Adding Salt to an Aqueous Solution of t-Butanol: Is Hydrophobic Association Enhanced or Reduced?

Details Adding Salt to an Aqueous Solution of t-Butanol: Is Hydrophobic Association Enhanced or Reduced? Adding Salt to an Aqueous Solution of t-Butanol: Is Hydrophobic Association Enhanced or Reduced?

2005-07-22

arxiv.org/abs/cond-mat/0507529v2

Physics

Condensed Matter

Soft Condensed Matter

15 pages twocolumn revtex, 11 figures

Scientific paper

10.1063/1.2188398

Recent neutron scattering experiments on aqueous salt solutions of amphiphilic t-butanol by Bowron and Finney [Phys. Rev. Lett. {\bf 89}, 215508 (2002); J. Chem. Phys. {\bf 118}, 8357 (2003)] suggest the formation of t-butanol pairs, bridged by a chloride ion via ${O}-{H}...{Cl}^-$ hydrogen-bonds, and leading to a reduced number of intermolecular hydrophobic butanol-butanol contacts. Here we present a joint experimental/theoretical study on the same system, using a combination of molecular dynamics simulations and nuclear magnetic relaxation measurements. Both theory and experiment clearly support the more intuitive scenario of an enhanced number of hydrophobic contacts in the presence of the salt, as it would be expected for purely hydrophobic solutes [J. Phys. Chem. B {\bf 107}, 612 (2003)]. Although our conclusions arrive at a structurally completely distinct scenario, the molecular dynamics simulation results are within the experimental errorbars of the Bowron and Finney work.

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