Solvation effect on kinetic rate constant of reactions in supercritical solvents

Chialvo, Ariel A.; Cummings, Peter T.; Kalyuzhnyi, Yu. V.

doi:10.1002/aic.690440315

Cited by 42 publications

(26 citation statements)

References 47 publications

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“…͑14͒ provides an explicit macroscopic definition of the coefficients k ij ͑T , P͒, here we seek to identify the microscopic analogs to link them to the microstructural behavior of the reference system, i.e., the solvation behavior of the infinitely dilute system. For that purpose we invoke the general molecular-based solvation formalism for infinite dilute solutes in compressible solvents, 3,8,23 from which we have that…”

Section: Molecular-based Interpretation Of the Coefficients K Ijmentioning

confidence: 99%

“…16 In turn, this partition allowed us to split any ͑thermomechanical͒ partial molar property of an infinite dilute species in solution into its short-ranged ͑solvation͒ contribution caused by the rearrangement of the solvent around the species in solution ͑local solvent density perturbation͒ and its long-ranged ͑compressibility-driven͒ contribution linked to the propagation of the local density perturbation across the system. 3,5,6,11,23 The outstanding feature of this solvation formalism for infinite dilute solutes is that, by isolating the compressibility-driven contributions to the infinite dilution ͑thermomechanical͒ partial molar properties, i.e., partial molar volumes, enthalpies, and entropies at infinite dilution, the solvation process can be analyzed in terms of a finite pressure, solvent coordination, or volumetric perturbation whose molecular analogs are unambiguously defined. 24 Therefore, the above solvation formalism becomes a strong candidate as the infinite dilution reference to build the composition dependence for the Gibbs free energy of the actual system, in terms of truncated composition expansions and constrained by some essential thermodynamic requirements.…”

Section: Introductionmentioning

confidence: 99%

“…3 ͔ P,T = ͑k 22 x 2 + k23 R͒/ ͑1 − x 2 − R͒ ͑ F6͒and, after integration along R = x 3 it follows thatln 1 ͑P,T,x 2 ,x 3 ,R͒ = ln 1 o − ͓Rk 23 + k 22 ͑1 + R͔͒ln ͓͑1 + R − x 2 ͒/͑1 + R͔͒ − k 22 x 2 , ͑F7͒i.e.,ln 1 ͑P,T,x 2 ,x 3 ͒ = ln 1 o − ͓k 22 ͑1 + x 3 ͒ + k 23 x 3 ͔ln ͓͑1 + x 3 − x 2 ͒/͑1 + x 3 ͔͒ − k 22 x 2 . ͑F8͒…”

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confidence: 97%

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Solvation phenomena in dilute multicomponent solutions I. Formal results and molecular outlook

Chialvo

Simonson

et al. 2008

The Journal of Chemical Physics

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We derive second-order thermodynamically consistent truncated composition expansions for the species residual partial molar properties--including volume, enthalpy, entropy, and Gibbs free energy--of dilute ternary systems aimed at the molecular account of solvation phenomena in compressible media. Then, we provide explicit microscopic interpretation of the expansion coefficients in terms of direct and total correlation function integrals over the microstructure of the corresponding infinite dilution reference system, as well as their pressure and temperature derivatives, allowing for the direct prediction of the species partial molar properties from the knowledge of the effective intermolecular interactions. Finally, we apply these formal results (a) to derive consistent expressions for the corresponding properties of the binary system counterparts, (b) to illustrate how the formal expressions converge, at the zero density limit, to those for multicomponent mixtures of imperfect gases obeying the virial equation of state Z = 1 + BPkT, and (c) to discuss, and highlight with examples from the literature, the thermodynamic inconsistencies encountered in the currently available first-order truncated expansions, by pinpointing the mathematical origin and physical meaning of the inconsistencies that render the first-order truncated expansions invalid.

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Section: Molecular-based Interpretation Of the Coefficients K Ijmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 97%

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Solvation phenomena in dilute multicomponent solutions I. Formal results and molecular outlook

Chialvo

Simonson

et al. 2008

The Journal of Chemical Physics

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“…The Krichevskii function J reflects the variation of the pressure of the system when exchanging a solvent molecule (methanol) by one solute (ILs, [BMIM] [BF 4 ]) molecule at constant volume and temperature. In terms of the direct correlation function (DCF) c ij (r) between molecules of type i and j [62][63][64][78][79][80][81][82][83] the Krichevskii function J is defined as …”

Section: Structural Propertiesmentioning

confidence: 99%

High-pressure densities and derived volumetric properties (excess, apparent, and partial molar volumes) of binary mixtures of {methanol (1)+[BMIM][BF4] (2)}

Abdulagatov

Tekin

Safarov

et al. 2008

The Journal of Chemical Thermodynamics

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“…Therefore, reactions in SCFs can be much faster than reactions in liquids, which is especially important for reactions with mass transfer limitations [5]. Furthermore, negative partial molar volumes in supercritical systems can be exploited to adjust rate constants of various reactions [6,7]. These aspects in combination with the high mass transfer rates observed for SCFs means that these solvents offer some specific advantages for homogeneous catalysis.…”

Section: Introductionmentioning

confidence: 99%

Membrane reactor for homogeneous catalysis in supercritical carbon dioxide

Goetheer

Verkerk

Broeke

et al. 2003

Journal of Catalysis

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A membrane reactor is presented for homogeneous catalysis in supercritical carbon dioxide with in situ catalyst separation. This concept offers the advantages of benign high-density gases, i.e., the possibility of achieving a high concentration of gaseous reactants in the same phase as the substrates and catalyst as well as easy catalyst localization by means of a membrane. For the separation of the homogeneous catalyst from the products an inorganic microporous membrane is used. The concept is demonstrated for the hydrogenation of 1-butene using a fluorous derivative of Wilkinson's catalyst [RhCl{P-(C 6 H 4 -p-SiMe 2 CH 2 CH 2 C 8 F 17 ) 3 } 3 ]. The size of Wilkinson's catalyst, 2-4 nm, is clearly larger than the pore diameter, 0.5-0.8 nm, of the silica membrane. The membrane will, therefore, retain the catalyst, while the substrates and products diffuse through the membrane. Stable operation and continuous production of n-butane has been achieved at a temperature of 353 K and a pressure of 20 MPa. A turnover number of 1.2 × 10 5 has been obtained during 32 h of reaction. The retention of the catalyst was checked using UV-vis spectroscopy and ICP-AAS; no rhodium or phosphorous species were detected at the permeate side of the membrane.

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Solvation effect on kinetic rate constant of reactions in supercritical solvents

Cited by 42 publications

References 47 publications

Solvation phenomena in dilute multicomponent solutions I. Formal results and molecular outlook

Solvation phenomena in dilute multicomponent solutions I. Formal results and molecular outlook

High-pressure densities and derived volumetric properties (excess, apparent, and partial molar volumes) of binary mixtures of {methanol (1)+[BMIM][BF4] (2)}

Membrane reactor for homogeneous catalysis in supercritical carbon dioxide

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