Solvent Density Inhomogeneities in Supercritical Fluids

Tucker, Susan C.

doi:10.1021/cr9700437

Cited by 408 publications

(446 citation statements)

References 157 publications

Supporting

Mentioning

413

Contrasting

Unclassified

Order By: Relevance

“…The results of our calculations are presented in Fig. 3a as a function of xenon number density ρ Xe and clearly show an increase in the xenon induced shift near the critical point, similar in behavior and magnitude to that observed for P − (ρ P ) in Ar [11,12] and Kr [13] and for UV-vis absorption bands [32].…”

Section: Resultssupporting

confidence: 73%

Energy of the quasi-free electron in xenon

Shi¹,

Li²,

Evans³

et al. 2006

Chemical Physics Letters

View full text Add to dashboard Cite

Field ionization of trimethylamine and of N,N-dimethylaniline doped into xenon is presented as a function of xenon number density up to the density of the triple point liquid, both at noncritical temperatures and along the critical isotherm. These data exhibit a decrease in the xenon induced shift of the dopant ionization energy near the xenon critical point. The energy of the quasi-free electron, arising from dopant field ionization, in xenon is calculated within a local Wigner-Seitz model to within ±0.3% of experiment at noncritical temperatures and for the critical isotherm.

show abstract

Section: Resultssupporting

confidence: 73%

Energy of the quasi-free electron in xenon

Shi¹,

Li²,

Evans³

et al. 2006

Chemical Physics Letters

View full text Add to dashboard Cite

show abstract

“…Supercritical fluids are applied as solvents in food-and pharmaceutical processing [3,4] and as propellants [5,6]. Nonetheless, our understanding of these thermodynamic states is still limited: it has become clear that the notion of the supercritical state-space as a featureless domain has to be revised: Experiments show that in extension to the subcritical coexistence line (CL), there exists a supercritical crossover line across which fluid properties change continuously from a liquid-like to a gas-like state over a small temperature interval [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Similarity law for Widom lines and coexistence lines

2017

View full text Add to dashboard Cite

show abstract

“…29,30 Several excellent recent reviews have been written on these spectroscopic results. 22,31 Finally, X-ray and neutron scattering experiments done on supercritical fluids reveal the presence of large correlation lengths and long-range density fluctuations in the near-critical fluid. 32,33 One of the fundamental questions involves the role of attractive solute-solvent interactions in SCFs.…”

Section: Introductionmentioning

confidence: 99%

“…Strong solutesolvent attraction may give rise to enhanced local solvent density (solvent clusters) around a solute, particularly near the critical point. 22,31,34,35 It has been suggested that the formation of clusters can account for anomalous experimental observations of solute properties in SCFs. 22,31 However, in connection with the vibrational relaxation experiments, 8,36 a theoretical approach was used that was based on the changing solvent properties to account for the density dependence of T 1 , and attractive solutesolvent interactions were not part of the description of the solute/ solvent spatial distribution.…”

Section: Introductionmentioning

confidence: 99%

Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory

et al. 2000

View full text Add to dashboard Cite

Vibrational lifetime and spectral shift data for the asymmetric CO stretching mode of W(CO) 6 in supercritical ethane, carbon dioxide, and fluoroform as a function of density at two temperatures are presented, and the lifetime (T 1 ) measurements are compared to theory. The data and theory are refinements of previous work. Measurements at zero density allow the contribution from solute-solvent interactions to be separated from strictly intramolecular contributions to T 1 . The results in the polyatomic SCFs are compared to data in Ar. The density functional/thermodynamic theory 1 has been extended to include contributions at large wavevector (k). Very good, quantitative agreement between theory and data taken in ethane and fluoroform is achieved, but the agreement for data taken in carbon dioxide, while reasonable, is not as good. The theory uses a variety of input information on the SCF properties obtained from the fluids' equations of state and other tabulated thermodynamic data. The solute-solvent spatial distribution is described in terms of hard spheres. The theory is able to reproduce the data without solute-solvent attractive interactions or clustering in the calculation of the spatial distribution.

show abstract

Solvent Density Inhomogeneities in Supercritical Fluids

Cited by 408 publications

References 157 publications

Energy of the quasi-free electron in xenon

Energy of the quasi-free electron in xenon

Similarity law for Widom lines and coexistence lines

Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory

Contact Info

Product

Resources

About