Examination of the inert solvent assumption in the ideal associated solution model. Enthalpy of chloroform–triethylamine complex dissociation

1989 ◽  
Vol 67 (7) ◽  
pp. 1153-1157 ◽  
Author(s):  
John F. Smith ◽  
Loren G. Hepler
Keyword(s):  
Complex Formation ◽  
Binary Mixtures ◽  
Excellent Agreement ◽  
Binary Systems ◽  
Solution Model ◽  
Ideal Associated Solution Model ◽  
Inert Solvent ◽  
Associated Solution Model ◽  
Associated Solution ◽  
The Ideal

We have made new measurements of the enthalpies of adding cyclohexane to mixtures of chloroform + triethylamine + cyclohexane at 25 °C. The results of these measurements have been analysed in terms of the ideal associated solution model to obtain ΔHθ for the dissociation of the chloroform-triethylamine complex. Our value of ΔHθ is in excellent agreement with a published value that was obtained from results of measurements on binary mixtures of chloroform + triethylamine. This agreement indicates that it is usefully accurate to treat mixtures of chloroform + triethylamine + cyclohexane as ideal mixtures of chloroform, triethylamine, cyclohexane, and chloroform-triethylamine complex. This result has important implications for studies of associated systems dissolved in "inert" solvents and helps to provide a connection between complex formation in dilute solutions and in binary systems (A + B, no solvent). Keywords: ideal associated solution model, chloroform, triethylamine, inert solvent, hydrogen bonded complex.

Thermodynamics of complex formation in chloroform + 1,4-dioxane

1989 ◽  
Vol 67 (7) ◽  
pp. 1225-1229 ◽  
Author(s):  
L. Barta ◽  
Z. S. Kooner ◽  
L. G. Hepler ◽  
G. Roux-Desgranges ◽  
J.-P. E. Grolier
Keyword(s):  
Complex Formation ◽  
Solution Model ◽  
Vapor Pressures ◽  
Chemical Interactions ◽  
Ideal Solution Behavior ◽  
Ideal Associated Solution Model ◽  
Thermodynamics Of Complex Formation ◽  
Associated Solution Model ◽  
Associated Solution ◽  
The Ideal

We have made new measurements of excess heat capacities and excess volumes of mixtures of chloroform and dioxane. In combination with published vapor pressures and excess enthalpies the results have been analyzed using the ideal associated solution model to yield K, ΔHθ, ΔCpθ, and ΔVθ for the formation of AB and A2B complexes. It is demonstrated that the ideal associated solution model is consistent with all of the available thermodynamic data for this system, indicating that chemical interactions of the two components can account for nearly all of the deviations from ideal solution behavior. The results of our thermodynamic analysis are discussed in relation to the results of similar analyses of other systems in which there are strong chemical interactions of chloroform with electron-donor molecules. Keywords: complex formation, hydrogen bonding, ideal associated solution model, chloroform, 1,4-dioxane.

Viscosities of mixtures of chloroform + triethylamine: analysis in terms of three components (A, B, and AB)

1989 ◽  
Vol 67 (3) ◽  
pp. 446-448 ◽  
Author(s):  
Richard P. Schutte ◽  
Terry C. Liu ◽  
Loren H. Hepler
Keyword(s):  
Complex Formation ◽  
Type A ◽  
Adjustable Parameter ◽  
Solution Model ◽  
New Combination ◽  
Model Based ◽  
Ideal Associated Solution Model ◽  
Associated Solution Model ◽  
Associated Solution ◽  
The Ideal

Viscosities and densities of highly non-ideal mixtures of chloroform (A) + triethylamine (B) have been measured at 25 °C. It has been shown that the Grunberg equation (one adjustable parameter) can account for these viscosities over the whole range of compositions. It has also been shown that a new combination of the ideal associated solution model, based on consideration of an equilibrium of the type A + B = AB, with an ideal viscosity equation (also one adjustable parameter) accounts more accurately for all of the viscosities. This latter treatment also has the advantage of offering a clear pictorial model of the mixtures. Keywords: viscosity of solution, complex formation in solution, chloroform + triethylamine, triethylamine + chloroform.

Thermal and volumetric properties of chloroform+benzene mixtures and the ideal associated solution model of complex formation

1987 ◽  
Vol 16 (9) ◽  
pp. 745-752 ◽  
Author(s):  
Jean-Pierre E. Grolier ◽  
Genevieve Roux-Desgranges ◽  
Zorawar S. Kooner ◽  
John F. Smith ◽  
Loren G. Hepler
Keyword(s):  
Complex Formation ◽  
Solution Model ◽  
Volumetric Properties ◽  
Ideal Associated Solution Model ◽  
Associated Solution Model ◽  
Associated Solution ◽  
The Ideal
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