Proton solvation in the lower aliphatic alcohols with emphasis on isopropyl alcohol and tert-butyl alcohol

Lisi, R. De; Goffredi, M.; Liveri, Vincenzo Turco

doi:10.1021/j100440a018

Cited by 17 publications

(15 citation statements)

References 3 publications

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“…The Setchenov constant is correlated to the standard free energy of transfer of alcohol from water to the copolymer aqueous phase (w → aq) as , To calculate the standard free energy of transfer ( ) of alcohol from the aqueous to the micellar phases, the K value was converted into the partition constant ( K C ), which in the molarity scale can be expressed as Note that for the classical surfactants studied 30 the ( m C − cmc) V M term can be neglected; this is not the case here since the V M value of L64 is 1 order of magnitude larger than that of the classical surfactants. So, the K C value taken in the following is that calculated at a given m C corresponding to the average value of m C in the range of copolymer concentration used in the minimizing procedure.…”

Section: Resultsmentioning

confidence: 99%

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K

Lisi

Milioto

1999

Langmuir

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Density measurements of poly(ethylene oxide)13−poly(propylene oxide)30−poly(ethylene oxide)13 (L64)−water and alcohol−L64−water systems were carried out at 293 and 301 K. The alcohols studied are propanol to pentanol and 2,2,2-trifluoroethanol (F3EtOH) to 2,2,3,3,4,4,4-heptafluorobutanol (F7BuOH). From the experimental data of the water−L64 binary system as functions of L64 concentration (m C), the partial molar volumes of L64 in the standard state and in the aqueous and micellar phases were calculated. At both temperatures L64 micelle is formed by a core of pure polypropylene oxide units and a hydrated shell of poly(ethylene oxide) units. In the case of the ternary systems, the apparent molar volumes of alcohol (V Φ ,R), at a fixed concentration, as functions of m C were determined. At 293 K, only the premicellar region was studied because the viscosity of the solutions in the micellar region did not permit us to obtain reliable density values. For hydrogenated alcohols as well as for F3EtOH, V Φ ,R as functions of m C are concave curves while for F7BuOH the curve is convex. At 301 K, V Φ ,R of hydrogenated alcohols slightly depends on m C up to the cmc beyond which it increases monotonically with the concentration. The trends of V Φ ,R vs m C for the fluorinated alcohols are peculiar since at ≈0.07 mol kg-1 (micellar region) they show anomalies which are more pronounced the more hydrophobic the alcohol is. The latter were ascribed to structural changes of the aggregates. On the basis of an equation previously reported, from the V Φ ,R data as functions of m C, the partial molar volumes of alcohol in the aqueous and the micellar phases and the distribution constant of alcohol between the two pseudophases were derived.

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Section: Resultsmentioning

confidence: 99%

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K

Lisi

Milioto

1999

Langmuir

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“…Much less studied was the thermodynamics of additive solubilization in micellar solutions as functions of temperature and pressure. In recent years, water + surfactant + solute ternary systems have been intensively studied by means of different techniques at 25 °C and atmospheric pressure. − As a result, the structure of the aggregate and the thermodynamic properties of solutes in aqueous and micellar phases are well-known. It was observed that they depend on the nature of both the surfactant and the additive.…”

Section: Introductionmentioning

confidence: 99%

Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solute in Micellar Solutions

1996

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Density measurements of pentanol (PentOH)-dodecyltrimethylammonium bromide (DTAB)-water mixtures as functions of both alcohol and surfactant (m S ) concentrations were carried out at 0.1 MPa from 45 to 75°C and at 19 MPa from 25 to 130°C. The standard (infinite dilution) partial molar volumes and expansibilities of DTAB in water and the corresponding properties in the micellar phase were calculated from the experimental data. As far as PentOH in DTAB micellar solutions is concerned, with the exception of the standard partial molar volume (V°R) data at 130°C and 19 MPa, all the V°R Vs m S trends are monotonic curves with m S . The data of V°R as a function of m S were treated by means of an equation previously used for data obtained at ambient conditions. So it was possible to evaluate simultaneously the distribution constant (K) of PentOH between the aqueous and micellar phases and the standard partial molar volume of alcohol in the aqueous (V°R ,f ) and the micellar (V°R ,m ) phases. The standard free energy of transfer (∆G°t) of PentOH from the aqueous to the micellar phases was calculated from K values. By using experimental literature data for the present system at 25°C, ∆G°t values as functions of temperature and pressure were calculated. The very good agreement between the simulated and experimental values indicates that the model used also holds at higher temperatures. Equations correlating the standard free energy, enthalpy, and entropy of transfer to temperatures up to 130°C and pressures up to 19 MPa were proposed.

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“…We consider next the dependence of the excess volume properties of the watermethanol-l,4-dioxane mixtures analysed here on the water concentration. The density values used in the calculations were evaluated from eqn (1) and (2) only in the range of low water composition, in which the filled equations reproduce all the experimental data to within the experimental precision.…”

Section: Resultsmentioning

confidence: 99%

Effect of 1,4-dioxane on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures at 25 °C

Goffredi¹

1987

J. Chem. Soc., Faraday Trans. 1

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Proton solvation in the lower aliphatic alcohols with emphasis on isopropyl alcohol and tert-butyl alcohol

Cited by 17 publications

References 3 publications

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K

Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solute in Micellar Solutions

Effect of 1,4-dioxane on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures at 25 °C

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Proton solvation in the lower aliphatic alcohols with emphasis on isopropyl alcohol and tert-butyl alcohol

Cited by 17 publications

References 3 publications

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)13−Poly(propylene oxide)30− Poly(ethylene oxide)13 Triblock Copolymer at 293 and 301 K

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)13−Poly(propylene oxide)30− Poly(ethylene oxide)13 Triblock Copolymer at 293 and 301 K

Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solute in Micellar Solutions

Effect of 1,4-dioxane on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures at 25 °C

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Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K

Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)₁₃−Poly(propylene oxide)₃₀− Poly(ethylene oxide)₁₃ Triblock Copolymer at 293 and 301 K