ELUCIDATION OF LIQUID FORCE FIELDS IN METHYL FLUORIDE BY MEANS OF VAPOR PRESSURE ISOTOPE EFFECTS.
Item
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Title
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ELUCIDATION OF LIQUID FORCE FIELDS IN METHYL FLUORIDE BY MEANS OF VAPOR PRESSURE ISOTOPE EFFECTS.
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Identifier
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AAI8212214
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identifier
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8212214
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Creator
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SHULMAN, JAN EDWARD.
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Contributor
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Takanobu Ishida
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Date
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1982
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Physical
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Abstract
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The vapor pressure isotope effects (VPIE) of the three isotopic methyl fluorides: ('12)CH(,3),F, ('13)CH(,3)F, and ('12)CD(,3)F, were studied using differential manometry and a precision cryostat. Absolute pressures were measured using a spiral quartz gauge, and differential pressures were obtained by use of capacitance gauges. The gases were purified to better than 99.995% by preparative gas chromatography and a gas-solid adsorption system. Vapor pressures were measured between 132.52(DEGREES)K and 213.12(DEGREES)K which correspond to the pressures of 3.712 and 1887.1 torr.;Analysis of the vapor pressure data revealed an inverse isotope effect (ln(f(,c)/f(,g)) 0) for the ('12)CH(,3)F/('12)CD(,3)F isotopic pairs. A series of calculations using Wilson's FG-matrix method and a modified Schachtschneider-Snyder program resulted in a temperature-dependent internal-external interaction in the condensed phase: A strongly temperature-dependent internal-external interaction between the C-F stretching motion and a translational motion in the direction of its figure axis is necessary to explain the observed isotopic vapor pressures.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
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Program
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Chemistry
