Vapor pressure estimating from boiling point

The critical properties have been experimentally measured for bromobenzcnc, chlorobenzene, and fluorobcn-Mnc s.s.iuj.w Lydcrsen s method wus used U calculate the critical properties of benzyl chloride 1 Literature data arc reported for the vnpnr pressure ot bru-mobenzene, chlorobenzene, and fluorobcn/ertc up to the critical point, -1" 271 Stull has compiled the vapor pressure data on benzyl chloride up to its boiling point J Ashcroft pce cms data from 48T to I I C. 275 The vapor pressure above the boiling point was estimated ... 

The constants a and b are specific to each group of solvents. Figure 2.3.12 shows that estimation of flash point from vapor pressure of solvent is less aceurate than its estimation from boiling point. 

In a very similar way as discussed above for estimating pi from boiling point data, one can treat the vapor pressure curve below the melting point. Again we use the Clausius-Clapeyron equation ... 

In the calculation of total pressure and vapor composition from boiling point data using the indirect method, the greatest source of error lies in the liquid-phase composition. We have attempted to characterize the frequency distribution of the error in the calculated vapor composition by the standard statistical methods and this has given a satisfactory result for the methanol- vater system saturated with sodium chloride when the following estimates of the standard deviation were used x, 0.003 y, 0.006 T, 0.1° C and tt, 2 mm Hg. This work indicates that in the design of future experiments more data points are required and, for each variable, a reliable estimate of the standard deviation is highly desirable. 

Several conclusions can be drawn from this work. First, in the calculation of total pressure and vapor composition from boiling point data the greatest source of error lies in the liquid-phase composition, particularly at low concentration. Second, the estimates of the standard deviation for vapor composition and temperature of 0.006 and 0.1°C,... 

When a vapor pressure estimate is not available from the literature, it can be estimated approximately using Trouton s rule, which is that the entropy of vaporization is 21.2 times the boiling temperature (K) in cal/mol, i.e., the entropy of vaporation at the normal boiling point is 21.2 cal/mol K. An integrated form of... 

Figure 5.12 Estimated normal boiling point temperatures, of [C Cjim][Nty ionic liquids as a function of alkyl side chain length, n. O, 3" using the Eotvos equation with the data under discussion [26] , using the Guggenheim equation with the data under discussion [26] A, using the Guggenheim equation with data from [1] , using the Clausius-Clapeyron relation with experimental vapor pressure values from [33-35].

When criticals cannot he estimated with reasonable accuracy, the method of Maxwell and BonnelP is recommended. The normal boiling point and the specific gravity at 60 F (15.5 C) are required inputs. According to what vapor pressure range is expected, the vapor pressure is calculated from Eqs. (2-34), (2-35), or (2-36). If the wrong range is selected, the procedure will need to be repeated. 

To design a supercritical fluid extraction process for the separation of bioactive substances from natural products, a quantitative knowledge of phase equilibria between target biosolutes and solvent is necessary. The solubility of bioactive coumarin and its various derivatives (i.e., hydroxy-, methyl-, and methoxy-derivatives) in SCCO2 were measured at 308.15-328.15 K and 10-30 MPa. Also, the pure physical properties such as normal boiling point, critical constants, acentric factor, molar volume, and standard vapor pressure for coumarin and its derivatives were estimated. By this estimated information, the measured solubilities were quantitatively correlated by an approximate lattice equation of state (Yoo et al., 1997). 

The four coefficients A, B, C, and D have been derived, for example, with selected hydrocarbons [25, 26], Equation 7.4.3 accurately represents the vapor pressure function over the entire temperature range between the triple point and the critical point. If the coefficients are not available for a given compound, they can be calculated. D is calculated from the pressure van der Waals constant, a, which can be estimated from group contributions. B is calculated directly from group contributions. Then the coefficients A and C can be estimated from two pv/T points (e.g., normal boiling point and critical point). This approach has been evaluated for various classes of hydrocarbons commonly encountered in petroleum technology [25, 26]. 

ACTIVITY COEFFICIENT. A fractional number which when multiplied by the molar concentration of a substance in solution yields the chemical activity. This term provides an approximation of how much interaction exists between molecules at higher concentrations. Activity coefficients and activities are most commonly obtained from measurements of vapor-pressure lowering, freezing-point depression, boiling-point elevation, solubility, and electromotive force. In certain cases, activity coefficients can be estimated theoretically. As commonly used, activity is a relative quantity having unit value in some chosen standard state. Thus, the standard state of unit activity for water, dty, in aqueous solutions of potassium chloride is pure liquid water at one atmosphere pressure and the given temperature. The standard slate for the activity of a solute like potassium chloride is often so defined as to make the ratio of the activity to the concentration of solute approach unity as Ihe concentration decreases to zero. 

Another use for this set of curves is for estimating the azeotropic boiling point and composition at pressures other than atmospheric. Consider the azeotrope methanol-benzene. Since the vapor pressure curves of methanol and benzene are known, the difference in boiling point, A, can be obtained at any pressure. From this value of A and the C-A curve for methanol-hydrocarbons the azeotropic concentration C at that pressure can be determined. For example, the effect of pressure on the methanol-benzene azeotrope is shown in Table I. 

For comparison purposes, a boiling point was estimated from measured vapor pressure data (1.87 x 10-5 mm Hg 25°C), and this estimate was taken as the "true" boiling point for purposes of calculating a method error. 

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