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Mincer, Adam Mieczyslaw Alexander (1958) A study of the solubility of hydrogen halides in organic compounds containing oxygen. Doctoral thesis, Northern Polytechnic.
Association of hydrogen chloride with organic compounds containing oxygen has been studied by determination of the solubility of the former in alcohols, ethers, carbonates and esters containing phosphorus, silicon and boron. The solubility was also measured in some inert solvents for comparison with those containing oxygen. In some cases observations were extended to low temperatures, where remarkably high values were obtained. For work at room temperatures the simple weight increase method was employed, while the chloride content of solutions at low temperatures was found by Volhard's method. It has been confirmed that in these systems the degree of association between hydrogen chloride and the solvent is controlled by the electron density on the oxygen atom, i.e. by the basic strength of the solvent. Thus electron repelling groups in the solvent molecule, such as methyl, will increase the solubility, while electron attractors such as chlorine will reduce it. The effect of the inorganic atom follows the same pattern; the basic character of phosphorus increases the solubility but boron lowers it by back-coordination from the oxygen. Hydrogen bromide has been found to be rather more reactive than expected, but a few solubility curves have been obtained indicating that the same principles are operating.
A linear relationship between the logarithm of the absolute temperature and the sole fraction of solute has been found to hold for some compounds over a wide range of temperature, but not for the silanes, tri-n-butyl phosphate and n-hexyl chloride.
A start has been made on the measurement of vapour pressures of hydrogen chloride from its solutions in alcohols and silanes by a simple static method. From the results the heats of solution in n-butyl alcohol and tetra-4-methylpentyl-2-oxysilane have been calculated over a small range of concentration and temperature.
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