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.

Temperature dependence of rate constants for reaction of oxygen atoms, O(3P), with allene and 1,3-butadiene

1979 ◽  
Vol 57 (9) ◽  
pp. 949-952 ◽  
Author(s):  
W. S. Nip ◽  
D. L. Singleton ◽  
R. J. Cvetanović
Keyword(s):  
Nitrous Oxide ◽  
Phase Shift ◽  
Temperature Dependence ◽  
Rate Constants ◽  
Arrhenius Equation ◽  
Confidence Limits ◽  
Average Value ◽  
Shift Technique ◽  
Decomposition Of Nitrous Oxide ◽  
Oxygen Atoms

Rate constants were determined for the reactions of O(3P) atoms with allene and with 1,3-butadiene by a phase shift technique in which oxygen atoms were generated by modulated mercury photosensitized decomposition of nitrous oxide and monitored by the chemiluminescence from their reaction with NO. Over the temperature interval 297–574 K, the Arrhenius equation for the O(3P) + allene reaction is k1A = (2.99 ± 0.41) × 10−11 exp [(−941 ± 54)/T] cm3 molecule−1 s−1, where the indicated uncertainties are 95% confidence limits. At 299 and 488 K, the rate constant for O(3P) + 1,3-butadiene is essentially the same, within 10%, with an average value of 2.07 × 10−11 cm3 molecule−1 s−1.

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.

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.

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

The thermal decomposition of nitrous oxide I. Secondary catalytic and surface effects

1955 ◽  
Vol 231 (1185) ◽  
pp. 162-178 ◽  
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Surface Reaction ◽  
Order Rate Constant ◽  
Side Reactions ◽  
Chain Reactions ◽  
First Order ◽  
Reaction Vessels ◽  
Decomposition Of Nitrous Oxide

In the region of pressure 0 to 500 mrn approximately to the equation the thermal decomposition of nitrous oxide conforms approximately to the equation k = an /1 + a'n + bn , where k is the form al first-order rate constant, — (1/n) d n /d t , n the initial concentration and a, a' and b are nearly constant. Above about 100 m m this expression approximates to k = A + bn , which holds up to several atmospheres. Fresh and more detailed experiments have once again disproved the suggestion that the first term in these expressions is due to a surface reaction. (In certain states of reaction vessels, made of a particular brand of silica, a surface reaction may appear but is immediately recognizable by special criteria, and can be eliminated.) Detailed study of the formation of nitric oxide in the course of the decomposition, and of the effect of inert gas upon this process, shows that side reactions involving oxygen atoms, chain reactions and catalysis by nitric oxide play only minor parts in determining the shape of the k-n curve. The form of this curve, which is an inherent character of the reaction N 2 O = N 2 + O, raises theoretical questions of considerable interest.

Determination of the Rates of Hydrogen Atom Reaction with NO by a Modulation Technique

1973 ◽  
Vol 51 (3) ◽  
pp. 370-372 ◽  
Author(s):  
R. Atkinson ◽  
R. J. Cvetanović
Keyword(s):  
Nitric Oxide ◽  
Hydrogen Atom ◽  
Phase Shift ◽  
Rate Constants ◽  
Hydrogen Atoms ◽  
Arrhenius Parameters ◽  
Modulation Technique ◽  
The Absolute

A modulation technique has been used to determine from phase shift measurements the absolute values of the rate constants and the Arrhenius parameters of the reaction of hydrogen atoms with nitric oxide.

THE REACTION OF NITROGEN ATOMS WITH OXYGEN ATOMS IN THE ABSENCE OF OXYGEN MOLECULES

1961 ◽  
Vol 39 (8) ◽  
pp. 1601-1607 ◽  
Author(s):  
C. Mavroyannis ◽  
C. A. Winkler
Keyword(s):  
Nitric Oxide ◽  
Nitrogen Atom ◽  
Rate Constant ◽  
Rate Constants ◽  
Flow System ◽  
Titration Method ◽  
Active Nitrogen ◽  
Reaction Tube ◽  
Fast Flow ◽  
Oxygen Atoms

The reaction has been studied in a fast-flow system by introducing nitric oxide in the gas stream with excess active nitrogen. The nitrogen atom consumption was determined by titrating active nitrogen with nitric oxide at different positions along the reaction tube. The rate constant is found to be k1 = 1.83(± 0.2) × 1015 cc2 mole−2 sec−1 at pressures of 3, 3.5, and 4 mm, and with an unheated reaction tube.The homogeneous and surface decay of nitrogen atoms involved in the above system were studied using the nitric oxide titration method, and the rate constants were found to be k3 = 1.04 ± 0.17 × 1016 cc2 mole−2 sec−1, and k4 = 2.5 ± 0.2 sec−1 (γ = 7.5 ± 0.6 × 10–5), respectively, over the range of pressures from 0.5 to 4 mm with an unheated reaction tube.

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