0000000000002066
AUTHOR
M. Goffredi
Study of lecithin reverse micelles by FT-IR spectroscopy
FT-IR spectra of water/lecithin/deuterated cyclohexane microemulsions as a function of water/lecithin molar ratio R (R=[water]/[lecithin]) at various lecithin volume fractions (φ) have been recorded. After elimination of the spectral contributions due to the deuterated cyclohexane and normalization, the band parameters of the CO and PO4 vibrational modes due to lecithin have been found dependent only upon R. This behaviour has been interpreted in terms of a progressive structural modification of the water/lecithin interface superimposed to the progressive hydration of CO and PO4 groups. Moreover, no correlation between the CO and PO4 band parameters and the formation of gel-like micellar so…
Refractive index of water-AOT-n-heptane microemulsions
Refractive index measurements on water/AOT/n-heptane microemulsions as a function of the volume fraction ϕ of the dispersed phase (water plus AOT) and of the water/AOT molar ratio R have been performed at 25°C. The refractive index was found to vary monotonically with ϕ without any change in rate during the crossover of the percolation threshold. Such a behavior suggested that, well above the percolation threshold, the water-AOT-n-heptane microemulsions are still formed by water-containing AOT reversed micelles dispersed in the oil phase. The analysis of the experimental data allowed an evaluation the fraction of the water molecules bonded to the AOT head group as a function of R.
Effect of tetrahydrofuran on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures
The molar conductance of dilute solutions of HCl in wet (68.5% methanol + 31.5% tetrahydrofurane mixtures at 25°C have been measured. The data were analyzed using the Fuoss-Hsia equation to calculate the infinite dilution molar conductances and association constants. The trend of the limiting conductances in these mixtures as a function of the water content shows, once more, the peculiar minimum due to the anomalous proton conductance mechanism. From these data the limiting molar conductance in the anhydrous binary solvent system was evaluated. The percentage excess proton mobility with respect to potassium ion has also been determined. All these data are compared to those found in a binary…
Entropy of transfer of n-nitroalkanes from n-octane to water at 25�C
Entropy of transfer of nitromethane, nitroethane, 1-nitrobutane, 1-nitropentane, and 1-nitrohexane from n-octane to water at 25°C is calculated using an electrostatic model. The calculations indicate that the electrostatic transfer entropy depends primarily on the dipole moment and the size of the-C−NO2 group, showing a trend which is similar to that previously found for the transfer free energy of the same process.
Free energy of transfer ofn-nitroalkanes fromn-octane to water at 25�C
Calorimetric determinations of the thermodynamics of transfer of nitromethane, nitroethane, 1-nitrobutane, 1-nitropentane, and 1-nitrohexane from n-octane to water at 25°C have been made. Transfer free energies calculated by four different models agree reasonably well with observations. Calculations indicate that the dipolar part of the transfer free energy depends only on the dipole moment and size of the-C−NO2 group and is independent of the length of the alkyl chain in nitroalkanes.
Electrical conductivity and permittivity of water-AOT-n-heptane microemulsions
Measurements of the electrical conductivity and of the complex permittivity of water-sodium bis(2-ethylhexyl) sulfosuccinate (AOT)-n-heptane microemulsions are reported. The experimental results are rationalized in terms of a hopping mechanism of AOT anions within clusters of reversed micelles. The dependence of the hopping rate and of the cluster dimensions upon the ratio [water]/[AOT] and temperature is discussed.
Calorimetric investigation of the precipitation of calcium monohydrogen phosphate in water/AOT/n-heptane microemulsions
Abstract The molar enthalpies of precipitation of calcium monohydrogen phosphate (CaHPO 4 ) in water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/ n -heptane microemulsions were measured at 25°C by a calorimetric technique as a function of the molar ratio R ( R = [water]/[AOT]) at a fixed AOT concentration. Calorimetric data indicate the formation of CaHPO 4 nanoparticles encapsulated in the aqueous core of the AOT reversed micelles displaying a slow growing process with time. Their energetic state is initially different from that in bulk water approaching the value in water at longer times. The observed growing process results to be completely inhibited by the presence of small amounts o…
Dielectric Behavior of Aqueous Solutions of α,β-Poly(aspartyl hydrazide) and α,β-Poly(N-hydroxyethyl aspartamide): An Investigation of the Structural and Dynamic Properties
The dielectric properties of aqueous solutions of α,β-poly(aspartyl hydrazide) (PAHy) and of α,β-poly( N-hydroxyethyl aspartamide) (PHEA) were measured at 25 ° C in the frequency range of 100 MHz to 15 GHz using a time domain reflection method (TDR). Single time relaxation processes were found at 2 GHz and 15 GHz, respectively. The low frequency dispersion was inter preted in terms of the dynamics of polymeric segments based on the dielectric relaxation strength and the relaxation time. The high frequency process which is attributed to the rotational relaxation of water, indicated that water mole cules surrounding the polymeric backbone and in the pure state have a similar rotational behav…
Physico-chemical properties of dense water/copper(II) bis(2-ethylhexyl) sulfosuccinate/CCl4 microemulsions
Measurements of some physico-chemical properties (density, viscosity, conductance, infra-red spectra) of water/copper(II) bis(2-ethylhexyl) sulfosuccinate (Cu(DEHSS)2)/CCl4 microemulsions, as a function of the volume fraction O of the dispersed phase (0 < O < 0.6) and of the molar ratio R (R = [water]/[DEHSS−]), have been performed at 25 °C. At each value of R, the density of the micellar phase is practically independent of O whereas the viscosity of microemulsions diverges above threshold O values. A divergent behavior for the electrical conductivity has also been observed but only at certain R values. These results, together with those from infra-red spectra, suggest that in percolated mi…
Physico-chemical characterization of Pd nanoparticles synthesized in w/o microemulsions
Abstract The long time stability of surfactant-coated Pd nanoparticles in w/o microemulsions has been investigated. It has been proven that in suitable conditions, the use of the functionalized surfactant Pd(AOT)2 allows to obtain very stable nanosized Pd particles and to finely control their average size.
Physicochemical Properties of Copper(II) Bis(2-ethylhexyl) Sulfosuccinate Reversed Micelles
Abstract Measurements of some physicochemical properties (density, viscosity, conductance, UV–vis spectra, IR spectra) of the water/copper(II) bis(2-ethylhexyl) sulfosuccinate (Cu(DEHSS) 2 )/CCl 4 microemulsions, at a fixed surfactant molal concentration ([Cu (DEHSS) 2 ] = 0.05003 mol kg −1 ), as function of the molar ratio R ( R = [water]/[DEHSS − ]) have been performed at 25°C. Information on some structural and dynamical properties of the water-containing Cu(DEHSS) 2 reversed micelles and of their evolution with R are derived from the experimental results. The comparison with the same properties of water-containing sodium bis(2-ethylhexyl) sulfosuccinate reversed micelles allows to evide…
Conductance of potassium halides near the temperature of maximum density of water
The conductances of dilute aqueous solutions of KCl, KBr, and KI have been measured over the temperature range 2 to 8°C and have been analyzed by the Fuoss-Hsia equation. The ionic Walden products at infinite dilution have been discussed in terms of local viscosity. The temperature dependence of these products suggest that near the temperature of maximum density of water, the structure-breaking ability of these ions changes in a regular way.
Study of the growth of ZnS nanoparticles in water/AOT/n-heptane microemulsions by UV-absorption spectroscopy
Abstract ZnS nanoparticles were synthesized at 25°C using water-containing AOT reversed micelles as nanoreactors and characterized by UV–vis spectroscopy. The time dependence of the spectra emphasizes a slow growing process of the ZnS nanoparticles coupled with a change of their photophysical properties. Both processes are well described by power laws. The nanoparticle size can be controlled by the molar ratio R ( R =[water]/[AOT]), i.e. by the micellar size. The deposits obtained by evaporation of the volatile components of the microemulsions are found to be composed of a surfactant matrix containing ZnS nanoparticles smaller and more stable than that in the corresponding microemulsions.
Calorimetric investigation of water/lecithin/cyclohexane microemulsions
The enthalpies of dilution of water/lecithin/cyclohexane microemulsion-gels at variousR values (R=[water]/[lecithin]) and molar enthalpies of solution of water in lecithin/cyclohexane at a fixed lecithin concentration were determined calorimetrically at 25°C. Through a description of the process of dilution of water/lecithin/cyclohexane microemulsion-gels as one involving mainly the scission of lecithin reversed micelles in to smaller ones, the concentration dependence of the enthalpy was rationalized. Surprisingly, in order to account for the dilution enthalpies, it was not necessary to hypothesize a thermal effect arising from the breakage of the micellar network present in the micremulsi…
Calorimetric investigation of the formation of ZnS nanoparticles in w/o microemulsions
The enthalpies of precipitation of ZnS nanoparticles within water containing reversed micelles of sodium bis(2-ethylhexyl) solfosuccinate, L-α phosphatidylcholine, tetraethyleneglycol-mono-n-dodecyl ether and didodecyldimethylammonium bromide as a function of the molar concentration ratioR (R=[water]/[surfactant]) were measured by calorimetric technique. The results indicate that the energetic state of ZnS nanoparticles confined in the aqueous core of the reversed micelles is different from that in bulk water. Effects due to nanoparticle size, adsorption of HS− ions on the nanoparticle surface and interactions between nanoparticles and water/surfactant interfaces are discussed.
Study of AOT-stabilized microemulsions of formamide and n-methylformamide dispersed in n-heptane
Abstract A wide investigation of some physicochemical properties (density, viscosity, conductance, IR spectra, permittivity) of AOT-stabilized dispersions of formamide and n -methylformamide in n -heptane has been performed. The experimental data are consistent with the hypothesis that these highly hydrophilic substances are encapsulated within AOT reversed micelles and that this structure is maintained for both systems well above the volume fraction of the dispersed phase where a percolative transition occurs. In addition, the observed properties of these microemulsions reveal the pivotal role of intermicellar attractive interactions in driving the percolative transition. A marked modifica…
Volumetric and transport properties of aerosol-OT reversed micelles containing light and heavy water
Densities and viscosities of sodium bis(2-ethylhexyl) sulfosuccinate (AOT in-heptane system containing light and heavy water, as a function of the molar ratio R (R=[H2O or D2O]/[AOT]) were measured at 0, 5, 25 and 40°C. At low R values, the apparent molar volume of deuterium oxide is smaller than that of light water. The difference is related to the strength of the hydrogen bonding H2O and D2O. The viscosities of both H2O-AOT-n-heptane and D2O-AOT-n-heptane systems were explained in terms of intermicellar interactions mainly governed by hydration of the head groups of AOT.