Thesis (M.S.)--Rochester Institute of Technology, 1992. / Typescript. Includes bibliographical references (leaves 56-58).

O objetivo deste trabalho foi desenvolver métodos para a determinação simultânea de Pb, Si e P em gasolinas por ICP OES em conformidade com a Agência Nacional de Petróleo (ANP). O mercado da gasolina no Brasil é regulado pela Agência Nacional do Petróleo (ANP) e pela Lei Federal 9.478/97 (Lei do Petróleo) e, conforme Resolução ANP n°40, de 25.10.2013, a determinação de chumbo é exigida quando houver suspeita de contaminação. O chumbo era adicionado, desde 1922 para elevar o índice antidetonante da gasolina, mas devido a sua toxicidade foi mundialmente substituído. A determinação do silício passou a ser exigida em 1 de Janeiro de 2014 nas gasolinas, porque frações leves contaminadas com silício, quando usadas como combustíveis, podem gerar problemas aos motores automotivos, uma vez que os aditivos antiespumantes, a base de oligômeros contendo silício, são adicionados durante o processo de refino. O fósforo é um aditivo estimulante da extração do petróleo, sua determinação também é exigida quando houver suspeita de contaminação, pois concentrações acima do limite máximo podem desativar os catalisadores dos carros. No preparo de amostras foram utilizadas duas estratégias, a primeira diluição da gasolina com solventes orgânicos 10% da gasolina e 90% de Premisolv-Constan, com a vantagem da int rodução direta, porém necessita câmara refrigerada e fluxo de O2. E preparo da amostra por emulsão tipo óleo/água (O/W), preparada utilizando 1 mL de gasolina com 3 mL de surfactante Tergitol TMN-6® (20% m v-1), o qual foi escolhido entre 4 surfactantes (TritonTM X-100,TritonTM X-114, TergitolTMTMN-6 e TergitolTM 15-S-9) por ter apresentado melhor desempenho na formação da emulsão e menor branco analítico. Essa segunda estratégia apresentou vantagens em relação a primeira, pois reduz a introdução da matéria orgânica para 10% e dispensa o uso de câmara especial e fluxo de O2. As amostras foram analisadas com a construção de curvas de adição padrão a fim de eliminar os efeitos de matriz. Também foram analisadas amostras dopadas com padrão orgânico nas concentrações dos limites estabelecidos pela Resolução ANP. As recuperações foram de 86% a 98% para Pb, 90% a 106% para Si e 86% a 110% para P. Portanto o método desenvolvido demonstrou a possibilidade da determinação simultânea de Si, Pb e P nos limites estabelecidos pela legislação (Pb = 5 mg LTM-1, P = 1,3 mg L-1 e Si limite máximo ainda não estabelecido) e está de acordo com a Química Verde e Gestão de Saúde Meio Ambiente e Segurança. / The objective of this work was to develop methods for the simultaneous determination of Pb, Si and P in gasoline by ICP-OES in accordance with the National Petroleum Agency (ANP). The Brazilian gasoline market is regulated by the National Petroleum Agency (ANP) and Federal Law 9.478 / 97 (Petroleum Law) and according to ANP Resolution No. 40, dated 10.25.2013, the determination of lead is required when there is suspected contamination. Lead was added since 1922 to raise the antiknock index of gasoline, but because of its toxicity it has been worldwide replaced. The determination of silicon was required on 1 January 2014 in gasoline. Light fractions contaminated with silicon, when used as fuel, can cause problems for automotive engines, since antifoaming additives, based on silicon-containing oligomers, are added during the refining process. Phosphorus is a stimulating additive to petroleum extraction; its determination is also required when contamination is suspected, as concentrations above the upper limit can deactivate the catalysts of the cars. In the preparation of samples, two strategies were used, the first dilution of gasoline with organic solvents 10% of the gasoline and 90% of Premisolv-Constan, with the advantage of direct introduction, however, requires refrigerated chamber and O2 flow. Preparation of the sample by oil / water (O / W) emulsion, using 1 ml of gasoline with 3 ml of Tergitol TMN-6 surf surfactant (20% m v-1), which was chosen among 4 surfactants (TritonTM X-100, TritonTM X-114, TergitolTM TMN-6 e TergitolTM 15-S-9), because it showed better performance in the formation of the emulsion and lower analytical blank. This second strategy presents advantages over the first one because it reduces the introduction of the organic matter to 10% and dispenses with the use of special chamber and O2 flow. Samples were analyzed by constructing standard addition curves to eliminate matrix effects. We also analyzed doped samples with organic standards in the concentrations of the limits established by ANP Resolution. The recoveries were 86% to 98% for Pb, 90% to 106% for Si and 86% to 110% for P. Therefore, the method developed demonstrated the possibility of simultaneous determination of Si, Pb and P within the limits established by the legislation (Pb = 5 mg L-1, P = 1,3 mg L-1 and Si maximum limit not yet established) and is in accordance with the Green Chemistry and Health Management Environment and Safety.

O objetivo deste trabalho foi desenvolver métodos para a determinação simultânea de Pb, Si e P em gasolinas por ICP OES em conformidade com a Agência Nacional de Petróleo (ANP). O mercado da gasolina no Brasil é regulado pela Agência Nacional do Petróleo (ANP) e pela Lei Federal 9.478/97 (Lei do Petróleo) e, conforme Resolução ANP n°40, de 25.10.2013, a determinação de chumbo é exigida quando houver suspeita de contaminação. O chumbo era adicionado, desde 1922 para elevar o índice antidetonante da gasolina, mas devido a sua toxicidade foi mundialmente substituído. A determinação do silício passou a ser exigida em 1 de Janeiro de 2014 nas gasolinas, porque frações leves contaminadas com silício, quando usadas como combustíveis, podem gerar problemas aos motores automotivos, uma vez que os aditivos antiespumantes, a base de oligômeros contendo silício, são adicionados durante o processo de refino. O fósforo é um aditivo estimulante da extração do petróleo, sua determinação também é exigida quando houver suspeita de contaminação, pois concentrações acima do limite máximo podem desativar os catalisadores dos carros. No preparo de amostras foram utilizadas duas estratégias, a primeira diluição da gasolina com solventes orgânicos 10% da gasolina e 90% de Premisolv-Constan, com a vantagem da int rodução direta, porém necessita câmara refrigerada e fluxo de O2. E preparo da amostra por emulsão tipo óleo/água (O/W), preparada utilizando 1 mL de gasolina com 3 mL de surfactante Tergitol TMN-6® (20% m v-1), o qual foi escolhido entre 4 surfactantes (TritonTM X-100,TritonTM X-114, TergitolTMTMN-6 e TergitolTM 15-S-9) por ter apresentado melhor desempenho na formação da emulsão e menor branco analítico. Essa segunda estratégia apresentou vantagens em relação a primeira, pois reduz a introdução da matéria orgânica para 10% e dispensa o uso de câmara especial e fluxo de O2. As amostras foram analisadas com a construção de curvas de adição padrão a fim de eliminar os efeitos de matriz. Também foram analisadas amostras dopadas com padrão orgânico nas concentrações dos limites estabelecidos pela Resolução ANP. As recuperações foram de 86% a 98% para Pb, 90% a 106% para Si e 86% a 110% para P. Portanto o método desenvolvido demonstrou a possibilidade da determinação simultânea de Si, Pb e P nos limites estabelecidos pela legislação (Pb = 5 mg LTM-1, P = 1,3 mg L-1 e Si limite máximo ainda não estabelecido) e está de acordo com a Química Verde e Gestão de Saúde Meio Ambiente e Segurança. / The objective of this work was to develop methods for the simultaneous determination of Pb, Si and P in gasoline by ICP-OES in accordance with the National Petroleum Agency (ANP). The Brazilian gasoline market is regulated by the National Petroleum Agency (ANP) and Federal Law 9.478 / 97 (Petroleum Law) and according to ANP Resolution No. 40, dated 10.25.2013, the determination of lead is required when there is suspected contamination. Lead was added since 1922 to raise the antiknock index of gasoline, but because of its toxicity it has been worldwide replaced. The determination of silicon was required on 1 January 2014 in gasoline. Light fractions contaminated with silicon, when used as fuel, can cause problems for automotive engines, since antifoaming additives, based on silicon-containing oligomers, are added during the refining process. Phosphorus is a stimulating additive to petroleum extraction; its determination is also required when contamination is suspected, as concentrations above the upper limit can deactivate the catalysts of the cars. In the preparation of samples, two strategies were used, the first dilution of gasoline with organic solvents 10% of the gasoline and 90% of Premisolv-Constan, with the advantage of direct introduction, however, requires refrigerated chamber and O2 flow. Preparation of the sample by oil / water (O / W) emulsion, using 1 ml of gasoline with 3 ml of Tergitol TMN-6 surf surfactant (20% m v-1), which was chosen among 4 surfactants (TritonTM X-100, TritonTM X-114, TergitolTM TMN-6 e TergitolTM 15-S-9), because it showed better performance in the formation of the emulsion and lower analytical blank. This second strategy presents advantages over the first one because it reduces the introduction of the organic matter to 10% and dispenses with the use of special chamber and O2 flow. Samples were analyzed by constructing standard addition curves to eliminate matrix effects. We also analyzed doped samples with organic standards in the concentrations of the limits established by ANP Resolution. The recoveries were 86% to 98% for Pb, 90% to 106% for Si and 86% to 110% for P. Therefore, the method developed demonstrated the possibility of simultaneous determination of Si, Pb and P within the limits established by the legislation (Pb = 5 mg L-1, P = 1,3 mg L-1 and Si maximum limit not yet established) and is in accordance with the Green Chemistry and Health Management Environment and Safety.

This thesis describes selected reactivity studies of the N-heterocyclic carbene, IPr, towards a range of main group compounds. The synthesis and characterisation of sixty-three compounds, all of which incorporate IPr as a ligand in one of three coordination modes, are detailed herein. The deprotonation of IPr allowed for the isolation of an anionic source of the aIPr: ligand which was synthesised as a novel potassium salt and along with the previously reported lithium salt, was employed in reactions with group 12 and 14 bis(trimethylsilyl)amides and tetrahalides. The further chemistry of such novel products was investigated towards both electrophilic and nucleophilic reagents making use of both the pendant nucleophilic carbene functionality and the electrophilic main group centre. An alternative route to such species was investigated by the spontaneous isomerisation of IPr in the coordination sphere of group 14 tetrabromides and group 15 tribromides. The scope of this reactivity was subsequently investigated and was found to provide a simpler route to access the abnormal coordination mode of IPr. The aIPr ligand which is generated may be deprotonated by additional IPr thereby affording aIPr: ligands. The addition of halide abstracting agents allowed for the synthesis of cationic species stabilised by the coordination of either IPr or aIPr ligands. A unique, spontaneous reductive coupling of two phosphorus centres was discovered to take place upon heating a THF solution of (IPr)PBr₃. This allowed for the isolation of a bromide bridged P–P bond with reduced phosphorus centres. This facile reduction chemistry was further explored by reaction with mild reducing agents which provide access to low oxidation state phosphorus compounds in high yields. This chemistry was found to be possible (and more effective) due to the presence of the weaker phosphorus bond to bromine relative to the commonly employed chlorine ligands.