The formation of O2(a1Δg) in homogeneous and heterogeneous atom recombination

1986 ◽  
Vol 64 (12) ◽  
pp. 1614-1620 ◽  
Author(s):  
A. A. Ali ◽  
E. A. Ogryzlo ◽  
Y. Q. Shen ◽  
P. T. Wassell
Keyword(s):  
Kinetic Study ◽  
Gas Phase ◽  
Molecular Oxygen ◽  
Rate Constant ◽  
Room Temperature ◽  
High Efficiency ◽  
Flow System ◽  
Order Reaction ◽  
Third Order ◽  
First Order

The recombination of oxygen atoms has been studied in a discharge flow system at room temperature. The yield of O2(a1Δg) in the recombination on Pyrex has been found to be 0.08 (±0.02). In the gas phase, O2(a) was found to be formed in a process that is second order in [O] and first order in [N2]. The rate constant for this third-order reaction was found to be 3.4 (±0.4) × 10−34 cm6∙molecule−2∙s−1, representing a yield of 0.07 (±0.02). In the presence of molecular oxygen, the rate of production of O2(a) was found to increase. A kinetic study of this effect led to the conclusion that collisions of molecular oxygen with an unidentified precursor can produce O2(a) with high efficiency.

scholarly journals THE STUDY OF ELECTRICALLY DISCHARGED O2 BY MEANS OF AN ISOTHERMAL CALORIMETRIC DETECTOR

1959 ◽  
Vol 37 (10) ◽  
pp. 1680-1689 ◽  
Author(s):  
L. Elias ◽  
E. A. Ogryzlo ◽  
H. I. Schiff
Keyword(s):  
Gas Phase ◽  
Molecular Oxygen ◽  
Surface Recombination ◽  
Negative Temperature ◽  
Recombination Coefficient ◽  
Third Order ◽  
Atom Concentration ◽  
Electrodeless Discharge ◽  
First Order ◽  
A Value

Molecular oxygen was subjected to an electrodeless discharge in the pressure range 0.1–3 mm Hg. The oxygen atom concentration was measured as a function of time in a flow system by means of a movable atom detector which consisted of a platinum wire coated with a suitable catalyst for atom recombination. The atom concentration was calculated from the heat liberated when the detector was operated under isothermal conditions. The surface recombination was found to be first order in the atom concentration. A value of 7.7 × 10−5 was obtained for the recombination coefficient (γ) on Pyrex. No temperature dependence for γ was observed. The gas phase recombination of oxygen atoms was found to be consistent with the mechanism[Formula: see text]The rate constant for the third-order reaction was found to have a value of 1.0 × 1014 cc2 mole−2 sec−1, and a small negative temperature dependence.Evidence was also obtained for the presence of considerable amounts of excited molecular oxygen in electrically activated O2.

THE THERMAL CIS–TRANS ISOMERIZATION OF CROTONONITRILE

1963 ◽  
Vol 41 (10) ◽  
pp. 2487-2491 ◽  
Author(s):  
James N. Butler ◽  
Robert D. McAlpine
Keyword(s):  
Gas Phase ◽  
Rate Constant ◽  
Side Reaction ◽  
Order Reaction ◽  
First Order Reaction ◽  
Kcal Mole ◽  
Surface Polymerization ◽  
First Order ◽  
Trans Isomerization

The thermal cis–trans isomerization of crotononitrile has been studied in the gas phase at pressures from 0.2 to 20 mm and temperatures from 300 °C to 560 °C. For the equilibrium cis → trans, ΔH = 0.17 ± 0.12 kcal/mole, and ΔS = −0.39 ± 0.19 cal/mole °K. The isomerization is a homogeneous, unimolecular, reversible first-order reaction, the rate constant for the reaction cis → trans being given by[Formula: see text]The only side reaction with appreciable rate was a surface polymerization.

scholarly journals Determination of exothermic batch reactor specific model parameters

2019 ◽  
Vol 292 ◽  
pp. 01063
Author(s):  
Lubomír Macků
Keyword(s):  
Rate Constant ◽  
Reaction Rate ◽  
Batch Reactor ◽  
Specific Model ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
First Order Reaction ◽  
Model Parameters ◽  
Reactor Model ◽  
First Order

An alternative method of determining exothermic reactor model parameters which include first order reaction rate constant is described in this paper. The method is based on known in reactor temperature development and is suitable for processes with changing quality of input substances. This method allows us to evaluate the reaction substances composition change and is also capable of the reaction rate constant (parameters of the Arrhenius equation) determination. Method can be used in exothermic batch or semi- batch reactors running processes based on the first order reaction. An example of such process is given here and the problem is shown on its mathematical model with the help of simulations.

scholarly journals The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate

2000 ◽  
Vol 65 (12) ◽  
pp. 857-866
Author(s):  
Mladjen Micevic ◽  
Slobodan Petrovic
Keyword(s):  
Kinetic Data ◽  
Reaction Rate ◽  
Frequency Factor ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
Activation Entropy ◽  
Second Order Reaction ◽  
Third Order ◽  
First Order ◽  
Kinetics Of

The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate (soman) was examined with a series of alkoxides and in corresponding alcohols: methanol, ethanol, 1-propanol, 2-propanol, 2-methoxyethanol and 2-ethoxyethanol. Soman reacts with the used alkoxides in a second order reaction, first order in each reactant. The kinetics of the reaction between 1,2,2-trimethylpropyl-methylfluorophosphonate and ethanol in the presence of diethylenetriamine was also examined. A third order reaction rate constant was calculated, first order in each reactant. The activation energy, frequency factor and activation entropy were determined on the basis of the kinetic data.

Vibroacoustic Comparisons and Acoustic Power Insulation Mechanisms of Multidirectional Stiffened Laminated Plates

2015 ◽  
Vol 137 (2) ◽  
Author(s):  
Xiongtao Cao ◽  
Hongxing Hua
Keyword(s):  
Fourier Transform ◽  
High Efficiency ◽  
Three Dimensional ◽  
Acoustic Power ◽  
Higher Order ◽  
Laminated Plates ◽  
Transverse Displacement ◽  
Third Order ◽  
First Order ◽  
Implicit Equations

Vibroacoustic characteristics of multidirectional stiffened laminated plates with or without compliant layers are explored in the wavenumber and spatial domains with the help of the two-dimensional continuous Fourier transform and discrete inverse fast Fourier transform. Implicit equations of motion for the arbitrary angle ply laminated plates are derived from the three-dimensional higher order and Reddy third order shear deformation plate theories. The expressions of acoustic power of the stiffened laminated plates with or without complaint layers are formulated in the wavenumber domain, which is a significant method to calculate acoustic power of the stiffened plates with multiple sets of cross stiffeners. Vibroacoustic comparisons of the stiffened laminated plates are made in terms of the transverse displacement spectra, forced responses, acoustic power, and input power according to the first order, Reddy third order, and three-dimensional higher order plate theories. Sound reduction profiles of compliant layers are further examined by the theoretical deductions. This study shows the feasibility and high efficiency of the first order and Reddy third order plate theories in the broad frequency range and allows a better understanding the principal mechanisms of acoustic power radiated from multidirectional stiffened laminated composite plates with compliant layers, which has not been adequately addressed in its companion paper. (Cao and Hua, 2012, “Sound Radiation From Shear Deformable Stiffened Laminated Plates With Multiple Compliant Layers,” ASME J. Vib. Acoust., 134(5), p. 051001.)

Effect of Cyclodextrins on Photodegradation of 4,4-Bis(4-Hydroxyphenyl)Pentanoic Acid under UV Irradiation

2014 ◽  
Vol 665 ◽  
pp. 455-458
Author(s):  
Li Guo ◽  
Jin Huang ◽  
Jun Wu ◽  
Lei Lei Luo
Keyword(s):  
Aqueous Solutions ◽  
Fluorescence Spectra ◽  
High Efficiency ◽  
Uv Light ◽  
Order Reaction ◽  
Pentanoic Acid ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Inclusion Interaction ◽  
Pseudo First Order

The photodegradation of 4,4-bis (4-hydroxyphenyl) pentanoic acid (DPA) with two cyclodextrins (α-CD and β-CD ) in aqueous solutions induced by UV-light was studied in this paper by means of fluorescence spectra and high efficiency liquid chromatography. The result suggested that DPA with α-CD or β-CD formed inclusion compound in aqueous solutions. The photodegradation of DPA with two cyclodextrins or without cyclodextrin was pseudo-first order reaction. The photodegradation of DPA was accelerated by the addition of β-CD in aqueous solutions, but the that of DPA was inhibited in case of adding α-CD. These differences were due to the differences in inclusion interaction of DPA with α-CD or β-CD.

The Near-ultraviolet Absorption Spectrum of Diimide in Liquid Ammonia and its Decomposition between −65 and −38 °C

1974 ◽  
Vol 52 (13) ◽  
pp. 2513-2515 ◽  
Author(s):  
R. A. Back ◽  
C. Willis
Keyword(s):  
Absorption Spectrum ◽  
Gas Phase ◽  
Room Temperature ◽  
Liquid Ammonia ◽  
Vibrational Structure ◽  
Ultraviolet Absorption ◽  
Ultraviolet Absorption Spectrum ◽  
First Order ◽  
Rapid Decomposition ◽  
Near Ultraviolet

The near-ultraviolet absorption spectrum of diimide in liquid ammonia at −50 °C is shifted about 500 Å to the red compared with the gas-phase spectrum, with λmax = 4000 Å. The spectrum is also broadened and the vibrational structure largely obscured. It is suggested that hydrogen bonding is responsible for these changes.Diimide is much more stable in liquid ammonia between −65 and −38 °C than in the gas phase at room temperature. A first-order decay is observed with Arrhenius parameters of A = 1.9 × 103 s−1 and E = 6.6 kcal/mol; this is always preceded by a more rapid, higher-order initial decay which may be related to the rapid decomposition observed during vaporization.

The thermal decomposition of cyclobutane-1,2-dione

1985 ◽  
Vol 63 (11) ◽  
pp. 2945-2948 ◽  
Author(s):  
J.-R. Cao ◽  
R. A. Back
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Vapor Pressure ◽  
Gas Phase ◽  
Rate Constant ◽  
Surface Reaction ◽  
Order Rate Constant ◽  
Reaction Vessel ◽  
Arrhenius Parameters ◽  
First Order

The thermal decomposition of cyclobutane-1,2-dione has been studied in the gas phase at temperatures from 120 to 250 °C and pressures from 0.2 to 1.5 Torr. Products were C2H4 + 2CO, apparently formed in a simple unimolecular process. The first-order rate constant was strongly pressure dependent, and values of k∞ were obtained by extrapolation of plots of 1/k vs. 1/p to1/p = 0. Experiments in a packed reaction vessel showed that the reaction was enhanced by surface at the lower temperatures. Arrhenius parameters for k∞, corrected for surface reaction, were log A (s−1) = 15.07(±0.3) and E = 39.3(±2) kcal/mol. This activation energy seems too low for a biradical mechanism, and it is suggested that the decomposition is probably a concerted process. The vapor pressure of solid cyclobutane-1,2-dione was measured at temperatures from 22 to 62 °C and a heat of sublimation of 13.1 kcal/mol was estimated.

Polymerization Reactions under high Pressure. I. Some Experiments with Isoprene and Butyraldehyde

1930 ◽  
Vol 3 (3) ◽  
pp. 472-482
Author(s):  
J. B. Conant ◽  
C. O. Tongberg
Keyword(s):  
High Pressure ◽  
Room Temperature ◽  
High Pressures ◽  
Order Reaction ◽  
Pressure Coefficients ◽  
First Order ◽  
Rate Of Polymerization ◽  
Energy Relationships ◽  
Temperature And Pressure ◽  
Autocatalytic Effect

Abstract 1. The rate of polymerization of isoprene under high pressures has been studied. The reaction is subject to positive catalysis by peroxides and negative catalysis by hydroquinone. Although the reaction is of a high order, the rate is approximately in accord with a first order reaction presumably because of an autocatalytic effect. The temperature and pressure coefficients of the rate have been estimated. The solubility and elasticity of the product depend on the extent to which the isoprene has been polymerized; when the polymerization is practically complete at room temperature at 12,000 atm. the product is very insoluble 2. The action of high pressures on n-butyraldehyde produces a solid only slightly soluble in organic solvents. It reverts to n-butyraldehyde rapidly. It is suggested that this polymer is similar to the well-known polymers of formaldehyde but that the energy relationships are such that the polymer is stable only at high pressures.

The Initial Stages of the Pyrolysis of Dimethyl Ether

1975 ◽  
Vol 53 (18) ◽  
pp. 2742-2747 ◽  
Author(s):  
Philip D. Pacey
Keyword(s):  
Dimethyl Ether ◽  
Rate Constant ◽  
Arrhenius Plot ◽  
Flow System ◽  
Order Rate Constant ◽  
Chain Termination ◽  
Rate Coefficients ◽  
First Order ◽  
Order Rate ◽  
Initiation Reaction

Dimethyl ether was pyrolized in a flow system at 782–936 K and 25–395 Torr with conversions from 0.2–10%. Product analyses were consistent with a simple Rice–Herzfeld mechanism with most chain termination by the recombination of CH3 radicals. The rate coefficients for both the initiation and termination reactions appeared to be slightly pressure dependent. The first-order rate constant for the initiation reaction,[Formula: see text]calculated from the rate of C2H6 formation, was k1 = 1015.0±0.5exp (−318 ± 8 kJ mol−1/RT) s−1, corresponding to ΔHf0(CH3O) = −5 ± 8 kJmol−1. Comparison of CH4 and C2H6 yields enabled calculation of the rate constant for the reaction of CH3 with dimethyl ether. From 373−936 K, the Arrhenius plot for this reaction is a curve.

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