A COMPARISON OF SLATER'S THEORY OF UNIMOLECULAR REACTIONS WITH EXPERIMENTAL DATA

1959 ◽  
Vol 37 (6) ◽  
pp. 1035-1037 ◽  
Author(s):  
Everett Thiele ◽  
David J. Wilson
Keyword(s):  
Experimental Data ◽  
High Pressure ◽  
Lower Bounds ◽  
Rate Constant ◽  
Unimolecular Reactions ◽  
Pressure Limit ◽  
Nitrogen Pentoxide ◽  
Simplified Method ◽  
Experimental Values

Slater's theory of unimolecular reactions is tested by comparing theoretical and experimental values of the pressure at which the rate constant has fallen off from the high-pressure limit by 5%. A simplified method is used for calculating lower bounds to the theoretical value of this pressure. Agreement with experimental data on cyclobutane, cyclobutene, and nitrogen pentoxide is rather poor; experimental values are lower than the calculated lower bounds.

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.

scholarly journals A computational study of the fluctional behaviour of group 14 substituted ortho-semiquinone radicals

2011 ◽  
Vol 89 (2) ◽  
pp. 235-240 ◽  
Author(s):  
K. U. Ingold ◽  
Gino A. DiLabio
Keyword(s):  
Experimental Data ◽  
Density Functional Theory ◽  
Rate Constant ◽  
Density Functional ◽  
Computational Study ◽  
Group 14 ◽  
Functional Theory ◽  
Semiquinone Radicals ◽  
Experimental Values ◽  
Good Agreement

The dynamics of the 1,4-migration of some O-substituted 3,5-di-tert-butyl-ortho-semiquinone radicals have been calculated by density-functional theory (DFT). There is very good agreement in the rate constant and Arrhenius parameters between these calculations and experimental values for migration of H, D, and the Me3Si group. For the Me3Sn group, the calculations indicate an incredibly fast migration (k293K = 2.0 × 1012 s–1), a result that is consistent with experimental data (k293K > 109 s–1). Other O-substituents examined by DFT and compared with experimental data were H3C and Me2ClSn.

THE HIGH PRESSURE LIMIT OF UNIMOLECULAR REACTIONS

1961 ◽  
Vol 65 (2) ◽  
pp. 373-373 ◽  
Author(s):  
M. C. Flowers ◽  
H. M. Frey
Keyword(s):  
High Pressure ◽  
Unimolecular Reactions ◽  
Pressure Limit

scholarly journals Applicability of Different Isothermal EOS at Nanomaterials

2013 ◽  
Vol 2013 ◽  
pp. 1-9
Author(s):  
Deepika P. Joshi ◽  
Anjali Senger
Keyword(s):  
Experimental Data ◽  
High Pressure ◽  
Pressure Range ◽  
Theoretical Study ◽  
Isothermal Bulk Modulus ◽  
Relative Compression ◽  
Experimental Values ◽  
Murnaghan Equation ◽  
Two Parameter ◽  
Good Agreement

The present study explains the behaviour of nanomaterials such as AlN, CdSe, Ge, WC, and Ni- and Fe-filled-MWCNTs under high pressure. Among the number of isothermal EOSs available, we prefer only two parameter-based isothermal equations (i.e., Murnaghan equation, usual Tait's equation, Suzuki equation and Shanker equation). The present work shows the theoretical study of thermo-elastic properties especially relative compression (V/V0), isothermal bulk modulus (KP/K0), and compressibility (αP/α0) of nanomaterials. After comparing all formulations with available experimental data, we conclude that pressure dependence of relative compression (V/V0) for the nanomaterials, are in good agreement for all the equations at lower pressure range. At higher pressure range, Suzuki and Shanker formulations show some deviation from experimental values.

A CONTRIBUTION TO THE QUALITATIVE GC ANALYSIS OF SOME NON-CHLORINATED XENOBIOTIC CHEMICALS IN WASTE WATERS

1994 ◽  
Vol 30 (3) ◽  
pp. 91-93 ◽  
Author(s):  
Biljana D. Škrbic ◽  
Mirjana B. Vojinovic-Miloradov
Keyword(s):  
Experimental Data ◽  
Stationary Phases ◽  
Retention Indices ◽  
Waste Waters ◽  
Gc Analysis ◽  
Experimental Values ◽  
Xenobiotic Chemicals

Gas chromatographic unified retention indices of some chlorinated xenobiotic chemicals, as pollutants in waste waters, on OV-101 and SE-30 stationary phases are presented. These values agree well with the corresponding experimental values used in the statistical treaunent of the experimental data.

scholarly journals An Additive Model to Predict the Rheological and Mechanical Properties of Polypropylene Blends Made by Virgin and Reprocessed Components

Recycling ◽  
2021 ◽  
Vol 6 (1) ◽  
pp. 2
Author(s):  
Francesco Paolo La Mantia ◽  
Maria Chiara Mistretta ◽  
Vincenzo Titone
Keyword(s):  
Experimental Data ◽  
Mechanical Properties ◽  
Additive Model ◽  
Industrial Process ◽  
Theoretical Predictions ◽  
Experimental Values ◽  
Polypropylene Blends ◽  
Polypropylene Sample

In this work, an additive model for the prediction of the rheological and mechanical properties of monopolymer blends made by virgin and reprocessed components is proposed. A polypropylene sample has been reprocessed more times in an extruder and monopolymer blends have been prepared by simulating an industrial process. The scraps are exposed to regrinding and are melt reprocessed before mixing with the virgin polymer. The reprocessed polymer is, then, subjected to some thermomechanical degradation. Rheological and mechanical experimental data have been compared with the theoretical predictions. The results obtained showed that the values of this simple additive model are a very good fit for the experimental values of both rheological and mechanical properties.

scholarly journals Correction and accuracy improvement of non-parallel shear zone model

2018 ◽  
Vol 207 ◽  
pp. 02002
Author(s):  
Yaoke Wang ◽  
Meng Kou ◽  
Wei Ding ◽  
Huan Ma ◽  
Liangshan Xiong
Keyword(s):  
Experimental Data ◽  
Cutting Force ◽  
Shear Zone ◽  
Coordinate Transformation ◽  
Chip Thickness ◽  
Zone Model ◽  
Aisi 1045 Steel ◽  
Aisi 1045 ◽  
Experimental Values ◽  
1045 Steel

When applying the non-parallel shear zone model to predict the cutting process parameters of carbon steel workpiece, it is found that there is a big error between the prediction results and the experimental values. And also, the former approach to obtain the relevant cutting parameters of the non-parallel shear zone model by applying coordinate transformation to the parallel shear zone model has a theoretical error – it erroneously regards the determinant (|J|) of the Jacobian matrix (J) in the coordinate transformation as a constant. The shape of the shear zone obtained when |J| is not constant is drew and it is found that the two boundaries of the shear zone are two slightly curved surfaces rather than two inclined planes. Also, the error between predicted values and experimental values of cutting force and cutting thrust is slightly smaller than that of constant |J|. A corrected model where |J| is a variable is proposed. Since the specific values of inclination of the shear zone (α, β), the thickness coefficient of the shear zone (as) and the constants related to the material (f0, p) are not given in the former work, a method to obtain the above-mentioned five constants by solving multivariable constrained optimization problem based on experimental data was also proposed; based on the obtained experimental data of AISI 1045 steel workpiece cutting force, cutting thrust, chip thickness, the results of five above-mentioned model constants are obtained. It is found that, compared with prediction from uncorrected model, the cutting force and cutting thrust of AISI 1045 steel predicted by the corrected model with the obtained constants has a better agreement with the experimental values obtained by Ivester.

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