Vibrational Relaxation in Several Derivatives of Benzene

Abstract

Acoustical spectroscopy at frequencies up to 10 GHz gives the possibility of the investigation of liquid substances, where the relaxation process observed is caused by energy transfer between translational and vibrational degrees of freedom. The compounds presented in this article belong to this group of liquids. The acoustic investigations in the group of benzene derivatives, particularly research of the dependencies of acoustic parameters and the structure of organic liquids, demonstrated some interesting regularities in the group of these compounds in gas and liquid states. In this article, the results of research on five cyclic liquids: bromo-, chloro-, fluoro-, iodo-, and nitrobenzene as well as toluene and aniline are discussed and compared to benzene. The acoustic relaxation observed in all these compounds was found to result from Kneser's processes (vibrational relaxation). Based on investigations reported in this article, as well as by other authors, and taking into account experimental and literature data concerning a great number of compounds, one can draw a conclusion that almost all acoustic relaxation (Kneser-type) processes in liquids can be described using a single relaxation time. It also seems that all vibrational degrees of freedom of the molecule take part in this process. It is known that the appearance of differences in transition probabilities could be caused by additional attraction in interactions of molecules having dipole moments. Halogen derivatives have higher values of dipole moments than benzene. This difference could be responsible for the 123 Int J Thermophys (2012) 33:664-679 665 difference of transition probabilities and changes in the relaxation times. However, benzene derivatives with amino, nitro, and methyl groups and halides show the other type of relaxation.