STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: IV. THE DECOMPOSITION OF PARA-n-BUTYRALDEHYDE AND PARA-ISOBUTYRALDEHYDE

1933 ◽  
Vol 9 (6) ◽  
pp. 603-609 ◽  
Author(s):  
C. C. Coffin
Keyword(s):  
Experimental Error ◽  
Degrees Of Freedom ◽  
Activation Energies ◽  
Energy Of Activation ◽  
Velocity Constant ◽  
First Order ◽  
Temperature Range ◽  
Measurable Rate ◽  
Gas Reactions ◽  
Internal Degrees Of Freedom

The gaseous decompositions of para-n-butyraldehyde and para-isobutyraldehyde to n-butyraldehyde and isobutyraldehyde respectively are homogeneous and first order over the pressure and temperature range investigated (1.3 to 55 cm. of mercury; 215 to 261 °C). Under these conditions the reactions go to completion at a measurable rate without complications. Within experimental error the activation energies of these reactions are equal and are approximately the same as that of the paracetaldehyde decomposition. This value is between 42,000 and 44,000 calories per mole. The rates of decomposition of the two parabutyraldehydes are very nearly the same at any temperature. At 500° abs. the velocity constant of the iso-compound is about 15% greater than that of the normal and about 100% greater than that of paracetaldehyde. The velocity constants at any temperature are given by the equations: para-n-butyraldehyde, [Formula: see text]; para-isobutyraldehyde, [Formula: see text]. The data are consistent with the idea that, for a series of reactions with the same energy of activation, an increase in the number of contributory internal degrees of freedom of a molecule will increase the probability of reaction.

STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: II. THE DECOMPOSITION OF THE ISOMERIC ESTERS BUTYLIDENE DIACETATE AND ETHYLIDENE DIPROPIONATE

1932 ◽  
Vol 6 (4) ◽  
pp. 417-427 ◽  
Author(s):  
C. C. Coffin
Keyword(s):  
Activation Energy ◽  
Degrees Of Freedom ◽  
Maximum Energy ◽  
Velocity Measurements ◽  
First Order ◽  
Gas Reactions ◽  
Points Of View ◽  
The Stability ◽  
Future Work ◽  
Internal Degrees Of Freedom

The gaseous decompositions of the esters butylidene diacetate and ethylidene dipropionate have been studied from points of view previously outlined in papers on the decomposition of ethylidene diacetate (2, 3). The decomposition velocities have been measured at initial pressures of from 5 to 56 cm. of mercury and at temperatures between 211 and 265 °C. The reactions are homogeneous and of the first order. They agree with the Arrhenius equation and give 100% yields (within experimental error) of an aldehyde and an anhydride. The preparation of the compounds and improvements in the technique of the velocity measurements are described.While the specific velocities of the three reactions at any temperature are somewhat different, their activation energies are the same. It is suggested that in the case of such simple reactions, which are strictly localized within the molecular structure, the activation energy can be identified as the maximum energy that the reactive bonds may possess and still exist; i.e., it may be taken as a measure of the stability of the bonds which are broken in the reaction. The suggestion is also made that for a series of reactions which have the same activation energy, the specific velocities can be taken as a relative measure of the number of internal degrees of freedom that contribute to the energy of activation. On the basis of these assumptions it becomes possible to use reaction-velocity measurements for the investigation of intramolecular energy exchange. The theoretical significance of the data is further discussed and the scope of future work in this connection is indicated.The monomolecular velocity constants (sec−1) of the decomposition of ethylidene diacetate, ethylidene dipropionate and butylidene diacetate are given respectively by the equations [Formula: see text], [Formula: see text], and [Formula: see text].

STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: VIII. THE DECOMPOSITION OF TRICHLORETHYLIDENE DIACETATE AND TRICHLORETHYLIDENE DIBUTYRATE

1937 ◽  
Vol 15b (6) ◽  
pp. 254-259 ◽  
Author(s):  
N. A. D. Parlee ◽  
J. R. Dacey ◽  
C. C. Coffin
Keyword(s):  
Activation Energy ◽  
Experimental Error ◽  
Acid Anhydride ◽  
Exchange Energy ◽  
Reaction Velocity ◽  
First Order ◽  
Measurable Rate ◽  
Gas Reactions

Trichlorethylidene diacetate and trichlorethylidene dibutyrate have been found to decompose at temperatures between 200° and 290 °C. at a measurable rate to give chloral and an acid anhydride. The reactions are homogeneous and of the first order, and have the same specific velocity in both the liquid and vapor states. The activation energy is identical (within experimental error) with that previously found for non-chlorinated members of this series of esters. The two compounds decompose at the same rate, in agreement with the hypothesis that the anhydride radicals do not easily exchange energy with the bonds that break. This reaction velocity, which is somewhat smaller than that of ethylidene diacetate at any temperature, is given by the equation [Formula: see text].

Reactions of trifluoromethyl radicals. II. Hydrogen abstraction from monochlorosilane

1973 ◽  
Vol 26 (6) ◽  
pp. 1269 ◽  
Author(s):  
NL Arthur ◽  
BR Harman
Keyword(s):  
Hydrogen Atom ◽  
Rate Constant ◽  
Experimental Error ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Hydrogen Atom Abstraction ◽  
Temperature Range ◽  
Average Value

Hydrogen atom abstraction from SiH3Cl by CF3 radicals ����������������� CF3 + SiH3Cl → CF3H+SiH2Cl������������������� (1) has been studied in the temperature range 69-168�. The rate constant, based on Ayscough's value of 1013.36 cm3 mol-1 s-1 for the recombination of CF3 radicals, is given by (k1 in cm3 mol-1 s-1, E in kJ mol-1): ������������������ logk1 = (12.38�0.06)-(25.72�0.41)/2.303RT At 400 K, the rate constant for CF3 + SiH3Cl is greater than the average value reported for CF3+SiHCl3 by a factor of 3.6. This is due to a difference in A factors since the activation energies are equal within experimental error.

Self-diffusion in Molten Zinc Bromide

1963 ◽  
Vol 18 (12) ◽  
pp. 1247-1248 ◽  
Author(s):  
Carl-Axel Sjöblom
Keyword(s):  
Diffusion Coefficient ◽  
Experimental Error ◽  
Activation Energies ◽  
Zinc Bromide ◽  
Molten Zinc ◽  
Temperature Range ◽  
Self Diffusion ◽  
Bromide Ion

The diffusion coefficient of the bromide ion in molten zinc bromide has been measured in the temperature range 415—547°C. The results can be described by the following equation1:D = 0.114 exp [ — (17 050 ± 500) /R T].D is expressed in cm2s-1, R in cal · mole-1 · degree-1 and T in degrees KELVIN. A comparison with earlier measurements 2 shows that the activation energies of cation and anion are equal within the experimental error, and that D- is considerably greater than D+ in the whole temperature range.

EXCHANGE REACTIONS OF IODIDE ION WITH AROMATIC IODIDES

1951 ◽  
Vol 29 (2) ◽  
pp. 154-161 ◽  
Author(s):  
A. M. Kristjanson ◽  
C. A. Winkler
Keyword(s):  
Activation Energies ◽  
Second Order ◽  
Exchange Reactions ◽  
First Order ◽  
Temperature Range ◽  
Iodide Ion

The exchange reactions of iodide ion with o- and p-nitroiodobenzene in the temperature range about 170°–238°C were apparently second order with activation energies of approximately 29 and 33.5 kcal. per mole respectively. In the same temperature range the exchange of iodide ion with iodobenzene and m-nitroiodobenzene appeared to be first order reactions, with activation energies of approximately 25 kcal. per mole.

Allene–methylacetylene isomerization over silica-supported cobalt and iron catalysts

1978 ◽  
Vol 56 (22) ◽  
pp. 2791-2796 ◽  
Author(s):  
C. P. Khulbe ◽  
R. S. Mann
Keyword(s):  
Reaction Mechanism ◽  
Active Sites ◽  
Iron Catalyst ◽  
Product Distribution ◽  
Energy Of Activation ◽  
Iron Catalysts ◽  
First Order ◽  
Temperature Range ◽  
Initial Reactant ◽  
First Order Kinetics

Equilibrium between allene and methylacetylene was studied over iron catalyst in the temperature range of 165 to 200 °C, with allene or methylacetylene as the initial reactant. In both cases similar equilibrium product-distribution (allene 16% and methylacetylene 84%), fairly close to the calculated value, is observed.Kinetics of allene-methylacetylene isomerization was studied between 70 and 165 °C. The order of reaction was always one and temperature independent. Both activity and calculated energy of activation (11.8 and 11.2 kcal/mol over iron and cobalt respectively) were similar for the two catalysts, suggesting that active sites for the reaction were also similar. This similarity, as well as the first order kinetics, are fully explained by a reaction mechanism based on adsorbate migration.

STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: VI. THE DECOMPOSITION OF METHYLENE DIACETATE, METHYLENE DIPROPIONATE, AND METHYLENE DIBUTYRATE

1937 ◽  
Vol 15b (5) ◽  
pp. 229-236 ◽  
Author(s):  
C. C. Coffin ◽  
W. B. Beazley
Keyword(s):  
Activation Energy ◽  
Experimental Error ◽  
Pressure Change ◽  
Reaction Rates ◽  
Reaction Velocity ◽  
First Order ◽  
Exact Position ◽  
Gas Reactions ◽  
Homogeneous Decomposition ◽  
Large Experimental Error

The homogeneous decomposition of methylene diacetate vapor to formaldehyde and acetic anhydride at temperatures between 220° and 305 °C. and at pressures ranging from several centimetres of mercury to several atmospheres has been studied. Reaction rates were determined by analytical and by pressure change methods. The first order decomposition is opposed by a second order recombination. A secondary reaction makes it impossible to determine the exact position of the resulting equilibrium. Within the rather large experimental error, methylene diacetate has the same activation energy (33,000 cal.) as its homologues. Its specific reaction velocity is smaller than that of the ethylidene esters. Methylene dipropionate and dibutyrate decompose at the same rate as the diacetate. These facts are in accord with the hypothesis that the extent to which a radical can contribute to the energy of activation is dependent upon its position in the molecule. Veolcity constants are given by the equation [Formula: see text]

Reversibly Sampling Conformations and Binding Modes Using Molecular Darting

2020 ◽  
Author(s):  
Samuel C. Gill ◽  
David Mobley
Keyword(s):  
Monte Carlo ◽  
Ligand Binding ◽  
Binding Sites ◽  
Degrees Of Freedom ◽  
Dynamics Simulation ◽  
Hiv Integrase ◽  
Binding Modes ◽  
System A ◽  
Multiple Binding ◽  
Internal Degrees Of Freedom

<div>Sampling multiple binding modes of a ligand in a single molecular dynamics simulation is difficult. A given ligand may have many internal degrees of freedom, along with many different ways it might orient itself a binding site or across several binding sites, all of which might be separated by large energy barriers. We have developed a novel Monte Carlo move called Molecular Darting (MolDarting) to reversibly sample between predefined binding modes of a ligand. Here, we couple this with nonequilibrium candidate Monte Carlo (NCMC) to improve acceptance of moves.</div><div>We apply this technique to a simple dipeptide system, a ligand binding to T4 Lysozyme L99A, and ligand binding to HIV integrase in order to test this new method. We observe significant increases in acceptance compared to uniformly sampling the internal, and rotational/translational degrees of freedom in these systems.</div>

scholarly journals High-Temperature Deformation of Naturally Aged 7010 Aluminum Alloy

Metals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 581
Author(s):  
Abdulhakim A. Almajid
Keyword(s):  
Activation Energy ◽  
Aluminum Alloy ◽  
High Temperature ◽  
Threshold Stress ◽  
Activation Energies ◽  
Temperature Deformation ◽  
High Temperature Range ◽  
Temperature Range ◽  
True Activation Energy ◽  
Two Temperatures

This study is focused on the deformation mechanism and behavior of naturally aged 7010 aluminum alloy at elevated temperatures. The specimens were naturally aged for 60 days to reach a saturated hardness state. High-temperature tensile tests for the naturally aged sample were conducted at different temperatures of 573, 623, 673, and 723 K at various strain rates ranging from 5 × 10−5 to 10−2 s−1. The dependency of stress on the strain rate showed a stress exponent, n, of ~6.5 for the low two temperatures and ~4.5 for the high two temperatures. The apparent activation energies of 290 and 165 kJ/mol are observed at the low, and high-temperature range, respectively. These values of activation energies are greater than those of solute/solvent self-diffusion. The stress exponents, n, and activation energy observed are rather high and this indicates the presence of threshold stress. This behavior occurred as a result of the dislocation interaction with the second phase particles that are existed in the alloy at the testing temperatures. The threshold stress decreases in an exponential manner as temperature increases. The true activation energy was computed by incorporating the threshold stress in the power-law relation between the stress and the strain. The magnitude of the true activation energy, Qt dropped to 234 and 102 kJ/mol at the low and high-temperature range, respectively. These values are close to that of diffusion of Zinc in Aluminum and diffusion of Magnesium in Aluminum, respectively. The Zener–Hollomon parameter for the alloy was developed as a function of effective stress. The data in each region (low and high-temperature region) coalescence in a segment line in each region.

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