Mechanism of the Direct Photochemical Decomposition of Thietane and its Derivatives in the Vapor Phase, in Solution, and in Glassy Matrices

1975 ◽  
Vol 53 (12) ◽  
pp. 1744-1755 ◽  
Author(s):  
David R. Dice ◽  
Ronald P. Steer
Keyword(s):  
Low Temperature ◽  
Gas Phase ◽  
Vapor Phase ◽  
Low Temperatures ◽  
Condensed Media ◽  
Photochemical Decomposition ◽  
Glassy Matrices

The direct photolyses of thietane, 3-ethyl-2-propylthietane, and 3-methylthietane in the vapor phase, in solution, and in glassy matrices at low temperatures have been examined. The effects of varying the photolysis wavelength, the temperature, the pressure and the phase of the substrate, and of adding inert thermalizers on the nature and yields of the various products have been measured. The results are interpreted in terms of initial C—S cleavage to give a 1,4-biradical which may, in the gas phase, decompose or ring close before complete equilibration of the various rotamers is achieved, or which may be thermalized in condensed media and trapped in glassy matrices at low temperature.

scholarly journals Low temperature gas phase reaction rate coefficient measurements: Toward modeling of stellar winds and the interstellar medium

2019 ◽  
Vol 15 (S350) ◽  
pp. 382-383
Author(s):  
Niclas A. West ◽  
Edward Rutter ◽  
Mark A. Blitz ◽  
Leen Decin ◽  
Dwayne E. Heard
Keyword(s):  
Low Temperature ◽  
Interstellar Medium ◽  
Gas Phase ◽  
Low Temperatures ◽  
Reaction Rate ◽  
Rate Coefficient ◽  
Building Blocks ◽  
Rate Coefficients ◽  
Stellar Winds ◽  
Phase Reaction

AbstractStellar winds of Asymptotic Giant Branch (AGB) stars are responsible for the production of ∼85% of the gas molecules in the interstellar medium (ISM), and yet very few of the gas phase rate coefficients under the relevant conditions (10 – 3000 K) needed to model the rate of production and loss of these molecules in stellar winds have been experimentally measured. If measured at all, the value of the rate coefficient has often only been obtained at room temperature, with extrapolation to lower and higher temperatures using the Arrhenius equation. However, non-Arrhenius behavior has been observed often in the few measured rate coefficients at low temperatures. In previous reactions studied, theoretical simulations of the formation of long-lived pre-reaction complexes and quantum mechanical tunneling through the barrier to reaction have been utilized to fit these non-Arrhenius behaviours of rate coefficients.Reaction rate coefficients that were predicted to produce the largest change in the production/loss of Complex Organic Molecules (COMs) in stellar winds at low temperatures were selected from a sensitivity analysis. Here we present measurements of rate coefficients using a pulsed Laval nozzle apparatus with the Pump Laser Photolysis - Laser Induced Fluorescence (PLP-LIF) technique. Gas flow temperatures between 30 – 134 K have been produced by the University of Leeds apparatus through the controlled expansion of N2 or Ar gas through Laval nozzles of a range of Mach numbers between 2.49 and 4.25.Reactions of interest include those of OH, CN, and CH with volatile organic species, in particular formaldehyde, a molecule which has been detected in the ISM. Kinetics measurements of these reactions at low temperatures will be presented using the decay of the radical reagent. Since formaldehyde and the formal radical (HCO) are potential building blocks of COMs in the interstellar medium, low temperature reaction rate coefficients for their production and loss can help to predict the formation pathways of COMs observed in the interstellar medium.

scholarly journals Low Temperature Experiments on Gas-Phase Chemical Processes

2000 ◽  
Vol 197 ◽  
pp. 237-250 ◽  
Author(s):  
B. R. Rowe ◽  
C. Rebrion Rowe ◽  
A. Canosa
Keyword(s):  
Low Temperature ◽  
Reaction Kinetics ◽  
Gas Phase ◽  
Low Temperatures ◽  
Chemical Processes ◽  
Experimental Results ◽  
Phase Chemical

A review of the most recent experimental results concerning reaction kinetics at low temperatures is presented, most of them having been obtained using the CRESU technique. Some astrochemical consequences are also highlighted.

THE PHOTOLYSIS OF KETENE AT LOW TEMPERATURES

1957 ◽  
Vol 35 (10) ◽  
pp. 1137-1138 ◽  
Author(s):  
W. G. Paterson ◽  
H. Gesser
Keyword(s):  
Carbon Monoxide ◽  
Quantum Yield ◽  
Low Temperature ◽  
Low Temperatures ◽  
Photochemical Decomposition

The photochemical decomposition of ketene at 2700 Å has been investigated at −78 °C. The quantum yield of carbon monoxide is two, indicating that the recombination of methylene radicals does not occur at this low temperature.

scholarly journals Associative detachment (AD) paths for H and CN− in the gas-phase: astrophysical implications

2018 ◽  
Vol 20 (8) ◽  
pp. 5490-5500 ◽  
Author(s):  
Stanka V. Jerosimić ◽  
Franco A. Gianturco ◽  
Roland Wester
Keyword(s):  
Low Temperature ◽  
Gas Phase ◽  
Low Temperatures

The associative detachment reaction between H and CN− at low temperature becomes possible only along a selected range of approaching directions, thus showing that there is a preferential possibility at low temperatures of forming HCN in comparison with forming CNH.

scholarly journals Synthesis of Carbon Showing Weak Antiferromagnetic Behavior at a Low Temperature

2019 ◽  
Vol 4 (1) ◽  
pp. 33 ◽  
Author(s):  
Masashi Otaki ◽  
Shota Hirokawa ◽  
Hiromasa Goto
Keyword(s):  
Low Temperature ◽  
Vapor Phase ◽  
Low Temperatures ◽  
Quantum Interference ◽  
Short Communication ◽  
Radical Cations ◽  
Superconducting Quantum Interference Device ◽  
Ullmann Reaction ◽  
Benzene Rings ◽  
Antiferromagnetic Behavior

In this short communication, we report a new carbon material prepared from meta-linked polyaniline that exhibits weak antiferromagnetic interactions at low temperature. The synthesis of poly(meta-aniline), abbreviated as m-PANI, was conducted using the Ullmann reaction with the aid of Cu+ as a catalyst in the presence of K2CO3. After the generation of radical cations by vapor-phase doping with iodine, carbonization was performed to prepare carbon polyaniline (C-PANI), which comprises condensed benzene rings. Analysis with a superconducting quantum interference device revealed that the resultant carbon exhibits antiferromagnetism at low temperatures. The discovery of this weak antiferromagnetic carbon may contribute to the development of carbon magnets.

scholarly journals Synthetic Approaches to Complex Organic Molecules in the Cold Interstellar Medium

2022 ◽  
Vol 8 ◽  
Author(s):  
Eric Herbst ◽  
Robin T. Garrod
Keyword(s):  
Low Temperature ◽  
Interstellar Medium ◽  
Gas Phase ◽  
Low Temperatures ◽  
Organic Molecules ◽  
High Energy ◽  
Interstellar Space ◽  
Interstellar Clouds ◽  
Millimeter And Submillimeter Waves ◽  
Complex Organic

The observation and synthesis of organic molecules in interstellar space is one of the most exciting and rapidly growing topics in astrochemistry. Spectroscopic observations especially with millimeter and submillimeter waves have resulted in the detection of more than 250 molecules in the interstellar clouds from which stars and planets are ultimately formed. In this review, we focus on the diverse suggestions made to explain the formation of Complex Organic Molecules (COMs) in the low-temperature interstellar medium. The dominant mechanisms at such low temperatures are still a matter of dispute, with both gas-phase and granular processes, occurring on and in ice mantles, thought to play a role. Granular mechanisms include both diffusive and nondiffusive processes. A granular explanation is strengthened by experiments at 10 K that indicate that the synthesis of large molecules on granular ice mantles under space-like conditions is exceedingly efficient, with and without external radiation. In addition, the bombardment of carbon-containing ice mantles in the laboratory by cosmic rays, which are mainly high-energy protons, can lead to organic species even at low temperatures. For processes on dust grains to be competitive at low temperatures, however, non-thermal desorption mechanisms must be invoked to explain why the organic molecules are detected in the gas phase. Although much remains to be learned, a better understanding of low-temperature organic syntheses in space will add both to our understanding of unusual chemical processes and the role of molecules in stellar evolution.

In situ Tensile Experiments at Low Temperatures on Niobium Single Crystals by H.V.E.M.

1975 ◽  
Vol 33 ◽  
pp. 58-59
Author(s):  
F. H. Louchet ◽  
L. P. Kubin
Keyword(s):  
Electron Microscope ◽  
Transition Temperature ◽  
Low Temperature ◽  
Slip System ◽  
Low Temperatures ◽  
Tensile Axis ◽  
Image Intensifier ◽  
Screw Dislocations ◽  
Source Operation

Experiments have been carried out on the 3 MeV electron microscope in Toulouse. The low temperature straining holder has been previously described Images given by an image intensifier are recorded on magnetic tape.The microtensile niobium samples are cut in a plane with the two operative slip directions [111] and lying in the foil plane. The tensile axis is near [011].Our results concern:- The transition temperature of niobium near 220 K: at this temperature and below an increasing difference appears between the mobilities of the screw and edge portions of dislocations loops. Source operation and interactions between screw dislocations of different slip system have been recorded.

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