THE SOLUBILITY OF GASES IN LIQUIDS<sup>1</sup>

Pierotti, Robert A.

doi:10.1021/j100803a024

Cited by 393 publications

(186 citation statements)

References 3 publications

Supporting

Mentioning

185

Contrasting

Order By: Relevance

“…For the cavitation term, we employed the method suggested by Pierotti. 24 More details on the calculation of these nonelectrostatic contributions are given in ref 12. For geometry optimization in solution, we used the analytical energy gradients available in the GCOSMO method.…”

Section: Methodsmentioning

confidence: 99%

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Stefanovich¹,

Boldyrev²,

Truong³

et al. 1998

J. Phys. Chem. B

View full text Add to dashboard Cite

Solvation effects on the geometries and electronic and thermodynamic stabilities of a series of small multiply charged polyatomic anions, which are not electronically and thermodynamically stable in the isolated state, have been studied using the generalized conductor-like screening model of solvation. It was found that small doubly charged anions such as O 2-, CO 3 2-, and SO 4 2-are electronically very stable in water with estimated vertical electron detachment energies as high as 6-7 eV. Even the triply charged (BO 4-are not stable toward loss of one F -anion, but the doubly and triply charged anions were found to be thermodynamically stable in water. Surprisingly, the aqueous electron detachment energies are not very strongly dependent on the charge of the anion, and the thermodynamic stabilities of singly, doubly, and triply charged MgF (2+n) n-anions are very similar (as a result of which one can expect the coexistence of various charged anions in solutions and in melts).

show abstract

Section: Methodsmentioning

confidence: 99%

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Stefanovich¹,

Boldyrev²,

Truong³

et al. 1998

J. Phys. Chem. B

View full text Add to dashboard Cite

show abstract

“…Dispersion-repulsion contributions to the solvation free energy were calculated using Floris and Tomasi's method, 54 in conjunction with OPLS force field parameters. 45 Cavitation energy was calculated using a method suggested by Pierotti 55 and Huron and Claverie. 56 Geometry optimizations using analytical energy gradients 29 were performed using the restricted Hartree-Fock (RHF) approximation.…”

Section: Methodsmentioning

confidence: 99%

Theoretical Studies of Solid−Liquid Interfaces: Molecular Interactions at the MgO(001)−Water Interface

1998

View full text Add to dashboard Cite

We have applied a novel theoretical and computational method called CECILIA (combined embedded cluster at the interface with liquid approach) to study adsorption of molecular water on the MgO(001) surface and its interface with water. The MgO(001) surface is modeled by a quantum cluster embedded in a field of pseudopotentials and point charges. The effects of an aqueous environment are included by placing a dielectric continuum in the region above the embedded cluster. Calculated geometry, energetics, and electronic spectra for adsorbed water are in good agreement with available experimental and theoretical data. In particular, many features of the interfacial structure and dynamics (McCarthy, M. I.; Schenter, G. K.; Scamehorn, C. A.; Nicholas, J. B. J. Phys. Chem. 1996, 100, 16989) are well-reproduced in our calculations. These results demonstrate the suitability of the CECILIA model for studying chemical processes at solid-liquid interfaces.

show abstract

“…The values of AG:(H+) and AG~(OH-),,, and also AGy(0H-) are given in Table 6. Moreover, as per discussion and formulations given in the preceeding papers (1-3) we have also computed AG:, , , and A G :~~~~ for these ions using the scaled particle theory (SPT) (20) and the widely used simple Born equation (26), respectively. These values, when subtracted from AGP(i), values yielded AcP,,,,~~,(~) and are given in Table 6.…”

Section: A~ctoionization and Transfer Free Energiesmentioning

confidence: 99%

“…Similarly, although there are large number of studies (14-17) on salting-out and salting-in phenomena of various solutes, including benzoic acid (HBz) and p-nitroaniline (pNA), in various salt solutions and various theories have been proposed to explain the phenomena, so far very few attempts (1 1, 18, 19 have been made to study the temperature effects and the related structural changes of the solvent. However, in a series of papers 9) have recently demonstrated that ASP and particularly of p N A and HBz obtained by subtracting the cavity effect AS&,, (20) from AS: values, throw important suggestions on the structuredness of the aquoorganic solvents, as they are free from the "electrostatic" effect which confuses the structural content of AS: data of HX type of electrolytes (1-3, 8 , 9).…”

Section: Introductionmentioning

confidence: 99%

Ion–ion–solvent interactions in aqueous ionic cosolvent systems. IV. Transfer energetics of water, p-nitroaniline, and benzoic acid from emf/solubility measurements at different temperatures in aqueous sodium nitrate solvent system

Rudra¹,

Talukdar²,

Kundu³

1988

Can. J. Chem.

View full text Add to dashboard Cite

(K,) of aqueous mixtures of I , 2 , and 4 m sodium nitrate used as an ionic cosolvent system have been determined from emf measurements of the cell: Pt, H2 (g, 1 atm) / KOH (m I ) KC1 (tn2), solvent / AgC1-Ag at five equidistant temperatures ranging from 15535°C. The standard free energies (AGO) and entropies (AS') of autoionisation of the solvents were then evaluated from these data. Relative free energies (AGO) and entropies (AS') of autoionization of the solvents when coupled with the previously determined transfer free energies [AG:(H+)] and entropies [AS:(H++)] of H' yielded AGY(OH),,, [= AGY(0H-) -AG:(H,O)], As:(OH-), and ASF(H20). Values of AG:(Ht.) and A G Y ( 0 H ) obtained after correcting for AG;(H~o), as well as A@,,,,in,(H+) and AGfl,i,,(O~-) obtained after correcting the "cavity effect" and Born-type electrostatic effect suggests that while the "basicity" of the aqueous NaN03 solutions decreases, the "acidity" more or less increases with NaN03 concentration. The observed A$,,,.i,,(OH-)-and A~l r , i , , (~,~) -c o m p o s i t i o n profiles were also examined in the light of Kundu et al.'s four-step transfer process and the involved order-disorder phenomena, respectively, as proposed earlier.Standard free energies (A@) and entropies (AS:) of transfer of p-nitroaniline (pNA) and benzoic acid (HBz) for the solvent system have also been determined from solubility measurements at different temperatures. The observed AGY-and AGf,,,in,-composition profiles appear to reflect the salting-out effect of the salt and the AS,' -and A$,,,,in,-composition profiles confirm the applicability of either of these quantities rather than A$.,r,i,,(HX), as a better structural probe both for aquo-ionic and aquo-organic solvents. [Traduit par la revue] Introduction In our previous papers (1-3) we have reported the thermodynamics of HX, X = C1 (I), Br, and I (3), and also the transfer energetics of some electrolytes and the related "ion-ionsolvent" interactions (2) in aqueous solutions of 1, 2, and 4 rn NaN03 taking each composition as an individual solvent and taking the infinitely dilute solution of solutes in each solvent as the standard state as in aquo-organic solvent systems.Since autoionization constants of water in aquo-organic solvents reflect acidity and basicity of the solvents, it would be of particular interest to evaluate the same for this solvent system as well. Moreover, it is now increasingly recognised that thermodynamics of autoionization of water and the transfer energetics of various non-electrolytes including water, provide useful information regarding the three dimensional (3D) "structuredness" of the solvent (4-13). The basis of structural

show abstract

THE SOLUBILITY OF GASES IN LIQUIDS¹

Cited by 393 publications

References 3 publications

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Theoretical Studies of Solid−Liquid Interfaces: Molecular Interactions at the MgO(001)−Water Interface

Ion–ion–solvent interactions in aqueous ionic cosolvent systems. IV. Transfer energetics of water, p-nitroaniline, and benzoic acid from emf/solubility measurements at different temperatures in aqueous sodium nitrate solvent system

Contact Info

Product

Resources

About

THE SOLUBILITY OF GASES IN LIQUIDS1

Cited by 393 publications

References 3 publications

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Theoretical Studies of Solid−Liquid Interfaces: Molecular Interactions at the MgO(001)−Water Interface

Ion–ion–solvent interactions in aqueous ionic cosolvent systems. IV. Transfer energetics of water, p-nitroaniline, and benzoic acid from emf/solubility measurements at different temperatures in aqueous sodium nitrate solvent system

Contact Info

Product

Resources

About

THE SOLUBILITY OF GASES IN LIQUIDS¹