Heat of combustion calculation

One of the common errors made in these thermochemical calculations is to forget that the standard state for heat of combustion calculations is liquid water, and that if gaseous water is present, a phase change (the heat of vaporization or heat of condensation) must be included in the calculations. Don t you forget ... 

One such rule (W. M. Thornton, 1917) is that the heat of combustion is about — 52.5n kcal. per mole, where n is the number of atoms of oxygen required to bum a molecule of the compound. Heats of combustion calculated in this manner are in satisfactory agreement with observation for hydrocarbons, e.g., octane (CsHi ) calculated, — 1312 kcal., observed,... 

CHR.7 HEAT OF COMBUSTION CALCULATION 459 CHR.6 DECOMPOSITION OF ALKYL DICHLOROBENZENES... 

The following table gives the standard heat of combustion calculated in this manner for a few representative substances. 

Note that Joback s method estimates the values only at 298 K, and hence is not useful as a general method for estimating A//n- This is also true of the method based on the heat of combustion calculated from Equation 3.28 in kJ/ mol (Cardozo, 1986) ... 

A particularly useful property of the PX monomer is its enthalpy of formation. Conventional means of obtaining this value, such as through its heat of combustion, are, of course, excluded by its reactivity. An experimental attempt was made to obtain this measure of chemical reactivity with the help of ion cyclotron resonance a value of 209 17 kJ/mol (50 4 kcal/mol) was obtained (10). Unfortunately, the technique suffers from lack of resolution in addition to experimental imprecision. It is perhaps better to rely on molecular orbital calculations for the formation enthalpy. Using a semiempirical molecular orbital technique, which is tuned to give good values for heat of formation on experimentally accessible compounds, the heat of formation of /5-xylylene has been computed to be 234.8 kj/mol (56.1 kcal/mol) (11). 

Two now classical papers 61MI40400, 62JCS2927) contain almost all the experimental thermochemical data on pyrazole and indazole. Heats of combustion determined by Zimmerman (61MI40400) have been used by Dewar to calculate the heats of atomization (Table 25) (69JA796). Quantum mechanical calculations, carried out by Dewar (69JA796) or Olivella 81JHC1189), gave accurate empirical values. 

Furazano[3,4-/]quinoxaline, 7,8-diphenyl-synthesis, 6, 412 Furazanothiophene synthesis, 6, 417 Furazans, 6, 393-426 biological activity, 6, 425 bond angles, 6, 396 bond lengths, 6, 396 coordination compounds, 6, 403 diamagnetic susceptibilities, 6, 395 dipole moments, 6, 395, 400 heats of combustion, 6, 400 heterocyclic ring reactions, 6, 400-403 IR spectra, 6, 398 isoxazoles from, 6, 81 mass spectra, 6, 399 microwave spectroscopy, 6, 395, 396 MO calculations, 6, 395 monosubstituted... 

To make the necessary thermodynamic calculations, plausible reaction equations are written and balanced for production of the stated molar flows of all reactor products. Given the heat of reaction for each applicable reaction, the overall heat of reaction can be determined and compared to that claimed. However, often the individual heats of reaction are not all readily available. Those that are not available can be determined from heats of combustion by combining combustion equations in such a way as to obtain the desired reaction equations by difference. It is a worthwhile exercise to verify this basic part of the process. 

If the explosion occurs in an unconfined vapor cloud, the energy in the blast wave is only a small fraction of the energy calculated as the product of the cloud mass and the heat of combustion of the cloud material. On this basis, explosion efficiencies are typically in the range of 1-10%. 

The heat flux, E, from BLEVEs is in the range 200 to 350 kW/m is much higher than in pool fires because the flame is not smoky. Roberts (1981) and Hymes (1983) estimate the surface heat flux as the radiative fraction of the total heat of combustion according to equation 9.1-32, where E is the surface emitted flux (kW/m ), M is the mass of LPG in the BLEVE (kg) h, is the heat of combustion (kJ/kg), is the maximum fireball diameter (m) f is the radiation fraction, (typically 0.25-0.4). t is the fireball duration (s). The view factor is approximated by equation 9.1-34. where D is the fireball diameter (m), and x is the distance from the sphere center to the target (m). At this point the radiation flux may be calculated (equation 9.1-30). 

Section 3.5 mentions two approaches, the point-source model and the solid-flame model. In the point-source model, it is assumed that a certain fraction of the heat of combustion is radiated in all directions. This fraction is the unknown parameter of the model. Values for fireballs are presented in Section 3.5.1. The point-source model should not be used for calculating radiation on receptors whose plane intercepts the fireball (see Figure 6.9B). 

Calculate the combustion energy E (J) for each blast by multiplying the individual volumes of mixture by 3.5 x 10 J/m. Table 7.1 demonstrates that 3.5 X 10 J/m is a reasonable average value for the heat of combustion of a stoichiometric hydrocarbon-air mixture. 

The heats of formation of most organic compounds are derived from heats of reaction by arithmetic manipulations similar to that shown. Chemists find a table of AH values to be convenient because it replaces many separate tables of AH° values for individual reaction types and permits AH° to be calculated for any reaction, real or imaginary, for which the heats of formation of reactants and products are available. It is more appropriate for our purposes, however, to connect thermochemical data to chemical processes as directly as possible, and therefore we will cite heats of particular reactions, such as heats of combustion and heats of hydrogenation, rather than heats of formation. 

Heat of combustion is the heat liberated or absorbed when one gram mole of the substance is completely oxidized to liquid water and CO2 gas at one atmosphere and 20°C or 25°C. (Cj-C hydrocarbons and cyclohexane at 25°C, others at 20°C). The gross heating value in Btu/ft could be calculated as follows ... 

Figure 4.3 Cycloalkane strain energies, calculated by taking the difference between cycloalkane heat of combustion per CH2 and acyclic alkane heat of combustion per CH2, and multiplying by the number of CH2 units in a ring. Small and medium rings are strained, but cyclohexane rings are strain-free.

In formulating a set of bond-energy values we first calculated the energies of formation of molecules from experimental values of the heats of combustion of the compounds6 and thermochemical data pertaining to the products of combustion—carbon dioxide, water, nitrogen, etc. The same values for the latter quantities were used as previously.4... 

The value for this compound, omitted from the previous paper, is calculated from the heat of combustion by the methods described there. 

---