The use of densimetry and fixed-cell scanning calorimetry to probe solute and solution structure and reactions from 270 K to 400 K

We have used a vibrating-tube densimeter to investigate the densities and volumetric properties of aqueous solutions, and a fixed-cell scanning calorimeter to measure aqueous solution heat capacities. Solutions investigated include sugars, neutral weak acids and bases, neutralized acids and bases, neutral and protonated amino acids, surfactants, and both strong and ion-paired electrolytes. We have made measurements at molalities m from 0.005 mol·kg⁻¹ to 0.5 mol·kg⁻¹, at temperatures T from 278.15 K to 393.15 K, and at the pressure P = 0.35 MPa. We have calculated the apparent molar volumes V_φ and apparent molar heat capacities C_p,φ of the solutions and fit them by regression to equations that describe the surfaces (V_φ, T, m) and (C_p,φ, T, m). These results reflect changes and differences in both solute-solute and solute-solvent interactions. Standard state partial molar volumes V₂° and heat capacities C_p,2° were estimated by extrapolation to the M = 0 mol·kg⁻¹ plane of the fitted surfaces. We have calculated (Δ_r,C_p,m, T, m) surfaces for various proton dissociation reactions, and we have created surfaces representing (Δ_rH_m, T, m) and (pQ_a, T, m) by integration of our (Δ_rC_p,m, T, m) surfaces using values for (Δ_rH_m, m) and (pK_a, m) at a reference T as integration constants. We have also created surfaces representing (Δ_rS_m, T, m) and (Δ_rV_m, T, m) for these dissociation reactions.     

A two-dimensional pseudospectral model for time reversal and nonlinear elastic wave spectroscopy

One way to characterize metallic materials in the presence of defects like dislocation networks is to measure their large dynamic nonlinear elastic response. In this numerical study, a new method combining the nonlinear elastic wave spectroscopy (NEWS) method with a time reversal (TR) process is proposed. This method, called NEWS-TR, uses nonlinear analysis as a pretreatment of time reversal and then consists of retrofocusing only nonlinear components on the defect position. A two-dimensional pseudospectral time domain algorithm is developed here to validate the NEWS-TR method as a potential technique for damage location. Hysteretic nonlinear behavior of the materials being studied is introduced using the Preisach-Mayergoyz model. Moreover, in order to extend this solver in two dimensions, the Kelvin notation is used to modify the elastic coefficient tensor. Simulations performed on a metallic sample show the feasibility and value of the NEWS-TR methodology for microdamage imaging. Retrofocusing quality depends on different parameters such as the filtering method used to keep only nonlinear components and the nonlinear effect measured. In harmonic generation, pulse inversion filtering seems to be a more appropriate filtering method than classical harmonic filtering for most defect positions, mainly because of its ability to filter all fundamental components.     

Bellman Systems with Mean Field Dependent Dynamics

The authors deal with nonlinear elliptic and parabolic systems that are the Bellman like systems associated to stochastic differential games with mean field dependent dynamics. The key novelty of the paper is that they allow heavily mean field dependent dynamics. This in particular leads to a system of PDE’s with critical growth, for which it is rare to have an existence and/or regularity result. In the paper, they introduce a structural assumptions that cover many cases in stochastic differential games with mean field dependent dynamics for which they are able to establish the existence of a weak solution. In addition, the authors present here a completely new method for obtaining the maximum/minimum principles for systems with critical growths, which is a starting point for further existence and also qualitative analysis.     

Computing the canonical height on K3 surfaces

Let be a surface in given by the intersection of a (1,1)-form and a (2,2)-form. Then is a K3 surface with two noncommuting involutions and . In 1991 the second author constructed two height functions and which behave canonically with respect to and , and in 1993 together with the first author showed in general how to decompose such canonical heights into a sum of local heights . We discuss how the geometry of the surface is related to formulas for the local heights, and we give practical algorithms for computing the involutions , , the local heights , , and the canonical heights , .

     

Critical properties of non-spherical molecule fluids from the virial expansion

Critical constants of pure fluids (as important reference data in constructing vapour-liquid phase diagrams and basic input of various estimation methods) were determined for systems of non-spherical Kihara molecules; values of the critical temperature, density, compression factor and pressure of fluids composed of prolate and oblate molecules were evaluated from the fourth-order virial expansion. The second and third virial coefficients of the Kihara molecules were determined by applying the recently proposed method in which the effect of molecular core geometry and functional dependence of a pair interaction on the surface-surface distance are factorized and the former contribution determined from a formula for the corresponding hard convex body virial coefficient. The virial expansion for non-spherical Kihara molecules is applied to determine the critical constants of n-alkanes (methane to octane) and cyclic hydrocarbons (cyclopentane, cyclohexane, benzene and naphthalene); a fair agreement with experimental data was found.     

Critical properties of non-spherical molecule fluids from virial expansion

For systems of Kihara molecules with circular cores, the values of the reduced critical constants were determined from the fourth-order virial expansion as functions of the core diameter/thickness ratio. From expressions for the reduced functions both for the oblate and prolate shapes, the values of critical constants of four cyclic hydrocarbons and four branched alkanes were evaluated and compared with the experimental data and values obtained from the perturbation theory.     

Photo‐ and Electrocatalytic H2 Production by New First‐Row Transition‐Metal Complexes Based on an Aminopyridine Pentadentate Ligand

The synthesis and characterisation of the pentadentate ligand 1,4‐di(picolyl)‐7‐(p‐toluenesulfonyl)‐1,4,7‐triazacyclononane (Py₂^Tstacn) and their metal complexes of general formula [M(CF₃SO₃)(Py₂^Tstacn)][CF₃SO₃], (M=Fe ( 1_Fe ), Co ( 1_Co ) and Ni ( 1_Ni )) are reported. Complex 1_Co presents excellent H₂ photoproduction catalytic activity when using [Ir(ppy)₂(bpy)]PF₆ ( PS_Ir ) as photosensitiser (PS) and Et₃N as electron donor, but 1_Ni and 1_Fe result in a low activity and a complete lack of it, respectively. On the other hand, all three complexes have excellent electrocatalytic proton reduction activity in acetonitrile, when using trifluoroacetic acid (TFA) as a proton source with moderate overpotentials for 1_Co (0.59 V vs. SCE) and 1_Ni (0.56 V vs. SCE) and higher for 1_Fe (0.87 V vs. SCE). Under conditions of CH₃CN/H₂O/Et₃N (3:7:0.2), 1_Co (5 μM ), with PS_Ir (100 μM ) and irradiating at 447 nm gives a turnover number (TON) of 690 (n/n) and initial turnover frequency (TOF) (TON×t^?1) of 703 h^?1 for H₂ production. It should be noted that 1_Co retains 25 % of the catalytic activity for photoproduction of H₂ in the presence of O₂. The inexistence of a lag time for H₂ evolution and the absence of nanoparticles during the first 30 min of the reaction suggest that the main catalytic activity observed is derived from a molecular system. Kinetic studies show that the reaction is ?0.7 order in catalyst, and time‐dependent diffraction light scattering (DLS) experiments indicate formation of metal aggregates and then nanoparticles, leading to catalyst deactivation. By a combination of experimental and computational studies we found that the lack of activity in photochemical water reduction by 1_Fe can be attributed to the 1_Fe ^II/I redox couple, which is significantly lower than the PS_Ir ^III/II , while for 1_Ni the pK_a value (?0.4) is too small in comparison with the pH (11.9) imposed by the use of Et₃N as electron donor.     

ChemInform Abstract: Photoelectron Spectroscopy and ab initio Study of the Structure and Bonding of Al7N‐ and Al7N.

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