Nahordnung in Flüssigkeiten, V.NMR‐Verschiebungen, Verdampfungs‐Enthalpien und Zusatzfunktionen von Alkanen und Alkylchloriden in flüssigen Mischphasen

Ein in fruheren Arbeiten vorgestelltes Modell fur die Darstellung zwischenmolekularer Wechselwirkungen in organischen Flussigkeiten wird zur Beschreibung der Verdampfungsenthalpien und thermodynamischen Zusatzfunktionen von Alkanen und Alkylchloriden angewendet, und die Enthalpie-Inkremente fur die Wechselwirkungen zwischen den beteiligten funktionellen Gruppen werden bestimmt. Die aus NMR-Losungsmittelverschiebungen erhaltenen Parameter fur Wechselwirkungen mil dem H-Atom des Chloroforms stimmen mit den aus thermodynamischen Daten erhaltenen Werten uberein. Der Beitrag des freien Volumens zur Mischungsentropie wird in seiner Abhangigkeit von der Form und Grose der Molekule diskutiert, und das vorgestellte Kontaktpaar-Modell wird mit dem Gleichgewichtsmodell verglichen. The model developed to represent the molecular environment in organic liquids is used to describe heats of vapourization and excess functions of alkanes and alkylchlorides. The enthalpy increments of the interactions betweens functional groups have been determined. The values obtained from NMR solvent shifts for interactions with the chloroform proton are consistent with values obtained from thermodynamic data. The contribution of the free volume to the excess entropy is discussed as a function of size and shape of the molecules. Connections between the contact pair model and the equilibrium model are given.

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