat shorter and here the acceleratory process obeyed the cube law [eqn. (2), n = 3] and E = 113 kj mole-1. 

Singh and Palkar [726] identified an initial deceleratory reaction in the decomposition of silver fulminate. This obeyed first-order kinetics (E = 27 kJ mole-1) and overlapped with the acceleratory period of the main reaction, which obeyed the power law [eqn. (2), n = 2] with E = 119 kj mole-1. The mechanism proposed included the suggestion that two-dimensional growth of nuclei involved electron transfer from anion to metal. 

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