Estimation method for the thermochemical properties of polycyclic aromatic molecules

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2005.Includes bibliographical references.Polycyclic aromatic molecules, including polycyclic aromatic hydrocarbons (PAHs) have attracted considerable attention in the past few decades. They are formed during the incomplete combustion of hydrocarbon fuels and are precursors of soot. Some PAHs are known carcinogens, and control of their emissions is an important issue. These molecules are found in many materials, including coal, fuel oils, lubricants, and carbon black. They are also implicated in the formation of fullerenes, one of the most. chemically versatile class of molecules known. Clearly, models that provide predictive capability for their formation and growth are highly desirable. Thlermochemical properties of the species in the model are often the most important parameter, particularly for high temperature processes such as the formation of PAH and other aromatic molecules. Thermodynamic consistency requires that reverse rate constants be calculated from the forward rate constants and from the equilibrium constants. The later are obtained from the thermochemical properties of reactants and products. The predictive ability of current kinetic models is significantly limited by the scarcity of available thermochemical data.(cont.) In this work we present the development of a Bond-Centered Group Additivity method for the estimation of the thermochemical properties of polycyclic aromatic molecules, including PAHs, molecules with the furan substructure, molecules with triple bonds, substituted PAHs, and radicals. This method is based on thermochemical values of about two hundred polycyclic aromatic molecules and radicals obtained from quantum chemical calculations at the B3LYP/6-31G(d) level. A consistent set of homodesmic reactions has been developed to accurately calculate the heat of formation from the absolute energy. The entropies calculated from the B3LYP/6-31G(d) vibrational frequencies are shown to be at least as reliable as the few available experimental values. This new Bond-Centered Group Additivity method predicts the thermochemistry of C₆₀ and C₇₀ fullerenes, as well as smaller aromatic molecules, with accuracy comparable to both experiments and the best quantum calculations. This Bond-Centered Group Additivity method is shown to extrapolate reasonably to infinite graphene sheets.(cont.) The Bond-Centered Group Additivity method has been implemented into a computer code within the automatic Reaction Mechanism Generation software (RMG) developed in our group. The database has been organized as a tree structure, making its maintenance and possible extension very straightforward. This computer code allows the fast and easy use of this estimation method by non-expert users. Moreover, since it is incorporated into RMG, it will allow users to generate reaction mechanisms that include aromatic molecules whose thermochemical properties are calculated using the Bond-Centered Group Additivity method. Exploratory equilibrium studies were performed (l. Equilibrium concentrations of individual species depend strongly on the thermochemistry of the individual species, emphasizing the importance of consistent thermochemistry for all the species involved in the calculations. Equilibrium calculations can provide many interesting insights into the relationship between PAH and fullerenes in combustion.by Joanna Yu.Ph.D

The 21st Annual International Conference on Soils, Sediments and Water

Conference at a Glance Monday, October 17, 2005 Workshops (Workshops #1 and #2: 10:00am - 5:00pm; Workshop #3: 1:00 - 5:00pm; Workshop #4: 1:00 - 3:00pm, Workshop #5: 2:00 - 5:00pm) 1) Theory and Use of Field Portable X-ray Fluorescence for Soil Analysis 2) In-Situ Chemical Oxidation Workshop 3) The Role of Anaerobic Biodegradation Processes in Passive and Enhanced Monitored Natural Attenuation Programs 4) Application of Classic and Emerging Techniques in Environmental Forensics 5) Environmental Fate of Hydrocarbons in Soils and Groundwater Tuesday, October 18, 2005 Platform Presentations 8:30am – Noon Session 1: Environmental Biotechnology Session 2: Ecological Restoration and Natural Treatment Systems Session 3: Pesticides (10:30am – Noon) Session 4: Heavy Metals 1:30 – 5:30pm Session 1: Arsenic Session 2: Bioremediation Session 3: Bioremediation Strategies for Contaminated Soils and Sediments Session 4: Ozone Poster Session 4:00 – 6:00pm, Exhibit Area, First Floor, Campus Center Social 4:30-6:00pm, Exhibit Area, First Floor, Campus Center Workshops 7:00 - 10:00pm 6) Applied Environmental Forensics Workshop 7) Massachusetts Contingency Plan Method 2 Risk Characterizations Wednesday, October 19, 2005 Platform Presentations 8:30am – Noon Session 1: Perchlorate: Emerging Issues and Innovative Remedial Approaches Session 2: Soil Geochemical Background on a Continental Scale Session 3a: Environmental Fate Session 3b: Risk Assessment Session 4: Environmental Stewardship and Proactive Management at Small Arms Ranges 1:30 – 5:30pm Session 1: Ecoterrorism: Research Issues Session 2: Environmental Forensics Session 3a: Legal/Regulatory Session 3b: MTBE Session 4: Bioremediation of Acid Mine Drainage Wastes Poster Session 4:00 – 6:00pm Exhibit Area, First Floor, Campus Center Social 4:30-6:00pm, Exhibit Area, First Floor, Campus Center Workshops 7:00 - 10:00pm 8) In-Situ Thermal Remediation 9) Perchlorate: The Path to Regulatory Standards Setting and Future Assessment & Cleanup Implications 10) NIMS (National Incident Management System) and the Environment Thursday, October 20, 2005 Platform Presentations 8:30am – Noon Session 1: Evolving Strategies for Dealing with Contaminated Sediments Session 2: Pay-for-Performance Remediation Technologies - Methods & Case Studies of Science & Economics Session 3: Phytoremediation Session 4: Site Assessment 1:30 – 5:30pm Session 1: Remediation Session 2: Chemical Oxidation Session 3a: Analysis Session 3b: Indoor Ai

Zeolites and ordered porous solids: fundamentals and applications

Pérez Pariente, J.; Martínez Sánchez, MC. (2011). Zeolites and ordered porous solids: fundamentals and applications. Editorial Universitat Politècnica de València. http://hdl.handle.net/10251/11205Archivo delegad

Bioremediation of Petroleum Hydrocarbon-Contaminated Soils, Comprehensive Report

The US Department of Energy and the Institute for Ecology of Industrial Areas, Katowice, Poland have been cooperating in the development and implementation of innovative environmental remediation technologies since 1995. U.S. experts worked in tandem with counterparts from the IETU and CZOR throughout this project to characterize, assess and subsequently, design, implement and monitor a bioremediation system

Polycyclic- and sulfurcontaining-compounds: from polycyclic hydrocarbons to thiaspherophane

This thesis contains the examination of four, in first glance, unrelated topics. However, the overarching motivation behind these subjects are the same: The Art and Challenge of Organic Chemistry. I. The first chapter deals with the design, based on theoretical principles, and preparation of unsaturated spirocyclic compounds bearing sulfur functionalities with the aim of elucidating the charge-transport properties of such molecules on the level of single molecules. In collaboration with the Group of Professor Herre van der Zant from the Delft University of Technology preliminary conductance measurements of such spirocyclic structures could be gathered. The motivation for this joint endeavor is the prospect of using such spirocyclic structures as a molecular switch for the construction of molecular electronic devices. II. The second part shows our engagement in the long tradition among organic chemist to challenge our abilities to synthesize inspiring, complex and aesthetical pleasing structures. One such structure was identified by employing predictive computational methods by the group of Professor Jean-Louis Reymond. The structure of interest was recognized as one of the last three remaining and not yet synthesized fully-cyclic C11 isomers without strain. Encouraged by this finding, we accepted the challenge to synthesize this tetracyclic saturated hydrocarbon with the molecular formula C11H16 with the proposed trivial name of trinorbornane. III. Thirdly, Thiaspherophane: A highly symmetrical structure consisting of eight benzene rings bridged over twelve sulfur atoms describing a cuboctahedron: one of the 13 Archimedean solids. This elusive molecule, predicted over 25 years ago, bears the potential of being transformed into a cryptatium. Our efforts and progress on the synthesis of thiaspherophane will be discussed. IV. Unsymmetrical disulfides are ubiquitous in the field of chemistry and at the interface with physics, where nanotechnology emerges. In this chapter, our investigation of an efficient method for the preparation of unsymmetrical disulfides will be presented Whereby the potential of this method for the formation of functional units bearing multiple unsymmetrical disulfides was assessed with the aim of using these compounds for functionalization of gold surfaces