Kinetics of the Mercury-Photosensitized Decomposition of Neopentane. Part II. Reactions of the Methyl and Neopentyl Radicals

1972 ◽  
Vol 50 (8) ◽  
pp. 1123-1128 ◽  
Author(s):  
E. Furimsky ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
High Pressures ◽  
Frequency Factor ◽  
Heat Of Formation ◽  
Relative Importance ◽  
Methyl Radical ◽  
Heat Of Dissociation ◽  
Radical Processes ◽  
Low Pressures ◽  
Kinetics Of

The results of Part I are further analyzed with reference to certain of the elementary free-radical processes occurring. A fall-off in the methyl radical combination is observed at low pressures. Comparison of this process with the CH3 + neopentane abstraction yields for the latter an activation energy of 11.5 kcal/mol and a frequency factor of 4.9 × 1011 cc mol−1 s−1. The relative importance of CH3 + neopentyl and neopentyl + neopentyl is compared. The decomposition of the neopentyl radical into i-C4H8 + CH3 shows a fall-off at low pressures; the limiting activation energy at high pressures is 29.0 kcal/mol, while that at low pressure is 17.1 kcal/mol. The former value leads to 6.7 kcal/mol for the heat of formation of the neopentyl radical at 25 °C, to 21.3 kcal/mol for the heat of its dissociation into i-C4H8 + CH3, and to 98.5 kcal/mol for the heat of dissociation of neopentane into neopentyl + H. Entropy values are also calculated in an approximate manner.

THE KINETICS OF THE THERMAL DECOMPOSITIONS OF THE LOWER PARAFFINS: V. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF n-BUTANE

1940 ◽  
Vol 18b (1) ◽  
pp. 1-11 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Free Radical ◽  
High Pressures ◽  
Free Radical Processes ◽  
Temperature Range ◽  
Radical Recombination ◽  
Radical Processes ◽  
Kinetics Of ◽  
Good Agreement

A detailed investigation of the inhibition by nitric oxide of the thermal decomposition of n-butane has been carried out over the temperature range 500° to 550 °C.In all cases it was found that inhibition decreased with increasing butane concentration. This suggests that radical recombination occurs in the normal decomposition by ternary collisions with butane molecules acting as third bodies.The activation energies of the normal and inhibited reactions have been determined. For high pressures the two values are in good agreement, viz., 58,200 and 57,200 cal. per mole respectively. The products of the inhibited reaction were also found to be the same as those of the normal reaction.It is concluded that free radical processes predominate, involving comparatively short chains.

scholarly journals Investigation of the pyrolysis characteristics and kinetics of oil-palm solid waste by using Coats–Redfern method

2019 ◽  
Vol 38 (1) ◽  
pp. 298-309
Author(s):  
Fredy Surahmanto ◽  
Harwin Saptoadi ◽  
Hary Sulistyo ◽  
Tri A Rohmat
Keyword(s):  
Activation Energy ◽  
Solid Waste ◽  
Oil Palm ◽  
Frequency Factor ◽  
Nitrogen Atmosphere ◽  
Empty Fruit Bunch ◽  
Pyrolysis Kinetics ◽  
Pyrolysis Characteristics ◽  
Kinetics Of

The pyrolysis kinetics of oil-palm solid waste was investigated by performing experiments on its individual components, including empty fruit bunch, fibre, shell, as well as the blends by using a simultaneous thermogravimetric analyser at a heating rate of 10°C/min under nitrogen atmosphere and setting up from initial temperature of 30°C to a final temperature of 550°C. The results revealed that the activation energy and frequency factor values of empty fruit bunch, fibre, and shell are 7.58–63.25 kJ/mol and 8.045E-02–4.054E + 04 s−1, 10.45–50.76 kJ/mol and 3.639E-01–5.129E + 03 s−1, 9.46–55.64 kJ/mol and 2.753E-01–9.268E + 03, respectively. Whereas, the corresponding values for empty fruit bunch–fibre, empty fruit bunch–shell, fibre–shell, empty fruit bunch–fibre–shell are 2.97–38.35 kJ/mol and 1.123E-02–1.326E + 02 s−1, 7.95–40.12 kJ/mol and 9.26E-02–2.101E + 02 s−1, 9.14–50.17 kJ/mol and 1.249E-01–2.25E + 03 s−1, 8.35–45.69 kJ/mol and 1.344E + 01–4.23E + 05 s−1, respectively. It was found that the activation energy and frequency factor values of the blends were dominantly due to the role of the components with a synergistic effect occurred during pyrolysis.

scholarly journals The thermal decomposition of acetaldehyde and the existence of different activated states

1933 ◽  
Vol 141 (843) ◽  
pp. 41-55 ◽  
Keyword(s):  
High Pressures ◽  
Initial Pressure ◽  
Bimolecular Reaction ◽  
Bimolecular Reactions ◽  
First Order ◽  
Straight Line ◽  
Gas Reactions ◽  
Pass Through ◽  
Low Pressures ◽  
Kinetics Of

Homogeneous thermal gas reactions were at one time tacitly assumed to possess a definite order, unimolecular and bimolecular reactions, for example, being sharply distinguished. The kinetics of the decomposition of acetalde­ hyde, CH 3 CHO = CH 4 + CO, over the pressure range of 100 to 400 mm. were found to satisfy the criterion of a bimolecular reaction, namely, that the reciprocal of the time for half change (1/ t 1/2 ) )plotted against the initial pressure ( p 0 ) gave a straight line inclined to the axes. The line, however, did not pass through the origin, as may be seen in fig. 1 of the present paper. This indicated the presence of some first order reaction, the nature of which was not determined. Subsequently, in accordance with the collision theory of activation and deactivation, it was shown that certain reactions, sometimes called quasiummolecular, change their order from the second at low pressures to the first at high pressures. This apparently was the reverse of the behaviour shown by acetaldehyde.

scholarly journals CO2 Gasification Kinetics of Shenhua Bituminous Coal by Isothermal Thermo-Gravimetric Analysis

2020 ◽  
Author(s):  
Jinzhi Zhang ◽  
Zhiqi Wang ◽  
Ruidong Zhao ◽  
Jinhu Wu
Keyword(s):  
Activation Energy ◽  
Bituminous Coal ◽  
Thermo Gravimetric Analysis ◽  
Correlation Coefficients ◽  
Mathematical Expression ◽  
Frequency Factor ◽  
Gravimetric Analysis ◽  
Thermo Gravimetric ◽  
Kinetics Of ◽  
Compensation Relationship

Abstract This research performed the gasification kinetics of three Shenhua coal under CO2 atmosphere using isothermal thermogravimetry. Results showed that isothermal gasification curves for three different coal samples revealed different gasification behaviour. Among the eleven kinetic models, A2 was the most suitable one to describe the gasification kinetics of three coal samples, because it can reproduce the experimental data very well with reasonable correlation coefficients. The activation energy for sample A, B and C were 95.9, 79.1, and 69.4 kJ mol-1, respectively. The activation energy decreased with the increase of the particle size. The compensation relationship was observed between activation energy and frequency factor, and the mathematical expression was lnA=0.1041 E+0.54028 with the correlation coefficients of 0.999.

scholarly journals Kinetics Study of Thermal Degradation of Resin Derived from Salicylaldehyde, Ethylenediamine and Formaldehyde

2010 ◽  
Vol 7 (2) ◽  
pp. 564-568 ◽  
Author(s):  
Dhanraj. T. Masram ◽  
N. S. Bhave ◽  
K. P. Kariya
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Free Energy ◽  
Thermal Degradation ◽  
Frequency Factor ◽  
Entropy Change ◽  
Energy Change ◽  
Kinetics Study ◽  
Degradation Studies ◽  
Kinetics Of

The present paper reports the synthesis and kinetics of thermal degradation studies of resin salicylicldehyde -ethylenediamine -formaldehyde (SdEDF) derived by the condensation of salicylicldehyde and ethylenediamine with formaldehyde in the presence of catalyst hydrochloric acid in 1:1:2 molar proportions of reactants. Detailed thermal degradation studies of the SdEDF resin has been carried out to ascertain its thermal stability. Thermal degradation curve has been discussed in order to determine their mode of decomposition, order of reaction, apparent activation energy, frequency factor, free energy change, entropy change, and apparent energy change. Freeman - Carroll and Sharp- Wentworth methods have been applied for the calculation of kinetic parameters while the data from the Freeman - Carroll methods have been used to determine various thermodynamic parameters.

MODEL FREE KINETICS ANALYSIS OF IMPERATA CYLINDRICA (LALANG)

2016 ◽  
Vol 78 (8-3) ◽  
Author(s):  
Olagoke Oladokun ◽  
Arshad Ahmad ◽  
Tuan Amran Tuan Abdullah ◽  
Bemgba Bevan Nyakuma ◽  
Syie Luing Wong
Keyword(s):  
Activation Energy ◽  
Biomass Conversion ◽  
Frequency Factor ◽  
Isoconversional Methods ◽  
Green Energy ◽  
Imperata Cylindrica ◽  
Heating Rates ◽  
Model Free ◽  
Solid Biofuel ◽  
Kinetics Of

This study is the first attempt at investigating the solid state decomposition and the devolatilization kinetics of Imperata cylindrica (lalang) grass termed the “farmer’s nightmare weed” as a potential solid biofuel of the future. Biomass conversion technologies such as pyrolysis and gasification can be utilized for future green energy needs. However an important step in the efficient utilization and process optimizing of biomass conversion processes is understanding the thermal decomposition kinetics of the feedstock. Consequently, thermogravimetric analysis (TGA) of Imperata cylindrica was carried out in the temperature range of 30-1000 °C at four heating rates of 5, 10, 15, and 20 K min-1 using Nitrogen at a flow rate of 20 L min-1 as purge gas. Using the TGA results, the kinetic parameters activation energy (Ea) and pre-exponential frequency factor (ko) of the grass were estimated via the model free or isoconversional methods of Kissinger and Starink. The results obtained for Kissinger model were 151.36 kJ moI-1 and 5.83 x 109 min-1 for activation energy and pre-exponential frequency factor respectively. However, Starink model activation energy and pre-exponential frequency factor were a function of conversion (α) with average values of 159.93 kJ mol-1 and 6.33 x 1022 min-1 respectively. 

Pyrolysis of methylcyclohexane

1987 ◽  
Vol 52 (6) ◽  
pp. 1527-1544 ◽  
Author(s):  
Ulrika Králíková ◽  
Martin Bajus ◽  
Jozef Baxa
Keyword(s):  
Activation Energy ◽  
Coke Formation ◽  
Tubular Reactor ◽  
Frequency Factor ◽  
Order Reaction ◽  
The Other ◽  
First Order ◽  
Consecutive Reactions ◽  
Secondary Reactions ◽  
Kinetics Of

The kinetics of pyrolysis of methylcyclohexane was investigated from the viewpoint of coke formation in a steel tubular reactor (S/V = 6·65 cm-1) at 0·1 MPa, 700 to 820 °C and residence time 0·01 to 0·24 s. Decomposition of methylcyclohexane proceeds as a first order reaction with a frequency factor 6·31 . 1015 s-1 and activation energy 251·2 kJ mol-1. The course of secondary reactions associated with the formation of coke is discussed. Investigation of coke formation showed a greater tendency of methylcyclohexane to coking in comparison with heptane. A prominent role plays the course of dehydrogenation of cycloalkane radicals up to aromates, this being reflected by the overall conversion of methylcyclohexane, and, on the other hand the thus formed aromates enter the consecutive reactions leading to coke.

Die Kinetik des Zerfalls von tert. Butylperoxypivalat bei hohen Drücken und Temperaturen / The Kinetics of the Decomposition of tert.Butylperoxypivalate up to High Pressures and Temperatures

1981 ◽  
Vol 36 (12) ◽  
pp. 1371-1377 ◽  
Author(s):  
M. Buback ◽  
H. Lendle
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
High Pressures ◽  
Activation Volume ◽  
Rate Law ◽  
First Order ◽  
Order Rate ◽  
High Pressures And Temperatures ◽  
Kinetics Of

AbstractThe decomposition of tert. butylperoxypivalate dissolved in n-heptane has been measured ir-spectroscopically in optical high-pressure cells up to 2000 bar at temperatures between 65 °C and 105 °C. The reaction follows a first order rate law with an activation energy Ea = 122.3 ±3.0 kJ · mol-1 and an activation volume ⊿V≠ = 1.6 ± 1.0 cm3 mol-1 .

Kinetics of the Mercury-Photosensitized Decomposition of Propane. Part II. Reactions of the Propyl Radicals

1971 ◽  
Vol 49 (4) ◽  
pp. 549-554 ◽  
Author(s):  
M. M. Papic ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Kinetic Parameters ◽  
Dissociation Energy ◽  
Heat Of Formation ◽  
Entropy Changes ◽  
A Value ◽  
Yield Information ◽  
Temperature And Pressure ◽  
Kinetics Of

The results of the previous paper are analyzed to yield information about the reactions of the n-propyl and i-propyl radicals. The various combination and disproportionation reactions are considered. The rate of decomposition of the n-propyl radical was determined as a function of temperature and pressure, and limiting high-pressure and low-pressure kinetic parameters were obtained. The high-pressure activation energy is 32.6 kcal mol−1, and this leads to a value of 24.3 kcal mol−1 for the dissociation energy of the C—C bond in the n-propyl radical, to 22.2 kcal mol−1 for its heat of formation, and to 99.1 kcal mol−1 for the primary C—H dissociation energy in propane. Entropy changes are also calculated from the results.For the decomposition of the i-propyl E∞ = 38.7 kcal mol−1, and this leads to 37.7 kcal mol−1 for the C—H bond dissocation energy in this radical and to 19.3 kcal mol−1 for its heat of formation. The secondary C—H dissociation energy in propane is calculated to be 96.2 kcal mol−1. Corresponding entropy changes are calculated.

THE THERMAL DECOMPOSITION OF STYRENE–BUTADIENE POPCORN POLYMER

1950 ◽  
Vol 28b (1) ◽  
pp. 5-16
Author(s):  
C. A. Winkler ◽  
J. Halpern
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Linear Relation ◽  
Frequency Factor ◽  
Thermal Reaction ◽  
Cross Linking ◽  
First Order ◽  
Bond Scission ◽  
Styrene Butadiene ◽  
Kinetics Of

At temperatures of the order of 250 °C., popcorn polymer undergoes decomposition to soluble polymer. The reaction is catalyzed by peroxides present in the popcorn when the latter is formed. These peroxides may be removed by extracting the polymer with benzene. The kinetics of both the catalyzed and purely thermal solubilization reactions were investigated. The rates of both reactions are first order, the catalyzed degradation having a higher activation energy and a higher frequency factor. The rate of the thermal reaction decreases and its activation energy increases with increasing butadiene content of the polymer. A linear relation between the activation energy and the log of the frequency factor, for the decomposition of popcorn polymers of different butadiene contents, was observed. The results indicate that the rate of solubilization is determined by the activation energy of the bond scission process, and is independent of the degree of cross-linking of the polymer.

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