The ionization of perchloric and hydrofluoric acids in aqueous solution

Cyclical bifurcated hydrogen bonded structures are proposed for aqueous solutions of hydrofluoric acid and for the bifluoride ion which are consistent with the spectral data. The structure proposed for HF is also applicable to solutions in organic solvents. Raman spectra of tetramethylguanidinium perchlorate suggest that the corresponding Raman spectra of perchloric acid solutions may not be interpreted in terms of a completely dissociated acid. Other evidence including activity coefficient, heat capacity and partial molal volume data suggest that there is some association in relatively dilute perchloric acid solutions between the perchlorate ion and the hydrated proton. This association decreases in concentrated aqueous solutions.     

A generalized equation describing isotope exchange kinetics at solid-liquid interface

A generalization of the kinetic equation for the isotope exchange at solid—liquid interface is presented. The generalized equation may be used to describe kinetics of the isotope exchange process limited by surface reactions and diffusion without assumption of spherical symmetry of solid particles.

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Eine generalisierte Gleichung für die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen

Zusammenfassung Es wird eine generalisierte kinetische Gleichung angegeben, die die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen beschreibt, wobei der Austauschprozeß durch Oberflächenreaktionen und Diffusion ohne der Annahme sphärischer Symmetrie für die festen Partikel begrenzt ist.

     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.     

Theoretical study on intermolecular interactions in BrF/HnX adducts

Equilibrium geometries, interaction energies, and charge transfer for the intermolecular interactions between BrF and H_nX (HF, H₂O, and NH₃) were studied at the MP2/6-311++G(3d,3p) level. The halogen-bonded geometry and hydrogen-bonded geometry are observed in these interactions. The calculated interaction energies show that the halogen-bonded structures are more stable than the corresponding hydrogen-bonded structures. To study the nature of the intermolecular interactions, symmetry-adapted perturbation theory (SAPT) calculations were carried out and the results indicate that the halogen bonding interactions are dominantly inductive energy in nature, while electrostatic energy governs the hydrogen bonding interactions.     

Effect of hydrogen bonding of solvent on the thermodynamic stability of cadmium ethylenediamine complexes

Changes in the stability of the cadmium(ii) ethylenediamine complexes in mixed water—DMSO solvents were studied by pH-metry and calorimetry. Complex cations [Cd(en)]²⁺, [Cd(en)₂]²⁺, and [Cd(en)₃]²⁺ are formed in aqueous solutions, and the [Cd(en)₄]²⁺ complex with a partially dentate ligand is stable in DMSO. An increase in the DMSO content in a solvent increases the stability of the complexes. The maximum increase in logK is observed for coordinatively saturated compounds. The thermodynamics of complexation is discussed from the viewpoint of solvation approach. Principal differences in the influence of aqueous-alcohol and aqueous-aprotic solvents on the stability of the metal amino complexes were revealed. Protolytic solvents exert a destabilizing effect on the multiligand complexes, because the coordination sphere is involved in H bonding.     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

反应注射成型聚氨酯互穿聚合物网络研究——刚性网络对于体系形态及性能的影响

用微型反应注射成型机制备了以聚氨酯(PU)为弹性相的两类同步互穿聚合物网络(SIN),其刚性相分别采用保留仲羟基的乙烯基酯树脂(VERH)以及封闭仲羟基的乙烯基酯树脂(VERA)。用傅里叶变换红外光谱在线跟踪了这类互穿网络的生成过程,发现刚性网络抑制了PU网络中硬段有序结构的形成,两个网络间有一定程度的互穿,而两个网络间的化学键作用进一步削弱氢键强度。自旋—自旋弛豫时间的测定进一步表明网络间存在一定的互穿以及刚性相对于PU硬段结晶的抑制作用。材料的力学性能与其SIN的形态有关。VERA网络对PU表现出明显的增强作用,而由VERH网络形成的SIN则由于体系相分离进程受到严重阻碍而使材料性能恶化。     

Structural Elucidation of {[(CH3)2SnCl2·H2O]2·18-crown-6} n and its Hydrogen Bonding in Solution by HMBC Spectroscopy

Behavior of {[(CH₃)₂SnCl₂·H₂O]₂·18-crown-6}_n in solution have been investigated by HMBC NMR. The results show that coordination of water to tin containing species and its hydrogen bonding to crown ether remains intact in non-coordinating solvent in contrast to coordinating solvent. H-NMR reveals that the chemical shift of water in complex varies by solvent of crystallization.     

Study of Structures and Electronic Properties of Pdn–1Pb and Pdn （n≤8） Clusters

Geometric and electronic properties of Pdn–1Pb and Pdn (n≤8) clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic clusters. The average bond length of Pdn–1Pb (n≤8) bimetallic clusters is longer than that of pure palladium clusters except for n = 2 and 3. The most stable structure of Pdn–1Pb (n≤7) is the singlet where there is at least a Pd or Pb atom on its excited state. The energy gaps of Pd–Pb binary clusters are narrower than those of Pdn clusters, and then the chemical activity is strengthened when Pdn clusters are doped with Pb.     

Classification of oxide glasses: A polarizability approach

A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability α_O2−(n₀), optical basicity Λ(n₀), metallization criterion M(n₀), interaction parameter A(n₀), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials.