A Study of the Reactions of Free Ethyl Radicals from the Thermal Decomposition of Tetraethyllead1

1933 ◽  
Vol 55 (3) ◽  
pp. 979-989 ◽  
Author(s):  
Richard N. Meinert
Keyword(s):  
Thermal Decomposition ◽  
Ethyl Radicals

THE POLYMERIZATION OF ETHYLENE SENSITIZED BY ETHYL IODIDE

1956 ◽  
Vol 34 (1) ◽  
pp. 41-53 ◽  
Author(s):  
V. B. Sefton ◽  
D. J. Le Roy
Keyword(s):  
Thermal Decomposition ◽  
Mercury Vapor ◽  
Chain Termination ◽  
Ethyl Iodide ◽  
Predominant Formation ◽  
Equilibrium Processes ◽  
Ethyl Radicals ◽  
Radical Disproportionation

The polymerization of ethylene sensitized by the thermal decomposition of ethyl iodide in the presence of mercury vapor has been studied at 250°, 275°, and 300 °C. C14-labelled ethyl iodide was used in a number of experiments. The increase in the rate of decomposition of ethyl iodide in the presence of ethylene and the formation of butyl iodide are accounted for by equilibrium processes of the type RI + Hg = R + HgI. The important features of the reaction were established from the identity, quantity, and activity of the various products. The predominant formation of olefins is attributed to the isomerization and decomposition of large radicals. Very little of the butane is formed by the combination of ethyl radicals. Radical disproportionation is the most important chain termination step.

Pyrolysis of triethylgallium by the toluene carrier technique

1979 ◽  
Vol 57 (24) ◽  
pp. 3178-3181 ◽  
Author(s):  
Michellene C. Paputa ◽  
Stanley James W. Price
Keyword(s):  
Thermal Decomposition ◽  
Pressure Range ◽  
Hydrogen Abstraction ◽  
Significant Extent ◽  
Rate Determining Step ◽  
Surface Catalysis ◽  
Gas System ◽  
One Step ◽  
Gallium Hydride ◽  
Ethyl Radicals

The pyrolysis of triethylgallium has been studied in a toluene carrier gas system in the temperature range of 464.7 to 700.7 K and a pressure range of 0.82 to 3.73 kPa. From the data obtained from this work, the following mechanism for the thermal decomposition of the metal alkyl is proposed:[Formula: see text]where [1] is the rate determining step. After runs below 606 K were corrected for the contribution of a concurrent residual reaction, a least-squares analysis of experimental results from 567 to 651 K based on both product and residual alkyl analysis gave[Formula: see text]at 1.60 kPa.The rate constant, k1, is very slightly pressure-dependent as revealed by tests at 648.0 K (80% and 45% decomposition). Studies indicate there is no detectable surface catalysis effect. Similarly, no effect was observed for changes in concentration or contact time.The mechanism for the formation of polymeric gallium hydride in reaction [4] is not clearly defined and may consist of more than one step. Reaction [5] is slow but based on the C2H4:H2 ratio must occur to a significant extent (40–80%) during a run. Further decomposition occurs between runs, causing a build-up of H2 in the reaction vessel.Experimental data for the hydrogen abstraction by ethyl radicals from toluene[Formula: see text]yield the equation[Formula: see text]

THE THERMAL DECOMPOSITION OF ETHANE: PART I. INITIATION AND TERMINATION STEPS

1966 ◽  
Vol 44 (4) ◽  
pp. 505-514 ◽  
Author(s):  
M C. Lin ◽  
M. H. Back
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Rate Coefficients ◽  
First Order ◽  
Temperature Range ◽  
Order Rate ◽  
Ethyl Radical ◽  
Initiation Reaction ◽  
Ethyl Radicals

The rates of production of methane and butane in the pyrolysis of ethane have been measured over the temperature range 550–620 °C and at pressures of 40–600 mm. At high pressure the rates of formation of both products were first order in ethane, but below 200 mm the first-order rate coefficients decreased. The ratio of methane to butane was consistent with the interpretation that methane is a measure of the initiation reaction and that the combination and disproportionation of ethyl radicals is the main termination step. The order of the decomposition of the ethyl radical with respect to ethane varied between 0.38 and 0.59. The results are discussed in terms of the mechanism of the overall process.

PHOTOLYSIS OF 2, 2′, 4, 4′-TETRADEUTERODIETHYL KETONE

1951 ◽  
Vol 29 (12) ◽  
pp. 1092-1103 ◽  
Author(s):  
M. H. J. Wijnen ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Diethyl Ketone ◽  
Temperature Range ◽  
A Value ◽  
Ethyl Radicals

The photolysis of CH3CD2COCD2CH3 has been studied over a temperature range from 25°C. to 365°C. The results confirm several features of the mechanism, previously proposed for the photolysis of diethyl ketone. It is concluded that disproportionation of ethyl radicals occurs by a "head to tail" mechanism. As activation energy for the reaction[Formula: see text]a value E4 = 8.7 kcal. was found. As activation energy for Reaction (5)[Formula: see text]a value of E5 = 11.7 kcal. was found. An activation energy of ∼ 17 kcal. is estimated for the thermal decomposition of the pentanonyl radical

Applications of Photoelectron Microscopy

1976 ◽  
Vol 34 ◽  
pp. 506-507
Author(s):  
William J. Baxter
Keyword(s):  
Electron Microscopy ◽  
Thermal Decomposition ◽  
Chemical Composition ◽  
Ultraviolet Radiation ◽  
Thin Layer ◽  
Edge Effects ◽  
Electron Optics ◽  
Surface Layers ◽  
Crystalline Orientation ◽  
Fluorescent Screen

In this form of electron microscopy, photoelectrons emitted from a metal by ultraviolet radiation are accelerated and imaged onto a fluorescent screen by conventional electron optics. image contrast is determined by spatial variations in the intensity of the photoemission. The dominant source of contrast is due to changes in the photoelectric work function, between surfaces of different crystalline orientation, or different chemical composition. Topographical variations produce a relatively weak contrast due to shadowing and edge effects.Since the photoelectrons originate from the surface layers (e.g. ∼5-10 nm for metals), photoelectron microscopy is surface sensitive. Thus to see the microstructure of a metal the thin layer (∼3 nm) of surface oxide must be removed, either by ion bombardment or by thermal decomposition in the vacuum of the microscope.

Preparation and characterisation of vanadium pentoxide supported rhodium catalyst

1988 ◽  
Vol 46 ◽  
pp. 946-947
Author(s):  
A. Legrouri
Keyword(s):  
Aqueous Solution ◽  
Thermal Decomposition ◽  
Physicochemical Properties ◽  
Surface Area ◽  
Vanadium Pentoxide ◽  
High Purity ◽  
Gas Adsorption ◽  
Rhodium Catalyst ◽  
Optical Methods ◽  
Reducible Oxides

The industrial importance of metal catalysts supported on reducible oxides has stimulated considerable interest during the last few years. This presentation reports on the study of the physicochemical properties of metallic rhodium supported on vanadium pentoxide (Rh/V2O5). Electron optical methods, in conjunction with other techniques, were used to characterise the catalyst before its use in the hydrogenolysis of butane; a reaction for which Rh metal is known to be among the most active catalysts.V2O5 powder was prepared by thermal decomposition of high purity ammonium metavanadate in air at 400 °C for 2 hours. Previous studies of the microstructure of this compound, by HREM, SEM and gas adsorption, showed it to be non— porous with a very low surface area of 6m2/g3. The metal loading of the catalyst used was lwt%Rh on V2Q5. It was prepared by wet impregnating the support with an aqueous solution of RhCI3.3H2O.

Observations of the Thermal Decomposition of Brucite

1968 ◽  
Vol 26 ◽  
pp. 446-447
Author(s):  
P. L. Burnett ◽  
W. R. Mitchell ◽  
C. L. Houck
Keyword(s):  
Thermal Decomposition ◽  
Magnesium Oxide ◽  
Basal Plane ◽  
Magnesium Ions ◽  
A Value ◽  
Reaction Proceeds

Natural Brucite (Mg(OH)2) decomposes on heating to form magnesium oxide (MgO) having its cubic ﹛110﹜ and ﹛111﹜ planes respectively parallel to the prism and basal planes of the hexagonal brucite lattice. Although the crystal-lographic relation between the parent brucite crystal and the resulting mag-nesium oxide crystallites is well known, the exact mechanism by which the reaction proceeds is still a matter of controversy. Goodman described the decomposition as an initial shrinkage in the brucite basal plane allowing magnesium ions to shift their original sites to the required magnesium oxide positions followed by a collapse of the planes along the original <0001> direction of the brucite crystal. He noted that the (110) diffraction spots of brucite immediately shifted to the positions required for the (220) reflections of magnesium oxide. Gordon observed separate diffraction spots for the (110) brucite and (220) magnesium oxide planes. The positions of the (110) and (100) brucite never changed but only diminished in intensity while the (220) planes of magnesium shifted from a value larger than the listed ASTM d spacing to the predicted value as the decomposition progressed.

A magnetic super lattice

1987 ◽  
Vol 45 ◽  
pp. 360-361 ◽  
Author(s):  
M.D. Bentzon ◽  
J. v. Wonterghem ◽  
A. Thölén
Keyword(s):  
Thermal Decomposition ◽  
Oleic Acid ◽  
Magnetic Fluid ◽  
Magnetic Particles ◽  
Carbon Film ◽  
Thick Layer ◽  
Amorphous Iron ◽  
Super Lattice ◽  
Carrier Liquid ◽  
Median Diameter

We report on the oxidation of a magnetic fluid. The oxidation results in magnetic super lattice crystals. The “atoms” are hematite (α-Fe2O3) particles with a diameter ø = 6.9 nm and they are covered with a 1-2 nm thick layer of surfactant molecules.Magnetic fluids are homogeneous suspensions of small magnetic particles in a carrier liquid. To prevent agglomeration, the particles are coated with surfactant molecules. The magnetic fluid studied in this work was produced by thermal decomposition of Fe(CO)5 in Declin (carrier liquid) in the presence of oleic acid (surfactant). The magnetic particles consist of an amorphous iron-carbon alloy. For TEM investigation a droplet of the fluid was added to benzine and a carbon film on a copper net was immersed. When exposed to air the sample starts burning. The oxidation and electron irradiation transform the magnetic particles into hematite (α-Fe2O3) particles with a median diameter ø = 6.9 nm.

Supersonic jet spectrometry of chemical species resulting from thermal decomposition of polystyrene and polycarbonate

1992 ◽  
Vol 64 (19) ◽  
pp. 931A-940A ◽  
Author(s):  
Totaro Imasaka ◽  
Masami Hozumi ◽  
Nobuhiko Ishibashi
Keyword(s):  
Thermal Decomposition ◽  
Supersonic Jet ◽  
Chemical Species
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