Combined kinetic analysis of thermal degradation of polymeric materials under any thermal pathway

Combined kinetic analysis has been applied for the first time to the thermal degradation of polymeric materials. The combined kinetic analysis allows the determination of the kinetic parameters from the simultaneous analysis of a set of experimental curves recorded under any thermal schedule. The method does not make any assumptions about the kinetic model or activation energy and allows analysis even when the process does not follow one of the ideal kinetic models already proposed in the literature. In the present paper the kinetics of the thermal degradation of both polytetrafluoroethylene (PTFE) and polyethylene (PE) have been analysed. It has been concluded, without previous assumptions on the kinetic model, that the thermal degradation of PTFE obeys a first order kinetic law, while the thermal degradation of PE follows a diffusion-controlled kinetic model.     

Kinetic approach to partially overlapped thermal decomposition processes

Practical usefulness of the kinetic deconvolution for partially overlapped thermal decomposition processes of solids was examined by applying to the co-precipitated basic zinc carbonate and zinc carbonate. Comparing with the experimental deconvolutions by thermoanalytical techniques and mathematical deconvolutions using different statistical fitting functions, performance of the kinetic deconvolution based on an accumulative kinetic equation for the independent processes overlapped partially was evaluated in views of the peak deconvolution and kinetic evaluation. Two-independent kinetic processes of thermal decompositions of basic zinc carbonate and zinc carbonate were successfully deconvoluted by means of the thermoanalytical measurements in flowing CO₂ and by applying sample controlled thermal analysis (SCTA). The deconvolutions by the mathematical curve fittings using different fitting functions and subsequent formal kinetic analysis provide acceptable values of the mass-loss fractions and apparent activation energies of the respective reaction processes, but the estimated kinetic model function changes depending on the fitting functions employed for the peak deconvolution. The mass-loss fractions and apparent kinetic parameters of the respective reaction processes can be optimized simultaneously by the kinetic deconvolution based on the kinetic equation through nonlinear least square analysis, where all the parameters indicated acceptable correspondences to those estimated through the experimental and mathematical deconvolutions. As long as the reaction processes overlapped are independent kinetically, the simple and rapid procedure of kinetic deconvolution is useful as a tool for characterizing the partially overlapped kinetic processes of the thermal decomposition of solids.     

Scale-up of batch kinetic models

The scale-up of batch kinetic models was studied by examining the kinetic fitting results of batch esterification reactions completed in 75 mL and 5 L reactors. Different temperatures, amounts of catalysts, and amounts of initial starting reagents were used to completely characterize the reaction. A custom written Matlab toolbox called GUIPRO was used to fit first-principles kinetic models directly to in-line NIR and Raman spectroscopic data. Second-order kinetic models provided calibration-free estimates of kinetic and thermodynamic reaction parameters, time dependent concentration profiles, and pure component spectra of reagents and product. The estimated kinetic and thermodynamic parameters showed good agreement between small-scale and large-scale reactions. The accuracy of pure component spectra estimates was validated by comparison to collected NIR and Raman pure component spectra. The model estimated product concentrations were also validated by comparison to concentrations measured by off-line GC analysis. Based on the good agreement between kinetic and thermodynamic parameters and comparison between actual and estimated concentration and spectral profiles, it was concluded that the scale-up of batch kinetic models was successful.     

Recent developments in non-enzymatic catalytic oxidative kinetic resolution of secondary alcohols

The goal of this review is to collect the recent developments in non-enzymatic catalytic oxidative kinetic resolutions of secondary alcohols reported since the beginning of 2011. It is divided into four sections, dealing successively with manganese-catalysed oxidative kinetic resolutions of secondary alcohols, palladium-catalysed oxidative kinetic resolutions of secondary alcohols, oxidative kinetic resolutions of secondary alcohols catalysed by other metals and organocatalysed oxidative kinetic resolutions of secondary alcohols.     

Mechanistic study of the Soai autocatalytic reaction informed by kinetic analysis

Detailed kinetic studies of the Soai reaction affirm the basic mechanistic picture previously developed in kinetic, spectroscopic and molecular modelling studies, and also suggest that refinements to the proposed elementary reaction steps must be considered. The alkanol reaction product is driven strongly and without bias towards the formation of homochiral and heterochiral dimers. The reaction is catalyzed by only the homochiral dimers. Consideration of the kinetic profiles from reactions carried out with different initial dialkylzinc concentrations support a proposal for a tetrameric transition state, but further experimental work is required to delineate the nature of this species. The power of reaction calorimetry as a kinetic tool for discerning subtle effects of the shape of the kinetic profile is highlighted. The importance of combining kinetic evidence with spectroscopic and other characterization tools is emphasized.     

Kinetic Analysis of Non-isothermal DSC Data. Computer-aided test of its applicability

The applicability of the kinetic analysis of data obtained by non-isothermal differential scanning calorimetry (DSC) is discussed. The Johnson-Mehl-Avrami (JMA) model was used for the computer simulation of DSC traces subsequently analysed by common methods of kinetic analysis of non-isothermal data. For the temperature-independent kinetic exponent n of the JMA equation, the kinetic analysis was shown to provide correct results, e.g. a correct kinetic model and apparent activation energy. On the other hand, for the temperature-dependent kinetic exponent, there is a great possibility of erroneous determination of the correct kinetic model and apparent activation energy, especially at higher heating rates. Since the temperature dependence of n cannot be determined on the basis of non-isothermal DSC experiments, conclusions must be drawn with appropriate caution. This revised version was published online in August 2006 with corrections to the Cover Date.     

Analysis of DTA curves and calculation of kinetic data using computer technique

Principles of two computer programs useful for the evaluation of heterogeneous kinetics are described.The first program ALANTA allows to obtain the non-isothermal kinetic curve from the shape of general DTA peak using the DTA-equation derived elsewhere¹.The second program SQUEST determines the kinetic mechanism which is the most appropriate to a given non-isothermal kinetic curve and evaluates the corresponding kinetic parameters. The program decides between 19 kinetic models and uses both integral and differential methods of evaluation.     

Cationic crosslinking of solid dgeba resins with ytterbium(III) trifluoromethanesulfonate as initiator

Solid bisphenol-A epoxy resin of medium molecular mass was cured using a Lewis acid initiator (ytterbium(III) trifluoromethanesulfonate) in three different proportions (0.5, 1 and 2 phr). A kinetic study was performed in a differential scanning calorimeter. The complete kinetic triplet was determined (activation energy, pre-exponential factor, and integral function of the degree of conversion) for each system. A kinetic analysis was performed with an integral isoconversional procedure (free model), and the kinetic model was determined both with the Coats-Redfern method (the obtained isoconversional value being accepted as the effective activation energy) and through the compensation effect. All the systems followed the same isothermal curing model simulated from non-isothermal ones. The growth-of-nuclei Avrami kinetic model A_3/2 has been proposed as the polymerization kinetic model. The addition of initiator accelerated the reaction especially when 2 phr was added. 0.5 and 1 phr showed very few kinetic differences between them.     

基于Monte Carlo模拟的化学反应动力学参数估算

提出并采用基于MonteCarlo模拟与动力学实验相结合的化学反应动力学参数估算方法,由基元反应确定MonteCarlo模拟具体做法,将MonteCarlo模拟结果与动力学实验结果相比较,根据比较结果自动调整和优化动力学参数,从而无需事先确定动力学方程即可有效估算各种化学反应的动力学参数值.采用该方法估算了丙烯氨氧化反应动力学参数,并对估算结果进行了分析与讨论.     

Extraction of the contribution of kinetic profile for reaction of a chemical species in unknown matrices by standard addition method

A new and simple strategy is applied to resolve kinetic profile for the reaction of an analyte in unknown matrices, using standard addition method (SAM). The proposed method uses kinetic spectrophotometric data obtained by standard addition of analyte into unknown mixtures followed by the reaction of analyte with a proper reagent. The proposed method extracts kinetic profile for the reaction of an analyte by averaging the kinetic profiles obtained by subtraction of kinetic profiles after and before standard addition. The rate constant can be obtained using computational curve fitting. The performance of method was evaluated by using synthetic data as well as several experimental data sets. The proposed method can be applied to obtain kinetic profiles of the reactions in the presence of additive interference as well as multiplicative interferences. Hydroxylation reaction of diphenylcarbazide (DPCI) in the presence of diphenylcarbazone (DPCO) as a real system at various pHs was also studied by the present method. The rate constant and the order of the hydroxylation reaction were determined from extracted kinetic profiles.     

Kinetic models of stem cell growth

A kinetic equation of the growth of stem cell populations has been suggested based on the quasichemical model of biological growth proposed earlier. A cycle of sequential stages of the development of stem cells is represented by quasichemical equations. The kinetic equations that describe the cell cycle allow us to quantitatively predict the development of stem cell inoculates of different types depending on the conditions. A kinetic model was developed in which the kinetic parameters were the experimental characteristics of population growth, unlike the parameters of extrapolation imitation models. The kinetic model is in good agreement with experiment within the error of the measurement procedure.     

次亚磷酸根在镍电极上的电氧化机理与动力学

用电化学质谱(EMS)和动力学模型分析等方法研究了次亚磷酸根在镍电极上的电化学氧化机理和动力学.研究表明，次亚磷酸根的电化学氧化是通过从P－H键脱离一个原子H，形成磷中心自由基(PHO2－•)，而磷中心自由基(PHO2－•)进一步进行电化学反应形成最终产物亚磷酸。利用该模型，推导出相关动力学方程并通过与实验数据拟合获得动力学参数.结果表明，该模型能很好地模拟次亚磷酸根在镍电极上的电化学氧化过程.     

On the dependence of kinetic parameters and functions in non-isothermal kinetics

The approaches to overcoming local ambiguity due to the dependence of the kinetic equation parameters are considered. The application of the mathematical apparatus of the Jacobi matrices enables one to determine the number of both independent kinetic parameters and kinetic functions used to describe a process. No more than five parameters in the Šestak-Berggren equation and only some kinetic functions are found to possess independence.     

Combined kinetic analysis of solid-state reactions: a powerful tool for the simultaneous determination of kinetic parameters and the kinetic model without previous assumptions on the reaction mechanism

The combined kinetic analysis implies a simultaneous analysis of experimental data representative of the forward solid-state reaction obtained under any experimental conditions. The analysis is based on the fact that when a solid-state reaction is described by a single activation energy, preexponetial factor and kinetic model, every experimental T-alpha-dalpha/dt triplet should fit the general differential equation independently of the experimental conditions used for recording such a triplet. Thus, only the correct kinetic model would fit all of the experimental data yielding a unique activation energy and preexponential factor. Nevertheless, a limitation of the method should be considered; thus, the proposed solid-state kinetic models have been derived by supposing ideal conditions, such as unique particle size and morphology. In real systems, deviations from such ideal conditions are expected, and therefore, experimental data might deviate from ideal equations. In this paper, we propose a modification in the combined kinetic analysis by using an empirical equation that fits every f(alpha) of the ideal kinetic models most extensively used in the literature and even their deviations produced by particle size distributions or heterogeneities in particle morphologies. The procedure here proposed allows the combined kinetic analysis of data obtained under any experimental conditions without any previous assumption about the kinetic model followed by the reaction. The procedure has been verified with simulated and experimental data.     

Determination of kinetic parameters of Cu(II) interaction with chemically modified thin chitosan membranes

In this work, vanillin-modified thin chitosan membranes were utilized as adsorbents for the removal of Cu(II) from aqueous solutions. A rise of temperature accelerates mass transfer of Cu(II) to the membranes surfaces. The kinetic data did present a rough fit to the traditional Lagergren adsorption kinetic equations. An alternative Avrami kinetic equation was successfully fitted to the kinetic adsorption quantities. From this new equation, from one to three regions presenting distinct kinetic parameters were found, and the use of the parameter n was also related to the determination of the kinetic orders. Variations of the adsorption rate in relation to the contact time and the temperature were also calculated and are discussed.     

New strategy to identify radicals in a time evolving EPR data set by multivariate curve resolution-alternating least squares

Electron paramagnetic resonance (EPR) spectroscopy is a powerful technique that is able to characterize radicals formed in kinetic reactions. However, spectral characterization of individual chemical species is often limited or even unmanageable due to the severe kinetic and spectral overlap among species in kinetic processes. Therefore, we applied, for the first time, multivariate curve resolution-alternating least squares (MCR-ALS) method to EPR time evolving data sets to model and characterize the different constituents in a kinetic reaction. Here we demonstrate the advantage of multivariate analysis in the investigation of radicals formed along the kinetic process of hydroxycoumarin in alkaline medium. Multiset analysis of several EPR-monitored kinetic experiments performed in different conditions revealed the individual paramagnetic centres as well as their kinetic profiles. The results obtained by MCR-ALS method demonstrate its prominent potential in analysis of EPR time evolved spectra.     

Ni－海泡石催化剂催化苯气相加氢动力学

Ｎｉ－海泡石催化剂催化苯气相加氢动力学曹声春，杨礼嫦，彭峰，黄孟光（湖南大学化工系，长沙４１００８２）关键词镍，海泡石，负载型催化剂，苯，加氢，反应动力学Ｎｉ一海泡石催化剂通过制备工艺的优化，可使其苯加氢催化活性、选择性、热稳定性和抗毒性都优于现工业...     

Non-equilibrium thermodynamics and kinetic theory of gas mixtures in the presence of interfaces

A broad range of the boundary value problems of the kinetic theory of gases and gas mixtures is considered based on kinetic theory and non-equilibrium thermodynamics. The interrelation of the kinetic theory and non-equilibrium thermodynamics is discussed. The balance equations at the interface are obtained for the case of the boundary layers with peculiar properties. Procedures for deriving the boundary conditions for slightly rarefied gas mixtures are outlined. The problems of calculating slip coefficients are discussed. The specificity of the kinetic effects in the boundary conditions is shown. A set of general relations related to gas mixture flows in capillaries is deduced. The possibility of non-equilibrium kinetic effects in the form of a paradoxical distribution of non-equilibrium temperature is shown. Methods of non-equilibrium thermodynamics are used to obtain the phenomenological equations describing the thermophoresis and diffusiophoresis of particles and cross phenomena. The growth and evaporation of droplets is considered based on kinetic theory and non-equilibrium thermodynamics.     

催化动力学分光光度法测定痕量铜的研究与应用

评述近年来催化动力学分光光度法测定痕量铜的研究进展,包括催化褪色动力学分光光度法、催化显色动力学分光光度法和阻抑动力学分光光度法,主要探讨各反应体系及其条件、方法的检出限、测定范围、应用等.研究新的高灵敏度指示反应、寻找新的活化剂、提高监测技术的灵敏度、对反应的机理进行研究、将催化动力学分析与其它分析技术相结合将是催化...