Phase Diagram of the System NaF-KF-AlF3

The phase diagrams of the binary system KF-AlF₃ as well as the ternary system NaF-KF-AlF₃ in the range up to 50 mol% AlF₃, were measured using the thermal analysis method. In the system KF-AlF₃ the coordinates of the eutectic points are: E ₁: 8.0 mol% AlF₃, 821.2°C, and E ₂: 45.5 mol% AlF₃, 565.0°C. In the investigated concentration range of the ternary system 2 eutectic points have been found with the calculated coordinates: E ₁: 36.3 mol% NaF, 62.7 mol% KF, 1.0 mol% AlF₃; t=711.2°C; and E ₂: 51.9 mol% NaF, 27.4 mol% KF, 20.7 mol% AlF₃; t=734.5°C. Other eutectic points lie most probably beyond the investigated part of the system. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Analysis of the System Na3AlF6–NaVO3

Summary. The phase diagram of the system Na₃AlF₆–NaVO₃ was determined by means of thermal analysis. The system is a simple binary eutectic one. The eutectic point was estimated at x(NaVO₃) = 0.975 and t _eut = 617°C. The XRD patterns of samples after thermal analysis revealed the presence of cryolite and NaVO₃ only supporting the above assumption of a simple eutectic binary system.     

Discontinuous alkylation of diphenylamine with nonene for maximum catalyst utilization

This study examines the alkylation of diphenylamine (DPA) with nonene (NON) in a liquid phase catalyzed by acid-treated clay-based catalysts from commercial suppliers (Fulcat 22B, Nobelin MM, and Jeltar 300). Alkylations were conducted to achieve the highest possible selectivity of diisononyldiphenylamine (DNDPA), low selectivity of monoisononyldiphenylamine, and a maximum triisononyldiphenylamine yield of 4%. This study also examines the reaction conditions to selectively form dialkylated diphenylamine from DPA and NON in a batch reactor. Repeated use of the catalyst during the alkylation of DPA with NON was also investigated. Catalyst deactivation takes place during the alkylation of each batch and intensifies with repeated catalyst use, resulting in low DNDPA selectivity. The regenerated catalyst was sufficiently active only until the regeneration of the first and second batches. After the third batch, the catalyst’s selectivity for DNDPA was very low, and its reuse in the alkylation of DPA with NON was not efficient. Therefore, to achieve the maximum length of catalyst activity, the fresh catalyst was gradually added to the used catalyst from a previous batch, thus maintaining a high activity of eight batches. The reduction in catalyst activity was probably caused by the irreversible adsorption of substances on the surface, a loss of microporous structure, and a loss of surface acidity. DPA or alkylated products are adsorbed on the surface oxygen of the catalyst through nitrogen and form nitro formations. The fresh and regenerated catalysts were characterized by their surface area, surface acidity, pore size distribution, and pore volume.     

Phase diagrams of the KF-K<Subscript>2</Subscript>TaF<Subscript>7</Subscript> and KF-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> systems

The phase diagrams of the systems KF-K₂TaF₇ and KF-Ta₂O₅ were determined using the thermal analysis method. The phase diagrams were described by suitable thermodynamic model. In the system KF-K₂TaF₇ eutectic points at x _KF=0.716 and t=725.4°C and at x _KF=0.214 and t=712.2°C has been calculated. It was suggested that K₂TaF₇ melts incongruently at around 743°C forming two immiscible liquids. The system KF-Ta₂O₅ have been measured up to 8 mol% of Ta₂O₅. The eutectic point was estimated to be at x _KF∼0.9 and t∼816°C. The formation of KTaO₃ and K₃TaO₂F₄ compounds has been observed in the solidified samples.     

Phase diagram of the system NaF-SnF<Subscript>2</Subscript>

The phase diagram of the binary system NaF-SnF2 was determined by using the thermal analysis method. In addition to the crystallisation fields of pure components the formation of three other crystallisation fields was observed and these were attributed to the compounds: NaF·2SnF₂, NaF·SnF₂ and 2NaF·SnF₂. The coordinates of the four eutectic points are: e ₁: 70 mol% NaF, 30 mol% SnF₂ and 255°C e ₂: 58 mol% NaF, 42 mol% SnF₂ and 238°C e ₃: 44 mol% NaF, 56 mol% SnF₂ and 246°C e ₄: 18 mol% NaF, 82 mol% SnF₂ and 191°C The model independent on the real structure of the melt was applied for the calculation of phase diagram comprising the calculation of excess molar Gibbs energy of mixing. The probable inaccuracy in the calculated phase diagram is σ=2.0°C. XRD analysis of solidified mixtures was performed in order to confirm the formation of expected compounds.     

Electrochemical behaviour of the LiF-(CaF2)-La2O3 system

The electrochemical behaviour of the LiF-La₂O₃ and LiF-CaF₂-La₂O₃ systems was investigated by means of cyclic voltammetry. Several types of working electrodes (spectrographic pure graphite, W, Mo, Ni, Cu) were used. It was found that chemical reactions take place in the system during the dissolution of lanthanum oxide. The reduction of lithium cations occurred at the most positive potential from the species formed in the melt on ‘inert’ cathodes (W, Mo). The reactive cathodes (Cu, Ni) allowed the lanthanum deposition with depolarisation.     

Kinetics of the conversion reaction of gypsum with ammonium carbonate

The reactivity of flue gas desulphurization gypsum with ammonium carbonate has been studied in the temperature range (20–50) °C. Mechanism of this reaction was suggested and the kinetics parameters characterizing the reaction were determined. A mathematical model suitable for the prediction of the conversion of gypsum was proposed. The reaction is of the second order. Influence of the size of gypsum particles on the relationship between the surface and volume of the particles is not significant. From the obtained experimental results, it follows that the reaction does not proceed at the surface of the solid gypsum particles, but in the liquid phase between dissolved gypsum and ammonium carbonate. The diffusion of the dissolved gypsum through the liquid film formed at the surface of the solid gypsum particles is the rate-limiting step of the conversion reaction.     

Electrochemical behaviour of lanthanum fluoride in molten fluorides

The electrochemical behaviour of lanthanum fluoride dissolved in molten lithium fluoride and in eutectic mixture LiF-CaF₂ was investigated by cyclic voltammetry and laboratory electrolysis. The cyclic voltammetry experiments were carried out at 900°C and 800°C, respectively, in a graphite crucible (counter electrode). Several types of working electrodes (Mo, W, Ni and Cu) were used. Ni/Ni(II) was used as a reference electrode. Laboratory electrolysis was carried out in the system LiF-CaF₂-LaF₃ at 800°C in galvanostatic (j _c = −0.21 A cm⁻²) and potentiostatic (E = 0.87 V) regimes. In both cases, nickel served as the cathode and graphite as the anode. It was found that no new separate reduction peak occurred on the molybdenum or tungsten electrodes in the investigated systems. When copper or nickel electrodes were used, new peaks corresponding to the reduction of lanthanum(III) to lanthanum metal appeared. This can be explained by the formation of alloys or intermetallic compounds of lanthanum with copper or nickel. X-ray microanalysis showed that lanthanum was electrodeposited together with calcium under formation of intermetallic compounds with the electrode materials in the galvanostatic regime. In the potentiostatic regime, mainly lanthanum was deposited, which enabled its separation.     

Phase diagram of the system KF-K<Subscript>2</Subscript>TaF<Subscript>7</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

As an asymmetric organic molecular crystal, p-N,N-dimethylaminobenzaldehyde (DAB) exhibits peculiar optical property. It was first grown by solution technique adopting slow evaporation method at room temperature using CCl₄ as growth medium. The solubility of DAB increases with temperature. Good quality transparent crystals of p-N,N-dimethylaminobenzaldehyde were carefully collected and subjected various characterization studies such as UV, FTIR, ¹H and ¹³CNMR spectral studies and thermal (TG-DTG) studies to determine the purity and application oriented properties of the grown crystals.     

Reactions of sulphides in molten cryolite

The freezing point depression of cryolite (Na₃AlF₆) by the addition of Al₂S₃ and FeS was investigated. It was found that for contents of up to 10 wt.% Al₂S₃, it brings into the melt three new species. X-ray analysis of solidified melts of the system Na₃AlF₆–Al₂S₃ showed that it contained chiolite, Na₅Al₃F₁₄ and Na₂S. Chiolite originates from a reaction between Na₃AlF₆ and AlF₃. This suggests that the system Na₃AlF₆–Al₂S₃ is a part of the reciprocal system NaF, AlF₃//Na₂S, Al₂S₃. The solubility of FeS in cryolite melt is so low that it cannot be determined by the thermal analysis. When FeO is added to the Na₃AlF₆–Al₂S₃ melt, Fe²⁺ cations and S²⁻ anions react under the formation of solid FeS. A similar reaction was observed for Ni²⁺ and S²⁻ ions.