Enthalpy sources

The last database of the eight key data items promised is enthalpy. I have broadly used the term enthalpy to signify all thermal properties that include specific heat, latent heat, and an absolute enthalpy value, expressed as Btu/lb. This section presents a table which, by interpolation, may be applied to any single component or component mixtures, or to any petroleum characterized component groupings. This enthalpy source table (Table 1.10) may be used conveniently and quickly to derive energy or heat values of both liquids and gases. It is compiled from data in Maxwell (pp. 98 to 127) [5]. 

The enthalpy source table (Table 1.10) offers data heat value points which are easily interpolated between. First, pure components are listed, and then petroleum fractions are listed, as in Maxwell s book. 

Table A-28 Calculation of the standard enthalpy sources of the data are indicated.

Conception of an Absorption Refrigerating System Operating at Low Enthalpy Sources... 

The computer subroutines for calculation of vapor-phase and liquid-phase fugacity (activity) coefficients, reference fugac-ities, and molar enthalpies, as well as vapor-liquid and liquid-liquid equilibrium ratios, are described and listed in this Appendix. These are source routines written in American National Standard FORTRAN (FORTRAN IV), ANSI X3.9-1978, and, as such, should be compatible with most computer systems with FORTRAN IV compilers. Approximate storage requirements and CDC 6400 execution times for these subroutines are given in Appendix J. 

The analysis of the heat exchanger network first identifies sources of heat (termed hot streams) and sinks (termed cold streams) from the material and energy balance. Consider first a very simple problem with just one hot stream (heat source) and one cold stream (heat sink). The initial temperature (termed supply temperature), final temperature (termed target temperature), and enthalpy change of both streams are given in Table 6.1. 

By comparison, Fig. 13.36 shows an exothermic reactor integrated below the pinch. Although heat is being recovered, it is being recovered into part of the process which is a heat source. The hot utility requirement cannot be reduced because the process above the pinch needs at least Q//m-,n to satisfy its enthalpy imbalance. 

It is possible to detemiine the equilibrium constant, K, for the bimolecular reaction involving gas-phase ions and neutral molecules in the ion source of a mass spectrometer [18]. These measurements have generally focused on tln-ee properties, proton affinity (or gas-phase basicity) [19, 20], gas-phase acidity [H] and solvation enthalpies (and free energies) [22, 23] ... 

A connnon approach has been to measure the equilibrium constant, K, for these reactions as a fiinction of temperature with the use of a variable temperature high pressure ion source (see section (Bl.7.2)1. The ion concentrations are approximated by their abundance in the mass spectrum, while the neutral concentrations are known from the sample mlet pressure. A van t Hoff plot of In K versus /T should yield a straight Ime with slope equal to the reaction enthalpy (figure B1.7.11). Combining the PA with a value for basicityG at one temperature yields a value for A.S for the half-reaction involving addition of a proton to a species. While quadnipoles have been tire instruments of choice for many of these studies, other mass spectrometers can act as suitable detectors [19, 20]. 

Procedure. Run one or more simultaneous equation programs to determine the C—C and C—H bond energies and interpret the results. The error veetor is the veetor of ealeulated values minus the veetor of bond enthalpies taken as tme from an aeeepted source. Caleulate the enor veetor using a standard souree of bond enthalpies (e.g., Laidler and Meiser, 1999 or Atkins, 1994). Expand the method for 2-butene (2-butene) = —11 kJ mol ] and so obtain the C—H, C—C,... 

With all components in the ideal gas state, the standard enthalpy of the process is exothermic by —165 kJ (—39.4 kcal) per mole of methane formed. Biomass can serve as the original source of hydrogen, which then effectively acts as an energy carrier from the biomass to carbon dioxide, to produce substitute (or synthetic) natural gas (SNG) (see Euels, synthetic). 

When the dryer is seen as a heat exchanger, the obvious perspective is to cut down on the enthalpy of the air purged with the evaporated water. Minimum enthalpy is achieved by using the minimum amount of air and cooling as low as possible. A simple heat balance shows that for a given heat input, minimum air means a high inlet temperature. However, this often presents problems with heat-sensitive material and sometimes with materials of constmction, heat source, or other process needs. AH can be countered somewhat by exhaust-air recirculation. 

For sources, units, and remarks, see Table 2-228. v = specific volume, mVkg h = specific enthalpy, kj/kg s = specific entropy, kJ/(kg-K) c = specific beat at constant pressure, kJ/(kg-K) i = viscosity, 10 Pa-s and k = tberni conductivity, VW(m-K). For specific beat ratio, see Table 2-200 for Prandtl number, see Table 2-369. 

Values rounded off from Chappell and Cockshutt, Nat. Res. Counc. Can. Rep. NRC LR 759 (NRC No. 14300), 1974. This source tabulates values of seven thermodynamic functions at 1-K increments from 200 to 2200 K in SI units and at other increments for two other unit systems. An earlier report (NRC LR 381, 1963) gives a more detailed description of an earlier fitting from 200 to 1400 K. In the above table h = specific enthalpy, kj/kg, and = logio for m isentrope. In terms of... 

Extracted from TsederLerg, Popov, et al., Theimodynamic and Theimophysical Propeities of Helium, Atomizdat, Moscow, 1969, and NBS-NSF TT 50096, 1971. Copyriglit material. Reproduced hy permission. This source contains entries for many more temperatures and pressures than can he reproduced here, v = volume, mVkg h = enthalpy, kj/kg s = entropy, kJ/(kg-K). 

Enthalpy of Formation The ideal gas standard enthalpy (heat) of formation (AHJoqs) of chemical compound is the increment of enthalpy associated with the reaction of forming that compound in the ideal gas state from the constituent elements in their standard states, defined as the existing phase at a temperature of 298.15 K and one atmosphere (101.3 kPa). Sources for data are Refs. 15, 23, 24, 104, 115, and 116. The most accurate, but again complicated, estimation method is that of Benson et al. " A compromise between complexity and accuracy is based on the additive atomic group-contribution scheme of Joback his original units of kcal/mol have been converted to kj/mol by the conversion 1 kcal/mol = 4.1868 kJ/moL... 

The terms may be quantities or rates of flow of material or enthalpy. Inputs and outputs are streams that cross the vessel boundaries. A heat of reaction within the vessel is a. source. A depletion of reactant in the vessel is a. sink. Accumulation is the time derivative of the content of the reference quantity in the vessel of the volume times the concentration, 3V C /df, or of the total enthalpy of the vessel contents, d[WCfT-T,i)]/dt. 

Data on the gas-liquid or vapor-liquid equilibrium for the system at hand. If absorption, stripping, and distillation operations are considered equilibrium-limited processes, which is the usual approach, these data are critical for determining the maximum possible separation. In some cases, the operations are are considerea rate-based (see Sec. 13) but require knowledge of eqmlibrium at the phase interface. Other data required include physical properties such as viscosity and density and thermodynamic properties such as enthalpy. Section 2 deals with sources of such data. 

---