THE THERMAL DECOMPOSITION OF ETHANE: PART III. SECONDARY REACTIONS

1966 ◽  
Vol 44 (20) ◽  
pp. 2369-2380 ◽  
Author(s):  
M. C. Lin ◽  
M. H. Back
Keyword(s):  
High Temperatures ◽  
Low Temperatures ◽  
High Pressures ◽  
Thermal Dissociation ◽  
First Order ◽  
Butyl Radical ◽  
Secondary Reactions ◽  
Low Pressures ◽  
Kinetics Of ◽  
Subsequent Decomposition

The kinetics of the secondary reactions producing methane, butane, and butene-1 in the pyrolysis of ethane have been investigated over the temperature range 550–726 °C and at pressures from 600–10 mm. The rate of secondary methane production was second order in ethylene at high pressures but was first order in ethylene at low pressures and high temperatures. In the latter region it is concluded that isomerization of the n-butyl radical to sec-butyl with subsequent decomposition to CH3 + C3H6 was the main source of methane. The rate of butane formation increased with time at low temperatures and decreased with time at high temperatures. It is shown that the decrease in rate was mainly due to the thermal dissociation of butane. The main source of butene-1 was probably decomposition of the n-butyl radical.

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 Theoretical Study of C2H5 + NCO Reaction: Mechanism and Kinetics

2018 ◽  
Vol 2018 ◽  
pp. 1-8 ◽  
Author(s):  
Nan-Nan Wu ◽  
Shun-li OuYang ◽  
Liang Li
Keyword(s):  
Low Temperatures ◽  
High Pressures ◽  
Theoretical Study ◽  
Single Point ◽  
Structure Information ◽  
Theoretical Investigations ◽  
Mechanism And Kinetics ◽  
Combustion Processes ◽  
Low Pressures ◽  
Kinetics Of

Theoretical investigations are performed on mechanism and kinetics of the reactions of ethyl radical C2H5 with NCO radical. The electronic structure information of the PES is obtained at the B3LYP/6-311++G(d,p) level of theory, and the single-point energies are refined by the CCSD(T)/6-311+G(3df,2p) level of theory. The rate constants for various product channels of the reaction in the temperature range of 200–2000 K are predicted by performing VTST and RRKM calculations. The calculated results show that both the N and O atoms of the NCO radical can attack the C atom of C2H5 via a barrierless addition mechanism to form two energy-rich intermediates IM1 C2H5NCO (89.1 kcal/mol) and IM2 C2H5OCN (64.7 kcal/mol) on the singlet PES. Then they both dissociate to produce bimolecular products P1 C2H4 + HOCN and P2 C2H4 + HNCO. At high temperatures or low pressures, the reaction channel leading to bimolecular product P2 is dominant and the channel leading to P1 is the secondary, while, at low temperatures and high pressures, the collisional stabilization of the intermediate plays an important role and as a result IM2 becomes the primary product. The present results will enrich our understanding of the chemistry of the NCO radical in combustion processes.

The kinetics of hydration of tricalcium silicate

1970 ◽  
Vol 48 (21) ◽  
pp. 3291-3299 ◽  
Author(s):  
K. G. McCurdy ◽  
B. P. Erno
Keyword(s):  
Reaction Mechanism ◽  
Intermediate Product ◽  
Activation Energies ◽  
Tricalcium Silicate ◽  
Rate Data ◽  
Large Excess ◽  
First Order ◽  
Kinetics Of ◽  
Subsequent Decomposition

An investigation has been made of the kinetics of hydration of tricalcium silicate at several temperatures in a large excess of water in the presence of various added ions. The rate data have been interpreted by a reaction mechanism which involves: (a) the first order hydration of tricalcium silicate to form an intermediate product, 1.5CaO•SiO2, which can react by two pathways, (b) the direct first order decomposition of intermediate, 1.5CaO•SiO2, to form lime and silica or (b′) complexing of intermediate with silica and subsequent decomposition to form lime and silica. This reaction mechanism predicts the rate of production of base during the hydration. The effect of various added ions is interpreted in terms of the proposed mechanism.Rate constants and activation energies for the various steps in the proposed mechanism are reported.

THE THERMAL DECOMPOSITION OF HYDROGEN PEROXIDE VAPOUR. II.

1947 ◽  
Vol 25b (2) ◽  
pp. 135-150 ◽  
Author(s):  
Paul A. Giguère
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Thermal Decomposition ◽  
Low Temperatures ◽  
Hydrocyanic Acid ◽  
Quartz Surface ◽  
First Order ◽  
Acid Washing ◽  
Reaction Vessels ◽  
Low Pressures

The decomposition of hydrogen peroxide vapour has been investigated at low pressures (5 to 6 mm.) in the temperature range 50° to 420 °C., for the purpose of determining the effect of the nature and treatment of the active surfaces. The reaction was followed in an all-glass apparatus and, except in one case, with one-litre round flasks as reaction vessels. Soft glass, Pyrex, quartz, and metallized surfaces variously treated were used. In most cases the decomposition was found to be mainly of the first order but the rates varied markedly from one vessel to another, even with vessels made of the same type of glass. On a quartz surface the decomposition was preceded by an induction period at low temperatures. Fusing the glass vessels slowed the reaction considerably and increased its apparent activation energy; this effect was destroyed by acid washing. Attempts to poison the surface with hydrocyanic acid gave no noticeable result. The marked importance of surface effects at all temperatures is considered as an indication that the reaction was predominantly heterogeneous under the prevailing conditions. Values ranging from 8 to 20 kcal. were found for the apparent energy of activation. It is concluded that the decomposition of hydrogen peroxide vapour is not very specific as far as the nature of the catalyst is concerned.

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: I. n-BUTANE

1938 ◽  
Vol 16b (5) ◽  
pp. 176-193 ◽  
Author(s):  
E. W. R. Steacie ◽  
I. E. Puddington
Keyword(s):  
Reaction Rate ◽  
High Pressures ◽  
The Other ◽  
First Order ◽  
Decomposition Reactions ◽  
Temperature And Pressure ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Good Agreement ◽  
Mechanism Of The Reaction

The kinetics of the thermal decomposition of n-butane has been investigated at pressures from 5 to 60 cm. and temperatures from 513 to 572 °C. The initial first order rate constants at high pressures are given by[Formula: see text]The results are in good agreement with the work of Frey and Hepp, but differ greatly from that of Paul and Marek. The reaction rate falls off strongly with diminishing pressure; this is rather surprising for a molecule as complex as butane. The first order constants in a given run fall rapidly as the reaction progresses. The last two facts suggest that chain processes may be involved.A large number of analyses of the products of reaction have been made at various pressures, temperatures, and stages of the reaction, the method being that of low-temperature fractional distillation. The products are virtually independent of temperature and pressure over the range investigated. The initial products, obtained by extrapolation to zero decomposition, are:—H2, 2.9; CH4, 33.9; C3H6, 33.9; C2H4, 15.2; C2H6, 14.1%. The mechanism of the reaction is discussed, and the results are compared with those of the other paraffin decompositions.

THE REACTION OF HYDROGEN AND DEUTERIUM ATOMS WITH PROPANE

1939 ◽  
Vol 17b (12) ◽  
pp. 371-384 ◽  
Author(s):  
E. W. R. Steacie ◽  
N. A. D. Parlee
Keyword(s):  
Activation Energy ◽  
High Temperatures ◽  
Low Temperatures ◽  
Hydrogen Atoms ◽  
Temperature Range ◽  
Secondary Reactions

The reaction of hydrogen atoms with propane has been investigated over the temperature range 30° to 250 °C. by the Wood-Bonhoeffer method. The products are solely methane at low temperatures, and methane, ethane, and ethylene at higher temperatures.It is concluded that the results can be explained only by the assumption that the reaction[Formula: see text]is of importance. The bearing of this on the Rice-Herzfeld mechanisms is discussed. The activation energy of the reaction is 10 ± 2 Kcal.The main steps in the postulated mechanism are:Primary Reaction[Formula: see text]Secondary Reactions at Low Temperatures[Formula: see text]Additional Secondary Reactions at High Temperatures[Formula: see text]The reaction of deuterium atoms with propane was also investigated. It was found that the methane and ethane produced were highly deuterized, while the propane was not appreciably exchanged.

scholarly journals The effect of thermal agitaion on atomic arrangement in alloys—II

1935 ◽  
Vol 151 (874) ◽  
pp. 540-566 ◽  
Keyword(s):  
High Temperatures ◽  
Experimental Work ◽  
Low Temperatures ◽  
Theoretical Treatment ◽  
X Ray ◽  
Atomic Arrangement ◽  
Metal Atoms ◽  
Theoretical Investigations ◽  
The Subject ◽  
Kinetics Of

The transformations between a disordered arrangement of the metal atoms in an alloy at high temperatures and an ordered arrangement of the atoms at low temperatures have formed the subject of many experimental and theoretical investigations. The process of segregation into regular positions was first envisaged by Tammann in 1919. It was proved to take place in the gold-copper and other alloy systems by Johannson and Linde by X-ray investigation. Theoretical treatments of the problem have been given in papers by Borelius, Johannson, and Linde, Gorsky, and Dehlinger and Graf, and the same authors have published a large amount of experimental work on this type of transformation in the Au-Cu system. Some experiments on order-disorder transformations in the Fe-Al system, carried out by Bradley and Jay in this laboratory, led us to examine the kinetics of the change, and we recently published a paper in these Proceedings dealing with various aspects of it. Since publishing this paper, we have become aware that our theoretical treatment has in several respects a closer parallelism to those of Borelius, Gorsky, and Dehlinger than we realized at the time of writing it. We shall try to make a proper acknowledgment in the present paper.

Studies on Metal Hydroxy Compounds. XIII. Thermal Analyses and Decomposition Kinetics of Hydroxystannates of Bivalent Metals

1971 ◽  
Vol 49 (17) ◽  
pp. 2813-2816 ◽  
Author(s):  
P. Ramamurthy ◽  
E. A. Secco
Keyword(s):  
Thermal Analyses ◽  
Decomposition Reaction ◽  
Decomposition Kinetics ◽  
Order Reaction ◽  
First Order ◽  
Calorimetric Measurements ◽  
Bivalent Metals ◽  
Hydroxy Compounds ◽  
Kinetics Of ◽  
Subsequent Decomposition

The thermal analyses of hexahydroxystannates of bivalent metals of the type Me[Sn(OH)6], where Me = Zn, Co, Cu, Ni, Mn, Ca, Mg, Cd, Sr, reveal that the primary mode of decomposition occurs by dehydroxylation and subsequent decomposition of the metastannate residue occurs in the Zn, Cu, Mn, Ca, and Mg compounds. Calorimetric measurements along with related enthalpic values for the decomposition reaction are given. The kinetics of thermal decomposition of all compounds studied, except the Cd and Mg analogues, follow first order reaction kinetics up to α ~ 0.9.

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