Thermochemical equations state functions

The principal feature of this relationship is that F values are derived solely from molecular formulae and chemical structures and require no prior knowledge of any physical, chemical or thermochemical properties other than the physical state of the explosive that is, explosive is a solid or a liquid [72]. Another parameter related to the molecular formulae of explosives is OB which has been used in some predictive schemes related to detonation velocity similar to the prediction of bri-sance, power and sensitivity of explosives [35, 73, 74]. Since OB is connected with both, energy available and potential end products, it is expected that detonation velocity is a function of OB. As a result of an exhaustive study, Martin etal. established a general relation that VOD increases as OB approaches to zero. The values of VOD calculated with the use of these equations for some explosives are given in the literature [75] and deviations between the calculated and experimental values are in the range of 0.46-4.0%. 

The adopted C data from 273.15 to 373.15 K are taken from the very accurate calorimetric measurements of Osborne et al. (4). Heat capacity data taken from the recent equation of state formulation of Haar et al. (5) agree with the adopted data to within 0.06% above 320 K with deviations up to 0.12% being noted near 305 K. In the latter region the experimental C data go through a single smooth minimum while data derived from the equation of state exhibit an incipient double minimum behavior. These deviations are very small and would lead to nearly negligible differences in the thermochemical functions. 

Carbon is also a major detonation product. A successful thermochemical library must include an accurate equation of state for carbon. Our carbon equation of state [13] is based on an explicit functional form for G(P,T). It is more often the case that the pressure of a system is known than its volume. This makes a (P,T) equation of state very convenient in practical application. 

The present study calculates thermochemical properties of intermediates, transition states and products important to the degradation of the aromatic ring in the phenyl radical + O2 reaction system. Kinetic parameters are developed for the important elementary reaction paths through each channel as a function of temperature and pressure. The calculation is done via a bimolecular chemical activation and master equation analysis for fall-ofif. 

Equation (8-18a) shows that the temperature, T, is proportional to the fractional conversion, jca, for an adiabatic flow reactor at steady state. If the fractional conversion is known, the corresponding temperature can be calculated. Of comse, the thermochemical data required to calculate A/Ir and aU of the Cp,-, as functions of T, must be available. 

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