The heat of mixing of nonelectrolytic liquids is important in predicting the type of molecular interactions which exist in solutions of nonelectrolyted. The problem was to construct a calorimeter in which these heats of mixing could be measured accurately. Once constructed, the calorimeter was used to measure the heats of mixing of some binary and a ternary solutions. The systems chosen for study were the three liquid pairs formed between benzane, carbon tetrachloride, and cyclohexane, and the ternary mixture of the three. The results of the experimentation are summarized by the following equations. (1) H_12^M = X_1x_2 [103.2 + 13.1(x_1 - x_2) - 13.3(x_1 - x_2)^2] (2) H_23^M = x_2x_3 [729.6 + 102.4(x_2 - x_3)^2] (3) H_13^M = x_1x_3 [160.8 + 18.9(x_1 - x_3) - 20.2(x_1 - x_3)^2] (4) H_123^M = H_12^M + H_23^M + H_13^M + x_1x_2x_3 [128 + 161(x_1 - x_3) - 1636(x_1 - x_3)^2] where H^M stands for heat of mixing and x for mole fraction. Here, (1) is carbon tetrachloride, (2) is benzene, and (3) is cyclohexane. The value of the heat of mixing as calculated from the equation has the dimensions of caloried per mole. The measurements were all made at 25.0°C. The plots of heat of mixing against mole fraction for the three binaries are approximately symmetrical with respect to the line x + 0.500. The plot for the ternary mixture is symmetrical with respect to the line x_3 = 0.44. Furthermore, the heats of mixing of the ternary can be predicted from the binaries to within 5%.

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Lower critical solubility temperatures (LCST) have been measured for polyethylene (PE), polypropylene, ethylene-propylene copolymers, polybutene-1, polypentene-1 and poly 4-methylpentene-1 (P4MP1) in twenty-five isomeric alkanes. The LCST for PE are much lower than for branched polyolefins, especially in branched alkanes. The results are not predicted by the Prigogine-Flory-Patterson theory but are understood in terms of correlations of molecular orientations in the PE melt. / Fusion thermodynamics of P4MP1 confirm the existence of ordered conformations in the melt. The thermoreversible gelation of P4MP1 solutions depends on solvent and thermal history. It is studied by calorimetry, viscosimetry and wide angle X-ray diffraction. The gel crosslinks are presumably of a fringed-micellar nature and their formation is tentatively associated with the existence of helical conformations of P4MP1 in solution. The latter is also responsible for the obtaining of four different crystalline structures of P4MP1 from solutions and gels. Preliminary measurements of dynamic mechanical properties of P4MP1 gels are reported.

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viii, 160 leaves : ill., tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1978

viii, 160 leaves : ill., tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1978

Thesis (Ph.D.)-- University of Adelaide, Dept of Physical and Inorganic Chemistry, 1978.