The non-oxidative thermal degradation of poly (Di-2-chloroethyl itaconate)

The non-oxidative thermal degradation of poly (di-2-chloroethyl itaconate) (PD2CEI) was studied by TG and by analysing the thermal products. The major processes occurring during thermal analysis are crosslinking, depolymerisation and carbonisation. The thermal degradation activation energy increased with increasing sample mass loss. The thermal degradation of PD2CEI was compared to that of the structurally similar poly(2-chloroethyl methacrylate) (P2CMA).     

Inclusion by a fluorenyl diol host with substituted pyridines

The structures of the inclusion compounds formed by the host 9,9’-(ethyne-1,2-diyl)bis(fluoren-9-01) with pyridine and picolines are similar and display tubular topology. The host discriminates poorly between these guests. The kinetics of desorption of the pyridine compound is governed by the Avrami-Erofe’ev equation A2, with an activation energy of 111(7) kJ mol⁻¹.     

Thermoanalytical study of glibenclamide and excipients

Summary Taking into account the problems of desertification and agricultural practices able to provide income to the population at the semi-arid region of North-East Brazil, this work presents the results of the chemical and thermal characterization by TG and DSC of the seed derivatives of Cnidoscolus quercifolius, hereinafter called faveleira, aiming at the application of these materials as an alternative of food source for animals and for the human population at this region. The faveleira seed derivatives present thermodynamic properties similar to the ones of other foods utilized for human use, as well as an acceptable calorific value. According to TG and DSC results, was verified that the faveleira derivatives presents good thermal and oxidative stabilities.     

高岭石无定形化的动力学研究

Amorphous kaolinite derivatives were prepared through mixing kaolinite with HCOOK and KOH solution. Ki-netics of kaolinite being turned into amorphous derivatvies was investigated by XRD. It showed that the transfor-mation included dynamic and diffuse controlling stages. And the active energy E₁=26.8kJ·mol^-1; E₂=12.2 kJ·mol^-1. TEM and SEM images showed that particle size of the amorphous derivatives was about 50nm. And the amorphous derivatives seemed like alumnsilicate gel， accompanied by some aggregates.     

Relative kinetics of the homolytic addition of 2-phenyl-1,3-dioxolane to unsaturated compounds

The CH₂ = CHX olefins form a series relative to their reactivity in reactions with 2-phenyl-1,3-dioxolan-2-yl radicals, which qualitatively correlates with the electron-withdrawing capacity of substituent X: CN CO₂Me >> SiMe₃ C₄H₉. This behavior indicates that the dioxolanyl radical is nucleophilic.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1663–1666, July, 1992.     

Stopped-flow injection analysis. The influence of diffusion on dispersion of normal and reverse flow injection

A relationship is derived to enable the comparison of the dispersion heights of normal and reverse flow injection analysis (FIA). A single channel flow system is employed in the absence of a chemical reaction. The stopped-flow injection method is used to probe the influence of molecular diffusion on the overall dispersion of normal and reverse FIA, which appeared to demonstrate fundamentally different diffusion behaviors. Small discrepancies are observed between the dispersion heights, which are enhanced by the stopped-flow period, especially when unmatched matrix ionic compositions of the indicator and counter solutions were involved. For these conditions, the diffusion flux rate is enhanced considerably, displaying a peak, in addition to the transient, for both methods. The influence of diffusion on the dispersion characteristics of normal and reverse FIA is discussed theoretically. Diffusion in the proposed model is postulated to oppose dispersion by convection. The latter initiates concentration gradients in the injection zone and propagates it with flow time over the dispersion zone profile. The diffusion flux then reacts in order to confine the indicator dispersion for normal FIA and to enhance it for reverse FIA. This model is consistent with the experimental results and accounts for most of the phenomena encountered. Probably owing to the influence of secondary flow phenomena, the use of coiled tubes has suppressed the effects of diffusion on the overall dispersion behavior.Part of the experimental work was performed at IMI Institute for Research and Development, Haifa, Israel.     

Kinetics of thermal decomposition of alkaline phosphates

Summary The thermal behavior of KH₂PO₄, NaH₂PO₄ and Na₂HPO₄ under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedmans differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.     

Kinetics of the surface tension of micellar solutions: Comparison of different experimental techniques

The kinetics of the surface tension of micellar solutions of nonionic surfactant Triton X-100 is measured experimentally by means of three different techniques: oscillating jet, maximum bubble pressure and inclined plate. They allow to study the micellization kinetics at various time scales (from a few milliseconds to a few seconds) in fairly large concentration region up to 50 times CMC. The experimental data are satisfactorily explained by a theoretical model accounting for the kinetics of micellization, diffusion of surfactant species and expansion of the bubble interface. By this model are computed the characteristic times of diffusion and micellization, which are of comparable magnitude (about 5 to 200 ms), and the Gibbs' elasticity. The micellization time constant corresponds to the slow relaxation process known to coincide with the disintegration of micelles. Comparing our data with other data from literature one can conclude that more realistic information for the micellization kinetics is obtained by the maximum bubble pressure and the oscillating jet method. The inclined plate seems too slow to measure the relaxation processes in micellar solutions of this surfactant.     

La—Ba—Na—O催化剂上甲烷氧化偶联宏观反应动力学研究

甲烷氧化偶联反应在不同催化剂体系上动力学的研究各不相同,我们已报道了La-Ba-O系复合氧化物催化剂对此反应的优良催化性能。本文则是对该催化剂上的甲烷氧化偶联反应的动力学进行初步探讨。     

Combined use of high resolution TGA with the isoconversion method: Kinetic analysis of the thermal dehydration of KNbWO6·H2O

In the present study was combined the use of high resolution TGA with the isoconversion method, giving us a suitable methodology for determining the stages that occur during a reaction, and providing further insights about the kinetics of the processes involved. As a model reaction was used the thermal dehydration of KNbWO₆·H₂O. The results shown that the dehydration process is controlled by internal water diffusion (intra-crystallite); with activation energy values between 43 and 36 kJ/mol. This value is consistent with a diffusion mechanism dominated by van der Waals attractions. The estimated kinetic parameters are supported with a structural analysis, that suggest lower dimensionality character for water diffusion due to the specific orientations of 〈1 1 0〉 open channels in the pyrochlore framework. This would explain why the two-dimensional (D2) mechanism appears to be the most probable.