PRESSURE-INDEPENDENT FLOW SYSTEM PYROLYSIS OF DIMETHYL MERCURY

1963 ◽  
Vol 41 (2) ◽  
pp. 224-227 ◽  
Author(s):  
M. Krech ◽  
S. J. Price
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Rate Constants ◽  
Flow System ◽  
Kcal Mole ◽  
Carrier System ◽  
Pressure Independent

The pyrolysis of HgMe2 has been investigated in a benzene carrier system using temperatures from 693 °K to 800 °K and pressures from 0.36 cm to 26.0 cm. High-pressure limiting rate constants were obtained above approximately 10 cm pressure. The high-pressure activation energy, E0, of 53.7 ± 0.5 kcal/mole is identified with D(MeHg—Me) within the limits D < E0 < D + RT.

PRESSURE-INDEPENDENT FLOW SYSTEM PYROLYSIS OF DIMETHYL CADMIUM

1965 ◽  
Vol 43 (7) ◽  
pp. 1929-1933 ◽  
Author(s):  
M. Krech ◽  
S. J. Price
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Rate Constants ◽  
Flow System ◽  
Kcal Mole ◽  
Pressure Independent

The pyrolysis of CdMe2 has been investigated in a benzene carried flow system using temperatures from 743 °K to 800 °K and pressures from 1.63 cm to 16.2 cm. High pressure limiting rate constants were obtained above approximately 8 cm pressures. The high pressure activation energy, E0, of 48.8 ± 1 kcal/mole is identified with D(MeCd—Me) within the limits D < E0 < D + RT.

THE PYROLYSIS OF TOLUENE

1962 ◽  
Vol 40 (7) ◽  
pp. 1310-1317 ◽  
Author(s):  
S. J. Price
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Rate Constants ◽  
Contact Time ◽  
Flow System ◽  
Kcal Mole ◽  
Homogeneous Process ◽  
First Order ◽  
Order Rate ◽  
Toluene Concentration

The pyrolysis of toluene has been studied in a flow system from 913 to 1143 °K. First-order rate constants are independent of the toluene concentration but decrease approximately 9% when the contact time is reduced from 1.0 to 0.41 second. Increasing the contact time from 1.0 second to 2.07 seconds does not affect the rate constant. The overall rate has been resolved into homogeneous and heterogeneous components. It is suggested that the activation energy of the homogeneous process, 85 kcal/mole, may be associated with D(C6H5CH2—H).

The pyrolysis of trimethylarsine

1970 ◽  
Vol 48 (20) ◽  
pp. 3209-3212 ◽  
Author(s):  
S. J. W. Price ◽  
J. P. Richard
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Rate Constants ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Methyl Radicals ◽  
Product Analysis ◽  
First Order ◽  
Carrier Flow ◽  
Pressure Limit

The pyrolysis of trimethylarsine has been studied in a toluene carrier flow system from 764 to 858 °K using total pressures from 6.35 to 35.5 mm. Contact times varied from 0.9 to 3.7 s and the amount of decomposition, from 1.2 to 73 %. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed. No heterogeneous reaction was detected and the first order rate constants appear to have been determined at approximately the high pressure limit. In seven runs the undecomposed alkyl was also measured. The quantity found was in agreement with the product analysis if three methyl radicals are released for each molecule undergoing reaction.Least squares analysis of the results gives[Formula: see text]The activation energy should be a good approximation to D[(CH3)2As—CH3]. The product analysis and the values of k4/k51/2 are consistent with the simple consecutive release of three methyl radicals but thermodynamic and kinetic considerations may preclude this possibility.

Vulcanization of Elastomers. 40. Vulcanization of Natural Rubber and Synthetic Rubber with Sulfur in Presence of Sulfenamides. III

1965 ◽  
Vol 38 (1) ◽  
pp. 189-203 ◽  
Author(s):  
W. Scheele ◽  
J. Helberg
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Natural Rubber ◽  
Rate Constants ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Synthetic Rubber ◽  
Chemical Constitution ◽  
Induction Times ◽  
Kinetics Of

Abstract Vulcanization of natural rubber with sulfur was studied in presence of six sulfenamides, to determine the effect of the chemical constitution of the sulfenamide on sulfur decrease and on crosslinking. The results can be condensed as follows: (1) The kinetics of sulfur disappearance is in every respect qualitatively independent of the chemical constitution of the sulfenamide. (2) For the sulfenamides investigated, the smallest and largest rate constants for sulfur decrease differed only by a factor of two. (3) Greater differences are encountered in the induction times for sulfur decrease and for crosslinking. The latter are notably longer than those for sulfur disappearance. (4) The same activation energy, 23 kcal/mole, is derived from the temperature dependence of the induction times for all the sulfenamides. (5) The dissociation of sulfenamides in solution and their reaction with mercaptobenzothiazole were investigated further. The results provide the basis for a proposed reaction mechanism, which is presented in detail and can account for a number of the features typical of sulfenamide-accelerated vulcanization. (6) The drop in sulfur concentration goes at practically the same rate, if one introduces, instead of N, N-dicyclohexyl-2-benzothiazolesulfenamide, the corresponding ammonium mercaptide in equimolar concentration.

The Vulcanization of Elastomers. XI. The Vulcanization of Natural Rubber with Sulfur in the Presence of Mercaptobenzothiazole. I

1957 ◽  
Vol 30 (3) ◽  
pp. 911-927 ◽  
Author(s):  
Otto Lorenz ◽  
Elisabeth Echte
Keyword(s):  
Activation Energy ◽  
Zinc Oxide ◽  
Natural Rubber ◽  
Kinetic Analysis ◽  
Rate Constants ◽  
Network Formation ◽  
Zinc Salt ◽  
Kcal Mole ◽  
Minimum Quantity ◽  
First Order

Abstract 1. The decrease of free sulfur occurs according to the first order law during the vulcanization of natural rubber accelerated by mercaptobenzothiazole in the presence of zinc oxide. The activating energy for this reaction amounts to 30.5 kcal./mole. 2. If zinc benzothiazolylmercaptide is used as an accelerator, one obtains the same rate constants for the sulfur decrease as in the presence of mercaptobenzothiazole. These seem to be equivalent as regards their effectiveness of acceleration. 3. A kinetic analysis of the reciprocal swelling, which represents a measure of network formation, indicates that the reaction is first order. Sulfur decrease and reciprocal swelling prove to be equal processes as regards rate. This is true where vulcanization is accelerated with mercaptobenzothiazole or with the zinc salt. 4. During vulcanization there occurs a decrease of accelerator concentration. This is dependent upon the temperature and is tied in with the combination sulfur with rubber. 5. If the quantity of the accelerator added is changed, the rate constants for sulfur decrease and for reciprocal swelling do not change, provided that a minimum quantity of accelerator is present. 6. In vulcanization accelerated with zinc benzothiazolylmercaptide, zinc oxide being absent, sulfur decrease again occurs according to the first order law but considerably faster, without thereby changing the activation energy. These investigations are being continued and the results will be discussed in detail in relation to other published contributions in this field.

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.

THE PYROLYSIS OF TRIMETHYLTHALLIUM

1965 ◽  
Vol 43 (7) ◽  
pp. 1961-1967 ◽  
Author(s):  
M. G. Jacko ◽  
S. J. W. Price
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Total Pressure ◽  
Flow System ◽  
Total Darkness ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Homogeneous Process ◽  
Carrier Flow ◽  
Reaction Proceeds

The pyrolysis of trimethylthallium has been studied in a toluene carrier flow system from 458 to 591 °K using total pressures from 5.6 to 33.0 mm. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed and, in 21 runs, by direct thallium analysis. All preparative and kinetic work was carried out in total darkness where possible. A shielded 10 W lamp was used when some illumination was necessary.The decomposition is approximately 80% heterogeneous in an unconditioned vessel and 14–27% heterogeneous in a vessel pretreated with hot 50% HF for 10 min. The reaction proceeds by the simple consecutive release of three methyl radicals. The rate constant depends only slightly on the total pressure in the system so that the activation energy of the homogeneous process, 27.4 kcal/mole, may be equated to D[(CH3)2Tl—CH3].

scholarly journals The Pyrolysis of Tetramethyltin

1972 ◽  
Vol 50 (1) ◽  
pp. 50-54 ◽  
Author(s):  
R. P. Johnson ◽  
S. J. W. Price
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Flow System ◽  
Heterogeneous Reaction ◽  
Methyl Radicals ◽  
Product Analysis ◽  
First Order ◽  
Carrier Flow ◽  
Pressure Limit

The pyrolysis of tetramethyltin has been studied in a toluene carrier flow system from 803–941 °K using total pressures of 10.6 to 52.4 mm. Contact times varied from 0.49 to 13.8 s and the amount of decomposition from 1.35–98.7%. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed. No appreciable heterogeneous reaction was detected and the first order rates constants appear to have been determined at the high pressure limit. The quantity of undecomposed alkyl was also measured and was found to be in agreement with the product analysis if four methyl radicals are released for each molecule undergoing reaction.Least squares analysis gives[Formula: see text]with an estimated uncertainty in E of ± 1 kcal mol−1. The activation energy should be a good approximation to D[(CH3)3Sn—CH3].

THE KINETICS OF THE REACTION OF ATOMIC HYDROGEN WITH METHANE

1964 ◽  
Vol 42 (7) ◽  
pp. 1638-1644 ◽  
Author(s):  
J. W. S. Jamieson ◽  
G. R. Brown
Keyword(s):  
Activation Energy ◽  
Electric Discharge ◽  
Atomic Hydrogen ◽  
Flow System ◽  
Steric Factor ◽  
Primary Reaction ◽  
Kcal Mole ◽  
Hydrogen Atoms ◽  
Fast Flow ◽  
Kinetics Of

Reinvestigation of the reaction of hydrogen atoms, produced by electric discharge, with methane in a fast flow system has given an activation energy of 7.4 ± 1.1 kcal/mole and a steric factor of about 10−3 for the primary reaction, H + CH4 → H2 + CH3.

Vulcanization of Elastomers. 21. Vulcanization of Natural Rubber with Thiuram Disulfides. VI

1959 ◽  
Vol 32 (2) ◽  
pp. 566-576
Author(s):  
Walter Scheele ◽  
Klaus Hummel
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Temperature Dependence ◽  
Sulfur Content ◽  
Rate Constants ◽  
Order Reaction ◽  
First Order Reaction ◽  
Kcal Mole ◽  
First Order ◽  
Limiting Value

Abstract Bound sulfur in a pure thiuram vulcanizate increases relatively rapidly at first at all temperatures, reaches a poorly defined maximum at about 27 to 30%, independent of temperature, and then recedes slightly to reach a limiting value of 25% also independent of temperature, based on the original thiuram disulfide. The rise in sulfur content at the start points to a temperature-independent limiting value of 33%. It is shown that the combination of sulfur in this region initially follows a first order reaction, and goes at the same rate as the reduction in concentration of thiuram disulfide. It can be seen from the above that sulfur may be combined in thiuram vulcanization without simultaneous crosslinking. The dithiocarbamate formation increases rapidly in the region of longer vulcanization times, after the maximum in bound sulfur has been reached, without further combination of sulfur with the vulcanizate. The rate constants for thiuram decrease, for dithiocarbamate increase and for sulfur combination were calculated. The temperature dependence of each of these reactions has practically the same activation energy, 23 kcal/mole. The bound sulfur content of the vulcanizates in pure thiuram vulcanizations is no criterion of the state of vulcanization.

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