The correlation of the stability constants of 1,3-dicarbonylic monochelates of Iron(III) with the acid dissociation constants of the ligand

The variation of the logrithms of stability constants of iron(III) monochelated compounds with structurally similar 1,3-dicarbonylic compounds has been found to be an essentially linear function of the negative logarithms of the acid ionization constant of the ligands. An analytical correlation which could be useful to predict equilibrium constants of iron(III) chelates has been developed. From spectrophotometric and potentiometric data a quantitative evaluation of the stability of the complex has been carried out. Results have provided information regarding substituent effects on the equilibrium constants.     

Enthalpies of formation of methoxybenzoic acids and their dependence on structure

The energy of combustion of 2,5-dimethoxybenzoic acid has been determined using a static bomb calorimeter. The vapor pressures of the compound have been measured over a 18 K temperature interval by the Knudsen effusion technique. Heat capacity measurements betweenT=270 K andT=338 K were carried out by DSC. From these experimental results the standard molar enthalpies of combustion, sublimation, and formation in the crystalline and gaseous state at the temperature 298.15 K have been derived. With this compound, the series of mono- and dimethoxy-benzoic acids have been completed. Their_f H _m ^o values were expressed by an additive relationship, taking into account the number of methoxy groups and the number of all 1,2 interactions: an accuracy of 3.3 kJ·mol^–1 was achieved. In an alternative approach the substituent effect of the methoxy groups was evaluated within the framework of isodesmic reactions. The effect of disubstitution was referred to mono derivatives and the excess energy—the so-called buttressing effect—was evaluated (2–24 kJ· mol^–1 for individual bis derivatives). These values were explained in terms of the conformation of the methoxy group around the C_ar-O bond.     

Synthesis of new colloidal formations during the strengthening of different activated hydrated metallurgical slags

This paper reports on a comparison of experimental researches on the hydration hardening of different types of dumped ferrous slag (DFS) (blast furnace, open hearth, electric steel and converter), non-activated and activated with small (2%) additions of Portland cement or lime. Activation was found to accelerate the strengthening processes in the early stages of hydration resulting from the growth of colloidal sol–gel new formations in a more alkaline environment. Over time, these formations became denser and transformed into stone-like amorphous materials with a uniaxial strength of up to 47.6 MPa at 1 year of age. All these types of slag can, therefore, be used in different applications, for example, like traditional binders, such as Portland cement, to different ceramic goods, new construction materials, etc. But till now the results of this research were used only for the preparing of binder materials for natural soils strengthening as road bases in Russia. Highways whose roadbeds were built with these DFS as binder materials have shown excellent performance indices in different parts of Russia, including Siberia and northern regions.     

The extraordinary ability of guanidinate derivatives to stabilize higher oxidation numbers in dimetal units by modification of redox potentials: structures of Mo(2)(5+) and Mo(2)(6+) compounds

Full characterization of the first homologous series of dimolybdenum paddlewheel compounds having electronic configurations of the types sigma(2)pi(4)delta(x), x = 2, 1, 0, and Mo-Mo bond orders of 4, 3.5, and 3, respectively, has been accomplished with the guanidinate-type ligand hpp (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). Essentially quantitative oxidation of Mo(2)(hpp)(4), 1, by CH(2)Cl(2) gives Mo(2)(hpp)(4)Cl, 2. The halide in 2 can be replaced by reaction with TlBF(4) to produce Mo(2)(hpp)(4)(BF(4)), 3. Further oxidation of 2 by AgBF(4) produces Mo(2)(hpp)(4)ClBF(4), 4. The change from bond order 4 (in 1) to 3.5 in Mo(2)(hpp)(4)Cl is accompanied by an increase in the Mo-Mo bond length of 0.061 to 2.1280(4) A. A further increase of 0.044 A in the Mo-Mo distance to 2.172(1) A is observed as the bond order decreases to 3 in 4. At the same time, the Mo-N distances decrease smoothly as the oxidation state of the Mo atoms increases. Electrochemical studies have shown two chemically reversible processes at very negative potentials, E(1)(1/2)= -0.444 V and E(2)(1/2)= -1.271 V versus Ag/AgCl. These correspond to the processes Mo(2)(6+/5+) and Mo(2)(5+/4+), respectively. The latter potential is displaced by over 1.5 V relative to those of the Mo(2)(formamidinate)(4) compounds and the first one has never been observed in such complexes. Thus, in surprising contrast to previously observed behavior of the dimolybdenum unit, when it is surrounded by the very basic guanidinate ligand hpp, there is an extraordinary stabilization of the higher oxidation numbers of the molybdenum atoms.     

Asymptotic stability at infinity of planar vector fields

Let >0 andX be aC ¹ vector field on the plane such that: (i) for allq², Det(DX(q))>0; and (ii) for allp², with p, Trace(D(X(p))<0. IfX has a singularity and ² Trace(DX)dxdy is less than 0 (resp. greater or equal than 0), then the point at infinity of the Riemann sphere ²{} is a repellor (resp. an attractor) ofX.     

Determination of metal impurities in electrolytic iron by GF-AAS using electric dispersion in liquid medium

A laboratory-built electrospark system, operated in liquid medium, is used as dispersion method for metallic samples. The metallic colloidal solutions formed upon electrocorrosion behave as typical lyophobic colloidal systems, which are highly stable. The parameters influencing the formation of the colloidal solutions are optimized so that the electrospark system can be used in combination with graphite furnace-atomic absorption spectrometry for trace metal determinations. Dispersion rates for electrolytic iron range from 50 to 125 g min^–1, depending on the power. The colloidal solutions show the same atomization behaviour as true solutions, which makes calibration with aqueous standards feasible. The method has been used to determine manganese, chromium und copper in the NIST SRM 665 electrolytic iron.     

Quantum field theory in curved space-time as thermo field dynamics

The strong analogy between states defined in the context of quantum field theory in curved space-time (QFT-CST) and the ones defined in the thermo field dynamics (TFD) of Takahashi and Umezawa [1] is shown. This analogy is useful in order to introduce the entropy operator in CST in the same way as in TFD. When the extremum condition in the thermodynamical potential is imposed, a family of Bogoliubov transformations that give us a planckian spectrum is found, even in pathological cases such as the minimally coupled scalar field.     

Normsets and determination of unique factorization in rings of algebraic integers

The image of the norm map from to (two rings of algebraic integers) is a multiplicative monoid . We present conditions under which is a UFD if and only if has unique factorization into irreducible elements. From this we derive a bound for checking if is a UFD.