SINGLET METHYLENE FROM THERMAL DECOMPOSITION OF DIAZOMETHANE. UNIMOLECULAR REACTIONS OF CHEMICALLY ACTIVATED CYCLOPROPANE AND DIMETHYLCYCLOPROPANE MOLECULES

1962 ◽  
Vol 40 (7) ◽  
pp. 1425-1451 ◽  
Author(s):  
D. W. Setser ◽  
B. S. Rabinovitch
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
Vibrational Energy ◽  
Kcal Mole ◽  
Thermal Systems ◽  
Geometric Isomerization ◽  
Wide Range ◽  
Structural Isomerization ◽  
Quantum Statistical ◽  
Singlet Methylene

The thermal decomposition of diazomethane (DM) into singlet methylene radicals and nitrogen has been studied from 225° to 450° in 10:1 olefin–diazomethane mixtures. At 2.5 cm pressure, k = 1.2 × 1012 exp (−34,000/RT) sec−1. The methylene radicals have similar reactivity to methylene generated from photolytic decomposition of DM, as judged by the follow-up reactions with ethylene and cis-butene-2. The structural isomerization reactions of energized cyclopropane and the structural and geometric isomerization of 1,2-dimethyl-cyclopropane (DMC), formed from the addition of the thermally generated methylene to the olefins, were measured from 250° to 450° over a wide range of pressures. For comparison, cyclopropane formed from photolysis at 4358 Å and 25° of DM and ethylene was studied. As judged from comparison of the experimental isomerization rate constants, the energy of the cyclopropanes formed at 350° in the thermal DM system is about the same as for cyclopropanes formed by photolysis at 4358 Å of DM at 25°. The experimental rate constants obtained on the assumption of strong collisions are compared with calculated rate constants which are based on quantum statistical models for kE which fit literature data on conventional thermal isomerization of cyclopropane and DMC. From this comparison, the average energies of the formed molecules in the thermal systems are estimated to be between 107 and 115 kcal/mole, depending upon the temperature. Photolysis at 25° of the ketene–ethylene system (3200 Å) and of DM–ethylene system (4358 Å) give cyclopropane characterized as being at 103 and 111 kcal/mole respectively. These energies deduced from kinetic data are compared with available thermochemical quantities; the existing value of ΔHf0(CH2N2) is questioned. Further support for fast intramolecular relaxation of vibrational energy in DMC, relative to the relaxation process for reaction, is noted. Comparison of data in the literature on the ketene and DM photolytic systems strongly suggests that a larger fraction of the excess light energy resides with methylene from ketene (0.65–0.8) than with methylene from DM (0.3–0.5). Various approximations for the calculation of kE are examined and are compared with accurate quantum statistical evaluation.

THE THERMAL DECOMPOSITION OF METHYL HYDROPEROXIDE

1965 ◽  
Vol 43 (8) ◽  
pp. 2236-2242 ◽  
Author(s):  
Alexander D. Kirk
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Gas Phase ◽  
Rate Constants ◽  
Dimethyl Phthalate ◽  
Kcal Mole ◽  
First Order ◽  
Methyl Hydroperoxide ◽  
Expected Values ◽  
Homogeneous Decomposition

The thermal decomposition of methyl hydroperoxide has been studied in solution and in the gas phase. The decomposition was found to be partly heterogeneous in solution in dimethyl phthalate and no reliable rate constants were obtained. Use of the toluene carrier method for the gas phase work enabled measurement of the rate constant for the homogeneous decomposition. The first order rate constants obtained range from 0.19 s−1 at 292 °C to 1.5 s−1 at 378 °C, leading to log A, 11± 2, and activation energy, 32 ± 5 kcal/mole. These results are compared with the expected values of log A, 13–14, and activation energy, 42 kcal/mole. The significance of these findings is discussed.

scholarly journals Vibrational Energy Transfer in CO+N2 Collisions: A Database for V–V and V–T/R Quantum-Classical Rate Coefficients

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7152
Author(s):  
Qizhen Hong ◽  
Massimiliano Bartolomei ◽  
Cecilia Coletti ◽  
Andrea Lombardi ◽  
Quanhua Sun ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Rate Constants ◽  
Potential Energy Surfaces ◽  
Vibrational Energy ◽  
Classical Method ◽  
Rate Coefficients ◽  
Collision Dynamics ◽  
Aerospace Applications ◽  
Wide Range ◽  
Experimental Values

Knowledge of energy exchange rate constants in inelastic collisions is critically required for accurate characterization and simulation of several processes in gaseous environments, including planetary atmospheres, plasma, combustion, etc. Determination of these rate constants requires accurate potential energy surfaces (PESs) that describe in detail the full interaction region space and the use of collision dynamics methods capable of including the most relevant quantum effects. In this work, we produce an extensive collection of vibration-to-vibration (V–V) and vibration-to-translation/rotation (V–T/R) energy transfer rate coefficients for collisions between CO and N2 molecules using a mixed quantum-classical method and a recently introduced (A. Lombardi, F. Pirani, M. Bartolomei, C. Coletti, and A. Laganà, Frontiers in chemistry, 7, 309 (2019)) analytical PES, critically revised to improve its performance against ab initio and experimental data of different sources. The present database gives a good agreement with available experimental values of V–V rate coefficients and covers an unprecedented number of transitions and a wide range of temperatures. Furthermore, this is the first database of V–T/R rate coefficients for the title collisions. These processes are shown to often be the most probable ones at high temperatures and/or for highly excited molecules, such conditions being relevant in the modeling of hypersonic flows, plasma, and aerospace applications.

Substituent Effects on the Thermal Decomposition of Phosphate Esters on Ferrous Surfaces

2019 ◽  
Author(s):  
James Ewen ◽  
Carlos Ayestaran Latorre ◽  
Arash Khajeh ◽  
Joshua Moore ◽  
Joseph Remias ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Film Formation ◽  
Substituent Effects ◽  
Vapour Phase ◽  
Industrial Applications ◽  
Phosphate Esters ◽  
Antiwear Additives ◽  
Formation Mechanisms ◽  
Phosphate Ester ◽  
Wide Range

<p>Phosphate esters have a wide range of industrial applications, for example in tribology where they are used as vapour phase lubricants and antiwear additives. To rationally design phosphate esters with improved tribological performance, an atomic-level understanding of their film formation mechanisms is required. One important aspect is the thermal decomposition of phosphate esters on steel surfaces, since this initiates film formation. In this study, ReaxFF molecular dynamics simulations are used to study the thermal decomposition of phosphate esters with different substituents on several ferrous surfaces. On Fe<sub>3</sub>O<sub>4</sub>(001) and α-Fe(110), chemisorption interactions between the phosphate esters and the surfaces occur even at room temperature, and the number of molecule-surface bonds increases as the temperature is increased from 300 to 1000 K. Conversely, on hydroxylated, amorphous Fe<sub>3</sub>O<sub>4</sub>, most of the molecules are physisorbed, even at high temperature. Thermal decomposition rates were much higher on Fe<sub>3</sub>O<sub>4</sub>(001) and particularly α-Fe(110) compared to hydroxylated, amorphous Fe<sub>3</sub>O<sub>4</sub>. This suggests that water passivates ferrous surfaces and inhibits phosphate ester chemisorption, decomposition, and ultimately film formation. On Fe<sub>3</sub>O<sub>4</sub>(001), thermal decomposition proceeds mainly through C-O cleavage (to form surface alkyl and aryl groups) and C-H cleavage (to form surface hydroxyls). The onset temperature for C-O cleavage on Fe<sub>3</sub>O<sub>4</sub>(001) increases in the order: tertiary alkyl < secondary alkyl < primary linear alkyl ≈ primary branched alkyl < aryl. This order is in agreement with experimental observations for the thermal stability of antiwear additives with similar substituents. The results highlight surface and substituent effects on the thermal decomposition of phosphate esters which should be helpful for the design of new molecules with improved performance.</p>

pH-Dependent Thermal Stability of Vibrio cholerae L-asparaginase

2019 ◽  
Vol 26 (10) ◽  
pp. 743-750 ◽  
Author(s):  
Remya Radha ◽  
Sathyanarayana N. Gummadi
Keyword(s):  
Vibrio Cholerae ◽  
Conformational Changes ◽  
Kinetic Studies ◽  
Structural Features ◽  
Structure Stability ◽  
Kcal Mole ◽  
Scanning Calorimetry ◽  
Wide Range ◽  
Ph Dependent ◽  
Ph Range

Background:pH is one of the decisive macromolecular properties of proteins that significantly affects enzyme structure, stability and reaction rate. Change in pH may protonate or deprotonate the side group of aminoacid residues in the protein, thereby resulting in changes in chemical and structural features. Hence studies on the kinetics of enzyme deactivation by pH are important for assessing the bio-functionality of industrial enzymes. L-asparaginase is one such important enzyme that has potent applications in cancer therapy and food industry.Objective:The objective of the study is to understand and analyze the influence of pH on deactivation and stability of Vibrio cholerae L-asparaginase.Methods:Kinetic studies were conducted to analyze the effect of pH on stability and deactivation of Vibrio cholerae L-asparaginase. Circular Dichroism (CD) and Differential Scanning Calorimetry (DSC) studies have been carried out to understand the pH-dependent conformational changes in the secondary structure of V. cholerae L-asparaginase.Results:The enzyme was found to be least stable at extreme acidic conditions (pH< 4.5) and exhibited a gradual increase in melting temperature from 40 to 81 °C within pH range of 4.0 to 7.0. Thermodynamic properties of protein were estimated and at pH 7.0 the protein exhibited ΔG37of 26.31 kcal mole-1, ΔH of 204.27 kcal mole-1 and ΔS of 574.06 cal mole-1 K-1.Conclusion:The stability and thermodynamic analysis revealed that V. cholerae L-asparaginase was highly stable over a wide range of pH, with the highest stability in the pH range of 5.0–7.0.

scholarly journals RELaTED Project: New Developments on Ultra-Low Temperature District Heating Networks

Proceedings ◽  
2020 ◽  
Vol 65 (1) ◽  
pp. 25
Author(s):  
Antonio Garrido Marijuan ◽  
Roberto Garay ◽  
Mikel Lumbreras ◽  
Víctor Sánchez ◽  
Olga Macias ◽  
...  
Keyword(s):  
Low Temperature ◽  
High Performance ◽  
Waste Heat ◽  
District Heating ◽  
Hot Water ◽  
Thermal Systems ◽  
Heating Source ◽  
Wide Range ◽  
Thermal Sources ◽  
Heating Networks

District heating networks deliver around 13% of the heating energy in the EU, being considered as a key element of the progressive decarbonization of Europe. The H2020 REnewable Low TEmperature District project (RELaTED) seeks to contribute to the energy decarbonization of these infrastructures through the development and demonstration of the following concepts: reduction in network temperature down to 50 °C, integration of renewable energies and waste heat sources with a novel substation concept, and improvement on building-integrated solar thermal systems. The coupling of renewable thermal sources with ultra-low temperature district heating (DH) allows for a bidirectional energy flow, using the DH as both thermal storage in periods of production surplus and a back-up heating source during consumption peaks. The ultra-low temperature enables the integration of a wide range of energy sources such as waste heat from industry. Furthermore, RELaTED also develops concepts concerning district heating-connected reversible heat pump systems that allow to reach adequate thermal levels for domestic hot water as well as the use of the network for district cooling with high performance. These developments will be demonstrated in four locations: Estonia, Serbia, Denmark, and Spain.

Singlet Methylene Removal Rate Constants from the (0,1,0) Vibrational Level: Enhancement via Complex-Mediated Vibrational Relaxation

2001 ◽  
Vol 215 (6) ◽  
Author(s):  
M.A. Buntine ◽  
G.J. Gutsche ◽  
W.S. Staker ◽  
M.W. Heaven ◽  
K.D. King ◽  
...  
Keyword(s):  
Vibrational Level ◽  
Rate Constants ◽  
Vibrational Relaxation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Removal Rate ◽  
Laser Flash ◽  
Laser Absorption ◽  
Photolysis Laser ◽  
Singlet Methylene

The technique of laser flash photolysis/laser absorption has been used to obtain absolute removal rate constants for singlet methylene,

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

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