Numerical method of non-isothermal curve analysis by means of electrical resistance measurement during cooling

The temperature-dependence of the electrical resistance of Al-Zn 78 wt.% was measured during linear cooling of the samples in the range of eutectoidal decomposition. The resulting resistancevs. temperature curves were analysed by:

deriving the temperature-dependence of the volume fractionx(T) of theη precipitate;

fitting the theoretical functionx(T)=x _h (T)+x _c (T) following from numerical integration of the reaction rate equations for the simultaneously occurring homogeneous (H) and cellular (C) precipitation processes.

As a result, the activation energiesE _h andE _c , the JMA exponentsn _h andn _c , the rate constantsk _h andk _c , and the critical temperaturesT _o of the two processes were estimated.     

Effect of Mobile Phase pH* on Chromatographic Behaviour in Chiral Ligand-Exchange Thin-Layer Chromatography (CLETLC) of Amino Acid Enantiomers

The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated. It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7. The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7.     

On the separation of nonadditive symmetric mixtures in nanoscopic slitlike pores: A simple model for racemic fluids

A grand canonical ensemble Monte Carlo simulation method is used to study the adsorption of nonadditive symmetric mixtures of Lennard-Jones spherical particles in nanoscopic slitlike pores. The walls of the pore are assumed to be formed by the parallel (100) planes of the model face centered cubic crystal of adjustable corrugation potential. It is demonstrated that depending on the nonadditivity effects in the mixture and the pore width the condensed phases formed inside the pore may have different structures. In particular, it is shown that the mixture may separate into layers containing only one component each and the stacking may depend on the pore width and properties of the mixture.     

pH gradient high-performance liquid chromatography: theory and applications

pH gradient high-performance liquid chromatography (HPLC) is a method of reversed-phase high-performance liquid chromatography suitable for ionogenic substances. It consists in programmed increase during the chromatographic process of the eluting strength of eluent with respect to the analytes separated. On the analogy of the conventional organic modifier gradient reversed-phase HPLC, in the pH gradient approach the eluting strength of the mobile phase increases due to its changing pH: increasing in case of acids or decreasing in case of bases. At the same time the content of organic modifier remains constant. A theory of the pH gradient HPLC has been elaborated. The resulting mathematical model is easily manageable. Its ability to predict changes in retention and separation of analytes following the changes in chromatographic conditions is demonstrated. The pH gradient method is uniquely suitable to determine pKa values of analytes. An equation is presented allowing to calculate pKa values basing on appropriate retention data. The effects on pKa are discussed of the concentration of methanol in the mobile phase. The RP HPLC-derived pKa data correlate to the reference pKa values (w(w)pKa) but are not identical. That may be explained by the effects on the chromatographically determined pKa of the specific interactions of analytes with stationary phases. The proposed pH gradient RP HPLC procedure offers a fast and convenient means to get comparable acidity parameters for larger series of compounds, like drug candidates, also when the analytes are available only in minute amounts and/or as complex mixtures.     

Nitrate ion association with Nd3+

The overall stability constantsK ₁ andK ₂ of NdNO ₃ ²⁺ and Nd(NO₃) ₂ ⁺ complexes were determined (K ₁=1.77;K ₂=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio ₁/₂ of the stepwise stability constants is discussed. It was established that the Nd(NO₃) ₂ ⁺ complex was an outer-sphere ion pair.

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Die Assoziation von Nitrat-Ion mit Nd³⁺

Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK ₁ undK ₂ von NdNO ₃ ²⁺ - und Nd(NO₃)⁺-Komplexen bestimmt (K ₁=1.77;K ₂=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis ₁/₂ der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO₃)⁺-Komplex als ein Outer-Shere-Ionenpaar vorliegt.

     

The kinetics of tritium-hydrogen exchange in xanthosine,theobromine and monomethylated derivatives of xanthine

Tritium exchange at C-8 of xanthosine, theobromine, 1-, 3- and 7-methylxanthine in water has been studied. The rates of detritiation of these compounds have been determined over a pH range at constant temperature. Several mechanisms of exchange involving various ionic forms of substrate operating at different pH have been suggested.     

A study of the composition and properties of the ion-association complex of Rhodamine B with silicomolybdic acid, with a view to its analytical application

The composition of the ion-association complex of Rhodamine B with silicomolybdate has been examined by Job's method and spectrophotometric titration. The ratio of Rhodamine B to silicon in the complex is 4 : 1. The same ratio is obtained by analysis of the crystalline complex. The composition of the complex is identical in aqueous medium, an organic solvent (ethanol) and in the crystalline state (C(28)H(30)N(2)O(3))(4)SiMo(12)O(40)). The complex is stable in the organic solvent and has its absorption maximum at 555 nm and a molar absorptivity of 5 x 10(5) 1.mole(-1)cm(-1). The complex can be advantageously used for the determination of silicon.     

Solid-state equilibrium relations in the Ternary Systems TeO2?MoO3?MoO2 and TeO2?MoO3?Te

In a study of the solid-state reactions in the ternary systems TeO₂? MoO₃? MoO₂ and TeO₂? MoO₃? Te, approximately 70 selected compositions were sintered at 550°C to attain equilibrium conditions, and solid-state equilibrium relations were characterized by x-ray diffraction. In a large composition range, the interaction of TeO₂ and MoO₃ with the reducing agents MoO₂ or Te leads to the reduced ternary oxide TeMo₄O₁₃ (m. p. 748°C), in addition to Te₂MoO₇, Te and (intermediate) molybdenum oxides. The compatibility relations for the binary systems TeO₂? MoO₂ and MoO₃? Te are presented for the first time. In the TeO₂? MoO₂ system, three-phase regions are found: (Te₂MoO₇? TeO₂? Te) on the TeO₂? and (TeMo₄O₁₃? MoO₂? Te) on the MoO₂-rich sides with (TeMo₄O₁₃? Te₂MoO₇? Te) in the intermediate region. In the MoO₃? Te system, three-phase regions (TeMo₄O₁₃? MoO₂? Te), (TeMo₄O₁₃? Mo₄O₁₁? MoO₂) and (TeMo₄O₁₃? MoO₃? Mo₄O₁₁) were detected. TeMo₄O₁₃ presents two allotropic forms (α′ for T < 450°C, α for T > 450°C). Both structures have been characterized by I.R. and optical reflectance spectroscopy. Unit cell dimensions are also given.     

Optimization of stepwise gradient elution in reversed-phase chromatography

Summary Equations describing multi-step gradient elution with a mobile phase of constant composition in each step were derived. These equations useful for calculating the retention volumes in both gradient HPLC and TLC were derived on the basis of the relationship between the isocratic capacity factor and the volume fraction of the organic modifier. The validity of the equations was experimentally verified in a LiChrosorbRP-18-water/methanol system for 11 methyl- and chlorobenzenes and phenols. A satisfactory agreement between the theoretical and experimental k′ values was found.     

Synthesis and structure of a new rhodium(I) complex [Rh{P(OPh)3}3CN]

Summary The [Rh(acac){P(OPh)₃)}₂] complex (Hacac = 2,4-pentadione) reacts in solution with gaseous HCN in the presence of P(OPh)₃ to give [Rh{P(OPh)₃}₃CN]. Structural investigations of this complex including its³¹P n.m.r. spectra are reported.