NDLI: Complex formation and self-association in ternary mixtures. Apparent heat capacities for alcohol–methyl acetate–hydrocarbon and acetone–chloroform

Content Provider	Royal Society of Chemistry (RSC)
Author	Costas, Miguel Yao, Zutao Patterson, Donald
Copyright Year	1989
Abstract	Apparent molar heat capacities, ϕc, have been measured for hexan-1-ol and 2-methylcyclohexanol at 25 °C in their binary mixtures with methyl acetate (MA) and the following ternary mixtures: hexan-1-ol–(p wt % of MA–n-dodecane) where p= 2, 4.3, 10.2 and 30 and 2-methylcyclohexanol–(p wt % of MA–n-decane) where p= 1.5, 5 and 50. The measurements were made from extreme dilution up to 10 wt % of alcohol. The ternaries acetone–(p wt % of chloroform–cyclohexane) where p= 4.5 and 7.4 are also reported. Plots of ϕc against alcohol concentration show that the high maximum obtained for the binary alcohol–hydrocarbon mixture (OH–I) is progressively decreased for the ternary mixtures as the concentration of MA increases until, for the binary alcohol–MA mixture (OH–MA) the ϕc curve has been flattened. This behaviour is explained quantitatively by the Treszczanowicz–Kehiaian (TK) model for associated mixtures extended to include the possibility of complex formation between the alcohol and the proton-acceptor, MA. In a MA–hydrocarbon environment, ϕc drops owing to the partial destruction of hydrogen bonds between alcohol molecules and the corresponding formation of a hydrogen-bonded complex between the alcohol and MA. At low alcohol concentrations, ΔCp of mixing is negative for the OH–I binary, turning positive when the hydrocarbon is replaced by a mixture of hydrocarbon with an increasing amount of MA. Further increase in MA concentrations decreases ΔCp until for the binary OH–MA it is again negative. These changes are explained by the TK model in terms of the different amounts of self-associated and complex species in solution. The TK model has been applied to ϕc data for the mixture acetone–chloroform–cyclohexane, where only complex formation is present in solution, and found to be qualitatively successful.
Starting Page	2211
Ending Page	2227
Page Count	17
File Format	PDF
ISSN	03009599
Volume Number	85
Issue Number	8
Journal	Journal of the Chemical Society, Faraday Transactions 1
DOI	10.1039/F19898502211
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Hydrocarbon Molar mass Methyl acetate Acetone Hydrogen bond
Content Type	Text
Resource Type	Article
Subject	Chemistry

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