Phase equilibria in very dilute mixtures of water and unsaturated chlorinated hydrocarbons and of water and benzene

Cooling, M.R.; Khalfaoui, B.; Newsham, D.M.T.

doi:10.1016/0378-3812(92)85153-y

Cited by 28 publications

(17 citation statements)

References 7 publications

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“…While for compounds having P 1 s (293.15 K) of the order of 10 kPa directly measured values known to better than 1% are typically available, for compounds whose P 1 s (293.15 K) are about 1 kPa or lower, the values had to be obtained by extrapolation, and thus they are much more inaccurate. As clearly seen in Figure 4, the accord of our measurements with a great majority of recent literature data is within Wright et al (1992); 2, Barr and Newsham (1987); 0, Bao et al (1993); O, Cooling et al (1992); 4, Li et al (1993); ], Hansen et al (1993). For 1,1,2-trichloroethane, data encountered essentially split into two values, 2.2 kPa and 2.4 kPa; preference was given here to the lower value, matching well results of our previous ebulliometric measurements at higher temperatures (Dohnal and Fenclová , 1985).…”

Section: Resultssupporting

confidence: 91%

“…Virial coefficients to account for vapor-phase nonideality were obtained from Hayden and O'Connell's correlation (Hayden and O'Connell, 1975) with parameters from Prausnitz et al (1980) and CDATA (1991). γ 1 ∞ ) 12 960 obtained by Cooling et al (1992) using GLC or γ 1 ∞ ) 13 400 derived from the recommended value of aqueous solubility (Horvath et al, 1985). The total correction for the second-order approximation effects amounted typically from 1 to 3%, and just in extreme cases (1,1-dichloroethane and 1,2-dichloroethylenes) extended to 5%.…”

Section: Resultsmentioning

confidence: 99%

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Determination of Air−Water Partitioning of Volatile Halogenated Hydrocarbons by the Inert Gas Stripping Method

Hovorka

Dohnal

1997

J. Chem. Eng. Data

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Air-water partitioning for 21 volatile chlorinated or brominated alkanes, alkenes, and aromatics was measured at 20°C by the inert gas stripping method. Results of the measurements are presented in the form of Henry's law constants (H 12 ), air-water partition coefficients (K aw ), and limiting activity coefficients (γ 1 ∞ ), accurate γ 1 ∞ values being obtained only if accurate pure solute vapor pressure data are available.The halocarbons studied in this work are hydrophobic and exhibit enhanced volatilities from their dilute aqueous solutions representing approximately ranges of γ 1 ∞ from 230 to 70 000 and H 12 from 2 to 70MPa. Correct performance of the stripping method for such systems requires special precautions. As confirmed by test measurements on benzene, chlorobenzene, 1,1,1-trichloroethane, and 1,1,2-trichloroethane, the complete equilibration in the stripping cell can be achieved under vigorous mixing of the cell, low stripping gas flow rates (approximately 10 cm 3 ‚min -1 ), and low relative elution rates (0.01 min -1 ). Choosing for each system a cell of a suitable volume made it possible to comply with the latter requirement. The results compare well with recent literature values obtained by various methods for some of the halocarbons. For two selected halocarbons (bromobenzene and 1,1-dichloroethane), detailed measurements of the temperature dependence of air-water partitioning were carried out in the range of (10-50)°C. These measurements corresponding to the range of H 12 from 5 to 72 MPa provide additional support for the validity of the method.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Determination of Air−Water Partitioning of Volatile Halogenated Hydrocarbons by the Inert Gas Stripping Method

Hovorka

Dohnal

1997

J. Chem. Eng. Data

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“…Limiting activity coefficient of water γ 1 ∞ in aromatic halogenates as a function of temperature T plotted in van’t Hoff coordinates: ■, α,α,α-trifluorotoluene; ●, chlorobenzene (this work); ○, and dashed line, chlorobenzene; ⊕, chlorobenzene; ▲, bromobenzene (this work); △ and dashed line, bromobenzene . Solid lines are fits of data by eq .…”

Section: Resultsmentioning

confidence: 99%

“…thus fitting the measured values well within the measurement reproducibility. The values of the adjustable parameters of eq 11 optimized by the least-squares method, along with the Figures 8 and 9 display for comparison also some literature data that are available just for phenetole, 9 chlorobenzene, 10,11 and bromobenzene. 10 The involved literature data originate from either single vapor−liquid equilibrium studies 9,11 or a regression of critically evaluated solubility values from multiple sources.…”

Section: Resultsmentioning

confidence: 99%

Dilute Vapor Absorption: A New Accurate Technique for Measurement of the Limiting Activity Coefficient of Water in Hydrophobic Solvents of Lower Volatility

Haidl

Dohnal

2017

J. Chem. Eng. Data

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An accurate experimental method for the determination of the limiting activity coefficient of water in hydrophobic solvents was described theoretically; the pertinent apparatus was built and its performance was duly verified. The method is based on continuously saturating the solvent by a gas stream of a constant and known humidity up to the attainment of the steady state and subsequent determination of the water content in the solvent by Karl Fischer titration. Using this new method, accurate values of the limiting activity coefficient of water were determined in eight selected solvents. The measurements were carried out at several temperatures and from these data the infinite dilution dissolution enthalpy and entropy of water in the solvents were evaluated. They both exhibit highly positive values reflecting the breakage of the hydrogen bonding network of water upon its dissolution in the solvents. Prediction of the water limiting activity coefficients was further attempted using the Modified UNIFAC method and found to fail dramatically, the calculated values being lower than the experimental ones by a factor ranging from 2 to 10. General lack of reliable limiting water activity coefficient data and their unreliable prediction indicate the significance of both the new method and the acquired data.

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“…Structural parameters for the relevant subgroups were obtained from the work of Hansen et al [1991] with water assigned as 1 × H 2 0 (group 7), cis ‐DCE assigned as 1 × HC=C (group 2) and 2 × Cl‐C=C (group 37), and PCE assigned as 1 × C=C (group 2) & 3 × Cl‐C=C (group 37). Interaction parameters between groups m and n are a m,n and a n,m , both defined in Kelvin, where: a m,m = a n,n = 0 (by definition); a 2,7 = 785.6, a 7,2 = −26.52 [ Cooling et al , 1992]; a 7,37 = 651.9, a 37,7 = 1100 [ Cooling et al , 1992]; and a 2,37 = 237.3 and a 37,2 = −3.167 [ Gmehling et al , 1982].…”

Section: Methodsmentioning

confidence: 99%

Analytical modeling of degradation product partitioning kinetics in source zones containing entrapped DNAPL

Ramsburg

Christ

Douglas

et al. 2011

Water Resources Research

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[1] Liquid-liquid equilibrium experiments indicate that there is a strong thermodynamic driving force for the reversible sequestration of cis-dichloroethene (DCE) within microbially active dense nonaqueous phase liquid (DNAPL) source zones containing chlorinated ethene solvents. Assessment of the importance of degradation product sequestration, however, requires accurate description of the mass transfer kinetics. Partitioning kinetics of cis-DCE were assessed in a series of transport experiments conducted in sandy columns containing uniformly entrapped tetrachloroethene (PCE)-nonaqueous phase liquids (NAPL). Effluent data from these experiments were simulated using an analytical solution adapted from the sorption literature. The solution permits interrogation of the relative importance of mass transfer resistance in the aqueous phase and NAPL. Column data and simulations suggest that the kinetic exchange of cis-DCE may be described with mass transfer correlations developed for the dissolution of pure component NAPLs. Diffusive transport within the entrapped ganglia was relatively fast, offering limited resistance to mass exchange. These results (1) establish the applicability of dissolution-based mass transfer correlations for modeling both absorption and dissolution of degradation products, (2) quantify the thermodynamic driving force for the partitioning of cis-DCE in PCE-NAPL by assessing the ternary phase behavior, and (3) guide incorporation and deployment of partitioning kinetics into multiphase compositional simulators when assessing or designing metabolic reductive dechlorination within DNAPL source zones. While focus is placed on examining degradation product partitioning in DNAPL source zones, results may also be useful when considering rate limitations in other liquid-liquid partitioning processes, such as partitioning tracer tests.

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Phase equilibria in very dilute mixtures of water and unsaturated chlorinated hydrocarbons and of water and benzene

Cited by 28 publications

References 7 publications

Determination of Air−Water Partitioning of Volatile Halogenated Hydrocarbons by the Inert Gas Stripping Method

Determination of Air−Water Partitioning of Volatile Halogenated Hydrocarbons by the Inert Gas Stripping Method

Dilute Vapor Absorption: A New Accurate Technique for Measurement of the Limiting Activity Coefficient of Water in Hydrophobic Solvents of Lower Volatility

Analytical modeling of degradation product partitioning kinetics in source zones containing entrapped DNAPL

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