Publication | Open Access
Vapour Pressure Isotope Effects of Chloroform
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1983
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Organic GeochemistryEnvironmental ChemistryChemical ThermodynamicsEngineeringMolecular ThermodynamicsPhysicochemical AnalysisIsotope GeochemistryApplied PhysicsPhysical ChemistryCl Isotope EffectsExperimental ThermodynamicsThermodynamicsChemistryChcl 3Volatile ElementSpectra-structure CorrelationIsotope Effects
Abstract The vapour pressure difference between CHCl 3 and CDCl 3 is measured by differential capacitance manometry between -60 and +60 °C. The results can be expressed by the equation ln(p H /p D ) = 5.507 × 10 -3 -6.269/T. The vapour pressure of CHCl 3 between -98 and +62°C has also been determined. The experimental H/D vapour pressure isotope effect data together with the available literature values on the 12 C/ 13 C and 35 C1/ 37 Cl isotope effects are interpreted within the framework of the statistical mechanical theory of isotope effects in condensed systems. The results show that the anharmonicity constant of the CH stretching vibration decreases by about 4% on the vapour-liquid transition.