KINETICS AND MECHANISMS OF THE PYROLYSIS OF n-BUTANE: PART I. THE UNINHIBITED DECOMPOSITION

1963 ◽  
Vol 41 (4) ◽  
pp. 838-847 ◽  
Author(s):  
N. H. Sagert ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
Surface Effect ◽  
Frequency Factor ◽  
Radical Mechanism ◽  
Free Radical Mechanism ◽  
Surface Catalysis ◽  
Initiation Reaction ◽  
Pressure Changes ◽  
Ethyl Radicals ◽  
Kinetics Of

The kinetics of the pyrolysis of n-butane have been studied at temperatures from 520° to 590 °C, and at pressures from 30 to 600 mm Hg; the rate was followed from pressure changes and by gas chromatography. The reaction was accurately of the three-halves order; the activation energy was found to be 59.9 kcal mole−1, and the frequency factor 3.24 × 1015 cc1/2 mole−1/2 sec−1. The reaction is sensitive to surface; packing the vessel and 'conditioning' it usually led to a decrease in rate and an increase in activation energy. The reaction is concluded to be largely homogeneous, and to occur almost entirely by a free-radical mechanism; the initiation reaction is considered to be the dissociation of a butane molecule into two ethyl radicals, in its first-order region, and termination is believed to be the second-order combination of ethyl radicals. The mechanism proposed is shown to account satisfactorily for the observed behavior. The surface effect is attributed to a certain amount of initiation by abstraction, by a surface atom, of a hydrogen atom from butane, and to surface catalysis of the recombination of ethyl radicals.

KINETICS AND MECHANISMS OF THE PYROLYSIS OF n-BUTANE: PART II. THE REACTION INHIBITED BY NITRIC OXIDE

1963 ◽  
Vol 41 (4) ◽  
pp. 848-857 ◽  
Author(s):  
N. H. Sagert ◽  
K. J. Laidler
Keyword(s):  
Nitric Oxide ◽  
Main Chain ◽  
Frequency Factor ◽  
Radical Mechanism ◽  
Quantitative Interpretation ◽  
Kcal Mole ◽  
Free Radical Mechanism ◽  
Initiation Step ◽  
Kinetics Of ◽  
Short Induction Period

The kinetics of the pyrolysis of n-butane, when maximally inhibited by nitric oxide, were studied at temperatures from 540° to 610 °C, and at pressures from 30 to 550 mm Hg. The reaction has a short induction period and is accurately of the three-halves order; the activation energy was 65.9 kcal mole−1 and the frequency factor 5.3 × 1016 cc1/2 mole−1/2 sec−1. The reaction was somewhat less inhibited by surface than was the uninhibited reaction. Excess of carbon dioxide had no effect on the rate. The results are explained in terms of a free-radical mechanism for the maximally inhibited decomposition. It is proposed that the initiation step in the inhibited decomposition is mainly C4H10 + NO → C4H9 + HNO. This is followed by the ordinary chain-propagating reactions, and by processes such as C2H5 + NO → C2H5NO. The main chain-terminating step, of the type β + βNO, is concluded to be C2H5 + C2H5NO → C4H10 + NO or C2H6 + C2H4 + NO. This scheme leads to three-halves-order kinetics, and provides a satisfactory quantitative interpretation of the experimental behavior.

Copper Catalyzed Autoxidation of Sulphur Dioxide and Inhibition by Methanoic Acid

2020 ◽  
Vol 10 (1) ◽  
pp. 33-46
Author(s):  
Arun Kumar Sharma ◽  
Devarkonda Satay Narayan Prasad
Keyword(s):  
Acid Rain ◽  
Atmospheric Chemistry ◽  
Harmful Effect ◽  
Frequency Factor ◽  
Rain Water ◽  
Radical Mechanism ◽  
Gravimetric Analysis ◽  
Free Radical Mechanism ◽  
Organic Inhibitors ◽  
Methanoic Acid

Background:: Today, acid rain problem is one of the serious global problems to the environment in which pH of the rain water decreases, causing harmful effect to nature, buildings, monuments, vegetation and human being as well. Therefore, the objective of the paper to find out some organic inhibitors present in the atmosphere that inhibited the acid rain. Objective:: In this paper, we studied the chemistry of Cu (II)-methanoic acid-S(IV)-O2 in acetate buffered medium by earlier reported methods in literature. Gravimetric analysis was carried out to find the end product and confirmed that it was sulphate with 98 % recovery. Methods:: Experiments were carried out at 303 ≤ T/K ≤ 313, 4.0 ≤ pH ≤ 5.35, 1.0×10−3 mol/dm3 ≤ S(IV) ≤ 10.0×10−3 mol/dm3, 5×10−6 mol/dm3 ≤ [Cu(II)] ≤ 2.5×10−5 mol/dm3, 6×10−6 mol/dm3≤[methanoic acid]≤7×10-4 mol/dm3. The value of apparent activation energy and inhibition parameter B was calculated in the presence of methanoic acid found as 29.07 kJ mol-1and 3.18 x 103 mol dm-3, respectively. The thermodynamic parameters were found as frequency factor (1.59 x 10-6s-1), entropy (-358.92 J K-1 mol-1), enthalpy (20.97 k J mol-1), and Gibbs free energy (172.83k J mol-1), respectively. Results:: We observed that methanoic acid acts as an inhibitor in copper catalyzed autoxidation of SO2 in acidic medium. Therefore, on the basis of the observed results a free radical mechanism has been identified. The results are useful for modeling rain water acidity and therefore a great use of meteorology and atmospheric chemistry. This study is important in understanding the mechanism of the oxidation of S(IV) by O2. Conclusion:: This study suggests that since organic inhibitors are found in the atmosphere, their concentrations and their influence on the oxidation of aqueous SO2 should be taken into account. The intervention of methanoic acid in the autoxidation of aqueous SO2 plays a role in deciding the fate of both methanoic acid and SO2. The influence of inhibitors may be used to calculate the lifetime of SO2, Methanoic acid has high values of kinh and, therefore, it would be degraded by sulfate radical anions in atmospheric waters.

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.

The kinetics of the oxidation of ammonia by nitrous oxide

1964 ◽  
Vol 17 (2) ◽  
pp. 202 ◽  
Author(s):  
TN Bell ◽  
JW Hedger
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Free Radical ◽  
Rate Equation ◽  
Radical Mechanism ◽  
15N Isotope ◽  
Free Radical Mechanism ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Decomposition Of Nitrous Oxide

Ammonia is oxidized by nitrous oxide smoothly and homogeneously at temperatures between 658 and 730� and total pressures up to 250 mm. The products of reaction, nitrogen, water, and hydrazine are accounted for by a free-radical mechanism initiated by oxygen atoms which result from the thermal decomposition of nitrous oxide. Ammonia labelled with the 15N-isotope was used to distinguish between the nitrogen formed from the nitrous oxide and that from the ammonia. The kinetics follow an empirical rate equation, ������������� Rate = k'[N2O]1.56 + k"[N2O]0.61[NH3]. This is of a form which shows the importance of the ammonia molecule participating in the activation of nitrous oxide through bimolecular collision. Assigning a collisional efficiency of unity for like N2O-N2O collisions, the efficiency of ammonia in the process ������������ NH3 + N2O → NH3 + N2O* is determined as 0.85.

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.

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.

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.

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