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The Non-Parametric Kinetics A New Method for the Kinetic Study of Thermoanalytical Data 总被引:1,自引:0,他引:1
The application of the new method non-parametric kinetics for kinetic analysis is discussed. It is shown that this method
is able to obtain all the kinetic information needed to reproduce accurately the experimental data. To validate this method
a set of numerical simulations of the most commonly used kinetic models has been performed and analysed with the method.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
3.
对于非等温过程中的动力学方程,正确的Arrhenius方程的温度积分应该是从T2到T1,但是许多动力学方程中的温度积分是从T到0 K,例如Ozawa等方程。我们的研究指出对于某些反应,这些方程中的活化能存在较大的误差,因此我们提出了一个新的动力学方程。凭借等转化率法,应用新的方程可以精确求解线性或非线性加热过程中化学反应的活化能。用新方程对2个经典反应(聚酰胺的热裂解和一水草酸钙的热分解)的研究表明:Ozawa方程的活化能有时是精确的,有时偏差太大。 相似文献
4.
The most accurate and up-to-date approach to modeling biomass pyrolysis is to adopt the distributed activation energy model
(DAEM). In this study, a pattern search method to be used for the determination of DAEM kinetic parameters from the nonisothermal
thermogravimetric analysis (TGA) data of biomass has been introduced. The method has been applied to the nonisothermal TGA
data of peanut shell sample, and DAEM kinetic parameters of biomass samples have been determined. Calculated model results
from determined kinetic parameters have been compared with nonisothermal TGA data of biomass. 相似文献
5.
介绍一种处理动力学数据的新方法——反应进程动力学分析法(Reaction Progress Kinetic Analysis)。该方法通过反应速率除以一个反应物的浓度对另外一个反应物的浓度作图,结合不同超额浓度和相同超额浓度的3个实验,得到反应级数以及催化剂稳定性等信息。 相似文献
6.
Arrhenius parameters values, in non-isothermal kinetic vaporisation processes for a series of compounds with related structures,
have been calculated. This was made using a method of calculation that allows to find the most probable vaporisation mechanisms.
According to this method DTG curves were compared with some theoretical ones reported in literature, whose shape results to
be only a function of the mechanisms. In this way the choice of the mathematical functions which can be inserted in the kinetic
equations, was influenced by the shape of the DTG plots and other thermal analysis signals thus allowing to choose the most
probable mechanisms.
The kinetic parameters derived from these mechanisms were compared, using statistical analysis, with those obtained from another
method of calculation based on ‘a priori’ vaporisation mechanism chosen for the investigated liquid–gas transition.
The standard deviations of the slope and of the intercept, together with the standard deviation and the square correlation
coefficient (r
2) of the linear regression equations related to the mechanisms of the two methods were calculated. Student t-test, Fisher F-test, confidence intervals (c.i.) and residuals valueswere also given.
Statistical analysis shows that the mechanisms obtained with the former method (diffusive and geometrical models) and the
related Arrhenius parameters result to be more significant (in terms of probability) than the corresponding quantities of
the latter for which a first-order model was chosen.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
7.
Małecki A. Prochowska-Klisch B. Wojciechowski K. T. 《Journal of Thermal Analysis and Calorimetry》1998,54(1):399-406
A detailed analysis is presented of the applicability of several dependences commonly used for the determination of activation
energies from non-isothermal measurements. Reactions proceeding according to different kinetic equations are simulated and
the validity of the activation energy values obtained is discussed. The general conclusion is drawn that none of the examined
dependences should be used to determine the activation energy. For a rough estimation of activation energy, the Kissinger
equation can be applied according to Ockham's razor.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
8.
In
this research, thermal characterization and kinetics of Karakus crude oil
in the presence of limestone matrix is investigated. Thermogravimetry (TG/DTG)
is used to characterize the crude oil in the temperature range of 20-900°C,
at 10°C min -1 heating rate using air
flow rate of 20 mL min -1. In combustion
with air, three distinct reaction regions were identified known as low temperature
oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO).
Five different kinetic methods used to analyze the TG/DTG data to identify
reaction parameters as activation energy and Arrhenius constant. On the other
hand different f(α) models from literature
were also applied to make comparison. It was observed that high temperature
oxidation temperature (HTO) activation energy of Karakus crude oil is varied
between 54.1 and 86.1 kJ mol -1, while low
temperature oxidation temperature (LTO) is varied between 6.9 and 8.9 kJ mol -1. 相似文献
9.
Kök M. V. Pokol G. Keskin C. Madarász J. Bagci S. 《Journal of Thermal Analysis and Calorimetry》2004,75(3):781-789
In this study the combustion characteristics of crude oils (Karakuę and Beykan) in the presence of a limestone matrix were
determined using the thermogravimetry (TG/DTG). Experiments were performed at a heating rate of 10°C min-1, whereas the air flow rate was kept constant at 10 L h-1 in the temperature range of 20-900°C. In combustion with air, three distinct reaction regions were identified in all crude
oil/limestone mixtures studied known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation
(HTO). The individual activation energies for each reaction region may be attributed to different reaction mechanisms, but
they do not give any indication of the contribution of each region to the overall reactivity of the crude oils. Depending
on the characteristics, the mean activation energy of samples varied between 50.3 and 55.8 kJ mol-1.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
10.
The integral methods are extensively used for performing the kinetic analysis of solid-state reactions. As the Arrhenius integral
function p(u) does not have an exact analytical solution, many approximations have been proposed. One popular type of approximations is
called the exponent approximation which can be put in the form . In this study, a systematic analysis of the errors involved in the determination of the kinetic parameters calculated by
the integral methods based on the exponent approximations for p(u) has been carried out. The results have shown that the precision of the kinetic parameters computed from the integral methods
analyzed in this paper depends on u and the errors of the kinetic parameters determined from Doyle approach are the largest. 相似文献
11.
过氧铌杂多钨酸盐热分解动力学参数的测定 总被引:9,自引:0,他引:9
钼和钨的杂多配合物由于其高催化活性及抗病毒性吸引着人们的关注[1]。杂多配合物的组成改变能调变其酸性、氧化性、反应性等,因此,混配型杂多配合物的研究近二十年来十分活跃。铌取代的杂多配合物在催化方面具有很独特的性质,其催化的工业应用及其机理已引起广泛的兴趣[2]。我们发现,过氧铌杂多配合物比非过氧杂多配合物具有更高的催化活性[3]。杂多酸盐的热稳定性是影响多相催化活性的重要性质,迄今有关过氧杂多配合物的热性质和热分解反应动力学参数的研究未见报道。本文用TG、DTA、DSC溶解度试验,变温红外和X一… 相似文献
12.
A. K. Galwey 《Journal of Thermal Analysis and Calorimetry》2006,86(1):267-286
This critical
survey argues that the theory, conventionally used to interpret kinetic data
measured for thermal reactions of initially solid reactants, is not always
suitable for elucidating reaction chemistry and mechanisms or for identifying
reactivity controls. Studies of solid-state decompositions published before
the 1960s usually portrayed the reaction rate as determined by Arrhenius type
models closely related to those formulated for homogeneous rate processes,
though scientific justifications for these parallels remained incompletely
established. Since the 1960s, when thermal analysis techniques were developed,
studies of solid-state decompositions contributed to establishment of the
new experimental techniques, but research interest became redirected towards
increasing the capabilities of automated equipment to collect, to store and
later to analyze rate changes for selected reactions. Subsequently, much less
attention has been directed towards chemical features of the rate processes
studied, which have included a range of reactants that is much more diverse
than the simple solid-state reactions with which early thermokinetic studies
were principally concerned. Moreover, the theory applied to these various
reactants does not recognize the possible complexities of behaviour that may
include mechanisms involving melting and/or concurrent/consecutive reactions,
etc. The situation that has arisen following, and attributable to, the eclipse
of solid-state decomposition studies by thermal analysis, is presented here
and the consequences critically discussed in a historical context. It is concluded
that methods currently used for kinetic and mechanistic investigations of
all types of thermal reactions indiscriminately considered by the same, but
inadequate theory, are unsatisfactory. Urgent and fundamental reappraisal
of the theoretical foundations of thermokinetic chemical studies is now necessary
and overdue.
While there are important, but hitherto unrecognized,
delusions in thermokinetic methods and theories, an alternative theoretical
explanation that accounts for many physical and chemical features of crystolysis
reactions has been proposed. However, this novel but general model for the
thermal behaviour and properties of solids has similarly remained ignored
by the thermoanalytical community. The objective of this article is to emphasize
the now pressing necessity for an open debate between these unreconciled opinions
of different groups of researchers. The ethos of science is that disagreement
between rival theories can be resolved by experiment and/or discussion, which
may also strengthen the foundations of the subject in the process. As pointed
out below, during recent years there has been no movement towards attempting
to resolve some fundamental differences of opinion in a field that lacks an
adequate theory. This should be unacceptable to all concerned. Here some criticisms
are made of specific features of the alternative reaction models available
with the stated intention of provoking a debate that might lead to identification
of the significant differences between the currently irreconciled views. This
could, of course, attract the displeasure of both sides, who will probably
criticise me severely. Because I intend to retire completely from this field
soon, it does not matter to me if I am considered to be ‘wrong’,
if it contributes to us all eventually agreeing to get the science ‘right’. 相似文献
13.
The conventional linear integral isoconversional methods may lead to important errors in the determination of the activation energy when the significant variation of the activation energy with the conversion degree occurs. Vyazovkin proposed an advanced nonlinear isoconversional method, which allows the activation energy to be accurately determined [Vyazovkin, J Comput Chem 2001, 22, 178]. However, the use of the Vyazovkin method raises the problem of the time‐consuming minimization without derivatives. A new iterative linear integral isoconversional method for the determination of the activation energy as a function of the conversion degree has been proposed, which is capable of providing valid values of the activation energy even if the latter strongly varies with the conversion degree. Also, the new method leads to the correct values of the activation energy in much less time than the Vyazovkin method. The application of the new method is illustrated by processing of theoretically simulated data of a strongly varying activation energy process. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009 相似文献
14.
Two well-known isoconversion methods, the first one developed by Ozawa-Flynn-Wall and the second one developed by Friedman, are confronted with calculations made using modulated thermogravimetry (MTG). The latter variant is free from a number of assumptions and restrictions made in the isoconversion computations. In particular, it allows the use of a single decomposition curve and it remains in force even in the case of multistage decomposition with conjugated processes.To obtain the model-fitting methods from the model-free methods one should replace some functions averaged over isoconversion levels by the functions calculated on the basis of kinetic models. In the Ozawa-Flynn-Wall method it is the averaged reduced time (integral of Arrhenius exponential over time). In the method of Friedman it is the averaged differential conversion function.In MTG, the perturbations caused by the sinusoidal temperature modulation are connected with derivatives of mass loss by simple scaling, where activation energy plays a role of a scaling parameter. The ratio of the experimentally measured perturbations to the experimental derivative is used for the model-free computation of activation energy. If a theoretical derivative replaces the experimental one, this procedure leads to the model-fitting method. Even a rough approximation of the experimental derivative should not lead to an excessive error in activation energy. If in a vicinity of peaks maxima in derivatives of mass loss the decomposition is controlled by single rate-limiting processes, modulated thermogravimetry should give realistic activation energies for these processes. Inasmuch as the results of MTG are weakly sensitive to selection of kinetic models, this method should have a high predictive force. 相似文献
15.
The kinetics for the reaction of diazide (4,4′-biphenyl dibenzyl azide) and diyne (dipropargyl bisphenol A) catalyzed by CuBr-PMDETA (N, N, N′, N″, N″-pentamethyldiethylenetriamine) was studied in this paper by means of nuclear magnetic resonance spectra (1H-NMR) and differential scanning calorimetry (DSC). 1H-NMR was carried out to analyze solution polymerizations under different CuBr-PMDETA ratios in DMSO-d6. The results showed that CuBr-PMDETA catalytic system was easy to be oxidation under ambient condition. However, different CuBr-PMDETA ratios influenced the catalytic efficiency and the optimal ratios were found in nitrogen gas. DSC was carried out to analyze bulk polymerizations. The results showed that the apparent activation energy (Eα) calculated by Kissinger's method was 69.2 kJ/mol, which was confirmed by Friedman's method. The two tests indicated that the catalyzed polymerization of diazide and diyne was a second order reaction. 相似文献
16.
A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10C min–1 with excess air. Reaction rates increased progressively with increasing temperature. The rate data were fitted to an Arrhenius equation; the plots showed three distinct reaction regions. Weighted mean activation energies (E
wm), of the crude oils were calculated and a correlation was established betweenE
wm, API gravity and peak temperatures during high-temperature oxidation. 相似文献
17.
Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.The experimental part of this research was supported in part by NATO-SFS Project TU-Energy II. The authors express their appreciation to the NATO-SFS program for providing financial support for this project. 相似文献
18.
一种基于检测酶反应中间体而测定漆酶活性的动力学分析法 总被引:4,自引:0,他引:4
在反相胶束(AOT/n-octane)介质中,漆酶(laccase)-邻苯二胺(o-phenylenediamine,OPDA)本系的酶催化反应呈现“超级活性”,并且酶催化反应中间体与产物2,3-二氨基吩嗪(2,3-diaminophemazine,DAP)的吸收光谱能很好的剥离分开。通过理论,表明酶催化反应中间体生成的初始速率与漆酶活性存在定量关系,采用初始速率法测定中间体的浓度,建立了一种基于检测酶催化反应中间体而测定漆酶活性的动力学分析新方法。该方法由于在反相胶束介质中采用初始速率法进行测定,具有较高的灵敏度和选择性。测定漆酶活性的线性范围为0-2.5U;检出限为0.033U。 相似文献
19.
20.
Daviti M. Chrissafis K. Paraskevopoulos K. M. Polychroniadis E. K. Spassov T. 《Journal of Thermal Analysis and Calorimetry》2002,70(2):605-614
The kinetics of the α-β phase transition of HgI2 were investigated by isothermal and non-isothermal differential scanning calorimetry. The effective activation energy of
the transition, 415±40 kJ mol-1, was determined applying the methods of Kissinger and Ozawa. The transition kinetics were described by the Johnson-Mehl-Avrami
model and the value of the Avrami exponent n was found to range from high values (n>3) at the early stages to lower values at later stages of the transformation, with an average value of 2.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献