Ternary Reciprocal System K,Pb∥Cl,WO<Subscript>4</Subscript>

The phase diagram of the ternary reciprocal system K, Pb∥Cl, WO₄ was studied for the first time by the calculation–experimental method and differential thermal and X-ray powder diffraction analyses. Chemical interactions between components were described, metathesis and complexation reactions were revealed, and the coordinates of binary and ternary eutectics were found (mol %): e₄(410°C, 48% KCl, 52% PbCl₂), e₅(424°C, 23% KCl, 77% PbCl₂), P(490°C, 63.5% KCl, 36.5% PbCl₂), e₆(487°C, 91% PbCl₂, 9% PbWO₄), e₇(428°C, 30.5% KCl, 60.5% PbCl₂, 9% PbWO₄) (eutectic in the stable section D₂–PbWO₄), e₈(650°C, 80% KCl, 20% PbWO₄), e₉(650°C, 70% KCl, 15% K₂WO₄, 15% PbWO₄) (binary eutectic in the stable section D₁–KCl), E₁(620°C, 59% KCl, 34% K₂WO₄, 7% PbWO₄), E₂(640°C, 75% KCl, 5% K₂WO₄, 20% PbWO₄), E3(400°C, 46% KCl, 6% PbWO₄, 48% PbCl₂), E₄(410°C, 21% KCl, 9% PbWO₄, 70% PbCl₂), and P_о(468°C, 56% KCl, 10% PbWO₄, 34% PbCl₂).     

Study of phase equilibria and boundary elements in the KBr-KVO3-K2MoO4 ternary system

By differential thermal analysis, the coordinates of the following characteristic points in the KBr-KVO₃-K₂MoO₄ system were determined: a eutectic in the KBr-KVO₃ system (12% KBr, 88% KVO₃, T _melt = 458°C), a eutectic in the KBr-KVO₃-K₂MoO₄ ternary system (12.8% KBr, 84.7% KVO₃, 2.5% K₂MoO₄,T _melt = 430°C), and also three points of polymorphic transitions in K₂MoO₄ ((1) δ ? γ: 21.7% KBr, 72.3% KVO₃, 6% K₂MoO₄,T _melt = 476°C; (2) γ ? β: 19% KBr, 78% KVO₃, 3% K₂MoO₄,T _melt = 450°C; and (3) γ ? β: 6% KBr, 89% KVO₃, 5% K₂MoO₄,T _melt = 450°C). For elements of the ternary system, phase equilibria were described.     

LiF-LiBr-LiVO<Subscript>3</Subscript> and LiBr-Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>-LiVO<Subscript>3</Subscript> ternary systems

Phase equilibria in the LiF-LiBr-LiVO₃ and LiBr-Li₂SO₄-LiVO₃ systems have been investigated by differential thermal analysis. Eutectic compositions have been revealed (mol %). In the LiF-LiBr-LiVO₃ system, 16.8% LiF, 52.0% LiBr, 31.2% LiVO₃ with a melting point of 428°C; in the LiBr-Li₂SO₄-LiVO₃ system, 52.0% LiBr, 38.0% LiVO₃, 10.0% Li₂SO₄ with a melting point of 444°C. Crystallization fields of the phases have been demarcated.     

Solubility in the LaCl<Subscript>3</Subscript>-LnCl<Subscript>3</Subscript>-HCl-H<Subscript>2</Subscript>O (Ln = Pr,Nd) Systems at 25°C

The solubility in the quaternary water-salt systems LaCl₃-NdCl₃-HCl-H₂O (1) and LaCl₃-PrCl₃-HCl-H₂O (2) at 25°C was studied in the section of 40 wt % hydrochloric acid, a system with a eutonic discontinuity. The composition at the point of discontinuity for the eutonic solution is the following. In system 1: 4.67 wt % LaCl₃ · 7H₂O, 0.37 wt % PrCl₃ · 7H₂O, 37.98 wt % HCl, and 56.98 wt % H₂O; in system 2: 4.37 wt % LaCl₃ · 7H₂O, 0.93 wt % NdCl₃ · 6H₂O, 37.88 wt % HCl, and 56.82 wt % H₂O.     

Use of Neodymium Diiodide in the Synthesis of Organosilicon, ‐Germanium and ‐Tin Compounds

The reactivity of neodymium diiodide, NdI₂ ( 1 ), towards organosilicon, ‐germanium and ‐tin halides has been investigated. Compound 1 readily reacts with Me₃SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Me₃Si)₂O (19 %). The reaction with Et₃SiBr in THF results in formation of Et₃SiSiEt₃ (17 %) and Et₃SiOBuⁿ (34 %). Alkylation of Me₃SiCl with PrⁿCl in the presence of 1 in THF affords Me₃SiPrⁿ (10 %), Me₃SiOBuⁿ (52 %) and Me₃SiSiMe₃ (1 %). The main product identified in the reaction mixture formed upon interaction of 1 with dichlorodimethylsilane Me₂SiCl₂ in THF is di‐n‐butoxydimethylsilane Me₂Si(OBuⁿ)₂ (54 %) together with minor amounts of Me₂Si(OBuⁿ)Cl. The reaction of 1 with Me₃GeBr under the same conditions produces Me₃GeGeMe₃ (44 %), Me₃GeH (3 %), and Me₃GeI (7 %). An analogous set of products was obtained in the reaction with Et₃GeBr. Treatment of trimethyltin chloride with 1 causes reduction of the former to tin metal (74 %). Me₃SnH (7 %) and hexamethyldistannane (11 %) were identified in the volatile products. The reaction of 1 with Me₃SiI provides straightforward access to hepta‐coordinated NdI₃(THF)₄ ( 2 ), the structure of which was determined by X‐ray diffraction.     

Solid–liquid Equilibria in the Quaternary System Na+, Mg2+//Cl–, SO2–4–H2O at 25 and 30°C

The isoplethic sections in the diagram of the quaternary system Na⁺ , Mg²⁺ //Cl^– , SO^2– ₄ –H₂ O were established at 25 and 30oC by analytical and conductometric measurements. Three compounds can be observed in the isoplethic sections: NaCl, Na₂ SO₄ and MgNa₂ (SO₄ )₂ 4 H₂ O. Seven fields are determined, relating to the precipitation of one, two or three salts. The solubility range of MgNa₂ (SO₄ )₂ 4 H₂ O is wide, while the liquidus curve of Na₂ SO₄ is very short. The compositions, expressed in Jänecke coordinates, at the eutonic and peritonic points, respectively, were: 42.70% Cl^– and 745% H₂ O; 79.47% Cl^– and 787% H₂ O; 71.6% Cl^– and 744% H₂ O at 25°C; and 48.80% Cl^– and 715% H₂ O; 80.20% Cl^– and 778% H₂ O; 70.14% Cl^– and 707% H₂ O at 30°C.     

Multicomponent systems LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript> and LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>

Phase equilibria in the LiCl–LiBr–Li₂SO₄ ternary system and the LiCl–LiBr–Li₂SO₄–Li₂MoO₄ quaternary system were studied by differential thermal analysis. The compositions and temperatures of minima in the ternary and quaternary systems were determined to be (31.2 mol % LiCl, 46.8 mol % LiBr, 22.0 mol % Li₂SO₄, 460°C) and (25.2 mol % LiCl, 30.2 mol % LiBr, 14.6 mol % Li₂SO₄, 30.0 mol % Li₂MoO₄, 411°C), respectively.     

Li,K‖Cl,MoO4 ternary mutual system

Phase equilibria in the Li,K‖Cl,MoO₄ ternary mutual system were studied by differential thermal analysis (DTA). The characteristics of the following three ternary eutectics were determined: E ₁: 348°C, 41 mol % KCl, 7.75 mol % Li₂MoO₄, and 51.25 mol % LiCl; E ₂: 475°C, 44 mol % KCl, 17.25 mol % Li₂MoO₄, and 38.75 mol % LiCl; and E ₂: 477°C, 35 mol % KCl, 47 mol % Li₂MoO₄, and 18 mol % LiCl.     

High Temperature Oxidation of Fe22Cr-alloy

The isothermal and constant heating rate oxidation behaviour of the alloy Fe₇₈Cr₂₂ was examined in air with 1% H₂O and in 7% H₂/93% Ar with 1% or 12% H₂O. The measurements were performed in the temperature range 700–1300°C. The effect of surface treatment prior to oxidation was examined. A Cr₂O₃ scale developed slowly up to900°C. At 1100°C a catastrophic oxidation was observed after heat treatment for 70 h in air with 1% H₂O and in 7% H₂/93% Ar with 12% H₂O. The scale developed in these cases consisted of iron rich oxides such as Fe₂O₃ or FeCr₂O₄, in contrast to the more protective Cr₂O₃ scale seen under other test conditions. Possible causes for the catastrophic oxidation are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Enrichment of Zinc and Iron Micronutrients in Lentil (Lens culinaris Medik.) through Biofortification

Biofortification of pulse crops with Zn and Fe is a viable approach to combat their widespread deficiencies in humans. Lentil (Lens culinaris Medik.) is a widely consumed edible crop possessing a high level of Zn and Fe micronutrients. Thus, the present study was conducted to examine the influence of foliar application of Zn and Fe on productivity, concentration, uptake and the economics of lentil cultivation (LL 931). For this, different treatment combinations of ZnSO₄·7H₂O (0.5%) and FeSO₄·7H₂O (0.5%), along with the recommended dose of fertilizer (RDF), were applied to the lentil. The results of study reported that the combined foliar application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at pre-flowering (S1) and pod formation (S2) stages was most effective in enhancing grain and straw yield, Zn and Fe concentration, and uptake. However, the outcome of this treatment was statistically on par with the results obtained under the treatment ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. A single spray of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage enhanced the grain and straw yield up to 39.6% and 51.8%, respectively. Similarly, Zn and Fe concentrations showed enhancement in grain (10.9% and 20.4%, respectively) and straw (27.5% and 27.6% respectively) of the lentil. The increase in Zn and Fe uptake by grain was 54.8% and 68.0%, respectively, whereas uptake by straw was 93.6% and 93.7%, respectively. Also the benefit:cost was the highest (1.96) with application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. Conclusively, the combined use of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage can contribute significantly towards yield, Zn and Fe concentration, as well as uptake and the economic returns of lentil to remediate the Zn and Fe deficiency.     

Oxidative Dehydrogenation of Propane to Propene over Barium Promoted Ni-Mo-O Catalyst

Oxidative dehydrogenation of propane to propene was investigated over Ba- promoted Ni_0.9MoO₄ catalysts (molar ratio of Ba/Mo: 1%, 3%, 6%, 9%, 12%, 15%). The selectivity for propene increases with the increasing number of basic sites on the catalyst, and molybdenum ions play an important role in propane activation. No significant deactivation of the 6% Ba- Ni_0.9MoO₄ and Ni_0.9MoO₄ at 773 K for 80 h and for 40 h, respectively, appeared, indicating that the 6% Ba- Ni_0.9MoO₄ has great advantage over the Ni_0.9MoO₄. This revised version was published online in June 2006 with corrections to the Cover Date.     

The effects of surface treated carbon fibers and CaCO<Subscript>3</Subscript> nanoparticles inclusions on the mechanical performances of PA6/ABS-based composites

The mechanical and morphological characteristics of PA6/ABS (60/40)-based hybrid composite containing HNO₃-treated short carbon fibers (HSCF) and CaCO₃ nanoparticles have been experimentally studied. A counter-rotating twin-screw extruder and an injection molding machine were employed to produce different samples containing 10 wt % of HSCF and 0, 2, 5 and 8 wt % of CaCO₃ nanoparticles. The SEM observations indicated high-quality adhesion between HNO₃-surface treated carbon fibers and PA6/ABS polymer matrix. In addition, the morphological studies showed that the inclusion of CaCO₃ nanoparticles caused a significant effect on the ABS particle dispersion in PA6/ABS matrix. The mechanical properties assessments revealed that the incorporation of 10 wt % HSCF into the PA6/ABS can significantly improve tensile strength (82%), tensile modulus (107%), flexural strength (98%), flexural modulus (104%) and impact resistance (24%). The inclusion of CaCO₃ nanoparticles, in the presence of 10 wt % HSCF, led to the noticeable improvements of tensile strength (128% for 2 wt % CaCO₃), tensile modulus (199% for 5 wt % CaCO₃), flexural strength (146% for 5 wt % CaCO₃), flexural modulus (204% for 5 wt % CaCO₃) and impact resistance (46% for 2 wt % CaCO₃). The surface treatment of carbon fibers, dispersion conditions of nanoparticles and ABS phase in polymeric matrix were found to be the major important factors affecting the mechanical properties.     

Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides

The potential of trichloroisocyanuric acid (TCCA) as a chlorination agent for efficient conversion of Si-H functional silanes and siloxanes to the corresponding Si-Cl functional moieties was explored. In comparison to methods using other chlorinating agents, TCCA is inexpensive, results in a much faster reaction and produces a high purity product with a conversion that is essentially quantitative. A variety of chloro derivatives of linear and cyclic structures have been synthesized from silicon hydrides using this reagent with impressive yields that typically exceed 90%: PhSiCl₃ (97.5%); PhMeSiCl₂ (95.5%); Ph₃SiCl (97.5%); Vi₃SiCl (98.7%); (EtO)₃SiCl (99.7%); t-Bu₃SiCl (∼100%); (MeClSiO)₄ (86.5%); (MeClSiO)₅ (95%); (MeClSiO)₇ (96.5%); Ph(OEt)₂SiCl (98%); ClMe₂SiOSiMe₂Cl (98.6%); ClMe₂SiOSiMeClOSiMe₂Cl (94.6%); ClMe₂Si(OSiMeCl)₂OSiMe₂C l (92.3%); (Me₃SiO)₃SiCl (97%); Me₃SiOSiClPhOSiMe₃ (99%); Me₃SiO(SiMeClO)₃SiMe₃ (95.7%); ClSi(OSiMe₃)₂OSi(OSiMe₃) ₂Cl (93.6%).For monohydridosilanes, dichloromethane (CH₂Cl₂) was a suitable solvent in which nearly quantitative conversion was observed within several minutes following the addition of the silanes to TCCA. For certain cyclic and linear siloxanes, and especially silanes containing multiple hydrogen atoms on the same silicon for which the reaction is sluggish in CH₂Cl₂, tetrahydrofuran (THF) was the preferred solvent. For a sterically demanding silane that did not undergo chlorination even in THF viz., HSi(OSiMe₃)₂O-Si(OSiMe₃)₂H, 1,2-dichloroethane was the best solvent.     

Transport Coefficients of Ag–SiO<Subscript>2</Subscript> Plasmas

Calculated values of viscosity, thermal and electrical conductivities of plasma formed in mixtures of silver (Ag) and silica (SiO₂) are presented. The calculations, which assume local thermodynamic equilibrium, are performed for three pressures (1, 10 and 30 atm) in the temperature range from 4,000 to 30,000 K. All the data for the potential interactions and the necessary formulations to obtain values of transport coefficients are given in details. For atmospheric pressure, five mixtures (100% Ag, 75% Ag and 25% SiO₂, 50% Ag and 50% SiO₂, 25% Ag and 75% SiO₂, 100% SiO₂) in weight percentage are studied. In order to analyse the pressure influence on the transport coefficients, three samples of Ag–SiO₂ mixtures (100% Ag, 50% Ag and 50% SiO₂, 100% SiO₂) in weight percentage are discussed for pressures of 1, 10 and 30 atm. In addition for the test case of oxygen plasma, we compare the computation code results with values obtained by other authors: discrepancies are found and explained.      

Catalysis of heteropoly acidic salts for synthesis of diethylene glycol ethyl ether with diethylene glycol and ethanol

Ag₃PW₁₂O₄₀ and Ag₄SiW₁₂O₄₀ showed high activity and stability in the synthesis of diethylene glycol ethyl ether with diethylene glycol and ethanol, on which the conversion is 80.2% and 78.4%, respectively, and the selectivity of diethylene glycol ether is 75.4% and 80.6%, respectively. After the third reaction cycle, Ag₃PW₁₂O₄₀ and Ag₄SiW₁₂O₄₀) still showed higher activity and selectivity, on which the conversion is 72. 6% and 77.5% respectively. But the activity of Ag₃PMo₁₂O₄₀ is lower, the conversion is only 21.0%. IR, XRD, TG and n‐butylamine titrimetry showed that the catalysis may be connected with two kinds of acidic centers owned by heteropoly acidic salt.     

Aromatic polyamides. III. Copoly(4,4′-oxanilideterephthalamide—4,4′-phenyleneterephthalamide): Synthesis,wet-spinning,fiber thermal characterization,and stability in sulfuric acid

Copoly(4,4′-oxanilideterephthalamide—4,4′-phenyleneterephthalamide) (A-202/PPD) was synthesized by reaction of 4,4′-diaminooxanilide, p-phenylenediamine, and terephthaloyl chloride in organic solvents. Copolymer inherent viscosities in H₂SO₄ as high as 10.3 were obtained. Isotropic copolymer solutions (4%—5% concentration) of A-202/40%–80% PPD were spun to fibers with tenacity/elongation/modulus at 1% extension in the 13–14 gpd/1.5%–2%/700–1000 gpd range. Oxamide and amide stabilities in 98–100% H₂SO₄ and 20% oleum were compared. Poly(4,4′-oxanilideterephthalamide) (A-202), A-202/PPD copolymers, and poly(4,4′-phenyleneterephthalamide) (PPT) were unstable in 20% oleum, but all proved relatively stable in 100% H₂SO₄. However, the oxamide linkage proved less stable than the amide linkage in 98% H₂SO₄. A-202 and A-202/PPD copolymers formed stable anisotropic spinning solutions in 1% oleum at 10–20% concentrations. Dynamic mechanical analyses (Vibron) showed no glass transition temperature (T_g) below 200°C. Dilatometric measurement of A-202/50% PPD revealed a T_g at 257°C. Differential thermal analyses of A-202/40–80% PPD exhibited endotherms at 470–480°C. Thermogravimetric analyses showed no significant weight loss below 400°C.     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Oxidation of carbon monoxide in the presence of hydrogen on the CuO, CoO, and Fe2O3 oxides supported on ZrO2

The catalytic activity of the CuO/ZrO₂, CoO/ZrO₂, Fe₂O₃/ZrO₂, and CuO/(CoO, Fe₂O₃)/ZrO₂ systems in the reaction of selective CO oxidation in the presence of hydrogen was studied at 20–450°C over the oxide concentration range of 2.5–10 wt % on the surface of ZrO₂. The conversion of CO on the CoO/ZrO₂ systems was almost independent of the concentration of CoO: 88 or 90% for 2.5 or 10% CoO, respectively. TPR data allowed us to relate the catalytic activity of CoO/ZrO₂ to Co-O-Zr clusters, the amount of which was almost constant over the test range of CoO concentrations. The conversion of CO on 2.5% CuO/ZrO₂ was 32% (190°C) or 62–66% on 5–10% CuO/ZrO₂ (170°C). According to TPR data, clusters like Cu-O-Zr occurred on the surface of ZrO₂, and the amount of these clusters reached a maximum upon supporting 5% CuO. The catalytic properties of 5% CuO/5% CoO/ZrO₂ and 5% CoO/5% CuO/ZrO₂ samples were identical to those of 5% CuO/ZrO₂ samples. It is likely that the formation of active reaction sites upon consecutively supporting the oxides occurred on the same surface sites of ZrO₂. In this case, Co and Cu oxides competed for cluster formation, and the copper cation can displace the cobalt cation from the formed clusters. The Fe₂O₃ samples were inactive; a maximum conversion of 34% (290°C) was observed on 10% Fe₂O₃/ZrO₂. The catalytic properties of CuO/Fe₂O₃/ZrO₂ were also identical to those of CuO/ZrO₂, and they depended on the presence of Cu-O-Zr clusters on the surface.     

Microwave-assisted extraction of ginsenosides from ginseng root

The extractions of ginsenosides Rg₁ and Rb₁ from ginseng root under atmospheric pressure by focused microwave-assisted technique have been investigated. The parameters used for the optimization were solvent composition, extraction time, and applied microwave power. The ginsenosides were quantified by high-performance liquid chromatography equipped with UV/Vis detector. The results of the 15-min microwave-assisted extraction (0.28% of Rg₁ obtained in 70% water-ethanol and 1.31% of Rb₁ obtained in 30% water-ethanol under 150 W of microwave power) were better than that from 10-h conventional solvent extraction (0.22% of Rg₁ and 0.87% of Rb₁ obtained in 70% water-ethanol).     

Li, K‖Br, VO3 ternary mutual system

Phase equilibria in the Li, K‖Br, VO₃ ternary mutual system were studied by differential thermal analysis. The composition square of the ternary mutual system is divided into two phase triangles, LiVO₃-KBr-KVO₃ and LiBr-LiVO₃-KBr. The ternary eutectics E ₁ at 331°C and E ₂ at 330°C have the compositions 40.0 mol % LiVO₃, 6.0 mol % KBr, 54.0 mol % KVO₃ and 58.0 mol % LiBr, 3.2 mol % LiVO₃, 38.8 mol % KBr, respectively. The fields of phases crystallizing in the system were delimited.