Made available in DSpace on 2014-10-09T12:25:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:21Z (GMT). No. of bitstreams: 1 01015.pdf: 998775 bytes, checksum: 24043b75e9a372f6fca29bba4af963d3 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Química - Universidade de São Paulo - IQ/USP

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The physical and inorganic chemistry of solutions in difluorophosphoric acid, HPO₂F₂, has been studied, as part of a general study of solutions in non-aqueous protonic solvents. Difluorophosphoric acid is a colourless, associated liquid which might be expected to have solvent properties similar to those of other protonic systems such as H₂O, H₂SO₄ and HSO₃F. However, electrical conductivity studies of solutions of various electrolytes and nuclear magnetic resonance studies of solutions of alkali metal difluorophosphates indicate that the acid is a poor solvent for electrolytes and that ion-pairing is probably extensive. Acid-base behaviour in HPO₂F₂ has been extensively investigated. Compounds which behave as bases in this system include metal difluorophosphates, chlorides, nitrates and carbonates, organic amines, and some organic nitro-compounds and carboxylic acids. Inorganic molecules such as H₂SO₄, HSO₃F and SbF₅ behave as acids. Reaction between an acid and a base in HPO₂F₂ commonly result in the formation of an insoluble salt. The reaction between KPO₂F₂ and SbF₅, for example, has been used to prepare the new compound KSbF₅PO₂F₂. To further investigate the factors affecting acid strengths, cryoscopic and electrical conductivity studies of various inorganic oxy-acids were carried out in nitrobenzene, as solvent. The acids H₂SO₄, HSO₃F and HPO₂F₂ appeared to be virtual non-electrolytes in nitrobenzene, with H₂SO₄ apparently exhibiting some polymerization. / Science, Faculty of / Chemistry, Department of / Graduate

This work showcases the utility of switchable materials. Included are a switchable room-temperature ionic liquid, a switchable solvent, a switchable heterogeneous catalyst system, and a switchable gel. First, the switchable ionic liquid 2-butyl-1,1,3,3-tetramethylguanidium methylcarbonate is fully investigated. Its use in a complete chemical process (including reaction, separation, reformation, and recycle) is demonstrated with several reactions. Furthermore, its potential use for bitumen separation and purification and SO2 capture/isolation are discussed, and preliminary data is presented. Next, piperylene sulfone (PS), a switchable solvent, is synthesized and fully characterized. Anionic nucleophilic substitution reactions were performed in PS, the products were isolated in high yields, and then the PS was reformed for reuse. Then, we designed an immobilized fluorous microphase system that uses F-MonoPhos to induce high enantioselectivities as a switchable heterogeneous catalyst system. Finally, stable reversible polyethyleimine-CO2 gels have been synthesized with 1-octanol. Our findings indicate that PEI-1200/octanol/CO2 gels have potential as a possible drug carrier matrix for transdermal delivery applications.

The work in this thesis couples reactions with separations through the use of switchable and tunable solvents. Tunable solvents are mixed solvents which can be easily altered to afford conditions optimal for reaction or separation. Switchable solvents are solvents that can be switched when desired to alter their properties affording conditions suitable for separation. Other studies are of the reaction of CO2 with the amidine base DBU, and an NMR study of solvent-to-solute nuclear Overhauser effects. These examples constitute a marriage of reaction environment with separation environment, significantly, to the benefit of both.

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The solubility of diuron was determined in binary and ternary cosolvent-water systems. The binary systems were composed of a completely miscible organic solvent (CMOS) and water while the ternary systems incorporate partially miscible organic solvents (PMOS) into the binary systems. Due to the low aqueous solubilities of trichloroethylene and toluene, the PMOS's do not behave as cosolvents and they do not play an important role in altering solubility.

<p>Chlorinated solvents are common contaminants in soil and water. Under anaerobic conditions microbes are capable of transforming chlorinated solvents into ethylene which would result in a remediation of the contaminated area. In order to use natural attenuation as a remediation method evidence of continuous degradation is required. Furthermore, the degradation must occur at a sufficient rate and continuous monitoring of the site is needed until the demanded levels are achieved. A field study was performed on the basis of data from a dry-cleaning facility contaminated mainly by perchloroethylene. The purpose of the study was to define the existing situation regarding distribution and transformation of contaminant in order to evaluate the possibilities of using natural attenuation as a method of remediation. Degradation of perchloroethylene proceeds through successive removal of chlorine, with the formation of trichloroethylene, dichloroethylene, vinyl chloride and ethylene. There exists evidence of degradation as far as vinyl chloride on the site but whether transformation continues to ethylene is not established. The computer model Biochlor was used to simulate distribution and degradation of the contaminants. The site possesses a complex hydrogeology and the existing data are not sufficient to distinguish the effect of degradation from other factors such as spreading of contaminant between different layers of soil. Since degradation failed to be quantified, natural attenuation can not be recommended as a safe remediation method at the considered site without further investigations.</p> / <p>Klorerade lösningsmedel är vanligt förekommande föroreningar i mark och vatten. Under anaeroba förhållanden kan mikrober omvandla klorerade kolväten till eten vilket leder till rening av det förorenade området. För att kunna använda denna naturliga nedbrytning som saneringsmetod krävs bevis för att nedbrytning fortskrider i tillräcklig utsträckning för att rena området och därefter krävs kontinuerlig provtagning till dess målen för saneringen har uppnåtts. En fallstudie utfördes utifrån data från en kemtvättsfastighet förorenad av i första hand perkloreten. Syftet var att kartlägga föroreningssituationen med avseende på spridning och nedbrytning av de klorerade föreningarna för att undersöka om naturlig nedbrytning var en möjlig framtida saneringsmetod. Nedbrytning av perkloreten sker stegvis genom att klor avspjälkas, under bildande av produkterna trikloreten, dikloreten, vinylklorid och etengas. Nedbrytning av förorening har konstaterats ske på fastigheten fram till vinylklorid men huruvida nedbrytning avstannat där eller fullföljts till etengas är ej klarlagt. Datormodellen Biochlor användes för att simulera spridning och nedbrytning av utsläppet. Fältplatsen har en komplex hydrogeologi och befintliga fältdata var inte tillräckliga för att särskilja nedbrytningens effekt från faktorer såsom spridning av förorening mellan olika jordlager. Eftersom nedbrytningen inte kunde kvantifieras kan naturlig nedbrytning inte rekommenderas som säker saneringsmetod på denna fältplats utan kompletterande analyser.</p>

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