Isothermal liquid-vapor equilibriums for system methanol-water

McGlashan, M. L.; Williamson, Arthur

doi:10.1021/je60069a019

Cited by 136 publications

(76 citation statements)

References 11 publications

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“…Williamson; (32) , Kurihara et al; (33) +, Griswold and Wong (34) at T = 373.137 K; , Bao et al (35) for each temperature. The differences in the p s measurements at each temperature are within ±0.5 kPa.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic properties of {xCH3OH +(1−x)H2O} withx= (1.0000 and 0.4993) in the temperature range from 320K to 420K at pressures up to 200MPa

Osada

Sato

Uematsu

1999

The Journal of Chemical Thermodynamics

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Section: Resultsmentioning

confidence: 99%

Thermodynamic properties of {xCH3OH +(1−x)H2O} withx= (1.0000 and 0.4993) in the temperature range from 320K to 420K at pressures up to 200MPa

Osada

Sato

Uematsu

1999

The Journal of Chemical Thermodynamics

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“…An exponential curve with respect to temperature for experimental compressibilities starting at 273 K was found to be the best fit for these data, and this was extrapolated to the lower temperatures. To verify the accuracy of the extrapolation, the literature compressibilities for hexane were plotted against literature density data, [71][72][73][74][75] which included densities at T below 273 K, and an exponential curve was found to fit best the relation between compressibility and density. As the density exhibits a linear dependence on temperature, a successful exponential fit for T vs would imply the same fit for T vs T. The values for T obtained from the exponential fit with respect to were then fitted to the corresponding temperatures and were indeed found to fit them exponentially.…”

Section: Discussionmentioning

confidence: 99%

Nitroxide spin exchange due to re-encounter collisions in a series of n-alkanes

Kurban

Perić

Bales

2008

The Journal of Chemical Physics

100

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Bimolecular collisions between perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-l-oxyl molecules in three alkanes have been studied by measuring the electron paramagnetic resonance ͑EPR͒ spectral changes induced by spin exchange. We define an "encounter" to be a first-time collision followed by a series of re-encounters prior to the diffusing pair's escaping each other's presence. The present work stems from a recent proposal ͓B. L. Bales et al., J. Phys. Chem. A 107, 9086 ͑2003͔͒ that an unexpected linear dependence of the spin-exchange-induced EPR line shifts on spin-exchange frequency can be explained by re-encounters of the same probe pair during one encounter. By employing nonlinear least-squares fitting, full use of the information available from the spectral changes allows us to study encounters and re-encounters separately. The encounter rate constants appear to be dominated by hydrodynamic forces, forming a common curve for hexane, decane, and hexadecane when plotted against T / , where is the shear viscosity. Unexpectedly, encounters are not dependent on the ratio = a / a s , where a and a s are the van der Waals radii of the nitroxide probe and the solvent, respectively. It is argued that the near coincidence of the resulting encounter rate constant with the hydrodynamic prediction is likely due to a near cancellation of terms in the general diffusion coefficient. Thus, the semblance of hydrodynamic behavior is coincidental rather than intrinsic. In contrast, the mean times between re-encounters do depend on the relative sizes of probe and solvent. For hexane at lower temperatures, the Stokes-Einstein equation apparently describes re-encounters well; however, at higher temperatures and for decane and hexadecane, departures from the hydrodynamic prediction become larger as becomes smaller. This is in qualitative agreement with the theory of microscopic diffusion of Hynes et al. ͓J. Chem. Phys. 70, 1456 ͑1979͔͒. These departures are well correlated with the free volume available in the solvent; thus, the mean times between re-encounters form a common curve when plotted versus the free volume. Because free volume is manifested macroscopically by the isothermal compressibility, it is expected and observed that the re-encounter rate also forms a common curve across all three solvents when plotted with respect to compressibility. The existence of a common curve for alkanes raises the prospect of using EPR to determine the compressibility of substances such as fossil fuels and biological membranes.

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“…46 Due to the overlap in methanol and water liquid phase peaks the methanol/water ratio in the droplet cannot be directly determined from the O1s spectrum. Instead, this ratio is determined by the following method.…”

Section: Proof Of Principle Experimentsmentioning

confidence: 99%

A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces

Starr

Wong

Worsnop

et al. 2008

Phys. Chem. Chem. Phys.

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We describe a combined ambient pressure photoelectron spectroscopy/droplet train apparatus for investigating the nature and heterogeneous chemistry of liquid/vapor interfaces. In this instrument a liquid droplet train with typical droplet diameters from 50…150 µm is produced by a vibrating orifice aerosol generator (VOAG). The droplets are irradiated by soft X-rays (100…1500 eV) in front of the entrance aperture of a differentially pumped electrostatic lens system that transfers the emitted electrons into a conventional hemispherical electron analyzer.The photoemission experiments are performed at background pressures of up to several Torr, which allows the study of environmentally important liquid/vapor interfaces, in particular aqueous solutions, under equilibrium conditions. The exposure time of the droplet surface to the background gases prior to the XPS measurement can be varied, which will allow future kinetic

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Isothermal liquid-vapor equilibriums for system methanol-water

Cited by 136 publications

References 11 publications

Thermodynamic properties of {xCH3OH +(1−x)H2O} withx= (1.0000 and 0.4993) in the temperature range from 320K to 420K at pressures up to 200MPa

Thermodynamic properties of {xCH3OH +(1−x)H2O} withx= (1.0000 and 0.4993) in the temperature range from 320K to 420K at pressures up to 200MPa

Nitroxide spin exchange due to re-encounter collisions in a series of n-alkanes

A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces

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