Effects of heating rate (1–300° h−1) on the non-isothermal thermogravimetry of CuSO4 · 5 H2O

The course of the reaction CuSO₄ · 5 H₂O ? CuSO₄ · H₂O + 4 H₂O was studied by non-isothermal thermogravimetry with various heating rates ranging from 1 to 300° h^?. The measurements were made either in static air, in a dry nitrogen stream, or in water vapor at a reduced pressure (9 mm Hg). In static air, the shape of the TG curve changed drastically at a heating rate of 13 to 15° h^?, and this change was explained by considering the nature of the plateaus and inflections present. In a dry nitrogen stream, the dehydration is made much easier at slow heating rates and occurs almost in one step at 2° h^?; in water vapor at 9 mm Hg, on the other hand, a very distinct two-step curve is obtained at 1° h^?. This can reasonably be compared with the phase diagram of copper sulfate.     

Aspects of the Chemistry of Poly (Ethylene Terephthalate). IV. Hydrolysis of Poly(Ethylene Terephthalate) in the Melt Phase

The effect of water vapor pressure on the molecular weight of molten poly (ethylene terephthalate) has been followed by measurement of the changes which occur in the intrinsic viscosity and the end-group concentrations upon hydrolysis. It was found that phosphoric acid is highly effective as a stabilizer; the hydrolysis rate constant (K_h) decreasing from 7.6 × 10^?7 mol^?1s^?1 for nonstabilized to 2.5 × 10^?7 mol^?1s^?1 for the stabilized polyester at 290°C and water vapor pressure of 20 mmHg.     

Mechanism of Substitution in Carbonated Apatites

Single-phase AB-type carbonate apatites were prepared by sintering appropriate mixtures of CaHPO₄ and CaCO₃ at 870°C in a CO₂ atmosphere with a partial water vapor pressure of 5 mm Hg. Chemical and physical analyses indicate that at a constant CO₃^2?/OH^? ratio in the hydroxyl sublattice, carbonate substitutes for phosphate on a 1:1 mole basis. For every three PO₄^3? ions substituted, two vacancies in the Ca²⁺ sublattice and one in the OH^? sublattice are created. The same substitution mechanism seems to apply in pure B-type carbonate apatite.     

Radiation-Induced Solid-State Polymerization of Derivatives of Methacrylic Acid. VII. A Differential Scanning Calorimetric Investigation of the Dehydration and Polymerization of Barium Methacrylate

Abstract

Barium methacrylate monohydrate showed two dehydration steps (at 80 and 110°C), in small crystals, but only one step (at 80° C) in fine powder. The equilibrium water vapor pres-sure was independent of the degree of hydration and its temperature dependence was found to be log₁₀ p_H2O (Torr)=10.70 - 2858/T, giving ΔH (dehyd)=54 ±4 kJ mole^?1. Small doses of γ-irradiation at 78° C suppressed the second de-hydration endotherm and shifted the first to higher temperatures. Larger radiation doses caused the endotherm to diminish and be re-placed by a polymerization exotherm. The variations in position with scan rate gave E_a=163 kJ mole^?1, similar to the value from isothermal polymerization rate measurements. There was no evidence of polymerization in the anhydrate except at the decompo-sition temperature.     

Electrical conductivity of CaMoO4

The electrical conductivity and ionic transport number of CaMoO₄ has been measured as a function of the partial pressure of oxygen (1–10^?18 atm) at 750, 800, and 850°C. Two sets of samples were studied: (1) CaMoO₄ annealed at 1100°C in the presence of CaO, and (2) CaMoO₄ annealed in MoO₃ vapor at 1100°C. Sample 1 is a mixed ionic/electronic conductor while Sample 2 is essentially an electronic conductor. A defect structure model is proposed to explain the results.     

Studies of layered uranium(VI) compounds. II. Thermal stability of hydrogen uranyl phosphate and arsenate tetrahydrates

By means of accurate TGA, we have shown that the proton-conducting solid electrolytes HUO₂PO₄·4H₂O (HUP) and HUO₂AsO₄·4H₂O (HUAs) are more correctly represented as $\text{HUO}{}_2\text{P}\text{AsO}{}_4\text{·(A?x)}\text{H}{}_2\text{O}$, where A is assumed to be the integral number 4. The water deficiency x was estimated to be less than 0.03 at 295°K, but increased respectively by less than 0.1 and 0.05 when HUP and HUAs were heated in air to approximately 315°K. At higher temperatures, dehydration of HUP under isothermal conditions produced, over a temperature interval of less than 2°K, a lower hydrate phase having approximately 1.5 waters of crystallization. Equilibrium dehydration temperatures were established for HUP over a range of humidities, and varied from 297°K at 0.4 mm Hg water vapor pressure, to 318°K at 16 mm Hg pressure. An explanation of the apparently high standard molar enthalpy for dehydration is suggested in terms of small losses of a phosphorus-containing compound accompanying the water loss. The overall phase relationships of HUP are discussed.     

Crystal growth of Zinc Oxide from Vapor Phase

Single crystals of ZnO were grown at 1 050–1200°C by the oxidation of zine vapor which was continuously evolved at constant rate of 7.2 × 10^?5 mol/min. Favourable flow rate of oxygen was 4.3–6.6 × 10^?5 mol/min and was 1.2–1.8 times than theoretical value to oxidize zine vapor. The crystals grew larger with raising up growing temperature. Large crystals having maximum size of 2–4 mm ini diameter and 22 mm long were grown at 1200°C for 55 hours. The crystals were light gray and transparent. Representative forms of the crystals were both platelet with developed (100) face and hexagonal prism-type.     

Electrotransport properties of a high-temperature phase of CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript> and composite systems with silicon dioxide at different humidities

Investigations of the electrotransport and thermodynamic properties of CsH₂PO₄ and composite systems (1 ? x)CsH₂PO₄?xSiO₂ (x=0–0.5) synthesized on the basis of silicon dioxide with different magnitude of the specific surface area are conducted while varying the partial pressure of water vapor. It is demonstrated that the superionic phase transition, which is observed in CsH₂PO₄ at a temperature of 230°C, has nothing to do with the process of dehydration. A strong surface interaction of the salt with the matrix is discovered in composites of different compositions synthesized on the basis of uniformly porous silicon dioxides with specific surface areas of 41–520 m₂ g^?1 and the value of pH ～7. The interaction is found to lead to dehydration and to small values of conductivity in the systems heated to temperatures in excess of 230°C. An analysis of the dehydration products is conducted and conditions conducive to the existence of phases with certain compositions are determined.     

Elevated pressure and temperature effects on flammability hazard assessment for acetone and water solutions

Flammable chemicals are frequently encountered in industrial processes. Under the safe operation basis and for fire/explosion danger prevention, it is imperative to recognize the flammability characteristics of these processes, especially under the working scenarios for elevated pressure and temperature. This study was conducted to investigate fire and explosion properties, including the explosion limits (LEL and UEL), maximum explosion overpressure (P _max), maximum rate of explosion pressure rise (dP/dt)_max, gas or vapor deflagration index (K _g) and explosion class (St) of various acetone/water solutions (100, 75, 50 and 25 vol.%) at higher initial pressure/temperature up to 2 atm and 200°C via a 20-L-Apparatus. We further discussed the safety-related parameters and fire/explosion damage degree variations in the above aqueous acetone within 1 atm and 150°C. The results offered a successful solution for evaluating the flammability hazard effect in such a relevant crucial process with elevated pressure and temperature.     

Tensile properties of ultradrawn polyethylene

High-density polyethylene filaments prepared by a solid-state deformation in an Instron capillary rheometer show unusually high crystal orientation, chain extension, axial modulus, and ultimate tensile strength. The Young's modulus and ultimate tensile strength have been determined from stress–strain curves. Gripping of this high modulus polyethylene has been a problem heretofore, but the measurement of ultimate tensile strength has now been made feasible by a special gripping procedure. Tensile moduli show an increase with sample preparation temperature and pressure. Values as high as 6.7 × 10¹¹ dyne/cm² are obtained from samples extruded at 134°C and 2400 atm and tested at a strain rate of 3.3 × 10^?4 sec^?1. The effect of strain rate and frequency on modulus has also been evaluated by a combination of stress–strain data and dynamic tension plus sonic measurements over nine decades of time.     

Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) at high temperature

The Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) were determined at temperatures of 24, 90, 120, 150, and 170°C for weight fractions of vinyl chloride between 0.2 × 10^?3 and 0.8 × 10^?3. Above 90°C, Henry's law applies; values of the constant increase with temperature from 1.8 × 10² to 5.5 × 10² atm per unit weight fraction of dissolved vinyl chloride. The heat of desorption is about 15 kJ/mole. At 24°C, the nominal Henry's law constant was smaller than would have been obtained by extrapolating the values found at higher temperature. The diffusion constants increase with temperature from about 2 × 10^?13 to 3 × 10^?7 cm²/sec. The activation energy for diffusion is about 110 kJ/mole between 90 and 170°C. Although all values were determined in the absence of air, it is likely that they apply to polymer in air. They may, therefore, be used to calculate the vinyl chloride content in the gas above poly(vinyl chloride) under specific processing conditions.     

The thermal decomposition of oxalates Part 14. Dehydration of magnesium oxalate dihydrate

The isothermal dehydration of magnesium oxalate dihydrate has been studied under various pressures of water vapour by use of a thermogravimetric balance. The rate of dehydration was found to be dependent upon the water vapour pressure.The reaction rate at temperatures below 124°C decreases sharply with an increase in water vapour pressure up to 0.5 mm Hg. With further increase in pressure an increase in rates is observed; this rises to a maximum and then falls again as the pressure is increased. The limitation of this phenomena to a limited temperature range is shown in the case of magnesium oxalate dihydrate. Above 124°C the initial fall in rate is not observed, the rate rises with increasing pressure from vacuum to a maximum and the falls. X-ray diffraction studies indicated that the anhydrous product prepared in the second region where a decrease of rate of dehydration occurred was crystalline but the sample dehydrated under vacuum or in the first region produced an amorphous anhydrous salt. A compensation effect is demonstrated with plots of the activation energy against the logarithm of the pre-exponential term in the Arrhenius equation.     

Évolution thermique d'un hydroxyde de nickel lamellaire mal organisé avec des molécules d'eau en insertion entre les feuillets: comparaison avec l'hydroxyde de nickel cristallisé Ni(oH)2

The authors have studied the thermal decomposition of a turbostratic nickel hydroxide by means of DTA, TGA and isothermal analysis. The turbostratic compound has been described as a random stacking of parallel and equidistant nickel hydroxide layers with intercalary water layers.Well crystallized Ni(OH)₂ has been used as reference. The preparation and the main properties of both hydroxides have been indicated. It was found that the removal of intercalary water takes place simultaneously with the removal of hydroxyl groups at a temperature, not very different from the dehydration temperature of Ni(OH)₂. NO₃^? ions from the starting material and trapped water have been found on the dehydration product. The very fine nickel oxide shows a quite important increase of the lattice parameter (4.215 instead of 4.177 Å). A reversible variation of the inter-layer spacing from 8.5 to 7Å has been pointed out when the turbostratic hydroxide is heated up to 150°C.     

Gas-phase and supercritical <Emphasis Type="Italic">n</Emphasis>-pentane isomerization on H-mordenite

The skeletal isomerization of supercritical n-pentane on the H form of mordenite under flow conditions was studied for the first time. It was found that the conversion of supercritical n-pentane was 30–35% at 90% selectivity for isopentane at 260°C, 130 atm, and a liquid hourly space velocity of 30 h^?1. The catalyst was deactivated as the temperature was increased above 280°C. According to differential thermal analysis data, the deactivation was related to the deposition of condensation products on the surface. The resistance of the H form of the zeolite to poisoning in n-pentane isomerization in a gas phase at 1–8 atm was lower than that under supercritical conditions. It was found that H-mordenite deactivated under gas-phase reaction conditions at 260°C and 8 atm can be regenerated by passing to supercritical isomerization conditions (260°C and 130 atm).     

The effect of the water vapor pressure on the kinetics of thermal dehydration of manganese(II) formate dihydrate

The effect of the water vapor pressure on the thermal dehydration of manganese(II) formate dihydrate was studied by means of isothermal gravimetry under various water vapor pressure, ranging from 4.6 to 24.4 torr. The kinetics of dehydration was described by a two-dimensional phase-boundary model,R ₂. The rate of dehydration decreased with increasing atmospheric water vapor pressure, but the Smith-Topley phenomenon was not observed for the present dehydration. The activation energy and the frequency factor for the dehydration were 110–170 kJ·mol⁻¹ and 10¹⁰–10¹⁶ cm·s⁻¹, respectively. These values increased with increasing water vapor pressure, and were much larger than those reported for the dehydration in vacuum.     

The kinetic and thermodynamic study of KNiPO4·H2O from DSC and TG data

The DSC and TG data showed the dehydration process occurring over the range of 160?C300?°C. The XRD patterns of the synthesized KNiPO₄·H₂O and the calcined product at 350?°C with exposing in the air over 8?h are indexed as the KNiPO₄·H₂O structure, whereas at 600?°C is indexed as KNiPO₄ structure. Hence, these data confirmed that the water molecule was eliminated from the structure at 300?°C, after that the spontaneously reversible hydration?Crehydration process was observed. The activation energy and pre-exponential factor were calculated by Kissinger, Ozawa, and KAS equations. According to the DSC curves, the enthalpy change (??H) of dehydration process can be calculated and was found to be 100.12?kJ?mol^?1. Besides, we suggested another new method to determine the isokinetic temperature value using spectroscopic data. The surface area of synthesized hydrate and its calcined product at 350?°C with exposing in the air at over 8?h were found to be 21.48 and 134.3?m²?g^?1, respectively. The reversible hydration?Crehydration process was observed, and the surface area of final product at 350?°C (aging time over 8?h) is higher than that of the synthesized compound. This behavior is important to develop alternative desiccant materials or other process based on the rehydration mechanism with increasing the surface area.     

Alkylation of isobutane with C<Subscript>4</Subscript> olefins under conventional and supercritical conditions

The solid acid alkylation of isobutane with butylenes on the ultrastable zeolite Y is studied in the temperature range from 120 to 150°C and in a pressure range of 20–120 atm. The catalyst service life becomes longer on passing from the conventional (liquid- and gas-phase) conditions of alkylation to supercritical conditions. The maximum period of complete butylene conversion at 150°C and 120 atm is 3.5 h. The composition of the reaction products is determined by the phase state of the reaction mixture, the reaction time, and the conversion of the C₄ olefins. When the alkylation is carried out under supercritical conditions, the C₈ hydrocarbon selectivity varies between 30 and 40%. Thermoanalytical data suggest that the surface of the spent catalyst contains carbon deposits indicating the formation of oligomeric and cyclic structures.     

Electrical conductivity and defect structure of Nd2O3+x

The electrical conductivity and departure from the stoichiometry of Nd₂O₃ have been measured over the temperature range of 900° to 1100°C and oxygen partial pressure of 1 to 10^?16 atm. The hole conductivity of Nd₂O₃ is found to be proportional to , where n are 4.6, 4.9, and 5.1 at 900°, 1000°, and 1100°C, respectively. From the oxygen partial pressure dependence of the hole conductivity, it is shown that the predominant point defects in nonstoichiometric NdO_1·+x are fully ionized and partially doubly ionized metal vacancies. From the thermogravimetric measurements, the departure from stoichiometry, x in NdO_1·5+x, is 2.0 × 10^?3 at 1000°C and 1 atm. By combining the electrical conductivity and weight change data, it is shown that the hole mobility is 6.3 × 10^?4 (cm²/V·sec) at 1000°C and 1 atm.     

Radiation-induced polymerization at high pressure of 2,3,3,3-tetrafluoropropene in bulk and with tetrafluoroethylene

The radiation-induced polymerization of 2,3,3,3-tetrafluoropropene was studied as a function of temperature (22–100°C) and pressure (autogenous to 10⁴ atm). Rates have varied 100-fold for the same reaction conditions probably because of trace impurities. The most rapidly polymerizing material has a rate of 4.5%/hr at 6000 atm, 22°C, and 1500 rad/hr. The activation enthalpy and volume are 4 kcal/mole and ?13 cc/mole, respectively. Rates are proportional to the square root of the radiation intensity. Degrees of polymerization varied between 2 × 10³ and 2 × 10⁶. In copolymerization with tetrafluoroethylene the reactivity ratios at 22°C and 5000 atm are 0.37 (the ratio for addition to the tetrafluoroethylene-ended radical) and 5.4 (the ratio for addition to the tetrafluoropropene-ended radical). Comparison of ratios for the copolymerization of other fluorinej-containing monomers with tetrafluoroethylene shows that they generally disfavor incorporation of the latter.     

Radiation-induced grafting of styrene vapor to polyethylene

The radiation-induced grafting of styrene vapor to low-density polyethylene film of 0.063 mm thickness was studied at 23°C at a dose rate of 1.98 × 10⁴ rad/hr. The concentration C of monomer in the film was measured as a function of pre-irradiation exposure time to monomer vapor. The concentration-dependent diffusion coefficient of styrene in polyethylene was calculated to be 4.9 × 10^?9 exp {2.0C/C₀} cm²/sec, where C₀ is the saturation concentration of styrene in the film, and a linear boundary diffusion coefficient for styrene vapor into polyethylene film was found to be 2.0 × 10^?7 cm/sec. The rate of grafting was determined as a function of the concentration of styrene absorbed in the film. The maximum graft yield was obtained with an initial styrene concentration in the film of 4 wt-%. Under conditions of low initial monomer concentration, the grafting rate increases with irradiation time. The results are compared with previously published data on grafting of polyethylene from methanol–styrene solutions. They are explained in terms of the viscosity of the amorphous region as a function of styrene content and the resistance to the diffusion of monomer at the film–vapor interface.