Sato, Takaaki and Buchner, Richard (2003) The cooperative dynamics of the H-bond system in 2-propanol/water mixtures: Steric hindrance effects of nonpolar head group. JOURNAL OF CHEMICAL PHYSICS, 119 (20). pp. 10789-10800. ISSN 0021-9606, 1089-7690
Full text not available from this repository.Abstract
We have determined the complex dielectric spectra of 2-propanol/water mixtures employing time domain reflectometry for the entire mixing range in 0.1<&LE;ν/GHz&LE;25 at 20&DEG;C, 25&DEG;C, and 30&DEG;C. At the specific concentrations, a frequency range was expanded up to 89 GHz with the help of waveguide interferometry. The excess activation free energy, &UDelta;G(E), enthalpy, &UDelta;H-E, and entropy, &UDelta;S-E, and their partial molar quantities, &UDelta;G(i)(E), DeltaH(i)(E), and DeltaS(i)(E) [i=2-propanol (2PA) and water (W)] were derived from the relaxation time of the cooperative process, tau(1). In the water-rich region, DeltaH(E) and DeltaS(E) exhibit conspicuous behavior with large positive values, which suggests an increase of the "time averaged'' number and the strength of H-bonds. tau(1) becomes considerably larger for 2-propanol/water than that for 1-propanol/water, resulting in similar to10% larger maxima of DeltaH and DeltaS. This indicates that the steric hindrance caused by the nonpolar group is more efficient for the branched isopropyl unit than that for the linear n-propyl moiety in preventing "disturbing fifth neighbor water molecules'' from acting as new H-bond partners for a hydroxyl group of alcohols. The two pertinent maxima in DeltaH(2PA)(E) and DeltaS(2PA)(E) at X(molar fraction of 2-propanol) similar to0.03 and similar to0.07 support the view that around Xsimilar to0.05, water molecules are pushed out of the first coordination shell of the nonpolar group into the bulk due to solute-solute association, commonly called hydrophobic interaction. In Xgreater than or equal to0.15, DeltaH(2PA)(E) and DeltaS(2PA)(E) become nearly zero, suggesting the generation of zigzag H-bonded alcohol chains similar to the pure alcohol. The analysis of the effective correlation factor, g(eff), revealed a strong structural perturbation effect of water in 0.5less than or equal toXless than or equal to1.0. (C) 2003 American Institute of Physics.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DIELECTRIC-RELAXATION SPECTROSCOPY; LOCAL ENERGY FLUCTUATIONS; PARTIAL MOLAR ENTHALPIES; ETHANOL-WATER MIXTURES; GLASS-FORMING LIQUIDS; TEMPERATURE-DEPENDENCE; MOLECULAR-DYNAMICS; TERTIARY BUTANOL; HYDROPHOBIC HYDRATION; COMPLEX PERMITTIVITY; |
| Subjects: | 500 Science > 530 Physics 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > PD Dr. Richard Buchner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 27 Jul 2021 11:04 |
| Last Modified: | 27 Jul 2021 11:04 |
| URI: | https://pred.uni-regensburg.de/id/eprint/38399 |
Actions (login required)
 |
View Item |
