Atomic and molecular oxygen collision processes over some crystalline solids

The elementary processes of atomic and molecular oxygen over the solid surfaces of graphite and β–cristobalite have been studied theoretically. The aim of the study is to widen the knowledge about the behaviour of materials used as a Thermal Protection Systems in space vehicles during its re-entry o...

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Detalles Bibliográficos
Autor: Morón Tejero, Víctor
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2011
País:España
Institución:CBUC, CESCA
Repositorio:TDR. Tesis Doctorales en Red
OAI Identifier:oai:www.tdx.cat:10803/84165
Acceso en línea:http://hdl.handle.net/10803/84165
Access Level:acceso abierto
Palabra clave:Química d'interfases
Processos de col·lisió
Catàlisi
Química de interfases
Procesos de colisión
Catálisis
Interfaces chemistry
Collision Processes
Catalysis
Ciències Experimentals i Matemàtiques
544
Descripción
Sumario:The elementary processes of atomic and molecular oxygen over the solid surfaces of graphite and β–cristobalite have been studied theoretically. The aim of the study is to widen the knowledge about the behaviour of materials used as a Thermal Protection Systems in space vehicles during its re-entry on the Earth’s atmosphere. For the oxygen interaction over graphite, a Density Functional Theory study has been carried out for the main heterogeneous elementary processes. Minima and transition states have been characterized for the atomic and molecular adsorption, as also the main features of atomic diffusion and O2 formation via Eley-Rideal and Langmuir-Hinshelwood processes. The rate constants for each of the beforementioned processes have been computed by means of the Transition State Theory and then used in a Kinetic model in order to study the overall effect of the processes occurring at the same time. This model allows estimating the atomic recombination coefficient, widely used in computational fluid dynamics simulations. In order to understand the microscopic mechanism of these processes, a dynamical study has been carried out by means of the quasiclassical trajectory method over several potential energy surfaces (PES). For the atomic interaction with the surface an analytical surface (using the Flexible Periodic Lodon-Eyring-Polanyi-Sato, FPLEPS method) and an interpolated one (using the Modified Shepard method) have been constructed. In the case of two atoms interacting with the surface, a FPLEPS surface has been used. From these calculations, reaction probabilities, scattering angles and other properties has been obtained. The dynamical study of oxygen interacting with β–cristobalite has been completed, specifically for the interaction of an oxygen atom with a precovered surface and for the molecular oxygen over a clean surface. Using these results, the reaction rate constants have been computed and used in a microkinetic model in order to understand the effect of all of the elementary processes considered at the same time. Furthermore, an estimation of the atomic recombination coefficient and the energetic accommodation coefficient has been carried out.