Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents: Part 4 - The selection of extra thermodynamic assumptions

Marcus, Yizhak

doi:10.1351/pac198658121721

Cited by 76 publications

(37 citation statements)

References 5 publications

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“…The ordinate of the intersection point between each line gives an approximate value for the absolute solvation free energy of the proton, so in all, 6 individual determinations can be made from the data shown in Figure 1 (The 4 straight lines give 6 unique intersection points between different values of n.) To determine the best value of the absolute solvation free energy of the proton, we used the same method of statistical analysis as in our earlier work. 56 For this, the average intersection ordinate of the ith straight line with all others (Y i ) is given by (27) where (28) In the above equation, y ij is the ordinate of the intersection point between the ith and jth straight line, and mi i and b i are the slope and intercept, respectively, of the ith straight line. We take the best value for the absolute solvation free energy of the proton to equal the unweighted average of the four Y i values determined using eqs 27 and 28.…”

Section: Methanolmentioning

confidence: 99%

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

2006

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The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents.

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Section: Methanolmentioning

confidence: 99%

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

2006

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“…Marcus has shown (ref. 6) that the least objectionble extrathermodynamic assumption for the splitting of the values of of electrolytes into the contributions from individual ions is the rererence electrolyte method. The implementation of this method that has been tested and applied most extensively is the TATB one, which states that…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of ion hydration and its interpretation in terms of a common model

Marcus¹

1987

Pure and Applied Chemistry

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-The relationship between the conventional standard molar thermodynamic quantities of hydration of an ion and the corresponding quantities of solvation, that are due entirely to its interactions with its aqueous environment, is presented. The TATB assumption, i.e., that quantities pertaining to the tetraphenylarsonium cation equal those pertaining to the tetraphenylborate anion, is applied to the standard enthalpy, entropy, and Gibbs energy of hydration of ions, and to the standard partial molar heat capacity and volume of aqueous ions. A model of the hydrated ion, consisting of a layer of completely immobilized water molecules surrounded by a dielectric continuum affected by the field of the ion and water the structure of which is modified, is presented. The thickness of the first layer and the number of water molecules in it is proportional to the radius of the ion. The model is shown to be compatible with all these thermodynamic quantities.

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“…In addition, there have been valuable compilations of transfer of ions from water to organic solvents and mixed aqueous-organic solvents, by Marcus et al [44][45][46][47]. Experiments on the Gibbs free energies of transfer of ions from water to another solvent yield only values for electrically neutral combinations of ions, for example G o t (Na + + Cl − ).…”

Section: The Data To Be Usedmentioning

confidence: 99%

Descriptors for ions and ion-pairs for use in linear free energy relationships

Abraham

Acree

2016

Journal of Chromatography A

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Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents: Part 4 - The selection of extra thermodynamic assumptions

Abstract: Abstract

Cited by 76 publications

References 5 publications

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

Thermodynamics of ion hydration and its interpretation in terms of a common model

Descriptors for ions and ion-pairs for use in linear free energy relationships

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