Thermoanalytical study of fluoxetine hydrochloride

The thermal decomposition of two inclusion compounds Mn(HCOO)₂·1/3C₄H₈O₂ and Mn(HCOO)₂·1/3C₄H₈O was studied in the inert atmosphere. The process of both dioxane, and tetrahydrofurane removal has two steps; the intermediate phase is unstable and kinetically hindered. Manganese formate is stable up to 330°C. Thermogravimetric data (obtained at different rates of linear heating) were processed with computer program (with ‘Model free’ approach). Kinetic parameters were calculated for the first decomposition step, and the process is described by equation of n-order reaction with autocatalysis.     

The kinetics of thermal decomposition of bismuth oxohydroxolaurate

The bismuth salt of lauric (dodecanic) acidBi₆O₄(OH)₄(C₁₁H₂₃COO)₆ was studied earlier. This salt has layer structure (the interlaminardistance=37.50 Å), under heating this liquid-crystalline state has themesomorphic transformation, turns to the amorphous state, decomposes stepwisewith the formation of well-ordered layers of bismuth nanoparticles. DSC-curveswere used for the study of the decomposition kinetics in the area of decompositionwith small mass loss and exothermic effect (423–483 K).     

Study of thermal decomposition of silver acetate

Thermal decomposition of silver acetate was studied (TG, DSC, mass-spectrometry, X-ray analysis, electron microscopy). Non-isothermal thermogravimetric data (obtained at two different rates of linear heating) were used for kinetic studies. Kinetic parameters were calculated only for the chosen decomposition step.     

Thermal stability of high-energy compounds

The influence of molecular structure on the stability of high-energy compounds is considered. The kinetic parameters of the decomposition of various energy-rich groups in monofunctional compounds are established. Data on decomposition of compounds with mixed functional groups are described. The sites of primary breakdown are determined and the mutual influence of functional groups on the stability is considered. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 231–234, February, 2000.     

Synthesis and structural aspects of urea/dialkylamine inclusion compounds

The synthesis and structural aspects of urea host-guest inclusion compounds containing linear secondary alkylamines (dibutyl-,dipentyl-, dihexyl-, dioctyl-) at 25°C are reported. Elemental analysis,¹³C CP-MAS NMR and¹H-NMR Spectroscopy, and Powder X-ray Diffraction Analysis confirm the inclusion process. The basic host structure of the products is similar to that of urea-hydrocarbon systems.¹³C MAS-NMR experiments show chemical shift differences for the confined guest molecule with respect to the liquid phase. Stoichiometry and |c _g| values for the inclusion compounds with dipentyl-and dihexylamine suggest a commensurate structure.     

Structure and thermal stability of difluoroamino compounds in the liquid state

The kinetics of decomposition of 15 difluoroamino compounds with NF₂ groups at primary, secondary, and tertiary carbon atoms in the liquid state was investigated. Activation energies (E _a) for all of the compounds were in the interval 100–120 kJ · mol^–1. The reaction rate does not depend on the electronic effects of the substituents and decreases only in the case of steric shielding of the NF₂ group. ForN-difluorobenzylamine it was shown that the gas-phase elimination of HF is characterized byE = 176 kJ·mole^–1, while the rate of decomposition in a solution depends on the dielectric constant of the medium. Based on the results obtained, a mechanism for liquid-phase decomposition, which involves heterolysis of the N-F bonds, is suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 336–338, February, 1994.     

Kinetic and thermodynamic stability of cluster compounds under heating

A new polymorphic form of Norfloxacin has been identified and fully characterized by a variety of methods including powder X-ray diffraction, vibrational spectroscopy (IR and Raman), thermal analysis (DSC and TG), SEM and solid-state NMR spectroscopy. The relationship between the new form C and the previously known forms A and B have been studied. Moreover, the crystal structure of the known form A has been solved by single-crystal methods.     

Thermal Stability and Non-isothermal Decomposition Kinetics. Heteropolynuclear compounds of Cu(II)

Data concerning the thermal behaviour of four heteropolynuclear compounds with the general formula [CuML(CH₃COO)₃] whereM=Ni(II), Zn(II), Mn(II) and Co(II); LH=2-amino-5-mercapto-1,2,3-thiadiazole were obtained. For the kinetically workable decomposition steps the values of the kinetic parameters were estimated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal stability and decomposition of pharmaceutical compounds

Thermal analysis of fusion and decomposition processes were carried out on recently synthetized pharmaceutical compounds in order to establish thermal stability criteria. This study was carried out using thermogravimetry, TG, and differential scanning calorimetry, DSC. Degradation and fusion temperatures have been produced as thermal data with the aim of to study the thermal stability of the compounds. Relationship is found among stability and a series of effects of structure of the compounds. The compounds which present an amide functional group in the central molecule are more stable because they have a comparatively higher fusion and degradation temperature. In addition, the stability of this type of compounds depends on the position of the electrophilic substitution (in ortho, meta or para). Likewise, the groups linked to the aromatic ring with high electronic density give stability, and therefore are able to delocalize the charge in a greater spacial interval. Therefore, criteria for the selection of substituents have established that improve the stability of compounds     

Thermal stability of some new complexes bearing ligands with polymerizable groups

A series of new complexes with mixed ligands of the type M(4,4’-dipy)(C₃H₃O₂)₂(H₂O)_y ((1) M=Mn, y=2; (2) M=Ni, y=2; 4,4’-dipy: 4,4’-dipyridyl and C₃H₃O₂ is acrylate anion) and respectively M₂(4,4’-dipy)(C₃H₃O₂)₄(H₂O)_y ((3) M=Cu, y=0; (4) M=Zn, y=1). The modification evidenced in IR spectra was correlated with the presence of acrylate ion as unidentate in the case of complex (1) and as bidentate for others complexes. The electronic reflectance spectra showed the d–d transition for complex (1) and (2) characteristic for the octahedral surrounding while the spectrum for complex (3) have the characteristic pattern for square-pyramidal stereochemistry. The thermal behaviour steps were investigated. The thermal transformations are complex processes according to TG and DTG curves including dehydration, acrylate ion oxidative degradation and thermolysis process of aromatic amine. The final products of decomposition are the most stable metal oxides.     

Thermal stability of new zinc acetate-based complex compounds

New zinc acetate based complex compounds (of general formula Zn(CH₃COO)₂·1?2L·nH₂O) containing one or two molecules of urea, thiourea, coffeine and phenazone were prepared namely: Zn(CH₃COO)₂·2.5H₂O, Zn(CH₃COO)₂·2u·0.5H₂O, Zn(CH₃COO)₂·tu·0.5H₂O, Zn(CH₃COO)₂·2tu, Zn(CH₃COO)₂·cof·2.5H₂O, Zn(CH₃COO)₂·2cof·3.5H₂O, Zn(CH₃COO)₂·2phen·1.5H₂O. The compounds were characterized by IR spectroscopy, chemical analysis and thermal analysis. Thermal analysis showed that no changes in crystallographic modifications of the compounds take place during (heating in nitrogen before) the thermal decompositions. The temperature interval of the stability of the prepared compounds were determined. It was found that the thermal decomposition of hydrated compounds starts by the release of water molecules. During the thermal decomposition of anhydrous compounds in nitrogen the release of organic ligands take place followed by the decomposition of the acetate anion. Zinc oxide and metallic zinc were found as final products of the thermal decomposition of the zinc acetate based complex compounds studied. Carbon dioxide and acetone were detected in the gaseous products of the decomposition of the compounds if ZnO is formed. Carbon monoxide and acetaldehyde were detected in the gaseous products of the decomposition, if metallic Zn is formed. It is supposed that ZnO and Zn resulting from Zn acetate complex compounds here studied, possess different degree of structural disorder. Annealing takes place by further heating above 600°C.     

On the thermal stability and thermal decomposition kinetics of some mono- and disubstituted furan-2,3-dions

The thermal behaviour of some compounds derived from 5-phenylfuran-2,3-dione was studied. The thermoanalytical data relating to the decomposition steps and intermediates were completed with mass spectrometric analysis and infrared spectroscopy results. For some of the investigated reactions, the kinetic and structural data correlated satisfactorily.     

Thermal stability evaluation of doping compounds before GC-MS analysis by DSC

The Medical Commission of the International Olympic Committee forbids the use of anabolic androgenic steroids, β-agonists, stimulant and narcotic compounds to improve athletic performance. In this work, we evaluated the thermal stability of 17 compounds by the use of the DSC for their potential GC-MS analysis either under free form or under TMS derivative form. In DSC, esterified and unesterified anabolic steroids were characterized by a true melting peak, followed by a large exothermic peak at about 251–316°C due to oxidative degradation. They could be analysed by GC-MS mainly under TMS derivatives. Hydroxylated and unhydroxylated stimulant compounds (xanthines) seemed to be more stable at high temperature. As unhydroxylated xanthines were not silylated with BSTFA - TMCS, their GC analysis would be done under their free forms. TMS derivatisation of albuterol hemisulfate and codeine phosphate is preferable. In our conditions, to analyse by GC-MS all 17 doping compounds in the same GC-MS run, the optimal silylation temperature and best column initial temperature were determined at both 60°C.     

Combinations of natural and synthetic inclusion compounds and their thermal stability

Inclusion compounds do not belong to the group of simple compounds. They consist of molecules of the host and guest components. Some of them form supermolecules and exhibit super-molecular properties.Combinations of inclusion compounds as even more complicated systems need more methods to be used for their identification. Thermoanalytical study enables to study the sorption during their formation and the progressive liberation of their individual components and parts. Many layered silicates, phosphates and other similar synthetic and natural compounds enclosing or adsorbing cyclodextrins, pharmaceuticals, aromatics, various agrochemicals and inorganics are analysed from the view of their formation and properties.     

Formation of isolated guest dimers vs. host-guest coordination. X-Ray crystal structures of four carboxylic acid inclusion compounds formed by roof-shaped and scissor-like host molecules

The crystal structures of the inclusion compounds oftrans-9,10-dihydro-9,10-ethano-anthracene-11,12-dicarboxylic acid host (1) with formic acid (1a), acetic acid (1b), and propionic acid (1c) as guests, and of the coordinatoclathrate of the 1,1-binaphthyl-2,2-dicarboxylic acid host (2) with acetic acid as guest (2b) have been studied by single crystal X-ray diffraction. These studies show that inclusion of small carboxylic acids by carboxylic acid hosts like1 and2 results in formation of isolated, hydrogen-bonded guest dimers. Additional H-bond contacts between host and guest carboxylic groups are only formed in cases1a and2b. The dimeric acidic guest units are sitting in the cavities of the host or host-guest framework and have no other interactions than those of a weak Van der Waals' type with the neighbouring molecules. Crystal data:1·formic acid (1:2): triclinic (P),a = 11.6769(6),b = 9.4067(4),c = 9.0020(4) Å,a = 81.522(4), = 100.310(6), = 104.208(6)°,Z = 2,R = 0.048 for 2392 reflections;1·acetic acid (1:1): monoclinic (P2₁/n),a = 9.717(2),b = 14.462(2),c = 13.038(3)Å, = 104.27(1)°,Z=4,R=0.046 for 3042 observations;1·propionic acid (1:1): monoclinic (P2₁/n),a = 9.897(4),b = 14.671(7),c = 13.284(7) Å, = 105.92(6)°,Z = 4,R = 0.056 for 2302 reflections;2·acetic acid (2:3): triclinic (P),a = 12.746(1),b = 17.781(2),c = 11.010(1) Å, = 105.606(4), = 112.992(8), = 81.175(6)°,Z = 2,R = 0.067 for 4375 observations.     

Influence of purity on the thermal stability of solid organic compounds

DSC method was used to study thermal stability of nitrocompounds. It was assumed the model to estimate stability of solid phase in which perfect solid phase is totally stable and amorphous-liquid domains connected with impurities decompose according to the kinetic model determined for the liquid phase above the melting point. The influence of sample purity on relative stability, which is k _l/k _s — ratio of decomposition rate constants in liquid and solid phase, at temperature 20 K below the melting point was predicted. The increase of liquid domains in solid phase causes decrease of k _l/k _s ratio (relative stability) at chosen temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Linear stability analysis of a reaction–diffusion model of solid-phase combustion

 The dynamic behavior of a reaction–diffusion model of solid-phase combustion is investigated by using the linear stability analysis method. The diffusion coefficients of the oxygen gas and the vapor of the combustible solid (Mg) are taken as two controlling parameters in the analysis. The bifurcation map obtained shows three dynamic regions. Region I only shows stable combustion. Regions II and III both show stable combustion and oscillatory combustion depending on the ratio of the two diffusion coefficients. Interestingly region II also shows a small range of a bistable state consisting of a stable focus and an oscillating state, which is like the critical phenomena in phase transitions. The results indicate that the occurrence of oscillating combustion requires that the value of the diffusion coefficient of the Mg vapor should be comparable to or less than that of the oxygen gas at the same temperature. Received: 6 November 2001 / Accepted: 25 March 2002 / Published online: 13 June 2002     

The kinetic behaviour and thermal stability of commercially available explosives

Summary Manufactures of commercially available explosives guarantee a certain lifetime of their products. In the commercial field this lifetime is usually large enough. The explosive is normally used long before the end of its lifetime. It may happen that these explosives are stored for a long time in a bunker where they sometimes exceed their lifetime. A large set of commercial explosives is characterized with a TG by heating small samples in aluminium sample cups from room temperature to 550°C, under a nitrogen atmosphere, with three different heating rates (2, 5 and 10 K min^-1). The activation energy of the decomposition step is determined in several different ways. After this characterization, a selection of the samples (based on economical value) is artificially aged for periods of 2, 4 and 6 weeks. After these ageing profiles the samples are re-investigated with the TG under the same conditions (heating rates and atmosphere) followed by the calculation of the kinetic parameters of the artificially aged materials. According to the TG measurements almost all tested explosives appear to have a much longer lifetime than the values given by the manufacturer. From kinetic point of view, the different methods for calculating the activation energy result in approximately the same parameters. It may conclude that TG seems to be a reliable and quick method for the determination of the lifetime of commercial explosives.     

Theoretical model and experimental study of pore growth during thermal expansion of graphite intercalation compounds

Summary A new technique, which allows one to simultaneously follow the mass and volume of graphite intercalation compounds (GICs) during thermal transformation into expanded graphite, was developed. This enabled us to elucidate the mechanism for the thermal expansion of GICs and formulate a quantitative model for the process. Effective activation parameters of the thermal decomposition of new GICs were obtained by using non-isothermal kinetics procedure. Thermal decomposition was described as a break of intermolecular bonds followed by diffusion.