Kinetic Study of the Pyrolysis of Formaldehyde

1972 ◽  
Vol 50 (7) ◽  
pp. 992-998 ◽  
Author(s):  
C. J. Chen ◽  
D. J. McKenney

Kinetics of the thermal decomposition of pure formaldehyde were studied over a temperature range of 466–516 °C and a pressure range of ~ 50–160 Torr. Arrhenius parameters and rate laws were determined for carbon monoxide, hydrogen and methanol as follows:[Formula: see text]A mechanism is postulated which is qualitatively consistent with the experimental results but the activation energy for reaction 1[Formula: see text]is ~15 kcal/mol lower than predicted from recent thermochemical data, suggesting the possibility of a heterogeneous reaction.

1969 ◽  
Vol 47 (4) ◽  
pp. 615-617 ◽  
Author(s):  
Arthur T. Blades

The thermal decomposition of cyclobutanone into cyclopropane and carbon monoxide has been shown to occur simultaneously with the major decomposition to ethylene and ketene. The relative rate constant expression is given by [Formula: see text] Both reactions are pressure sensitive below 10 Torr and this quasi-unimolecular behavior is most pronounced in the cyclopropane forming reaction, consistent with the higher activation energy. The data are also discussed in relation to the photochemical decomposition and it is shown that cyclopropane formation from the ground singlet is an important feature of the photolysis at 3130 Å.


1960 ◽  
Vol 38 (8) ◽  
pp. 1261-1270 ◽  
Author(s):  
Margaret H. Back ◽  
A. H. Sehon

The thermal decomposition of phenylacetic acid was investigated by the toluene-carrier technique over the temperature range 587 to 722 °C. The products of the pyrolysis were carbon dioxide, carbon monoxide, hydrogen, methane, dibenzyl, and phenylketene. From the kinetics of the decomposition it was concluded that the reaction[Formula: see text]was a homogeneous, first-order process and that the rate constant of this dissociation step was represented by the expression k = 8 × 1012.e−55,000/RT sec−1. The activation energy of this reaction may be identified with D(C6H5CH2—COOH). The possible reactions of carboxyl radicals are discussed.


2013 ◽  
Vol 641-642 ◽  
pp. 144-147 ◽  
Author(s):  
Ming Hua Chen ◽  
Tao Zhang ◽  
Wen Ping Chang ◽  
Xiao Biao Jia

The thermal decomposition kinetics of RDX at different rates was studied by thermogravimetric analyzer(TG) and the activation energy of RDX was calculated by distributed activation energy model. It is shown that the thermal decomposition processes of RDX were divided into three stages according to the TG curves, they are molten stage, thermal decomposition stage and eng stage. The activation energies of RDX are all between 124.34 and 181.48KJ•mol-1 in the thermal decomposition stage of non-monotonously increasing. The activation energy of RDX is 139.98 KJ•mol-1 in the molten stage, and the thermal decomposition stage is167.24KJ•mol-1.


2019 ◽  
Vol 956 ◽  
pp. 181-191
Author(s):  
Jian Lin Xu ◽  
Bing Xue Ma ◽  
Cheng Hu Kang ◽  
Cheng Cheng Xu ◽  
Zhou Chen ◽  
...  

The thermal decomposition kinetics of polybutylene terephthalate (PBT) and flame-retardant PBT (FR-PBT) were investigated by thermogravimetric analysis at various heating rates. The kinetic parameters were determined by using Kissinger, Flynn-Wall-Ozawa and Friedman methods. The y (α) and z (α) master plots were used to identify the thermal decomposition model. The results show that the rate of residual carbon of FR-PBT is higher than that of PBT and the maximum mass loss rate of FR-PBT is lower than that of PBT. The values of activation energy of PBT (208.71 kJ/mol) and FR-PBT (244.78 kJ/mol) calculated by Kissinger method were higher than those of PBT (PBT: 195.54 kJ/mol) and FR-PBT (FR-PBT: 196.00 kJ/mol) calculated by Flynn-Wall-Ozawa method and those of PBT and FR-PBT (PBT: 199.10 kJ/mol, FR-PBT: 206.03 kJ/mol) calculated by Friedman methods. There is a common thing that the values of activation energy of FR-PBT are higher than that of PBT in different methods. The thermal decomposition reaction models of the PBT and FR-PBT can be described by Avarami-Erofeyev model (A1).


1973 ◽  
Vol 131 (2) ◽  
pp. 223-236 ◽  
Author(s):  
S. Ainsworth ◽  
N. Macfarlane

The paper reports a study of the kinetics of the reaction between phosphoenolpyruvate, ADP and Mg2+ catalysed by rabbit muscle pyruvate kinase. The experimental results indicate that the reaction mechanism is equilibrium random-order in type, that the substrates and products are phosphoenolpyruvate, ADP, Mg2+, pyruvate and MgATP, and that dead-end complexes, between pyruvate, ADP and Mg2+, form randomly and exist in equilibrium with themselves and other substrate complexes. Values were determined for the Michaelis, dissociation and inhibition constants of the reaction and are compared with values ascertained by previous workers.


1950 ◽  
Vol 28b (7) ◽  
pp. 358-372
Author(s):  
Cyrias Ouellet ◽  
Adrien E. Léger

The kinetics of the polymerization of acetylene to cuprene on a copper catalyst between 200° and 300 °C. have been studied manometrically in a static system. The maximum velocity of the autocatalytic reaction shows a first-order dependence upon acetylene pressure. The reaction is retarded in the presence of small amounts of oxygen but accelerated by preoxidation of the catalyst. The apparent activation energy, of about 10 kcal. per mole for cuprene growth between 210° and 280 °C., changes to about 40 kcal. per mole above 280 °C. at which temperature a second reaction seems to set in. Hydrogen, carbon monoxide, or nitric oxide has no effect on the reaction velocity. Series of five successive seedings have been obtained with cuprene originally grown on cuprite, and show an effect of aging of the cuprene.


Holzforschung ◽  
2017 ◽  
Vol 71 (3) ◽  
pp. 233-240 ◽  
Author(s):  
Ke-Chang Hung ◽  
Jyh-Horng Wu

Abstract Wood-SiO2 composites (WSiO2Cs) were prepared by means of the sol-gel process with methyltrimethoxysilane (MTMOS) as a reagent, and the physical properties, structure and thermal decomposition kinetics of the composites has been evaluated. The dimensional stability of the WSiO2Cs was better than that of unmodified wood, especially in terms of the weight percent gain (WPG), which achieved values up to 30%. The 29Si-NMR spectra show two different siloxane peaks (T2 and T3), which supports the theory about the formation of MTMOS network structures. Thermal decomposition experiments were also carried out in a TG analyzer under a nitrogen atmosphere. The apparent activation energy was determined according to the iso-conversional methods of Friedman, Flynn-Wall-Ozawa, modified Coats-Redfern, and Starink. The apparent activation energy between 10 and 70% conversion is 147–172, 170–291, 189–251, and 192–248 kJ mol−1 for wood and WSiO2Cs with WPGs of 10, 20, and 30%, respectively. However, the reaction order between 10 and 70% conversion calculated by the Avrami theory was 0.50–0.56, 0.35–0.45, 0.33–0.44, and 0.28–0.48. These results indicate that the dimensional and thermal stability of the wood could be effectively enhanced by MTMOS treatment.


1953 ◽  
Vol 31 (4) ◽  
pp. 418-421 ◽  
Author(s):  
Arthur T. Blades

The thermal decomposition of vinyl isopropyl ether in the presence of toluene has been studied in a flow system in the temperature range 447–521 °C. In this range, the data indicate a purely intramolecular decomposition into propylene and acetaldehyde, the activation energy for the reaction being in close agreement with that found for the decomposition of vinyl ethyl ether. At 570 °C. a minor free radical decomposition of the ether becomes apparent. Some qualitative studies of the decomposition of vinyl isobutyl ether are also reported.


1985 ◽  
Vol 63 (11) ◽  
pp. 2945-2948 ◽  
Author(s):  
J.-R. Cao ◽  
R. A. Back

The thermal decomposition of cyclobutane-1,2-dione has been studied in the gas phase at temperatures from 120 to 250 °C and pressures from 0.2 to 1.5 Torr. Products were C2H4 + 2CO, apparently formed in a simple unimolecular process. The first-order rate constant was strongly pressure dependent, and values of k∞ were obtained by extrapolation of plots of 1/k vs. 1/p to1/p = 0. Experiments in a packed reaction vessel showed that the reaction was enhanced by surface at the lower temperatures. Arrhenius parameters for k∞, corrected for surface reaction, were log A (s−1) = 15.07(±0.3) and E = 39.3(±2) kcal/mol. This activation energy seems too low for a biradical mechanism, and it is suggested that the decomposition is probably a concerted process. The vapor pressure of solid cyclobutane-1,2-dione was measured at temperatures from 22 to 62 °C and a heat of sublimation of 13.1 kcal/mol was estimated.


2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
Pakamon Pintana ◽  
Nakorn Tippayawong

Thermal behaviors and combustion kinetics of Thai lignite with different SO3-free CaO contents were investigated. Nonisothermal thermogravimetric method was carried out under oxygen environment at heating rates of 10, 30, and 50°C min−1from ambient up to 1300°C. Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods were adopted to estimate the apparent activation energy (E) for the thermal decomposition of these coals. Different thermal degradation behaviors were observed in lignites with low (14%) and high (42%) CaO content. Activation energy of the lignite combustion was found to vary with the conversion fraction. In comparison with the KAS method, higherEvalues were obtained by the FWO method for all conversions considered. High CaO lignite was observed to have higher activation energy than the low CaO coal.


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