Excess volumes and enthalpies as chiral discriminants in liquids / Zadjia Atik (1982) 

Public ISBD Titre : Excess volumes and enthalpies as chiral discriminants in liquids Type de document : texte imprimé Auteurs : Zadjia Atik, Auteur ; M. L. McGlashan, Directeur de thèse Editeur : University of London Année de publication : 1982 Importance : 160 f. Présentation : ill. Format : 30 cm Note générale : Thèse de Doctorat : Génie Chimique : Angleterre, University of London : 1982 Bibliogr. f. 161 - 167 . - Annexe [15] f Langues : Anglais (eng) Mots-clés : Chiral discrimination Method dilatometric Method calorimetric Smoothing equation Index. décimale : D004182 Résumé : Chiral discrimination in liquids has been studied using dilatometric and calorimetric methods. Continuous dilution dilatometry has been used to determine chiral discrimination by measuring the excess molar volumes Vᴱm of mixtures of the (+) and (-) enantiomers of limonene, fenchone, and α-methylbenzylamine at temperatures close to 3000 K and pressures close to 100 kPa. The experimental results have been fitted to a smoothing equation, where x is the mole fraction of (-) enantiomer. The smoothing equation contains only even powers of (1 - 2x), aquivalent to assuming that the effect of optical impurities on Vᴱm is negligible. Small but definite chiral discrimination has been revealed in Vᴱm, where the corresponding values of Vᴱm are all very small and negative. Continuous dilution calorimetry has been used to determine chiral discrimination by measuring the excess molar enthalpies Hᴱm of mixtures of the (+) and (-) enantiomers of fenchone and α-methylbenzylamine at temperatures close to 313 K and pressures close to 100 kPa. The experimental results have been fitted to a smoothing equation. The smoothing equation has been allowed to contain odd powers of (1 - 2x), when these are statistically significant, so as to take account of a possible effect of optical impurities on Hᴱm. Chiral discrimination has also been revealed in Hᴱm. For mixtures of fenchones Hᴱm is very small and negative, whereas for mixtures of α-methylbenzylamines Hᴱm though very small is positive. The magnitudes and signs of such chiral discriminations form a stimulating challenge to theoreticians. Excess volumes and enthalpies as chiral discriminants in liquids [texte imprimé] / Zadjia Atik, Auteur ; M. L. McGlashan, Directeur de thèse . - University of London, 1982 . - 160 f. : ill. ; 30 cm. Thèse de Doctorat : Génie Chimique : Angleterre, University of London : 1982 Bibliogr. f. 161 - 167 . - Annexe [15] f Langues : Anglais (eng) Mots-clés : Chiral discrimination Method dilatometric Method calorimetric Smoothing equation Index. décimale : D004182 Résumé : Chiral discrimination in liquids has been studied using dilatometric and calorimetric methods. Continuous dilution dilatometry has been used to determine chiral discrimination by measuring the excess molar volumes Vᴱm of mixtures of the (+) and (-) enantiomers of limonene, fenchone, and α-methylbenzylamine at temperatures close to 3000 K and pressures close to 100 kPa. The experimental results have been fitted to a smoothing equation, where x is the mole fraction of (-) enantiomer. The smoothing equation contains only even powers of (1 - 2x), aquivalent to assuming that the effect of optical impurities on Vᴱm is negligible. Small but definite chiral discrimination has been revealed in Vᴱm, where the corresponding values of Vᴱm are all very small and negative. Continuous dilution calorimetry has been used to determine chiral discrimination by measuring the excess molar enthalpies Hᴱm of mixtures of the (+) and (-) enantiomers of fenchone and α-methylbenzylamine at temperatures close to 313 K and pressures close to 100 kPa. The experimental results have been fitted to a smoothing equation. The smoothing equation has been allowed to contain odd powers of (1 - 2x), when these are statistically significant, so as to take account of a possible effect of optical impurities on Hᴱm. Chiral discrimination has also been revealed in Hᴱm. For mixtures of fenchones Hᴱm is very small and negative, whereas for mixtures of α-methylbenzylamines Hᴱm though very small is positive. The magnitudes and signs of such chiral discriminations form a stimulating challenge to theoreticians.

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