New semi-empirical rules for estimating cross second virial coefficients

1980 ◽  
Vol 45 (4) ◽  
pp. 1155-1158 ◽  
Author(s):  
Anatol Malijevský ◽  
Josef P. Novák

By using the statistical-thermodynamic interpretation of the theorem of corresponding states, new rules have been derived for estimating cross second viral coefficients.

The principle of corresponding states, in a form that makes no reference to any particular equation, is extended to apply to mixtures. The principle, thus extended, is used to calculate the second virial coefficients. of gaseous mixtures. The values so calculated agree with the experimental values nearly always to within 1cm. 3 /mole and often much better.


The second virial coefficients of some binary mixtures of organic vapours have been measured at temperatures between 50 and 120° C. Mixtures of n -hexane with chloroform and of n -hexane with diethyl ether show a linear variation of second virial coefficient with composition. This is shown to be in accordance with prediction from the principle of corresponding states. Mixtures of chloroform with diethyl ether show a linear variation at 120° C, but pronounced curvature at lower temperatures. This is interpreted quantitatively as being due to association by hydrogen bonding with an energy of 6020 cal/mole.


1971 ◽  
Vol 24 (3) ◽  
pp. 465 ◽  
Author(s):  
MV Pandya ◽  
AG Williamson

A general equation based upon a modified principle of corresponding states and the principle of congruence is used to correlate the second virial coefficients of n-alkanes and their mixtures with each other and with hydrogen. The same procedure is extended to perfluoro-n-alkanes and alk-l-enes.


2016 ◽  
Vol 68 ◽  
pp. 242-251 ◽  
Author(s):  
Giovanni Di Nicola ◽  
Gianluca Coccia ◽  
Mariano Pierantozzi ◽  
Matteo Falone

An apparatus for the measurement of the second virial coefficients of vapours is described. It is designed so that a sample of the gas under investigation can be compared directly with a reference gas (nitrogen). This differential method has practical advantages over direct methods. The apparatus has been used to measure the second virial coefficients of the series of n-alkanes from propane to n-octane from near room temperature to about 140 °C. The results form a family showing deviations from the principle of corresponding states which increase regularly with increasing chain length. A simple formula based on the principle of corresponding states has been found to fit not only the present measurements, but also, previous measurements by other workers at higher temperatures on these substances, and also previous measurements on methane and on ethane. Measurements have also been made on equimolar mixtures of propane + n -heptane and of propane + n -octane. The results are in much better agreement with a slight extension of a rule of Guggenheim & McGlashan (1951) based on the principle of corresponding states than with the rule of Lewis & Randall (1923)-


1955 ◽  
Vol 8 (2) ◽  
pp. 149 ◽  
Author(s):  
SD Hamann ◽  
JA Lambert ◽  
RB Thomas

The second virial coefficients of the mixtures CH4-C(CH3)4, CH4-Si(CH3)4, and CH4-SF6 have been measured for several compositions and at several temperatures. Values of the coefficients B12, derived from the results, fail to conform to Guggenheim and McGlashan's (1951) extension of the principle of corresponding states. Reasons are given for this disagreement.


2000 ◽  
Vol 65 (9) ◽  
pp. 1464-1470 ◽  
Author(s):  
Anatol Malijevský ◽  
Tomáš Hujo

The second and third virial coefficients calculated from the Bender equation of state (BEOS) are tested against experimental virial coefficient data. It is shown that the temperature dependences of the second and third virial coefficients as predicted by the BEOS are sufficiently accurate. We conclude that experimental second virial coefficients should be used to determine independently five of twenty constants of the Bender equation. This would improve the performance of the equation in a region of low-density gas, and also suppress correlations among the BEOS constants, which is even more important. The third virial coefficients cannot be used for the same purpose because of large uncertainties in their experimental values.


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