Thermodynamics

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By Ascher H. Shapiro

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The most conveniently operated version of this type is described by Williamson and Their apparatus is shown in Figure 17. Known masses of two liquids are injected into the vessels A and B and are confined over mercury, the two vessels being separated by a thread of mercury in S. The mercury levels are adjusted to near R, and Rz in the precision-bore capillary. The amounts of the two liquids are determined by weighing from a hypodermic syringe. Mercury is withdrawn into the bulb Y resulting in the transfer of liquid from A to B.

M. Izatt, P. J. Watts, and R. M. Hart, Rev. Sci. , 1973, 44, 481. E. Kauer, D. Kirchner, D. Haupt, and H. J. Bittrich, Z . phys. Chem. (Leiptig), 1972, 250, 153. 36 Chemical Thermodynamics restored to that of the unmixed liquid. The molar excess enthalpy and the mole fraction x of component B are given by HE = PKfi + fi), x = Mfl + fa), (42) where fi and fs are the molar flow rates of the two components. Few measurements have been made with flow calorimeters. ls Their apparatus is shown in Figure 15.

J. L. Gustin and H. Renon, J. Chem. and Eng. Data, 1973,18, 164. S . R. Goodwin and D. M. T. Newsham, J. Chem. Thermodynamics, 1971,3, 325. llDhave described an interesting calorimeter. By reducing the time taken to reach a steady state in a flow calorimeter to less than 1 min and by continuously varying the flow rates of the two liquids they managed to obtain the complete excess enthalpy curve in less than 1 h. lZ0have described a continuous method which requires two runs to cover the composition range.

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