Concetta LaMarca

Design of kinetically coupled complex reaction systems

Abstract The reaction kinetics of multicomponent mixtures were explored through the mathematical and experimental analyses of binary pyrolysis systems. The mathematical model was of parallel Rice-Herzfeld chains that were coupled through hydrogen transfer and termination elementary steps. Analytical rate expressisons for the coupled systems led to criteria for the classification of binary interactions. This, in turn, provided rationale for “optimizing” the type of observed interaction. Experiments with the model compounds dibenzyl ether and phenethyl phenyl ether provided an experimental example of kinetically coupled Rice-Herzfeld pyrolysis chains.

Hydrolysis and oxidation in supercritical water

Abstract The continuity of the liquid and gaseous states, and the existence of critical temperatures for specific gases, was discovered by Thomas Andrews in 1861. This had important implications for the liquefaction of the supposedly ‘permanent’ gases and the creation of an important new industry. Currently, the chemistry of reactions in supercritical fluids, especially water, is the subject of much research, especially in the context of treating industrial waste.

Mechanistic Modelling of Polymer Pyrolysis Using Monte Carlo Methods

Abstract Reaction modelling techniques using Monte Carlo Simulation are applied to the reactions of poly (arylether sulfones). We find that structure, reactions and diffusions may be described quantitatively in terms of a dynamic reaction lattice.

Semiempirical rate laws for rice-Herzfeld pyrolysis of mixtures : capturing chemistry with reasonable computational burden

Mechanism-derived rate laws for kinetically coupled Rice-Herzfeld pyrolysis were used to deduce the form of semiempirical rate laws (SERLs) that nevertheless represent the mechanistic chemistry. These SERLs strike a balance between the CPU demands of mechanistic models and the lack of chemical significance of purely empirical models. The mechanism-derived pyrolysis rate laws were phrased in terms of a pure component, initiation, propagation, and termination groups, akin to the kinetic term, the driving force, the adsorption group, and exponent of Langmuir-Hinshelwood-Hougen-Watson models