Environmental coordination chemistry: Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution. Ionic medium effects on equilibrium constants

The molar single activity coefficients associated with propionate ion (Pr) have been determined at 25 degrees C and ionic strengths comprised between 0.300 and 3.00 M, adjusted with NaClO4, as background electrolyte. The investigation was carried out potentiometrically by using a second class Hg/Hg2Pr2 electrode. It was found that the dependence of propionate activity coefficients as a function of ionic strength (I) can be assessed through the following empirical equation: log y(Pr) = -0.185 I-3/2 + 0.104 I-2. Next, simple equations relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous solution, at 25 degrees C, as a function of ionic strength were derived, allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as parameters associated with activity coefficients of the complex species in the equilibria are estimated. The body of results shows that the proposed calculation procedure is very consistent with critically selected experimental data.

Ionic medium effects on equilibrium constants .2. Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution

Simple equations were derived relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous sodium perchlorate media, at 25 degrees C, as a function of ionic strength (I), allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as activity coefficients of the species involved in the equilibria were estimated. The results show that the proposed calculation procedure is very consistent with critically selected experimental data.

Self-consistent equilibrium calculation through a direct variational technique in tokamak plasmas

A self-consistent equilibrium calculation, valid for arbitrary aspect ratio tokamaks, is obtained through a direct variational technique that reduces the equilibrium solution, in general obtained from the 2D Grad-Shafranov equation, to a 1D problem in the radial flux coordinate rho. The plasma current profile is supposed to have contributions of the diamagnetic, Pfirsch-Schluter and the neoclassical ohmic and bootstrap currents. An iterative procedure is introduced into our code until the flux surface averaged toroidal current density (J(T)), converges to within a specified tolerance for a given pressure profile and prescribed boundary conditions. The convergence criterion is applied between the (J(T)) profile used to calculate the equilibrium through the variational procedure and the one that results from the equilibrium and given by the sum of all current components. The ohmic contribution is calculated from the neoclassical conductivity and from the self-consistently determined loop voltage in order to give the prescribed value of the total plasma current. The bootstrap current is estimated through the full matrix Hirshman-Sigmar model with the viscosity coefficients as proposed by Shaing, which are valid in all plasma collisionality regimes and arbitrary aspect ratios. The results of the self-consistent calculation are presented for the low aspect ratio tokamak Experimento Tokamak Esferico. A comparison among different models for the bootstrap current estimate is also performed and their possible Limitations to the self-consistent calculation is analysed.

Ionic medium effects on equilibrium constants .1. Proton, copper(II), cadmium(II), lead(II) and acetate activity coefficients in aqueous solution

The molar single ion activity coefficients associated with hydrogen, copper(II), cadmium(II) and lead(II) ions were determined at 25 degrees C and ionic strengths between 0.100 and 3.00 M (NaClO4), whereas for acetate the ionic strengths were fixed between 0.300 and 2.00 M, held with the same inert electrolyte. The investigation was carried out potentiometrically by using proton-sensitive glass, copper, cadmium and lead ion-selective electrodes and a second-class Hg\Hg-2(CH3COO)(2) electrode. It was found that the activity coefficients of these ions (y(i)) can be assessed through the following empirical equations:log y(H) = -0.542I(0.5) + 0.451I; log y(Cu) = -1.249I(0.5) + 0.912I; log y(Cd) = -0.829I(0.5) + 0.448I(1.5);log y(Pb) = -0.404I(0.5) + 0.117I(2); and log y(Ac) = 0.0370I .

On the construction of perfect codes from HEX signal constellations

Recently, minimum and non-minimum delay perfect codes were proposed for any channel of dimension n. Their construction appears in the literature as a subset of cyclic division algebras over Q(zeta(3)) only for the dimension n = 2(s)n(1), where s is an element of {0,1}, n(1) is odd and the signal constellations are isomorphic to Z[zeta(3)](n) In this work, we propose an innovative methodology to extend the construction of minimum and non-minimum delay perfect codes as a subset of cyclic division algebras over Q(zeta(3)), where the signal constellations are isomorphic to the hexagonal A(2)(n)-rotated lattice, for any channel of any dimension n such that gcd(n,3) = 1. (C) 2012 The Franklin Institute. Published by Elsevier Ltd. All rights reserved.

Hydration-dependent conformational states of hemoglobin. Equilibrium and kinetic behavior

The equilibrium and kinetics of methemoglobin conversion to hemichrome induced by dehydration were investigated by visible absorption spectroscopy. Below about 0.20 g water per g hemoglobin only hemichrome was present in the sample; above this value, an increasing proportion of methemoglobin appeared with the increase in hydration. The transition between the two derivatives showed a time-dependent biphasic behavior and was observed to be reversible. The rates obtained for the transition of methemoglobin to hemichrome were 0.31 and 1.93 min-1 and for hemichrome to methemoglobin 0.05 and 0.47 min-1. We suggest that hemichrome is a reversible conformational state of hemoglobin and that the two rates observed for the transition between the two derivatives reflect the α- and β-chains of hemoglobin.

Bell's locality condition confronting perfect anti-correlations

We show that Local Realistic Theories, defined as obeying the Bells's locality condition, cannot satisfy the prefect anti-correlations without at the same time maximally violating rotational symmetry at the hidden variable level. We examine whether the rotational symmetry can be restored after the statistical average. We also comment on the question whether such theories are necessarily deterministic at the hidden variable leva. © 1999 Elsevier Science B.V. All rights reserved.

On the solution of mathematical programming problems with equilibrium constraints

Mathematical programming problems with equilibrium constraints (MPEC) are nonlinear programming problems where the constraints have a form that is analogous to first-order optimality conditions of constrained optimization. We prove that, under reasonable sufficient conditions, stationary points of the sum of squares of the constraints are feasible points of the MPEC. In usual formulations of MPEC all the feasible points are nonregular in the sense that they do not satisfy the Mangasarian-Fromovitz constraint qualification of nonlinear programming. Therefore, all the feasible points satisfy the classical Fritz-John necessary optimality conditions. In principle, this can cause serious difficulties for nonlinear programming algorithms applied to MPEC. However, we show that most feasible points do not satisfy a recently introduced stronger optimality condition for nonlinear programming. This is the reason why, in general, nonlinear programming algorithms are successful when applied to MPEC.

Central America - European Union Association Agreement: an assessment using general and partial equilibrium

Includes bibliography.

Equilibrium real exchange rates, misalignment and competitiveness in the Southern Cone

Includes bibliography

Chile: building a computable general equilibrium model with an application to the Bío Bío region

Includes bibliography

Trade and equilibrium among the ALADI countries

Includes bibliography

Construction of perfect space-time codes

In this work, we propose an innovative methodology to extend the construction of minimum and non-minimum delay perfect codes as a subset of cyclic division algebras over ℚ(ζ3), where the signal constellations are isomorphic to the hexagonal An 2 -rotated lattice, for any channel of any dimension n such that gcd{n, 3) = 1.