title: Thermodiffusion of polycyclic aromatic hydrocarbons in binary mixtures.
abstract: Thermodiffusion in liquid mixtures may explain some counter-intuitive but naturally occurring phenomena such as hydrocarbon reservoirs with heavier component(s) stratified on top of lighter ones. However, beyond benchmark systems, systematic measurements of thermodiffusion in binary organic mixtures are lacking. We use an optical beam deflection apparatus to simultaneously probe Fickian and thermal diffusion in binary solution mixtures of polycyclic aromatic hydrocarbons dissolved in alkanes, and measure both Fickian diffusion D and the Soret coefficient ST, and then obtain the thermodiffusion coefficient DT. In a series of nine binary mixtures, we vary both the size of the aromatic compound from two to four rings, as well as the length of the alkane chain from 6 to 16 carbons. To probe the effect of increasing ring size, we include a 6-ringed aromatic compound, coronene, and toluene as a solvent, due to the insolubility of coronene in alkanes. Our results suggest that Fickian diffusion increases with the inverse of solvent viscosity and also with decreasing molecular weight of the solute. While both of these trends match our intuition, the behavior of STand DTis more complicated. We find that STand DTincrease with the solute molecular weight when the solvent is held fixed and that the impact of solute ring size is higher in shorter chain alkane solvents.
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06510, USA.
authors.forename: Sara M
authors.initials: SM
authors.lastname: Hashmi
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06510, USA.
authors.forename: Sid
authors.initials: S
authors.lastname: Senthilnathan
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06510, USA.
authors.forename: Abbas
authors.initials: A
authors.lastname: Firoozabadi