No abstract

No abstract

The permittivities at 2 MHz and 25°for 1-octanol in carbon tetrachloride, benzene, and cyclohexane solutions have been measured over the entire alcohol concentration range, with particular attention being paid to the range below 0.1 M. By use of the Kirkwood-Frohlich equation the apparent dipole moment of the alcohol as a function of concentration has been evaluated; using this concentration dependence and infrared absorption results, the natures of the proposed associated species are considered. Equilibrium constants have been determined for a monomer-dimer-trimer equilibrium model of the alcohol self-association at low concentrations; the association follows a general pattern: monomer-small, high dipole moment polymer-low dipole moment cyclic polymer-high dipole moment polymers.

Availability of Henry's law constants of water in these alcohols would permit evaluation of log 8( 20) and hence log M78(H30+). It appears that H30+ at low water content (<0.5 M) is being further solvated by hydrogen bonding with alcohols while acetonitrile is a very poor hydrogen bond donor and acceptor as compared to the alcohols. In fact, the species H409+ is stable in acetonitrile.34

The OH and O D stretching bands of HDO in aqueous solutions containing the ions C10,-and BF4-are split into two components. The high-frequency component, A, does not shift with temperature. It is IntroductionExperimental The OH and OD stretching vibrations of H D 0 3 in aqueous solutions of electrolytes generally give rise to broad, single-peaked bands which resemble the bands of HDO in pure water (14). Hartman (2) has shown that for aqueous solutions of perchlorate salts, however, the bands are split; a new high-frequency component appears near 3575 cm-' for the OH stretching vibration of HDO. K~c k i and coworkers (5,6) have shown that the corresponding OD stretching band of HDO appears between 2618 and 2634 cm-' for various perchlorate salts.In this paper we are presenting data on the concentration and temperature dependence of the OD stretching bands of HDO in aqueous solutions of NaClO, and Mg(ClO,),. We also show that for aqueous solutions of the tetrafluoroborate ion, high-frequency components of the HDO stretching vibrations are observed and are similar to those of the perchlorate solutions. Further, the OH stretching band for solutions of NaC10, and LiCIO, in methanol is similarly split. Our findings, together with the results of our recent study of crystalline hydrates of perchlorate salts (7) are discussed in connection with the effect of ions on the spectrum and structure of water.