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- Author or Editor: Y. Chen x
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Abstract
A novel thermokinetic research method for determination of the rate constant of a reaction taking place in a batch conduction calorimeter under isothermal conditions is proposed: the double-thermoanalytical curve method. The method needs only the characteristic time parameter t m, the peak height Δm at time t m and the peak area a*m after time t m for two thermoanalytical curves measured with different initial concentrations of the reactants: it conveniently calculates the rate constants. The thermokinetics of four reaction systems were studied with this method, and its validity was verified by the experimental results.
Abstract
Thermal behaviour of tri(O,O'-diisopropyldithiophosphate)cobalt(III), Co(dptp)3 and bis (O,O'-diethyldithiophosphate)nickel(II), Ni(detp)2 and its adducts with pyridine, Ni(detp)2(py)2 or 4-methylpyridine, Ni(detp)(mpy)2 in a dynamic nitrogen atmosphere was investigated by TG-DTG and DSC techniques, which showed a medium endothermic peak for the evolution process of pyridine(or 4-methylpyridine) and a strong exothermic peak for that of O,O'-diethyldithiophosphate. The thermal stability and decomposition patterns for these compounds were compared and interpreted in terms of structural features such as bond character and steric effects. The kinetic parameters and mechanisms of every decomposition stage involved for all these complexes were obtained employing the non-isothermal kinetic analysis method suggested by Malek et al., which showed the kinetics mechanism for pyrolysis of pyridine(or 4-methylpyridine) is an S-B empirical model with lower activation energy, while that of O,O'-dialkyldithiophosphate is a diffusion model. These results are in accord with the fact that two ligands are of different type.
Abstract
A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.
Abstract
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.
Abstract
The flammability characteristics of chemical substances are very important for safety considerations in manufacturing processes. This study investigated the mixing of toluene and methanol mixtures with five vapor mixing ratios (100/0, 75/25, 50/50, 25/75 and 0/100 vol.%) at initial conditions of 1 atm and 150°C, and determined the flammability properties to identify their potential fire and explosion hazards. These safety-related parameters included lower explosion limit (LEL), upper explosion limit (UEL), maximum explosion overpressure (P max) and rate of maximum explosion pressure rise ((dP/dt)max); all of them were measured by a 20-L-Apparatus. In terms of flammability tests for this research, the experimental results indicated that when methanol was increased, which could induce a higher range of flammability, afterwards the situation could be triggered to a dangerous level, such as fire or explosion. Based on the above-mentioned, we could obtain a series of flammability properties and provide inherently safer design in related industrial processes for preventing serious fire and explosion accidents.
Abstract
A method of efficiency calibration for the measurement of 88Kr and 138Xe by HPGe γ-spectrometer is proposed in the present paper. The question for the efficient calibration is, how to achieve homogeneous sources of 88Kr-88Rb and 138Xe-138Cs. The fission product gases were obtained by irradiating a precisely measured amount of U3O8 (90% 235U) filled in a quartz glass ampoule. Source cell was first filled up with stearic acid, and then the fission product gases were charged into it. Xenon and krypton are not adsorbed on stearic acid, therefore, homogeneous sources of 88Kr-88Rb and 138Xe-138Cs can be prepared. The results of the experiment demonstrate that the method is feasible and successful.
Abstract
New complexes of the non-natural amino acid (p-iodo-phenylalanine) with divalent cobalt and nickel ions have been synthesized. The composition of the complexes is [M(IC6H4CH2CHNH2COO)2]2.5H2O (M=Co, Ni) and the crystal structure belongs to orthorhombic system. Infrared spectra indicate the nature of bonding in the complex. The first stage in the thermal decomposition process of the complex shows the presence of crystal water. The thermal decomposition process of cobalt complex differs from that of nickel. The intermediate and final residues in the thermal decomposition process have been analyzed to check the pyrolysis reactions. Thermal analysis indicates that the iodine atom of the ligand may coordinate to the metal ion in the lattice.
Abstract
This study was performed under the joint TRMC/INER program for the determination of low level85Kr and133Xe concentrations in the environmental air samples. Based on cryogenic adsorption of krypton and xenon on charcoal followed by chromatographic separation from other gases, the85Kr and133Xe recovered from 200 liters of atmospheric air can be determined by either on-line gas flow proportional counter or liquid scintillation counting. The recovery yields of krypton and xenon examined by using85Kr and133Xe tracers were nearly 100%. The minimum detectable activity of85Kr and133Xe by gas flow proportional counting is about 7.40 Bq. The method is satisfactory for environmental monitoring applications under abnormal conditions of nuclear facilities. However, for lower level environmental85Kr and133Xe measurements, the liquid scintillation counting method can be applied due to their extremely low detection limits (i.e. 0.107 Bq and 0.093 Bq for85Kr and133Xe, respectively). Using this method, the measurable limits of concentrations are 0.535 Bq/m3 and 0.466 Bq/m3 for85Kr and133Xe, respectively.
Abstract
The —T and d/dT—T curves of the FeCuNbSiB amorphous alloy, which are the relationship between the total saturated magnetic moment per unit mass and temperature, are investigated by magnetic thermogravimetry analysis (TG(M)) technique. It is found that the crystallization process of the samples can be divided into five stages. The studies of samples annealed in temperature range of 480–610°C for 1h show that when the annealing temperature (T a) is less than 540°C, the quantity of nanocrystalline -Fe(Si) phase increases evidently with T a, and the Curie temperature (T C) of residual amorphous phase also increases linearly with T a, i.e. T C=0.52T a+91.7°C, with correlation coefficient =0.98. The variation of volume fraction of -Fe(Si) nanocrystalline phase or residual amorphous phase with T a is measured by TG(M) technique.
Abstract
On the basis of the theory of thermokinetics proposed in the literature, a novel thermokinetic method for determination of the reaction rate, the characteristic parameter method, is proposed in this paper. Mathematical models were established to determine the kinetic parameters and rate constants. In order to test the validity of this method, the saponifications of ethyl benzoate, ethyl acetate and ethyl propionate, and the formation of hexamethylenetetramine were studied with this method. The rate constants calculated with this method are in agreement with those in the literature, and the characteristic parameter method is therefore believed to be correct.In the light of the characteristic parameter method, we have developed further two thermo-kinetic methods, the thermoanalytical single and multi-curve methods, which are convenient for simultaneous determination of the reaction order and the rate constant. The reaction orders and rate constants of the saponifications of ethyl acetate and ethyl butyrate and the ring-opening reaction of epichlorohydrin with hydrobromic acid were determined with these methods, and their validity was verified by the experimental results.