Solubility of gases in liquids. 13. High-precision determination of Henry's constants for methane and ethane in liquid water at 275 to 328 K

Rettich, Timothy R.; Handa, Y. P.; Battino, Rubin; Wilhelm, Emmerich

doi:10.1021/j150622a006

Cited by 232 publications

(159 citation statements)

References 20 publications

Supporting

Mentioning

145

Contrasting

Order By: Relevance

“…The thin lines were obtained as numerical derivatives of MIT-model fits whereas the symbols represent finite differences of the µ ex -data given in Table IV. We would like to point out the the experimental data shown here belong to the number density scale and are therefore smaller than the values given in the paper of Rettich et al [64], corresponding to the mole fraction scale. The experimental data shown here were obtained also as a numerical derivative of the experimental excess chemical potentials with respect to the temperature.…”

Section: B Hydrophobic Hydrationcontrasting

confidence: 69%

“…In the experimental literature [63,64,65,66], however, the properties are often discussed on the mole fraction scale with the solvation free energy being…”

Section: B Infinite Dilution Propertiesmentioning

confidence: 99%

“…[81]. The closed circles are according to the experimental data of Rettich et al [64]. The employed water densities are according to Wagner and Pruß [71].…”

Section: B Hydrophobic Hydrationmentioning

confidence: 99%

“…The The experimental data of c P,ex according to the solubility data of Methane of Rettich et al [64] was obtained to be 234 J K −1 mol −1 at 300 K, when transforming their data on the number density scale. This value has also been reported by Widom et al [47].…”

Section: B Hydrophobic Hydrationmentioning

confidence: 99%

See 3 more Smart Citations

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Paschek

2004

The Journal of Chemical Physics

274

326

View full text Add to dashboard Cite

We examine five different popular rigid water models (SPC, SPCE, TIP3P, TIP4P and TIP5P) using molecular dynamics simulations in order to investigate the hydrophobic hydration and interaction of apolar Lennard-Jones solutes as a function of temperature in the range between 275 K and 375 K along the 0.1 MPa isobar. For all investigated models and state points we calculate the excess chemical potential for the noble gases and Methane employing the Widom particle insertion technique. All water models exhibit too small hydration entropies, but show a clear hierarchy. TIP3P shows poorest agreement with experiment whereas TIP5P is closest to the experimental data at lower temperatures and SPCE is closest at higher temperatures. As a first approximation, this behaviour can be rationalised as a temperature-shift with respect to the solvation behaviour found in real water. A rescaling procedure inspired by information theory model of Hummer et al. (Chem.Phys. 258, 349-370 (2000)) suggests that the different solubility curves for the different models and real water can be largely explained on the basis of the different density curves at constant pressure. In addition, the models that give a good representation of the water structure at ambient conditions (TIP5P, SPCE and TIP4P) show considerably better agreement with the experimental data than the ones which exhibit less structured O-O correlation functions (SPC and TIP3P). In the second part of the paper we calculate the hydrophobic interaction between Xenon particles directly from a series of 60 ns simulation runs. We find that the temperature dependence of the association is to a large extent related to the strength of the solvation entropy. Nevertheless, differences between the models seem to require a more detailed molecular picture. The TIP5P model shows by far the strongest temperature dependence. The suggested density-rescaling is also applied to the chemical potential in the Xenon-Xenon contact-pair configuration, indicating the presence of a temperature where the hydrophobic interaction turns into purely repulsive. The predicted association for Xenon in real water suggest the presence a strong variation with temperature, comparable to the behaviour found for TIP5P water. Comparing different water models and experimental data we conclude that a proper description of density effects is an important requirement for a water model to account correctly for the correct description of the hydrophobic effects. A water model exhibiting a density maximum at the correct temperature is desirable.

show abstract

Section: B Hydrophobic Hydrationcontrasting

confidence: 69%

“…In the experimental literature [63,64,65,66], however, the properties are often discussed on the mole fraction scale with the solvation free energy being…”

Section: B Infinite Dilution Propertiesmentioning

confidence: 99%

“…[81]. The closed circles are according to the experimental data of Rettich et al [64]. The employed water densities are according to Wagner and Pruß [71].…”

Section: B Hydrophobic Hydrationmentioning

confidence: 99%

Section: B Hydrophobic Hydrationmentioning

confidence: 99%

See 2 more Smart Citations

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Paschek

2004

The Journal of Chemical Physics

274

326

View full text Add to dashboard Cite

show abstract

“…In addition, the contribution of the solvation heat capacity has been recognized recently [20,21,22,23,24,25,26,27]. In general, the dissolution of hydrophobic particles is accompanied with an increase of the associated heat capacity [28,29,30]. As a consequence, the dissolution of a hydrophobic particle is found to be increasingly enthalpically stabilized with decreasing temperature [27].…”

Section: Introductionmentioning

confidence: 99%

Low-temperature and high-pressure induced swelling of a hydrophobic polymer-chain in aqueous solution

Paschek

Nonn

Geiger

2005

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We report molecular dynamics simulations of a hydrophobic polymer-chain in aqueous solution between 260 K and 420 K at pressures of 1 bar, 3000 bar, and 4500 bar. The simulations reveal a hydrophobically collapsed state at low pressures and high temperatures. At 3000 bar and about 260 K and at 4500 bar and about 260 K, however, a transition to a swelled state is observed. The transition is driven by a smaller volume and a remarkably strong lower enthalpy of the swelled state, indicating a steep positive slope of the corresponding transition line. The swelling is stabilized almost completely by the energetically favorable state of water in the polymers hydrophobic first hydration shell at low temperatures. Although surprising, this finding is consistent with the observation of a positive heat capacity of hydrophobic solvation. Moreover, the slope and location of the observed swelling transition for the collapsed hydrophobic chain coincides remarkably well with the cold denaturation transition of proteins.

show abstract

Numerical investigation of methane and formation fluid leakage along the casing of a decommissioned shale gas well

Nowamooz

Lemieux

Molson

et al. 2015

Water Resources Research

View full text Add to dashboard Cite

Methane and brine leakage rates and associated time scales along the cemented casing of a hypothetical decommissioned shale gas well have been assessed with a multiphase flow and multicomponent numerical model. The conceptual model used for the simulations assumes that the target shale formation is 200 m thick, overlain by a 750 m thick caprock, which is in turn overlain by a 50 m thick surficial sand aquifer, the 1000 m geological sequence being intersected by a fully penetrating borehole. This succession of geological units is representative of the region targeted for shale gas exploration in the St. Lawrence Lowlands (Qu ebec, Canada). The simulations aimed at assessing the impact of well casing cementation quality on methane and brine leakage at the base of a surficial aquifer. The leakage of fluids can subsequently lead to the contamination of groundwater resources and/or, in the case of methane migration to ground surface, to an increase in greenhouse gas emissions. The minimum reported surface casing vent flow (measured at ground level) for shale gas wells in Quebec (0.01 m 3 /d) is used as a reference to evaluate the impact of well casing cementation quality on methane and brine migration. The simulations suggest that an adequately cemented borehole (with a casing annulus permeability k c 1 mD) can prevent methane and brine leakage over a time scale of up to 100 years. However, a poorly cemented borehole (k c ! 10 mD) could yield methane leakage rates at the base of an aquifer ranging from 0.04 m 3 /d to more than 100 m 3 /d, depending on the permeability of the target shale gas formation after abandonment and on the quantity of mobile gas in the formation. These values are compatible with surface casing vent flows reported for shale gas wells in the St. Lawrence Lowlands (Quebec, Canada). The simulated travel time of methane from the target shale formation to the surficial aquifer is between a few months and 30 years, depending on cementation quality and hydrodynamic properties of the casing annulus. Simulated longterm brine leakage rates after 100 years for poorly cemented boreholes are on the order of 10 25 m 3 /d (10 mL/d) to 10 23 m 3 /d (1 L/d). Based on scoping calculations with a well-mixed aquifer model, these rates are unlikely to have a major impact on groundwater quality in a confined aquifer since they would only increase the chloride concentration in a pristine aquifer to 1 mg/L, which is significantly below the commonly recommended aesthetic objective of 250 mg/L for chloride.

show abstract

Solubility of gases in liquids. 13. High-precision determination of Henry's constants for methane and ethane in liquid water at 275 to 328 K

Cited by 232 publications

References 20 publications

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Low-temperature and high-pressure induced swelling of a hydrophobic polymer-chain in aqueous solution

Numerical investigation of methane and formation fluid leakage along the casing of a decommissioned shale gas well

Contact Info

Product

Resources

About