Physical Sciences and Mathematics Commons^™

Outstanding Advantages, Current Drawbacks, And Significant Recent Developments In Mechanochemistry: A Perspective View, Silvina Pagola

Chemistry & Biochemistry Faculty Publications

Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed …

Investigations Of Aerobic Methane Oxidation In Two Marine Seep Environments: Part 1—Chemical Kinetics, Eric W. Chan, Allan M. Shiller, Dongjoo J. Joung, Eleanor C. Arrington, David L. Valentine, Molly C. Redmond, John A. Breier, Scott A. Socolofsky, John D. Kessler

School of Earth, Environmental, and Marine Sciences Faculty Publications and Presentations

Microbial aerobic oxidation is known to be a significant sink of marine methane (CH4), contributing to the relatively minor atmospheric release of this greenhouse gas over vast stretches of the ocean. However, the chemical kinetics of aerobic CH4 oxidation are not well established, making it difficult to predict and assess the extent that CH4 is oxidized in seawater following seafloor release. Here we investigate the kinetics of aerobic CH4 oxidation using mesocosm incubations of fresh seawater samples collected from seep fields in Hudson Canyon, U.S. Atlantic Margin and MC118, Gulf of Mexico to gain a fundamental chemical understanding of this …

Investigations Of Aerobic Methane Oxidation In Two Marine Seep Environments: Part 2—Isotopic Kinetics, Eric W. Chan, Allan M. Shiller, Dongjoo J. Joung, Eleanor C. Arrington, David L. Valentine, Molly C. Redmond, John A. Breier, Scott A. Socolofsky, John D. Kessler

School of Earth, Environmental, and Marine Sciences Faculty Publications and Presentations

During aerobic oxidation of methane (CH4) in seawater, a process which mitigates atmospheric emissions, the 12C‐isotopologue reacts with a slightly greater rate constant than the 13C‐isotopologue, leaving the residual CH4 isotopically fractionated. Prior studies have attempted to exploit this systematic isotopic fractionation from methane oxidation to quantify the extent that a CH4 pool has been oxidized in seawater. However, cultivation‐based studies have suggested that isotopic fractionation fundamentally changes as a microbial population blooms in response to an influx of reactive substrates. Using a systematic mesocosm incubation study with recently collected seawater, here we investigate the fundamental isotopic kinetics of aerobic …

Kinetic Study Of Free Radical-Radical Reactions Of Combustion Importance At Elevated Pressures, Chao Yan

Dissertations

Combustion mechanisms consist of hundreds elementary reactions of free radicals and stable molecules. Radical-radical elementary reactions play important roles due to the high concentration in which free radicals are accumulated in combustion systems. Radical-radical reactions are typically multi-channel. Some of the channels might be of chain propagation or even chain branching nature, while other channels might be of chain termination nature. The relative importance of different channels is pressure dependent. Compared to radical-molecule reactions, radical-radical reactions are much less studied. This is due to the difficulties of well characterized quantitative production of radical species as well as due to the …

Analysis Of Ar(1s5) Metastable Populations In High Pressure Argon-Helium Gas Discharges, Daniel J. Emmons Ii

Theses and Dissertations

Simulations of an argon-helium plasma are performed for two high pressure discharge scenarios to find a uniform, large-volume plasma with Ar(1s5) metastable densities on the order of 10¹³ cm^-3 for use as the ground state in an optically pumped rare gas laser. An analysis of a pulsed direct current discharge is performed for a 7% argon in helium mixture at a pressure of 270 Torr using both zero and one-dimensional models. Kinetics of species relevant to the operation of an optically pumped rare gas laser are analyzed throughout the pulse duration to identify key reaction pathways. Simulations are …

Oxyhalogen-Sulfur Chemistry: Kinetics And Mechanism Of Oxidation Of N-Acetylthiourea By Aqueous Bromate And Acidified Bromate, Kudzanai Chipiso, Wilbes Mbiya, Thai Tran, Reuben H. Simoyi

Chemistry Faculty Publications and Presentations

The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess bromate conditions. The reaction displays an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3: 4BrO 3 – +3(CH 3 CO)NH(NH 2 )C=S+3H 2 O®4Br – +3(CH 3 CO)NH(NH 2 )C=O+3SO 4 2– +6H + (A) with a complete desulfurization of ACTU to its urea analogue. In excess bromate conditions the stoichiometry was 8:5: 8BrO 3 – + 5(CH 3 CO)NH(NH 2 )C=S + H 2 O ® 4Br 2 + 5(CH 3 CO)NH(NH 2 …

A Symmetry-Based Approach To Selecting Membership Functions And Its Relation To Chemical Kinetics, Vladik Kreinovich, Olga Kosheleva, Jorge Y. Cabrera, Mario Gutierrez, Thavatchai Ngamsantivong

Departmental Technical Reports (CS)

In many practical situations, we encounter physical quantities like time for which there is no fixed starting point for measurements: physical properties do not change if we simply change (shift) the starting point. To describe knowledge about such properties, it is desirable to select membership functions which are similarly shift-invariant. We show that while we cannot require that each membership function is shift-invariant, we can require that the linear space of all linear combinations of given membership functions is shift-invariant. We describe all such shift-invariant families of membership functions, and we show that they are naturally related to the corresponding …

Kinetics Of The Electrical Discharge Pumped Oxygen-Iodine Laser, Matthew A. Lange

Theses and Dissertations

A systematic study of microwave discharges at 2.45 GHz has been performed through the pressure range of sustainable electric discharges in pure oxygen flows of 2 to 10 Torr. A corresponding study of 13.56 MHz has also been performed at pressures of 2, 4, and 7 Torr. Optical emissions from O2(a 1Δ), O2(b 1Σ), and O-atoms have been measured from the center of a μ-wave discharge. Discharge residence times from 0.1 to 5 ms have been reported. The O2(b 1Σ) emissions, with a spectral resolution of 0.01 nm, have been used to measure the temperature of the gas, which typically …

Development, Kinetic Analysis And Applications Of 2-D Nanostructured Layered Metal Hydroxides, Stephen Majoni

Dissertations (1934 -)

Nanodimensional layered metal hydroxides which include layered hydroxy salts (LHSs) and hydroxy double salts (HDSs) have the ability to accommodate species between the layers. The structural composition of these materials can be tuned so as to create materials with targeted physico-chemical properties for applications where it is advantageous to intercalate or release molecules. Some of the applications include ion-exchange, fire retardation, catalysis, and controlled release delivery. Anion exchange reactions are among methods used to optimize these materials for targeted applications, making the characterization of exchange kinetics of practical interest. In addition, understanding fundamental factors that control retention and release of …

Comparative Study Of Ethanol And Methanol Electro-Oxidation On A Platinum/Ceria Composite Electrode In Alkaline And Acid Solutions : Electro-Catalytic Performance And Reaction Kinetics, Carlos Humberto Hidalgo Martinez

Electronic Theses and Dissertations

A comparative study of the electro-oxidation of ethanol and methanol was carried out on a Pt/ceria composite electrode prepared by electro-deposition. Modification of the Pt electrode was realized by co-deposition from a 1.0 mM K₂PtCl₆ solution that also contained a 20 mM suspension of ceria. The electro-catalytic activities and stabilities of the Pt/ceria catalyst towards ethanol electro-oxidation reactions (EOR) and methanol electro-oxidation reactions (MOR) were investigated by potentiodynamic and potentiostatic methods in 0.5 M sulfuric acid and 1.0 M sodium hydroxide solutions at various concentrations of ethanol and methanol. The kinetics of ethanol and methanol on a Pt/ceria composite electrode …

Detection Of Quercetin Using Polymer Coated Quartz Crystal Microbalance And The Modification Of Á-Zirconium Phosphate To Develop A Sorbent For Organic Pollutant Removal, Darlington Mlambo

Dissertations (1934 -)

Sorption processes involve physical and chemical interactions of sorbents with analytes. These may involve the physical and/or chemical processes in which a substance is accumulated at an interface between two phases, or the intermixing of a substance with the matrix of a second phase. The two processes are referred to as adsorption and absorption respectively. The sorption capacities of different classes of sorbents have many potential and demonstrated applications such as sensor development, water treatment, environmental remediation and chromatographic separations. The goal of this work is to explore the sorption capacity of polymers as well as nanodimensional layered materials for …

Statistical Thermodynamics And Kinetics Of Dna Multiplex Hybridization Reactions, Albert S. Benight, M. T. Horne, D. J. Fish

Chemistry Faculty Publications and Presentations

A general analytical description of the equilibrium and reaction kinetics of DNA multiplex hybridization has been developed. In this approach, multiplex hybridization is considered to be a competitive multichannel reaction process: a system wherein many species can react both specifically and nonspecifically with one another. General equations are presented that can consider equilibrium and kinetic models of multiplex hybridization systems comprised, in principle, of any number of targets and probes. Numerical solutions to these systems for both equilibrium and kinetic behaviors are provided. Practical examples demonstrate clear differences between results obtained from more common simplex methods, in which individual hybridization …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The corrosion of structural materials is a major concern for the use of lead-bismuth eutectic (LBE) systems for nuclear applications such as in transmuter targets or fast reactors. Corrosion in liquid metal systems can occur through various processes, including, for example, dissolution, formation of inter-metallic compounds at the interface, and penetration of liquid metal along grain boundaries. Predicting the rate of these processes depends on numerous system operational factors: temperature, system geometry, thermal gradients, solid and liquid compositions, and velocity of the liquid metal, to name a few. Corrosion, along with mechanical and/or hydraulic factors, often contributes to component failure. …

The Kinetics Following Photolysis Of Nitrosyl Bromide, Lori A. Mahoney

Theses and Dissertations

One candidate for the development of a tunable laser in the mid-infrared for use as a defensive countermeasure against passive sensors exploits the nitric oxide (NO) transition at 5.4 μm. However, the difficulty with this mechanism is that when bromine (Br₂) and NO are present in a mixture, nitrosyl bromide (BrNO) is also created. The absorption bands present in BrNO complicate the design of such a laser. This thesis determines the forward and reverse rate constants of the reaction of Br₂ and NO to form BrNO following the photolysis of BrNO using Fourier Transform Infrared absorption spectroscopy. …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Trp Final Report 09/01/2003-08/31/2004, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Fourth Quarterly Report 06/01/2004-08/31/2004, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Third Quarterly Report 03/01/2004-05/31/2004, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: First Quarterly Report 01/12/04-02/29/04, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The corrosion of structural materials is a major concern for the use of lead-bismuth eutectic (LBE) systems for nuclear applications such as in transmuter targets or fast reactors. Corrosion in liquid metal systems can occur through various processes, including, for example, dissolution, formation of inter-metallic compounds at the interface, and penetration of liquid metal along grain boundaries. Predicting the rate of these processes depends on numerous system operational factors: temperature, system geometry, thermal gradients, solid and liquid compositions, and velocity of the liquid metal, to name a few. Corrosion, along with mechanical and/or hydraulic factors, often contributes to component failure. …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Fourth Quarterly Report 09/01/2003-11/30/2003, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Fourth Quarterly Report 06/01/2003-08/30/2003, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Annual Report -Phase Ii 09/01/2002-08/30/2003, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the TRP proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics - Phase Three, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The proposed work will combine chemical kinetics and hydrodynamics in target and test-loop lead-bismuth eutectic (LBE) systems to model system corrosion effects. This approach will result in a predicative tool that can be validated with corrosion test data, used to systematically design tests and interpret the results, and provide guidance for optimization in LBE system designs. The task includes two subtasks. The first subtask is to try to develop the necessary predictive tools to be able to predict the levels of oxygen and corrosion products close to the boundary layer through the use of Computational Fluid Dynamics (CFD) modeling. The …

Quarterly Report For The Trp Project, March–June 2003, Samir Moujaes, Yitung Chen, Kanthi Kiran Daiska, Chao Wu

Transmutation Sciences Materials (TRP)

The MTL is assumed to be a 5m long rectangular loop with a circular cross-section. Because of the non-symmetry, and due to the active participation of the secondary flows due to the elbows present in the rectangular loop model, the geometry is considered as a 3D model.

When the regions of maximum corrosion and precipitation are compared, they fall in the same zone for both the analytical and simulated models. The reason for a larger concentration flux in the case of turbulent flow than for the laminar flow can be explained by the concept of higher lateral diffusion in the …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Quarterly Progress Report 12/1/02- 2/28/03, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application.

Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with very limited density. The transport of oxygen and corrosion products, their interaction and variation of corrosion/precipitation along the flow are not well understood.

The first subtask of this project involves using a …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The corrosion of structural materials is a major concern for the use of lead-bismuth eutectic (LBE) systems for nuclear applications such as in transmuter targets or fast reactors. Corrosion in liquid metal systems can occur through various processes, including, for example, dissolution, formation of inter-metallic compounds at the interface, and penetration of liquid metal along grain boundaries. Predicting the rate of these processes depends on numerous system operational factors: temperature, system geometry, thermal gradients, solid and liquid compositions, and velocity of the liquid metal, to name a few. Corrosion, along with mechanical and/or hydraulic factors, often contributes to component failure. …

Modeling Of Corrosion In Oxygen Controlled Lead Bismuth Eutectic Systems With The Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen, Kanthi Kiran Dasika, Chao Wu

Transmutation Sciences Materials (TRP)

Objectives:

• To simulate a 2-D model of the Materials Test Loop by approximating it to be a toroid with a pie cross section for the purpose of comparing the simulated results with the analytical results.
• The temperature and concentration profiles on the wall boundaries imposed are similar to the actual test model.
• Geometry effects have great influence on local corrosion rate.
• A 2-D benchmark problem and a sudden expansion case are studied which show good consistency to analytical solution.
• Results from 2-D sudden expansion problem are similar to experimental data obtained by other researchers.

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Final Report -Phase I 09/01/2001-08/30/2002, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Quarterly Progress Report 03/16/02- 06/15/02, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with very limited density. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high oxygen concentration, …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Phase Two, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The proposed work will combine chemical kinetics and hydrodynamics in target and test-loop lead-bismuth eutectic (LBE) systems to model system corrosion effects. This approach will result in a predicative tool that can be validated with corrosion test data, used to systematically design tests and interpret the results, and provide guidance for optimization in LBE system designs. The task includes two subtasks. The first subtask is to try to develop the necessary predictive tools to be able to predict the levels of oxygen and corrosion products close to the boundary layer through the use of Computational Fluid Dynamics (CFD) modeling. The …