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It is common practice to add oxygenates, such as ethers or alcohols, to gasoline in areas suffering from ozone or smog problems in order to reduce pollution. The most commonly used oxygenates are ethanol (EtOH) and methyl tert-butyl ether (MTBE). However, MTBE is now forbidden by the environmental protection agency (EPA) because of the possibility of ground water contamination. The current trend is to use EtOH, therefore this work focuses on the analysis and quantification of EtOH in gasoline by solid phase microextraction (SPME). The major problem in quantifying EtOH in gasoline is the coelution of hydrocarbons with EtOH. There have been several approaches to solve this problem; among the chromatographic ones, three major types have been proposed: (1) the first one uses a detector selective for oxygen containing compounds; (2) the second one uses two or more columns; (3) and the third one uses an extraction step prior to GC analysis. In this work an extraction step with water is used prior to a solid phase microextraction (SPME) sample preparation coupled to a gas chromatographic (GC) analysis. Solid phase microextraction is a recent technique, invented by Pawliszyn in 1989, and available commercially since 1994. A fiber is used to extract small amounts (ppm, ppb, ppt) of analytes from a solution, usually water. The fiber is beneficial in concentrating analytes. Most work using SPME has been done with hydrophobic (non polar) analytes, extracted using a polydimethylsiloxane (PDMS; non polar) coating on a fused silica fiber. Since very little work has been done with polar analytes, the novel approach of this work is the extraction of EtOH. Since EtOH is the analyte of interest, a polar fiber, carboxen/polydimethyl siloxane (Car/PDMS) is used. Two methods are used for quantification of EtOH in gasoline: the method of a standard calibration curve, and the method of standard addition. They are both successful in quantifying the amount of EtOH in gasoline. The relative errors, with the method of standard addition, vary from 5.3% to 14%, while the ones with the method of calibration curve vary from 1.6% to 7.2%. Moreover, some extraction time studies for both direct and headspace sampling are performed. Direct sampling shows the presence of an equilibrium condition for the carboxen/PDMS fiber, for which no extraction theory is available. Conversely, headspace sampling shows no equilibrium state; after a sampling time of one hour, the amount of EtOH extracted decreases with sampling time. This is probably due to displacement of EtOH by other compounds in the fiber. / Master of Science

No description available.

Thesis advisor: Frank Gollop / This thesis explores the unanticipated consequences of producing ethanol for use as a transportation fuel in the United States. Statistical analysis is conducted to determine the effect that increased ethanol production has on the prices of two essential American commodities: corn and gasoline. A simultaneous system of the demand and supply of corn is developed to estimate the effect of ethanol on the price of corn. The results of this model suggest that during the period 1986-2001, corn demanded for ethanol production caused the price of corn to be 19% higher than it otherwise would have been. This result is noteworthy because the majority of American foods contain some type of corn product. A second simultaneous system is developed to determine the effect of ethanol on the price of gasoline. Neither a change in the price of ethanol nor a change quantity of ethanol per gallon of gasoline was found to have a significant impact on the price of gasoline. / Thesis (BA) — Boston College, 2009. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: College Honors Program. / Discipline: Economics Honors Program. / Discipline: Economics.

[pt] Foi estudada a determinação de mercúrio em gasolina pela técnica do vapor frio, com redução em meio orgânico e de solução de três componentes (microemulsão). Foram utilizadas várias metodologias empregando a técnica de geração de vapor frio e detecção em espectrômetro de absorção atômica, a saber: determinação direta em gasolina; determinação direta em gasolina estabilizada na forma de microemulsão, com e sem pré-concentração em rede de ouro; e determinação direta em gasolina estabilizada na forma de microemulsão utilizando uma armadilha para vapores de gasolina antes da pré-concentração em rede de ouro. Analisando os resultados, foi verificado que a determinação de mercúrio em gasolina estabilizada na forma de microemulsão fornece medidas mais repetitivas do que em gasolina in natura; além disso, foi observada a necessidade de utilizar pré-concentração em rede de ouro, devido aos baixos níveis de mercúrio em gasolina; entretanto, foi detectado que os vapores de gasolina envenenam o ouro. Dentre as armadilhas estudadas para evitar o envenenamento do ouro, foi escolhida a armadilha com solução de K2Cr2O7/H2SO4, na qual, os vapores rovenientes do frasco de reação foram borbulhados e o Hg0, oxidado; posteriormente, a solução foi reduzida com SnCl2/ H2SO4 e os vapores enviados para a rede de ouro. Assim, os resultados indicaram que o método para determinação de mercúrio total em gasolina, no qual o mercúrio é reduzido diretamente da gasolina como microemulsão, utilizando armadilha de K2Cr2O7/H2SO4 antes da pré-concentração em ouro, com detecção por CV-AAS, é recomendado. Após uma otimização multivariada, curvas analíticas apresentaram coeficientes de correlação de até 0,9999 com uma massa característica correspondente de 2ng de mercúrio. O limite de detecção obtido por este método foi de 0,10 ng/mL (0,14 ng/g). / [en] The mercury determination in gasoline by cold vapor and AAS, with reduction in organic liquids and in solution of three components (microemulsion)was studied. Some methodologies were used, with cold vapor generation and atomic absorption spectrometer, to know: direct determination in gasoline; direct determination in gasoline stabilized as microemulsion, with and without preconcentration in gold; and direct determination in gasoline stabilized as microemulsion using a trap for gasoline vapors before the preconcentration in gold. Analyzing the results, it was verified that the measurements from the gasoline stabilized as microemulsion supplies more repetitive readings than the gasoline in nature; moreover, it was observed that is necessary to use preconcentration in gold, due to the lower mercury levels in gasoline; however, it was detected that the gasoline vapors poison the gold. Amongst the studied traps to prevent the poisoning of the gold, the trap with solution of K2Cr2O7/ H2SO4 was chosen, in which, the vapors proceeding from the reaction bottle had been bubbled and the Hg0, oxidated; later, the solution was reduced with SnCl2/ H2SO4 and vapors sent to the gold. Thus, the results had indicated that the method for total mercury determination in gasoline, in which the mercury is reduced directly from the gasoline as microemulsion, using the K2Cr2O7/H2SO4 trap before the preconcentration in gold, with CV-AAS detection, is recommended. After multivariate optimization analytical curves showed coefficients of correlation as good as 0.9999 with a corresponding characteristic mass of 2ng of mercury. The limit of detection obtained for this method was 0.10 ng/mL (0.14 ng/g).

As powertrains and IC engines continue to grow in complexity, many vehicle manufacturers (OEMs) are turning to simulation in an effort to reduce design validation and calibration costs. Ultimately, their aim is to complete this process entirely within the virtual domain, without the need for any physical testing. Practical simulation techniques for the prediction of knock in spark ignition (SI) engines rely on empirical ignition delay correlations (IDCs). These IDCs are used to approximate the complex ignition delay characteristics of real and surrogate fuel compositions with respect to temperature, pressure and mixture composition. Over the last 40 years, a large number of IDCs have been put forward in the literature, spanning a broad range of fuels, operating conditions and calibration methods. However, the applicability of these tools has yet to be verified at the high brake mean effective pressure (BMEP) operating conditions relevant to highly boosted, downsized engines. Here, the applicability of 16 gasoline-relevant IDCs for predicting knock onset at high loads (BMEP > 30bar) has been investigated by comparing the knock predictions from each IDC against experimentally measured knock onset times. Firstly, a detailed investigation into cylinder pressure data processing techniques was performed to determine which knock detection and angle of knock onset (aKO) measurement methods were most appropriate at high loads. A method based on the maximum amplitude pressure oscillation (MAPO) during knock-free operation best estimated cycle classifications, whilst Shahlari’s Signal Energy Ratio technique [1] most accurately predicted knock onset. To the author’s knowledge, this is the first time that such a comprehensive study on the accuracy of these techniques at such high loads has been conducted. Importantly, these findings represent a valuable framework to inform other researchers in the field of knocking combustion on which techniques are needed to extract accurate and relevant information from measured cylinder pressure records. Secondly, the data processing techniques derived were applied to experimental data collected across a wide range of high BMEP operating conditions (up to a maximum of 32 bar) using a 1.6 litre, 4-cylinder SI engine. Trapped charge composition and temperature were predicted using a calibrated 1D model of the engine, whilst the temperature of a hypothetical hotspot in the unburned zone was estimated separately by assuming adiabatic compression from a point after intake valve closing and by mapping γ (the ratio of specific heat capacities) as a function of temperature. This revealed that none of the IDCs tested performed well at conditions relevant to modern, downsized engines. The IDC that achieved the best overall balance between aKO accuracy and cycle-classification agreement was the “cool-flame” correlation for iso-octane proposed by Ma [2]. However, this had an unacceptably high average aKO error of ±3.5° compared to the ±2°CA limit observed within the literature, and its average cycle-classification accuracy was below 60%. The main reason for this relatively modest accuracy was a large number of false-positive cycle classifications, which mainly occurred in slow or late burning cycles. Further work should therefore focus on methods to reduce the number of false positive classifications obtained with this correlation, which could be achieved using empirical correlations to describe the latest point in the cycle for which knock would be permitted to occur in terms other measureable combustion parameters. Overall, this research has generated a unique insight into combustion at very high loads, as well as an extensive dataset that can be used for future research to improve the accuracy of empirical knock modelling techniques. Furthermore, this work has demonstrated that for the purposes of virtual spark timing calibration and the avoidance of knock, the current crop of practical simulation tools is not accurate enough at the conditions relevant to modern SI engines and has provided a better understanding of their limitations. These findings represent a major contribution to the field from both a research perspective and for industrial applications.

Gasoline spills are sources of groundwater contamination. In the event of a spill, timely remediation efforts can advert most of the potential groundwater contamination due to the immiscibility of gasoline in water. Ethanol functions as a cosolvent that can increase the solubility of gasoline in water. Therefore, the risk of groundwater contamination in the event of a fuel spill increases as the ethanol content in automobile fuels increases. This study examines the effect fuel spill size and ethanol content has on the quantities of toluene, ethylbenzene, m-xylene and o-xylene (TEMO) that dissolve into the aqueous phase at equilibrium. Laboratory experiments were preformed to determine the mass fractions of TEMO in waters that were in contact with various volumes of gasoline and ethanol. UNIFAC is a model capable of predicting the concentrations of TEMO in the aqueous phase of a gasoline-ethanol-water system at equilibrium. In this study, the generalized UNIFAC-LLE method, designed for chemical engineering applications, was used to model the laboratory experiments. New UNIFAC-LLE parameters were developed to improve the model's accuracy in predicting the solubilities of aromatic species in ethanol-water mixtures. The new UNIFAC-LLE parameters were also used to model the laboratory experiments. The modeled results were compared to the analogous laboratory experiments. The UNIFAC-LLE parameters developed in this study improved the model's accuracy in predicting the solubilities of TEMO when the aqueous ethanol mass fraction was between 0.114 and 0.431.

A contaminação do ar e do meio ambiente por combustíveis derivados de petróleo tem sido objeto de crescente pesquisa no Brasil. Dentre os tipos de poluição ao meio ambiente, a poluição atmosférica é a que causa mais incômodo à população. Esta exerce efeitos sobre a saúde humana, causando desde simples irritações até câncer de pulmão. Dos poluentes mais perigosos encontrados nesses ambientes, são destaques os hidrocarbonetos e os compostos monoaromáticos como o benzeno, tolueno e xilenos (BTX), presentes nesses combustíveis, que são extremamente tóxicos à saúde humana. Para controle desses compostos orgânicos voláteis, é necessário quantificá-los e compará-los aos valores limites de tolerância legislados no Brasil. A utilização da técnica de cromatografia gasosa e da técnica de espectroscopia por infravermelho permite realizar essa tarefa de maneira relativamente simples e rápida. Portanto o objetivo deste trabalho foi apresentar a composição química de amostras de gasolina do tipo C comercializadas nos postos revendedores da Região Metropolitana do Estado do Rio de Janeiro. Foram feitas análises quantitativas dos principais grupos químicos (parafínicos, olefínicos, naftênicos e aromáticos) e etanol por Cromatografia Gasosa de Alta Resolução e da composição de benzeno, tolueno e xileno (BTX) pela técnica de absorção no infravermelho. Os resultados foram comparados com os limites dados pela especificação da ANP (Portaria n 309) para a qualidade da gasolina, com o objetivo de se verificar se estão em conformidade com este agente regulamentador. Os resultados mostraram que todos os teores encontrados de olefínicos e aromáticos foram abaixo do limite especificado. Alguns postos apresentaram os teores de benzeno acima do limite especificado, indicando um nível de ação por parte da ANP principalmente pela ação tóxica do benzeno / The air contamination and the environment by fuels derived from crude oil has been object of increasing research in Brazil. Amongst the types of pollution to the environment, the atmospheric pollution is the one that cause more discomfort to the population. This exerts effects on the human health, causing since simple irritations until lung cancer. Among the most dangerous pollutants found in these environments are prominences the aliphatic hydro carbons and monoaromatic hydrocarbons compounds as benzene, toluene and xylems (BTX), present in these fuels that are extremely toxic to the human health. To control these volatile organic compounds, is necessary to quantify and to compare them with the tolerance limits value legislated in Brazil. The gas chromatography and infra-red ray spectroscopy techniques utilization allows realizing easily and fast these tasks. Therefore the objective of this work was to present the type C gasoline samples chemical composition commercialized on the gas station of the metropolitan region on Rio de Janeiro state. Had been made quantitative analyses for the main chemical groups (paraffins, olefins, naphthenics and aromatics) and ethanol by high resolution Gas Chromatography and the composition for benzene, toluene and xylem (BTX), by infra-red ray absorption technique. The results had been compared with the limits given by ANP specification (Portaria n 309) for the gasoline quality, with the objective to verify if they are in compliance with this regulatory agent. The results had shown that all amount founded for aromatics and olefinics had been below of the specified limit. Some gas station had presented amount for benzene above of the specified limit, indicating that ANP need to take some actions toward these gas station, mainly for the benzene toxicity action

Because of the limited supply of imported crude oil and environmental degradation, renewable energy is becoming commercially feasible and environmentally desirable. In this research, biological and thermal (pyrolysis) conversion pathways for biofuel production from lignocellulosic feedstocks were compared. For biological conversions of sorghum, ethanol yield was improved using M81-E variety (0.072 g/g juice) over Umbrella (0.065 g/g juice) for first-generation biomass (sorghum juice), and 0.042 g/g sorghum was obtained from the cellulosic portion of second-generation biomass. When ultrasonication was combined with hot water pretreatment, yields increased by 15% and 7% for cellulose to glucose, and hemicellulose to pentose, respectively. Ethanol yield was 10% higher when this pretreatment was combined with Accellerase 1500+XC for saccharification. Biological conversion yielded 1,600?2,300 L ethanol/ha for first-generation biomass, and 4,300?4,500 L ethanol/ha from lignocellulosic biomass. For thermal (pyrolysis) conversion of lignocellulosic switchgrass at 600 degrees C, product yield was 37% bio-oil, 26% syngas, and 25% bio-char. At 400 degrees C, product yield was 22% bio-oil, 8% syngas, and 56% bio-char. Bio-oil from pyrolysis was highly oxygenated (37 wt%). It required chemical transformation to increase its volatility and thermal stability, and to reduce its viscosity by removing objectionable oxygen, so the product could be used as transportation fuel (gasoline). As a consequence of upgrading bio-oil by catalytic hydrogenation, bio-oil oxygen decreased from 37?2 wt%, carbon increased from 50?83 wt%, hydrogen increased from 9?15 wt% and heating value increased from 36?46 MJ/kg, resulting in a fuel that was comparable to gasoline. The upgraded product passed the thermal stability test when kept under an oxygen-rich environment. The upgraded product consisted of 14.8% parrafins, 21.7% iso-parrafins, 3% napthene, 42.6% aromatics, 4.7% olefin, 4.7% DMF, 8% alcohol, and 0.6% ketone on a mass basis. Comparing the two pathways, biological conversion had 11 wt% ethanol yield from sorghum, and thermal conversion had 13 wt% gasoline yield from switchgrass. For process efficiency, thermal conversion had 35% energy loss versus 45% energy loss for biological conversions. For the biological pathway, ethanol cost was $2.5/gallon ($4/gallon, gasoline equivalent), whereas for the thermal pathway, switchgrass gasoline cost was $3.7/gallon, both with 15% before tax profit.

Since 1970, vehicle’s exhaust pollutions have received increasing attention as a source of air pollution at both local (human health concerns) and global (global warming) scales. This study mainly discusses diesel and gasoline vehicles because, today, over 90% of vehicles on the road use gasoline and diesel fuels. The major concerns of gasoline exhaust contaminants are carbon monoxide (CO), hydrocarbon (HC), carbon dioxide (CO2) and polycyclic aromatic hydrocarbons (PAHs); the major concerns of diesel exhaust emissions contaminants are nitrogen oxides (NOX) and particulate matter (PM). The aim of this study is mainly to compare gasoline and diesel fuels, and to determine which fuel and its developed forms are less harmful to humans, and which are most suitable for the natural environment at both a local and global level. The results show that burning gasoline fuels will emit less PM and NOX emissions than burning diesel fuels, but it will generate about 50% more CO2 than diesel fuels, and it also emit about ten times more CO, PAHs and around five times more HC than diesel fuels; burning diesel fuels will produce less CO2 emissions than gasoline fuels, but will emit around ten times more NOX and PM than gasoline fuels. Consequently using a gasoline car in urban areas might help to reduce the human health effects; using a diesel car on motorways or in rural areas might help to reduce the greenhouse gas (GHG) emissions and minimize the global warming effects. Biofuels, biodiesel and ethanol, have the potential to minimize the vehicle exhaust emissions and adverse effects. Nonetheless, there are still many debatable issues around biodiesel, such as insufficient fuel supply and health concerns (especially, ultrafine particles (UFPs)). In the future, there remains a need to continue the further studies of vehicle exhaust emissions, and to improve the understanding of all vehicle exhaust emissions and all of their impacts, especially the vehicle exhaust health research.