Homo- and hetero-nuclear chromium(III) complexes with natural ligands. Part 2. Oxo- and hydroxo-bridged chromium(III)/vanadium(V) species

Six new heteropolynuclear chromium(III)/vanadium(V) complexes with natural ligands: glycine, glutaminic, nicotinic and asparginic acids, have been isolated and physicochemically characterised. The complexes have been analysed using spectroscopic (diffuse reflectance u.v.–vis., i.r.), magnetic methods and by FAB mass spectra. Spectral analyses with the digital filter and band deconvolution methods are presented. Additionally, preliminary toxicity studies have been performed.     

Isotachophoretic determination of carboxylic acids in biodegradation samples

In the current study a method of isotachophoretic separation of selected carboxylic acids was developed. The method was used for the determination of carboxylated oligo(ethylene glycol)s and their degradation products in biodegradation tests of PEG 250 DA [a mixture of dicarboxylated oligo(ethylene glycol)s]. Two tests were performed in the studies: the Organization for Economic Cooperation and Development (OECD) screening test and the river water die-away test. Both the biodegradation tests proved relatively fast biodegradation of the studied compounds. In the OECD screening test the biodegradation was faster than in the river water die-away test which can be ascribed to a higher concentration of bacteria in the biodegradation liquor. The minimal sample pretreatment and relatively low cost of analysis by the isotachophoretic method used here make it a good alternative to existing methods of carboxylic acids analysis.     

Microanalysis of Volatile Organic Compounds (VOCs) in Water Samples – Methods and Instruments

Volatile organic compounds (VOCs), due to their toxicity and persistence in the environment, are particularly important pollutants. Some of these compounds are mutagens, teratogens or carcinogens, while others are responsible for the degradation of organoleptic parameters such as taste and odour of water. This review focuses on a number of key procedural steps in the analysis of volatile organic compounds (VOCs) in water samples. A wide spectrum of techniques for the isolation and preconcentration of the aforementioned pollutants for trace organic analysis by gas chromatography are presented and discussed. The advantages and disadvantages of these techniques are discussed and novel developments are also taken into consideration.     

Theory of electronic transport in two-dimensional systems in the presence of magnetic fields

Three parts of the paper [Czech. J. Phys.41 (1991) 620,7 are focused on the Landauer-Büttiker approach to the study of transport in two-dimensional electron systems, with particular attention to the influence of an external magnetic field. In the previous parts the Landauer formalism was generalized for two-dimensional systems in quantizing magnetic fields. In the present part we applied the formalism to an analysis of magnetoresistance measurements. The two-dimensional electron gas preserved in the non-dissipative quantum Hall regime acts as the ideal leads necessary in the Landauer-Büttiker approach. The voltage, applied to the gate, forms a scattering region in the gated part of the sample, in between of its undisturbed parts (ideal leads). The dependence of the resistance on the gate voltage and the number of available channels within the ideal leads are discussed.The author wishes to thank to Professor P. Steda for cooperation and to Professor L. Smrka for his encouragement and support. Dr. R. J. Haug should be acknowledged for providing his experimental results.     

Theory of electronic transport in two-dimensional systems in the presence of magnetic fields

The paper of three parts is focused on the Landauer-Büttiker approach to the study of transport in two-dimensional electron systems, with particular attention to the influence of an external magnetic field. In the previous part the total conductance of such a system was shown to be proportional to the transmission current. In the present part we give a detailed proof, based on the linear response theory, to the last statement. The value of the magnetic field may be arbitrary and possible inhomogeneity of the electric field is also considered.The author wishes to thank to Professor P. Steda and Professor L. Smrka for discussions and encouragement.     

The classification of differential structures on quantum 2-spheres

Exterior algebras of differential forms on quantum 2-spheresS _qc ² ,q[–1, 1]/{0},c[0, ] (c=0 forq=±1), are classified. In the definition of exterior algebras we assume the invariance w.r.t. the action of the quantumSU(2) group and dimensionality conditions (which imply that we deal with two-dimensional manifolds). The exterior algebras exist only forc=0 and are unique in that case. The corresponding generalized directional derivatives are provided.     

Non-smoothness of event horizons of Robinson-Trautman black holes

It is shown that generic small data Robinson-Trautman space-times cannot beC ¹²³ extended beyond the r=2m Schwarzschild-like event horizon. This implies that an observer living in such a space-time can determine by local measurements whether or not he has crossed the event-horizon of the black-hole.     

Self-diffusion of V-48 in the FeV σ-phase and in an Fe-47 wt.% V solid solution

Self-diffusion coefficients of vanadium in the FeV -phase and in the corresponding -solid solution (Fe-47 wt.% V) measured in the temperature ranges 1002–1115 °C (-phase) and 1230–1320 °C are reported. The found results differ fundamentally and significantly from the relations in ordered and disordered solid solutions [9]. The diffusivity in -phase at the transition temperature (T _/=1200 °C) is cca 14 times lower than the diffusivity in the b.c.c. solid solution, the chemical composition of which is the same. The lowering is caused by the different values of frequency factors,D _O=0.11 cm²/s andD _O=45 cm²/s. The effect of the corresponding activation enthalpiesH =252 kJ/mole andH =293 kJ/mole is small and quite opposite. The occurence of higher activation enthalpyH in the -solid solution at temperaturesT>T _/ may be attributed to a certain amount of the f.c.c. phase coexisting in the b.c.c. matrix at concentrationsc _v>27 wt.% at sufficiently high temperatures [7]. A comparison of vanadium self-diffusion characteristics measured in the -phase to the extrapolated values obtained on the basis of the previous measurements [1] in the Fe-V primary solid solutions ₁ shows that the diffusivity ratioD ₁/D (1473 K)=33 and that the activation enthalpyH is by about 3% higher than the valuesH ₁ (eq. (5)) measured in the uniphase b.c.c. solid solutions.     

Mechanism and nanosize products of the sol-gel reaction using diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as precursors

We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm.     

Thes-f model with Coulomb repulsion: Thermodynamics of two atomic cluster. Spin 1/2

A cluster of two atoms described by thes-f model with Coulomb repulsion has been considered. The interaction between localized 4f electrons (S=1/2) is taken in the molecular field approximation. The thermodynamic quantities like magnetization, specific heat and correlation functions n , n , S ^z n , S ^z n , S ^z (n –n ), n n and S ⁺ a ⁺ a as functions of temperature are presented for different band fillingN=0, 0.5, 1, 1.5, 2. The dependence of Curie temperature onN is calculated. The phase diagram forN=1 (T=0K) shows the possibility of existence of two phases: paramagnetic and ferromagnetic.The Curie temperature and the specific heat as functions ofN exhibit similar trends as found in experiments on doped magnetic semiconductors.