Water Calorimetry: The Heat Defect

Domen developed a sealed water calorimeter at NIST to measure absorbed dose to water from ionizing radiation. This calorimeter exhibited anomalous behavior using water saturated with gas mixtures of H₂ and O₂. Using computer simulations of the radiolysis of water, we show that the observed behavior can be explained if, in the gas mixtures, the amount-of-substance of H₂ and of O₂ differed significantly from 50 %. We also report the results of simulations for other dilute aqueous solutions that are used for water calorimetry—pure water, air-saturated water, and H₂-saturated water. The production of H₂O₂ was measured for these aqueous solutions and compared to simulations. The results indicate that water saturated with a gas mixture containing an amount-of-substance of H₂ of 50 % and of O₂ of 50 % is suitable for water calorimetry if the water is stirred and is in contact with a gas space of similar volume. H₂-saturated water does not require a gas space but O₂ contamination must be guarded against. The lack of a scavenger for OH radicals in “pure” water means that, depending on the water purity, some “pure” water might require a large priming dose to remove reactive impurities. The experimental and theoretical problems associated with air-saturated water and O₂-saturated water in water calorimeters are discussed.     

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).     

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.     

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.     

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 Polyethylene Predicted from Paraffin Data

Thermodynamic data on the n-paraffins from n-C₆H₁₄ through n-C₁₈H₃₈ have been used to obtain values for the specific heat, entropy, enthalpy, and Gibbs free energy of a large, ideal CH₂-chain crystal from 0 to 420 °K and of the liquid above 200 °K. Analytical expressions are given for the properties of the crystal and liquid above 200 °K. For the crystal, a modified Einstein function was used to adjust the melting temperature to 414.3 °K. Values between 975 and 1025 cal/mole for the heat of fusion were found to be the ones most consistent with the data. Comparison of the results with polyethylene data shows reasonable agreement.     

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.     

A Standard for the Measurement of the pH of Blood and Other Physiological Media

A buffer solution containing potassium dihydrogen phosphate (0.008695 molal) and disodium hydrogen phosphate (0.03043 molal) is proposed as a pH standard for the physiologically important range, pH 7 to 8. The proposed standard solution is prepared by dissolving 1.179 g (air weight) of potassium dihydrogen phosphate and 4.303 g (air weight) of disodium hydrogen phosphate in ammonia-free water and diluting to 1 liter at 25 °C. The ionic strength is 0.1.Standard pH values (pH_s) were assigned to this reference solution at temperatures from 0 to 50 °C by means of emf measurements of hydrogen-silver chloride cells without liquid junction. The activity coefficient of chloride ion, upon which the assignment of pH_s depends, was evaluated by means of a recently proposed convention. By this means, standard values precise to ± 0.001 unit could be derived from the emf data. At 25 °C pH_s is 7.414, and at 38 °C it is 7.382. The operational consistency of these standard values with those for the 0.025-m equimolal phosphate buffer (one of the NBS primary standards) was demonstrated.     

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.     

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.     

Multivariate polynomial fit: Decay heat removal system and pectin degrading Fe3O4‐SiO2 nanobiocatalyst activity

Herein, multivariate Lagrange''s interpolation polynomial (MLIP) and multivariate least square (MLS) methods are used to derive linear and higher‐order polynomials for two varied applications. (1) For an effective fabrication of Pectin degrading Fe₃O₄‐SiO₂ Nanobiocatalyst activity (IU/mg). Here, the three parameters namely: pH value, pectinase loading and temperature as independent variables are optimized for the maximal of anobiocatalyst activity as a dependent variable. (2) For a passive system reliability estimation of decay heat removal (DHR) of a nuclear power plant. The success criteria of the system depend on three types temperature that do not exceed their respective design safety limits and are considered as dependent variables and 14 significant parameters were used as independent variables. Statistically, the validation of these multivariate polynomials are done by testing of hypothesis. Comparative study of the proposed approach gives significance results in the first application have the optimum conditions for maximum activity using linear MLIP method is: 58.64 with pH = 4, pL = 250 and Temp = 4°C. The maximum activity using second order MLIP method is 59.825 and method of MLS is 59.8249 with the optimized values of an independent variables pH = 4, pL = 300 and Temp = 8°C depicted in Table 1. In DHR system, the significance results are obtained and depicted in Table 2.     

Antifungal and antiovarian cancer properties of α Fe2 O3 and α Fe2 O3 /ZnO nanostructures synthesised by Spirulina platensis

Candida albicans (C. albicans) infection shows a growing burden on human health, and it has become challenging to search for treatment. Therefore, this work focused on the antifungal activity, and cytotoxic effect of biosynthesised nanostructures on human ovarian tetracarcinoma cells PA1 and their corresponding mechanism of cell death. Herein, the authors fabricated advanced biosynthesis of uncoated α‐Fe₂ O₃ and coated α‐Fe₂ O₃ nanostructures by using the carbohydrate of Spirulina platensis. The physicochemical features of nanostructures were characterised by UV–visible, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. The antifungal activity of these nanostructures against C. albicans was studied by the broth dilution method, and examined by 2′, 7′‐dichlorofluorescein diacetate staining. However, their cytotoxic effects against PA1 cell lines were evaluated by MTT and comet assays. Results indicated characteristic rod‐shaped nanostructures, and increasing the average size of α‐Fe₂ O₃ @ZnO nanocomposite (105.2 nm × 29.1 nm) to five times as compared to α‐Fe₂ O₃ nanoparticles (20.73nm × 5.25 nm). The surface coating of α‐Fe₂ O₃ by ZnO has increased its antifungal efficiency against C. albicans. Moreover, the MTT results revealed that α‐Fe₂ O₃ @ZnO nanocomposite reduces PA1 cell proliferation due to DNA fragmentation (IC₅₀ 18.5 μg/ml). Continual advances of green nanotechnology and promising findings of this study are in favour of using the construction of rod‐shaped nanostructures for therapeutic applications.Inspec keywords: nanocomposites, toxicology, nanofabrication, cellular biophysics, X‐ray diffraction, iron compounds, biochemistry, cancer, antibacterial activity, transmission electron microscopy, biomedical materials, wide band gap semiconductors, DNA, II‐VI semiconductors, visible spectra, molecular biophysics, ultraviolet spectra, nanomedicine, zinc compounds, nanoparticles, microorganisms, Fourier transform infrared spectraOther keywords: Spirulina platensis, antifungal activity, α‐Fe₂ O₃ nanoparticles, antiovarian cancer properties, Candida albicans infection, cytotoxic effect, biosynthesised nanostructures, human ovarian tetracarcinoma cell PA1, cell death, uncoated α‐Fe₂ O₃ , coated α‐Fe₂ O₃ nanostructures, α‐Fe₂ O₃ ‐ZnO nanocomposite, carbohydrate, physicochemical features, UV‐visible spectroscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, broth dilution method, 2′, 7′‐dichlorofluorescein diacetate staining, PA1 cell lines, comet assays, MTT assays, rod‐shaped nanostructures, surface coating, PA1 cell proliferation, DNA fragmentation, green nanotechnology, Fe₂ O₃ ‐ZnO, Fe₂ O₃      

Uranium-Platinum System

The phase diagram of the uranium-platinum system was constructed from data obtained by thermal analysis, metallographic examination, and X-ray diffraction. The system is characterized by four intermetallic compounds: UPt, formed peritectoidally at 961° C; UPt₂, formed peritectically at 1,370° C; UPt₃, melting congruently at 1,700° C; and UPt₅, formed peritectically at 1,460° C. One eutectic occurs at 1,005° C and 12 a/o platinum, and a second at 1,345° C and 87.5 a/o platinum. The maximum solubilities are 4.5 a/o uranium in platinum and 5 a/o platinum in gamma-uranium. Platinum lowers the gamma-beta uranium transformation to 705° C and the beta-alpha transformation to 589° C.     

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      

Synthesis and properties of β type Bi(III)2?2xDy(II)2xO3 ? xx solid solution

In the present work, tetragonal β type Bi(III)_{2 − 2x}Dy(II)_2xO_{3 − x}■_x (■:,empty oxygen site) solid solutions have been synthesized in the ranges 0.06 ≤ x ≤ 0.08 at 750°C and 0.05 ≤ x ≤ 0.09 at 800°C by doping small amounts of Dy₂O₃ into monoclinic α -Bi₂O₃. X-ray powder diffraction (XRD) has been used for characterisation of the doped Dy₂O₃ powders as well as for calculation of the unit cell parameters. The polymorphic phase transitions, crystallographic properties, particle sizes, the scanning electron microscope (SEM) microprobe analysis and Dy₂O₃ content dependence of the lattice parameters of the observed β-phase has been reported. The obtained solid solutions had nonstoichiometric character and nonstoichiometry increases with the increasing amount of Dy₂O₃ addition. The experimental results suggested that oxygen vacancies are present in the crystal structure of Dy₂O₃ doped β type solid solutions.     

Reactivity towards water of silicon nitride: Energy of interaction and hydration dehydration mechanism

The heat of adsorption and adsorbed amounts of H₂O_(vap) have been measured on an industrial crystalline Si₃N₄ outgassed at 400 and 800° C. A nearly uniform surface is present after the 400° C thermal treatment, where H₂O is adsorbed via hydrogen bonding to surface OH and NH groups with a heat of adsorption of 50 kJ mol^–1. After 800° C thermal treatment, which involves the dehydration and condensation of OH and NH groups, water is readily dissociated at the surface (–H > 50 kJ mol^–1) and the pristine surface is formed on which water is hydrogen bonded again. No hydrophobic patches are detected. The results are discussed in comparison with SiO₂ behaviour in similar conditions.     

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.     

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.     

Effects of changes in temperature on Zika dynamics and control

When a rare pathogen emerges to cause a pandemic, it is critical to understand its dynamics and the impact of mitigation measures. We use experimental data to parametrize a temperature-dependent model of Zika virus (ZIKV) transmission dynamics and analyse the effects of temperature variability and control-related parameters on the basic reproduction number (R₀) and the final epidemic size of ZIKV. Sensitivity analyses show that these two metrics are largely driven by different parameters, with the exception of temperature, which is the dominant driver of epidemic dynamics in the models. Our R₀ estimate has a single optimum temperature (≈30°C), comparable to other published results (≈29°C). However, the final epidemic size is maximized across a wider temperature range, from 24 to 36°C. The models indicate that ZIKV is highly sensitive to seasonal temperature variation. For example, although the model predicts that ZIKV transmission cannot occur at a constant temperature below 23°C (≈ average annual temperature of Rio de Janeiro, Brazil), the model predicts substantial epidemics for areas with a mean temperature of 20°C if there is seasonal variation of 10°C (≈ average annual temperature of Tampa, Florida). This suggests that the geographical range of ZIKV is wider than indicated from static R₀ models, underscoring the importance of climate dynamics and variation in the context of broader climate change on emerging infectious diseases.