Photolyse de pentène-1 dans l'ultraviolet à vide

1973 ◽  
Vol 51 (5) ◽  
pp. 724-731 ◽  
Author(s):  
Patrick M. Perrin ◽  
Guy J. Collin
Keyword(s):  
Double Bond ◽  
Low Pressure ◽  
Hydrogen Atoms ◽  
Ethyl Radical ◽  
Excited Molecules

Photolysis of 1-pentene molecules at 8.4 eV (xenon photolysis) and 10.0 eV (krypton photolysis) was studied. Excited molecules decompose to produce mainly ethylene, propadiene, 1,3-butadiene, acetylene, and other minor products. Hydrogen atoms add to the double bond of the monomer and the resulting excited pentyl radical decomposes at low pressure (P < 1 Torr) into propene and ethyl radical. Isomerization of excited 1-pentene molecules is unimportant at these energies.

Photolyse du butène-1 dans l'ultraviolet à vide

1973 ◽  
Vol 51 (17) ◽  
pp. 2853-2859 ◽  
Author(s):  
Guy J. Collin
Keyword(s):  
Double Bond ◽  
Hydrogen Atom ◽  
Kinetic Energy ◽  
Thermal Energy ◽  
Hydrogen Atoms ◽  
Excited Molecules

The vacuum u.v. photolysis of 1 -butene was studied in the 147–105 nm region. The main products formed from the fragmentation of excited molecules are allene, 1,3-and 1,2-butadienes, ethylene, and acetylene. The addition of a hydrogen atom to the double bond produces mainly secondary butyl radicals (91%) at 147 nm. At 123.6 nm, this proportion becomes 82%. Thus at shorter wavelengths (10 and 11.6–11.8 eV), hydrogen atoms are produced with a kinetic energy higher than the thermal energy.

Photolyse du méthyl-2-butène-1, du méthyl-3-butène-1 et du cis-pentène-2 à 174, 163 et 147 nm

1979 ◽  
Vol 57 (8) ◽  
pp. 863-869 ◽  
Author(s):  
Guy J. Collin ◽  
Hélène Deslauriers ◽  
Sylvain Auclair
Keyword(s):  
Double Bond ◽  
Photon Energy ◽  
Rate Constant ◽  
Pressure Effect ◽  
Low Pressure ◽  
Decomposition Process ◽  
Fragmentation Process ◽  
Quantum Yields ◽  
Methyl Radicals ◽  
Hydrogen Atoms

Photolysis of 2-methyl-1-butene (M2B1), cis-2-pentene (CP2), and 3-methyl-1-butene (M3B1) has been systematically studied at 163 nm. Pressure effect has been measured at 147, 163, and 174 nm. The main fragmentation process of the photoexcited olefine is the C—C split of the bond located in position β relative to the double bond:[Formula: see text] α-Methallyl radicals obtained in the M3B1 and CP2 photolysis decompose partly at low pressure, giving rise to the formation of 1,3-butadiene and hydrogen atoms. β-Methallyl radicals decompose also at low pressure into allene and methyl radicals. Butadiene and allene quantum yields follow the Stern–Volmer law, and this allows us to determine the ratio of the rate constant of dissociation relative to the rate constant of stabilization, kd/ks, through collision of the α- and β-methallyl radicals. From these values, we conclude that the excess of photon energy is not statistically distributed into the fragments, and that the decomposition process follows one (or several) particular law(s).

Photodissociation of H2 near Threshold Energies

1970 ◽  
Vol 25 (2) ◽  
pp. 237-242 ◽  
Author(s):  
F. J. Comes ◽  
U. Wenning
Keyword(s):  
Electric Field ◽  
Cross Section ◽  
Configuration Interaction ◽  
Atomic Hydrogen ◽  
Molecular Hydrogen ◽  
Hydrogen Atoms ◽  
Dissociation Cross Section ◽  
Excited Molecules ◽  
Threshold Energies ◽  
Near Threshold

Abstract Measurements of the atomic hydrogen fluorescence (Lyα) yield important information on the dissociation behavior of molecular hydrogen under photon impact. Under certain assumptions the dissociation cross section of the molecule can be deduced from such experiments. By applying an appropriate electric field in the observation region those dissociations leading to the formation of metastable hydrogen atoms can be quantitatively determined. This information opens the possibility to describe the predissociation of the excited H2-molecules in the C-, D-and B″-states. The experiments show that the excited molecules in these particular states dissociate into H(1S) and H(2S) by configuration interaction with the B′-state.

The reaction of hydrogen atoms with ethylene

1970 ◽  
Vol 316 (1527) ◽  
pp. 575-591 ◽  
Keyword(s):  
Hydrogen Atom ◽  
Rate Constant ◽  
Recombination Reaction ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Ethyl Radical ◽  
Cracking Reaction ◽  
Computer Calculations ◽  
First Time

A detailed study has been made of the products from the reaction between hydrogen atoms and ethylene in a discharge-flow system at 290 ± 3 K. Total pressures in the range 8 to 16 Torr (1100 to 2200 Nm -2 ) of argon were used and the hydrogen atom and ethylene flow rates were in the ranges 5 to 10 and 0 to 20 μ mol s -1 , respectively. In agreement with previous work, the main products are methane and ethane ( ~ 95%) together with small amounts of propane and n -butane, measurements of which are reported for the first time. A detailed mechanism leading to formation of all the products is proposed. It is shown that the predominant source of ethane is the recombination of two methyl radicals, the rate of recombination of a hydrogen atom with an ethyl radical being negligible in comparison with the alternative, cracking reaction which produces two methyl radicals. A set of rate constants for the elementary steps in this mechanism has been derived with the aid of computer calculations, which gives an excellent fit with the experimental results. In this set, the values of the rate constant for the addition of a hydrogen atom to ethylene are at the low end of the range of previously measured values but are shown to lead to a more reasonable value for the rate constant of the cracking reaction of a hydrogen atom with an ethyl radical. It is shown that the recombination reaction of a hydrogen atom with a methyl radical, the source of methane, is close to its third-order region.

Reactions of vibrationally excited molecules. I. The reaction of methylene with iso butene

1959 ◽  
Vol 250 (1262) ◽  
pp. 409-421 ◽  
Keyword(s):  
Double Bond ◽  
Kinetic Energy ◽  
Hydrogen Bonds ◽  
Excess Energy ◽  
Vibrationally Excited ◽  
Carbon Double Bond ◽  
Sufficient Energy ◽  
Carbon Hydrogen Bonds ◽  
Excited Molecules

The photolysis of diazomethane in the presence of iso butene has been investigated. The results obtained are explained on the basis that the methylene initially produced may be vibrationally excited, to an extent which depends on the wavelength of the radiation employed in the photolysis, and may also contain considerable kinetic energy. The methylene resets before this excess energy is lost, attacking the carbon hydrogen bonds and carbon carbon double bond in iso butene. The latter attack yields 1.1 -dimethyl cyclo Zopropane which contains sufficient energy to isomerize, and does so, unless stabilized by collision. The results obtained are compared with those published for the photolysis of keten in the presence of iso butene.

scholarly journals Quinine dihydrochloride hemihydrate

IUCrData ◽  
2021 ◽  
Vol 6 (4) ◽  
Author(s):  
Grace I. Anderson ◽  
Sophia Bellia ◽  
Matthias Zeller ◽  
Patrick C. Hillesheim ◽  
Arsalan Mirjafari
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Double Bond ◽  
Long Range ◽  
Title Compound ◽  
Asymmetric Unit ◽  
Hydrogen Atoms ◽  
Non Covalent Interactions ◽  
Long Range Ordering ◽  
Covalent Interactions

Numerous non-covalent interactions link together discrete molecules in the crystal structure of the title compound, 2C20H26N2O2 2+·4Cl−·H2O {systematic name: 4-[(5-ethenyl-1-azoniabicyclo[2.2.2]octan-2-yl)(hydroxy)methyl]-6-methoxyquinolin-1-ium dichloride hemihydrate}. A combination of hydrogen bonding between acidic H atoms and the anions in the asymmetric unit forms a portion of the observed hydrogen-bonded network. π–π interactions between the aromatic portions of the cation appear to play a role in the formation of the long-range ordering. One ethylene double bond was found to be disordered. The disorder extends to the neighboring carbon and hydrogen atoms.

Site of H Atom Attack on Uracil and Its Derivatives in Aqueous Solution

1985 ◽  
Vol 40 (3-4) ◽  
pp. 292-294 ◽  
Author(s):  
Suresh Das ◽  
David J. Deeble ◽  
Clemens von Sonntag
Keyword(s):  
Aqueous Solution ◽  
Double Bond ◽  
Pulse Radiolysis ◽  
Hydrogen Abstraction ◽  
Methyl Groups ◽  
Oh Radicals ◽  
Hydrogen Atoms ◽  
Sugar Moiety ◽  
Reducing Properties

Hydrogen atoms from the radiolysis of water at pH 1.6 add to the 5,6-double bond of pyrimidines. The preferen­tial site of attack is the C(5) position (values in brackets) in the case of 6-methyluracil (87%), 1,3-dimethyluracil (71%), uracil (69%) and poly(U) (60%). This reaction yields a radical of reducing properties which can be monitored by its reaction with tetranitromethane in a pulse radiolysis experiment. In thymine (37%), thymidine (32%) and 1,3-dimethylthymine (25%) H-addition no longer pre­ferentially occurs at C(5), but addition is now mainly at C(6). Hydrogen abstraction from the methyl groups or the sugar moiety is negligible (≦ 5.5%). A comparison is made with literature values for the equivalent reactions of OH radicals.

scholarly journals How Hydrogen Admixture Changes Plasma Jet Characteristics in Spray Processes at Low Pressure

2020 ◽  
Author(s):  
Georg Mauer
Keyword(s):  
Thermal Conductivity ◽  
Plasma Jet ◽  
Low Pressure ◽  
Atmospheric Conditions ◽  
Hydrogen Atoms ◽  
Electron Densities ◽  
Radial Temperature ◽  
Jet Characteristics ◽  
Plasma Enthalpy ◽  
Plasma Jet Characteristics

AbstractIn plasma spraying, hydrogen is widely used as a secondary working gas besides argon. In particular under low pressure, there are strong effects on the plasma jet characteristics even by small hydrogen percentages. Under such conditions, fundamental mechanisms like diffusion and recombination are affected while this is less relevant under atmospheric conditions. This was investigated for argon–hydrogen mixtures by optical emission spectroscopy (OES). The small electron densities under the investigated low pressure conditions implied specific difficulties in the application of several OES-based methods which are discussed in detail. Adding hydrogen to the plasma gas effected an increased plasma enthalpy. Moreover, the jet expanded radially as the reactive part of the thermal conductivity was enhanced by recombination of atomic hydrogen so that the shock waves were less reflected at the cold jet rims. In the jet cores, the lowest temperatures were found for the highest hydrogen admixture because the energy consumption due to the dissociation of molecular hydrogen outbalanced the increase of the plasma enthalpy. Variations in the radial temperature profiles were related to the jet structure and radial thermal conductivity. The local hydrogen–argon concentration ratios revealed an accumulation of hydrogen atoms at the jet rims. Clear indications were found, that higher hydrogen contents promoted the fast recombination of electrons and ions. However, it is assumed that the transport properties of the plasma were hardly affected by this, since the electron densities and thus the ionization degrees were generally small due to the low pressure conditions.

Numerical Simulation of a Multi-Component Reacting Flow in a Supersonic DC Torch Nozzle

1996 ◽  
Author(s):  
C. George ◽  
E. Pfender ◽  
H.-D. Steffens
Keyword(s):  
Numerical Simulation ◽  
Time Scales ◽  
Fluid Dynamic ◽  
Low Pressure ◽  
Reacting Flow ◽  
Exchange Reactions ◽  
Hydrogen Atoms ◽  
Species Transport ◽  
Pressure Plasma ◽  
Low Pressure Plasma

Abstract Maximizing dissociated species transport in plasma assisted chemical vapor deposition (CVD), is important in many low pressure plasma jet processes. To deposit high quality diamond by low pressure plasma assisted CVD, it is important to maximize the atomic hydrogen transport to the substrate. One route to process improvement is to explore ways in which unstable species transport can be maximized. A two-dimensional computational model of a supersonic contoured nozzle attached to a dc torch will be described for examining the chemical non-equilibrium of the flow. If the fluid dynamic time scales of interest are faster than the kinetic time scales of interest, it is believed that unstable precursor transport can be controlled, improved and optimized. This paper will examine an implicit formulation for the numerical simulation of a multi-component reacting Ar-H2 plasma. It is found that dissociation, ionization and charge exchange reactions must all be included in a reaction model. The ionic species significantly alter the temperature profiles upstream of nozzle choking. However, to increase the number of hydrogen atoms at the nozzle exit, the arc attachment should be positioned as close as possible to the converging-diverging nozzle throat.

The kinetics of the interaction of atomic hydrogen with olefines. V. Results obtained for a further series of compounds

1950 ◽  
Vol 202 (1069) ◽  
pp. 181-202 ◽  
Keyword(s):  
Double Bond ◽  
Hydrogen Atom ◽  
Atomic Hydrogen ◽  
Methyl Radicals ◽  
Hydrogen Atoms ◽  
Alkyl Radicals ◽  
Kinetics Of ◽  
Interesting Generalization

In this paper the efficiency of interaction of a hydrogen atom with a series of olefines has been determined, the olefines being members of the series obtained by progressively replacing the hydrogen atoms of ethylene by methyl radicals. The interesting generalization which emerges from this is that the efficiency of interaction does not vary very much with the nature of the alkyl substituents in the molecule, and calculations involving the heats of addition of a hydrogen atom to a double bond confirm this generalization. The data presented here are discussed critically in relation to information available on the reaction of CCl 3 radicals with olefines and of alkyl radicals with olefines, complete general agreement being demonstrated.

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