Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on October 15, 2007) Vita. Includes bibliographical references.

Thesis (M.S. in Operations Research)--Naval Postgraduate School, March 2007. / Thesis Advisor(s): Daniel A. Nussbaum. "March 2007." Includes bibliographical references (p. 95-99). Also available in print.

21, [58] leaves : ill. ; 28 cm.

Ph.D. (Chemistry) / The main objective of this study was to develop sample preparation methods based on separation and preconcentration of trace metals in organic matrices (alcohols, diesel and gasoline). The presence of metals in organic matrices is undesirable, unless they are used as additives. Therefore, it is important to control and monitor their concentrations in fuel and petrochemical products as they tend to affect the quality of these products. Solid phase extraction (SPE), solid phase microextraction (SPME) and hollow fiber-liquid phase microextraction (HF-LPME were used for separation and preconcentration of Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, V and Zn prior to their inductively coupled plasma optical emission/mass spectrometric (ICP OES/-MS) determination. For solid phase extraction, the exchange efficiencies of different commercial ion exchange resins, namely Dowex 50W-x8, Dowex 1-x8, Dowex MAC-3 and Chelex 100, for preconcentration of metal ions in alcohol and fuel samples, were investigated. The results obtained indicated that Dowex 50W-x8 was suitable for simultaneous preconcentration of cations such as Cd, Co, Ni, Cu, Fe, Mn and Zn, among other metals while Dowex 1-x8 was suitable for metal ions that exists in more than one oxidation states, namely, As, Cr, Mo, Sb and V. Chelex-100 and Dowex MAC-3 were found to be selective to a limited number of target metal analytes. For further applications, Dowex 50W-x8 and Dowex 1-x8 were employed. Furthermore, the applicability of synthetic adsorbents such as nanometer-sized alumina and functionalized cellulose nanofibers for preconcentration of trace metals in gasoline samples, was investigated. Nanometer-sized alumina sorbent was found to be suitable for simultaneous separation and preconcentration of Co, Cr, Mn, Ni and Ti. Functionalized cellulose nanofibers on the hand, were suitable for simultaneous preconcentration of Cd, Cu, Fe, Pb and Zn. The optimization of the experimental parameters was achieved by both univariate and multivariate procedure. The second preconcentration technique was solid phase microextraction which was also used for extraction and enrichment of metal ions in diesel samples using two approaches of the SPME method. The first approach was hollow fiber-solid phase microextraction (HF–SPME) method using fiber-supported sol-gel combined with a cation exchange resin (Dowex 50W-x8). This method showed satisfactory results for the preconcentration of Cd, Cu, Fe, Pb and Zn in diesel and gasoline samples. The second approach was based on membrane solid phase microextraction (MSPME) using titania-alumina hollow fiber. The MSPME method applied was used for extraction and preconcentration of trace amounts of Co, Cr, Mo, Ni, Sb and V in liquid fuel samples. Multivariate techniques were used for optimization of experimental parameters for both approaches. The last preconcentration technique that was developed was hollow fiber- liquid phase microextraction (HF-LPME). In this method fuel samples were first digested before being subjected to HF-LPME system. Ammonium pyrrolidine dithiocarbamate (APDC) and [C6MIM][PF6] ionic liquid were both used as chelating agent and acceptor phase, respectively. Two level factorial and central composite designs were used for multivariate optimization of experimental parameters. Satisfactory results were obtained for extraction and preconcentration of Ag, Al, As, Mn and Ti.

In the last decade or so political scientists have found the pluralist and marxist theoretical perspectives wanting for their inadequate attention to the causal role of states. In response, a burgeoning international literature has emerged which sets out to develop a state-centred theoretical perspective. This study is deeply informed by the emerging statist theoretical perspective. This thesis explores the relative capacity of the federal state to increase its autonomy in relation to the powerful oil MNCs in the period 1973-84 through an expanded federal presence in the energy sector. Whereas many scholars have assumed that a positive relationship existed between state capacity and the effectiveness of state intervention, Evans and Ikenberry for instance argue that an almost inverse relationship exists between the magnitude of intervention and its effectiveness. In Canada the literature on federalism has long been cognizant of the important role of states. This thesis therefore attempts to fuse the two bodies of literature, namely statism and federalism, in order to shed added light on the development of federal oil policy during 1973-84. The fact that the Canadian state is federal accounts for the recurring tendency for the energy issue to be redefined from its "obvious" focus on state-oil industry relations to intrastate issues (federal-provincial relations). A major contribution of this thesis is to explore the circumstances in which jurisdictional concerns deflect attention from policy substance - and also to those in which the reverse occurs. The thesis finds that when one level of government sought to become more independent of dominant societal actors, such as the oil industry, the intervention, whether so intended or not, was redefined to follow intergovernmental lines of conflict, rather than state-society lines of conflict. The nature of the issues also changed as distributional problems became subsumed under and were driven by the jurisdictional concerns of governments. This increased the policy interdependence between the two levels of government, squeezed out industry interests from intergovernmental deliberations, and generated intervention aimed directly at curtailing the power of the other level of government. This intervention which at first rendered the aggregate state less dependent on the oil industry by for example the creation of Petro-Canada, and later by the NEP, ultimately backfired on the state, at both levels. Important world oil market changes, intergovernmental conflicts and stalemates, deteriorating economic performance, industry reactions, and other mounting economic and political problems undermined the federal government's intervention and led to concessions for the industry. Such concessions were therefore the product of an increasingly irrelevant regulatory framework rather than purely a reflection of the power of the oil industry as such. This thesis confirms in general terms Ikenberry's finding that an inverse relationship exists between the degree and magnitude of intervention and its effectiveness. Evans and Ikenberry see this most clearly in relation to NOCs, that is in their propensity to evade state control schemes and to undermine centralized state control. In Canada the opposite change.exacerbated conflicts, namely the efforts by governments to shore up their capabilities as corporate actors and the emergence of "political federalism" which saw decision-making becoming centralized within each government, in the hands of decision-makers with jurisdiction-wide concerns. The ensuing process of intrajurisdictional policy coordination not only exacerbated conflicts but also oriented the emerging policy instruments along intergovernmental lines. Another contributing factor was the learning process that decision-makers underwent in the intergovernmental arena. In addition, 'policy mobilization' in the NEP served to link Petro-Canada closer to the political objectives of federal elites. Therefore, while the effects are the same in Canada, the process is almost the reverse of the one described by Evans and Ikenberry. Evans and Ikenberry see ineffective state intervention largely as the product of state actors mobilizing societal actors and state and societal actors becoming more closely linked. This study supplements the statist literature by noting that the attempts of a number of interventionist governmental actors to introduce comprehensive and more independent interventionist strategies heightened conflicts, generated inefficiencies and essentially caused the intervention to fail. / Arts, Faculty of / Political Science, Department of / Graduate

The objectives of this dissertation are to explain the production behavior of OPEC's member countries from 1971 to 1987 and to determine whether there was any structural shift in OPEC's production behavior after the organization attempted to assign a quota to each member. This study focused on political and social as well as economic variables, in order to overcome the misspecification of previous models. In order to achieve the above objectives, the study used the following four models, with modifications: the cartel, competitive, target revenue, and property rights models. The double log multiple linear regression technique was used to operationalize the cartel, competitive, and target revenue models; simple linear regression was used to estimate the property rights model. The cartel model was based not only on economic variables but also on social and political variables. The internal political instability of each OPEC country was measured by the number of armed attacks within the country. The structural shift in OPEC's production behavior between the 1971-1982 period and the 1983-1987 period was evaluated using the Chow-test. The Chow-test showed no significant difference between these two periods for OPEC overall or for individual members. Thus, the two periods were combined so that the study was performed for the entire 1971-1987 period. Because this period of analysis was relatively short, alternative models were applied to pool the data and thereby increase the reliability of the model estimates. A cross-sectional correlated and time-wise auto-regressive model (CCTA) was selected to pool the data and to estimate OPEC's production coefficients. Then each individual OPEC member's production model was estimated and compared to the pooled model. The results indicate that OPEC behaved as a cartel, and that a partial market-sharing hypothesis was significant for all 11 OPEC members. These findings indicate that OPEC was a loose cartel, with only partially effective cooperation on production decisions. Political instability was found to be significant (at the 10-percent level) overall, and it negatively affected production. It was also significant at the 5-percent level for the price-pusher group (Iran, Venezuela, and Algeria). This group was also the only one pooled using least squares with dummy variables (LSDV), because of its common slope and different intercepts. Overall results suggest that OPEC members were basing their production decisions on crude oil prices, excess production capacity, and each member's share of total OPEC output.

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The process of catalytic cracking of petroleum hydrocarbons invariably produces a carbonaceous deposit on the surface of the solid catalyst which serves to reduce the activity of the catalyst. This investigation was undertaken to determine the effect of the feed rate and the length of the cracking period on the carbon formation on the catalyst. A vertical, fixed-bed, externally heated reactor was constructed. The reactor contained a bed of synthetic silica-alumina Socony-Vacuum bead catalyst. The necessary auxiliary apparatus required to handle the feed and the products of reaction was provided. The amount of carbon deposited on the catalyst was determined by burning it and measuring the carbon dioxide thus formed. The feed material used was Esso Diesel Oil (208). It was exposed to the catalyst at a temperature of about 900 degrees Fahrenheit for a series of ten minute periods while the feed rate was varied from 0.42 to 5.55 volumes of feed per volume of catalyst per hour. Another series of tests was performed at the same temperature, the feed rate being held at approximately two volumes of feed per volume of catalyst per hour; while the length of the cracking period was varied between thirty-five seconds and thirty minutes. It was found that during the ten minute cracking periods the amount of carbon deposited on the catalyst was independent of the feed rate between the limits of 0.91 and 5.55 volumes of feed per volume of catalyst deposited on the catalyst was related to the length of the cracking period by a parabolic function. Further analysis of the data revealed that the amount of feed converted into carbon was related to the degree of conversion by a parabolic function. From the three relations mentioned above, an equation relating the conversion, the feed rate and the cracking period was derived. The form of this equation is as follows: V³⋅⁰ = (9.60 x 10⁵)/R_fv t⁰⋅⁷⁵ where V is the percent conversion, R_fv is the feed rate and t is the cracking time in minutes. It was further found that the activity of the catalyst was not materially decreased after a series of twenty-nine tests, but that the substitution of quartz chips for the catalyst in the reactor decreased the conversion obtained by 75 per cent. / M.S.