Zur Thermodynamik der Systeme Tetrachlormethan mit Toluol, Äthylbenzol, Chlorbenzol und Pyridin

Kind, R.; Kahnt, G.; Schmidt, Dieter; Schumann, J. Petra; Bittrich, H.‐J.

doi:10.1515/zpch-1968-23831

Cited by 14 publications

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“…Such calculated values for the 14 systems listed in Table 1 were compared both with the vapor pressures given by the spline fit of the raw P-x data and with the experimental values themselves. Thus the root mean-square deviation between computed pressures and those of the spline fit is given for the 14 systems in Table TABLE 2 (Guthrie et al, 1952) 187.10c 269.06d 3.23c 27.29 (Osborn & Douslin, 1968) 27.63 (Kind et al, 1968) 1 as ul, and similarly the deviation between computed and experimental pressures is given as uz. The average value of u1 for all 14 systems is 0.26 mm Hg, and the average value of u2 is 0.40 mm Hg.…”

Section: Discussionmentioning

confidence: 99%

Vapor‐liquid equilibrium: Part II. Correlations from P‐x data for 15 systems

1973

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SCOPEThe apparatus described by Gibbs and Van Ness (1972) has been used systematically to measure solution vapor pressures as a function of liquid composition at 3OoC for 15 binary systems in vapor-liquid equilibrium (VLE). Data reduction by the method described in the preceding paper for P-x data yields correlating equations for the excess Gibbs free energy and the activity coefficients, from which the P-x-y relationship at 3OoC may be calculated. The systems studied are CC&, CHCl3, and CH2C12, each with tetrahydrofuran and with furan; tetrahydrofuran with furan; CH2C12 with methyl acetate, with acetone, and with l,4-dioxane; CHC13 with 1,4-dioxane; pyridine with acetone, with CHC13, and with CH2C12; and n-pentanol with n-hexane. Heat-of-mixing data, which are available in the literature for most of the systems reported, allow extension of these results to other conditions. CONCLUSIONS A N D SIGNIFICANCEThe rapidity with which P-x data may be taken commends the use of such data as the basis for formulation of VLE relationships for binary systems. These are useful in themselves, and they serve also in predictive schemes for multicomponent systems, for which experimental determination is much more tedious.Routine methods of data reduction are available, as reviewed in the preceding paper, and the reliability of the method depends solely on the reliability of the P-x data.Gibbs and Van Ness (1972) demonstrated for the ethanoln-heptane system agreement between results obtained with the present apparatus and data from the literature based on measurements with an equilibrium still. The results presented here are for systems representing a wide range of behavior, from large positive to large negative deviations from ideality.The experimental apparatus used in this work is fully described by Gibbs and Van Ness ( 1972). Liquid solutions of known composition are prepared in a thermostated test cell by volumetric metering of degassed liquids from accurate piston-injectors. Direct measurement of pressure in the cell provides for the solution vapor pressure. The raw data' therefore consist of pairs of values for pressure and liquid mole fraction at constant temperature and cover the full composition range from x1 = 0 to x1 = 1.As indicated by the discussion of P-x data in the preceding paper, the raw data are fit by the least-squares spline-fit procedure of Klaus and Van Ness (1967), and this provides the input for the numerical procedure of Mixon et al. (1965) which yields the g = GE/RT versus x1 relationship in accord with Equation (9b) of the preceding paper. The resulting numerical values of g/xlx2 or of ln(yl/yz) are then fit with respect to x1 by an appro-

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Section: Discussionmentioning

confidence: 99%

Vapor‐liquid equilibrium: Part II. Correlations from P‐x data for 15 systems

1973

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Vapour‐liquid equilibria of the carbon tetrachloride‐toluene system

Wang

Boublikova

1970

J. Appl. Chem.

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Zur Zwischenmolekularen Wechselwirkung in binären Systemen Tetrachlormethan‐Aromaten

Kind

Bittrich

1970

J. Prakt. Chem.

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Es werden Beziehungen für die Separierung der freien Exzeßenthalpien von binären Systemen aus Tetrachlormethan mit Benzol und verschiedenen alkylsubstituierten Benzolen entsprechend den Formen der zwischenmolekularen Wechselwirkungen abgeleitet. Für die nichtspezifische Wechselwirkung wurde das Kontinuumsmodell von LINDER auf binäre Systeme ausgedehnt. Der Beitrag der Elektronendonator‐Akzeptor‐Wechselwirkung wurde mit einem Modell der idealen Mischung für die AB‐Bildung berechnet und die Gleichgewichtskonstanten aus der Beziehung zum Ionisationspotential mit Hilfe der experimentellen Werte von PRAUSNITZ u. a. für Benzol, Mesitylen und Hexamethylbenzol berechnet. Der aus der Störung der Flüssigkeitsstruktur der aromatischen Komponente resultierende Anteil wurde nach einem Modell der ideal assoziierten Lösung angesetzt, das Simultangleichgewicht tierativ gelöst und die als adjustierbare Parameter gewonnenen Gleichgewichtskonstanten als Funktion der Ionisierungsenergien diskutiert. Sie sind den von McGLASHAN auf anderem Weg ge wonnenen Konstanten proportional. Damit ist eine physikalisch sinnvolle Deutung der freien Exzeßenthalpie einer Gruppe von binären Systemen möglich.

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Zur Thermodynamik der Systeme Tetrachlormethan mit Toluol, Äthylbenzol, Chlorbenzol und Pyridin

Cited by 14 publications

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Vapor‐liquid equilibrium: Part II. Correlations from P‐x data for 15 systems

Vapor‐liquid equilibrium: Part II. Correlations from P‐x data for 15 systems

Vapour‐liquid equilibria of the carbon tetrachloride‐toluene system

Zur Zwischenmolekularen Wechselwirkung in binären Systemen Tetrachlormethan‐Aromaten

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