This study is concerned with the association characteristics of solutions of alcohols in some non-polar solvents. The permittivities at 2 MHz and 25°C for solutions of the straight chain octanols in cyclohexane, carbon tetrachloride and benzene have been examined over the entire solute concentration range, with particular attention -1 being paid to the range below 0.1 molℓ⁻¹ By applying the Kirkwood- Fröhlich equation to these data, the apparent dipole moments of the alcohols as a function of concentration have been evaluated. These concentration dependencies have been correlated with infrared absorption results on the same systems to provide information on the sizes and configurations of the proposed hydrogen bonded multimers. It is concluded that, at very low solute concentrations, the alcohol molecules exist as monomers; but with increasing concentration, two types of hydrogen bonded multimers are formed, the first (at low concentrations) being of high dipole moment and the second (at higher concentrations) being of low dipole moment. At high concentrations, the molecules associate to form a three-dimensional network. Attempts have been made to determine equilibrium parameters for molecular models which are consistent with the qualitative understanding of the association behaviour. These parameters were obtained by applying least-squares, curve-fitting techniques to the low concentration permittivity data. A similar investigation has been conducted on solutions of 2,3,4-trimethyl-3-pentanol in the same solvents. The steric hindrance around the hydroxyl group of this alcohol modifies the association behaviour so that a three-dimensional network does not form at high solute concentrations. Proton magnetic resonance chemical shifts for the hydroxyl proton of this alcohol in carbon tetrachloride solutions have been measured. Attempts have also been made to determine equilibrium parameters which describe formation of the hydrogen bonded multimers. To extend this study to include solutes other than octanols, similar experiments have been conducted on solutions of t-butanol in hexadecane, a system which has recently been investigated by other workers using different experimental techniques. The association behaviour of this system is qualitatively similar to that of the straight-chain octanols. The combination of permittivity and infrared measurements, although proving extremely powerful in interpreting the association characteristics of dilute alcohol solutions, is less adequate at high solute concentrations. Attention was therefore directed towards dielectric relaxation and viscosity studies to investigate concentrated solutions. The relaxation times at 20°C of the low frequency dispersion have been measured for solutions of 1-propanol, 1-butanol, 1-hexanol, 1-octanol and 1-decanol in cyclohexane using time domain reflectometry techniques. Similar measurements have also been made on solutions of 1-butanol and 1-octanol in carbon tetrachloride and in benzene. The concentration dependence of the viscosities of certain of these systems has also been examined in an independent study. The ratio of the dielectric relaxation time to the viscosity, the "reduced relaxation time", is qualitatively similar for each system studied. This similarity leads to an explanation of the molecular process responsible for the low frequency dispersion in terms of the proximity of the hydroxyl groups in concentrated alcohol solutions and the fraction of the groups which are not involved in hydrogen bonding.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:rhodes/vital:4454 |
| Date | January 1975 |
| Creators | Campbell, Colin |
| Publisher | Rhodes University, Faculty of Science, Chemistry |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Doctoral, PhD |
| Format | 289 leaves, pdf |
| Rights | Campbell, Colin |
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