Thermodynamic properties of solution of nonspherical molecules determined from gas-liquid chromatography and calculated by the scaled particle theory using the Kihara potential.

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The free energies, enthalpies, and entropies of solution have been determined for nonspherical molecules by gas-liquid chromatography and the data are discussed on the basis of a simple theory of solution, the scaled particle treatment. The solutes used are normal alkanes from pentane to decane and the solvents used are 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (DDCO), 9-heptadecanone (HPDN), and squalane. Some basic equations are derived for the nonspherical molecules by regarding the alkane solutes, HPDN and squalane as spherocylinders and DDCO as a disk and by incorporating the Kihara potential in estimating the nonspherical interactions. The enthalpies and entropies observed can be reproduced fairly well by assigning appropriate values of the sizes and potential constants for the solutes as well as for the solvents. However, these two properties tend to cancel each other in yielding the free energies, and the free energies are not reproduced so well as the enthalpies and entropies separately are. The presence of long alkyl chains in HPDN and squalane needs be allowed for better prediction of the entropies and, especially, the free energies. The present method of calculation is also applied to a spherical solute of tetramethyltin in the solvents of HPDN and DDCO with reasonable results. In this way, a relatively simple treatment of the scaled particle theory and the Kihara potential is shown to be fruitful in discussing the thermodynamic properties of solution for nonspherical molecules.
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Thermodynamic properties of solution of nonspherical molecules determined from gas-liquid chromatography and calculated by the scaled particle theory using the Kihara potential.

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