Cette thèse propose une approche de modélisation d'un processus adaptatif et itératif de collecte des données, ainsi qu'un outil de validation via des indicateurs d'efficacité opérationnelle de l'équipement. Une approche nommée "Tropos", établie grâce à la théorie de l'information, est donc développée pour modéliser et évaluer le processus de collecte de données. L'approche, originale, permet de synthétiser trois indicateurs qui caractérisent l'efficacité du processus de collecte : 1) utilité des données, 2) complexité du processus, 3) gain d'information par une activité élémentaire du processus. Un modèle original, basé sur les réseaux de Pétri stochastiques colorés couplé à la simulation Monte Carlo, est également proposé pour valider l'efficacité du processus de collecte de données. Ce modèle utilise comme données d'entrée les modèles des processus stochastiques de dégradation, de défaillance et de maintenance des composants de l'équipement. Les paramètres des modèles d'entrée sont supposés connus et extraits des données collectées. Les propriétés du modèle réseau de Pétri stochastique coloré permettent d'extraire les coupes minimales indispensables à l'évaluation de l'état et de l'efficacité opérationnelle de l'équipement. Elles permettent également de traiter les systèmes de structure k/n. L'effectivité de l'approche proposée est enfin illustrée sur un système de production d'énergie multi-source renouvelable, grâce à l'implémentation des algorithmes du modèle sous le logiciel Silab / This thesis proposes a modeling approach of an adaptive and iterative data collection process, and a validation tool via operational effectiveness features for equipment. An approach, named "Tropos", established based on the information theory, is developed to modeling and evaluating data collection processes. This is an original approach, which allows synthesizing three features that characterize the effectiveness of a data collection process: 1) data usefulness, 2) process complexity, 3) gain of information by a basic process activity. An original model, based on colored stochastic Petri nets coupled to the Monte Carlo simulation, has also been developed to validate the effectiveness of the data collection process. This model uses as input, stochastic process models of degradation, of failure and of maintenance of equipment components. The input parameters of the models are assumed to be known and obtained from the collected data. The properties of colored stochastic Petri net model are also used to derive the minimum cuts required to assess the equipment condition and operational effectiveness. These properties also allow to treating systems of k/n structures. The effectiveness of the proposed approach is finally illustrated on a multi-source renewable energy production system, by implementing the algorithms of the model under the Silab software environment

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-08-11T20:35:45Z No. of bitstreams: 1 CleberPereira.pdf: 3089056 bytes, checksum: ab85b5af73443dbf91e821cbac7192ab (MD5) / Made available in DSpace on 2017-08-11T20:35:45Z (GMT). No. of bitstreams: 1 CleberPereira.pdf: 3089056 bytes, checksum: ab85b5af73443dbf91e821cbac7192ab (MD5) Previous issue date: 2010-08-09 / The proposed modeling system for assessing undergraduate degree courses, according to the parameters required by ENADE emerges from the need of the IES adjust its methodology and assessment procedures to the terms set by the exam. The proposed solution does not address a specific undergraduate course and may be applied for any knowledge area. The use of software agents is justified on the grounds of a classical computer application not being able to adapt to the reality of each student, delivering the second behavioral questions identified during the evaluation process.The statistics generated from this reasoning will serve both for students and for teachers in order to reevaluate the teaching and learning process. The modeling was performed according to the UML 2.0 TROPOS methodology was used for the modeling of agents and their implementation was done in JADE. / A proposta de modelagem de sistema de avaliação dos cursos superiores de graduação, segundo os parâmetros exigidos pelo ENADE, emerge da necessidade das IES adequarem sua metodologia e procedimentos de avaliação aos moldes estabelecidos pelo exame. A solução proposta não se dirige a um curso específico de graduação, podendo ser utilizada para qualquer área do conhecimento. O uso de agentes de software em seu desenvolvimento justifica-se em razão de uma aplicação computacional clássica não ser capaz de adaptar-se à realidade de cada aluno, entregando quesitos segundo o comportamento identificado durante o processo de avaliação. As estatísticas geradas a partir deste raciocínio servirão tanto para os alunos como para os docentes no sentido de reavaliar o processo de ensino aprendizagem. A modelagem foi efetuada segundo a UML 2.0, foi utilizada a metodologia TROPOS para a modelagem dos agentes e sua implementação foi realizada no JADE.

Submitted by admin tede (tede@pucgoias.edu.br) on 2017-10-10T16:57:14Z No. of bitstreams: 1 Telmo De Maia Pimentel.pdf: 328271 bytes, checksum: ccfc3c3b41c19e7ccdc6f8b5528cd6f4 (MD5) / Made available in DSpace on 2017-10-10T16:57:14Z (GMT). No. of bitstreams: 1 Telmo De Maia Pimentel.pdf: 328271 bytes, checksum: ccfc3c3b41c19e7ccdc6f8b5528cd6f4 (MD5) Previous issue date: 2010-08-01 / The following study intends highlight a reading of the book Os Sertões by Euclides da Cunha, in which We will bring to the surface, among other critical concerns, problems of fiction, generally reflected and elaborated in the modern novel, the closed relationship between History and Literature, as well as the passage of history to the narrative-fictional . Added to this, we will discuss dessemantization of the word, emptying the code, the tropes of speech or change of direction that was focused on the facts, so we can verify as that the metaphorical aspect involves the three parts of the book, "Earth, Man and Fight. Our intention is to shed light on the literariness in Os Sertões, as the euclidean narrator driven by rare artistic talent deals with the backcountry imaginary, Antonio Conselheiro and the Republic so that we can detect certain convictions before us unfathomable in the light of the historiographical discourse, but that, using the mythical and fictional discourse, new hypotheses are suggested, as the reasons of non delivery, no surrender, heroism, fundamentalism as present in the analyzed work. Thus, we propose a possible reading in a work whose complexity analysis and discussion is an impassable ocean, inexhaustible, capable of transcending time and history itself. / O estudo a seguir se trata de uma leitura da obra Os Sertões de Euclides da Cunha na qual traremos à tona, dentre outras preocupações da crítica, os problemas da ficção, de modo geral refletidos e elaborados no romance moderno, a estreita relação entre a História e a Literatura, bem como, a passagem do histórico para o narrativo-historial. Somado a isso, iremos discutir a dessemantização da palavra, o esvaziamento do código, os tropos do discurso ou a mudança de direção que houve no enfoque dos fatos, para então podermos verificar todo aspecto metafórico que envolve as três partes da obra, “Terra, Homem e Luta”. Nosso intuito é lançar luzes sobre a literariedade em Os Sertões, de como o narrador euclidiano, movido por raríssimo talento artístico aborda a questão do imaginário do sertanejo, de Antônio Conselheiro e da República a fim de que possamos detectar certas convicções que se nos apresentam insondáveis à luz do discurso historiográfico, mas que, recorrendo ao discurso mítico-romanesco, novas hipóteses são aventadas, como os porquês da não entrega, da não rendição, do heroísmo, do fundamentalismo tão presentes na obra em análise. Destarte, propomos uma possibilidade de leitura em uma obra cuja complexidade de análise e discussão é um oceano intransponível e inesgotável, capaz de transcender o tempo e a própria História.

This thesis presents a preliminary goal oriented modeling of situation awareness in a command and control system. Tropos, an agent oriented software development methodology, has been used for modeling. Use of Tropos allows us to represent, at the knowledge level, the Command and Control actors along with their goals and interdependencies. Through refinement we aim to derive an architectural design for the Situation Awareness component of an Air Defense Command and Control system. This work suggests that goal oriented methodologies can be successfully used in the modeling of the complex systems at the requirement analysis phase. By analyzing dependencies between Command and Control entities, it should be possible to improve the modularity of the Command and Control system architecture.

Made available in DSpace on 2014-06-11T19:29:40Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-04Bitstream added on 2014-06-13T18:59:21Z : No. of bitstreams: 1 derossi_lh_me_sjrp.pdf: 1783577 bytes, checksum: 3017df90989f2b4b05b6bc1d87eb42ce (MD5) / Nas últimas duas décadas, diversos sistemas de ensino para Web foram desenvolvidos e amplamente utilizados. Com o surgimento da Web Semântica, a qual integra os conceitos da Web e da área de Inteligência Artificial, foi possível conceber novos sistemas de ensino, os Sistemas de Ensino Baseados na Web Semântica (Semantic Web-based Educational Systems - SWBES). Os SWBES são caracterizados por representar o conteúdo e o conhecimento na forma de ontologias e contar com agentes inteligentes que permitem às máquinas entenderem o conteúdo publicado na Web. Neste trabalho são apresentados e discutidos os padrões arquiteturais utilizados para desenvolvimento dos sistemas baseados na Web Semântica, em especial os sistemas educacionais. Como resultado do estudo é proposta uma arquitetura para os SWBES. As arquiteturas dos SWBES que utilizam a abordagem multiagente, normalmente, são concebidas de forma empírica, ou seja, apenas com a experiência do seu desenvolvedor. Neste trabalho, para a concepção do modelo multiagentes adotado na arquitetura do SWBES, foi utilizada uma metodologia de desenvolvimento de sistemas multiagentes, o framework Tropos. São apresentadas as fases do framework Tropos para o projeto de um modelo multiagentes utilizado na arquitetura de um SWBES. Utilizando a arquitetura desenvolvida foi implementado um SWBES. Para estudo de caso dessa arquitetura, foi realizada uma implementação de um Sistema de Ensino de Rochas Carbonáticas. Para esse sistema foram definidas três ontologias: ontologia de Domínio de Rochas Carbonáticas, ontologia de Perfil e ontologia de Material de Aprendizagem. Os comportamentos dos agentes e as interações entre eles são detalhadas. Finalmente, é apresentado um estudo de casos da utilização do sistema no ensino do curso de Rochas Carbonáticas / In the past two decades, several Web educational systems were designed and widely used. With the appearing of the Semantic Web, which integrates Web and Artificial Intelligence area concepts, it was possible to conceive new educational concepts, the Educational Systems Based on the Semantic Web (Semantic Web-based Educational Systems - SWBES). The SWBES represent the content and the knowledge in the form of ontology and count on intelligent agents that allow machines understand the content published on the web. In this work, architectural standards used to develop new systems based on the Semantic Web will be presented and discussed, especially the educational ones. As a result of this study, it is proposed the architecture for the SWBES. The architecture for the SWBES that use multi-agent approach generally is conceived empirically, that is, only with its developer experience. In this work, for the conception of the multi-agents model adopted in the architecture of the SWBES, a methodology of multi-agents systems development was used, the Tropos framework. The phases of Tropos framework for the project of a multi-agent model used in the architecture of SWBES are presented. A SWBES was implemented by using the architecture that was developed. For the study case of this architecture, it was held an implementation of the Educational System of Carbonate Rock. For this system, three ontologies were defined: Domain Ontology of Carbonate Rocks, Profile Ontology and Learning Material Ontology. The behavior of agents and interaction among them are detailed

Made available in DSpace on 2016-08-17T14:53:15Z (GMT). No. of bitstreams: 1 Fernando Pinheiro Costa Junior.pdf: 2747809 bytes, checksum: 341087c9b5282e045ab5af119473be1e (MD5) Previous issue date: 2010-12-13 / The present study attempts, through the methodology TROPOS, modeling a Multi- Agent System for Stock Exchange whose goal is make negotiations among agents in a Virtual Stock Exchange. The agents will act as investors in the Stock Market making the purchase and sale of stocks. This model is intended to specify agents with the ability to decide the best time for investing according to market indicators, i.e., when is the better time to buy or sell stocks. The model can identify the agents, the interaction protocols between agents, the applied technologies and the structures of the application. Therefore, the JADE platform will support the development of agents regarding the negotiation process. Such platform will provide communication between agents creating Broker Agents to provide communication with other Intermediate Agents whose information is collected in its Knowledge Base in order to make the negotiation. The after examining this study, conclusions could be taken about the subject explained and future suggested improvements can be implemented. / O presente trabalho busca, através da metodologia TROPOS, modelar um Sistema Multi-Agente para Bolsa de Valores com o objetivo de realizar negociações entre agentes em uma Bolsa de Valores virtual. Os agentes irão desempenhar a função de investidores na Bolsa de Valores, efetuando operações de compra e venda de ações. Esta modelagem tem o propósito de especificar agentes com a capacidade de decidir qual o melhor momento para realização dos investimentos pautado nos indicadores de mercado, ou seja, qual a melhor hora para comprar ou vender títulos de créditos. Neste sentido, serão identificados os agentes, os protocolos de interação entre agentes, as tecnologias aplicadas, as estruturas da aplicação. Portanto, a plataforma JADE dará suporte para o desenvolvimento dos agentes no tocante ao processo de negociação. Tal plataforma proporcionará a comunicação entre os agentes, criando Agentes Corretores a fim de proporcionar a comunicação com outro Agente Intermediário com as informações adquiridas em sua Base de Conhecimento para que assim seja realizada a negociação. Assim, após a análise desta obra poderão ser retiradas conclusões acerca do tema explanado e sugeridas melhorias para que no futuro possam ser implementadas.

Resumo: Nas últimas duas décadas, diversos sistemas de ensino para Web foram desenvolvidos e amplamente utilizados. Com o surgimento da Web Semântica, a qual integra os conceitos da Web e da área de Inteligência Artificial, foi possível conceber novos sistemas de ensino, os Sistemas de Ensino Baseados na Web Semântica (Semantic Web-based Educational Systems - SWBES). Os SWBES são caracterizados por representar o conteúdo e o conhecimento na forma de ontologias e contar com agentes inteligentes que permitem às máquinas entenderem o conteúdo publicado na Web. Neste trabalho são apresentados e discutidos os padrões arquiteturais utilizados para desenvolvimento dos sistemas baseados na Web Semântica, em especial os sistemas educacionais. Como resultado do estudo é proposta uma arquitetura para os SWBES. As arquiteturas dos SWBES que utilizam a abordagem multiagente, normalmente, são concebidas de forma empírica, ou seja, apenas com a experiência do seu desenvolvedor. Neste trabalho, para a concepção do modelo multiagentes adotado na arquitetura do SWBES, foi utilizada uma metodologia de desenvolvimento de sistemas multiagentes, o framework Tropos. São apresentadas as fases do framework Tropos para o projeto de um modelo multiagentes utilizado na arquitetura de um SWBES. Utilizando a arquitetura desenvolvida foi implementado um SWBES. Para estudo de caso dessa arquitetura, foi realizada uma implementação de um Sistema de Ensino de Rochas Carbonáticas. Para esse sistema foram definidas três ontologias: ontologia de Domínio de Rochas Carbonáticas, ontologia de Perfil e ontologia de Material de Aprendizagem. Os comportamentos dos agentes e as interações entre eles são detalhadas. Finalmente, é apresentado um estudo de casos da utilização do sistema no ensino do curso de Rochas Carbonáticas / Abstract: In the past two decades, several Web educational systems were designed and widely used. With the appearing of the Semantic Web, which integrates Web and Artificial Intelligence area concepts, it was possible to conceive new educational concepts, the Educational Systems Based on the Semantic Web (Semantic Web-based Educational Systems - SWBES). The SWBES represent the content and the knowledge in the form of ontology and count on intelligent agents that allow machines understand the content published on the web. In this work, architectural standards used to develop new systems based on the Semantic Web will be presented and discussed, especially the educational ones. As a result of this study, it is proposed the architecture for the SWBES. The architecture for the SWBES that use multi-agent approach generally is conceived empirically, that is, only with its developer experience. In this work, for the conception of the multi-agents model adopted in the architecture of the SWBES, a methodology of multi-agents systems development was used, the Tropos framework. The phases of Tropos framework for the project of a multi-agent model used in the architecture of SWBES are presented. A SWBES was implemented by using the architecture that was developed. For the study case of this architecture, it was held an implementation of the Educational System of Carbonate Rock. For this system, three ontologies were defined: Domain Ontology of Carbonate Rocks, Profile Ontology and Learning Material Ontology. The behavior of agents and interaction among them are detailed / Orientador: Ivan Rizzo Guilherme / Coorientador: Simone das Graças Domingues Prado / Banca: Hilda Carvalho de Oliveira / Banca: Flávia Linhalis Arantes / Mestre

The ubiquitous abundance of organic compounds in natural and anthorpogenically influenced eco-systems has put these compounds into the focus of atmospheric research. Organic compounds have an impact on air quality, climate, and human health. Moreover, they affect particle growth, secondary organic aerosol (SOA) formation, and the global radiation budget by altering particle properties. To investigate the multiphase chemistry of organic compounds and interactions with the aqueous phase in the troposphere, modelling can provide a useful tool. The oxidation of larger organic molecules to the final product CO2 can involve a huge number of intermediate compounds and tens of thousands of reactions. Therefore, the creation of explicit mechanisms relies on automated mechanism construction. Estimation methods for the prediction of the kinetic data needed to describe the degradation of these intermediates are inevitable due to the infeasibility of an experimental determination of all necessary data. Current aqueous phase descriptions of organic chemistry lag behind the gas phase descriptions in atmospheric chemical mechanisms despite its importance for the multiphase chemistry of organic compounds. In this dissertation, the gas phase mechanism Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) has been advanced by a protocol for the description of the oxidation of organic compounds in the aqueous phase. Therefore, a database with kinetic data of 465 aqueous phase hydroxyl radical and 129 aqueous phase nitrate radical reactions with organic compounds has been compiled and evaluated. The database was used to evaluate currently available estimation methods for the prediction of aqueous phase kinetic data of reactions of organic compounds. Among the investigated methods were correlations of gas and aqueous kinetic data, kinetic data of homologous series of various compound classes, reactivity comparisons of inorganic radical oxidants, Evans-Polanyi-type correlations, and structure-activity relationships (SARs). Evans-Polanyi-type correlations have been improved for the purpose of automated mechanism self-generation of mechanisms with large organic molecules. A protocol has been designed based on SARs for hydroxyl radical reactions and the improved Evans-Polanyi-type correlations for nitrate radical reactions with organic compounds. The protocol was assessed in a series of critical sensitivity studies, where uncertainties of critical parameters were investigated. The advanced multiphase generator GECKO-A was used to generate mechanisms, which were applied in box model studies and validated against two sets of aerosol chamber experiments. Experiments differed by the initial compounds used (hexane and trimethylbenzene) and the experimental conditions (UV-C lights off/on and additional in-situ hydroxyl radical source no/yes). Reasonable to good agreement of the modelled and experimental results was achieved in these studies. Finally, GECKO-A was used to create two new CAPRAM version, where, for the first time, branchingratios for different reaction pathways were introduced and the chemistry of compounds with up to four carbon atoms has been extended. The most detailed mechanism comprises 4174 compounds and 7145 processes. Detailed investigations were performed under real tropospheric conditions in urban and remote continental environments. Model results showed significant improvements, especially in regard to the formation of organic aerosol mass. Detailed investigations of concentration-time profiles and chemical fluxes refined the current knowledge of the multiphase processing of organic compounds in the troposphere, but also pointed at current limitations of the generator protocol, the mechanisms created, and current understanding of aqueous phase processes of organic compounds. / Das zahlreiche Vorkommen organischer Verbindungen in natürlichen und anthropogen beeinflussten Ökosystemen hat diese Verbindungen in den Fokus der Atmosphärenforschung gerückt. Organische Verbindungen beeinträchtigen die Luftqualität, die menschliche Gesundheit und das Klima. Weiterhin werden Partikelwachstum und -eigenschaften, sekundäre organische Partikelbildung und dadurch der globale Strahlungshaushalt durch sie beeinflusst. Um die troposphärische Multiphasenchemie organischer Verbindungen und Wechselwirkungen mit der Flüssigphase zu untersuchen, sind Modellstudien hilfreich. Die Oxidation großer organischer Moleküle führt zu einer Vielzahl an Zwischenprodukten. Der Abbau erfolgt in unzähligen Reaktionen bis hin zum Endprodukt CO2. Bei der Entwicklung expliziter Mechanismen muss deshalb für diese Verbindungen auf computergestützte, automatisierte Methoden zurückgegriffen werden. Abschätzungsmethoden für die Vorhersage kinetischer Daten zur Beschreibung des Abbaus der Zwischenprodukte sind unabdingbar, da eine experimentelle Bestimmung aller benötigten Daten nicht realisierbar ist. Die derzeitige Beschreibung der Flüssigphasenchemie unterliegt deutlich den Beschreibungen der Gasphase in atmosphärischen Chemiemechanismen trotz deren Relevanz für die Multiphasenchemie. In dieser Arbeit wurde der Gasphasenmechanismusgenerator GECKO-A (“Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere”) um ein Protokoll zur Oxidation organischer Verbindungen in der Flüssigphase erweitert. Dazu wurde eine Datenbank mit kinetischen Daten von 465 Hydroxylradikal- und 129 Nitratradikalreaktionen mit organischen Verbindungen angelegt und evaluiert. Mit Hilfe der Datenbank wurden derzeitige Abschätzungsmethoden für die Vorhersage kinetischer Daten von Flüssigphasenreaktionen organischer Verbindungen evaluiert. Die untersuchten Methoden beinhalteten Korrelationen kinetischer Daten aus Gas- und Flüssigphase, homologer Reihen verschiedener Stoffklassen, Reaktivitätsvergleiche, Evans-Polanyi-Korrelationen und Struktur-Reaktivitätsbeziehungen. Für die Mechanismusgenerierung großer organischer Moleküle wurden die Evans-Polanyi-Korrelationen in dieser Arbeit weiterentwickelt. Es wurde ein Protokol für die Mechanismusgenerierung entwickelt, das auf Struktur-Reaktivitätsbeziehungen bei Reaktionen von organischen Verbindungen mit OH-Radikalen und auf den erweiterten Evans-Polanyi-Korrelationen bei NO3-Radikalreaktionen beruht. Das Protokoll wurde umfangreich in einer Reihe von Sensitivitätsstudien getestet, um Unsicherheiten kritischer Parameter abzuschätzen. Der erweiterte Multiphasengenerator GECKO-A wurde dazu verwendet, neue Mechanismen zu generieren, die in Boxmodellstudien gegen Aerosolkammerexperimente evaluiert wurden. Die Experimentreihen unterschieden sich sowohl in der betrachteten Ausgangssubstanz (Hexan und Trimethylbenzen) und dem Experimentaufbau (ohne oder mit UV-C-Photolyse und ohne oder mit zusätzlicher partikulärer Hydroxylradikalquelle). Bei den Experimenten konnte eine zufriedenstellende bis gute Übereinstimmung der experimentellen und Modellergebnisse erreicht werden. Weiterhin wurde GECKO-A verwendet, um zwei neue CAPRAM-Versionen mit bis zu 4174 Verbindungen und 7145 Prozessen zu generieren. Erstmals wurden Verzweigungsverhältnisse in CAPRAM eingeführt. Außerdem wurde die Chemie organischer Verbindungen mit bis zu vier Kohlenstoffatomen erweitert. Umfangreiche Untersuchungen unter realistischen troposphärischen Bedingungen in urbanen und ländlichen Gebieten haben deutliche Verbesserungen der erweiterten Mechanismen besonders in Bezug auf Massenzuwachs des organischen Aerosolanteils gezeigt. Das Verständnis der organischen Multiphasenchemie konnte durch detaillierte Untersuchungen zu den Konzentrations-Zeit-Profilen und chemischen Flüssen vertieft werden, aber auch gegenwärtige Limitierungen des Generators, der erzeugten Mechanismen und unseres Verständnisses für Flüssigphasenprozesse organischer Verbindungen aufgezeigt werden.

The ubiquitous abundance of organic compounds in natural and anthorpogenically influenced eco-systems has put these compounds into the focus of atmospheric research. Organic compounds have an impact on air quality, climate, and human health. Moreover, they affect particle growth, secondary organic aerosol (SOA) formation, and the global radiation budget by altering particle properties. To investigate the multiphase chemistry of organic compounds and interactions with the aqueous phase in the troposphere, modelling can provide a useful tool. The oxidation of larger organic molecules to the final product CO2 can involve a huge number of intermediate compounds and tens of thousands of reactions. Therefore, the creation of explicit mechanisms relies on automated mechanism construction. Estimation methods for the prediction of the kinetic data needed to describe the degradation of these intermediates are inevitable due to the infeasibility of an experimental determination of all necessary data. Current aqueous phase descriptions of organic chemistry lag behind the gas phase descriptions in atmospheric chemical mechanisms despite its importance for the multiphase chemistry of organic compounds. In this dissertation, the gas phase mechanism Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) has been advanced by a protocol for the description of the oxidation of organic compounds in the aqueous phase. Therefore, a database with kinetic data of 465 aqueous phase hydroxyl radical and 129 aqueous phase nitrate radical reactions with organic compounds has been compiled and evaluated. The database was used to evaluate currently available estimation methods for the prediction of aqueous phase kinetic data of reactions of organic compounds. Among the investigated methods were correlations of gas and aqueous kinetic data, kinetic data of homologous series of various compound classes, reactivity comparisons of inorganic radical oxidants, Evans-Polanyi-type correlations, and structure-activity relationships (SARs). Evans-Polanyi-type correlations have been improved for the purpose of automated mechanism self-generation of mechanisms with large organic molecules. A protocol has been designed based on SARs for hydroxyl radical reactions and the improved Evans-Polanyi-type correlations for nitrate radical reactions with organic compounds. The protocol was assessed in a series of critical sensitivity studies, where uncertainties of critical parameters were investigated. The advanced multiphase generator GECKO-A was used to generate mechanisms, which were applied in box model studies and validated against two sets of aerosol chamber experiments. Experiments differed by the initial compounds used (hexane and trimethylbenzene) and the experimental conditions (UV-C lights off/on and additional in-situ hydroxyl radical source no/yes). Reasonable to good agreement of the modelled and experimental results was achieved in these studies. Finally, GECKO-A was used to create two new CAPRAM version, where, for the first time, branchingratios for different reaction pathways were introduced and the chemistry of compounds with up to four carbon atoms has been extended. The most detailed mechanism comprises 4174 compounds and 7145 processes. Detailed investigations were performed under real tropospheric conditions in urban and remote continental environments. Model results showed significant improvements, especially in regard to the formation of organic aerosol mass. Detailed investigations of concentration-time profiles and chemical fluxes refined the current knowledge of the multiphase processing of organic compounds in the troposphere, but also pointed at current limitations of the generator protocol, the mechanisms created, and current understanding of aqueous phase processes of organic compounds.:1 Introduction and motivation 2 Theoretical background 2.1 General overview of the tropospheric multiphase chemistry of organic compounds 2.1.1 Gas phase chemistry 2.1.2 Phase transfer 2.1.3 Aqueous phase chemistry 2.2 Tropospheric multiphase chemistry mechanisms 2.2.1 Gas phase mechanisms 2.2.2 Aqueous phase mechanisms 2.2.3 The multiphase mechanism MCMv3.1-CAPRAM 3.0n 2.2.3.1 MCMv3.1 2.2.3.2 CAPRAM 3.0n 2.3 Multiphase chemistry box models 2.3.1 Overview 2.3.2 The model SPACCIM 2.3.2.1 Overview 2.3.2.2 The microphysical scheme 2.3.2.3 The chemical and phase transfer scheme 2.3.2.4 The coupling scheme 2.4 Prediction of aqueous phase kinetic data 2.4.1 Simple correlations 2.4.2 Evans-Polanyi-correlations 2.4.3 Structure-activity relationships 2.5 The generator GECKO-A 3 Evaluation of kinetic data and prediction methods 3.1 Compilation and evaluation of aqueous phase kinetic data 3.2 Extrapolation of gas phase rate constants to the aqueous phase 3.3 Homologous series of compound classes 3.4 Radical reactivity comparisons 3.5 Evans-Polanyi-type correlations 3.5.1 OH rate constant prediction 3.5.2 NO3 rate constant prediction 3.5.3 Development of an advanced Evans-Polanyi-type correlation 3.6 Structure-activity relationships 3.7 Conclusions from the evaluation process 4 Development of the new aqueous phase protocol and its implementation into GECKO-A 4.1 Initialisation and workflow of GECKO-A 4.2 Estimation of phase transfer data 4.3 OH reactions of stable compounds 4.4 NO3 reactions of stable compounds 4.5 Hydration of carbonyl compounds 4.6 Hydrolysis of carbonyl nitrates 4.7 Dissociation of carboxylic acids 4.8 Degradation of radical compounds 4.8.1 RO2 recombinations and cross-reactions 4.8.2 HO2 elimination of ff-hydroxy peroxy radicals 4.8.3 Degradation of acylperoxy radicals 4.8.4 Degradation of fi-carboxyl peroxy radicals 4.8.5 Degradation of alkoxy radicals 4.8.6 Degradation of acyloxy radicals 5 Investigation and refinement of crucial parameters in GECKO-A and CAPRAM mechanism development 5.1 Formation and degradation of polycarbonyl compounds in the protocol 5.2 Influence of the mass accommodation coefficient on the organic multiphase chemistry and composition 5.3 Influence of the cut-off parameter for minor reaction pathways 5.4 Influence of the chosen SAR in the protocol 5.5 Processing of organic mass fraction in the protocol 5.5.1 Parameterisations for radical attack of the overall organic mass fraction 5.5.2 Detailed studies of organic nitrate sinks and sources 5.5.3 Phase transfer of oxygenated organic compounds in the protocol 5.5.4 Decay of alkoxy radicals in the protocol 5.5.5 Revision of the GROMHE thermodynamic database 5.6 Influence of the nitrate radical chemistry 5.7 The final protocol for aqueous phase mechanism self-generation 5.8 CAPRAM mechanism development 5.8.1 CAPRAM 3.0 5.8.2 CAPRAM 3.5 5.8.3 CAPRAM 4.0 6 Model results and discussion 6.1 Comparisons of model results with aerosol chamber experiments 6.1.1 Design of the aerosol chamber experiments 6.1.1.1 Hexane oxidation experiment 6.1.1.2 Trimethylbenzene oxidation experiment 6.1.2 Mechanism generation and model setup 6.1.2.1 Hexane oxidation experiment 6.1.2.2 Trimethylbenzene oxidation experiment 6.1.3 Evaluation of the model versus aerosol chamber results 6.1.3.1 Hexane oxidation experiment 6.1.3.2 Trimethylbenzene oxidation experiment 6.2 Simulations with a ‘real atmosphere’ scenario 6.2.1 Model setup 6.2.2 Meteorological and microphysical parameters 6.2.3 Influence of the extended organic scheme on the particle acidity and SOA formation 6.2.3.1 Particle acidity 6.2.3.2 Particle mass 6.2.4 Influence of the extended organic scheme on inorganic radical oxidants 6.2.4.1 OH chemistry 6.2.4.2 NO3 chemistry 6.2.4.3 Comparison of OH and NO3 chemistry 6.2.4.4 HO2/O2- chemistry 6.2.5 Influence of the extended organic scheme on inorganic non-radical oxidants 6.2.5.1 H2O2 chemistry 6.2.5.2 O3 chemistry 6.2.6 Influence of the extended organic scheme on inorganic particulate matter 6.2.6.1 Sulfate chemistry 6.2.6.2 Nitrate chemistry 6.2.6.3 TMI chemistry 6.2.7 Detailed investigations of selected organic subsystems 6.2.7.1 Monofunctional organic compounds 6.2.7.2 Carbonyl compounds 6.2.7.3 Dicarboxylic acids and functionalised monocarboxylic acids 7 Conclusions References Glossary Acronyms List of symbols List of Figures List of Tables Acknowledgements Curriculum Vitae List of relevant publications Peer-reviewed publications Oral conference contributions Poster conference contributions Appendix A Overview of selected compound classes of tropospheric relevance B Detailed description of the function of SARs C The kinetic database C.1 Reactions of hydroxyl radicals with organic compounds C.2 Reactions of nitrate radicals with organic compounds D Detailed information about the evaluation of prediction methods D.1 Rate data used for the derivation and evaluation of gas-aqueous phase correlations D.2 Explanation of the use of box plots D.3 Additional correlations of homologous series of various compound classes D.4 Additional information of Evans-Polanyi-type correlations D.5 Additional information of structure-activity relationships E Additional information for the development of the protocol of GECKO-A E.1 Investigations on the decay of acylperoxy radicals E.2 Additional information about the sensitivity of mass accomodation coefficients E.3 Additional information about the sensitivity studies concerning the decay of polycarbonyls E.4 Additional information about the sensitivity studies concerning the omission of minor reaction pathways E.5 Additional information about the sensitivity studies concerning the processing of the organic mass fraction E.6 Additional information about the influence of the nitrate radical chemistry F Additional information about the mechanism generation and model initialisation F.1 List of primary compounds used for the generation of CAPRAM 3.5 F.2 List of primary compounds used for the generation of CAPRAM 4.0 F.3 Model initialization of the ‘real atmosphere’ scenarios G The CAPRAM oxidation scheme G.1 Photolysis processes G.2 Inorganic chemistry G.2.1 Phase transfer processes G.2.2 Chemical conversions G.3 Organic chemistry G.3.1 Phase transfer processes G.3.2 Chemical conversions H Detailed information about the model validation with chamber experiments H.1 Additional information about the initialisation of the hexane oxidation experiment H.2 Additional model results from the hexane oxidation experiment H.3 Additional information about the sensitivity runs used in the trimethylbenzene oxidation experiment H.4 Additional results from the TMB oxidation experiment I Additional results from the ‘real atmosphere’ scenario I.1 Particle acidity and SOA formation I.2 Radical oxidants I.3 Organic compounds References of the Appendix / Das zahlreiche Vorkommen organischer Verbindungen in natürlichen und anthropogen beeinflussten Ökosystemen hat diese Verbindungen in den Fokus der Atmosphärenforschung gerückt. Organische Verbindungen beeinträchtigen die Luftqualität, die menschliche Gesundheit und das Klima. Weiterhin werden Partikelwachstum und -eigenschaften, sekundäre organische Partikelbildung und dadurch der globale Strahlungshaushalt durch sie beeinflusst. Um die troposphärische Multiphasenchemie organischer Verbindungen und Wechselwirkungen mit der Flüssigphase zu untersuchen, sind Modellstudien hilfreich. Die Oxidation großer organischer Moleküle führt zu einer Vielzahl an Zwischenprodukten. Der Abbau erfolgt in unzähligen Reaktionen bis hin zum Endprodukt CO2. Bei der Entwicklung expliziter Mechanismen muss deshalb für diese Verbindungen auf computergestützte, automatisierte Methoden zurückgegriffen werden. Abschätzungsmethoden für die Vorhersage kinetischer Daten zur Beschreibung des Abbaus der Zwischenprodukte sind unabdingbar, da eine experimentelle Bestimmung aller benötigten Daten nicht realisierbar ist. Die derzeitige Beschreibung der Flüssigphasenchemie unterliegt deutlich den Beschreibungen der Gasphase in atmosphärischen Chemiemechanismen trotz deren Relevanz für die Multiphasenchemie. In dieser Arbeit wurde der Gasphasenmechanismusgenerator GECKO-A (“Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere”) um ein Protokoll zur Oxidation organischer Verbindungen in der Flüssigphase erweitert. Dazu wurde eine Datenbank mit kinetischen Daten von 465 Hydroxylradikal- und 129 Nitratradikalreaktionen mit organischen Verbindungen angelegt und evaluiert. Mit Hilfe der Datenbank wurden derzeitige Abschätzungsmethoden für die Vorhersage kinetischer Daten von Flüssigphasenreaktionen organischer Verbindungen evaluiert. Die untersuchten Methoden beinhalteten Korrelationen kinetischer Daten aus Gas- und Flüssigphase, homologer Reihen verschiedener Stoffklassen, Reaktivitätsvergleiche, Evans-Polanyi-Korrelationen und Struktur-Reaktivitätsbeziehungen. Für die Mechanismusgenerierung großer organischer Moleküle wurden die Evans-Polanyi-Korrelationen in dieser Arbeit weiterentwickelt. Es wurde ein Protokol für die Mechanismusgenerierung entwickelt, das auf Struktur-Reaktivitätsbeziehungen bei Reaktionen von organischen Verbindungen mit OH-Radikalen und auf den erweiterten Evans-Polanyi-Korrelationen bei NO3-Radikalreaktionen beruht. Das Protokoll wurde umfangreich in einer Reihe von Sensitivitätsstudien getestet, um Unsicherheiten kritischer Parameter abzuschätzen. Der erweiterte Multiphasengenerator GECKO-A wurde dazu verwendet, neue Mechanismen zu generieren, die in Boxmodellstudien gegen Aerosolkammerexperimente evaluiert wurden. Die Experimentreihen unterschieden sich sowohl in der betrachteten Ausgangssubstanz (Hexan und Trimethylbenzen) und dem Experimentaufbau (ohne oder mit UV-C-Photolyse und ohne oder mit zusätzlicher partikulärer Hydroxylradikalquelle). Bei den Experimenten konnte eine zufriedenstellende bis gute Übereinstimmung der experimentellen und Modellergebnisse erreicht werden. Weiterhin wurde GECKO-A verwendet, um zwei neue CAPRAM-Versionen mit bis zu 4174 Verbindungen und 7145 Prozessen zu generieren. Erstmals wurden Verzweigungsverhältnisse in CAPRAM eingeführt. Außerdem wurde die Chemie organischer Verbindungen mit bis zu vier Kohlenstoffatomen erweitert. Umfangreiche Untersuchungen unter realistischen troposphärischen Bedingungen in urbanen und ländlichen Gebieten haben deutliche Verbesserungen der erweiterten Mechanismen besonders in Bezug auf Massenzuwachs des organischen Aerosolanteils gezeigt. Das Verständnis der organischen Multiphasenchemie konnte durch detaillierte Untersuchungen zu den Konzentrations-Zeit-Profilen und chemischen Flüssen vertieft werden, aber auch gegenwärtige Limitierungen des Generators, der erzeugten Mechanismen und unseres Verständnisses für Flüssigphasenprozesse organischer Verbindungen aufgezeigt werden.:1 Introduction and motivation 2 Theoretical background 2.1 General overview of the tropospheric multiphase chemistry of organic compounds 2.1.1 Gas phase chemistry 2.1.2 Phase transfer 2.1.3 Aqueous phase chemistry 2.2 Tropospheric multiphase chemistry mechanisms 2.2.1 Gas phase mechanisms 2.2.2 Aqueous phase mechanisms 2.2.3 The multiphase mechanism MCMv3.1-CAPRAM 3.0n 2.2.3.1 MCMv3.1 2.2.3.2 CAPRAM 3.0n 2.3 Multiphase chemistry box models 2.3.1 Overview 2.3.2 The model SPACCIM 2.3.2.1 Overview 2.3.2.2 The microphysical scheme 2.3.2.3 The chemical and phase transfer scheme 2.3.2.4 The coupling scheme 2.4 Prediction of aqueous phase kinetic data 2.4.1 Simple correlations 2.4.2 Evans-Polanyi-correlations 2.4.3 Structure-activity relationships 2.5 The generator GECKO-A 3 Evaluation of kinetic data and prediction methods 3.1 Compilation and evaluation of aqueous phase kinetic data 3.2 Extrapolation of gas phase rate constants to the aqueous phase 3.3 Homologous series of compound classes 3.4 Radical reactivity comparisons 3.5 Evans-Polanyi-type correlations 3.5.1 OH rate constant prediction 3.5.2 NO3 rate constant prediction 3.5.3 Development of an advanced Evans-Polanyi-type correlation 3.6 Structure-activity relationships 3.7 Conclusions from the evaluation process 4 Development of the new aqueous phase protocol and its implementation into GECKO-A 4.1 Initialisation and workflow of GECKO-A 4.2 Estimation of phase transfer data 4.3 OH reactions of stable compounds 4.4 NO3 reactions of stable compounds 4.5 Hydration of carbonyl compounds 4.6 Hydrolysis of carbonyl nitrates 4.7 Dissociation of carboxylic acids 4.8 Degradation of radical compounds 4.8.1 RO2 recombinations and cross-reactions 4.8.2 HO2 elimination of ff-hydroxy peroxy radicals 4.8.3 Degradation of acylperoxy radicals 4.8.4 Degradation of fi-carboxyl peroxy radicals 4.8.5 Degradation of alkoxy radicals 4.8.6 Degradation of acyloxy radicals 5 Investigation and refinement of crucial parameters in GECKO-A and CAPRAM mechanism development 5.1 Formation and degradation of polycarbonyl compounds in the protocol 5.2 Influence of the mass accommodation coefficient on the organic multiphase chemistry and composition 5.3 Influence of the cut-off parameter for minor reaction pathways 5.4 Influence of the chosen SAR in the protocol 5.5 Processing of organic mass fraction in the protocol 5.5.1 Parameterisations for radical attack of the overall organic mass fraction 5.5.2 Detailed studies of organic nitrate sinks and sources 5.5.3 Phase transfer of oxygenated organic compounds in the protocol 5.5.4 Decay of alkoxy radicals in the protocol 5.5.5 Revision of the GROMHE thermodynamic database 5.6 Influence of the nitrate radical chemistry 5.7 The final protocol for aqueous phase mechanism self-generation 5.8 CAPRAM mechanism development 5.8.1 CAPRAM 3.0 5.8.2 CAPRAM 3.5 5.8.3 CAPRAM 4.0 6 Model results and discussion 6.1 Comparisons of model results with aerosol chamber experiments 6.1.1 Design of the aerosol chamber experiments 6.1.1.1 Hexane oxidation experiment 6.1.1.2 Trimethylbenzene oxidation experiment 6.1.2 Mechanism generation and model setup 6.1.2.1 Hexane oxidation experiment 6.1.2.2 Trimethylbenzene oxidation experiment 6.1.3 Evaluation of the model versus aerosol chamber results 6.1.3.1 Hexane oxidation experiment 6.1.3.2 Trimethylbenzene oxidation experiment 6.2 Simulations with a ‘real atmosphere’ scenario 6.2.1 Model setup 6.2.2 Meteorological and microphysical parameters 6.2.3 Influence of the extended organic scheme on the particle acidity and SOA formation 6.2.3.1 Particle acidity 6.2.3.2 Particle mass 6.2.4 Influence of the extended organic scheme on inorganic radical oxidants 6.2.4.1 OH chemistry 6.2.4.2 NO3 chemistry 6.2.4.3 Comparison of OH and NO3 chemistry 6.2.4.4 HO2/O2- chemistry 6.2.5 Influence of the extended organic scheme on inorganic non-radical oxidants 6.2.5.1 H2O2 chemistry 6.2.5.2 O3 chemistry 6.2.6 Influence of the extended organic scheme on inorganic particulate matter 6.2.6.1 Sulfate chemistry 6.2.6.2 Nitrate chemistry 6.2.6.3 TMI chemistry 6.2.7 Detailed investigations of selected organic subsystems 6.2.7.1 Monofunctional organic compounds 6.2.7.2 Carbonyl compounds 6.2.7.3 Dicarboxylic acids and functionalised monocarboxylic acids 7 Conclusions References Glossary Acronyms List of symbols List of Figures List of Tables Acknowledgements Curriculum Vitae List of relevant publications Peer-reviewed publications Oral conference contributions Poster conference contributions Appendix A Overview of selected compound classes of tropospheric relevance B Detailed description of the function of SARs C The kinetic database C.1 Reactions of hydroxyl radicals with organic compounds C.2 Reactions of nitrate radicals with organic compounds D Detailed information about the evaluation of prediction methods D.1 Rate data used for the derivation and evaluation of gas-aqueous phase correlations D.2 Explanation of the use of box plots D.3 Additional correlations of homologous series of various compound classes D.4 Additional information of Evans-Polanyi-type correlations D.5 Additional information of structure-activity relationships E Additional information for the development of the protocol of GECKO-A E.1 Investigations on the decay of acylperoxy radicals E.2 Additional information about the sensitivity of mass accomodation coefficients E.3 Additional information about the sensitivity studies concerning the decay of polycarbonyls E.4 Additional information about the sensitivity studies concerning the omission of minor reaction pathways E.5 Additional information about the sensitivity studies concerning the processing of the organic mass fraction E.6 Additional information about the influence of the nitrate radical chemistry F Additional information about the mechanism generation and model initialisation F.1 List of primary compounds used for the generation of CAPRAM 3.5 F.2 List of primary compounds used for the generation of CAPRAM 4.0 F.3 Model initialization of the ‘real atmosphere’ scenarios G The CAPRAM oxidation scheme G.1 Photolysis processes G.2 Inorganic chemistry G.2.1 Phase transfer processes G.2.2 Chemical conversions G.3 Organic chemistry G.3.1 Phase transfer processes G.3.2 Chemical conversions H Detailed information about the model validation with chamber experiments H.1 Additional information about the initialisation of the hexane oxidation experiment H.2 Additional model results from the hexane oxidation experiment H.3 Additional information about the sensitivity runs used in the trimethylbenzene oxidation experiment H.4 Additional results from the TMB oxidation experiment I Additional results from the ‘real atmosphere’ scenario I.1 Particle acidity and SOA formation I.2 Radical oxidants I.3 Organic compounds References of the Appendix

Submitted by Priscila Oliveira (priscila.b.oliveira@ufes.br) on 2016-07-12T12:40:28Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) cp128327.pdf: 6590453 bytes, checksum: 5654758329fe7af83bec07339d8a3ffb (MD5) / Approved for entry into archive by Patricia Barros (patricia.barros@ufes.br) on 2016-08-15T18:10:11Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) cp128327.pdf: 6590453 bytes, checksum: 5654758329fe7af83bec07339d8a3ffb (MD5) / Made available in DSpace on 2016-08-15T18:10:11Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) cp128327.pdf: 6590453 bytes, checksum: 5654758329fe7af83bec07339d8a3ffb (MD5) / Business process modelling basically comprises an activity whose main goal is to provide a formalization of business processes in an organization or a set of cooperating organizations (Recker, et al., 2006) (van der Aalst, et al., 2003). By modelling an organization’s business processes, it is possible to capture how the organization coordinates the work and resources with the aim of achieving its goals and strategies (Sharp, et al., 2001). Since business processes and goals are intrinsically interdependent, establishing an alignment between the process and the goal domains arises as a natural approach. This thesis reports on a real-life exploratory case study in which we investigated the relationship between the elements of the enterprise (modeled in the ARIS framework) and the goals (modeled in the Tropos framework and modeling language) which are attained by these elements. The case study has been conducted in the Rheumatology Department of a University Hospital in Brazil. In the course of the case study, we have identified the need of splitting this effort into three phases: the elicitation phase (in which goal models and business process models are captured from the organizational domain), the harmonization phase (in which the goal domain is structured for alignment according to the business processes structures that will support it) and the alignment phase (in which the relationships between the goal domain and the elements of the organizational domain are established). In order to investigate the relation between goals and enterprise elements, we propose an ontological account for both architectural domains. We recognize the importance in considering the business process as the means for implementing an enterprise’s strategy, but we do not exclude the remaining enterprise elements. Furthermore, we are concerned with both the identification of the relationships and with a classification for their nature.