Enthalpies of dilution of aqueous solutions of amides and alcohols

Enthalpies of dilution of aqueous systems containing formamide, dimethyl-formamide, the mixture of these amides, and each amide separately with mannitol, inositol, and cyclohexanol have been determined at 25°C. The data have been treated in terms of the Savage-Wood additivity principle and in combination with literature data. New values for the methylene-amide, carbinol-amide, and amide-amide group interaction enthalpies are presented. These may be used with data on a wider variety of solute systems to obtain interaction enthalpies for new groups.     

The Mechanism of Photochemical Release of Nitric Oxide from S-Nitrosoglutathione

Abstract— Laser flash photolysis of S-nitroso complexes of glutathione (GSNO) and bovine serum albumin (BSANO) via excitation at 355 nm has been used to investigate the photogeneration of nitric oxide (NO) and subsequent radical reactions. In the case of GSNO, liberation of NO was confirmed by its oxidation of oxyhemoglobin to met hemoglobin. Initial NO release is via homolytic cleavage of the S-N bond to produce the glutathione thiyl radical, GS, which can subsequently react with (a) ground-state GSNO (k= 1.7 × 10⁹M^?1/i> s^?1) to yield additional NO and oxidized glutathione, GSSG; and (b) oxygen (k= 3.0 × 10⁹M^?1 s^?1) to give the glutathione peroxy radical, GSOO, which subsequently reacts with ground-state GSNO (k= 3.8 × 10⁸M^?1 s^?1), also producing additional NO and GSSG. The relative concentrations of oxygen and GSNO in the system determine the major pathway for removal of G'. These secondary reactions occur at such high rates that they preclude radical recombination under low-intensity irradiation conditions. The quantum yield of overall loss of GSNO thus varies with both GSNO and oxygen concentrations; a value of 0.66 was determined for an aerated solution of GSNO (0.86 mM). In the case of GSNO, therefore, generation of NO is not due solely to homolysis of the S-N bond; secondary reactions of the radicals formed lead to further NO liberation. In rationalizing the known phototoxicity of GSNO, possible contributions from thiyl and thiyl-derived radicals should be considered. In contrast to GSNO, direct excitation of BSANO (containing one bound NO group per molecule) led to photodecomposition with a quantum yield of 0.09 but no evidence was obtained for liberation of NO into the bulk medium.     

Electrical conductances of aqueous Na2SO4, H2SO4, and their mixtures: limiting equivalent ion conductances, dissociation constants, and speciation to 673 K and 28 MPa

The electrical conductivities of aqueous solutions of Na(2)SO(4), H(2)SO(4), and their mixtures have been measured at 373-673 K at 12-28 MPa in dilute solutions for molalities up to 10(-2) mol kg(-1). These conductivities have been fit to the conductance equation of Turq et al.(1) with a consensus mixing rule and mean spherical approximation activity coefficients. Provided the concentration is not too high, all of the data can be fitted by a solution model that includes ion association to form NaSO(4)(-), Na(2)SO(4)(0), HSO(4)(-), H(2)SO(4)(0), and NaHSO(4)(0). The adjustable parameters of this model are the dissociation constants of the SO(4)(-) species and the H(+), SO(4)(-2), and HSO(4)(-) conductances (ion mobilities) at infinite dilution. For the 673 K and 230 kg m(-3) state point with the lowest dielectric constant, epsilon = 3.5, where the Coulomb interactions are the strongest, this model does not fit the experimental data above a solution molality of 0.016. Including the species H(9)(SO(4))(5)(-) gave satisfactory fits to the conductance data at the higher concentrations.     

The finite element approximation of a coupled reaction-diffusion problem with non-Lipschitz nonlinearities

Summary. A coupled semilinear elliptic problem modelling an irreversible, isothermal chemical reaction is introduced, and discretised using the usual piecewise linear Galerkin finite element approximation. An interesting feature of the problem is that a reaction order of less than one gives rise to a "dead core" region. Initially, one reactant is assumed to be acting as a catalyst and is kept constant. It is shown that error bounds previously obtained for a scheme involving numerical integration can be improved upon by considering a quadratic regularisation of the nonlinear term. This technique is then applied to the full coupled problem, and optimal and error bounds are proved in the absence of quadrature. For a scheme involving numerical integration, bounds similar to those obtained for the catalyst problem are shown to hold. Received May 25, 1993 / Revised version received July 5, 1994     

Pulsed photothermal laser deflection for low-level smoke and NO2 measurements in engine exhausts

Pulsed Photothermal Laser Deflection (PLD) is developed to make temporally and spatially resolved measurements of NO₂ and smoke. The rapid response PLD signal is produced when a HeNe probe beam is deflected by a thermal lens produced by a pulsed XeCl-excimer laser pumped dye laser. The fast time response (30 ns) and good spatial resolution make the PLD method a candidate for future in situ measurements in turbulent engine exhausts. The PLD signals, measured in a sample cell, exhibit a linear response for NO₂ concentrations from 3 ppm to 208 ppm and for smoke concentrations from 0.3 mg/m³ to 10 mg/m³. With a low pulse energy of 4 mJ, single-shot PLD measurements in a sample cell have accuracies of ± 14 ppm for NO₂ indicating accuracies of ±0.7 mg/m³ for smoke. With increased pulse energy and multi-shot averaging, sensitivities of ± 0.4 ppm of NO₂ or ± 20 µg/m³ of smoke are expected.