Factors that Influence the Kinetics of the Degradation of Poly(vinyl Chloride)

The degradation of five samples of PVC having different degrees of polymerization has been studied by a technique that permits a precise measurement of the rate of hydrogen chloride elimination as % HCl/min. All samples followed acceleratory kinetics at both low and high conversions. The conversion rate, which changed from the beginning to the end of a degradation, depended primarily upon the fraction of chains producing hydrogen chloride. The fraction of producing chains and the kinetic pattern were influenced by the presence of hydrogen chloride, the physical state of the sample, the previous degradation history, and the presence of intentionally added substances. Zipper kinetics permit the reproduction of kinetic data in terms of three parameters: k₁, the fraction of chains initiating per second, k₂, the fraction of a zip chain that zips per second, and k₃, an arbitrary parameter that accounts for residual hydrogen chloride after degradation has ceased.     

The Kinetics and Mechanism of the Thermal Dehydrochlorination of Poly(vinyl Chloride)

Poly(vinyl chloride) degrades thermally by an acceleratory reaction in which the rate of hydrogen chloride evolution is slow at the beginning, increases with time (passing through a maximum), and then decreases. A kinetic model based on the zipper mechanism shows excellent agreement with observed data from the initial to the final stages of each dehydrochlorination. Hydrogen chloride is shown to be essential for the initiation of zip chains and may or may not be essential for the zip reaction. When hydrogen chloride is removed in a stream of inert gas, as it is in some tests purported to study the kinetics of degradation, the initiation of zip chains is significantly inhibited. The zip reaction, once it has been initiated, is not inhibited or stopped even by long exposure to atmospheric conditions.     

Modelling dewatering behaviour through an understanding of solids formation processes. Part I--Solids formation considerations

An understanding of the mechanisms which control solids formation can provide information on the characteristics of the solids which are formed. These characteristics will in turn impact on dewatering behaviour. In this paper a model for solids formation is proposed. The first part of the model considers the hydrodynamics in the precipitation vessel, from which a reactant mixing model is developed. Spatially variant solution conditions are quantified (dynamically) using an equilibrium speciation model. These calculations are performed in conjunction with an adsorption model, accounting for equilibria involving adsorbed species. The kinetics of solids formation, including nucleation, growth and aggregation, are described empirically using spatially variant supersaturation profiles. These, together with moment transformations of the solids population balance, describe the evolution of particle sizes throughout the precipitation process. Precipitation of nickel hydroxide is explored experimentally, and models developed are fitted to the results. Comments are offered on the impact of simplifications required for computational reasons, and assumptions required due to lack of information, on the accuracy of the model. In part II of this paper, the use of model outputs in predicting filtration behaviour is explored.     

Time-parameter Method for Studying Kinetics of Consecutive First-order Reactions in Calorimeter

Thermogravimetric analysis (TG) was used in this work to study the degradation kinetics of industrial PVC plastisols. In order to model the pyrolitic degradation of plastisols in nitrogen, a kinetic model based on phenomenological considerations was developed. Two different processes were observed during the first degradation stage. The model parameters, such as activation energies and pseudo orders of reaction, were calculated using a non-linear regression analysis. The model developed was able to describe the degradation behaviour both in isothermal and in dynamic modes. The results of such analysis were applied to obtain long-term data from short-term experiments as an engineering approach to evaluate the thermal resistance of plastisols. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚羟基烷酸酯酶降解动力学研究

研究了羟基丁酸 羟基戊酸共聚物 (PHBV)在脂肪酶中的降解行为 ,用滴定法测定降解速度并进行酶促反应动力学研究 .探讨了降解速度与酶浓度和底物浓度的数学关系和Michaelis Menten常数 ,从实验上和理论上证实了PHBV的物理形态和几何尺寸对酶降解过程的影响 ,以及实验数据与非均相动力学模型的拟合     

Remarks on the suitability of Chatterjee's method for the kinetic analysis of TG traces

It is shown that Chatterjee's method cannot be used at all to determine the value ofn in reactions of thermal degradation of solids followingn-order kinetics. It has been demonstrated that, if heat and mass transfer effects are avoided, the reaction order obtained from this method will be equal to one whatever the reaction mechanism.     

The effects of fast neutron,gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate powder-aluminum particle mixtures

The thermal decomposition kinetics of irradiated and unirradiated ammonium perchlorate and ammonium perchlorate powder-aluminum particle mixtures has been studied by determining decomposition gas pressurevs. heating time with samples at a controlled temperature Qualitatively the radiation induced changes are similar to those obtained in previous studies on ‘pure’ ammonium perchlorate. The induction period is shortened and the acceleratory and decay period rate constants are increased. The data have been analyzed using Avrami-Erofeev kinetics. The results for pure unirradiated material are in accord with published results. The activation energies for the induction, acceleratory and decay periods for pure pellets were found to be 133.5±6.7, 131.8±6.7 and 127.2±6.7 kJ·mol, respectively. Samples were exposed to either a single gamma-ray irradiation, fission neutron irradiation followed by a gamma-ray irradiation, or to a proton irradiation. When compared on an equal energy deposited basis, the fast neutron induced changes are appreciably larger than the gamma-ray changes. However, the proton induced changes are comparable or slightly more than the gamma-ray effects. Some, or all, of the fast neutron effects can be attributable to the concentrated radiation damage ‘spikes’ along the path of lattice atom recoils. It is likely that these become thermal decomposition sites when the crystals are heated. Protons create fewer spikes than fast neutrons. Overall, the results indicate that any ammonium perchlorate-aluminum propellant mixtures that may be exposed to radiation environments, such as used in this study, should be subjected to a thorough radiation effects analysis if reliable performance is required. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Mechanism of phenol degradation processes induced by direct-current atmospheric-pressure discharge in air

The phenol degradation kinetics and the buildup kinetics of the products hydroxyphenols, nitrophenols, carboxylic acids, and formaldehyde in electrolytic-cathode direct-current discharge have been studied, as well as the formation of nitric acid. On the basis of the results, a scheme of the processes has been proposed; calculations according to this scheme describe well the experimental data on the degradation kinetics of phenol and the formation/decay kinetics of its transformation products.     

Applicability of one-stage chemical reaction kinetic equation to describe non-isothermal destruction processes

The applicability of the traditional kinetic power equation to describe the thermal destruction of solids, and in particular polymers, is discussed. It is shown that in the majority of cases the use of such an equation is reasonable, even though the true mechanism of the process under study is either obscure or so complex that it cannot be analytically described in detail. In such cases the effective rather than the true kinetic parameters are obtained and provide certain useful information on the process. The fixed conversion temperature dependence on the heating rate is analyzed with examples on the model process and the thermal degradation of an epoxy binder.     

乙醇的低温光催化氧化实验研究

利用傅里叶变换红外光谱仪(FT-IR)，在间歇式反应器中研究了高浓度乙醇的低温光催化氧化特性。研究结果表明，FT-IR技术能够用来研究气态有机物的光催化降解特性；在乙醇的光催化降解过程中，有乙醛等中间产物生成，乙醇先被氧化为乙醛，再被氧化为二氧化碳；在间歇式反应器中，乙醇的循环流量对乙醇的瞬时降解速率影响不大；高浓度乙醇的低温光催化氧化过程可以用单步Langmuir-Hinshelwood 方程来描述；温度对乙醇光催化氧化的初始反应速率的影响十分显著，高浓度乙醇的初始反应速率随温度的升高而迅速提高。     

Hybrid neural modeling of bioprocesses using functional link networks

The objective of this work was to develop a model for an extractive ethanol fermentation in a simple and rapid way. This model must be sufficiently reliable to be used for posterior optimization and control studies. A hybrid neural model was developed, combining mass and energy balances with neural networks, which describe the process kinetics. To determine the best model, two structures of neural networks were compared: the functional link networks and the feedforward neural networks. The two structures are shown to describe well the process kinetics, and the advantages of using the functional link networks are discussed.     

Kinetic analysis of the thermal degradation of an epoxy-based intumescent coating

The aim of this work is to analyse and to simulate the kinetics of pyrolysis of an intumescent formulation designed to protect steel in the case of hydrocarbon and jet fires. The coating is based on a thermoset epoxy-amine resin system into which two fire retardant agents, boric acid and ammonium polyphosphate derivative have been incorporated. Industrial tests (jet fire tests) are usually used to evaluate the degradation mode of an intumescent coating. But these tests are quite expensive, and as the heating rates are extremely high (between 500 and 800 °C/min), it is not possible to evaluate the thermal degradation behaviour of the intumescent coating directly by thermogravimetric analyses. That is why it is necessary to develop predictive models of kinetics of degradation of these intumescent coatings. In this work, the coating has been pyrolyzed at different heating rates and a predictive model of its kinetics of degradation has been developed.     

A Thermogravimetric Approach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid)

Summary: An amorphous grade Poly (lactic acid) (PLA) was selected for an accelerated burial in soil test during 450 days. Thermogravimetric analyses were carried out to study the effects of degradation in soil on the thermal stability and the thermal decomposition kinetics. A single stage decomposition process is observed for all degradation times. It is shown that the thermal stability of PLA is slightly affected by degradation in soil. Concerning the study of the thermal decomposition kinetics, Criado master curves were plotted from experimental data to focus the study of the thermodegradation kinetic model.The kinetic methods proposed by Broido and Chang were used to calculate the apparent activation energies (Ea) of the degradation mechanism. These results were compared to the Ea values obtained by the method developed by Coats and Redfern in order to prove the applicability of the former methods to the kinetic study. As expected, non-linear tendency is found out for Ea variation along the degradation times, which can be explained as an evolution by stages.     

A study of the mechanism and kinetics of cyclooctene epoxidation catalyzed by iron(III) tetrakispentafluorophenyl porphyrin

A study has been conducted of the mechanism and kinetics of cyclooctene epoxidation by hydrogen peroxide catalyzed by iron(III) tetrakispentafluorophenyl [F(20)TPPFe(III)] porphyrin. The formation of cyclooctene oxide, the only product, was determined by gas chromatography, and the consumption of hydrogen peroxide was determined by (1)H NMR. UV-visible spectroscopy was used to identify the state of the porphyrin as a function of solvent composition and reaction conditions and to follow the kinetics of porphyrin degradation. F(20)TPPFe(III) was found to be inactive in the chloride-ligated form, but became active when the chloride ligand was replaced by a methoxide ligand. The methoxide-ligated form of F(20)TPPFe(III) reacts with hydrogen peroxide to form an iron(III) hydroperoxide species, which then undergoes both heterolytic and homolytic cleavage to form iron(IV) pi-radical cations and iron(IV) oxo species, respectively. The iron(IV) pi-radical cations are responsible for the epoxidation of cyclooctene, whereas the iron(IV) oxo species are responsible for hydrogen peroxide decomposition. The kinetics of cyclooctene epoxidation and hydrogen peroxide decomposition developed from the proposed mechanism describe the experimentally observed kinetics accurately. The rate parameters derived from a fit of the model to the experimental data are consistent with previous estimates of the magnitude of these parameters.     

DSC study of the kinetics of the thermal dehydration of BaCl2 · 2H2O and BaCl2 · H2O

The kinetics of the thermal dehydration of various kinds of BaCl₂ · 2H₂O and of BaCl₂ · H₂O are investigated using a differential scanning calorimeter. The loss of H₂O proceeds in two steps: BaCl₂ · 2H₂O→BaCl₂ · H₂O→BaCl₂ and is therefore revealed by two endothermic peaks. In the experiments at varying temperature both steps follow a contracting-circle law, after an initial acceleratory stage according to a (n=2) power law. In the experiments at constant temperature, after an initial acceleratory stage according to a (n=2) power law, both steps (except BaCl₂ · 2H₂O single-crystals which follow a contracting-circle law) follow an Avrami-Erofeev law (withn=2) in the form used by Galwey and Jacobs. The activation energies for the various steps are compared and the different kinetic behaviour is discussed.     

A collision theory-based derivation of semiempirical equations for modeling dispersive kinetics and their application to a mixed-phase crystal decomposition

In recent works, the author has shown the utility of new, semiempirical kinetic model equations for treating dispersive chemical processes ranging from slow (minute/hour time scale) solid-state phase transformations to ultrafast (femtosecond) reactions in the gas phase. These two fundamental models (one for homogeneous/deceleratory sigmoidal conversion kinetics and the other for heterogeneous/acceleratory sigmoidal kinetics; isothermal conditions), based on the assumption of a "Maxwell-Boltzmann-like" distribution of molecular activation energies, provide a novel, quantum-based interpretation of the kinetics. As an extension to previous work, it is shown here that the derivation of these dispersive kinetic equations is supported by classical collision theory (i.e., for gas-phase applications). Furthermore, the successful application of the approach to the kinetic modeling of the solid-state decomposition of a binary system, CO2.C2H2, is demonstrated. Finally, the models derived appear to explain some of the (solid-state) kinetic data collected using isoconversional techniques such as those often reported in the thermal analysis literature.     

Photo-crosslinked acrylates degradation kinetics

A series of crosslinked polyurethane acrylate solids with glass transition temperatures ranging from –49 to +65 °C was prepared by photopolymerization of specially formulated solvent-free resins. The kinetics of thermooxidative and thermal (in N₂) degradation of these crosslinked acrylate networks at temperatures ranging from 100 to 400 °C was studied as a function of crosslink density using thermogravimetry. The polyacrylate network degradation rate decreased with the increase of crosslink density, while apparent activation energy of degradation increased. Polyacrylate thermal stability increase with crosslinking was explained by decreased rate of oxygen and volatile products diffusion and/or slowing of depolymerization due to increased radical recombination rate, and decreased chain segments mobility in systems with higher crosslink density.     

Phase behavior of ranitidine HCl in the presence of degradants and atmospheric moisture--impact on chemical stability

For hydrophilic organic solids, it is well recognized that degradation is often promoted by exposure to humid conditions. Although this is an important issue for certain classes of materials, in particular pharmaceuticals, the factors which dictate the sensitivity of a given compound to moisture are not well understood. The goal of this work was to elucidate the synergistic influence of self-originating impurities and water vapor on the degradation kinetics of the histamine H2 receptor antagonist, ranitidine HCl. Physical mixtures of the drug and each of three major degradation products were subjected to conditions of elevated temperature and relative humidities. Pure samples showed a sigmoidal-shaped degradation profile for all storage conditions studied. During the lag time, the pure drug gained minimal quantities of moisture. Once degradation commenced, the samples started to absorb moisture. When mixed with the degradant, the lag period was eliminated for all storage conditions, even at low partial pressures of water. The extent of moisture gain by samples containing impurities could not be attributed to the presence of the impurity alone. It was found that the presence of impurities in contact with the surface of the drug, in combination with water vapor, promoted a phase transition of the crystalline material to the solution phase. A ternary phase diagram was constructed to visualize the proportion of the drug in the solid and solution phases as a function of impurity and moisture content. The increased mobility of molecules in solution presumably leads to enhanced reactivity relative to the crystalline material.