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• W2046323162 abstract "The excess heat capacity (CEp) has been measured for acetone + 2,2,4,4,6,8,8-heptamethylnonane (br-C16) (10 and 25°C), +n-C12 (15 and 25°C) and +n-C6 (25°C). CEp is large and positive but becomes negative at both extremes of the concentration range, i.e. it is W-shaped. It becomes rapidly more positive on loweringT, approaching phase separation at the UCST. br-C16 mixed with 2-butanone, 3-hexanone, 4-heptanone and 5-nonanone also give W-shapedCEp(x) curves although the negativeCEp appearing at very high ketone mole fraction (0.95) are extremely small, less than 0.05 J K−1 mol−1. As the length of the ketone molecule is increased, the W-shape becomes less pronounced and has disappeared for br-C16 + 4-decanone where CEp is negative throughout the composition range. The present systems, which show W-shapeCEp, and those in the literature, have large equimolarHE values, ⋍ 1000 J mol−1 or larger, and often are close to phase separation. It is suggested that the W-shape arises from twoCEp contributions. One is negative and of parabolic concentration dependence. The other, due to non-randomness and associated with extremely largeHE and GE values, is shown by the Guggenheim quasi-chemical theory to be positive, concave downwards in the middle of the composition range, but concave upwards at the extremes, i.e. it has the correct concentration dependence to give the W-shape. The excess volume has been measured for acetone + br-C16, +n-C12 and +n-C6. It is large and positive while dVE/dT, for systems near the UCST, is more positive than predicted by the Flory theory, i.e. its behavior is analogous to CEp. It is suggested that: (1) polar (but not H-bonded) systems where HE is very large, ⋍ 1000 J mol−1 or larger should exhibit the W-shapeCEp, becoming more pronounced with decrease of temperature, and (2) the curvature of HE/x1x2 againstx should be positive and large, increasing with decreasingT." @default.
• W2046323162 created "2016-06-24" @default.
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• W2046323162 date "1987-09-01" @default.
• W2046323162 modified "2023-09-25" @default.
• W2046323162 title "The w-shape concentration dependence of CEp and solution non-randomness: Ketones + normal and branched alkanes" @default.
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• W2046323162 doi "https://doi.org/10.1016/0378-3812(87)80015-8" @default.
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