THE PHOTOLYSIS OF ACETONE IN THE LIQUID PHASE: THE GASEOUS PRODUCTS

1955 ◽  
Vol 33 (8) ◽  
pp. 1304-1315 ◽  
Author(s):  
R. Pieck ◽  
E. W. R. Steacie
Keyword(s):  
Liquid Phase ◽  
Gas Phase ◽  
High Temperatures ◽  
Low Temperatures ◽  
Excited Molecule ◽  
Quantum Yields ◽  
Cage Effect ◽  
Gaseous Products ◽  
Ethane Formation ◽  
Liquid Acetone

An investigation has been made of the photolysis of liquid acetone in the temperature range from 55° to −25 °C. The quantum yields of all products are small, and decrease strongly with decreasing temperature. It is concluded that the low yields can be explained both on the basis of the 'cage effect', and by the deactivation of an excited molecule. At high temperatures and intensities the gaseous products can be accounted for on the assumption that radicals have escaped from the 'cage' and react analogously to the gas-phase mechanism. At low temperatures ethane formation in the 'cage' may be of importance.

The photolysis of tetrahydrofuran and of some of its methyl derivatives at 185 nm

1980 ◽  
Vol 58 (24) ◽  
pp. 2819-2826 ◽  
Author(s):  
Nuray Klzilkilic ◽  
Heinz-Peter Schuchmann ◽  
Clemens von Sonntag
Keyword(s):  
Liquid Phase ◽  
Quantum Yield ◽  
Gas Phase ◽  
Carbonyl Compounds ◽  
Quantum Yields ◽  
Product Analysis ◽  
A Value ◽  
Steric Factors ◽  
Methyl Derivatives ◽  
Group 1

The uv photolysis of tetrahydrofuran, 1, 2-methyltetrahydrofuran, 2, cis-2,5-dimethyltetrahydrofuran, 3, trans-2,5-dimethyltetrahydrofuran, 4, and 2,2,5,5-tetramethyltetrahydrofuran, 5, has been investigated by product analysis in the liquid phase, and quantum yields have been determined. The photolysis of tetrahydrofuran itself was also studied in the gas phase at pressures ranging from 1 to 120 atm (pressurizing gas N2); and very little difference was found between the photolytic behaviour of the vapour at 120 atm and that of the liquid. The major products are in ail cases the cyclopropanes and the corresponding carbonyl compounds, as well as the olefinic alcohols and the carbonyl compounds that are isomeric with the starting material. These products are considered to be formed by the two major primary processes [i] and [ii].[Formula: see text]The cyclopropanes formed in reaction [i] retain some excess energy (apparently more than is needed to realize the trimethylene form), and in the photolysis of tetrahydrofuran vapour the hot cyclopropane rearranges to a considerable extent into propene. The propene to cyclopropane yield ratio falls strongly with increasing pressure, to a value of 0.065 at 120 atm. A similar value is observed in the liquid phase photolysis.The five-membered oxyl alkyl diradical from reaction [ii] is the likely intermediate in the cis-trans photoisomerization that is observable with the 2,5-dimethyltetrahydrofurans [Formula: see text]. The photolysis of these compounds also demonstrates that steric factors have a strong bearing on the course of the reaction, e.g. the quantum yield of methylcyclopropane from the cis compound is 0.22, vs. 0.08 from the trans compound.Molecular hydrogen is produced if the tetrahydrofurans carry hydrogen in α-position. Its production is enhanced if the α-position is shared with a methyl group (1 gives a hydrogen quantum yield of 0.07, 2 of 0.17, 3 of 0.27, 4 of 0.29, and 5 of zero).

Weight loss and gas evolution during sintering of silicon nitride powders synthesized by silica reduction and imide decomposition

1998 ◽  
Vol 13 (12) ◽  
pp. 3468-3472 ◽  
Author(s):  
Yasuhiro Goto ◽  
Yoshiyuki Ohnuma
Keyword(s):  
Weight Loss ◽  
Silicon Nitride ◽  
Liquid Phase ◽  
High Temperatures ◽  
Low Temperatures ◽  
Gas Evolution ◽  
Small Weight ◽  
Large Weight ◽  
Weight Losses ◽  
Silica Reduction

The relationships among weight loss, gas evolution, and other changes during sintering were investigated for silicon nitride powders synthesized by silica reduction and imide decomposition. Small weight losses were detected for all powders at low temperatures (below 1400 °C), and large weight losses were found to occur for the silica-reduction powders at high temperatures (1400–1800 °C). Only CO was detected in the sampled gases during sintering, and CO evolution peaks were seen at around 900–1200 (broad), 1400, and 1600 °C. The main deposited material around the samples was SiO. The weight losses at low temperatures were thought to be caused by evaporation of residual binder or adsorbed substances. The main causes of the large weight losses at high temperatures were thought to be CO and SiO evolutions, and CO evolution at around 1600 °C probably originated from the liquid phase accompanied by α–Si3N4 to β–Si3N4 transformation.

The Temperature Dependence of the Ratio kd/kc for Ethyl Radicals

1975 ◽  
Vol 53 (8) ◽  
pp. 1237-1244 ◽  
Author(s):  
D. G. Hooper ◽  
M. Simon ◽  
M. H. Back
Keyword(s):  
Liquid Phase ◽  
Transition State ◽  
Gas Phase ◽  
Rate Constants ◽  
Low Temperatures ◽  
Experimental Error ◽  
Hydrogen Atoms ◽  
Direct Photolysis ◽  
Temperature Range ◽  
Ethyl Radicals

The ratio of the rate constants for disproportionation and combination for ethyl radicals, kd/kc[Formula: see text]has been measured over the temperature range 298–173 K in the gas phase. Ethyl radicals were produced by direct photolysis of ethylene followed by addition of hydrogen atoms to ethylene. At low temperatures the only important reactions of the radicals were combination and disproportionation. The ratio kd/kc was obtained from measurements of the rates of formation of ethane, butane, and butene. No change in the ratio kd/kc was observed over the temperature range studied, leading to the conclusion that Ed − Ec = 0, within the experimental error. The significance of this result is discussed in relation to other measurements in both gas and liquid phase and to the nature of the transition state for this reaction.

Application of Disk Aerators to Recarbonation of Alkaline Wastewater from Wet Gasification of Carbide

1991 ◽  
Vol 24 (7) ◽  
pp. 277-284 ◽  
Author(s):  
E. Gomólka ◽  
B. Gomólka
Keyword(s):  
Carbon Dioxide ◽  
Liquid Phase ◽  
Gas Phase ◽  
Flue Gas ◽  
Carbonic Acid ◽  
Low Cost ◽  
Flue Gases ◽  
Carbon Dioxide Content ◽  
Patent Claim ◽  
Phase Dispersion

Whenever possible, neutralization of alkaline wastewater should involve low-cost acid. It is conventional to make use of carbonic acid produced via the reaction of carbon dioxide (contained in flue gases) with water according to the following equation: Carbon dioxide content in the flue gas stream varies from 10% to 15%. The flue gas stream may either be passed to the wastewater contained in the recarbonizers, or. enter the scrubbers (which are continually sprayed with wastewater) from the bottom in oountercurrent. The reactors, in which recarbonation occurs, have the ability to expand the contact surface between gaseous and liquid phase. This can be achieved by gas phase dispersion in the liquid phase (bubbling), by liquid phase dispersion in the gas phase (spraying), or by bubbling and spraying, and mixing. These concurrent operations are carried out during motion of the disk aerator (which is a patent claim). The authors describe the functioning of the disk aerator, the composition of the wastewater produced during wet gasification of carbide, the chemistry of recarbonation and decarbonation, and the concept of applying the disk aerator so as to make the wastewater fit for reuse (after suitable neutralization) as feeding water in acetylene generators.

Modeling of aerated upflow fixed bed reactors for nitrification

1999 ◽  
Vol 39 (4) ◽  
pp. 85-92 ◽  
Author(s):  
J. Behrendt
Keyword(s):  
Mathematical Model ◽  
Mass Transfer ◽  
Liquid Phase ◽  
Gas Phase ◽  
Fixed Bed ◽  
Fixed Bed Reactor ◽  
Bulk Liquid ◽  
Initial Value ◽  
Fixed Bed Reactors ◽  
Number Of Cells

A mathematical model for nitrification in an aerated fixed bed reactor has been developed. This model is based on material balances in the bulk liquid, gas phase and in the biofilm area. The fixed bed is divided into a number of cells according to the reduced remixing behaviour. A fixed bed cell consists of 4 compartments: the support, the gas phase, the bulk liquid phase and the stagnant volume containing the biofilm. In the stagnant volume the biological transmutation of the ammonia is located. The transport phenomena are modelled with mass transfer formulations so that the balances could be formulated as an initial value problem. The results of the simulation and experiments are compared.

Theoretical analysis of counter-current absorption of a poorly soluble gas based on the PDE-AD model

1986 ◽  
Vol 51 (6) ◽  
pp. 1222-1239 ◽  
Author(s):  
Pavel Moravec ◽  
Vladimír Staněk
Keyword(s):  
Experimental Data ◽  
Liquid Phase ◽  
Gas Phase ◽  
Transfer Functions ◽  
Packed Bed ◽  
Packed Bed Column ◽  
Interfacial Transport ◽  
Gaseous Component ◽  
Poorly Soluble ◽  
Counter Current

Expression have been derived in the paper for all four possible transfer functions between the inlet and the outlet gas and liquid steams under the counter-current absorption of a poorly soluble gas in a packed bed column. The transfer functions have been derived for the axially dispersed model with stagnant zone in the liquid phase and the axially dispersed model for the gas phase with interfacial transport of a gaseous component (PDE - AD). calculations with practical values of parameters suggest that only two of these transfer functions are applicable for experimental data evaluation.

Reesterification of ethyl acetate by propanol catalysed by glycidyl methacrylate copolymers containing sulphonic acid groups

1981 ◽  
Vol 46 (8) ◽  
pp. 1941-1946 ◽  
Author(s):  
Karel Setínek
Keyword(s):  
Liquid Phase ◽  
Ethyl Acetate ◽  
Kinetic Study ◽  
Gas Phase ◽  
Nonlinear Regression ◽  
Kinetic Data ◽  
Glycidyl Methacrylate ◽  
Kinetic Equations ◽  
Methacrylate Copolymers ◽  
Styrene Divinylbenzene

A series of differently crosslinked macroporous 2,3-epoxypropyl methacrylate-ethylenedimethacrylate copolymers with chemically bonded propylsulphonic acid groups were used as catalysts for the kinetic study of reesterification of ethyl acetate by n-propanol in the liquid phase at 52 °C and in the gas phase at 90 °C. Analysis of kinetic data by the method of nonlinear regression for a series of equations of the Langmuir-Hinshelwood type showed that kinetic equations which describe best the course of the reaction are the same as for the earlier studied sulphonated macroporous styrene-divinylbenzene copolymers. Compared types of catalysts differ, however, in the dependence of their activity on the degree of crosslinking of the copolymer used.

Low solubility of alumina in enstatite and uncertainties in estimated palaeogeotherms

1978 ◽  
Vol 288 (1355) ◽  
pp. 471-486 ◽  
Keyword(s):  
High Temperatures ◽  
Low Temperatures ◽  
Alumina Content ◽  
Equilibrium Solubility ◽  
Low Solubility

Spurious kinks in estimated palaeogeotherms may result from small errors in the calibration of the geothermometers and geobarometers. New data indicate that the equilibrium solubility of alumina in enstatite is even less than shown by recent studies, and that the slopes (d T /d P ) of the isopleths of equal alumina content are steeper than hitherto believed. Consequently, pressures of equilibration estimated from current formulations of the orthopyroxene-garnet geobarometer will be too high at high temperatures (> 1200 °C) and too low at low temperatures.

Sign in / Sign up

Export Citation Format

Share Document