J Phys Chem B. 2017 Dec 07;121(48):10882-10892. doi: 10.1021/acs.jpcb.7b06930. Epub 2017 Nov 21.

Diffusion of Aromatic Isomers in Acetone: An Investigation on the Effects of Intramolecular and Intermolecular Hydrogen Bonding.

The journal of physical chemistry. B

T C Chan, W Y Tang, N W Chang, Cherie H C Chan

PMID: 29115128 DOI: 10.1021/acs.jpcb.7b06930

Abstract

Limiting mutual diffusivities of o- and m-isomers of methylaniline, nitroaniline, nitrophenol, and aminophenol were measured in acetone at 298.2 K by the Taylor dispersion method. The data reveal that all of the o-substituted solutes capable of intramolecular hydrogen bonding diffuse faster than their m-counterparts without such bonding. By taking into account of the small corrections for the differences in molecular shape and steric hindrance between the o- and m-isomers that can form solute-solvent complexes, the net effects of intramolecular hydrogen bonding were uncovered to render the o-isomers greater in diffusivity by 3-15% as compared to their m-isomers in this study. For aromatic amines and phenols diffusing in acetone, the overall effects of intermolecular hydrogen bonding on diffusivity were ascertained by comparing the available diffusivity data of the associated aromatic solutes with those of the nonassociated ones. The intermolecular effects that cause solutes to diffuse slower were found to vary from approximately 12-39% in the present work. The results indicate that both of the opposite intra- and intermolecular effects are significant. In addition, the quantified effects were analyzed to show that they are closely related to the nature and position of the functional groups contained in the aromatic solutes, including those that are unable to form hydrogen bonds with acetone. A relation that can correlate the diffusivities of the hydrogen-bonded aromatic amines and phenols in acetone with the overall acidities of the compounds is also presented.

Publication Types

• Journal Article
• Research Support, Non-U.S. Gov't