THE EFFECT OF MOLECULAR OXYGEN ON THE REACTION OF OXYGEN ATOMS WITH cis-2-PENTENE

1959 ◽  
Vol 37 (5) ◽  
pp. 953-965 ◽  
Author(s):  
S. Sato ◽  
R. J. Cvetanović
Keyword(s):  
Nitric Oxide ◽  
Nitrous Oxide ◽  
Nitrogen Dioxide ◽  
Molecular Oxygen ◽  
Reaction Mechanisms ◽  
Room Temperature ◽  
Pressure Independent ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

The effect of the presence of nitrogen, oxygen, and nitric oxide on the reaction between cis-2-pentene and oxygen atoms has been investigated at room temperature (25 ± 2 °C). For production of oxygen atoms use was made of mercury-photosensitized decomposition of nitrous oxide and of the photolysis of nitrogen dioxide at 3660 Å.In the N2O work, the presence of molecular oxygen induced the formation of acetaldehyde, propanal, methanol, and ethanol. In the NO2 work, the amounts of acetaldehyde, propanal, and ethyl nitrate formed increased rapidly with increasing pressure of molecular oxygen. Possible reaction mechanisms for the formation of these compounds are discussed.Additional information was obtained on the pressure-independent fragmentation in the reaction of oxygen atoms with cis-2-pentene.

Temperature dependence of rate constants for the reactions of oxygen atoms, O(3P), with HBr and HI

1978 ◽  
Vol 56 (23) ◽  
pp. 2934-2939 ◽  
Author(s):  
D. L. Singleton ◽  
R. J. Cvetanović
Keyword(s):  
Nitric Oxide ◽  
Nitrous Oxide ◽  
Standard Deviation ◽  
Phase Shift ◽  
Rate Constants ◽  
Bond Energy ◽  
Bond Order ◽  
Shift Technique ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

Rate constants for the reactions O(3P) + HX → OH + X (X = Br, I) have been determined by a phase shift technique. Oxygen atoms were generated by modulated mercury photosensitized decomposition of nitrous oxide, and were monitored by the chemiluminescence from the reaction with nitric oxide. Over the temperature interval 298–554 K, the rate constants are satisfactorily represented by the Arrhenius expressions kO+HBr = (8.09 ± 0.86) × 109 exp (−3.59 ± 0.08)/RT and kO+HI = (2.82 ± 0.27) × 1010 exp (−1.99 ± 0.07)/RT, where the units are ℓ mol−1 s−1 and kcal mol−1. The indicated uncertainties are one standard deviation. The results of bond energy–bond order calculations, incorporating recently proposed modifications, are discussed.

PRELIMINARY STUDY OF PHOTOCHEMICAL BEHAVIOR IN THE SYSTEM NITROGEN DIOXIDE – ETHANE

1955 ◽  
Vol 33 (5) ◽  
pp. 843-848
Author(s):  
T. M. Rohr ◽  
W. Albert Noyes Jr.
Keyword(s):  
Nitric Oxide ◽  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Nitrogen Dioxide ◽  
Room Temperature ◽  
Reverse Reaction ◽  
Primary Process ◽  
Photochemical Behavior ◽  
Preliminary Study ◽  
Oxygen Atoms

The addition of ethane to nitrogen dioxide either during exposure to radiation transmitted by pyrex, or afterwards, reduces the amount of oxygen formed. At room temperature this is apparently due to the effectiveness of ethane in promoting the reverse reaction of nitric oxide and oxygen to form nitrogen dioxide. At temperatures over 100° there is a reaction which uses oxygen atoms produced in the primary process. Nitroethane (or nitrosoethane) is formed along with carbon monoxide, carbon dioxide, and some methane. The results suggest that acetaldehyde is an intermediate, but acetaldehyde could not be detected because it would react thermally with nitrogen dioxide. It is not possible to give a complete explanation of the results, but suggestions can be made which might form the basis for later work.

REACTION OF OXYGEN ATOMS WITH ACETALDEHYDE

1956 ◽  
Vol 34 (6) ◽  
pp. 775-784 ◽  
Author(s):  
R. J. Cvetanović
Keyword(s):  
Activation Energy ◽  
Nitrous Oxide ◽  
Room Temperature ◽  
Primary Process ◽  
Kcal Mole ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

Reaction of oxygen atoms, produced by mercury photosensitized decomposition of nitrous oxide, with acetaldehyde has been studied at room temperature. The major products of the reaction are water and biacetyl and the only primary process appears to be[Formula: see text]followed by[Formula: see text]and[Formula: see text]At room temperature oxygen atoms react with acetaldehyde 0.7 ± 0.1 times as fast as with ethylene, so that the activation energy of reaction [1] is likely to be close to 3 kcal./mole.

Reaction of excited oxygen atoms with nitrous oxide. Rate constants for reaction of ozone with nitric oxide and with nitrogen dioxide

1973 ◽  
Vol 77 (11) ◽  
pp. 1341-1345 ◽  
Author(s):  
J. A. Ghormley ◽  
R. L. Ellsworth ◽  
C. J. Hochanadel
Keyword(s):  
Nitric Oxide ◽  
Nitrous Oxide ◽  
Nitrogen Dioxide ◽  
Rate Constants ◽  
Excited Oxygen ◽  
Oxygen Atoms

Arrhenius parameters for the reactions of O(3P) atoms with several aldehydes and the trend in aldehydic C—H bond dissociation energies

1977 ◽  
Vol 55 (18) ◽  
pp. 3321-3327 ◽  
Author(s):  
D. L. Singleton ◽  
R. S. Irwin ◽  
R. J. Cvetanović
Keyword(s):  
Nitric Oxide ◽  
Nitrous Oxide ◽  
Ground State ◽  
Hydrogen Abstraction ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Shift Technique ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

The phase-shift technique has been used to determine the temperature dependence of the reaction of ground state oxygen atoms with several aldehydes. Oxygen atoms were generated by modulated photosensitized decomposition of nitrous oxide and were monitored by the chemiluminescence from their reaction with nitric oxide. The Arrhenius expressions determined over the temperature interval 298–472 K are: k1 (acetaldehyde) = (7.21 ± 1.49) × 109 exp (−1960 ± 153/RT); k1(propionaldehyde) = (7.78 ± 0.75) × 109 exp (−1727 ± 66/RT); k1(butyralde-hyde) = (9.99 ± 0.56) × 109 exp (−1702 ± 40/RT); k1(isobutyraldehyde) = (7.92 ± 1.02) × 109 exp (−1445 ± 91/RT), where the units are ℓ mol−1 s−1 and cal mol−1. The indicated uncertainties are one standard deviation. After small corrections were made for the potential abstraction of alkyl hydrogens, the activation energies of aldehydic hydrogen abstraction were used to estimate the aldehydic C—H bond dissociation energies, D(RCO—H). The trend of slightly decreasing values of D(RCO—H) thus obtained for the sequence H2CO, CH3CHO, C2H5CHO, n-C3H7CHO, i-C3H7CHO was also indicated by the aldehydic C—H stretching frequencies.

Kinetics of the reactions of diatomic sulfur with atomic oxygen, molecular oxygen, ozone, nitrous oxide, nitric oxide, and nitrogen dioxide

1987 ◽  
Vol 91 (5) ◽  
pp. 1199-1204 ◽  
Author(s):  
Alan J. Hills ◽  
Ralph J. Cicerone ◽  
Jack G. Calvert ◽  
John W. Birks
Keyword(s):  
Nitric Oxide ◽  
Nitrous Oxide ◽  
Nitrogen Dioxide ◽  
Molecular Oxygen ◽  
Atomic Oxygen ◽  
Kinetics Of

REACTION OF OXYGEN ATOMS WITH TOLUENE

1961 ◽  
Vol 39 (12) ◽  
pp. 2444-2451 ◽  
Author(s):  
G. R. H. Jones ◽  
R. J. Cvetanović
Keyword(s):  
Activation Energy ◽  
Nitrous Oxide ◽  
Room Temperature ◽  
Kcal Mole ◽  
General Similarity ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

The reaction of toluene with oxygen atoms produced by mercury photosensitized decomposition of nitrous oxide has been studied at room temperature. The reaction shows a general similarity to the corresponding reaction of benzene. Relative rates have been determined at 120 and 220 °C and the activation energy estimated at close to 4 kcal/mole.

THE CATALYTIC DECOMPOSITION OF NITROUS OXIDE AND THE THERMAL DECOMPOSITION OF NITROGEN DIOXIDE

1965 ◽  
Author(s):  
E. Stokes Fishburne ◽  
Daniel M. bergbauer ◽  
Rudolph Edse
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Nitrogen Dioxide ◽  
Catalytic Decomposition ◽  
Decomposition Of Nitrous Oxide

Role of Nitric Oxide in the Thermal Decomposition of Nitrous Oxide

1956 ◽  
Vol 25 (1) ◽  
pp. 106-115 ◽  
Author(s):  
Frederick Kaufman ◽  
Norman J. Gerri ◽  
Roger E. Bowman
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Decomposition Of Nitrous Oxide
Sign in / Sign up

Export Citation Format

Share Document