Kinetics and mechanisms of the thermal decomposition of ethane - II. The reaction inhibited by nitric oxide

1961 ◽  
Vol 260 (1300) ◽  
pp. 103-113 ◽  
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Induction Period ◽  
Volume Ratio ◽  
Frequency Factor ◽  
Inflexion Point ◽  
Kcal Mole ◽  
First Order ◽  
Pressure Time

The pressure-time curves for the decomposition of ethane when fully inhibited by nitric oxide have initially a point of inflexion. The initial rates are proportional to the first power of the pressure at higher pressures, and to the 3/2 power at lower pressures; the rates at the inflexion point are proportional to the pressure to a power which is slightly greater than unity. The acti­vation energy corresponding to the initial rates in the first-order region was found to be 77∙5 kcal/mole, and the frequency factor 3∙12 × 10 15 s -1 . The reaction was slightly inhibited by increasing the surface: volume ratio, and the induction period disappeared on addition of ethylene. The facts are shown to be consistent with a mechanism in which initiation occurs by the reaction NO + C 2 H 6 → C 2 H 5 + HNO, which is estimated to have an activation energy of 52 kcal. At the beginning of the reaction and at lower pressures termination is con­sidered to occur by H + HNO → H 2 + NO; as ethylene accumulates the ratio [C 2 H 5 ]/[H] increases and the termination step becomes C 2 H 5 + HNO → C 2 H 6 + NO. The mechanism is shown to account for the fact that propylene and other inhibitors give rise to the same limiting rate.

Kinetics and mechanisms of the thermal decomposition of propane II. The reaction inhibited by nitric oxide

1962 ◽  
Vol 270 (1341) ◽  
pp. 254-266 ◽  
Keyword(s):  
Nitric Oxide ◽  
Volume Ratio ◽  
Inflexion Point ◽  
Kcal Mole ◽  
Large Excess ◽  
First Order ◽  
Partial Pressures ◽  
Pressure Time ◽  
Initiation Reaction ◽  
Kinetics Of

The kinetics of the pyrolysis of propane inhibited by nitric oxide were investigated from 640 to 560 °C and at partial pressures of propane from 25 to 550 mm Hg. The pressure-time curves were found to be S-shaped, and the induction period was lengthened considerably as the propane pressure was lowered. Complete inhibition by nitric oxide was obtained with 10 to 12% nitric oxide. The initial rates were found to be proportional to the 3/2 power of the pressure over most of the temperature range, and to a slightly lower power at the highest temperatures. The orders of reaction corresponding to the inflexion point are close to unity at the highest temperatures, and increase steadily as the temperature is lowered. The activation energy calculated from the inflexion rates in the first-order region was 69.4 kcal/ mole. The rates decreased with an increase in the surface to volume ratio. The addition of a large excess of carbon dioxide had no effect on the fully inhibited rates. The results are shown to be consistent with a mechanism in which the initiation reaction involves the abstraction of a hydrogen atom from propane by nitric oxide, and in which the termination reaction is between HNO and a propyl radical.

FREE RADICALS BY MASS SPECTROMETRY: XXXV. THE HEAT OF FORMATION OF ALLYL RADICAL FROM BIALLYL PYROLYSIS

1966 ◽  
Vol 44 (18) ◽  
pp. 2211-2217 ◽  
Author(s):  
J. B. Homer ◽  
F. P. Lossing
Keyword(s):  
Mass Spectrometry ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Total Pressure ◽  
Heat Of Formation ◽  
Kcal Mole ◽  
Allyl Radical ◽  
First Order ◽  
Secondary Reactions ◽  
Gas Pressures

The thermal decomposition of biallyl has been investigated from 977 – 1 070 °K at helium carrier gas pressures of 10–50 Torr. Under these conditions the rate of central C—C bond fission to give two allyl radicals can be measured without interference from secondary reactions. The reaction at the pressures employed is first order with respect to biallyl, but between first and second order in the total pressure. The temperature dependence of the rate constants, extrapolated to infinite pressure, and corrected to 298 °K, gives an activation energy of 45.7 kcal/mole for the reaction, corresponding to ΔHf(allyl) = 33.0 kcal/mole.

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.

scholarly journals The dissociation energy of the C-N bond in benzylamine

1949 ◽  
Vol 198 (1053) ◽  
pp. 285-292 ◽  
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Dissociation Energy ◽  
Heat Of Formation ◽  
Molar Ratio ◽  
Kcal Mole ◽  
First Order ◽  
First Order Kinetics ◽  
Permanent Gases ◽  
Kinetics Of

The kinetics of the thermal decomposition of benzylamine were studied by a flow method using toluene as a carrier gas. The decomposition produced NH 3 and dibenzyl in a molar ratio of 1:1, and small quantities of permanent gases consisting mainly of H 2 . Over a temperature range of 150° (650 to 800° C) the process was found to be a homogeneous gas reaction, following first-order kinetics, the rate constant being expressed by k = 6 x 10 12 exp (59,000/ RT ) sec. -1 . It was concluded, therefore, that the mechanism of the decomposition could be represented by the following equations: C 6 H 5 . CH 2 . NH 2 → C 6 H 5 . CH 2 • + NH 2 •, C 6 H 5 . CH 3 + NH 2 •→ C 6 H 5 . CH 2 • + NH 3 , 2C 6 H 5 . CH 2 •→ dibenzyl, and the experimentally determined activation energy of 59 ± 4 kcal./mole is equal to the dissociation energy of the C-N bond in benzylamine. Using the available thermochemical data we calculated on this basis the heat of formation of the NH 2 radical as 35.5 kcal./mole, in a fair agreement with the result obtained by the study of the pyrolysis of hydrazine. A review of the reactions of the NH 2 radicals is given.

THE THERMAL DECOMPOSITION OF METHYL HYDROPEROXIDE

1965 ◽  
Vol 43 (8) ◽  
pp. 2236-2242 ◽  
Author(s):  
Alexander D. Kirk
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Gas Phase ◽  
Rate Constants ◽  
Dimethyl Phthalate ◽  
Kcal Mole ◽  
First Order ◽  
Methyl Hydroperoxide ◽  
Expected Values ◽  
Homogeneous Decomposition

The thermal decomposition of methyl hydroperoxide has been studied in solution and in the gas phase. The decomposition was found to be partly heterogeneous in solution in dimethyl phthalate and no reliable rate constants were obtained. Use of the toluene carrier method for the gas phase work enabled measurement of the rate constant for the homogeneous decomposition. The first order rate constants obtained range from 0.19 s−1 at 292 °C to 1.5 s−1 at 378 °C, leading to log A, 11± 2, and activation energy, 32 ± 5 kcal/mole. These results are compared with the expected values of log A, 13–14, and activation energy, 42 kcal/mole. The significance of these findings is discussed.

scholarly journals STUDIES ON THE PERVANADIUM COMPLEX

1961 ◽  
Vol 39 (6) ◽  
pp. 1174-1183 ◽  
Author(s):  
G. A. Dean
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Acid Solution ◽  
Anionic Complex ◽  
Cationic Complex ◽  
Kcal Mole ◽  
Decomposition Products ◽  
First Order ◽  
Discrete Variations ◽  
Kinetics Of

The 'pervanadium complex' is investigated in a general manner. The kinetics of its thermal decomposition in acid solution are shown to be first order with respect to pervanadium, the apparent activation energy is 26.5 ± 1.0 kcal/mole, and possible mechanisms are suggested. The effect of various acids upon the nature of the decomposition products is determined: almost quantitative yields of vanadium (V) or vanadium (IV) are obtained in very dilute or concentrated acid, respectively. Spectrophotometric studies indicate that in acid solution two separate complexes exist: a red (1:1) cationic complex and a yellow (1:2) anionic complex. The stoichiometry of the equilibrium between the two complexes in solutions of sulphuric acid is investigated by a method of 'discrete variations'. The equilibrium could be described by[Formula: see text]where Kr/y = 2.2 ± 0.2 at 22 °C. The anion is shown to play an important part in determining the nature of the pervanadium complex.

The kinetics of the thermal decomposition of branched-chain paraffin hydrocarbons - II. The isomeric hexanes

1952 ◽  
Vol 214 (1118) ◽  
pp. 339-343 ◽  
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Order Transition ◽  
First Order ◽  
Single Transition ◽  
Branched Chain ◽  
Kinetics Of ◽  
Constant Activation Energy ◽  
Methyl Pentane

In the study of the thermal decomposition of paraffins the contrast of iso -butane with n -butane and of the branched pentanes with normal pentane has led to the investigation of the isomeric hexanes. The nitric oxide-inhibited reaction of neo -hexane possesses a constant, activation energy at different initial pressures and shows a single transition from second to first order with increasing pressure. The reactions of 2:3-dimethyl-butane, 2-methyl-pentane and 3-methyl-pentane show a double-order transition and a rise in activation energy at lower initial pressures, as previously found for the higher normal paraffins.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

The slow oxidation of methane

1956 ◽  
Vol 235 (1201) ◽  
pp. 158-173 ◽  
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Induction Period ◽  
Hydrofluoric Acid ◽  
Pressure Rise ◽  
Pressure Change ◽  
Kcal Mole ◽  
Gaseous Products ◽  
Oxidation Of Methane ◽  
Reproducible Manner

Mixtures of methane and oxygen behave in a reproducible manner at temperatures of 440 to 520°C and initial pressures of 100 to 350 mm when reacting in Pyrex vessels freshly cleaned with hydrofluoric acid. The apparent order of the reaction ranged from 2∙3 to 2∙6 and the overall activation energy from 29 to 41 kcal/mole. Analyses of the products formed have been made, together with measurements of pressure change. Formaldehyde is formed from the commencement of the reaction including the induction period, but its concentra­tion reaches a maximum near the stage where the pressure rise is a maximum, and then falls off. Hydrogen peroxide is also formed, less rapidly in the earliest stage, but its rate of formation overtakes that of formaldehyde and it reaches an even higher concentration. No other peroxides were detected, nor was methanol found. Hydrogen was present in the gaseous products. These observations are not in full accord with some of the conclusions derived from earlier investigations.

APPLICATION OF CVD DIAMOND FILMS FOR UV THERMOLUMINESCENCE DOSIMETER

2002 ◽  
Vol 16 (06n07) ◽  
pp. 1003-1007 ◽  
Author(s):  
J. AHN ◽  
B. GAN ◽  
Q. ZHANG ◽  
S. F. YOON ◽  
V. LIGATCHEV ◽  
...  
Keyword(s):  
Activation Energy ◽  
Glow Curve ◽  
Diamond Films ◽  
Frequency Factor ◽  
Cvd Diamond ◽  
Order Kinetic ◽  
First Order ◽  
Order Kinetic Model ◽  
Ionizing Radiations ◽  
Trap Activation

This study presents the investigation of CVD diamond for the application of an UV TL dosimeter. A 9-μm-thick film used in this study presents a TL glow curve with a well-defined first-order kinetic peak (at about 273 K), which norm ally presents in the glow curve from ionizing radiations, is not observed. By fitting the glow curve to a first-order kinetic model, the trap activation energy E t = 0.95 eV and frequency factor s = 5.6 x 106 s -1 have been resolved.

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