scholarly journals Use of scaled-particle theory in the assessment of the Ph4As+/Ph4B− assumption for single ions

1979 ◽  
Vol 57 (1) ◽  
pp. 71-76 ◽  
Author(s):  
Michael H. Abraham ◽  
Asadollah Nasehzadeh
Keyword(s):  
Free Energy ◽  
Recent Work ◽  
Scaled Particle Theory ◽  
Cavity Formation ◽  
Energy Term ◽  
Free Energies ◽  
Particle Theory ◽  
Novel Method ◽  
Energy Of Interaction ◽  
Solvent Molecules

A novel method for the assessment of the Ph4As+/Ph4B− assumption for free energies of transfer of single ions has recently been suggested by Treiner, and used by him to deduce that the assumption is not valid for transfers between water, propylene carbonate, sulpholane, dimethylsulphoxide, N-methyl-2-pyrrolidone, and perhaps also dimethylformamide. The basis of the method is the estimation of the free energy of cavity formation by scaled-particle theory, together with the hypothesis that the free energy of interaction of Ph4As+ (or Ph4B−) with solvent molecules is the same in all solvents, ΔGt0(int) = 0. It is shown in the present paper that (a) whether or not the Ph4As+/Ph4B− assumption applies to transfer to a given solvent depends on which other solvent is taken as the reference solvent in Treiner's method, (b) the calculation of the cavity free energy term by scaled-particle theory and by the theory of Sinanoglu – Reisse – Moura Ramos (SRMR) yields values so different that the method cannot be considered reliable, (c) the calculation of cavity enthalpies and entropies for Ph4As+ or Ph4B− by scaled-particle theory yields results that are chemically not reasonable, (d) the hypothesis that ΔGt0(int) = 0 conflicts with SRMR theory, and (e) the conclusions reached by Treiner are not in accord with recent work that in general supports the Ph4As+/Ph4B− assumption for solvents that are rejected by Treiner.

Thermodynamics of transfer of Ph4C; scaled-particle theory and the Ph4As+/Ph4B− assumption for single ions

1979 ◽  
Vol 57 (15) ◽  
pp. 2004-2009 ◽  
Author(s):  
Michael H. Abraham ◽  
Asadollah Nasehzadeh
Keyword(s):  
Free Energy ◽  
Total Free Energy ◽  
Scaled Particle Theory ◽  
Free Energies ◽  
Particle Theory ◽  
Free Energy Of Transfer ◽  
Enthalpy And Entropy ◽  
Interaction Term ◽  
Energy Of Transfer ◽  
Entropy Of Transfer

Free energies of transfer of Ph4C from acetonitrile to 20 other solvents have been calculated from literature data. The contribution of the cavity term to the total free energy has been obtained from scaled-particle theory and Sinanoglu–Reisse–Moura Ramos theory. It is shown that there is little connection between the cavity term and the total free energy of transfer, and that there must be, in general, a large interaction term. If the latter is important for transfer of Ph4C, we argue that it must also be important for transfer of the ions Ph4As+ and Ph4B−. Previous suggestions that the interaction term is zero for transfer of these two ions are thus seen to be unreasonable. We also show, for six solvents, that the interaction term for Ph4C is very large in terms of enthalpy and entropy, and that scaled-particle theory seems not to apply to transfers of Ph4C between pure organic solvents.The free energy, enthalpy, and entropy of transfer of Ph4As+ = Ph4B− have been calculated by dividing the total transfer values into neutral and electrostatic contributions; reasonable agreement is obtained between calculated and observed values.

Heat capacities and volumes of some non-electrolytes in N,N-dimethylformamide at 298.15 K

1987 ◽  
Vol 65 (12) ◽  
pp. 2810-2814 ◽  
Author(s):  
Henryk Piekarski
Keyword(s):  
Ethylene Glycol ◽  
Heat Capacities ◽  
Scaled Particle Theory ◽  
Partial Molal Volume ◽  
Cavity Formation ◽  
Particle Theory ◽  
Molal Volume ◽  
Analogous Data ◽  
Other Substances ◽  
Apparent Molal Heat Capacities

Heat capacities and densities of dilute solutions of formamide, acetone, tetrahydrofuran, ethylene glycol, 2-methoxyethanol, and 2-ethoxyethanol in N,N-dimethylformamide were determined at 298.15 K. Apparent molal heat capacities and volumes for these solutes in DMF were calculated and compared with the analogous data for other substances in DMF solution as well as with the data concerning solutions in methanol and water. Heat capacities of cavity formation (ΔCcav) in DMF were calculated on the basis of the Scaled Particle Theory. ΔCcav appeared to be linearly correlated with the standard partial molal volume of corresponding solutes in DMF. Similar dependences were also found for aqueous and methanolic solutions of the non-electrolytes.

scholarly journals A Simple Free Energy for the Isotropic-Nematic Phase Transition of Rods

2016 ◽  
Vol 2016 ◽  
pp. 1-6 ◽  
Author(s):  
Remco Tuinier
Keyword(s):  
Free Energy ◽  
Nematic Phase ◽  
Analytical Form ◽  
Orientation Distribution ◽  
Scaled Particle Theory ◽  
Particle Theory ◽  
Aspect Ratios ◽  
Wide Range ◽  
Hard Rods ◽  
Simple Analytical Form

A free energy expression is proposed that describes the isotropic-nematic binodal concentrations of hard rods. A simple analytical form for this free energy was yet only available using a Gaussian trial function for the orientation distribution function (ODF), leading, however, to a significant deviation of the predicted binodals. The new free energy proposed here is based upon a rationalized correction to the orientational and packing entropies when using the Gaussian ODF. In combination with Parsons-Lee theory or scaled particle theory, it enables describing the isotropic-nematic phase coexistence concentrations of rods accurately using the simple Gaussian ODF for a wide range of aspect ratios.

Solubilities of Amino Acids in Dioxane + Water Mixtures and the Determination of Transfer Free Energies of Interaction of Amino Acid from Water to Aquo-Organic Mixtures

2000 ◽  
Vol 214 (3) ◽  
Author(s):  
K. Majumder ◽  
K. Mrs. Majumder ◽  
Sujit Chandra Lahiri
Keyword(s):  
Amino Acids ◽  
Hydrophobic Interactions ◽  
Scaled Particle Theory ◽  
Solvent Mixtures ◽  
Formaldehyde Solution ◽  
Free Energies ◽  
Particle Theory ◽  
Transfer Free Energy ◽  
Organic Mixtures

The solubilities of amino acids (Glycine, α-alanine, L-asparagine, L-methionine, L-proline, L-valine, L-leucine, L-phenylalanine, L-glutamine) in dioxane-water mixtures (0-100%) have been determined colorimetrically as well as pH metrically using acid-free formaldehyde solution. The solubility decreases enormously with increase in percentage of dioxane. The results have been interpreted in terms of specific solvation and hydrophobic effects.In order to comprehend the results better, the scaled particle theory has been applied to determine the transfer free energy changes for interaction from water to aquo-organic solvent mixtures and the results are qualitatively in agreement. An estimate of the hydrophobic interactions due to constituent groups in different aquo-organic mixtures has been attempted.

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