Thermal degradation of polyesters by simultaneous TG-DTA/FT-IR analysis

A combination system of thermogravimetric/differential thermal analysis (TG-DTA) and Fourier-transform infrared absorption spectroscopy (FT-IR) was described. This simultaneous TG-DTA/FT-IR technique gave spectroscopic and weight loss information about the thermal degradation process of engineering polyesters; poly(ethylene terephthalate)(PET) and poly(butylene terephthalate)(PBT). The evolved gases from PET were benzoic acid, carbon dioxide and carbon monoxide, while those from PBT were terephthalic acid esters and benzoic acid esters.

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Zusammenfassung Es wird ein kombiniertes System aus TG-DTA und FT-IR beschrieben. Mit dieser simultanen TG-DTA/FT-IR-Technik wurden spektroskopische und Massenverlustangaben über die thermische Zersetzung technisch wichtiger Polyester, namentlich von Poly(ethylenterephthalat) (PET) und Poly(Butylenterephthalat) (PBT) ermittelt. Die aus PET freigesetzten Gase waren Benzoesäure, Kohlendioxid und Kohlenmonoxid, die aus PBT freigesetzten Gase hingegen Terephthalsäureester und Benzoesäureester.

     

A review on thermal decomposition and combustion of thermoplastic polyesters

An overview is presented of the literature on the thermal decomposition and combustion of thermoplastic polyesters, especially commercially important poly(ethylene terephthalate) (PET) and poly(1,4‐butylene terephthalate) (PBT). Although the literature is not clear as to whether heterolytic or homolytic scission of aliphatic fragments is the first step in the thermal decomposition of polyesters, in any case volatilization of light aliphatic fragments make polyesters easily ignitable polymers. Despite the presence of benzene groups in the main polymer chain, thermoplastic polyesters show very limited tendency to char, but instead, aromatic‐containing polymer fragments volatilize and feed the flame. Fire retardant additives, although they usually facilitate decomposition of the polyesters at lower temperature, also usually promote charring and therefore suppress combustion. Copyright © 2004 John Wiley & Sons, Ltd.     

A mechanism proposal for fluoxetine thermal decomposition

Thermal behavior of fluoxetine hydrochloride ((±)-N-methyl-3-phenyl-3-[4-(trifluoromethyl)phenoxy]propan-1-amine), an antidepressant of the selective serotonin reuptake inhibitor family, has been investigated using thermoanalytical techniques and evolved gas analysis performed with thermogravimetry coupled to Fourier transform infrared spectroscopy (TG-FTIR) and intermediate residue analysis by GC–MS. In inert atmosphere, the decomposition took place as two mass loss events with residue of 0.13% at the end of the run. In air atmosphere, decomposition occurred in three steps, the last one as a result of the oxidative burning of the carbonaceous matter. DTA and DSC curves demonstrated that sample melts at 159.6 °C (∆H _fus = 37.4 kJ mol⁻¹) without recrystallization on cooling. Hot-stage microscopy data corroborate these observations. TG-FTIR studies revealed that fluoxetine decomposes after melting, releasing 4-trifluoromethylphenol, methylamine. GC–MS analysis of the solid resulting from heating the fluoxetine hydrochloride up to 230 °C revealed the presence of the original sample and 4-trifluoromethylphenol as the main residue. Based on these results, a mechanism for fluoxetine thermal decomposition was proposed.

     

Studying of silane thermal decomposition mechanism

The mechanism of silane thermal decomposition is investigated in a flow reactor. The time dependencies of silane consumption and disilane formation were compared with those parameters of solid product (aerosol particles) such as concentration, total hydrogen content in solid product, and fraction of hydrogen contained in solid product as polyhydride groups (SiH₂)_n. Silane loss and gaseous product formation were analyzed using a mass spectrometer. The hydrogen content in solid product was analyzed by the methods of IR-spectroscopy and hydrogen evolution. Based on a simple kinetic scheme we qualitatively explained the experimental dependencies of silane conversion and disilane formation, the effective activation energy of the decomposition process, and the amount of polyhydride groups in the solid product on reaction time and initial silane concentration. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 99–110, 1998.     

On the thermal decomposition mechanism for dehydroxylation of alkaline-earth hydroxides

The activation energy for thermal dehydroxylation in vacuum of alkaline-earth hydroxides has been calculated from thermogravimetric data. The experimental results of Mg(OH)₂ Ca(OH)₂ and Sr(OH)₂ are in agreement with an unimolecular decay law and their activation energies are similar to the values of enthalpies of decomposition. In contrast, as the dehydroxylation process of Ba(OH)₂ takes place in liquid phase and the BaO does not dissolve into the molten Ba(OH)₂, a kinetic of zero order describes the reaction rate and the activation energy is lower than the enthalpy of decomposition.

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Zusammenfassung Die Aktivierungsenergie zur thermischen Dehydroxilierung von Erdalkali-Hydroxiden im Vakuum wurde aus thermogravimetrischen Daten errechnet. Die Versuchsergebnisse bezüglich Mg(OH)₂, Ca(OH)₂ und Sr(OH)₂ sind mit einem unimolekularen Zersetzungsgesetz in Übereinstimmung und die entsprechenden Aktivierungsenergien sind den Werten der Zersetzungsenthalpien ähnlich. Im Gegensatz hierzu wird im Falle von Ba(OH)₂, da der Dehydroxylierungsvorgang in der flüssigen Phase stattfindet und das BaO sich nicht im geschmolzenen Ba(OH)₂ löst, die Reaktionsgeschwindigkeit durch eine Kinetik nullter Ordnung beschrieben und die Aktivierungsenergie liegt hierbei niedriger als die Zersetzungsenthalpie.

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Résumé L'énergie d'activation de la déshydroxylation sous vide des hydroxydes des métaux alcalins est calculée à partir des données thermogravimétriques. Les résultats expérimentaux obtenus avec Mg(OH)₂, Ca(OH)₂ et Sr(OH)₂ sont en accord avec une loi de décomposition unimoléculaire et les énergies d'activation correspondantes sont du même ordre de grandeur que les enthalpies de décomposition. Par contre, du fait que la déshydroxylation de Ba(OH)₂ a lieu en phase liquide et que BaO ne se dissout pas dans Ba(OH)₂ fondu, la vitesse de la réaction est décrite par une cinétique d'ordre zéro et l'énergie d'activation est plus faible que l'enthalpie de décomposition.

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. Mg(OH)₂, Ca(OH)₂ Sr(OH)₂ . , Ba(OH)₂ BaO , , .

     

Primary mechanism of the thermal decomposition of tricyclodecane

To better understand the thermal decomposition of polycyclanes, the pyrolysis of tricyclodecane has been studied in a jet-stirred reactor at temperatures from 848 to 933 K, for residence times between 0.5 and 6 s and at atmospheric pressure, corresponding to a conversion between 0.01% and 25%. The main products of the reaction are hydrogen, methane, ethylene, ethane, propene, 1,3-cyclopentadiene, cyclopentene, benzene, 1,5-hexadiene, toluene, and 3-cyclopentylcyclopentene. A primary mechanism containing all the possible initiation steps, including those involving diradicals, as well as propagation reactions has been developed and allows experimental results to be satisfactorily modeled. The main reaction pathways of consumption of tricyclodecane and of formation of the main products have been derived from flow rate and sensitivity analyses.     

Kinetic mechanism of the thermal decomposition of tobacco

Equations have been derived to describe the chemical kinetic factors that affect the rate of formation of products when a mixture of solid components (tobacco) decomposes on heating. Using these equations, a computer model of tobacco pyrolysis has been constructed which can calculate the gas formation rate/temperature profile from a given set of reaction parameters. By comparing the predictions of the model with experimental results at heating rates between 0.8 and 25 deg C s^?1, a generalised kinetic mechanism for the thermal decomposition of tobacco has been developed. For carbon monoxide and other low molecular weight gases, the mechanism is an independent formation of each gas from one solid tobacco component in each temperature region. Pyrolysis of some individual tobacco components in other studies suggests that each gas is actually produced from many components in each temperature region. This more complex mechanism is kinetically equivalent to the deduced mechanism of independent formation from one component.The region in which a given decomposition reaction takes place moves to higher temperatures as the heating rate increases. The amounts of gases formed over any temperature region from 200 to 900°C can be calculated for a given heating rate using the mechanism and the kinetic constants. The present results imply that 75–90% of the carbon monoxide produced by tobacco decomposition at temperatures up to 900°C during a puff on a cigarette corresponds to that formed in the “low temperature region” (200–450°C) defined for pyrolysis experiments at the lower heating rates of 1–10 deg C s^?1.     

The mechanism of thermal decomposition of ionic oxalates

A mechanism for the thermal decomposition of ionic oxalates has been proposed on the basis of three quantitative relationships linking the quantitiesr _c/r _i (the ratio of the Pauling covalent radius and the cation radius of the metal atom in hexacoordination) andΣI _i (the sum of the ionization potentials of the metal atom in kJ mol^?1) with the onset oxalate decomposition temperature (T _d) (Eq. 1) the average C-C bond distance (¯d) (Eq. 2), and the activation energy of oxalate decomposition (E _a) (Eq. 3): (1) $$T_d = 516 - 1.4006\frac{{r_c }}{{r_i }}(\sum I_i )^{\frac{1}{2}}$$ (2) $$\bar d = 1.527 + 5.553 \times 10^{ - 6} \left( {122 - \frac{{r_c }}{{r_i }}(\sum I_i )^{\frac{1}{2}} } \right)^2$$ (3) $$E_a = 127 + 1.4853 \times 10^{ - 6} \left( {\left( {\frac{{r_c }}{{r_i }}} \right)^2 \sum I_i - 9800} \right)^2$$ On the basis of these results it is proposed that the thermal decomposition of ionic oxalates follows a mechanism in which the C-O bond ruptures first. From Eq. 3 it is further proposed that strong mutual electronic interactions between the oxalate and the cations restrict the essential electronic reorganization leading to the products, thereby increasingE _a.     

硝基甲烷热解机理的量子化学研究

用ab initio和NMDO 两种方法, 对CH~3NO~2沿C-N键断裂的热解反应过程 进行了较细致的计算研究。所得势能曲线(E-Rc-n) 彼此一致,并与Kaufman等[1]的近期结果相符。将各单点下所得正则离域化处理, 发现当C和N原子间的距离Rc-n=1.6-1.8A时, 定域成键σc-n-MO从能级较低的五的个占有MO跃升为HOMO(即第16个MO)。考察占有末占有前沿轨道 能级和位相, 可推在CH~3NO~2热 解的初抬阶段, 通过分子重排成C-O键的可能性较小 。其热解引发步骤可能是生成.CH~3和.NO~2双自由基。     

Kinetics and mechanism of thermal decomposition of copper hypophosphite

On the basis of an elaborate investigation of the thermal decomposition reaction for crystalline copper hypophosphite by kinetic, radiospectroscopic and optical methods, and by a study of the peculiarities of the copper hypophosphite structure and defects, it has been found possible to suggest the mechanisms by which the decomposition kinetics are regulated.     

Kinetics and mechanism of thermal decomposition of lead carbonate

Results are given on the kinetics and mechanism of the processes in the thermal decomposition of lead carbonate with the application of TG and DTA experimental investigation methods.The following mechanism was established: 3 PbCO₃=2 PbO.PbCO₃+2 CO₂ (1) 2 PbO.PbCO₃=3 PbO+CO₂ (2) PbO — melting (3)The following activation energy values were determined with TG methods for processes (1) and (2): 118.2 and 235.2 kJ/mole, respectively; and with DTA methods for processes (1), (2) and (3): 113.9, 246.6 and 294.9 kJ/mole, respectively.

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Zusammenfassung Die an Hand der TG- und DTA-Untersuchungen erhaltenen Ergebnisse über Kinetik und Mechanismus der bei der thermischen Zersetzung von Bleicarbonat auftretenden VorgÄnge werden beschrieben.Die folgenden Mechanismen des Vorganges wurden festgestellt: 3 PbCO₃=2 PbO.PbCO₃ + 2 CO₂ (1) 2 PbO.PbCO₃=3 PbO + CO₂ (2) PbO — Schmelzen (3)Die folgenden Werte der Aktivierungsenergie wurden durch TG-Versuche für die VorgÄnge (1) und (2) bestimmt: 118.2, bzw. 235.2 kJ/Mol, und durch DTA-Messungen für die VorgÄnge (1), (2) und (3): 113.9, 246.6, bzw. 294.9 kJ/Mol.

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Résumé La cinétique et le mécanisme des réactions qui se déroulent lors de la décomposition thermique du carbonate de plomb ont été étudiés par TG et ATD. Les mécanismes suivants ont été établis: 3 PbCO₃=2 PbO.PbCO₃+2 CO₂ (1) 2 PbO.PbCO₃=3 PbO + CO₂ (2) PbO — fusion (3)Pour les réactions (1) et (2), les valeurs de 118.2 et 235.2 kJ · mol^–1 ont été trouvées à partir des résultats TG et pour les réactions (1), (2) et (3) l'ATD a fourni respectivement 113.9, 246.6 et 294.9 kJ · mol^–1.

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, . : 3 ₃=2 PbO.PbCO₃+2 ₂ (1) 2 PbO.PbCO₃=3 +O₂ (2) — (3) (1) (2), 118.2 235.2 /. (1), (2) (3) : 113.9; 246.6 294.9 /.

     

Kinetics and mechanism of thermal decomposition of hydroxylammonium nitrate

The kinetics of thermal decomposition of melted hydroxylammonium nitrate have been investigated by the rate of heat production in the temperature range 84.8–120.9°C. The decomposition proceeds with autocatalysis and up to 60 % of conversion the rate of the process increases proportionally to the square of the degree of decomposition. The initial rate is proportional to the square of the concentration of HNO₃ formed due to dissociation of the salt. The activation energy of this process is 15.3±1.8 kcal/mol. It is suggested that the initial stage the process proceeds via interaction between N₂O₃ and NH₃OH⁺, whereas the subsequent acceleration is due to oxidation of NH₃OH⁺ by nitrogen oxides formed as well as by nitrous acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1897–1901, November, 1993.     

苯甲酸钐的水热合成和热分解反应机理

用水热法合成了无水苯甲酸钐配合物,经元素分析、IR和X射线粉末衍射表征了该配合物,系层状结构,属单斜晶系。用TG、DTA、IR、色谱-质谱联用仪研究了它的热分解机理。在氮气氛下,热分解分两步进行:第一步分解生成钐的二碳酸一氧盐和有机化合物。生成的有机化合物成分比较复杂,主要成分为苯甲酸、二苯甲酮、9,10-蒽醌和1,3-二苯基异苯并呋喃等。第二步二碳酸一氧盐进一步分解生成氧化钐和二氧化碳。     

New incremental isoconversional method for kinetic analysis of solid thermal decomposition

A simple and precise incremental isoconversional integral method based on Li-Tang (LT) method is proposed for kinetic analysis of solid thermal decomposition, in order to evaluate the activation energy as a function of conversion degree. The new method overcomes the limitation of LT method in which the calculated activation energy is influenced by the lower limit of integration. By applying the new method to kinetic analysis of both the simulated nonisothermal case and experimental case of strontium carbonate thermal decomposition, it is shown that the dependence of activation energy on conversion degree evaluated by the new method is consistent with those obtained by Friedman (FR) method and the modified Vyazovkin method. As the new method is free from approximating the temperature integral and not sensitive to the noise of the kinetic data, it is believed to be more convenient in nonisothermal kinetic analysis of solid decompositions.     

The kinetics and mechanism of thermal decomposition of alkyl isocyanates

The kinetics of the gas-phase decomposition of ethyl, isopropyl, and t-butyl isocyanates have been studied in the temperature range of 380–530°C. t-Butyl isocyanate decomposes almost exclusively by a unimolecular route to isobutene and HNCO, but in EtNCO and i-PrNCO this route competes with a free-radical chain which produces CO, CH₄, and HCN or CH₃CN. In i-PrNCO, however, the chain process is very rapidly inhibited by the propene formed in the parallel unimolecular route. A minor heterogeneous bimolecular decomposition in each case gives rise to carbon dioxide and a carbodiimide. Mechanisms and trends in the alkyl isocyanates from methyl through t-butyl are discussed.     

Kinetics and mechanism of the thermal decomposition of cyclopentyl cyanide

The thermal decomposition of cyclopentyl cyanide has been investigated in the temperature range of 905–1143 K using both conventional stirred-flow reactor and very low-pressure pyrolysis (VLPP) techniques. The results from both techniques are consistent. The main primary processes are HCN elimination to form cyclopentene: and ring fragmentation to form vinyl cyanide plus propylene and ethylene plus cyanopropenes: Under the experimental conditions cyclopentene undergoes further decomposition to cyclopentadiene plus hydrogen. There is evidence for conversion of some of the reactant to a solid residue, presumably polymer. From the stirred-flow reactor results the following Arrhenius expressions were obtained: log k₁(s^?1) = (12.8 ± 0.3) ? (65.6 ± 1.3)/θ and log k₂(s^?1) = (16.0 ± 0.3) ? (80.0 ± 1.1)/θ, where θ = 2.303RT kcal/mol. Application of RRKM theory shows that the VLPP experimental rate constants are consistent with high-pressure Arrhenius parameters given by log k₁(s^?1) = (12.8 ± 0.3) ? (67.8 ± 2.5)/θ for HCN elimination, and log k₄(s^?1) = (16.3 ± 0.3) ? (80.1 ± 2.0)/θ for the sum of the ring fragmentation pathways. The rate parameters for HCN elimination are in good agreement with previous VLPP studies of alkyl cyanides and with theoretical predictions. The difference in activation energies for the ring opening of cyclopentane and cyclopentyl cyanide is reasonably close to the established value for the cyano stabilization energy. This supports the assumption of a biradical mechanism.     

Kinetics and mechanism of the thermal decomposition of methyl isocyanate

The kinetics of gas-phase decomposition of methyl isocyanate have been investigated in the range of 427–548°C. Two decomposition routes are followed; the predominant one is a radical-chain process giving CO, H₂, and HCN as major products, which has an order of 1.5 and an Arrhenius equation given by log k(L^1/2/mol^1/2·s) = (13.12 ± 0.06) ? (56,450 ± 1670) cal/mol/2.303 RT. The minor route is the bimolecular formation of N,N′-dimethylcarbodiimide and CO₂, which from the low activation parameters E_a = 31.6 kcal, A = 10^5.30 L^1/2/mol^1/2·s, and the reaction order of 1.57 appears to be heterogeneous.