X-ray diffraction study of some mesogenic copper, nickel and vanadyl complexes

We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes.     

Rapid spectrophotometric determination of chlorate with dimedone bisthiosemicarbazone monohydrochloride

Summary Dimedone bisthiosemicarbazone monohydrochloride has been examined to evaluate its usefulness as a reagent for rapid and sensitive Spectrophotometric determination of chlorate (0.5–5.0 ppm) by oxidation of the reagent in 70% perchloric acid medium and measurement of the yellow product. The molar absorptivity at 417 nm is 1.86×10⁴ l·mole^–1·cm^–1. The relative standard deviation is 1.6% for 2.5 ppm of chlorate.

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Spektropbotometrische Bestimmung von Chlorat mit Dimedonbisthiosemicarbazon-monocblorhydrat (I)

Zusammenfassung Die Verwendbarkeit von I als Reagens für die rasche und empfindliche spektrophotometrische Bestimmung von 0,5–5,0 ppm Chlorat durch Oxydation von I in 70%iger Perchlorsäure und Messung des gelben Reaktionsproduktes wurde untersucht. Die molare Absorptivität bei 417 nm beträgt 1,86×10⁴ l·mol^–1·cm^–1. Die relative Standardabweichung beträgt 1,6% für 2,5 ppm Chlorat.

     

Consecutive reactions in chemical kinetics: A method for the treatment of experimental data

A method is proposed for the treatment of data from a kinetic system of first order consecutive reactions by using an optimization procedure which converges to the correct solution of the two mathematically possible solutions and which does not need initial estimates of the parameters close to those to be determined.

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Dehydrogenation of cyclohexane over supported Pd catalysts, II. Influence of the support and reduction temperature

We have studied the activity of Pd/sepiolite and Pd/SiO₂–AlPO₄ catalysts in cyclohexane aromatization. The catalysts were characterized by H₂ chemisorption measurements. The influence of support and reduction temperature on the metal surface properties and activity of the catalysts is discussed.     

A queueing system with linear repeated attempts,bernoulli schedule and feedback

We analyse a single-server retrial queueing system with infinite buffer, Poisson arrivals, general distribution of service time and linear retrial policy. If an arriving customer finds the server occupied, he joins with probabilityp a retrial group (called orbit) and with complementary probabilityq a priority queue in order to be served. After the customer is served completely, he will decide either to return to the priority queue for another service with probability ϑ or to leave the system forever with probability =1−ϑ, where 0≤ϑ<1. We study the ergodicity of the embedded Markov chain, its stationary distribution function and the joint generating function of the number of customers in both groups in the steady-state regime. Moreover, we obtain the generating function of system size distribution, which generalizes the well-knownPollaczek-Khinchin formula. Also we obtain a stochastic decomposition law for our queueing system and as an application we study the asymptotic behaviour under high rate of retrials. The results agree with known special cases. Finally, we give numerical examples to illustrate the effect of the parameters on several performance characteristics.     

The degree of hybridization in paramagnetic complexes

It is argued that in a series of complexes formed by ions of the same type and having the same geometry and ligand the degree of hybridization $\text{?}{}_{\mathrm{s}}\text{?}{}_{\mathrm{\sigma }}$ tends to decrease when covalency increases. This rule which discards any sp² explanation for the ligand hybridization has been well verified through series of d⁹ and s¹ complexes. The validity of such a rule, also useful for understanding the behaviour of $\text{?}{}_{\mathrm{s}}\text{?}{}_{\mathrm{gs}}$ in some D_2h systems, outlines that ligand core polarization effects are negligible in these cases.     

Ultrasonic studies of attenuation and dispersion in NH4Br near the order-disorder transition

Velocity and attenuation of sound wave propagation along the [100] direction in NH₄Br were measured near its transition temperature T_c = 234.5 K at frequencies of 30–150 MHz. The experimental results for the high-frequency attenuation and the dispersive velocity shifts are found to be in good agreement with the model of a single critical relaxation time.     

A simple model for magnetic after-effects in magnetite at room temperature

Magnetic after-effects in vacancy-doped magnetite at room temperature are considered on the basis of a statistical thermodynamic treatment. In this paper we study the kinetics of a very small vacancy concentration distributed on the four non-equivalent octahedral sites of the inverse spinel structure. It is to be noted that satisfactory agreement is found between recent experimental results and the theoretical model.     

Enhancement of the emission yield of silicon nanocrystals in silica due to surface passivation

The ability of surface passivation to enhance the photoluminescence (PL) emission of Si nanocrystals in SiO₂ has been investigated. Silicon precipitation in implanted samples takes place in a time scale of few minutes at 1100°C. For longer annealing at the same temperature, the PL intensity of the Si nanocrystals increases and eventually reaches saturation, while it correlates inversely with the amount of Si dangling bonds at the Si–SiO₂ interface (P_b centers), as measured by electron spin resonance. This combined behavior is independent on the silica matrix properties, implantation profiles and annealing atmosphere and duration. The observation that the light emission enhancement is directly related to the annealing of P_b centers is confirmed by treatment in forming gas. This mild hydrogenation at much lower temperature (450°C) leads to a complete passivation of the P_b defects, increasing at the same time the PL yield and the lifetime.