Properties, estimation combustion

Adiabatic flame temperatures agree with values measured by optical techniques, when the combustion is essentially complete and when losses are known to be relatively small. Calculated temperatures and gas compositions are thus extremely useful and essential for assessing the combustion process and predicting the effects of variations in process parameters (4). Advances in computational techniques have made flame temperature and equifibrium gas composition calculations, and the prediction of thermodynamic properties, routine for any fuel-oxidizer system for which the enthalpies and heats of formation are available or can be estimated. 

The thermodynamic properties of thiophene,2-methylthiophene, ° and 3-methylthiophene have been computed from careful measurements of the heat capacity of the solid, liquid, and vapor states, the heat of fusion, the heat of vaporization, and the heat of combustion. From the heat of combustion of thiophene and from thermochemical bond energies, the resonance energy of thiophene has been re-estimated to be only 20 kcal/mole. 

A preliminary indication of the potential hazards can be estimated by knowing something about the chemical structure. Specific functional groups that contribute to the explosive properties of a chemical through rapid combustion or detonation are illustrated in Table 13-1. 

The flame speed for a combustible hydrocarbon-air mixture is known to be 30cm/s. The activation energy of such hydrocarbon reactions is generally assumed to be 160kJ/mol. The true adiabatic flame temperature for this mixture is known to be 1600 K. An inert diluent is added to the mixture to lower the flame temperature to 1450 K. Since the reaction is of second-order, the addition of the inert can be considered to have no other effect on any property of the system. Estimate the flame speed after the diluent is added. 

In this paper, we demonstrate how mean maximum reflectance of vitrinite in oil (hereafter referred to as R ) can be used in place of conventional chemical-rank parameters (volatile matter and fixed carbon) to estimate the relative yields of carbonization products, specific properties of gas produced by carbonization, and chemical properties of coal such as calorific value and free swelling index (FS1). Further, we illustrate that measured R can be used to detect coal oxidation, to categorize coals for certain combustion uses, and to help classify coals by rank. 

This investigation shows that the average reflectance of vitrinite in coal (Ro) can be used to estimate carbonization product yields, by-product gas properties, chemical properties, oxidation effects, and combustion behavior. Moreover, R along with calorific value and volatile matter content might be employed to classify accurately and consistently coals of all ranks. 

Initially, we will be concerned with the physical properties of alkanes and how these properties can be correlated by the important concept of homology. This will be followed by a brief survey of the occurrence and uses of hydrocarbons, with special reference to the petroleum industry. Chemical reactions of alkanes then will be discussed, with special emphasis on combustion and substitution reactions. These reactions are employed to illustrate how we can predict and use energy changes — particularly AH, the heat evolved or absorbed by a reacting system, which often can be estimated from bond energies. Then we consider some of the problems involved in predicting reaction rates in the context of a specific reaction, the chlorination of methane. The example is complex, but it has the virtue that we are able to break the overall reaction into quite simple steps. 

A great number of studies related to thermochemical properties of QDO and PDO derivatives have been recently described by Ribeiro da Silva et al. [98-103]. These studies, which have involved experimental and theoretical determinations, have reported standard molar enthalpies of formation in the gaseous state, enthalpies of combustion of the crystalline solids, enthalpies of sublimation, and molar (N - O) bond dissociation enthalpies. Table 5 shows the most relevant determined parameters. These researchers have employed, with excellent results, calculations based in density functional theory in order to estimate gas-phase enthalpies of formation and first and second N - O dissociation enthalpies [103]. 

In assessing the potential value of a proposed energetic compound, important measures of performance are detonation velocity and pressure for explosives and specific impulse for propellants. One of the key factors in determining these properties is the energy that is produced in the decomposition or combustion process [1-4]. This can normally be estimated if the compound s heat of formation, AHf, is known. (There are also indications that the energy of decomposition is related to sensitivity toward initiation of detonation [5,6].) Thus a reliable value for AHf is essential to the evaluation of a compound. If the latter has not yet been synthesized, then its heat of formation must necessarily be obtained by a computational procedure. This may be true as well if only a very small amount has been prepared, or if the laboratory determination presents difficulties [7]. 

This would not be problematic if standardized, reliable, reproducible, and inexpensive laboratory tests were available to estimate each of the required properties. Although several specialized laboratory tests are available to measure some properties (e.g., specific heat capacity can be determined by differential scanning calorimetry [DSC]), many of these tests are still research tools and standard procedures to develop material properties for fire modeling have not yet been developed. Even if standard procedures were available, it would likely be so expensive to conduct 5+ different specialized laboratory tests for each material so that practicing engineers would be unable to apply this approach to real-world projects in an economically viable way. Furthermore, there is no guarantee that properties measured independently from multiple laboratory tests will provide accurate predictions of pyrolysis behavior in a slab pyrolysis/combustion experiment such as the Cone Calorimeter or Fire Propagation Apparatus. 

The relative ease or difficulty of incineration has been estimated on the basis of the heat of combustion, thermal decomposition kinetics, susceptibility to radical attack, autoignition temperature, correlations of other properties, and destruction efficiency measurements made in laboratory combustion tests. Laboratory studies have indicated that no single ranking procedure is appropriate for all incinerator conditions. In fact, a compound that can be incinerated easily in one system may be the most difficult to remove from another incinerator due to differences in the complex coupling of chemistry and fluid mechanics between the two systems. 

The prediction of rocket propellant specific impulse, as well as impulse under other conditions, may be reliably accomplished by calculation using as input the chemical composition, the heat of formation, and the density of the component propellant chemicals. Not only impulse but also the composition of exhaust species (and of species in the combustion chamber and the throat) may be calculated if the thermodynamic properties of the chemical species involved are known or can be estimated. The present standard computer code for such calculations is that described by Gordon and McBride.44 Theoretical performance predictions using such programs are widely used to guide propellant formulation efforts and to predict rocket propellant performance however, verification of actual performance is necessary. 

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