Search results for "Thermodynamics"

Thermodynamics of binary mixtures: Volumes, heat capacities, and dilution enthalpies for then-pentanol+2-methyl-2-butanol system

1983

The densities, heat capacities, and dilution enthalpies ofn-pentanol+2-methyl-2-butanol mixtures have been measured, in many cases as a function of temperature, over the complete mole fraction range. Excesses thermodynamic properties, apparent and partial molar heat capacities, volumes and expansibilities were derived. The concentration and temperature dependences of these functions are discussed in terms of the variations of the structure of the system caused by the participation of the two alcohol molecules (with quite different steric hindrance of the alkyl chain around the-OH group) in the dynamic intermolecular association process through hydrogen bonding.

Networks of Partially Hydrogenatedcis-1,4-Polybutadiene and ‘Rigid Rods’

1996

Networks of 'flexible' and 'rigid' chains were synthesized. As 'flexible' component we have used different partially hydrogenated cis-1,4-polybutadiene. The 'rigid' component was synthesized from bis(1,2,4-triazoline-3,5-dione)s and biscyclohexadienes via repetitive Diels-Alder reaction. A slight excess of bis(1,2, 4-triazoline-3,5-dione)s leads to polymers with 1,2,4-triazoline-3,5-dione end groups, which can easily react with the partially hydrogenated cis-1,4-polybutadiene. The influence of the extent of hydrogenation and the amount of crosslinker on the mechanical and thermal behaviour is described.

On The Incompatibility of Dextran and Pullulan in Aqueous Solutions and Its Modeling

2012

Joint aqueous solutions of branched dextran and linear pullulan are investigated with respect to their phase separation. The experiments demonstrate that the polymers are – depending on the molar mass of dextran – incompatible in aqueous solutions despite their chemical similarity. This finding can be modeled on the basis of an approach accounting for chain connectivity and conformational relaxation of the components. According to these calculations, the polymers exhibit a miscibility gap in joint solutions despite the favorable interactions between them. Using information on the subsystems H2O/dextran and H2O/pullulan, the assumption of complete miscibility of the polysaccharides is requir…

Heat capacities of butanol and pentanol in aqueous dodecyltrimethylammonium bromide solutions

1987

Heat capacities of the ternary systems water-dodecyltrimethylammonium bromide (DTAB)-butanol and water-DTAB-pentanol were measured at 25°C. The standard partial molar heat capacities of pentanol in micellar solutions show a maximum at about 0.35 mol-kg−1 DTAB that has been attributed to a micellar structural transition. This maximum tends to vanish by increasing the alcohol concentration and by decreasing the alcohol alkyl chain length; in the case of butanol it was not detected. The behavior of the standard partial molar heat capacities of alcohols in micellar solutions in the region above the cmc and below the structural transition was explained using a previously reported mass-action mod…

Ternary Polymer Solutions with Hydrogen Bonds, 1

2007

The Flory Huggins methodology coupled to AET has been extended to ternary polymer systems, in particular to solvent (A)/polymer 1 (B)/polymer 2 (C) systems, with the two polymers displaying H-bonding interactions. Because the H-bonding can perturb the randomness of polymeric conformations, the change in Gibbs free energy of mixing, AG, should arise from changes in combinatorial entropy as well as in interaction energy. The combinatorial part of AG is evaluated through AET as a function of the association constant η between B and C components, the autoassociation constant a between B components, and the independent number m of interaction sites of acceptor C. The enthalpic contribution is ev…

Correlation between transport and equilibrium properties through the ternary interaction parameter for cosolvent and cononsolvent polymeric systems

1992

A study of the ternary polymer systems dimethyl formamide-ethyl acetate-polystyrene, chloroform-1,4 dioxane-polystyrene and tetrahydrofuran-chloroform-polystyrene was carried out by viscosity and light scattering at 298 K. A good correlation has been found between the excess intrinsic viscosity, unperturbed polymer dimensions, second virial coefficient and the excess Gibbs free energy by using a ternary interaction parameter, dependent on molecular weight. This modification enables the conversion between transport and equilibrium properties.

Interfacial tension between coexisting polymer solutions in mixed solvents and its correlation with bulk thermodynamics: phase equilibria (liquid/gas…

2002

Abstract Vapor pressures, phase equilibria and interfacial tensions σ were measured for solutions of poly(dimethylsiloxane) (PDMS, M w [equals]75 kg/mol and M n [equals]50 kg/mol) in mixed solvents of toluene (TL) and ethanol (EtOH) at 30, 40, 50 and 60 °C. The experimental ternary phase diagrams can be modeled quantitatively from the determined concentration and temperature dependent binary interaction parameters χ ij if the experimentally inaccessible composition dependence of χ EtOH/PDMS is adjusted. The relations between σ and the equation of state of the system differ from that applying to single solvents. The exponents as well as the amplitude prefactors of the corresponding scaling l…

Computer simulations of undercooled fluids and the glass transition

2000

Abstract Two model studies are presented that attempt to describe the static and dynamic properties of glass-forming fluids via molecular dynamics simulations: The first model is an atomistically realistic model of SiO 2 , the second model provides a coarse-grained description of polymer liquids, i.e., typical `fragile' glassformers, while SiO 2 is the prototype of a `strong glassformer'. For both models, attention is given to the questions as to which range of temperatures are properties in equilibrium, and whether such simulations can help to interpret experiments and/or check theoretical predictions. While in the simulation of SiO 2 using the potential of van Beest, Kramer and van Santen…

Time–carbonyl groups equivalence in photo-oxidative aging of virgin/recycled polymer blends

2004

AbstractThe photo-oxidation behaviour of polymers is strongly dependent on the initial amount of carbonyl groups along the chains. The growing use of recycled post-consumer polymers coming from products used outdoors and then photo-oxidised, both pure and blended with the same virgin polymer, gives rise to an unpredictable behaviour of weathering resistance of products made with these materials. The present work shows that the carbonyl group–exposure time curves can be shifted along the time axis to give a single generalised master plot. It is then possible to predict the formation of the new carbonyl groups by knowing only the initial amount of the same carbonyl groups. The same shift fact…

1979