Comment on "New statistical mechanical model for calculating Kirkwood factors in self-associating liquid systems and its application to alkanol+cyclohexane mixtures" [J. Chem. Phys. 127, 114501 (2007)].
A brief overview of the current state of the research on calculation of Kirkwood factor of liquid alcohols and their mixtures is presented. On the basis of the accurate solution for the correlation factor, obtained in the author's published papers, it was stated that the formulas for Kirkwood factor of alcohols g(K) and their mixtures with inert solvents (hydrocarbons) obtained in the paper by Vasiltsova and Heintz [J. Chem. Phys. 127, 114501 (2007)], in the opinion of the present author, are erroneous and contradict all preceding results obtained in this area of research. On the basis of the rigorous solution for Kirkwood factor of liquids with predominant chainlike aggregation it has been shown that the generally accepted opinion based on the famous Kirkwood formula g(K)=1+z<cos gamma>, where z is coordination number, <cos gamma> is average cosine of angle between adjacent dipoles in liquids ([J. G. Kirkwood, J. Chem. Phys. 7, 911 (1939)], Eq. (19)) that Kirkwood factor as determined by the mean cosine of the angle between adjacent dipoles should be modified for the liquids consisting of nonlinear molecules with the complex type of the supramolecular organization. Alcohols are examples of such liquids, in which long-range intermolecular correlations beyond the nearest coordination shells are essential for their structural organization.
Durov
Vladimir A
VA