M. Carmen López

Excess properties of the ternary system cyclohexane + 1,3-dioxolane + 1-butanol at 298.15 and 313.15 K

Densities, speeds of sound and heats of mixing for the ternary system cyclohexane + 1,3-dioxolane + 1-butanol have been measured at atmospheric pressure at the temperatures of 298.15 and 313.15 K. Excess molar volumes, excess isentropic compressibilities and excess molar enthalpies have been calculated from experimental data and fitted by Cibulka equation. Excess molar properties were analysed in terms of molecular interactions and structural and packing effects.

Molecular Arrangement in Langmuir and Langmuir―Blodgett Films of a Mesogenic Bent-Core Carboxylic Acid

A different alternative to previous research on Langmuir and Langmuir-Blodgett (LB) films of bent-core liquid crystals is reported in this work. A bent-shaped molecule wearing a terminal carboxylic group has been used to obtain monomolecular films with their long molecular axis almost perpendicular to the aqueous surface. Langmuir films at the air-liquid interface (pH=9) have been characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and ultraviolet reflection spectroscopy. A condensed phase is reached at surface pressures up to 20 mN x m-1. In this condensed phase, molecules are packed forming H-aggregates with a well-defined molecular orientation. Langmuir films have been transferred onto quartz and silicon substrates and characterized by means of UV-vis spectroscopy and XRR. The transference is Z-type, with a constant deposition of the monolayers. The total LB monolayer film thickness is evaluated to be about 5.8 nm, which is in good agreement with the deduced orientation at the air-liquid interface as well as with the lamellar order observed within the solid obtained by cooling the sample from the mesophase.

Isobaric VLE data of the binary mixture (n-hexane+1-chlorobutane) and the ternary system (1-butanol+n-hexane+1-chlorobutane) at 101.3 kPa

Abstract Isobaric vapour–liquid equilibrium (VLE) for the ternary mixture, 1-butanol (1)+ n -hexane (2)+1-chlorobutane (3) and for the binary mixture, n -hexane (1)+1-chlorobutane (2) at 101.3 kPa has been experimentally studied. The activity coefficients were found to be thermodynamically consistent and were satisfactorily correlated with the Margules, van Laar, Wilson, NRTL and UNIQUAC equations. They have been also compared with the results obtained from the application of ASOG and the modified UNIFAC group contribution methods.

Phase equilibrium of liquid mixtures: experimental and modeled data using statistical associating fluid theory for potential of variable range approach.

A study of the phase equilibrium (experimental and modeled) of mixtures formed by a cyclic ether and haloalkanes has been derived. Experimental data for the isothermal vapor liquid equilibrium of mixtures formed by tetrahydrofuran and tetrahydropyran and isomeric chlorobutanes at temperatures of 298.15, 313.15, and 328.15 K are presented. Experimental results have been discussed in terms of both molecular characteristics of pure compounds and potential intermolecular interaction between them using thermodynamic information of the mixtures obtained earlier. The statistical associating fluid theory for potential of variable range (SAFT-VR) approach together with standard combining rules without adjustable parameters has been used to model the phase equilibrium. Good agreement between experiment and the prediction is found with such a model. Mean absolute deviations for pressures are of the order of 1 kPa, while less than 0.013 mole fraction for vapor phase compositions. In order to improve the results obtained, a new modeling has been carried out by introducing a unique transferable parameter k(ij), which modifies the strength of the dispersion interaction between unlike components in the mixtures, and is valid for all the studied mixtures being not temperature or pressure dependent. This parameter together with the SAFT-VR approach provides a description of the vapor-liquid equilibrium of the mixtures that is in excellent agreement with the experimental data for most cases. The absolute deviations are of the order of 0.005 mole fraction for vapor phase compositions and less than 0.3 kPa for pressure, excepting for mixtures containing 2-chloro-2-methylpropane which deviations for pressure are larger. Results obtained in this work in the modeling of the phase equilibrium with the SAFT-VR equation of state have been compared to the ones obtained in a previous study when the approach was used to model similar mixtures with clear differences in the thermodynamic behavior. We show how the SAFT-VR approach is capable of differentiating the molecular features of a relatively wide set of different mixtures.

Electrochemistry of Langmuir-Blodgett Films Incorporating Both a Viologen Derivative and Tetracyanoquinodimethane

A positively charged monolayer of a viologen derivative containing two long alkyl chains was prepared. Tetracyanoquinodimethane radical anions (TCNQ - ) were incorporated into the Langmuir-Blodgett film during the transference process as the counterions from a subphase containing an aqueous solution of LiTCNQ. Stable monolayers were transferred onto indium tin oxide electrodes and the electrochemical properties of the films were analyzed in terms of experimental variables including the nature of the counterions, the degree of order of the films, and the number of transferred layers. These well-ordered films show very reversible electrochemical processes for the viologen, quite negative redox potentials of the viologen moieties, a Γ c /Γ a ratio of 1, and no splitting of the first viologen reduction peak. The control of these properties is quite important in applications such as the catalytic reduction of a substrate.

Temperature dependence of surface tension of 2-methyl-1-propanol and 2-methyl-2-propanol+n-hexane mixtures

Surface tensions of binary mixtures of 2-methyl-1-propanol or 2-methyl-2-propanol with n-hexane have been measured in the temperature range 283.15 K–313.15 K for mixtures containing 2-methyl-1-propanol and from 298.15 K to 313.15 K for mixtures formed by 2-methyl-2-propanol, with a drop volume tensiometer. The corresponding surface tension deviations have been calculated and correlated. Using the temperature dependence of surface tensions, the entropy and enthalpy of surface formation per unit area were evaluated at the studied temperatures.

Influence of the liquid crystal behaviour on the Langmuir and Langmuir–Blodgett film supramolecular architecture of an ionic liquid crystal

A new luminescent ionic liquid crystal, called Ipz-2, has been synthesised and its mesophase behaviour and also at the air-liquid interface has been studied and compared with Ipz, another ionic pyrazole derivative, with a similar molecular structure, previously studied. The X-ray diffraction pattern shows that Ipz-2 exhibits hexagonal columnar mesomorphism, while Ipz adopts lamellar mesophases. Langmuir films of both compounds are flat and homogeneous at large areas per molecule, but create different supramolecular structures under further compression. Ipz-2 Langmuir films have been transferred onto solid substrates, and Atomic Force Microscopy (AFM) images of the Langmuir-Blodgett films have shown that large columnar structures hundreds of nm in diameter are formed on top of the initial monolayer, in contrast with well-defined trilayer LB films obtained for Ipz. Our results show that Ipz-2 has a tendency to stack in columnar arrangements both in liquid crystalline bulk and in Langmuir and Langmuir-Blodgett films.

Air-water interfacial behavior of linear-dendritic block copolymers containing PEG and azobenzene chromophores.

Fabrication of Langmuir films at the air-water interface of four linear-dendritic block copolymers (LDBCs) is described. The LDBCs are composed of a linear hydrophilic chain of poly(ethylene glycol) (PEG) and the first four generations of hydrophobic aliphatic polyester dendrons functionalized at the periphery with cyanoazobenzene chromophores. Langmuir films of the LDBCs, coded as PEG-AZOn (n indicates the number of cyanoazobenzene units at the periphery of the dendritic block), have been characterized by a combination of surface pressure versus area per molecule isotherms, UV-vis reflection spectroscopy and Brewster angle microscopy. The observed PEG-AZOn Langmuir film behavior depends strongly on the hydrophilic/hydrophobic ratio. A typical transition, related to PEG chains desorption from the air-water interface into the water subphase is observed for all the LDBCs, except for PEG-AZO16. In addition, PEG-AZO2 and PEG-AZO4 show a second transition whose nature has been studied in detail. Azobenzene chromophore interactions have been shown to be relevant in the organization of PEG-AZOn (n=4, 8 and 16) Langmuir films. Moreover, for PEG-AZO16 the orientation of the azobenzene units has been determined, revealing the formation of a well organized structure of azobenzene moieties at the air-water interface.

Study of an ethylene oxide-terminated bent-core compound: synthesis and Langmuir-Blodgett film structure.

Bent-core compounds have attracted interest due to their unusual supramolecular structures, uncommon physical properties such as ferro- and antiferroelectricity and potential applications in fields such as nonlinear optics. Their incorporation into nanostructured materials, however, needs to be improved in terms of accurate control of the packing and orientation of the molecules in practical structures. Here, we have synthesized a novel bent-core compound bearing a tetraethylene glycol (TEG) chain as the hydrophilic head group and studied its capacity to obtain monomolecular films by means of the Langmuir-Blodgett technique. We developed a synthetic route to the material and studied its behavior in Langmuir and Langmuir-Blodgett films by means of a variety of characterization techniques, including a new model for the interpretation of UV-Vis reflection spectra of bent-core compounds. We found that the new head group, while destroying the formation of bulk mesophases, stabilizes the formation of the monolayer at the air-water interface and allows core-core interactions to dominate film dynamics, thus providing a promising alternative to carboxylic acid head groups.

Refractive Properties of Binary Mixtures Formed by an Isomer of Chlorobutane and Butyl Ethyl Ether

Refractive indices of the binary mixtures containing an isomer of chlorobutane (1-chlorobutane, 2-chlorobutane, 2-methyl-1-chloropropane, or 2-methyl-2-chloropropane) and butyl ethyl ether have been measured at seven temperatures from T = 283.15 to 313.15 K From these data refractive index deviations were calculated and correlated with a Redlich-Kister polynomial expansion. The refractive index deviations were found positive. Finally, from these refractive indices both densities and surface tensions of the studied systems were predicted and compared with previously reported values.