New studies of the unimolecular reaction NO2O+NO. Part 2. Relation between high pressure rate constants and potential parameters

1999 ◽  
Vol 1 (1) ◽  
pp. 63-72 ◽  
Author(s):  
L B. Harding ◽  
H Stark ◽  
J Troe ◽  
V G. Ushakov
Keyword(s):  
High Pressure ◽  
Rate Constants ◽  
Unimolecular Reaction ◽  
Potential Parameters

Computational Study on the Kinetics and Mechanisms of Unimolecular Reactions of (Z)-(Z)-N-(λ5-phosphanylidene) Formohydrazonic Formic Anhydride: Intramolecular aza-Wittig Reaction in Competition with Mumm Rearrangement

2020 ◽  
Vol 17 (11) ◽  
pp. 884-889
Author(s):  
Somayeh Mirdoraghi ◽  
Hamed Douroudgari ◽  
Farideh Piri ◽  
Morteza Vahedpour
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Wittig Reaction ◽  
Computational Study ◽  
Single Step ◽  
Low Energy ◽  
Coupled Cluster ◽  
Unimolecular Reaction ◽  
Single Step Reaction ◽  
Good Agreement

For (Z)-(Z)-N-(λ5-phosphanylidene) formohydrazonic formic anhydride, Aza-Wittig reaction and Mumm rearrangement are studied using both density functional and coupled cluster theories. For this purpose, two different products starting from one substrate are considered that are competing with each other. The obtained products, P1 and P2, are thermodynamically favorable. The product of the aza-Wittig reaction, P1, is more stable than the product of Mumm rearrangement (P2). For the mentioned products, just one reliable pathway is separately proposed based on unimolecular reaction. Therefore, the rate constants based on RRKM theory in 300-600 K temperature range are calculated. Results show that the P1 generation pathway is a suitable path due to low energy barriers than the path P2. The first path has three steps with three transition states, TS1, TS2, and TS3. The P2 production path is a single-step reaction. In CCSD level, the computed barrier energies are 14.55, 2.196, and 10.67 kcal/mol for Aza-Wittig reaction and 42.41 kcal/mol for Mumm rearrangement in comparison with the corresponding complexes or reactants. For final products, the results of the computational study are in a good agreement with experimental predictions.

Unimolecular Reaction Rate Constants of NO2Just above D0

1999 ◽  
Vol 103 (49) ◽  
pp. 10268-10273 ◽  
Author(s):  
I. Bezel ◽  
D. Stolyarov ◽  
C. Wittig
Keyword(s):  
Rate Constants ◽  
Reaction Rate ◽  
Unimolecular Reaction ◽  
Reaction Rate Constants

scholarly journals Kinetic Study of Photocatalytic Degradation of Tolonium Chloride Under High Pressure Irradiation in Aquatic Buffer Systems

2011 ◽  
Vol 8 (s1) ◽  
pp. S19-S26 ◽  
Author(s):  
M. Montazerozohori ◽  
S. Nezami ◽  
S. Mojahedi
Keyword(s):  
High Pressure ◽  
Photocatalytic Degradation ◽  
Kinetic Study ◽  
Rate Constants ◽  
Order Kinetic ◽  
Optimum Conditions ◽  
First Order ◽  
Reactor Cell ◽  
Order Kinetic Model ◽  
Tolonium Chloride

Anatase titanium dioxide catalyzed photodegradation of tolonium chloride at various bufferic pH of 2, 7, 9 and 12 in aqueous solution is presented. The effect of some physicochemical parameters such as initial concentration of dye, catalyst amount and reaction time on photocatalytic degradation has been investigated in a photo-reactor cell containing high pressure mercury lamp to obtain the optimum conditions in each bufferic pH at constant temperature. A complete spectrophotometric kinetic study of tolonium chloride under high pressure irradiation at buffer media was performed. The photocatalytic degradation observed rate constants (kobs) were found to be 2.90×10-3, 3.30×10-3, 3.20×10-3and 5.20×10-3min-1for buffer pH of 2-12 respectively. It was found that a pseudo-first-order kinetic model based on Langmuir-Hinshelwood one is usable to photodegradation of this compound at all considered buffer pH. In addition to these, the Langmuir-Hinshelwood rate constants, krfor the titled compound at various pH are reported.

Temperature dependence of the limiting low- and high-pressure rate constants for the CH3O+NO2+He reaction over the 250–390 K temperature range

2000 ◽  
Vol 329 (3-4) ◽  
pp. 191-199 ◽  
Author(s):  
E. Martı́nez ◽  
J. Albaladejo ◽  
E. Jiménez ◽  
A. Notario ◽  
Y. Dı́az de Mera
Keyword(s):  
High Pressure ◽  
Temperature Dependence ◽  
Rate Constants ◽  
Temperature Range

The Rate-Constant for the Recombination of Methyl Radicals

1986 ◽  
Vol 39 (8) ◽  
pp. 1257 ◽  
Author(s):  
NL Arthur ◽  
JC Biordi
Keyword(s):  
Experimental Data ◽  
High Pressure ◽  
Rate Constant ◽  
Rate Constants ◽  
The Other ◽  
Methyl Radicals ◽  
Experimental Conditions ◽  
Temperature Range ◽  
Best Value ◽  
Limiting Value

Rate constants for the recombination of CH3 radicals have been measured by means of the rotating sector technique in the temperature range 373- 463 K, and at a pressure of 30 Torr . CH3 radicals were produced by the photolysis of acetone, and the experimental data were fitted to sector curves generated from Shepp's theory. The results give kb = (2.81�0.22)×1013 cm3 mol-1 s-1, which, under the chosen experimental conditions, is close to its high-pressure limiting value. A comparison is made with the other values of the rate constant reported in the literature, and a best value is suggested.

On the high pressure rate constants for the H/Mu + O2 addition reactions

2001 ◽  
Vol 3 (4) ◽  
pp. 505-507 ◽  
Author(s):  
J. M. C. Marques ◽  
A. J. C. Varandas
Keyword(s):  
High Pressure ◽  
Rate Constants ◽  
Addition Reactions

Simulation of Structural Parameters and Superconducting Transition Temperature of MgB2 under Pressure

2005 ◽  
Vol 475-479 ◽  
pp. 3319-3322
Author(s):  
Yang Shao ◽  
X. Zhang ◽  
Fu Ling Tang
Keyword(s):  
Experimental Data ◽  
High Pressure ◽  
Transition Temperature ◽  
Superconducting Transition Temperature ◽  
Pressure Effect ◽  
Structural Parameters ◽  
Experimental Results ◽  
Bcs Theory ◽  
Superconducting Transition ◽  
Potential Parameters

We successfully developed the potential parameters for simulation of MgB2. With these potential parameters, we calculate the lattice parameters and volume variations with pressure up to 240GPa. All these results agree well with experimental data under 40GPa and provide reasonable tendencies from 40GPa to 240GPa. By employing the McMillan expression, it is found that the lattice stiffening dominants the behavior of Tc under pressure in the scope of BCS theory. Using our calculated Grüneisen parameter G g , the simulated pressure effect on Tc accords well with experimental results. Our result shows that the Tc of MgB2 can be destroyed by high pressure.

The study of enzyme mechanisms by a combination of cosolvent, low-temperature and high-pressure techniques

1979 ◽  
Vol 12 (4) ◽  
pp. 521-569 ◽  
Author(s):  
Pierre Douzou
Keyword(s):  
High Pressure ◽  
Conformational Changes ◽  
Rate Constants ◽  
Enzyme Catalysis ◽  
Chemical Nature ◽  
Molecular Level ◽  
Essential Feature ◽  
Quantitative Understanding ◽  
Definition Of ◽  
Rapid Data Acquisition

It is generally assumed that the mechanism of enzyme-catalysed reactions would be defined if all the intermediates, complexes and conformational states of each enzyme could be characterized, and the rate-constants for their inter-conversion recorded. In spite of the introduction during the last decades of methods for rapid data acquisition, which permit detection of the number and sequence of intermediates and complexes, measurement of rate-constants, identification of the types of catalysis involved, etc., at best a semi-quantitative understanding of the mechanism of enzyme-catalysis is obtained. The definition of the exact chemical nature of intermediates and complexes is missing because techniques establishing the structures are restricted to the study of transient states which are stable for periods that exceed the half-life of most of typical intermediates. In such conditions, while conformational changes are obviously an essential feature of enzyme activity, the conformational basis of such activity cannot be understood at the molecular level, and enzyme catalysis is still termed a ‘miracle’ compared to the rate-enhancements and specificity of ordinary chemical catalysts.

scholarly journals Kinetics of the Toluene Reaction with OH Radical

Research ◽  
2019 ◽  
Vol 2019 ◽  
pp. 1-19 ◽  
Author(s):  
Rui Ming Zhang ◽  
Donald G. Truhlar ◽  
Xuefei Xu
Keyword(s):  
High Pressure ◽  
Low Temperature ◽  
Atmospheric Chemistry ◽  
Temperature Regime ◽  
Rate Constants ◽  
Chemical Activation ◽  
Reaction Rates ◽  
State Theory ◽  
Partition Functions ◽  
Kinetics Of

We calculated the kinetics of chemical activation reactions of toluene with hydroxyl radical in the temperature range from 213 K to 2500 K and the pressure range from 10 Torr to the high-pressure limit by using multistructural variational transition state theory with the small-curvature tunneling approximation (MS-CVT/SCT) and using the system-specific quantum Rice-Ramsperger-Kassel method. The reactions of OH with toluene are important elementary steps in both combustion and atmospheric chemistry, and thus it is valuable to understand the rate constants both in the high-pressure, high-temperature regime and in the low-pressure, low-temperature regime. Under the experimental pressure conditions, the theoretically calculated total reaction rate constants agree well with the limited experimental data, including the negative temperature dependence at low temperature. We find that the effect of multistructural anharmonicity on the partition functions usually increases with temperature, and it can change the calculated reaction rates by factors as small as 0.2 and as large as 4.2. We also find a large effect of anharmonicity on the zero-point energies of the transition states for the abstraction reactions. We report that abstraction of H from methyl should not be neglected in atmospheric chemistry, even though the low-temperature results are dominated by addition. We calculated the product distribution, which is usually not accessible to experiments, as a function of temperature and pressure.

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