Kinetics and mechanism of the silane decomposition

The homogeneous gas-phase decomposition kinetics of silane has been investigated using the single-pulse shock tube comparative rate technique (T = 1035–1184?K, P_total ≈? 4000 Torr). The initial reaction of the decomposition SiH₄ \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm SiH}_{\rm 4} \mathop \to \limits^1 {\rm SiH}_{\rm 2} + {\rm H}_{\rm 2} $\end{document} SiH₂ + H₂ is a unimolecular process in its pressure fall-off regime with experimental Arrhenius parameters of logk₁ (sec^?1) = 13.33 ± 0.28–52,700 ± 1400/2.303RT. The decomposition has also been studied at lower temperatures by conventional methods. The results confirm the total pressure effect, indicate a small but not negligible extent of induced reaction, and show that the decomposition is first order in silane at constant total pressures. RRKM-pressure fall-off calculations for four different transition-state models are reported, and good agreement with all the data is obtained with a model whose high-pressure parameters are logA₁ (sec^?1) = 15.5, E_1(∞) = 56.9 kcal, and ΔE^0±₀(1) = 55.9 kcal. The mechanism of the decomposition is discussed, and it is concluded that hydrogen atoms are not involved. It is further suggested that silylene in the pure silane pyrolysis ultimately reacts with itself to give hydrogen: 2SiH₂ → (Si₂H₄)* → (SiH₃SiH)* → Si₂H₂ + H₂. The mechanism of H ? D exchange absorbed in the pyrolysis of SiD₄-hydrocarbon systems is also 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 decomposition of N,N-dihalopeptides

The tripeptide alanylalanylalanine reacts with either HOCl or HOBr to form a N,N-dihalopeptide. These compounds decompose to the N-halo-N′-(α-iminoketo)peptides plus halide ion. The rate constants for these reactions in 0.4-M NaCl were determined to be where the activation energies are in cal/mol. The N-halo-N′-(α-iminoketo)-peptides slowly decompose either by a two-step hydrolysis reaction to form ammonia, halide ion, and an N-(α-acylketo)peptide, or by direct decomposition to a nitrile, an isocyanopeptide, and a halide ion.     

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.     

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.     

Kinetics and mechanism of the thermal decomposition of barium titanyl oxalate

Thermal analysis of barium titanyl oxalate reveals that the decomposition proceeds through four distinct rate processes. Among them, the decomposition of oxalate occurs in the temperature range 230–350°C, and has been studied by TG and gas pressure measurements, supplemented by IR spectroscopy, electron microscopy and chemical analysis. Oxalate decomposition proceeds differently in vacuum and in flowing gas atmospheres. Analytical results indicate the formation of a complex carbonate together with CO, CO₂ and water vapour below 400°C. Schemes for each type of decomposition are proposed and discussed. For decomposition in vacuum, kinetic observations fitted the three-dimensional, diffusion controlled, rate equation for almost the entire α-range (0.028≤α≤0.92). The activation energy is calculated to be3 189±6 kJ mol⁻¹. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Kinetics and mechanism of the decomposition of N-bromoalcoholamines in aqueous solution

The decomposition reactions of N-bromodiethanolamine, N-bromoethylethanolamine, and N-bromomethylethanolamine in aqueous solution have been studied kinetically under various experimental conditions. The results support a proposed reaction mechanism in which the rate controlling step is assumed to be the formation of an imine which is then hydrolyzed to the final decomposition products.     

Kinetics and mechanism of the shock induced thermal decomposition of n-propylsilane

The kinetics and mechanism of the thermal decomposition of n-propylsilane have been studied by the single pulse shock tube-comparative rate technique at pressures around 4700 torr between 1095–1240 K. The primary dissociation processes are 1,1 and 1,2 H₂ elimination with ø_1,1 ? 0.75 and ø_1,2 ? 0.25, respectively. Subsequent decompositions of the primary process product, n-propylsilylene, to propylene and ethylene is complete even in the presence of excess butadiene. Possible mechanistic paths for these decompositions are discussed and an activation energy range of 30 ± 4 kcal is established for both processes. Induced decomposition via silylene chains accounts for 36–46% of the overall reaction in the uninhibited decomposition of n-propylsilane. The silylene chains are quenched in excess butadiene, and studies under maximum inhibition give overall decomposition kinetics of, log k(nPrSiD₃, s^?1) = 15.26–65,300 ± 1950 cal/2.303. Computer modeling results of the overall reaction both in the absence and presence of butadiene are also presented and shown to be in acceptable agreement with the experimental observations.     

Synthesis of germanium sols via thermal decomposition of gaseous germane

A new approach to the synthesis of colloidal Ge nanoparticles in high-boiling solvent via thermal decomposition of germane is presented. Obtained products were analyzed by XRD, XRF, TEM, absorption spectrophotometry, Raman IR and PL spectroscopy. Ge nanoparticles have mean sizes about 4–5 nm, are apparently amorphous and nonspherical.     

Kinetics and mechanism of the thermal decomposition of 1-bromo-4-nitroxymethylcubane

The thermal decomposition kinetics of 1-bromo-4-nitroxymethylcubane in the liquid phase is typical of C-ONO₂ bond heterolysis, which occurs if the nitro ester has a strong donor substituent. A comparison between 1-bromo-4-nitroxymethylcubane and tert-butyl nitrate shows that bromocubyl is close to the tert-butyl group in induction properties and cubyl itself is a stronger donor than this group.     

Kinetics and mechanism of the decomposition of tetrathionate ion in alkaline medium

The kinetics of the alkaline decomposition of tetrathionate has been studied spectrophotometrically in the pH range of 9.2-12.2 using both phosphate/hydrogen phosphate and carbonate/hydrogen carbonate as buffer systems and by adjusting the ionic strength to I=0.5 M with sodium perchlorate at T=25.0+/-0.1 degrees C. Matrix rank analysis of the spectra recorded between 265 and 330 nm shows the presence of three independent absorbing species. Besides tetrathionate, thiosulfate and trithionate are identified as absorbing products of the decomposition, but sulfite and a trace amount of sulfate are also formed during the alkaline degradation process. With pentathionate, sulfoxylic acid (S(OH)2), S2O3OH-, and S3O3OH- as key intermediates, a 10-step kinetic model is proposed with six fitted kinetic parameters to take all the important characteristics of the experimental curves into account. On the basis of the stoichiometric measurements and the model proposed, it is also enlightened that the product distribution of the reaction continuously varies with pH; thus the kinetic traces cannot be evaluated by assuming a single stoichiometry in contrast to recent studies. Buffer dependence of the decomposition is also discussed.     

Kinetics and mechanism of the decomposition of N-brominated alanine in aqueous solution

Aqueous bromine reacts with alkyl-sidechain amino acids through a series of steps resulting in the formation of the corresponding alkyl aldelydes and nitriles. The kinetics and the mechanism of the interaction of bromine with alanine are examined. The products and the rates of this reaction are dependent in a complex way on the initial reactant concentration and pH. Acetaldeyde production is favored at low bromine-to-alanine ratios, low bromine concentrations, and pH values above 6. The first-order rate constant for the formation of acetaldelyde from alanine under these conditions is k₄ = 1.98 × 10¹⁵ e^?22,500/RT min^?1. At higher concentration the nitrile is formed through a bromoimine intermediate. Under most conditions the nitrile appears to form from a catalyzed decomposition of the bromoimine which is too fast to be followed by the methods used in this study. However, residual amounts of the bromoimine decay by a slower first-order mechanism. The rate constant for this slower reaction in the case of alanine at pH 6.8–6.9 and alanine concentrations of 1 × 10^?4M is k₆ = 1.75 × 10⁵ e^?10,400/RT min^?1.     

Kinetics and mechanism of thermal decomposition of insitu generated calcium carbonate

Thermogravimetric studies on two varieties of calcium carbonate viz., analytical reagentgrade and insitu generated from calcium oxalate monohydrate, were carried out. The kinetics and mechanism of their solid-state thermal decomposition reaction were evaluated from the TG data using integral methods and the effect of procedural factors such as heating rate, sample mass and method of computation on them were also studied. The procedural variables in the range studied had no marked influence on the results; however the kinetic parameters were marginally higher for the insitu generated calcium carbonate. This trend is explained by the presence of more micropores in the insitu generated calcium carbonate as well as the mechanism of its decomposition following phase boundary reaction with cylindrical symmetry.

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Zusammenfassung An zwei verschiedenen Arten von Calciumcarbonat (analytisch rein bzw. in situ hergestellt aus Calciumoxalatmonohydrat) wurden thermogravimetrische Untersuchungen durchgeführt. Die Kinetik und der Mechanismus der thermischen Feststoffzersetzungsreaktionen wurde unter Anwendung integrativer Verfahren aus TG-Daten ermittelt. Auch der Einfluß experimenteller Bedingungen, wie z.B. von Aufheizgeschwindigkeit, Probenmasse und Rechenmethode wurden untersucht. Die experimentellen Bedingungen haben im untersuchten Intervall keinen sichtlichen Einfluß auf die Ergebnisse; in jedem Falle hatten die kinetischen Parameter für in situ hergestelltes Calciumcarbonat wesentlich höhere Werte. Dies wird durch die Anwesenheit von wesentlich mehr Mikroporen in dem in situ hergestellten Calciumcarbonat erklärt. Der Reaktionsmechanismus der Zersetzung wird mittels Phasengrenzreaktionen mit zylindrischer Symmetrie erklärt.

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Dedicated to Prof. Dr. H. J. Seifert on the occasion of his 60^th birthday

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We thank Director, VSSC for the kind permission to publish this work. Thanks are due to Mr. A. Natarajan for the support in SEM studies.