title: HCl uptake through films of pentanoic acid and pentanoic acid/hexanol mixtures at the surface of sulfuric acid.
abstract: Molecular beam scattering experiments are used to investigate collisions and reactions of HCl with deuterated sulfuric acid containing 0-0.2 M pentanoic acid (PA) and mixtures of PA and hexanol. Surface tension measurements at 296 K indicate that PA segregates to the surface of the acid, reaching coverages of 58% and 52% of maximum packing on 60 and 68 wt % D(2)SO(4), respectively. We find that these films increase HCl entry into the acid at low PA surface coverage at 213 K. This enhancement is attributed to the dissociation of HCl molecules that come into contact with surface COOH groups and protonate them. At higher coverages, the PA film becomes more compact and impedes HCl uptake. Comparisons with films of pure hexanol and pentanoic acid/hexanol mixtures indicate that surface OH groups are more effective than COOH groups in catalyzing HCl entry. They also suggest that the PA films consist of patchy regions of tightly packed molecules, which are pushed away from the surface upon addition of the more surface active hexanol. HCl entry into the pure and mixed films can be analyzed quantitatively using a two-step model in which adsorbed HCl molecules penetrate between the alkyl chains and then dissociate at the surfactant-acid interface.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706-1322, USA.
authors.forename: Daniel K
authors.initials: DK
authors.lastname: Burden
authors.forename: Alexis M
authors.initials: AM
authors.lastname: Johnson
authors.forename: Gilbert M
authors.initials: GM
authors.lastname: Nathanson