Potentiometric Studies on Complexation of Cu(II) Ion with Methyl/Nitro-Substituted 1,10-Phenanthrolines and Selected Amino Acids

Protonation constants of methyl/nitro substituted 1,10-phenanthrolines {(m/n-sphen): 4-methyl-phenanthroline (4-mphen), 5-methyl-1,10-phenanthroline (5-mphen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10-phenanthroline (5-nphen)] and the amino acids (aa) l-tyrosine (tyr) and glycine (gly), and their corresponding binary and ternary stability constants with Cu(II), were determined in aqueous 0.1 mol·L^?1 KCl ionic media at 298.15 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. The species distribution diagrams were obtained using the “SPE” software package under the experimental conditions described. The order of stability of the ternary complexes in terms of the primary ligands is [Cu(tmphen)(aa)]⁺ > [Cu(dmphen)(aa)]⁺ > [Cu(4-mphen)(aa)]⁺ > [Cu(5-mphen)(aa)]⁺ > [Cu(5-nphen)(aa)]⁺. The stability constants of the ternary complexes decrease in the following order: [Cu(m/n-sphen)(gly)]⁺ > [Cu(m/n-sphen)(tyr)]⁺, which is identical to the sequence found for the binary complexes of Cu(II) with gly and tyr.     

Determination of low-level tritium concentrations in surface water and precipitation in the Czech Republic

Past tests of nuclear weapons in the atmosphere, nuclear energy facilities and tritium of natural origin are main sources of tritium in the environment. Thanks to its presence in environment and its favourable properties, tritium is used as a radiotracer. Since stopping of atmospheric nuclear tests, tritium in precipitation has been decreasing towards natural levels below 1 Bq l^?1 and precise analyses of low level tritium activities are necessary. This paper focuses on tritium development at sites not influenced by any technogenic release of tritium in Elbe River basin (Bohemia) in the Czech Republic using liquid scintillation measurement with electrolytic enrichment.     

Determination of vanadium in titanate-based ferroelectrics by INAA with discriminating gamma-ray spectrometry

Instrumental neutron activation analysis was used for determination of vanadium mass fraction in crystals of incipient ferroelectric strontium titanate and ferroelectric barium titanate. In order to improve vanadium limit of detection, discriminating gamma-ray spectrometry was used by inserting an absorption filter between the samples and an HPGe detector. The use of the absorption lead filter 6-mm thick yielded improvement of the vanadium limit of detection by a factor of two. The vanadium mass fraction determined in a quality control sample, which was NIST standard reference material SRM 1648 Urban Particulate Matter, was in close agreement with the certified value.

     

Determination of mechanical properties by instrumented indentation

The paper reviews the current state of the depth-sensing indentation (sometimes called nanoindentation), where the information on material behaviour and properties is obtained from the indenter load and depth, measured continuously during loading and unloading. It is shown how the contact parameters and principal characteristics are determined using pointed or spherical indenters. Indentation tests can be used for the measurement of hardness and elastic modulus, and also of the yield stress and for the construction of stress–strain diagrams, for the determination of the work of indentation and its components. Most devices use monotonic loading and unloading, but some also enable measurement under a small harmonic signal added to the basic monotonously increasing load. This makes possible continuous measurement of contact stiffness and the study of dynamic properties and the determination of properties of coatings. One section is devoted to the measurement on viscoelastic-plastic materials, where the delayed deforming must be considered during the measurement as well as in data evaluation. Instrumented indentation can also be used for the study of creep under high temperatures. The paper also discusses the errors arising in depth-sensing measurements and informs briefly about some other possibilities of the method.     

Inhomogeneous inverse problem in finite elasticity

For a class of materials for which the principal strain directions always coincide with the principal stress directions one can determine the stress field in an inhomogeneously deformed body from given boundary conditions and a known strain field without knowing the constitutive equations. Each point of the inhomogeneously deformed body contains information such as that derived from an individual homogeneous identification test. The practically important two-dimensional case leads to a problem of solving a linear hyperbolic system where two differential equations describe the principal stress components. The problem can be reduced to that of integration along characteristics.Under a certain globality condition the existence, uniqueness, and correctness of the solution are guaranteed in the whole test piece. It is shown that the globality condition is closely related to whether or not the test piece is isotropic and elastic. The influence of experimental error on the correctness of problem formulation is discussed.

---

Abstrakte Für die Klasse der Materialen, für welche die Grundspannungsrichtungen und die Grundverformungsrichtungen gleich sind, kann man das Spannungsfeld in einem inhomogen deformierten Körper für gegebene Randbedingungen und einem bekannten Verformungsfeld ohne Kenntnis der detailierten Form der Dehnungs-Spannungsgleichung bestimmen. Jeder Punkt des inhomogen deformierten Körpers liefert dieselbe Information wie ein individueller homogener Test. Der praktisch wichtige zweidimensionale Fall führt zu einem Problem der Lösung eines linear hyperbolischen Systems von zwei Differentialgleichungen für die Grundspannungskomponenten. Das Problem kann auf die Integration entlang der Charakteristik des Systems reduziert werden.Unter einer Bedingung der Globalität das die Existent, Eindeutigkeit und Richtigkeit der Lösung in der ganzen Testprobe gewährleistet sind. Es wird gezeigt, dass diese Globalitätsbedingung damit zusammenhängt eng, ob die Testprobe isotrop und elastisch ist. Der Einfluss der experimentellen Fehler auf die Richtigkeit der Formulation des Problems wird auch analysiert.

     

Rheological behaviour of two-phase flow of solid particles in a gas

The present investigation was concerned with the rheological behaviour of dilute suspensions of solid particles in a gas in a vertical cocurrent flow moving upwards. Starting from the experimentally determined dependence of the pressure drop on the concentration of solid particles and the Reynolds number of the carrier medium in the steady flow region, the rheological parameters were estimated using pseudo-shear diagrams. Air was the carrier medium and the dispersed phase was one of six fractions of polypropylene powder and five fractions of glass ballotini. The results show that the investigated two-phase systems have pseudoplastic character which becomes more pronounced with increases in concentration, equivalent diameter and density of solid particles in the flowing suspension. C _d coefficient of particle resistance - d _e equivalent diameter of particles - D column diameter - Fr Froude number - g gravitational acceleration - K rheological parameter - L length - n rheological parameter - p _t pressure drop due to friction - p _m total pressure drop - p _ag pressure drop due to acceleration of the gas phase - p _as pressure drop due to acceleration of the solid phase - p _g hydrostatic pressure of the gas phase - p _s specific effective weight of the dispersed phase - r radius - Re Reynolds number - Re _p Reynolds number of a particle - Re _G generalized Reynolds number - Re _G1 generalized Reynolds number relating to the end of the laminar flow region - Re _G2 generalized Reynolds number relating to the beginning of the turbulent flow region - w _z axial component of velocity - u _t steady free-fall velocity of a single particle - w average velocity - w _g average velocity of the gas phase - w _s average velocity of the dispersed phase of solid particles - relative mass fraction of solid particles - x _s volume fraction of solid particles - _g coefficient of pressure drop due to friction - µ dynamic viscosity - _g density of the gas phase - _m density of the suspension - _s density of solid particles - _ds density of the dispersed phase - _w shear stress at the wall     

Preparation,spectroscopic and magnetic characterization of Cu(cyclam)M(CN)<Subscript>4</Subscript> complexes exhibiting one-dimensional crystal structures (cyclam = 1,4,8,11-tetraazacyclotetradecane,M = Ni,Pd, Pt)

From the systems Cu(II)–cyclam–[M(CN)₄]^2? (cyclam = 1,4,8,11-tetraazacyclotetradecane; M = Ni, Pd, Pt), three cyanidocomplexes Cu(cyclam)M(CN)₄ [M = Ni (1), Pd (2), Pt (3)] were isolated and characterized by chemical analysis, IR and UV–VIS spectroscopy. The three compounds are isostructural, and their crystal structures are formed by quasi-linear chains exhibiting [–Cu(cyclam)–μ–NC–M(CN)₂–μ–CN–]_n composition. The Cu(II) atoms reside on centres of symmetry and are coordinated in the form of an elongated octahedron with mean equatorial Cu–N bonds of 2.015(12), 2.017(13) and 2.011(11) Å in (1), (2) and (3), respectively, and weakly N-bonded bridging cyanido ligands in the axial positions [2.5321(9) Å in (1), 2.518(2) Å in (2) and 2.549(3) Å in (3)]. Hydrogen bonds of the N–H···N_cyanido···H–N type link neighbouring chains, and a topologically square network of paramagnetic Cu(II) atoms is formed. The magnetic susceptibilities of all three complexes follow the Curie-Weiss law with a weak antiferromagnetic exchange coupling below 5 K.     

Low-density polyethylene in mixtures of hexane and benzene derivates

Preferential sorption, equilibrium swelling degree, and volume of the swollen membrane in systems low-density polyethylene + hexane + aromatic compound (benzene, methylbenzene, or ethylbenzene) were studied using gravimetric and dilatometric methods at the temperature of 25 °C. Aromatic compounds are preferentially sorbed in low-density polyethylene compared to hexane. Experimental volume changes of the membrane were found to be noticeably different from those calculated on the basis of mass sorption data under the assumption of additivity. This difference points to the existence of the interactions between the polymer and the surrounding liquid mixture. The volume swelling degree curves are close to each other in the whole concentration range of the binary liquid mixture (hexane + aromatics) suggesting that the attractive forces between the polymer chains are the deciding factor limiting the volume expansion of the membrane in all three systems to the same extent.     

Dependency of thermal and electrical conductivity on temperature and composition of Sn in Pb–Sn alloys

The variations of thermal conductivity with temperature for Pb–Sn alloys were measured using a radial heat flow apparatus. The variations of electrical conductivity with the temperature for same alloys were determined from the Wiedemann–Franz law by using the measured values of thermal conductivity. According to present experimental results, the thermal and electrical conductivity of Pb–Sn alloys linearly decrease with increasing temperature but exponentially increase with increasing the composition of Sn. The enthalpy of fusion and the change of specific heat for Pb–Sn alloys were also determined by means of differential scanning calorimeter (DSC) from heating trace during the transformation from eutectic liquid to eutectic solid.     

Mechanical properties of silica hydrogels prepared and aged at physiological conditions: testing in the compression mode

The mechanical properties for silica hydrogel prepared at physiological conditions are reported in this paper. The mechanical testing was performed in the compression mode determining the mechanical characteristics as a function of aging time in TRIS buffer up to 14 days. In addition to a typically used gradient method for Young’s modulus determination from the stress–strain curves, a new phenomenological model was proposed to describe the experimental data. The mechanical properties were stabilized after 2 days of aging, which was concluded from an increase in Young’s modulus between 90 and 400 kPa, an increase in stress at break between 50 and 100 kPa and by a decrease in relative deformation at break from 0.26 to 0.16. The height of samples was constant in the first three days of aging followed by a decrease by ~20%. Dissolving of silica hydrogel characterized through determination of silica content in TRIS buffer employing the molybdenum method was not found to be responsible for this phenomenon. The phenomenological model is proposed to be used for a reliable evaluation of mechanical properties of silica as well as other hydrogels exhibiting low Young’s modulus.