Search results for "VOLUME"

Effective pair potential between charged nanoparticles at high volume fractions

2017

Simulations of charged colloidal dispersions are technically challenging. One possible workaround consists in reducing the system to the colloids only, whose interactions are described through an effective pair potential, wf. Still, the determination of wf is difficult mainly because it depends on the colloidal density, ϕ. Here we propose to calculate wf from simulations of a pair of colloids placed in a cubic box with periodic boundary conditions. The variation in ϕ is mimicked by an appropriate change in the concentration of counterions neutralized by an homogeneous background charge. The method is tested at the level of the primitive model. A good description of the structure of the coll…

Volume and heat capacity studies to evidence interactions between cyclodextrins and nicotinic acid in water

2008

Density and heat capacity of the water+cyclodextrin (CD), water+nicotinic acid (NA) and water+CD+NA mixtures were determined at 298.15 K. CDs with different cavity size and alkylation were selected. From the experimental data the apparent molar properties were calculated. Assuming the formation of inclusion complexes of 1:1 stoichiometry, these properties were modeled and provided the stability constants of CD/NA inclusion complexes and the corresponding property change. The binding of NA with the smallest sized alpha-cyclodextrin (alpha-CD) generates more stable complexes accompanied by the lower volume and the heat capacity changes. These results are in agreement with earlier proposed bin…

Free energy of solvation of solutes and their partition coefficients in methanol-water binary mixtures

2001

A method is presented that permits semiquantitative estimation of the partitioning of any solute between any two media. The method is adapted to the simulation of multicomponent solvents. As an example, the free energies of solvation ΔG solv,aq o in methanol-water binary mixtures and the partition coefficientsP for organic solvent—aqueous solvent were calculated. The organic solvents studied were 1-octanol, cyclohexane and chloroform. Linear relationships were observed between the relative dielectric constant and the volume fraction of methanol in mixtures with water. The four hydrocarbon models studied were hexane, cyclohexane, hexatriene and benzene. The results are in agreement with calc…

1984

Sedimentation coefficients of S of polystyrene covering a broad range of molecular weights M, are measured in toluene and 2-butanone in the semidilute regime. The results are compared with literature data using a plot of S · NA · η/(1 − νρ) = M · η/f versus concentration c, allowing experiments in different solvents of different density ρ and viscosity η to be compared (ν: partial specific volume of polymer; f: friction coefficient; NA: Avogadro number). According to scaling theory for concentrations higher than a critical concentration c, linear plots are to be expected. This is true for the theta-solvent cyclohexane, but for the theta-solvent cyclopentane as well as for the thermodynamica…

A Novel Gas Chromatographic Method to Measure Sorption of Dense Gases into Polymers

2006

A novel experimental approach to determine the solubility of gaseous compounds inside polymers is here described. The method is based on the gas chromatographic determination of the composition of the fluid phase at equilibrium with the polymer. To take into account the effect of the volume swelling on the measurement a suitable probe, nonabsorbable by the polymer, was added to the fluid phase. Under the adopted configuration the apparatus can operate up to 35 MPa and 80°C. This experimental technique has been used to determine the solubility of carbon dioxide in poly(vinylidene fluoride) using argon as a probe. The latter was chosen because it is negligibly absorbed by the polymer and does…

Apparent molar volumes of potassium nitrate and sodium nitrate in ethanol + water at 298.15 K

1998

Densities of ethanol + water + potassium nitrate and ethanol + water + sodium nitrate mixtures have been measured with an oscillating-tube densimeter over a large range of concentrations of the salt and ethanol, at 298.15 K. From these densities, apparent molar volumes of both electrolytes in ethanol + water mixtures have been calculated, and partial molar volumes at infinite dilution have been evaluated.

Synthesis of Hyperbranched Polyglycerol in a Continuous Flow Microreactor

2007

Hyperbranched polymers have been synthesized in a microreactor for the first time, employing the known ring-opening multibranching polymerization of glycidol. Microreactors are well-known to be beneficial for highly exothermic reactions because of their capability to enhance mass and heat transfer due to short diffusion pathways and large interfacial areas per volume. The characteristics of the microstructured reaction system were utilized to engineer a continuous flow process for the preparation of well-defined hyperbranched polyglycerols with molecular weights up to 1,000 g/mol. Increased flow rates, as well as the use of highly polar solvents, led to the partial formation of very narrowl…

1979

The kinetics of the anionic polymerization of styrene were investigated under pressure (1≤p/bar < 1800) with Na+ as counter ion in tetrahydropyran (THP) as solvent and with Cs+ as counter ion in 1,2-dimethoxyethane (DME) as solvent. The results yielded the activation volume of the contact ion pair ΔV and the sum (ΔV + ΔVcs) of the activation volume of the solvent separated ion pair ΔV and the volume change upon formation of solvent separated ion pairs from contact ion pairs ΔVcs. The numerical values are negative. The activation volume of the solvent separated ion pairs could be estimated.

Stability of negatively charged platelets in calcium-rich anionic copolymer solutions.

2014

Controlling the stability of anisotropic particles is key to the development of advanced materials. Here, we report an investigation, by means of mesoscale molecular dynamics simulations, of the stability and structural change of calcium-rich dispersions containing negatively charged nanoplatelets, neutralized by calcium counterions, in the presence of either comb copolymers composed of anionic backbones with attached neutral side chains or anionic-neutral linear block copolymers. In agreement with experimental observations, small stacks of platelets (tactoids) are formed, which are greatly stabilized in the presence of copolymers. In the absence of polymers, tactoids will grow and aggregat…

Equilibrium and transport properties of ion-exchange membranes

1984

Abstract Specific properties (ion-exchange capacity, water content, pore volume fraction) and transport properties (counterion transport number and electrical conductivity) have been measured in four commercial cation-exchange membranes loaded with a variety of cations of different nature and charge. Not surprisingly, equivalent conductances are lower than in free solution and transport numbers decrease with valency of the counterion. This behavior is explained by taking into account a “tortuosity factor”, due to a lengthening of the pores across the membrane, except for a membrane with a lower water content and for ions of higher charge, in which electrostatic interactions between mobile a…