Possibilities of two non-isothermal procedures (temperature- or rate-controlled) for kinetical studies

The applicability of both conventional Thermal Analysis (TA) and Controlled Rate Thermal Analysis (CRTA) for kinetic analysis is discussed. It is shown that TA method can give a reliable kinetic information and meaningful kinetic parameters especially for solid state transformation. On the other hand the CRTA method is more suitable for decomposition process where one or more gasses are evolved. A consistent and reliable method of kinetic analysis is proposed for both techniques. This method is illustrated to analyze the crystallization process of chalcogenide glass and the decomposition of dolomite.     

Novel methods of modulated-temperature thermal analysis

Two novel methods of Modulated-Temperature Thermal Analysis are described. These are loosely-termed “Constrained Rate DSC” and “Modulated-Temperature TMA”. In the first, the sample response is used to control the temperature program of a DSC in a method analogous to Controlled Rate Thermal Analysis. This results in a temperature modulation which is variable in period, amplitude and underlying heating rate depending on the sample behaviour and user defined limits. Deconvolution of the signals into thermally “reversing” and “non-reversing” heat flows is still possible. Secondly, the application of Modulated-Temperature Programming to Thermomechanical Analysis is discussed.     

The kinetics of solid‐state reactions toward consensus,Part 3. Searching for consistent kinetic results: SCTA vs. conventional thermal analysis

This paper is the third part of a review of some of the controversial kinetic aspects of conventional thermal methods. We open a discussion about the necessity of developing new possibilities and techniques in the field of solid‐state reactions. In the last decade we have seen the commercialization of new instruments and apparatus by a number of manufacturers, which allows for carrying out more meaningful experiments. The Sample Controlled Thermal Analysis describes a family of new techniques such as Controlled Rate Thermal Analysis, Stepwise Isothermal Analysis, etc., which are based on the use of their own rate of reaction for controlling the reaction temperature. It is shown that these new approaches have much more effective control on heat and mass transfer phenomena and can provide enhanced resolution and sensitivity and improved kinetic data. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 223–236, 2002     

Application of CRTA to the study of microporosity by thermodesorption of pre-adsorbed water

Thermodesorption is here considered for its possibility of giving access to the microporosity of adsorbents. The requirements of this application (good separation of successive desorption steps, good control of the desorption pressure and temperature throughout the sample, possibility of a safe kinetic analysis of each step) are here fulfilled by carrying out the thermodesorption in the Controlled transformation Rate Thermal Analysis (CRTA) mode. The method is applied to 4 zeolites (3A, 4A, 5A and 13X) and a well characterized charcoal, from ?25 to 325°C, after pre-adsorption of water.     

Thermal analysis applied to the characterization of degradation in soil of polylactide: II. On the thermal stability and thermal decomposition kinetics

The disposal stage of polylactide (PLA) was assessed by burying it in active soil following an international standard. Degradation in soil promotes physical and chemical changes in the polylactide properties. The characterization of the extent of degradation underwent by PLA was carried out by using Thermal Analysis techniques. In this paper, studies on the thermal stability and the thermal decomposition kinetics were performed in order to assess the degradation process of a commercial PLA submitted to an accelerated soil burial test by means of multi-linear-non-isothermal thermogravimetric analyses. Results have been correlated to changes in molecular weight, showing the same evolution as that described by the parameters of thermal stability temperatures and apparent activation energies. The decomposition reactions can be described by two competitive different mechanisms: Nucleation model (A2) and Reaction Contracting Volume model (R3). The changes in the kinetic parameters and kinetic models are in agreement with the calorimetric and dynamic-mechanical-thermal results, presented in the Part I of the study [1].     

An improved preparation of 3,5-bis(trifluoromethyl)acetophenone and safety considerations in the preparation of 3,5-bis(trifluoromethyl)phenyl Grignard reagent

An improved and efficient bromination of 3,5-bis(trifluoromethyl)benzene was developed. A safe and reliable preparation of the potentially explosive 3,5-bis(trifluoromethyl)phenyl Grignard and 3-trifluoromethylphenyl Grignard reagents, from the precursor bromides, is described. Reaction System Screening Tool (RSST) and Differential Thermal Analysis (DTA) studies suggest these trifluoromethylphenyl Grignard reagents can detonate on loss of solvent contact or upon moderate heating. When prepared and handled according to the methods described herein, these Grignard reagents can be safely prepared and carried on to advanced intermediates.     

Kinetical possibilities of controlled transformation Rate Thermal Analysis (CRTA)

In the first part, this paper reviews several ways to derive kinetical results from Controlled transformation Rate Thermal Analysis (CRTA) experiments: applying the rate-jump method to measure the activation energy, determining the reaction mechanism simply from the shape of the curve and finally deriving both the activation energy and the reaction mechanism from a single CRTA experiment. Application to the 5 steps of the thermal analysis of UO₂(NO₃)2(H₂O)₂·4H₂O shows that the layered structure of the hydrate leads to 4 dehydration steps essentially following a mechanism of nucleation and 2-dimensional growth whereas the denitration step seems to be controlled by a double mechanism of diffusion and desorption. The first 4 water molecules to leave are in the same starting state but evolve in 2 steps, well separated by CRTA and involving 3 and 1 molecule, respectively, which is understood by structural considerations.

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Zusammenfassung Diese Arbeit gibt einen überblick über einige Verfahren zur Erstellung kinetischer Ergebnisse aus CRTA-Experimenten (Controlled transformation Rate Thermal Analysis): Anwendung des rate-jump-Verfahrens zur Messung der Aktivierungsenergie, Ermittlung des Reaktionsmechanismus lediglich aus der Kurvenform und letztlich die Ermittlung der Aktivierungsenergie und des Reaktionsmechanismus aus einem einzigen CRTA-Experiment. Eine Anwendung auf die 5 Schritte der thermischen Zersetzung von UO₂(NO₃)2(H₂O)₂·4H₂O zeigt, da\ die Schichtenstruktur des Hydrates zu 4 Dehydratationsschritten führt, denen im wesentlichen ein Mechanismus aus Keimbildung und 2-dimensionalem Wachstum zugrundeliegt, wÄhrend der Denitratationsschritt durch einen Doppelmechanismus aus Diffusion und Desorption bestimmt zu sein scheint. Die ersten 4 Wassermoleküle befinden sich im selben Ausgangszustand, werden aber in 2 Schritten abgegeben, mittels CRTA als 3+1 Moleküle separat beobachtbar, was mittels struktureller überlegungen verstanden werden kann.

     

Thermal Properties of the Aquadimethylsulfoxide Complexes [Ln(DMSO)n(H2O)m][Mo3S7Br7] where Ln=Pr,Nd, Eu,Tm

Synthesis, X-ray structural investigation, and study of the thermal properties of new aquadimethylsulfoxide complexes [Ln(DMSO)n(H2O)m][Mo3S7 Br7] containing the rare earth metals (Ln=Pr, Nd, Eu, Tm) were performed. In all complexes DMSO is co-ordinated through the O atoms. Thermal transformations of these salts were studied by quasi-equilibrium thermogravimetry a variant of CRTA (Controlled Rate Thermal Analysis) with constant rate of mass loss (0.3 mg min-1); helium flow keeps the partial pressure of self-generated DMSO/H2O atmosphere ~0.01 atm. [Pr(DMSO)6H2O]X where X=[Mo3S7Br7] decomposes with the formation of the intermediate phases Pr(DMSO)5X at 100-190°C and Pr(DMSO)3X at 250-270°C. Thermal decomposition of [Nd(DMSO)6(H2O)X·CH3CN leads to the intermediate phase Nd(DMSO)5X at 200-210°C. [Eu(DMSO)7(H2O)]X forms the intermediate phases Eu(DMSO)6X at 50-150°C and Eu(DMSO)5X at 190-210°C. Thermal decomposition of [Tm(DMSO)6(H2O)]X gives the intermediate phases Tm(DMSO)5X at 170-200°C and Tm(DMSO)4X at 240-250°C. The further decomposition takes place continuously for all phases. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interactions in dopamine and indole loaded thermosensitive hydrogels seen by high sensitivity microDSC. Implications for drug delivery

Journal of Thermal Analysis and Calorimetry - Controlled and targeted drug delivery systems consist of a carrier matrix and one or more active ingredients. One of the roles of the matrix is to...     

Development of master curves for discriminating the mechanism of solid state reactions from experimental data obtained by using the cyclic and controlled rate thermal analysis

The cyclic and Controlled Rate Thermal Analysis method (CRTA) has been used. The two rates automatically selected in the cyclic curve are small enough to allow the two states of the sample to be compared have nearly the same reacted fraction. Thus, the activation energy can be calculated without previous knowledge of the actual reaction mechanism. Provided that the activation energy,E, is known, a procedure has been developed for determining the kinetic law obeyed by the reaction by means of master curves that represent the values of the reacted fraction, α, as a function of?E/R(1/T-1/T _0.5),T _0.5 being the temperature at which α=0.5. This procedure has been tested by studying the thermal decomposition reaction of BaCO₃.     

Reaction of ketones with lithium hexamethyldisilazide: competitive enolizations and 1,2-additions

Reaction of 2-methylcyclohexanone with lithium hexamethyldisilazide (LiHMDS, TMS(2)NLi) displays highly solvent-dependent chemoselectivity. LiHMDS in THF/toluene effect enolization. Rate studies using in situ IR spectroscopy are consistent with a THF concentration-dependent monomer-based pathway. LiHMDS in pyrrolidine/toluene affords exclusively 1,2-addition of the pyrrolidine fragment to form an alpha-amino alkoxide-LiHMDS mixed dimer shown to be a pair of conformers by using (6)Li, (15)N, and (13)C NMR spectroscopies. Rate studies are consistent with a monomer-based transition structure [(TMS(2)NLi)(ketone)(pyrrolidine)(3)](). The partitioning between enolization and 1,2-addition is kinetically controlled.     

Thermal deamination kinetics of tris(ethylenediamine)nickel(II) sulphate in the solid-state

Thermogravimetric techniques have been used to study the kinetics of thermal deamination of tris(ethylenediamine)nickel(II) sulphate. The complex was synthesized and characterized by various chemical and spectral techniques. Thermal decomposition studies were carried at different heating rates (5, 10, 15 and 20°C min⁻¹) in dynamic air. The complex undergoes a four-stage decomposition pattern. The stages are not well resolved. Decomposition path can be interpreted as a two-stage deamination, and a two-stage decomposition. Reaction products at each stage were separated and identified by means of IR and XRD. The morphology of the complex and the residue were studied by means of SEM. Final residue of the decomposition was found to be crystalline NiO. The deamination kinetics was studied using model-free isoconversional methods viz., Friedman, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods. It is observed that the activation energy varies with the extent of conversion; indicating the complex nature of the deamination reaction.     

Thermal Decomposition of BaC2O4·0.5H2O Studied by Stepwise Isothermal Analysis and Non-Isothermal Thermogravimetry

Thermal decomposition of BaC2O4·0.5H2O in air was studied by a combination of stepwise isothermal analysis (SIA) and non-isothermal thermogravimetry. The results from both techniques show that the crystal water is released in one step and that anhydrous barium oxalate is decomposed in one step, while BaCO3 decomposes in three steps to BaO, forming two intermediate compounds with the formulas of BaCO3·(BaO)2 and (BaCO3)0.5·(BaO)2.5. Reaction mechanism analyses using the data from SIA measurements show that the controlling mechanism for all the five decomposition steps in isothermal conditions is a two-dimensional phase-boundary controlled process. Kinetic parameters are obtained for the five decomposition steps from the non-isothermal thermogravimetric data. This revised version was published online in July 2006 with corrections to the Cover Date.     

Characterization analysis of raw and pyrolyzed plane tree seed (Platanus orientalis L.) samples for its application in carbon capture and storage (CCS) technology

Journal of Thermal Analysis and Calorimetry - Raw and pyrolyzed samples of the plane tree seeds (PTS) were tested by various advanced analytical techniques including simultaneous TG-DSC technique,...     

Constant transformation rate thermal analysis of HGdP<Subscript>2</Subscript>O<Subscript>7</Subscript>·3H<Subscript>2</Subscript>O

Summary The aim of this work is the optimization of the preparation of anhydrous gadolinium hydrogen phosphate with good fluorescence properties. The products obtained by dehydration of gadolinium hydrogen phosphate trihydrate depend on the conditions chosen for the thermal treatment. For this reason, the dehydration was followed by Constant Rate Thermal Analysis whilst strictly controlling the water vapour pressure above the sample. Intermediate samples, obtained during dehydration were characterised by IR spectroscopy and X-ray diffraction. It has thus been shown that the thermal pathway taken for the dehydration depends on the water vapour pressure above the sample in the region from 10^-2to 5 mbar. Under the lowest water vapour pressure (5·10^-3mbar), the elimination of the crystallization water is carried out in a continuous way and produces a quasi-amorphous intermediate. Under higher water vapour pressure (5 mbar), well crystallized intermediate products are obtained. The results obtained suggest that the trihydrate contains zeolitic water which confirms a prior structural study.     

Thermal analysis applied to the characterization of degradation in soil of polylactide: I. Calorimetric and viscoelastic analyses

An accelerated soil burial test has been performed on a commercial polylactide (PLA) for simulating non-controlled disposal. Degradation in soil promotes physical and chemical changes in polylactide properties, which can be characterized by Thermal Analysis techniques. Physical changes occurred in polylactide due to the degradation in soil were evaluated by correlating their calorimetric and viscoelastic properties. It is highly remarkable that each calorimetric scan offers specific and enlightening information. Degradation in soil affects the polylactide chains reorganization. A multimodal melting behavior is observed for buried PLA, degradation in soil also promotes the enlarging the lamellar thickness distribution of the population with bigger average size. Morphological changes due to degradation in soil lead to an increase in the free volume of the polylactide chains in the amorphous phase that highly affected the bulk properties. Thermal Analysis techniques provide reliable indicators of the degradation stage of polylactide induced by degradation in soil, as corroborated by molecular weight analysis.     

Analytical properties of the amidoxime group. XII

Journal of Thermal Analysis and Calorimetry - The acid-base equilibria of succinediamidoxime (SIDA) were studied by means of potentiometric and thermometric techniques. RefinedpK values (pK...     

Fast heating in µ-thermal analysis</o:p>

Summary Thermal analysis of the 10 μm surface of materials using TA Instruments' μ-TA thermal probe and pulsed force mode AFM has shown promising results. This addresses the need of additional surface characterization based on principle of Thermal Analysis, which is complementary to other surface characterization techniques, i.e., Surface-IR, TOF-SIMS, etc. The method calls for identification of surface landscape by imaging first, followed by fast heating the spots of interest. The micro thermal probe is viewed to heat a small material with a tiny heater rather than to heat small material with a large heater in conventional thermal analysis. In this paper, we demonstrate the applicability in the adhesion temperature of the topical coatings of Tyvek? HDPE sheets, fusion of the heat-processed polyethylene fibers in a bundle, the surface crystallinity of PET pellets, and two examples of phase images of toughened Nylon 66. Comparisons were made where it is possible with standard thermal analysis techniques as well as with the microscopic techniques of AFM, TEM and optical.     

Reaction pathways of zirconocene-catalyzed silylation of alkenes with chlorosilanes

Reaction pathways as well as stereochemistries and stoichiometries of zirconocene-catalyzed silylation of olefins with chlorosilanes in the presence of ⁿBuMgCl were studied and discussed in detail. Rate determining steps were examined by kinetic studies and labeling experiments.     

h-MoO3 phase transformation by four thermal analysis techniques

Journal of Thermal Analysis and Calorimetry - Molybdenum trioxide (MoO3) has been studied by four thermal analysis techniques. The as-synthesized material has hexagonal structure (h-MoO3). The...