Mesogenic system simulation in the liquid state of aggregation

The results of computer simulation of nematic liquid crystals under the conditions of the liquid state of aggregation are presented. The problems and advantages of such an approach are considered.     

Solid state reactions between nickel(II) sulphide and oxides of manganese and iron

Thermogravimetry and differential thermal analysis have shown that, when nickel(II) sulphide and manganese or iron oxides are heated together, several reactions occur depending on the molar ratio of the reactants. Detailed examinations of these reactions have shown that there are a number of intermediate stages, including the formation of sulphates.

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Zusammenfassung Thermogravimetrie und Differentialthermoanalyse zeigen, daß bei gemeinsamer Erhitzen von Nickel(II)-Sulfid und Manganoder Eisenoxiden, in Abhängigkeit von dem Molarverhältnis der Reaktionspartner verschiedene Reaktionen stattfinden. Das eingehende Studium dieser Reaktionen zeigte das Auftreten einer Anzahl Zwischenstufen, darunter auch die Bildung von Sulfaten.

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Résumé On montre par thermogravimétrie et analyse thermique différentielle que plusieurs réactions peuvent se produire suivant les rapports molaires des constituants lorsque l'on chauffe du sulfure de nickel(II) avec des oxydes de manganèse ou de fer. L'étude détaillée de ces réactions a mis en évidence un certain nombre d'étapes intermédiaires, avec formation de sulfates.

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A permeation liquid membrane system for determination of nickel in seawater

The use of a permeation liquid membrane system for the preconcentration and separation of nickel in natural and sea waters and subsequent determination by atomic absorption spectroscopy is presented. 2-Hydroxybenzaldehyde N-ethylthiosemi-carbazone (2-HBET) in toluene is used as the active component of the liquid membrane. A study strategy based on a simplex design has been followed. Several chemical and physical parameters were optimized. Maximum permeation coefficient was obtained at a feed solution pH of 9.4, 0.3 mol l⁻¹ of HNO₃ in the stripping solution and 1.66 mmol l⁻¹ of 2-HBTE in toluene as carrier. The precision of the method was 4.7% at 95% significance level and a detection limit of 0.012 μg l⁻¹ of nickel was achieved. The preconcentration procedure showed a linear response within the studied concentration range from 3 to 500 μg l⁻¹ of Ni in the feed solution. The method was validated with different spiked synthetic seawater and certified reference water samples: TMDA-62 and LGC 6016, without matrix interferences and showing good concordance with the certified values, being the relative errors −5.9% and −2.2%, respectively. Under optimal conditions, the average preconcentration yield for real seawater samples was 98 ± 5%, with a nickel preconcentration factor of 20.83 and metal concentrations ranging between 2.8 and 5.4 μg l⁻¹.     

Phase state of iron system colloidal catalyst in butadiene polymerization

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Density of nickel + nickel chloride liquid mixtures

The density of liquid NiCl₂ and Ni + NiCl₂ liquid mixtures has been determined at 1323 K by the γ-ray absorption method, described previously. This method has been used for the first time in the measurement of the absolute density of a molten salt. The excess molar volume of the Ni + NiCl₂ mixtures is zero within the accuracy of the measurement.     

Non-destructive determination of nickel in iron meteorites

Application of a portable radioisotope X-ray fluorescence analyser for the determination of nickel in iron meteorites is described. The error of the XRF method was ±0.5% Ni at the 95% confidence level, which was confirmed by comparison with the results of other authors. In spite of limited accuracy this version of the radioisotope XRF method may find a wide application in meteorite studies, for rapid and non-destructive verification and classification of collected meteorite specimens.     

Features of phase formation and state of iron in the quasibinary system FeTe1.65-TiTe1.65

A series of tellurides Fe_xTi_1?x Te_1.65 (x = 0, 0.1, 0.2 …, 1.0) synthesized at 850°C were studied by X-ray phase and X-ray fluorescent analysis and Møssbauer spectroscopy on ⁵⁷Fe. In this series two solid solutions are formed: phases I and II with homogeneity regions within the limits of 0 ≤ x ≤ 0.3 and 0.9 ≤ x ≤ 1.0, respectively. Iron in this series exists in two various states: Fe²⁺ _sym and Fe²⁺ _asym as differentiated from the series of tellurides Fe_xTi_1?x Te_1.45 where three states of iron Fe²⁺ _sym, Fe²⁺ _asym, and Fe⁰ were found. On passing from Fe_xTi_1?x Te_1.45 to Fe_xTi_1?x Te_1.65 the number of formed phases decreases, and phase relations become simpler. The absence of Fe⁰ from phase I of tellurides Fe_xTi_1?x Te_1.65 can point to the fact that TiTe_1.45 and TiTe_1.65 belong to different homogeneity regions.     

One-dimensional iron(II) compounds exhibiting spin crossover and liquid crystalline properties in the room temperature region

A novel series of 1D Fe(II) metallomesogens have been synthesized using the ligand 5-bis(alkoxy)- N-(4 H-1,2,4-triazol-4-yl)benzamide (C n -tba) and the Fe(X) 2. sH 2O salts. The polymers obey the general formula [Fe(C n -tba) 3](X) 2. sH 2O [X = CF 3SO 3 (-), BF 4 (-); n = 4, 6, 8, 10, 12]. The derivatives with n = 4, 6 exhibit spin transition behavior like in crystalline compounds, whereas those with n = 8, 10, 12 present a spin transition coexisting with the mesomorphic behavior in the room-temperature region. A columnar mesophase has been found for the majority of the metallomesogens, but also a columnar lamellar mesophase was observed for other derivatives. [Fe(C 12-tba) 3](CF 3SO 3) 2 represents a new example of a system where the phase transition directly influences the spin transition of the Fe(II) ions but is not the driving energy of the spin crossover phenomenon. The compounds display drastic changes of color from violet (low-spin state, LS) to white (high-spin state, HS). The compounds are fluid, and it is possible to prepare thin films from them.     

High-performance liquid chromatography of deferoxamine and ferrioxamine: interference by iron present in the chromatographic system

The assay of the complexed (ferrioxamine) and uncomplexed forms of deferoxamine, a strong iron(III) chelating agent, by reversed-phase high-performance liquid chromatography was investigated. Complex formation with trace amounts of iron in the chromatographic system hinders the assay of deferoxamine by causing appearance of unexpected peaks, reaction zones and variations in retention time. By purging the column with deferoxamine and using EDTA in the mobile phase, these adverse effects in the determination of deferoxamine were eliminated. No interference by iron contamination of the chromatographic system was found in the assay of ferrioxamine, which is facilitated by the strong absorption of the analyte at 430 nm.     

Chemical analysis in the submillimetre spectral region with a compact solid state system

A new analytical system that uses the rotational signatures of gas phase molecules is described and demonstrated. It uses a solid state source to probe molecular systems in the millimetre and submillimetre wave range, the only region of the electromagnetic spectrum not yet used extensively for analytical purposes. It employs the FAst Scan Submillimetre Spectroscopy Technique (FASSST), which leads to an especially simple system architecture. Among the attributes of the system are generality, sensitivity, 'absolute' specificity, small size, simplicity, and the potential for very low cost. Applications to problems of analytical interest are also discussed.     

Anion-exchange separation of iron,cobalt and nickel

From 90% acetone-10% 6 M hydrochloric acid medium, cobalt and nickel are strongly adsorbed on the anion-exchange resin Dowex I-X8; iron is not adsorbed and can thus be separated from cobalt and nickel. Cobalt and nickel are then separated by elution with 70% acetone-30% 2 M hydrochloric acid; nickel is eluted before cobalt. The method can be applied to the determination of nickel and cobalt in materials with high iron content such as steels ; compleximetric titrations are used for the final step.     

Quantitative colorimetric-imaging analysis of nickel in iron meteorites

A quantitative analytical imaging approach for determining the nickel content of metallic meteorites is proposed. The approach uses a digital image of a series of standard solutions of the nickel-dimethylglyoxime coloured chelate and a meteorite sample solution subjected to the same treatment as the nickel standards for quantitation. The image is processed with suitable software to assign a colour-dependent numerical value (analytical signal) to each standard. Such a value is directly proportional to the analyte concentration, which facilitates construction of a calibration graph where the value for the unknown sample can be interpolated to calculate the nickel content of the meteorite. The results thus obtained were validated by comparison with the official, ISO-endorsed spectrophotometric method for nickel.The proposed method is fairly simple and inexpensive; in fact, it uses a commercially available digital camera as measuring instrument and the images it provides are processed with highly user-friendly public domain software (specifically, ImageJ, developed by the National Institutes of Health and freely available for download on the Internet).In a scenario dominated by increasingly sophisticated and expensive equipment, the proposed method provides a cost-effective alternative based on simple, robust hardware that is affordable and can be readily accessed worldwide. This can be especially advantageous for countries were available resources for analytical equipment investments are scant. The proposed method is essentially an adaptation of classical chemical analysis to current, straightforward, robust, cost-effective instrumentation.     

Molar enthalpy at five compositions in the NaNO3NaOH system in the liquid and solid states

The molar enthalpies of the two compounds and three eutectics in the NaNO₃NaOH system were determined over the 450–630 K temperature range by means of drop calorimetry. The enthalpy changes over the 500–550 K range, which in all cases includes melting, are usefully large from the viewpoint of energy storage: 5.7 (79), 5.2 (83), 5.1 (87), 5.1 (93) and 3.5 (73) kcal mole^?1 (cal g^?1) in 0.710 NaNO₃·0.290 NaOH, 0.500 NaNO₃·0.500 NaOH, 0.411 NaNO₃·0.589 NaOH, 0.327 NaNO₃·0.673 NaOH and 0.178 NaNO₃·0.822 NaOH, respectively. At χ_NaOH = 0.822, a high, negative heat of mixing (0.7–0.8 kcal mole^?1) was noted. This is contrary to what has been observed in other common cation-mixed anion molten salt solutions.     

Polymorphic modifications of iron in the thin-film state

The structure of iron in the thin-film state on silicon (planes (100) and (111)) and quartz substrates was studied. The formation of a mixture of the α- and δ-iron phases on silicon plane (111) and the stabilization of the high-temperature δ phase by photon annealing were demonstrated. The orienting effect of plane (100) on the development of the δ → α transition with complete vanishing of the δ-iron phase during annealing was established. The crystallization of thin iron films only in the α modification on an amorphous substrate was shown.     

Oxygen solubility in liquid nickel containing zirconium

The solubility of oxygen in liquid nickel containing zirconium at 1873 K has been experimentally studied for the first time. It has been shown that zirconium is a rather strong deoxidizing agent in liquid nickel. The equilibrium constant of the reaction of zirconium and oxygen dissolved in liquid nickel (logK_(1)(Ni) =–6.788), the interaction parameters characterizing these solutions (e_Zr(Ni)^O =–2.01; e_O(Ni)^Zr =–0.35; e_Zr(Ni)^Zr = 0.24), and the activity coefficient of zirconium in nickel at infinite dilution (γ_Zr(Ni)^o = 1.03 × 10^–8) have been determined. The zirconium content at the minimum of the oxygen solubility curve and the corresponding oxygen concentration have been determined.     

On-line microdialysis-nano-Au/TiO2-high-performance liquid chromatography system for the simultaneous determination of cobalt and nickel in water

An on-line configuration of microdialysis (MD), Au/TiO2 nanoparticle preconcentration, and high-performance liquid chromatography-ultraviolet (HPLC-UV) detection method was developed for the simultaneous measurement of cobalt (Co) and nickel (Ni) concentrations in water. The sample matrix was first cleaned with an MD system using a MD probe. A continuously flowing dialysate stream was introduced into tubing coated with Au/TiO2 nanoparticles to adsorb metals, followed by elution by an acidic eluent. The enriched samples were derivatized on-line using 8-hydroxyquinoline. The separation of Co and Ni were achieved by using a LC-C18 column. The three aforementioned system components were connected on-line using a valve control. The UV detection was performed at 319nm. Validation experiments demonstrate good linearity, precision, accuracy, and recovery. The proposed method offers a simple and reliable procedure to determine the levels of Co and Ni in environmental water samples. Moreover, the methodology described in this study adheres to the concept of green chemistry, including the absence of organic solvents in the MD sampling and extraction processes. To the best of our knowledge, the proposed method is the first reported on-line connection of MD, Au/TiO2 nanoparticle tubing, and HPLC devices for the measurement of Co and Ni concentrations in water.     

Reversed phase foam chromatography : Separation of iron from copper,cobalt and nickel in the tri-n-butyl phosphate-hydrochloric acid system

The separation of iron from cobalt, copper and nickel by reversed-phase foam chromatography was investigated. The distribution of Fe, Co and Cu in TBP-HCl and TBP(polyurethane foam)-HCl systems was measured. Iron can be separated from the three other metals on polyether-type polyurethane foam columns loaded with TBP. The break-through curve of iron on TBP (polyurethane foam) columns was measured. The column was found suitable for the separation of ⁵⁸Co and ⁵⁹Fe isotopes.