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1 
Quantitative StructureProperty Relationships Modeling of Rate Constants of Selected Micropollutants in Drinking Water Treatment Using Ozonation and UV/H2O2Jin, Xiaohui 16 May 2012 (has links)
Concern over the occurrence of micropollutants in drinking water and their health effects is increasing. Therefore, there is a growing interest in understanding micropollutant removal during drinking water treatment. Ozonation and advanced oxidation processes (AOPs) have been found to be effective in the degradation of many micropollutants. Ozonation involves reactions with both molecular ozone (direct pathway) and hydroxyl radicals (indirect pathway), while hydroxyl radicals are the main oxidants in advanced oxidation processes. Reaction rate constants of micropollutants with molecular ozone (kO3) and hydroxyl radicals (kOH) are indicators of their reactivity and are therefore useful in assessing their removal efficiency in ozonation and AOPs. However, to date, only a limited number of rate constants are available for micropollutants, especially emerging micropollutants such as endocrine disrupting chemicals (EDCs) and pharmaceuticals. Quantitative structureproperty relationships (QSPR) are therefore desirable for predicting rate constants of numerous untested micropollutants without experimentation. The overall objective of this thesis was to develop predictive QSPR models which correlate the rate constants of a wide range of structural diverse micropollutants to their structural characteristics.
To ensure the wide applicability of the QSPR models, the training set compound selection is critical and a group of heterogeneous compounds which are structurally representative of many others is preferred. A systematic compound selection approach which involves principal component analysis (PCA) and Doptimal onion design was applied for the first time in water treatment research. As a result, 22 micropollutants with diverse structures were selected as representatives from a large pool of micropollutants of interest (182 compounds). In addition, 12 molecular descriptors were identified which link relevant structural features to the removal mechanisms of oxidation processes.
The kO3 and kOH values of the 22 selected micropollutants were then determined experimentally in benchscale reactors at neutral pH using high performance liquid chromatography equipped with a photodiode array detector (HPLCPDA). Three methods, competition kinetics, compound monitoring, and ozone monitoring were used for kO3 measurement, and competition kinetics was used for kOH measurement. As expected, kO3 values span a wide range from 102 to 107 M1 s1 because of the selective nature of molecular ozone. The general trends of micropollutant reactivity with ozone can be explained by the micropollutant structures and the electrophilic nature of ozone reactions. The kOH values range from 108 to 1010 M1 s1 because hydroxyl radicals are relatively nonselective in their reactions. For the majority of these micropollutants kO3 and kOH values were not reported prior to this study. Thus they provide valuable information for modeling and designing of ozonation and AOP treatment.
QSPR models for kO3 and kOH prediction were then developed with special attention to model validation, applicability domain and mechanistic interpretation. With the experimentally determined rate constants, QSPR models were developed for predicting kO3 values using the selected 22 micropollutants as the training set and the 12 identified descriptors as model variables. As a result, two QSPR models were developed using piecewise linear regression (PLR) both showing an excellent goodnessoffit. Model 1 was governed by average molecular weight and number of phenolic functional groups, and Model 2 was dominated by two principal components extracted from the descriptor matrix. The models were then validated using an external validation set collected from the literature, showing good predictive power of both models. Prior to applying these models to unknown micropollutants they need to be classified as highreactive (logkO3 > 2 M1 s1) or lowreactive (logkO3 2 M1 s1), so that the appropriate submodel of the PLR can be applied. A classification function using linear discriminant analysis (LDA) was therefore developed which worked very well for both training and validation sets. With the help of additional compounds collected from the literature, and DRAGON molecular descriptors, a QSPR model for kOH prediction in the aqueous phase was developed using multiple linear regression. As a result, 7 DRAGON descriptors were found to be significant in modeling kOH, which related kOH of micropollutants to their electronegativity, polarizability, presence of double bonds and Hbond acceptors. The model fitted the training set very well and showed great predictive power as assessed by the external validation set. In addition, the model is applicable to a wide range of micropollutants. The model’s applicability domain was defined using a leverage approach.
The main contributions of this thesis lie in the successful development of QSPR models for kO3 and kOH value prediction which, for the first time, can be used for a wide range of structurally diverse micropollutants. In addition, all QSPR models were externally validated to verify their predictive power, and the applicability domains were defined so that the applicability of the models to new compounds can be determined.
Finally, the applicability of the model to natural water was explored by combining the QSPR models with the established Rct concept which predicts micropollutant removals during ozone treatment of natural water but requires kinetic data as input. Results show that the kinetic data from the QSPR model predictions worked well in the Rct model providing reliable estimations for most of the selected micropollutants. This approach can therefore be used in water treatment for initial assessment and estimation of ozonation efficiency.

2 
Ozonation of erythromycin and the effects of pH, carbonate and phosphate buffers, and initial ozone doseHuang, Ling, 1988 29 September 2011 (has links)
The ubiquitous presence and chronic effect of pharmaceuticals is one of the emerging issues in environmental field. As a result of incomplete removal by sewage treatment plants, pharmaceuticals are released into the environment and drinking water sources. On the other hand, conventional drinking water treatment processes such as coagulation, filtration and sedimentation are reported to be ineffective at removing pharmaceuticals. Therefore, the potential presence of pharmaceuticals in finished drinking water poses a threat on public health. Antibiotics, as an important group of pharmaceuticals, are given special concerns because the potential development of bacteriaresistance. Ozonation and advanced oxidation processes are demonstrated to be quite effective at removing pharmaceuticals. The oxidation of pharmaceuticals is caused by ozone itself and hydroxyl radicals that are generated from ozone decomposition. Whether ozone or hydroxyl radicals are the primary oxidant depends on the specific pharmaceutical of interest and the background water matrix. In this research, erythromycin, a macrolide antibiotic, was chosen as the target compound because of its high detection frequency in the environment and its regulation status. The objective of this research was to investigate the removal performance of erythromycin by ozonation from the standpoint of kinetics. The effects of pH, carbonate and phosphate buffers, and initial ozone dose on ozonation of erythromycin were also studied. The secondorder rate constant for the reaction between deprotonated erythromycin and ozone was determined to be 4.44x10⁹ M⁻¹·s⁻¹ while protonated erythromycin did not react with ozone. Ozone was determined to be the primary oxidant for erythromycin removal by ozonation. pH was found to have great positive impact on the degradation of erythromycin by ozonation due to the deprotonation of erythromycin at high pH. Carbonate and phosphate buffers were found to have negligible effects on the degradation of erythromycin by ozonation. Initial ozone dose showed a positive impact on the total erythromycin removal rate by ozonation. / text

3 
Resistance Switching Charateristics of Titaniumdoped silicon oxide thin film with Supercritical Fluid TreatmentJiang, JhaoPing 27 August 2012 (has links)
The resistance random access memory (RRAM) is one of the most popular of the next generation memories with the high operating speed, reliability and the smallest miniature size. RRAM has metalinsulatormetal structure that can greatly reduce the difficulty of entry, but the biggest problem is how to choose the insulator. We selected siliconbased materials to match the intergrated circuits manufacturing process.
In this work, sputtering titanium doping in the silicon oxide thin film has a stable characteristic of resistance switching. By material analyzing, we found that supercritical carbon dioxide fluid (SCCO2) treatment can passivate the silicon oxide defect and the selfreduction of titanium oxide, but it also brought OH group into our thin film. So we observed the interface type characteristic of resistance switching. Using constant voltage sampling experiment extract the reaction rate constant (k) and the active energy, prove that the reaction is caused by OH injection.
Doublelayer structure with titaniumdoped and carbondoped silicon oxide RRAM promote lower operating current by hopping conduction, which is caused by graphite oxide doping. The SpaceCharge Limited Current mechanism for high limited current is proven by COMSOL electric field simulation.

4 
Effect of Cement Chemistry and Properties on Activation EnergyBienAime, Andre J. 01 January 2013 (has links)
The objective of this work is to examine the effect of cement chemistry and physical properties on activation energy. Research efforts indicated that time dependent concrete properties such as strength, heat evolution, and thermal cracking are predictable through the concept of activation energy. Equivalent age concept, which uses the activation energy is key to such predictions. Furthermore, research has shown that Portland cement concrete properties are affected by particles size distribution, Blaine fineness, mineralogy and chemical composition. In this study, four Portland cements were used to evaluate different methods of activation energy determination based on strength and heat of hydration of paste and mortar mixtures. Moreover, equivalency of activation energy determined through strength and heat of hydration is addressed. The findings indicate that activation energy determined through strength measurements cannot be used for heat of hydration prediction. Additionally, models were proposed that are capable of predicting the activation energy for heat of hydration and strength. The proposed models incorporated the effect of cement chemistry, mineralogy, and particle size distribution in predicting activation energy.

5 
Bulk deposition of pesticide mixtures in a Canadian prairie city and the influence of soil temperature fluctuations on 17βestradiol mineralizationAndronak, Lindsey Amy 16 August 2013 (has links)
Tests were conducted for 71 pesticides in weekly bulk (wet + dry) deposition samples collected from May 25 to September 21 over two years at two sites in the City of Winnipeg, Canada. Twentyone pesticides and their metabolites were detected in this study and 99% of samples collected contained mixtures of two or more pesticides. Malathion and glyphosate were the largest contributors to bulk deposition in 2010 and 2011, respectively. A second study examined the mineralization of 2,4D and 17βestradiol using a novel infield soil microcosm study and a series of laboratory experiments under different temperature incubations. Results indicated that temperature fluctuations do not greatly affect the amount or rate of mineralization relative to the traditionally constant laboratory incubations of 20°C; however longterm freezing of soil reduced potential mineralization over time. This research advances scientific knowledge of agrichemical fate and provides data for strengthening current environmental policy analysis in Canada.

6 
Bulk deposition of pesticide mixtures in a Canadian prairie city and the influence of soil temperature fluctuations on 17βestradiol mineralizationAndronak, Lindsey Amy 16 August 2013 (has links)
Tests were conducted for 71 pesticides in weekly bulk (wet + dry) deposition samples collected from May 25 to September 21 over two years at two sites in the City of Winnipeg, Canada. Twentyone pesticides and their metabolites were detected in this study and 99% of samples collected contained mixtures of two or more pesticides. Malathion and glyphosate were the largest contributors to bulk deposition in 2010 and 2011, respectively. A second study examined the mineralization of 2,4D and 17βestradiol using a novel infield soil microcosm study and a series of laboratory experiments under different temperature incubations. Results indicated that temperature fluctuations do not greatly affect the amount or rate of mineralization relative to the traditionally constant laboratory incubations of 20°C; however longterm freezing of soil reduced potential mineralization over time. This research advances scientific knowledge of agrichemical fate and provides data for strengthening current environmental policy analysis in Canada.

7 
A new method for computing anharmonic rovibrational densities of states of interstellar and atmospheric clusters at arbitrary angular momentaSarah Windsor Unknown Date (has links)
A new methodology is developed to calculate density of states of interstellar and atmospheric clusters that takes account of their loosely bound nature and incorporates kinetically important angular momentum constraints explicitly. The method is based on classical phase space integration for the intermonomer modes of the cluster with imposition of the constraints of selected total energy and total angular momentum. It achieves considerable efficiency via essentially analytic evaluation of the momentum space integrals coupled with efficient Monte Carlo sampling of configurations. The derivation for the equation for the density of states is outlined and all steps in the simplification of the accessible momentum space volume are detailed. The method is tested rigorously against an entirely analytic result obtained for the ideal case of a dimer with spherical top fragments and no interaction potential. Interstellar applications of the new approach are presented for (HCN)2 and (CO)2. The new intermononmer density of states has been integrated over metastable states to obtain the intermonomer partition function, which in turn is used to calculate the metastable equilibrium constants for interstellar clusters, which in turn is used tocalculate the second order rate constant of overall dimer formation in the interstellar environment. Atmospheric applications of the new approach are presented for (H2O)2. The new intermonomer density of states is convoluted with the intramonomer density of states to obtain the convoluted density of states. This convoluted density of states is then integrated over total energy and angular momentum to obtain the anharmonic partition function, which in turn is used to calculate the equilibrium constant for atmospheric clusters, which in turn is used to calculate the third order rate constant for overall dimer formation in the atmospheric environment. Kinetic quantities are also calculated with the intermonomer and convoluted density of states for interstellar and atmospheric clusters, respectively. These densities of states are combined with RRKM theory to compute unimolecular dissociation rate constants, which are then averaged with respect to the thermal capture flux distribution to compute average lifetimes as a function of temperature.

8 
A new method for computing anharmonic rovibrational densities of states of interstellar and atmospheric clusters at arbitrary angular momentaSarah Windsor Unknown Date (has links)
A new methodology is developed to calculate density of states of interstellar and atmospheric clusters that takes account of their loosely bound nature and incorporates kinetically important angular momentum constraints explicitly. The method is based on classical phase space integration for the intermonomer modes of the cluster with imposition of the constraints of selected total energy and total angular momentum. It achieves considerable efficiency via essentially analytic evaluation of the momentum space integrals coupled with efficient Monte Carlo sampling of configurations. The derivation for the equation for the density of states is outlined and all steps in the simplification of the accessible momentum space volume are detailed. The method is tested rigorously against an entirely analytic result obtained for the ideal case of a dimer with spherical top fragments and no interaction potential. Interstellar applications of the new approach are presented for (HCN)2 and (CO)2. The new intermononmer density of states has been integrated over metastable states to obtain the intermonomer partition function, which in turn is used to calculate the metastable equilibrium constants for interstellar clusters, which in turn is used tocalculate the second order rate constant of overall dimer formation in the interstellar environment. Atmospheric applications of the new approach are presented for (H2O)2. The new intermonomer density of states is convoluted with the intramonomer density of states to obtain the convoluted density of states. This convoluted density of states is then integrated over total energy and angular momentum to obtain the anharmonic partition function, which in turn is used to calculate the equilibrium constant for atmospheric clusters, which in turn is used to calculate the third order rate constant for overall dimer formation in the atmospheric environment. Kinetic quantities are also calculated with the intermonomer and convoluted density of states for interstellar and atmospheric clusters, respectively. These densities of states are combined with RRKM theory to compute unimolecular dissociation rate constants, which are then averaged with respect to the thermal capture flux distribution to compute average lifetimes as a function of temperature.

9 
A new method for computing anharmonic rovibrational densities of states of interstellar and atmospheric clusters at arbitrary angular momentaSarah Windsor Unknown Date (has links)
A new methodology is developed to calculate density of states of interstellar and atmospheric clusters that takes account of their loosely bound nature and incorporates kinetically important angular momentum constraints explicitly. The method is based on classical phase space integration for the intermonomer modes of the cluster with imposition of the constraints of selected total energy and total angular momentum. It achieves considerable efficiency via essentially analytic evaluation of the momentum space integrals coupled with efficient Monte Carlo sampling of configurations. The derivation for the equation for the density of states is outlined and all steps in the simplification of the accessible momentum space volume are detailed. The method is tested rigorously against an entirely analytic result obtained for the ideal case of a dimer with spherical top fragments and no interaction potential. Interstellar applications of the new approach are presented for (HCN)2 and (CO)2. The new intermononmer density of states has been integrated over metastable states to obtain the intermonomer partition function, which in turn is used to calculate the metastable equilibrium constants for interstellar clusters, which in turn is used tocalculate the second order rate constant of overall dimer formation in the interstellar environment. Atmospheric applications of the new approach are presented for (H2O)2. The new intermonomer density of states is convoluted with the intramonomer density of states to obtain the convoluted density of states. This convoluted density of states is then integrated over total energy and angular momentum to obtain the anharmonic partition function, which in turn is used to calculate the equilibrium constant for atmospheric clusters, which in turn is used to calculate the third order rate constant for overall dimer formation in the atmospheric environment. Kinetic quantities are also calculated with the intermonomer and convoluted density of states for interstellar and atmospheric clusters, respectively. These densities of states are combined with RRKM theory to compute unimolecular dissociation rate constants, which are then averaged with respect to the thermal capture flux distribution to compute average lifetimes as a function of temperature.

10 
A new method for computing anharmonic rovibrational densities of states of interstellar and atmospheric clusters at arbitrary angular momentaSarah Windsor Unknown Date (has links)
A new methodology is developed to calculate density of states of interstellar and atmospheric clusters that takes account of their loosely bound nature and incorporates kinetically important angular momentum constraints explicitly. The method is based on classical phase space integration for the intermonomer modes of the cluster with imposition of the constraints of selected total energy and total angular momentum. It achieves considerable efficiency via essentially analytic evaluation of the momentum space integrals coupled with efficient Monte Carlo sampling of configurations. The derivation for the equation for the density of states is outlined and all steps in the simplification of the accessible momentum space volume are detailed. The method is tested rigorously against an entirely analytic result obtained for the ideal case of a dimer with spherical top fragments and no interaction potential. Interstellar applications of the new approach are presented for (HCN)2 and (CO)2. The new intermononmer density of states has been integrated over metastable states to obtain the intermonomer partition function, which in turn is used to calculate the metastable equilibrium constants for interstellar clusters, which in turn is used tocalculate the second order rate constant of overall dimer formation in the interstellar environment. Atmospheric applications of the new approach are presented for (H2O)2. The new intermonomer density of states is convoluted with the intramonomer density of states to obtain the convoluted density of states. This convoluted density of states is then integrated over total energy and angular momentum to obtain the anharmonic partition function, which in turn is used to calculate the equilibrium constant for atmospheric clusters, which in turn is used to calculate the third order rate constant for overall dimer formation in the atmospheric environment. Kinetic quantities are also calculated with the intermonomer and convoluted density of states for interstellar and atmospheric clusters, respectively. These densities of states are combined with RRKM theory to compute unimolecular dissociation rate constants, which are then averaged with respect to the thermal capture flux distribution to compute average lifetimes as a function of temperature.

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