Reaction pathways to dimer in polystyrene pyrolysis: A mechanistic modeling study

A detailed mechanistic model for polystyrene pyrolysis was created that built on a modeling framework developed in our previous work and was used to probe three competing pathways to dimer formation: benzyl radical addition, 1,3-hydrogen shift, and 7,3-hydrogen shift, based on recent literature reports. To incorporate the chemistry involved in the 7,3-hydrogen shift pathway, the 1,7- and 7,3-hydrogen shift reaction families were added to the model. The updated version of the model tracks 75 species and over 3500 reactions. Rate parameters for all families were specified based on our previous work, more recent literature reports, and regression against limited experimental data. The model was able to accurately predict the experimental results for polystyrene pyrolysis for different reactor configurations for a temperature range of 100 °C and two orders of magnitude of initial molecular weight for experimental data collected in our own lab and from Bouster and coworkers and Bockhorn and coworkers. The results from our model were studied using net rate analysis to gain insight into the competitiveness of the various reaction pathways to dimer formation. The net rate analysis demonstrated that 7,3-hydrogen shift is the dominant reaction pathway to dimer formation at the temperatures studied. Benzyl radical addition becomes a more competitive reaction pathway as the temperature increases, which is caused predominantly by an increase in the benzyl radical concentration with increasing temperature. Overall, it is quantitatively shown that both 7,3-hydrogen shift and benzyl radical addition are important pathways for dimer formation, with their relative competitiveness influenced by temperature.     

Designing a Uniaxial Tension/Compression Test for Springback Analysis in High-Strength Steel Sheets

We describe an innovative design for an in-plane measurement technique that subjects thin sheet metal specimens to bidirectional loading. The goal of this measurement is to provide the critical performance data necessary to validate complex predictions of the work hardening behavior during reversed uniaxial deformation. In this approach, all of the principal forces applied to the specimen are continually measured in real-time throughout the test. This includes the lateral forces that are required to prevent out of plane displacements in the specimen that promote buckling. This additional information will, in turn, improve the accuracy of the compensation for the friction generated between the anti-bucking guides and the specimen during compression. The results from an initial series of experiments not only demonstrate that our approach is feasible, but that it generates data with the accuracy necessary to quantify the directionally-dependent changes in the yield behavior that occur when the strain path is reversed (i.e., the Bauschinger Effect).     

Isolation of pure disubstituted E olefins through Mo-catalyzed Z-selective ethenolysis of stereoisomeric mixtures

Monoaryloxide-pyrrolide (MAP) complexes of molybdenum were employed for the selective ethenolysis of 1,2-disubstituted Z olefins in the presence of the corresponding E olefins. Reactions were performed in the presence of 0.02-3.0 mol % catalyst at 22 °C under 20 atm ethylene. We have demonstrated that the Z isomer of an easily accessible E:Z mixture can be destroyed through ethenolysis and the E alkene thereby isolated readily in high yield and exceptional stereoisomeric purity.     

Stereocontrol of attosecond time-scale electron dynamics in ABCU using ultrafast laser pulses: a computational study

The attosecond time-scale electronic dynamics induced by an ultrashort laser pulse is computed using a multi configuration time dependent approach in ABCU (C(10)H(19)N), a medium size polyatomic molecule with a rigid cage geometry. The coupling between the electronic states induced by the strong pulse is included in the many electron Hamiltonian used to compute the electron dynamics. We show that it is possible to implement control of the electron density stereodynamics in this medium size molecule by varying the characteristics of the laser pulse, for example by polarizing the electric field either along the N-C axis of the cage, or in the plane perpendicular to it. The excitation produces an oscillatory, non-stationary, electronic state that exhibits localization of the electron density in different parts of the molecule both during and after the pulse. The coherent oscillations of the non-stationary electronic state are also demonstrated through the alternation of the dipole moment of the molecule.     

Mechanism of stereospecific polymerization of propylene with titanium trichloride–aluminum alkyl catalysts

The effect of various aluminum alkyls at varying concentrations on the rate and stereospecificity of propylene polymerizations with titanium trichloride was examined. It was concluded that dialkylaluminum halides were merely chemisorbed on the surface of the titanium trichloride while the trialkylaluminums reacted more extensively with the surface. In the case of diethylaluminum chloride standard chemisorption kinetics were observed. The rate of polymerization was also found to be a function of solvent, with certain aromatic solvents causing significant rate increases. With diethylaluminum chloride essentially no termination occurs; the polymers are “living polymers.”     

Untersuchungen in der toxikologischen Chemie

Ohne Zusammenfassung     

The weight twoK-theory of fields

We verify the weight-two portion of the Quillen-Lichtenbaum conjectures, relating the modn weight-twoK-groups of a field with the appropriate étale cohomology groups. This extends the work of Merkurjev and Suslin onK ₂ of a field, and the works of Suslin and the author on the indecomposableK ₃ of a field.Partially supported by the NSF.     

On the simultaneous measurement of position and momentum: Naimark embeddings and projections

Single and double meter simultaneous measurements of a harmonic oscillator are reviewed and compared. Naimark extensions are constructed and relevant projection properties are exhibited for both cases. The theory is extended to the simultaneous measurement of squeezed position and momentum measurements.