Estimation of heats of vaporization for non associating organic liquids from the boiling points at various pressures

1986 ◽  
Vol 64 (4) ◽  
pp. 635-640 ◽  
Author(s):  
J. Peter Guthrie

At any pressure the heat of vaporization can be expressed as a quadratic function of the boiling point at that pressure. A seven parameter equation expressing the simultaneous dependence on boiling point and pressure can be fitted to the data; six pressures from 1 to 760 Torr (1 Torr = 133.3 Pa) were used. ΔHvap = b11 + b12 In (p) + b13p + (b21 + b22 In (p))tbp + (b31 + b32 In (p))tbp2. This relationship served as a guide for developing a relationship between vapour pressure at 25 °C and the calorimetric heat of vaporization, and also a relationship between vapor pressure at 25 °C and the boiling point at some other pressure. Parameters for both these relationships could be derived from the parameters obtained for ΔHvap as a function of temperature and pressure. A third method was developed starting from an equation for vapor pressure and fitting to the heat of vaporization, the heat capacity of vaporization, and at least one t,p point. These methods allow the estimation of the vapor pressure at room temperature from very meager data. The problems of errors in estimated values are discussed.

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