Search results for "Thermodynamics"
showing 10 items of 2774 documents
A chiral molecular conductor: synthesis, structure, and physical properties of [ET]3[Sb2(L-tart)2].CH3CN (ET = bis(ethylendithio)tetrathiafulvalene; …
2004
The salt [ET](3)[Sb(2)(L-tart)(2)].CH(3)CN (1) has been obtained by electrocrystallization of the organic donor bis(ethylendithio)tetrathiafulvalene (ET or BEDT-TTF) in the presence of the chiral anionic complex [Sb(2)(L-tart)(2)](2-) (L-tart = (2R,3R)-(+)-tartrate). This salt crystallizes in the chiral space group P2(1)2(1)2(1) (a = 11.145(2) angstroms, b = 12.848(2) angstroms, c = 40.159(14) angstroms, V = 5750.4(14) angstroms(3), Z = 4) and is formed by alternating layers of the anions and of the organic radicals in a noncentrosymmetric alpha-type packing. This compound shows a room temperature electrical conductivity of approximately 1 S.cm(-1) and semiconducting behavior with an activa…
Supramolecular Polymers in Aqueous Media
2016
This review discusses one-dimensional supramolecular polymers that form in aqueous media. First, naturally occurring supramolecular polymers are described, in particular, amyloid fibrils, actin filaments, and microtubules. Their structural, thermodynamic, kinetic, and nanomechanical properties are highlighted, as well as their importance for the advancement of biologically inspired supramolecular polymer materials. Second, five classes of synthetic supramolecular polymers are described: systems based on (1) hydrogen-bond motifs, (2) large π-conjugated surfaces, (3) host-guest interactions, (4) peptides, and (5) DNA. We focus on recent studies that address key challenges in the field, provid…
Thermodynamics ofN,N,N-octylpentyldimethyl-ammonium chloride in water-urea mixtures
1997
Specific conductivities, densities, heat capacities, and enthalpies of dilution at 25‡C were measured forN,N,N-octylpentyldimethylammonium chloride (OPAC) in water-urea mixtures at various urea concentrations mu as functions of the surfactant concentration ms. From conductivity data, the cmc and the degree of the counterion dissociation Β of the OPAC micelles were calculated. The cmc increases linearly with increasingm u while Βvs. mu is a smooth concave curve. From the experimental thermodynamic data, the apparentY Φ and partialY 2 molar properties (volumes, heat capacities, and relative enthalpies) are derived as functions of mu andm s . The effect of urea on the dependences of the differ…
Heat capacities, volumes and solubilities of pentanol in aqueous alkyltrimethylammonium bromides
1988
Apparent molar heat capacities and volumes of pentanol, 0.05m in decyl-, tetradecyl- and hexadecyltrimethylammonium bromides micellar solutions, were measured at 25°C. They were assumed to approach the standard infinite dilution values and rationalized by means of previously reported equations following which the distribution constant between the aqueous and the micellar phase, heat capacity, and volume of pentanol in both phases are simultaneously derived. The present results show that the volume of the micellar core does not seem to have a significant effect on the apparent molar volume and heat capacity of pentanol in the micellar phase and on the free energy of transfer of pentanol from…
Kinetic studies of the interaction between DNA and polycations based on polyasparthylhydrazide
2008
Abstract In the present paper, a systematic kinetic study on the interaction between interpolyelectrolytes such as positive-charged polymers and DNA was carried out. In particular, a qualitative–quantitative kinetic investigation on the interaction between copolymers of the α,β-poly(aspartylhydrazide) and DNA calf thymus filaments was performed. This study gives a new model starting from a well known “pseudo-phase model”, and permits to give a qualitative explanation about the trends of experimentally observed kinetic constants by varying the concentration of one of the two poly-electrolytes. Moreover, this study permits to verify the dependence of the binding constants KPAHy–CPTA and KDNA …
Thermal diffusion of dextran in aqueous solutions in the absence and the presence of urea.
2006
The Ludwig-Soret effect was studied for aqueous solutions of dextran in the temperature range 15T55 degrees C taking into account the effect of the addition of urea. In the absence of urea, the Soret coefficient S(T) changes sign; it is positive for T45.0 degrees C but negative for T45.0 degrees C. The positive sign of S(T) means that the dextran molecules migrate toward the cold side of the fluid; this behavior is typical for polymer solutions, whereas a negative sign indicates the macromolecules move toward the hot side. The addition of urea to the aqueous solution of dextran rises S(T) and reduces the inversion temperature. For 2 M urea the change in the sign of S(T) is observed at T = 2…
Intrinsic viscosities of polyelectrolytes: specific salt effects and viscometric master curves.
2013
Dilute solutions of the sodium salt of polystyrene sulfonic acid (PSS-Na) were measured viscometrically as a function of composition in aqueous solvents of different salinity, where the extra salt was either NaCl or CaCl2. Such experiments yield {η}, the generalized intrinsic viscosities (hydrodynamic specific volume) of the polyelectrolyte for arbitrary polymer concentrations, c. In the limit of infinite dilution {η} becomes identical to the intrinsic viscosity [η]. For NaCl {η} decreases monotonously with rising c, whereas maxima are passed in the case of CaCl2. Condensing c and the concentration of extra salt in the mixed solvent into a single variable enables the establishment of predic…
Bulk and interfacial properties in colloid-polymer mixtures
2005
Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parameters.
Simulation and theory of fluid demixing and interfacial tension of mixtures of colloids and nonideal polymers.
2005
An extension of the Asakura-Oosawa-Vrij model of hard sphere colloids and non-adsorbing polymers, that takes polymer non-ideality into account through a repulsive stepfunction pair potential between polymers, is studied with grand canonical Monte Carlo simulations and density functional theory. Simulation results validate previous theoretical findings for the shift of the bulk fluid demixing binodal upon increasing strength of polymer-polymer repulsion, promoting the tendency to mix. For increasing strength of the polymer-polymer repulsion, simulation and theory consistently predict the interfacial tension of the free colloidal liquid-gas interface to decrease significantly for fixed colloi…
Calculation of phase diagrams not requiring the derivatives of the Gibbs energy for multinary mixtures
1996
A method for the calculation of phase diagrams (tie lines and binodal, spinodal, critical points and their stability) based exclusively on the Gibbs energy of mixing with no need of its derivatives with respect to the composition variables is extended to multinary mixtures for any number of components. The mathematical description of the (K-1)-dimensional phase diagram of a K-component mixture is presented. The method is demonstrated for a quinternary blend of five polymers exhibiting a closed miscibility gap; all binary, ternary and quaternary subsystems are completely miscible. The phase separation in the quinternary system is caused by very favorable interactions in the ternary subsystem…