Transfer activity coefficient of the proton in water-pyridine mixtures. A comparison of some extrathermodynamic assumptions

Various water-pyridine mixtures have been selected in order to compare several of the most popular extrathermodynamic assumptions involved in the determination of the transfer activity coefficient of the proton, _t(H⁺). Two techniques have been utilized for this purpose: voltammetry [study of the ferrocene, ferricyanide, or thallium(1) systems] and potentiometry at equilibrium (emf measurements of various galvanic cells, including liquid junctions and hydrogen electrode or silver electrode as a test electrode). The assumptions have been classified into various groups [e.g., _t(Z^p+)=_t(Z^q+) or _t(X^–)=_t(Y⁺)], and the values of _t(H⁺) have been experimentally determined in each case. The results vary depending upon the basic assumption (several pH units); less important differences (e.g., 0.5 pH unit) occur within a given group, and this may be assigned to the nature of the reference species chosen. A simple model of solvation has been also examined; the application of the law of mass action to the corresponding equilibrium provides results close to the _t(X^–) =_t(Y⁺)type of assumptions which ultimately leads to most self-consistent results.     

Phase separation of symmetrical polymer mixtures in thin-film geometry

Monte Carlo simulations of the bond fluctuation model of symmetrical polymer blends confined between two neutral repulsive walls are presented for chain lengthN _A=N _B=32 and a wide range of film thicknessD (fromD=8 toD=48 in units of the lattice spacing). The critical temperaturesT _c (D) of unmixing are located by finite-size scaling methods, and it is shown that , wherev ₃0.63 is the correlation length exponent of the three-dimensional Ising model universality class. Contrary to this result, it is argued that the critical behavior of the films is ruled by two-dimensional exponents, e.g., the coexistence curve (difference in volume fraction of A-rich and A-poor phases) scales as , where ₂ is the critical exponent of the two-dimensional Ising universality class ( ₂=1/8). Since for largeD this asymptotic critical behavior is confined to an extremely narrow vicinity ofT _c (D), one observes in practice effective exponents which gradually cross over from ₂ to ₃ with increasing film thickness. This anomalous flattening of the coexistence curve should be observable experimentally.     

The distribution of the likelihood ratio for mixtures of densities from the one-parameter exponential family

We here consider testing the hypothesis ofhomogeneity against the alternative of a two-component mixture of densities. The paper focuses on the asymptotic null distribution of 2 log _n , where _n is the likelihood ratio statistic. The main result, obtained by simulation, is that its limiting distribution appears pivotal (in the sense of constant percentiles over the unknown parameter), but model specific (differs if the model is changed from Poisson to normal, say), and is not at all well approximated by the conventional ₍₂₎ ² -distribution obtained by counting parameters. In Section 3, the binomial with sample size parameter 2 is considered. Via a simple geometric characterization the case for which the likelihood ratio is 1 can easily be identified and the corresponding probability is found. Closed form expressions for the likelihood ratio _n are possible and the asymptotic distribution of 2 log _n is shown to be the mixture giving equal weights to the one point distribution with all its mass equal to zero and the ²-distribution with 1 degree of freedom. A similar result is reached in Section 4 for the Poisson with a small parameter value (0.1), although the geometric characterization is different. In Section 5 we consider the Poisson case in full generality. There is still a positive asymptotic probability that the likelihood ratio is 1. The upper precentiles of the null distribution of 2 log _n are found by simulation for various populations and shown to be nearly independent of the population parameter, and approximately equal to the (1–2)100 percentiles of ₍₁₎ ² . In Sections 6 and 7, we close with a study of two continuous densities, theexponential and thenormal with known variance. In these models the asymptotic distribution of 2 log _n is pivotal. Selected (1–) 100 percentiles are presented and shown to differ between the two models.     

Necessary conditions for characterization of laws via mixed sums

SupposeX andY are independent and identically distributed, and independent ofU which satisfies 0U1. Recent work has centered on finding the lawsL(X) for whichX U(X+Y) where denotes equality in law. We show that this equation corresponds to a certain projective invariance property under random rotations. Implicitly or explicitly, it has been assumed that the characteristic function ofX has an expansion property near the origin. We show that solutions may be admitted in the absence of this condition when –logU has a lattice law. A continuous version of the basic problem replaces sums with a Lévy process. Instead we consider self-similar processes, showing that a solution exists only whenU is constant, and then all processes of a given order are admitted.This research was in part supported by NSERC grant A-8466.     

Continuous chromatographic separation of glucose-fructose mixtures using anion-exchange resins

Summary A semi-continuous, counter-current chromatographic refiner (SCCR) was packed with an anion resin in the bisulphite form and used to separate mixtures of sugars from different feedstocks. Products with purities of more than 99% were achieved and solid concentrations of the fructose products of 12% w/v were possible. The deterioration of the anion resin was controlled by simple precautions and thus its useful life was substantially prolonged.     

Multicomponent electrolyte systems: Dependence of ionic mobilities on aqueous organic solvent structure

Ionic mobility data for multicomponent electrolyte systems at low concentrations are scarce due to experimental difficulties and are actually restricted to aqueous solutions of alkali chlorides. Some new results are presented which have been obtained by using a radiotracer method valid even if one of the ionic species is present at very low concentrations (tracer ion). The following electrolyte systems (two electrolytes with a common ion in a solvent) have been investigated at a 0.5N total ionic strength: NaNO₃–AgNO₃, KNO₃–AgNO₃, LiNO₃–AgNO₃ either in pure water or in water-rich (acetonitrile or dimethylsulfoxide) mixed solvents. Since ionic conductivity data processing by an extended law generalized to mixtures, such as that proposed by Quint and Viallard, has proved to be delicate to handle, our experimental results have been compared with the qualitative predictions of the classical Onsager-Fuoss limiting law. The main conclusion of this work is to give clear experimental evidence of the inability of any continuum theory to predict the ionic mobilities when solvent structural effect have to be taken into account. Consequently, the ionic behavior, particularly that of the Ag⁺ ion, has been interpreted in terms of preferential solvation and solvent microscopic structure. The trace mobility measurements reflect the maximum structural effect on the ionic transport properties.     

Radiation grafting from binary monomer mixtures. I. Vinyl ether of monoethanolamine and vinyl ether of ethyleneglycol

Gamma-radiation grafting of vinyl ether of monoethanolamine and vinyl ether of ethyleneglycol (VEEG) on polyethylene films has been studied from binary monomer mixtures. The effect of co-monomer composition and total exposure radiation dose on the grafting process is investigated. A combination of potentiometric and gravimetric techniques is applied to determine the grafting degree of each monomer in the final graft copolymer. The presence of more active monomer VEEG in the mixture was found to enhance the grafting of both monomers because the increasing of copolymerization rate which in turn increases the total grafting degree. The modification of the hydrophilic properties of the graft copolymer is studied by examining the grafted films for water- and copper (II) ions uptake.     

Fluid phase equilibria of binary and ternary mixtures of supercritical carbon dioxide with tetradecanoic acid and docosane up to 43 MPa and 393 K: cosolvency effect and miscibility windows

Isothermal pressure (p)-mass fraction (w) phase diagrams were measured for CO₂ + tetradecanoic acid at six temperatures from 328.2 K to 373.2 K and for CO₂ + docosane at four temperatures from 343.2 K to 393.2 K as well as isobaric temperature (T)-mass fraction (w) phase diagrams for both systems at 34.5 MPa. In addition the isothermal and isobaric Gibbs phase prisms at 373.2 K and 34.5 MPa respectively were determined for the ternary system CO₂ + tetradecanoic acid + docosane, and and isobaric miscibility window was found between 333 K and 385 K at 34.5 MPa.     

A way of establishing quality of measurements in gas analysis—national and international aspects

Standardising quality of measurements at both the national and international level results in a unity in measurement that may be regarded a synonym of traceability. In gas analysis, the key issue in achieving this aim is production of gaseous reference materials. Establishing a network of secondary measurement standards at gaseous CRM producers’ sites in Ukraine might be interesting for those involved in gas analysis activities. Inevitably, problems concerning the recognition of measuring capabilities of both national metrological institutes and local CRM producers are now an international issue. Thus, the problems of national adoption of international standards, as well as harmonisation between different international documents are currently relevant, and Ukrainian experience may be useful to others in this field. Presented at the 3rd International Conference on Metrology, November 2006, Tel Aviv, Israel.     

Thermodynamic and spectroscopic properties of 2-pyrrolidinones. 2. Dielectric properties of 2-pyrrolidinone in binary mixtures

Dielectric permittivities of 2-pyrrolidinone - acetone, -dimethyl sulfoxide,-2-propanol, -dichloromethane and -water systems were measured as a function of mole fraction over the whole composition range at 30 and 50°C. The excess dielectric permittivities are predominantly negative for all the mixtures and the excess molar polarizations are negative except for 2-pyrrolidinone - water and 2-pyrrolidinone - dimethyl sulfoxide mixtures. The large negative excess quantities are indicative of the strong specific interactions between the like and unlike components of the solution mixtures.