Thermodynamics of a charged hard sphere in a compressible dielectric fluid. A modification of the Born equation to include the compressibility of the solvent

Wood, Robert H.; Quint, Jacques R.; Grolier, J.-P.E.

doi:10.1021/j150625a047

Cited by 64 publications

(67 citation statements)

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“…An Augmented van der Vaals equation was used successfully to include the effects of attractive forces on clustering for a variety of systems (Johnston et al, 1982). Clustering was described for water about an ion in the critical region using a modified Born equation (Wood et al, 1981). At 17.7 MPa (P, = 0.803) and 327OC…”

Section: Effects Of Clustering On Rate Constantmentioning

confidence: 99%

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

1987

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The reaction rate constant was adjusted continuously over two orders of magnitude for the unimolecular decomposition of a-chlorobenzyl methyl ether using the supercritical fluid solvent 1 , l difluoroethane. Activation volumes were observed as low as -6,000 cm3/mol, which is about an order of magnitude more negative than those reported previously in the literature for a homogeneous reaction. Spectral shift (solvatochromic) data were measured for phenol blue in the same fluid in order to interpret the rate data. A method is presented to predict solvent effects on rate constants at supercritical fluid conditions.

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Section: Effects Of Clustering On Rate Constantmentioning

confidence: 99%

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

1987

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“…Above 200"C, this decrease becomes dramatic, largely because of changes in the electrostatic properties of water along the steam saturation line (32,33). The simple electrostatic effects tend to cancel when reactions are written symmetrically, so that the charge on each reactant species is equal to that on one of the product species, as in reaction [6].…”

Section: H2s Ionization Versus Temperaturementioning

confidence: 99%

Apparent molal heat capacities and volumes of aqueous hydrogen sulfide and sodium hydrogen sulfide near 25 °C: the temperature dependence of H₂S ionization

Barbero¹,

McCurdy²,

Tremaine³

1982

Can. J. Chem.

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. Can. J. Chem. 60, 1872Chem. 60, (1982.A flow microcalorimeter and vibrating tube densimeter were used to obtain apparent molal heat capacities and volumes of aqueous NaHS and NazS from 0.1 to 1.0 mol kg-' and of aqueous H2S from 0.03 to 0.08 mol kg-' at 10,25, and 40°C. Standard state heat capacities and volumes for H2S and HS-were obtained by extrapolation to infinite dilution. Combining these results with 2S°C enthalpy data yields an expression for the temperature dependence of the equilibrium constant for H2S neutralization at pressures near those of steam saturation, H2S + OH-= HS-+ H 2 0 , log K , b = 19.84 + 930.8lT -2.800 In T, with an estimated uncertainty of k0.47 at 300°C. The heat capacity data for bulk aqueous NazS suggest that the relative concentration of SZ-at these molalities is small. Les donntes de capacitt calorifique pour la masse aqueuse de Na2S suggkrent que la concentration relative de S2-est petite a ces molalitts.[ The e n t h a l~~ of the ionization reaction at 25°C is and hydrometallurgical procedures for treating (49 5, and has been wed in the van't HOff sulfide ores. Low temperature measurements have equation to extrapolate K1 to high temperatures been made by many workers using a variety of (1). The standard volume and heat capacity of techniques (1) and the values for K, near 2 5 0~ are ionization are required in such an extrapolation to well established. Experiments above 100°C are account for the effects of pressure and7 more difficult, largely because aqueous sulfide poisons important7 changes in the e n t h a l~~ of reaction with the platinum electrodes commonly used to deter-temperature7 respectively. As yet7 no accurate mine ionization constants in high temperature values for these properties have been reported. We water. Ellis and co-workers (2) obtained data for have now measured apparent molal heat capacities K l , up to 276°C using a spectrophotometric meth-and for NaHS and at od, but noted that the results might be in emor since peratures of 10°C7 25"C, and 40°C. he results ~i e l d their technique did not permit in situ p~ measure-both infinite dilution and excess partial molal heat capacities and volumes for these important species 'Visiting scientist at the Oil Sands Research Department, which can then be combined with existing low

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“…We use a completely compressible (CC) continuum electrostatic model, described elsewhere [4,32], to represent a charged solute/SCW system. From this model we can extract both the structureless equilibrium solvent density distribution around the solute, qrY and the equilibrium Gibbs free energy of solvation Dq CC 3.…”

Section: Methodsmentioning

confidence: 99%

“…The ®nal ®eld, i x Y where x denotes the IC, CC or PC() model, is given by the solution of Poisson's equation with self-consistent values for the ®eld-dependent local dielectric constant x i x rY within the constraints of model x. The free energy of charging the solute in the presence of a model x solvent is then written in terms of the ®nal ®eld i x as [3,4,32,35] …”

Section: Methodsmentioning

confidence: 99%

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A case against large cluster-induced nonequilibrium solvent effects in supercritical water

Luo

Tucker

1997

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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Using a partially compressible continuum solvation model, we have shown that solvent compression in just the ®rst two solvation shells (or thereabouts) is all that is required to gain the bulk of the compressioninduced enhancement to the solvation energy of ions in supercritical water. This result is found to hold even when the direct, equilibrium solvent-solute cluster involves well over a hundred solvent molecules. We argue that, for charge variation reactions in supercritical water, the observed short-range behavior of the compression-induced solvation free energy precludes the existence of any anomalously large nonequilibrium solvent eects which might be expected on the basis of the very large size of the equilibrium clusters.

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Thermodynamics of a charged hard sphere in a compressible dielectric fluid. A modification of the Born equation to include the compressibility of the solvent

Cited by 64 publications

References 0 publications

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

Apparent molal heat capacities and volumes of aqueous hydrogen sulfide and sodium hydrogen sulfide near 25 °C: the temperature dependence of H₂S ionization

A case against large cluster-induced nonequilibrium solvent effects in supercritical water

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Thermodynamics of a charged hard sphere in a compressible dielectric fluid. A modification of the Born equation to include the compressibility of the solvent

Cited by 64 publications

References 0 publications

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

Extreme solvent effects on reaction rate constants at supercritical fluid conditions

Apparent molal heat capacities and volumes of aqueous hydrogen sulfide and sodium hydrogen sulfide near 25 °C: the temperature dependence of H2S ionization

A case against large cluster-induced nonequilibrium solvent effects in supercritical water

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Product

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Apparent molal heat capacities and volumes of aqueous hydrogen sulfide and sodium hydrogen sulfide near 25 °C: the temperature dependence of H₂S ionization