THE THERMAL DECOMPOSITION OF PERACETIC ACID IN THE VAPOR PHASE

1963 ◽  
Vol 41 (7) ◽  
pp. 1819-1825 ◽  
Author(s):  
C. Schmidt ◽  
A. H. Sehon
Keyword(s):  
Thermal Decomposition ◽  
Vapor Phase ◽  
Dissociation Energy ◽  
Peracetic Acid ◽  
Kcal Mole ◽  
Temperature Range ◽  
Primary Reactions

The thermal decomposition of peracetic acid in a stream of toluene was studied over the temperature range 127–360 °C. The main products of the reaction were CO2, CH3COOH, C2H6, CH4, HCHO, O2, and traces of CO. Dibenzyl was also formed.The overall decomposition of peracetic acid was partly heterogeneous and was represented by the two parallel primary reactions[Formula: see text] [Formula: see text]The dissociation energy of the O—O bond in peracetic acid was estimated to be 30–34 kcal/mole.

THE THERMAL DECOMPOSITION OF PERACETIC ACID IN AROMATIC SOLVENTS

1963 ◽  
Vol 41 (7) ◽  
pp. 1826-1831 ◽  
Author(s):  
F. W. Evans ◽  
A. H. Sehon
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Peracetic Acid ◽  
First Order ◽  
Aromatic Solvents ◽  
Temperature Range ◽  
Polymeric Compounds

The thermal decomposition of peracetic acid in toluene, benzene, and p-xylene was studied over the temperature range 75–95°C. The main products of decomposition were found to be CH4, CO2, CH3COOH; small amounts of methanol, phenols, and polymeric compounds were also detected.The rate of the overall decomposition was first order with respect to peracetic acid, and the results could be explained by postulating the participation of the two simultaneous reactions:[Formula: see text] [Formula: see text]The rate constant of reaction (1) was independent of the solvent, whereas k2 was dependent on the solvent. The ratio k2/k1 was about 10.

The thermal decomposition of RDX at temperatures below the melting point. II. Activation energy

1970 ◽  
Vol 23 (4) ◽  
pp. 749 ◽  
Author(s):  
JJ Batten ◽  
DC Murdie
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Melting Point ◽  
Kinetic Parameter ◽  
Arrhenius Equation ◽  
Kcal Mole ◽  
Decomposition Products ◽  
Sample Geometry ◽  
Temperature Range ◽  
Definition Of

The activation energy has been determined in the temperature range 170-198�. If the sample was spread the activation energy was independent of the definition of the kinetic parameter substituted in the Arrhenius equation and was 63 kcal mole-1. In the case of the unspread samples the activation energies of the induction, acceleration, and maximum rates were 49, 43, and 62 kcal mole-1 respectively. The effect that sample geometry has on the activation energy is attributed to gaseous decomposition products influencing the reaction.

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 reaction of methanol vapour with silver(I) oxide

1964 ◽  
Vol 17 (5) ◽  
pp. 529
Author(s):  
JA Allen
Keyword(s):  
Carbon Dioxide ◽  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Gas Phase ◽  
Kinetic Data ◽  
Kcal Mole ◽  
Collision Model ◽  
Temperature Range ◽  
Methanol Vapour ◽  
The Mean

The reaction of methanol with silver(I) oxide has been studied in the temperature range 56.5-78.4�. For complete reduction of the oxide at 78.4�, the available oxygen is fully accounted for by the products, formaldehyde, formic acid, carbon monoxide, carbon dioxide, and water. In the temperature range 56.5-70.2� the net measured rates of formation of these products are expressed by equations of the form, ������������������ rate = Aexp(-E/RT), and the kinetic data are interpreted as the consecutive formation of the products on the surface without complete desorption to the gas phase between each step. For the dominant product, carbon dioxide, at the mean temperature the values of A and E are 1028.5 μg oxygen per minute and 41.3 kcal mole-1 respectively. The former is interpreted in terms of a simple collision model and the latter compared with values obtained for the thermal decomposition of the oxide.

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Diazo Compounds ◽  
First Order ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Consecutive Reactions ◽  
Rate Processes ◽  
Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

The dissolution of beryllia in molten alkali metal hydroxides

1965 ◽  
Vol 18 (11) ◽  
pp. 1719 ◽  
Author(s):  
ME Shying ◽  
RB Temple
Keyword(s):  
Alkali Metal ◽  
Water Vapour ◽  
Beryllium Oxide ◽  
Major Product ◽  
Kcal Mole ◽  
Metal Hydroxides ◽  
Temperature Range ◽  
Alkali Metal Hydroxides ◽  
Reversible Formation

Beryllium oxide shows a limited reversible solubility in molten alkali-metal hydroxides only when dissolved water vapour is present. The reaction taking place has been studied in detail. The results obtained are consistent with the reversible formation of the beryllate ion [Be(OH)4]2- as the major product, according to the overall equation BeO(solid) + H2O(dissolved) + 2OH- ↔ [Be(OH)4]2-(dissolved) The enthalpy of the reaction has been calculated to be 4.8 kcal/mole over the temperature range 240-510�.

The C—Br bond dissociation energy in halogenated bromomethanes

1951 ◽  
Vol 209 (1096) ◽  
pp. 110-131 ◽  
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Methyl Bromide ◽  
Frequency Factor ◽  
Unimolecular Dissociation ◽  
Bond Dissociation Energies ◽  
Kcal Mole ◽  
Fast Reaction ◽  
Bond Dissociation ◽  
Dissociation Energies

The pyrolyses of methyl bromide and of the halogenated bromomethanes, CH 2 CI. Br, CH 2 Br 2 , CHCl 2 .Br, CHBr 3 , CF 3 Br, CCI 3 . Br and CBr 4 , have been investigated by the ‘toluene-carrier' technique. It has been shown that all these decompositions were initiated by the unimolecular process R Br → R + Br. (1) Since all these decompositions were carried out in the presence of an excess of toluene, the bromine atoms produced in process (1) were readily removed by the fast reaction C 6 H 5 .CH 3 + Br → C 6 H 5 . CH 2 • + HBr. Hence, the rate of the unimolecular process (1) has been measured by the rate of formation of HBr. The C—Br bond dissociation energies were assumed to be equal to the activation energies of the relevant unimolecular dissociation processes. These were calculated by using the expression k ═ 2 x 10 13 exp (- D/RT ). The reason for choosing this particular value of 2 x 10 13 sec. -1 for the frequency factor of these reactions is discussed. The values obtained for the C—Br bond dissociation energies in the investigated bromomethanes are: D (C—Br) D (C—Br) compound (kcal./mole) compound (kcal./mole) CH 3 Br (67.5) CHBr 3 55.5 CH 2 CIBr 61.0 CF 3 Br 64.5 CH 2 Br 2 62.5 CCI 3 Br 49.0 CHCl 2 Br 53.5 CBr 4 49.0 The possible factors responsible for the variation of the C—Br bond dissociation energy in these compounds have been pointed out.

The Kinetics of the Palladium-Catalyzed Vapor-Phase Thermal Decomposition of Ethanol

2001 ◽  
Vol 40 (1) ◽  
pp. 101-107 ◽  
Author(s):  
J. Michael Davidson ◽  
Caroline M. McGregor (née Shirrida ◽  
L. K. Doraiswamy
Keyword(s):  
Thermal Decomposition ◽  
Vapor Phase ◽  
Palladium Catalyzed ◽  
Kinetics Of
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