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UBC Theses and Dissertations

Optical study of the critical behaviour of pure fluids and binary mixtures Närger, Ulrike


Optical techniques were used to study the critical behaviour of the pure fluids CHF₃, CCIF₃ and Xe, and binary mixtures He-Xe and nicotine + water. We find that for all these substances, the order parameter is described by a power law in the reduced temperature t = (Tc - T)/Tc with a leading exponent β = 0.327 ± 0.002. Also, we determine the first correction to scaling exponent to be Δ = 0.43 ± 0.02 for the pure fluids and Δ = 0.50 ± 0.02 for the He-Xe system. The coexistence curve diameter in CHF₃ and CCIF₃ exhibits a deviation from rectilinear diameter, in agreement with a modern theory which interprets this behaviour as resulting from three-body effects. In contrast, no such deviation is observed in Xe where, according to that theory, it should be more pronounced than in other substances. In the polar fluid CHF₃, the order parameter, isothermal compressibility and the chemical potential along the critical isotherm were simultaneously measured in the same experiment in an effort to ensure self-consistency of the results. From the data, two amplitude ratios which are predicted to be universal are determined: Γ+⃘ /Γ-⃘= 4.8 ± 0.6 and D⃘Γ+⃘B⃘δ-₁ = 1.66 ± 0.14. In the binary liquid system nicotine + water, the diffusivity was measured both by light scattering and by interferometry. The results agree qualitatively, but differ by a factor of ≈ 2. From the light scattering data, the critical exponent of the viscosity is found to be zη = 0.044 ± 0.008. The interferometric experiments on Xe and He-Xe furnish a direct way to maesure the effects of wetting: From the data, the exponent of the surface tension is found to be n = 1.24 ± 0.06. The similarity of the order parameter and compressibility in Xe and a He-Xe mixture containing 5% He indicate that the phase transition in this He-Xe mixture is of the liquid-gas type rather than the binary liquid type.

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