Pure components, calculating

Mixture calculations are then identical to the pure-component calculations using these effective mixture parameters for the pure-component aa and h values. 

Dual-mode model Pure-component calculation KF... 

Figure 5.19. Determination of concentration profiles and spectral characteristics of pure components from fluorescence spectra collected in real time during a combinatorial melt-polymerization reaction of bisphenol-A polycarbonate in one of the mrcroreactors. (A) Concentration profile of the first component calculated using multivariate curve resolution (B) concentration profile of the second component calculated using multivariate curve resolution (C) spectra of two pure components calculated using multivariate curve resolution. Numbers 1 and 2 are the first and second reaction components, respectively. From ref. 47.

In modern separation design, a significant part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Enthalpy estimates are important not only for determination of heat loads, but also for adiabatic flash and distillation computations. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the Gibbs-Helmholtz equation. ... 

The computation of pure-component and mixture enthalpies is implemented by FORTRAN IV subroutine ENTH, which evaluates the liquid- or vapor-phase molar enthalpy for a system of up to 20 components at specified temperature, pressure, and composition. The enthalpies calculated are in J/mol referred to the ideal gas at 300°K. Liquid enthalpies can be determined either with... 

This chapter presents quantitative methods for calculation of enthalpies of vapor-phase and liquid-phase mixtures. These methods rely primarily on pure-component data, in particular ideal-vapor heat capacities and vapor-pressure data, both as functions of temperature. Vapor-phase corrections for nonideality are usually relatively small. Liquid-phase excess enthalpies are also usually not important. As indicated in Chapter 4, for mixtures containing noncondensable components, we restrict attention to liquid solutions which are dilute with respect to all noncondensable components. 

Subroutine BIJS2. This subroutine calculates the pure-component and cross second virial coefficients for binary mixtures according to the method of Hayden and O Connell (1975). 

CALCULATE PURE COMPONENT LIQUID FUGACITY AT SPECIFIED TEMP AND ZERO PRESSURE IF IVAP.LE.2 C PURE CCMPDNENT VAPOR PRESSURE IF IVAP.EQ.3... 

CALCULATE TEMPERATURE-INDEPENOENT PARAMETERS FOR PURE COMPONENTS... 

PURE calculates pure liquid standard-state fugacities at zero pressure, pure-component saturated liquid molar volume (cm /mole), and pure-component liquid standard-state fugacities at system pressure. Pure-component hypothetical liquid reference fugacities are calculated for noncondensable components. Liquid molar volumes for noncondensable components are taken as zero. 

PURF CALCULATES PURE COMPONENT LIQUID FUGACITIES, FIP, AT SYSTEM... 

To extend the applicability of the characterization factor to the complex mixtures of hydrocarbons found in petroleum fractions, it was necessary to introduce the concept of a mean average boiling point temperature to a petroleum cut. This is calculated from the distillation curves, either ASTM or TBP. The volume average boiling point (VABP) is derived from the cut point temperatures for 10, 20, 50, 80 or 90% for the sample in question. In the above formula, VABP replaces the boiling point for the pure component. 

The current calculation methods are based on the hypothesis that each mixture whose properties are sought can be characterized by a set of pure components and petroleum fractions of a narrow boiling point range and by a composition expressed in mass fractions. 

Characteristics are the experimental data necessary for calculating the physical properties of pure components and their mixtures. We shall distinguish several categories ... 

From the analytical results, it is possible to generate a model of the mixture consisting of an number of constituents that are either pure components or petroleum fractions, according to the schematic in Figure 4.1. The real or simulated results of the atmospheric TBP are an obligatory path between the experimental results and the generation of bases for calculation of thermodynamic and thermophysical properties for different cuts. 

Calculation of the total fugacity of the pure component in the liquid phase. ... 

Appendix 1 comprises a series of tables giving the principal characteristics of pure components most commonly found in the petroleum industry and supplying data for calculation of some useful properties. 

Ideal Adsorbed Solution Theory. Perhaps the most successful approach to the prediction of multicomponent equiUbria from single-component isotherm data is ideal adsorbed solution theory (14). In essence, the theory is based on the assumption that the adsorbed phase is thermodynamically ideal in the sense that the equiUbrium pressure for each component is simply the product of its mole fraction in the adsorbed phase and the equihbrium pressure for the pure component at the same spreadingpressure. The theoretical basis for this assumption and the details of the calculations required to predict the mixture isotherm are given in standard texts on adsorption (7) as well as in the original paper (14). Whereas the theory has been shown to work well for several systems, notably for mixtures of hydrocarbons on carbon adsorbents, there are a number of systems which do not obey this model. Azeotrope formation and selectivity reversal, which are observed quite commonly in real systems, ate not consistent with an ideal adsorbed... 

Basic pure component constants required to characterize components or mixtures for calculation of other properties include the melting point, normal boiling point, critical temperature, critical pressure, critical volume, critical compressibihty factor, acentric factor, and several other characterization properties. This section details for each propeidy the method of calculation for an accurate technique of prediction for each category of compound, and it references other accurate techniques for which space is not available for inclusion. 

Transfer of material between phases is important in most separation processes in which two phases are involved. When one phase is pure, mass transfer in the pure phase is not involved. For example, when a pure liqmd is being evaporated into a gas, only the gas-phase mass transfer need be calculated. Occasionally, mass transfer in one of the two phases may be neglec ted even though pure components are not involved. This will be the case when the resistance to mass transfer is much larger in one phase than in the other. Understanding the nature and magnitudes of these resistances is one of the keys to performing reliable mass transfer. In this section, mass transfer between gas and liquid phases will be discussed. The principles are easily applied to the other phases. 

Physical property specifications placed on the composition of the final produc t. For blends of various products, we usually assume that a composite property can be calculated through the averaging of pure component physical properties. 

A variety of equations-of-state have been applied to supercritical fluids, ranging from simple cubic equations like the Peng-Robinson equation-of-state to the Statistical Associating Fluid Theoiy. All are able to model nonpolar systems fairly successfully, but most are increasingly chaUenged as the polarity of the components increases. The key is to calculate the solute-fluid molecular interaction parameter from the pure-component properties. Often the standard approach (i.e. corresponding states based on critical properties) is of limited accuracy due to the vastly different critical temperatures of the solutes (if known) and the solvents other properties of the solute... 

From the y(jc) functions and the two melt temperatures used, and by using the viscosity curves from rheological examinations (Fig. 11), viscosity distributions T](jc) of the two pure components were easily determined, as shown in Figs. 15a and 15b. Subsequently, the viscosity ratio functions 6(jc) were also calculated (Fig. 16). All four curves fall slightly from the core to the outside. 

The use of the K-factor charts represents pure components and pseudo binary systems of a light hydrocarbon plus a calculated pseudo heavy component in a mixture, when several components are present. It is necessary to determine the average molecular weight of the system on a methane-free basis, and then interpolate the K-value between the two binarys whose heavy component lies on either side of the pseudo-components. If nitrogen is present by more than 3-5 mol%, the accuracy becomes poor. See Reference 79 to obtain more detailed explanation and a more complete set of charts. 

As Mollier charts are available for only a few pure components and practically no mixtures, this calculation method is very limited. For example, it cannot be used for most process calculations because these gases are usually mixtures. Some of the charts available for mixtures are the H-S charts presented by Brown for natural gases of gravities from 0.6 to 1.0. ... 

Now that we have spectra for each of the pure components, we can put the concentration values for each sample into the Beer-Lambert Law to calculate the absorbance spectrum for each sample. But first, let s review various ways of... 

To produce a calibration using classical least-squares, we start with a training set consisting of a concentration matrix, C, and an absorbance matrix, A, for known calibration samples. We then solve for the matrix, K. Each column of K will each hold the spectrum of one of the pure components. Since the data in C and A contain noise, there will, in general, be no exact solution for equation [29]. So, we must find the best least-squares solution for equation [29]. In other words, we want to find K such that the sum of the squares of the errors is minimized. The errors are the difference between the measured spectra, A, and the spectra calculated by multiplying K and C ... 

This will cause CLS to calculate an additional pure component spectrum for the G s. It will also give us an additional row of regression coefficients in our calibration matrix, Kc , which we can, likewise, discard. 

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