scholarly journals The second virial coefficient of a gas of non-spherical molecules

1948 ◽  
Vol 192 (1029) ◽  
pp. 275-292 ◽  
Keyword(s):  
Virial Coefficient ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Intermolecular Forces ◽  
Mean Values ◽  
Breadth Ratio ◽  
Thomson Coefficient ◽  
Low Pressures ◽  
Spherical Molecule ◽  
Critical Constants

Tables are given for the second virial coefficient and Joule-Thomson coefficient (at low pressures) of a gas whose molecules are non-polar, approximately cylindrical, and stiff. The tables cover the range of length/breadth ratio consistent with the last assumption. The tables can be used for the analysis of observed virial coefficients of gases whose molecules satisfy these assumptions, and give an estimate of the intermolecular forces between these molecules at any relative orientation. For small ratio of length to breadth the virial coefficient is nearly the same as that of a spherical molecule with certain mean values of the parameters defining the intermolecular field. This makes it possible to relate these mean parameters to the critical constants and to the parachor. The virial coefficients of nine gases are analysed. The data on seven hydrocarbons enable one to estimate the law of force between molecules of the lower non-polar hydrocarbons.

Measurement of the temperature variation of virial coefficients. III. The second virial coefficient of Carbon Disulphide, Methyl Chloride, Acetone, and Methanol, and certain of their binary mixtures

1967 ◽  
Vol 20 (9) ◽  
pp. 1789 ◽  
Author(s):  
GA Bottomley ◽  
TH Spurling
Keyword(s):  
Atmospheric Pressure ◽  
Pressure Range ◽  
Virial Coefficient ◽  
Carbon Disulphide ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Methyl Chloride ◽  
Intermolecular Forces ◽  
Second Virial Coefficients ◽  
Similar Work

Second virial coefficients have been determined for carbon disulphide, methyl chloride, acetone, and methanol over the temperature range of 50-150� with some additional results at lower temperatures. Similar work has been conducted on the selected mixtures methyl chloride-carbon disulphide, methyl chloride-acetone, acetone-carbon disulphide, and methyl chloride-argon. Methanol, exceptionally, shows very significant third virial contributions in the sub-atmospheric pressure range. A comparison is made with recent models pertaining to molecular interactions between unlike molecules possessing dipolar and quadrupolar contributions to the intermolecular forces.

The second virial coefficients of mixed polar vapours

1959 ◽  
Vol 249 (1258) ◽  
pp. 414-426 ◽  
Keyword(s):  
Methyl Acetate ◽  
Virial Coefficient ◽  
Methyl Formate ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Ethyl Formate ◽  
Carbonyl Oxygen ◽  
Second Virial Coefficients ◽  
Theoretical Significance ◽  
Boyle’S Law

The second virial coefficients of binary mixtures of chloroform with methyl formate, n -propyl formate, methyl acetate, ethyl acetate and diethylamine have been measured in a ‘Boyle’s law apparatus’ at temperatures between 50 and 95 °C. The measured values are consistently higher than predicted by the theory of corresponding states, and a quantitative interpretation is proposed, based on the hypothesis that the esters and amine are partially dimerized and are involved in association with the chloroform by hydrogen bonding. A linear relation is shown to exist between the heats and entropies of association for the various mixtures, and the theoretical significance of this is discussed. There is some evidence that hydrogen bonds are formed through the alkoxyl oxygen by formate esters and through the carbonyl oxygen by acetate esters. The paper includes data on the second virial coefficient for the pure esters and for ethyl formate and methyl propionate.

Parameters of the Bender Equation of State for Chloro Derivatives of Methane and Chlorobenzene

2001 ◽  
Vol 66 (6) ◽  
pp. 833-854 ◽  
Author(s):  
Ivan Cibulka ◽  
Lubomír Hnědkovský ◽  
Květoslav Růžička
Keyword(s):  
Experimental Data ◽  
Equation Of State ◽  
Virial Coefficient ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Liquid Equilibrium ◽  
Second Virial Coefficients ◽  
Equilibrium Data ◽  
State Behaviour ◽  
Derivatives Of

Values of adjustable parameters of the Bender equation of state evaluated for chloromethane, dichloromethane, trichloromethane, tetrachloromethane, and chlorobenzene from published experimental data are presented. Experimental data employed in the evaluation included the data on state behaviour (p-ρ-T) of fluid phases, vapour-liquid equilibrium data (saturated vapour pressures and orthobaric densities), second virial coefficients, and the coordinates of the gas-liquid critical point. The description of second virial coefficient by the equation of state is examined.

Intermolecular forces and properties of fluid. I. The automatic calculation of higher virial coefficients and some values of the fourth coefficient for the Lennard-Jones potential

1960 ◽  
Vol 254 (1279) ◽  
pp. 487-498 ◽  
Keyword(s):  
Virial Coefficient ◽  
Mathematical Problem ◽  
Virial Coefficients ◽  
Intermolecular Forces ◽  
Lennard Jones Potential ◽  
Intermolecular Potentials ◽  
Jones Potential ◽  
Lennard Jones ◽  
Experimental Values ◽  
First Time

The prediction of the virial coefficients for particular intermolecular potentials is generally regarded as a difficult mathematical problem. Methods have only been available for the second and third coefficient and in fact only few calculations have been made for the latter. Here a new method of successive approximation is introduced which has enabled the fourth virial coefficient to be evaluated for the first time for the Lennard-Jones potential. It is particularly suitable for automatic computation and the values reported here have been obtained by the use of the EDSAC I. The method is applicable to other potentials and some values for these will be reported subsequently. The values obtained cannot yet be compared with any experimental results since these have not been measured, but they can be used in the meantime to obtain more accurate experimental values of the lower coefficients.

The second virial coefficients of mixed organic vapours

1952 ◽  
Vol 210 (1103) ◽  
pp. 557-564 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Binary Mixtures ◽  
Diethyl Ether ◽  
Virial Coefficient ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Corresponding States ◽  
Linear Variation ◽  
Second Virial Coefficients

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.

The statistical mechanics of assemblies of axially symmetric molecules - II. Second virial coefficients

1954 ◽  
Vol 221 (1147) ◽  
pp. 508-516 ◽  
Keyword(s):  
Carbon Dioxide ◽  
General Theory ◽  
Force Field ◽  
Virial Coefficient ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Intermolecular Potential ◽  
Crystal Data ◽  
Axially Symmetric ◽  
Second Virial Coefficients

A general theory of the second virial coefficient of axially symmetric molecules is developed, the directional part of the intermolecular field being treated as a perturbationon the central-force part. The method is applicable to any type of intermolecular potential, particular models of directional interaction being obtained by suitable choices of parameters. Simple expressions are given for the second virial coefficient due to several types of directional force. The theory is illustrated by some calculations on the force field of carbon dioxide and its relation to the second virial coefficient and crystal data. These indicate that there is strong quadrupole interaction between carbon dioxide molecules.

Measurement of the temperature variation of virial coefficients. I. Application to the second virial coefficient of n-butane

1964 ◽  
Vol 17 (5) ◽  
pp. 501 ◽  
Author(s):  
GA Bottomley ◽  
TH Spurling
Keyword(s):  
Temperature Dependence ◽  
Temperature Variation ◽  
Virial Coefficient ◽  
Small Volume ◽  
Second Virial Coefficient ◽  
Virial Coefficients ◽  
Absolute Pressure ◽  
Isothermal Expansion ◽  
Volume Increment

An unconventional apparatus, described in detail, determines, through a measured small volume increment, the temperature dependence of the second virial coefficient of a vapour without the necessity for isothermal expansion. Absolute pressure determinations are avoided by working differentially, vapour against nitrogen reference gas. Results for n-butane at 0-150� agree with established work.

The second virial coefficient of benzene at low pressures

1958 ◽  
Vol 246 (1247) ◽  
pp. 514-520 ◽  
Keyword(s):  
Virial Coefficient ◽  
Second Virial Coefficient ◽  
Full Correction ◽  
Low Pressures

The density of benzene vapour at about 70% saturation at 22 °C has been determined experimentally by the microbalance method using nitrogen as the comparison gas. The adsorption of the benzene vapour on the particular working parts of the two balances used in the work was determined in separate experiments, so that full correction of the density determinations for this influence was possible. The second virial coefficient of the vapour has been deduced at 22 °C and, from similar measurements, at 35 °C.

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