Polymorphism of Bismuth Sesquioxide. I. Pure Bi2O3

Stability relationships of the four polymorphs of bismuth oxide have been determined by means of DTA and high-temperature x-ray studies. The stable low-temperature monoclinic form transforms to the stable cubic form at 730 ±5 °C, which then melts at 825 ± 5 °C. By controlled cooling, the metastable tetragonal phase and/or the metastable body-centered cubic (b.c.c.) phase appear at about 645 °C. Whereas b.c.c. can be preserved to room temperature, tetragonal will transform to monoclinic between 550 and 500 °C. Tetragonal Bi₂O₃, however, is easily prepared by decomposing bismutite (Bi₂O₃·CO₂) at 400 °C for several hours. The greatest transition expansion occurs at the monoclinic to cubic inversion, and cubic Bi₂O₃ shows the greatest coefficient of volume expansion. With exposure to air, Bi₂O₃ carbonates and partially transforms to bismutite and an unknown phase.     

Multifaceted activities of plant gum synthesised platinum nanoparticles: catalytic,peroxidase, PCR enhancing and antioxidant activities

A single pot, green method for platinum nanoparticles (Pt NP) production was devised with gum ghatti (Anogeissus latifolia). Analytical tools: ultraviolet–visible (UV‐vis), dynamic light scattering, zeta potential, transmission electron microscope, X‐ray diffraction (XRD), and Fourier transform infrared spectroscopy were employed. Wide continuous UV‐vis absorption and black solution colouration proved Pt NP formation. Face‐centred cubic crystalline structure of NP was evidenced from XRD. NPs formed were nearly spherical with a mean particle size of 3 nm. NP demonstrated a myriad of properties including catalytic, peroxidase, polymerase chain reaction (PCR) enhancing and antioxidant activities. Catalytic action of NP was probed via NaBH₄ reduction of arsenazo‐III dye. NP displayed considerable peroxidase activity via catalysis of 3, 3′, 5, 5′‐tetramethylbenzidine oxidation by H₂ O₂. NP showed exceptional stability towards varying pH (3–11), temperature (25–100°C), salt concentration (0–100 mM) and storage time duration (0–12 months). In comparison with horse radish peroxidase, its applicability as an artificial peroxidase is advantageous. NP caused a two‐fold enhancement in PCR yield at 0.4 nM. Also showed significant 1′, 1′ diphenyl picryl‐hydrazyle scavenging (80.1%) at 15 µg/mL. Author envisages that the biogenic Pt NP can be used in a range of biological and environmental applications.Inspec keywords: nanofabrication, ultraviolet spectra, catalysis, molecular biophysics, enzymes, dyes, platinum, electrokinetic effects, transmission electron microscopy, particle size, X‐ray diffraction, visible spectra, pH, nanomedicine, nanoparticles, biochemistry, light scattering, scanning electron microscopy, Fourier transform infrared spectra, reduction (chemical), oxidationOther keywords: antioxidant activities, catalytic action, salt concentration, artificial peroxidase, two‐fold enhancement, PCR yield, multifaceted activities, plant gum synthesised platinum nanoparticles, gum ghatti, anogeissus latifolia, analytical characterisation tools, dynamic light scattering, zeta potential, X‐ray diffraction, XRD, black solution colouration, Pt NP formation, face‐centred cubic crystalline structure, peroxidase activity, ultraviolet‐visible spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, particle size, catalytic activity, PCR enhancing activity, single pot green method, wide continuous UV‐visible absorption, polymerase chain reaction enhancing activity, arsenazo‐III, azo dye decolourisation, 3, 3′, 5, 5′‐tetramethylbenzidine oxidation, pH, environmental conditions, 1′,1′ diphenyl picryl‐hydrazyle scavenging, time 0.0 month to 12.0 month, temperature 25.0 degC to 100.0 degC, Pt     

Systems Silver Iodide-Sodium Iodide and Silver Iodide-Potassium Iodide

The phase relations for the systems AgI-NaI and AgI-KI have been determined for the temperature range from room temperature to 685° C, using differential thermal analysis techniques. The AgI-NaI system has a eutectic at 50 mole percent NaI and 384° C. The AgI-KI system has eutectics at 20.8 and 28.5 mole percent KI and 254° C and 244° C, respectively. A compound of formula KAg₃I₄ is formed with a congruent melting point of 268° C.     

Phosphinoborine Compounds: Mass Spectra and Pyrolysis

The mass spectra of tetramethylphosphinoborine trimer, [P(CH₃)₂B(CH₃)₂]₃ (I) and a a compound, P₅(CH₃)₉B₅H₉, (II) prepared from dimethylphosphinoborine were observed, and the compounds were pyrolyzed at 300 to 500° C. Most peaks in the spectrum of (I) came from the P—B, B—C, and P—C cleavages. The mass spectrum of (II) was much more complicated with evidence for methyl group redistribution.The pyrolysis of both compounds indicates a very complicated mechanism with many unidentifiable compounds. Trends in the formation of volatile products indicate that both compounds are completely decomposed in 4 hr at 450° C. Compound (I) produces trimethylboron, which disappears rapidly above 400° C. Neither (I) nor (II) formed ethane or elemental phosphorus.     

Phase Equilibrium Relations in the Binary System Barium Oxide-Niobium Pentoxide

A large portion of the phase equilibrium diagram for the binary system barium oxide-niobium pentoxide has been constructed from observations of fusion characteristics and X-ray diffraction data. In the system five binary compounds were observed with BaO: Nb₂O₅ ratios of 5:2, 1:1, 6:7, 3:5, and 1:3 and a 6:1 compound was postulated. The 1:1 compound was found to melt congruently at 1,455 °C and have only one stable polymorph, although a second metastable polymorph can also be prepared. The 5:2 compound melts congruently at 1,542 °C; the 6:7, 3:5, and 1:3 phases melt incongruently at 1,330, 1,290, and 1,315 °C, respectively. The phase relations of the 6:1 compound could not be determined due to the reaction between this phase and platinum metal. No 2:1 compound was observed in this system.     

Water Calorimetry: A Correction to the Heat Defect Calculations

In a recent publication, we used a reaction model (model III) to calculate the heat defect for the irradiation of aqueous solutions with ionizing radiation at 21 °C. Subsequent work has revealed that the literature value used for one of the rate constants in the model was incorrect. A revised model (model IIIR) incorporates the correct rate constant for 21 °C. Versions of models III and IIIR were created for irradiations at 4 °C. For our current water calorimetry protocol, the values of the heat defect for H₂/O₂-water (water saturated with a flow of 43 % H₂ and 57 % O₂, by volume) at 21 °C predicted by model III and model IIIR are similar but the value for 4 °C predicted by III is 30 % smaller than the value predicted by IIIR. Model IIIR predicts that the values of the heat defect at 21 °C and 4 °C lie within the range −0.023±0.002, in agreement with the values obtained from our water calorimetry measurements done using pure water and H₂-saturated water at 21 °C and 4 °C. The yields of hydrogen peroxide in H₂/O₂-water at 21 °C and 4 °C were measured and agree with the predictions of model IIIR. Our water calorimetry measurements made with pure water and H₂-saturated water are now of sufficient quality that they can be used to determine the heat defect for H₂/O₂-water better than can be done by simulations. However, consistency between the three systems continues to be an excellent check on water purity which is crucial, especially for the pure water system.     

Phase Equilibrium Relations in the Sc2O3-Ga2O3 System

The phase equilibrium diagram was determined for the Sc₂O₃-Ga₂O₃ system. A quenching furnace, wound with 60 percent Pt—40 percent Rh wire, was employed for experiments conducted at temperatures up to 1,800 °C. An induction furnace, having an iridium crucible susceptor, was used to obtain higher temperatures. Temperatures in the quenching furnace were measured with both an optical pyrometer and a 95 percent Pt—5 percent Rh versus 80 percent Pt—20 percent Rh thermocouple. The melting point of Ga₂O₃ was determined as 1,795 ±15 °C. Experiments at temperatures as high as 2,405 °C failed to melt Sc₂O₃. Two intermediate binary phases, a compound believed to be 6Sc₂O₃·5Ga₂O₃ and a solid solution occur in the system. The solid solution phase appears as a single phase in the region roughly defined by the compositional limits of 55 to 73 mole percent Ga₂O₃ at the solidus. The 6:5 compound, stable only at high temperatures, melts incongruently at 1,770 ±15 °C and decomposes below 1,700 ±15 °C. The compound appears to have orthorhombic symmetry with a=13.85 A, b= 9.80 A, and c=9.58 A. The indicated uncertainties in the melting points are a conservative estimate of the overall inaccuracies.     

Treasure of the Past VI: Standard Potential of the Silver-Silver-Chloride Electrode from 0° to 95° C and the Thermodynamic Properties of Dilute Hydrochloric Acid Solutions

From electromotive-force measurements of the cell without liquid junction: Pt;  H₂,  HCl (m),  AgCl;  Agthrough the range 0° to 95° C, calculations have been made of (1) the standard potential of the silver–silver-chloride electrode, (2) the activity coefficient of hydrochloric acid in aqueous solutions from m (molality) =0 to m=0.1 and from 0° to 90° C, (3) the relative partial molal heat content of hydrochloric acid, and (4) the relative partial molal heat capacity of hydrochloric acid.The extrapolations were made by the method of least squares with the aid of punch-card techniques. Data from at least 24 cells were analyzed at each temperature, and 81 cells were studied at 25° C. The value of the standard potential was found to be 0.22234 absolute volt at 25° C, and the standard deviation was 0.02 millivolt at 0° C, 0.01 millivolt at 25° C, and 0.09 millivolt at 95° C. The results from 0° to 60° C are compared with earlier determinations of the standard potential and other quantities derived from the electromotive force.     

Thermodynamic Properties of Some Methylphosphonyl Dihalides From 15 to 335 °K

Measurements of the heat capacity of methylphosphonyl difluoride (CH₃POF₂), methyl phosphonyl dichloride (CH₃POCl₂), and methylphosphonyl chlorofluoride (CH₃POClF) were made from about 15 to 335 °K by means of an adiabatic calorimeter. These highly reactive and toxic substances were purified in a completely closed glass apparatus by combining slow crystallization and fractional melting procedures. The purities determined by the freezing-curve method are shown to be generally in agreement with those values obtained by the calorimetric method. From the results of the heat measurements, the triple-point temperature, heat of fusion, and their corresponding estimated uncertainties were found to be, respectively, 236.34±0.05 °K and 11,878±12 J/mole for CH₃POF₂, 306.14± 0.02 °K and 18,076±15 J/mole for CH₃POCl₂, and 250.70± 0.20 °K and 11,853±30 J/mole for CH₃POClF. Triple-point temperatures obtained by the freezing-curve method are in agreement with the above values. A table of smoothed values of heat capacity, enthalpy, enthalpy function, entropy, Gibbs free energy, and Gibbs free energy function from 0 to 335 °K was obtained from the data. The entropy and its corresponding estimated uncertainty for CH3POF2, CH3POCl2, and CH3POClF in their respective condensed phase at 298.15 °K and saturation pressure was found to be 208.3± 0.3, 164.8± 0.3, and 216.4± 0.4 J/deg mole, respectively. The entropies in the gaseous state at 298.15 °K and 1 atm pressure were found to be 312.7±3, 339.7±3, and 335.0±3 J/deg mole, respectively.     

Heats of Solution,Transition, and Formation of Three Crystalline Forms of Metaboric Acid

The three crystalline forms of metaboric acid HBO₂ were prepared, purified, and analyzed. Heats of solution in water or of reaction with sodium hydroxide solution were compared with those of orthoboric acid H₃BO₃(c). The best values for the heats of transition at 25 °C are: (c,I) to (c,II), 2.33±0.23 kcal/mole; (c,II) to (c,III), 1.30±0.05 kcal/mole; (c,I) to (c,III), 3.63±0.24 kcal/mole. The following heats of formation at 25 °C were derived: −192.77 ± 0.35 kcal/mole for the cubic HBO₂(c,I), −190.43 ±0.34 kcal/mole for the monoclinic HBO₂ (c,II), and −189.13 ± 0.34 kcal/mole for the orthorhombic HBO₂(c,III).     

Rapid densification and reaction sequences in self-reinforced Y-α-SiAlON ceramics with barium aluminosilicate as an additive

Y-α-SiAlON (Y_1/3Si₁₀Al₂ON₁₅) ceramics with 5 wt.%BaAl₂Si₂O₈ (BAS) as an additive were synthesized by spark plasma sintering (SPS). The kinetic of densification, phase transformation sequences and grain growth during sintering process were investigated. Full densification could be achieved by 1600 °C without holding and using a heating rate of 100 °C min⁻¹, but the transformation from α-Si₃N₄ to α-SiAlON is not completed simultaneously with the densification process. The equilibrium phase assemblage could be reached after SPS at 1800 °C for 5 min and the resultant material possesses self-reinforced microstructure with high hardness of 19.2 GPa and fracture toughness of 6.8 MPa m^1/2. The complete crystallization of BAS is beneficial to the high temperature mechanical properties. The obtained could maintain the room strength up to 1300 °C.     

Suppression of spin fluctuations by alloying in UPt3

In order to investigate the normal state spin fluctuation behavior of UPt₃, we have measured the low temperature resistivity and specific heat C of U(Pt_0.8Pd_0.2)₃, which we find to be close to the phase stability boundary for the hexagonal UPt₃ structure. The evidence for spin fluctuations observed in UPt₃, aT ³ ln (T/T _SF) upturn inC/T below 10 K, is totally suppressed in U(Pt_0.8Pd_0.2)₃, and the value, proportional to the dressed density of states, is decreased by 50% compared to pure UPt₃. This extreme sensitivity to substitution by isoelectronic Pd for Pt indicates that the spin fluctuations in UPt₃ depend critically on the hybridization of the U electrons, U-U separation equal to 4.2 Å, with the electrons of the intervening atoms.     

Debye temperatures of uranium chalcogenides from their lattice dynamics

Phonon dispersion relations in uranium chalcogenides have been investigated using a modified three-body force shell model. From the phonon frequencies, their Debye temperatures are evaluated. Further, on the basis of the spin fluctuation in the heavy fermion uranium compounds, UPt₃ and UBe₁₃, the possible superconducting transition temperatures of chalcogenides are theoretically predicted. The Tc values are in the same range as of those in UPt₃ and UBe₁₃.     

Magnetic soy protein isolate–bovine serum albumin nanoparticles preparation as a carrier for inulinase immobilisation

Magnetic nanoparticles (NPs) were functionalised with soy protein isolate (SPI) and bovine serum albumin (BSA) for inulinase immobilisation. The results revealed the nanomagnetite size of about 50 nm with a polydispersity index (PDI) of 0.242. The average size of the SPI NPs prepared by using acetone was 80–90 nm (PDI, 0.277), and SPI–BSA NPs was 80–90 nm (PDI, 0.233), and their zeta potential was around −34 mV. The mean diameter of fabricated Fe₃ O₄ @SPI–BSA NPs was <120 nm (PDI, 0.187). Inulinase was covalently immobilised successfully through glutaraldehyde on Fe₃ O₄ @SPI–BSA NPs with 80% enzyme loading. Fourier transform infrared spectra, field emission scanning electron microscopy, and transmission electron microscopy images provided sufficient proof for enzyme immobilisation on the NPs. The immobilised inulinase showed maximal activity at 45°C, which was 5°C higher than the optimum temperature of the free enzyme. Also, the optimum pH of the immobilised enzyme was shifted from 6 to 5.5. Thermal stability of the enzyme was considerably increased to about 43% at 75°C, and K _m value was reduced to 25.4% after immobilisation. The half‐life of the enzyme increased about 5.13‐fold at 75°C as compared with the free form. Immobilised inulinase retained over 80% of its activity after ten cycles.Inspec keywords: magnetic particles, nanoparticles, proteins, molecular biophysics, nanofabrication, enzymes, Fourier transform spectra, infrared spectra, scanning electron microscopy, field emission ion microscopy, transmission electron microscopy, pH, biochemistry, nanobiotechnology, biomagnetism, electrokinetic effects, iron compoundsOther keywords: magnetic nanoparticles, soy protein isolate, bovine serum albumin, inulinase immobilisation, nanomagnetite, polydispersity index, SPI‐BSA NP, zeta potential, inulinase, glutaraldehyde, enzyme loading, Fourier transform infrared spectra, field emission scanning electron microscopy, transmission electron microscopy images, enzyme immobilisation, pH, size 80 nm to 90 nm, temperature 45 degC, temperature 75 degC, Fe₃ O₄      

Acid Dissociation Constant and Related Thermodynamic Quantities for Triethanolammonium Ion in Water From 0 to 50°C

Earlier studies of the dissociation constants of monoethanolammonium and diethanolammonium ions and the thermodynamic constants for the dissociation processes have been supplemented by a similar study of triethanolammonium ion from 0° to 50° C. The dissociation constant (K_bh) is given by the formula ?log K_bh = 1341.16/T + 4.6252 ? 0.0045666Twhere T is in degrees Kelvin. The order of acidic strengths of the ions is as follows: Triethanolammonium >diethanolammonium>monethanolammonium. Conversely, monoethanolamine is the strongest of the three bases. The thermodynamic constants for the dissociation of one mole of triethanolammonium ion in the standard state at 25° C are as follows: Heat content change (ΔH°) 33.450 joule mole⁻¹; entropy change (ΔS°), −36.4 joule deg⁻¹ mole⁻¹; heat-capacity change (ΔCp°), 52 joule deg⁻¹ mole⁻¹.     

Gamma Irradiation of Hexafluorobenzene

Mixtures of hexafluorobenzene and benzene were irradiated in liquid phase by means of a Co⁶⁰ gamma source at 20° and at 218° C. Perfluoroheptane and various binary mixtures involving perfluoroheptane, hexafluorobenzene, benzene, and cyclohexane were also irradiated at 20° C. Hexafluorobenzene resembled benzene very closely in its behavior upon radiolysis. Generally the fluorocarbon-hydrocarbon mixtures evolved much more SiF₄ (indicating the formation of HF, which reacts with the glass vessel) than the pure fluorocarbon components. The polymer from hexafluorobenzene-benzene mixtures was probably rich in cyclohexadiene and cyclohexene units, resembling that from pure benzene, and its composition ratio exhibited a strong “alternating” tendency. The results are discussed in terms of free-radical and excited-state mechanisms. At 218° C hexafluorobenzene and also its mixtures with benzene showed qualitative differences from their behavior at 20° C, although the G values for SiF₄ and polymer remained moderate.     

Experimental study of the Ca–Mg–Zn system using diffusion couples and key alloys

Nine diffusion couples and 32 key samples were prepared to map the phase diagram of the Ca–Mg–Zn system. Phase relations and solubility limits were determined for binary and ternary compounds using scanning electron microscopy, electron probe microanalysis and x-ray diffraction (XRD). The crystal structure of the ternary compounds was studied by XRD and electron backscatter diffraction. Four ternary intermetallic (IM) compounds were identified in this system: Ca₃Mg_xZn_15−x (4.6 ⩽ x ⩽ 12 at 335 °C, IM1), Ca_14.5Mg_15.8Zn_69.7 (IM2), Ca₂Mg₅Zn₁₃ (IM3) and Ca_1.5Mg_55.3Zn_43.2 (IM4). Three binary compounds were found to have extended solid solubility into ternary systems: CaZn₁₁, CaZn₁₃ and Mg₂Ca form substitutional solid solutions where Mg substitutes for Zn atoms in the first two compounds, and Zn substitutes for both Ca and Mg atoms in Mg₂Ca. The isothermal section of the Ca–Mg–Zn phase diagram at 335 °C was constructed on the basis of the obtained experimental results. The morphologies of the diffusion couples in the Ca–Mg–Zn phase diagram at 335 °C were studied. Depending on the terminal compositions of the diffusion couples, the two-phase regions in the diffusion zone have either a tooth-like morphology or contain a matrix phase with isolated and/or dendritic precipitates.     

Dissociation Constant of 4-Aminopyridinium Ion in Water From 0 to 50 °C and Related Thermodynamic Quantities

The dissociation constant of 4-aminopyridinium ion in water at 11 temperatures from 0° to 50° C has been determined from electromotive force measurements of 19 approximately equimolal aqueous buffer solutions of 4-aminopyridine and 4-aminopyridinium chloride. Cells without liquid junction were used; the cell is represented as follows: Pt; H₂(g), H₂NC₅H₄N ? HCl(m₁), H₂NC₅H₄N(m₂), AgCl; Agwhere m is molality.Between 0° and 50° C, the dissociation constant (K_bh) is given as a function of temperature (T) in degrees Kelvin by −logKbh=2575.8T+0.08277+0.0013093TThe changes of Gibbs free energy (ΔG°), of enthalpy (ΔH°), of entropy (ΔS°), and of heat capacity (ΔC_p°) for the dissociation process in the standard state were calculated from the constants of this equation. At 25° C the following values were found: −logKbh=9.114,ΔG°=52,013jmole−1,ΔH°=47,090jmole−1,ΔS°=−16.5jdeg−1mole−1,ΔCp°=−15jdeg−1mole−1.Thermodynamic constants for the basic dissociation of 4-aminopyridine at 25° C were also computed.     

Phase Equilibria in Systems Involving the Rare Earth Oxides. Part III. The Eu2O3?In2O3 System

The equilibrium phase diagram was determined for the Eu₂O₃−In₂O₃ system. An induction furnace, having an iridium crucible as the heating element (susceptor), was used to establish the solidus and liquidus curves. The 1:1 composition melts congruently at 1745 ± 10 °C. Melting point relations suggest that the 1:1 composition is a compound with solid solution extending both to 31 mole percent In₂O₃ and 71 mole percent In₂O₃. The compound is pseudohexagonal with a_H = 3.69 A and c_H = 12.38 A. Isostructural phases also occur in the 1:1 mixtures of both Gd₂O₃ and Dy₂O₃ with In₂O₃. The melting points of Eu₂O₃ and In₂O₃ were determined to be 2,240 ± 10 °C and 1910 ± 10 °C respectively. A eutectic occurs in the Eu₂O₃−In₂O₃ system at 1,730 °C and about 73 mole percent In₂O₃. The indicated uncertainties in the melting points are conservative estimates of the overall inaccuracies of temperature measurement.     

Mechanochemically synthesized CsH2PO4–H3PW12O40 composites as proton-conducting electrolytes for fuel cell systems in a dry atmosphere

Cesium dihydrogen phosphate (CsH₂PO₄, CDP) and dodecaphosphotungstic acid (H₃PW₁₂O₄₀·nH₂O, WPA·nH₂O) were mechanochemically milled to synthesize CDP–WPA composites. The ionic conductivities of these composites were measured by an ac impedance method under anhydrous conditions. Despite the synthesis temperatures being much lower than the dehydration and phase-transition temperatures of CDP under anhydrous conditions, the ionic conductivities of the studied composites increased significantly. The highest ionic conductivity of 6.58×10⁻⁴ Scm⁻¹ was achieved for the 95CDP·5WPA composite electrolyte at 170 °C under anhydrous conditions. The ionic conduction was probably induced in the percolated interfacial phase between CDP and WPA. The phenomenon of high ionic conduction differs for the CDP–WPA composite and pure CDP or pure WPA under anhydrous conditions. The newly developed hydrogen interaction between CDP and WPA supports anhydrous proton conduction in the composites.