Engineering Commons^™

Determination Of Transport And Electrochemical Kinetic Parameters Of Bare And Copper-Coated Lani4.27Sn0.24 Electrodes In Alkaline Solution, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

Electrochemical properties of bare and copper-coated LaNi_4.27Sn_0.24 electrodes were investigated in alkaline solution. The exchange current density, polarization resistance, and equilibrium potential were determined as functions of the state of charge in the electrodes. The symmetry factors for bare and copper-coated electrodes were estimated to be 0.53 and 0.52, respectively. By using a constant current discharge technique, the hydrogen diffusion coefficient in bare and coated LaNi_4.27Sn_0.24 was estimated to be 6.75 × 10^–11 cm²/s.

Application Of Porous Electrode Theory On Metal Hydride Electrodes In Alkaline Solution, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

Porous electrode theory was applied to estimate the exchange current density, the polarization resistance, and symmetry factor for LaNi_4.27Sn_0.24 hydride electrode in alkaline solution. The exchange current density, polarization resistance, and symmetry factor were determined from polarization curves which were obtained at low overpotentials.

Linear Algebra Used To Determine Independent Half‐Cell Equations, D. H. Coleman, Ralph E. White

Faculty Publications

No abstract provided.

Use Of A Hydrogen Anode For Nitrate Waste Destruction, E. E. Kalu, Ralph E. White, D. T. Hobbs

Faculty Publications

No abstract provided.

A Multiphase Mathematical Model Of A Nickel/Hydrogen Cell, Pauline De Vidts

Faculty Publications

No abstract provided.

Galvanostatic Pulse And Pulse Reverse Plating Of Zinc-Nickel Alloys From Sulfate Electrolytes On A Rotating Disc Electrode, Branko N Popov, M. Ramasubramanian, S. N. Popova, Ralph E. White, K-M. Yin

Faculty Publications

Galvanostatic pulse and pulse reverse techniques have been used to study the plating of zinc–nickel alloys in the presence of nonyl phenyl polyethylene oxide. The effects of average current density, rotation speed of disc electrode and the presence of nonyl phenyl polyethylene oxide in the electrolyte on deposition of zinc–nickel alloys were evaluated. Zinc–nickel plating bath solution chemistry was studied by determining the equilibrium concentrations at various pH levels. It was found that the alloy composition was determined by solution equilibria, mass transfer of the electroactive species within the diffusion layer and by the surface coverage of nonyl phenyl polyethylene …

A Model For The Galvanostatic Deposition Of Nickel Hydroxide, Mahesh Murthy, Gowri S. Nagarajan, John W. Weidner, John W. Van Zee

Faculty Publications

A mathematical model is presented for the galvanostatic deposition of Ni(OH)₂ films in stagnant Ni(NO₃)₂ solutions. The objective is to quantify the anomalous deposition behavior reported previously in which the utilization of the electrochemically generated OH^– species decreased drastically as the concentration of Ni(NO₃)₂ increased beyond 0.1 M. For example as the Ni(NO₃)₂ concentration increased from 0.1 to 2.0 M, the deposition rate decreased by a factor of ten at 2.5 mA/cm². At this high ratio of concentration to current density, a comparison with Faraday's …

Analysis Of Transient Hydrogen Uptake By Metal Alloy Particles, Wenlin Zhang, Supramaniam Srinivasan, Harry J. Ploehn

Faculty Publications

This paper describes a new approach to solving the equations comprising the shrinking core model for diffusion and reaction of a chemical species in a solid spherical particle. The reactant adsorbs on the particle surface, diffuses into the particle's interior, and reacts with the particle to form a solid product. The shrinking core model assumes a fast reaction rate compared to reactant diffusion so that the reaction is localized in the interfacial zone between the unreacted solid core and the surrounding shell of reacted product. Analytical solutions of the governing conservation equations usually invoke the pseudo-steady state (PSS) approximation which …

Investigation Of Wetting Hydrodynamics Using Numerical Simulations, David E. Finlow, Prakash R. Kota, Arijit Bose

Chemical, Biomolecular, and Materials Engineering Faculty Publications

Meniscus shapes from a simulation of a plate immersing into an infinitely deep liquid bath, for a range of outer length scales, have been obtained numerically. These have been compared with the leading‐order prediction from a three‐region asymptotic analysis done in the double limit, Capillary number, Ca→0, L_S/L_C→0, with Ca ln(L_C/L_S) of O(1), where L_S and L_C represent the slip length and an outer macroscopic length, respectively. For Ca<0.01, the numerically computed and the perturbation solutions show excellent agreement. Within this range of Ca, the meniscus slope at a distance 10L_S from the dynamic contact line is geometry independent, that is, does not vary with changes …

Combustion Modeling Of Rdx, Hmx And Gap With Detailed Kinetics, Jeffrey E. Davidson

Theses and Dissertations

A one-dimensional, steady-state numerical model of the combustion of homogeneous solid propellant has been developed. The combustion processes is modeled in three regions: solid, two-phase (liquid and gas) and gas. Conservation of energy and mass equations are solved in the two-phase and gas regions and the eigenvalue of the system (the mass burning rate) is converged by matching the heat flux at the interface of these two regions. The chemical reactions of the system are modeled using a global kinetic mechanism in the two-phase region and an elementary kinetic mechanism in the gas region. The model has been applied to …

Chemical Structure Of Coal Tar During Devolatilization, Thomas H. Fletcher, Mathew Watt

Faculty Publications

Three coals of different rank were pyrolyzed in a drop-tube reactor at a maximum temperature of 900 K and a residence time of 160 ms. The coal and char were analyzed with solid-state ¹³C NMR. The tar was dissolved in deuterated methylene chloride. It was found that the tar was only partially soluble in CD₂Cl₂. The nonsoluble tar portion was analyzed in the same manner as the coal and char, while the soluble tar portion was analyzed using a recently developed high-resolution 13CNMRtechnique developed for liquid phases. The tar structure was found to be significantly …

Chen, W., L. D. Smoot, S. C. Hill, And T. H. Fletcher, “Global Rate Expression For Nitric Oxide Reburning. Part 2,” Energy And Fuels, 10, 1046-1052 (1996)., Wei Chen, L Douglas Smoot, Scott C. Hill, Thomas H. Fletcher

Faculty Publications

An investigation of a global reburning-NO reaction, sum(C_iH_j) + NO => HCN + . . ., which is a reduction pathway of nitric oxide (NO) by reaction with gaseous hydrocarbons, was conducted. The global reburning-NO rate expression was deduced from a combination of elemental reactions. The global rate expression and its rate constants were then determined by correlating predicted species profiles from simple hydrocarbon flames. This global reburning-NO rate constant can be expressed as 2.7x10⁶ exp(-18,800/RT) (gmol/cm³ s). This expression and constants are applicable to atmospheric pressure with an equivalence ratio range of 1.0-2.08 …

A Computational Method For Determining Global Fuel-No Rate Expressions. Part 1, Wei Chen, L Douglas Smoot, Thomas H. Fletcher, Richard D. Boardman

Faculty Publications

Global chemical reaction rates used in the modeling of NO_x formation in comprehensive combustion codes have traditionally been obtained through correlation of experimental data. In this paper, a computational approach for obtaining global rates is presented. Several premixed flames were simulated, and sensitivity analysis of species concentration profiles was used to suggest global pathways in fuel-nitrogen conversion to NO. Based on these analyses, the global reaction rates were formulated. The predicted species concentration profiles and their derivatives were then used in the determination of the global rate constants. The correlation of rate constants for the two fuel-NO global rates …

Effects Of Pyrolysis Heating Rate On Intrinsic Reactivities Of Coal Chars, Thomas K. Gale, Calvin H. Bartholomew, Thomas H. Fletcher

Faculty Publications

The main objective of this work was to determine the effects of pyrolysis heating rate on intrinsic O₂ reactivity of coal chars. Relationships of intrinsic reactivity to other pyrolysis conditions and char physical and chemical structure were also investigated, and empirical correlations were obtained. Two different entrained flow reactors (a flat flame methane/air burner and a drop tube reactor) were used to prepare chars under a variety of different pyrolysis conditions at maximum particle temperatures and heating rates of 840-1627 K and 10⁴ to 2x10⁵ K/s, respectively. Intrinsic reactivities of a lignite and two bituminous coal chars …

Kinetic Analysis Of The Fate Of Nitric Oxide Synthesized By Macrophages In Vitro, Randy S. Lewis, Snait Tamir, Steven R. Tannenbaum, William M. Deen

Faculty Publications

To investigate the fate of nitric oxide (NO) synthesized by activated macrophages, the concentrations of NO and its principal reaction products, nitrite (NO2-) and nitrate (NO3-), were measured as a function of time in suspension cultures of RAW264.7 macrophages attached to microcarrier beads. Synthesis of NO became evident 2-5 h after stimulation of the cells, and steady concentrations of NO were achieved after about 9 h. The appearance of NO in the extracellular fluid coincided with the appearance of NO2- and NO3-, which were formed thereafter at approximately equal and constant rates. Using a kinetic model based on rate constants …

Structural Characterization Of Aluminum Films Deposited On Sputtered-Titanium Nitride/ Silicon Substrate By Metalorganic Chemical Vapor Deposition From Dimethylethylamine Alane, Xiaodong Li, Byoung-Youp Kim, Shi-Woo Rhee

Faculty Publications

Alfilmsdeposited on sputtered‐TiN/Si substrate by metalorganic chemical vapor deposition(MOCVD) from dimethylethylamine alane (DMEAA) were characterized using x‐ray diffraction(XRD),Auger electron spectroscopy(AES),atomic force microscopy(AFM), and transmission electron microscopy (TEM). The TiN filmsputtered on the Si has a preferred orientation along the growth direction with the 〈111〉 of the film parallel to the Si〈111〉. Sputtering of the TiN film on the Si induced strains at the interface. The TiN/Si interface is flat while the Al/TiN interface is rough. There exist many dislocations at the Al/TiN interface. The Al₂O₃ phase was formed at the Al/TiN interface during the early stages of …

Activation Of Precipitated Iron Fischer-Tropsch Catalysts, Mehul D. Shroff

Chemical and Biological Engineering ETDs

The Fischer-Tropsch Synthesis (FTS) is an important step in the manufacture of synthetic fuels from coal. The use of iron catalysts for FTS, though desirable from the standpoint of process economy, is hampered by problems relating to catalyst attrition and carbon buildup. In addition, from a research perspective, there has been a long-standing controversy in the literature with regard to the nature of the active phase.

The effect of activation and reaction treatments on the resulting phase transformations in a commercial, precipitated and spray-dried, Fe₂O₃ - CuO - K₂O Fischer-Tropsch catalyst have been studied. Different …

Catalytic Oxidation Of Methanol On Pt/C-Spe And Ptru/C-Spe Electodes, Aihua Su, Changzhi Li, Gongquan Sun, Ying Zhang, Tianhong Lu

Journal of Electrochemistry

Anode catalysts of methanol oxidation for direct methanol fuel cell, Pt/C and PtRu/C, ere prepared by chemical reduction in this work. The results indicated that the PtRu/C showed higher electrocatalytic activity than that of Pt/C. It was explained by XRD and XPS analyses that the existence of Ru enhanced the catalytic activity for electrochemical oxidation of methanol.

Study Of The Modified Electrolytic Manganese Dioxide, Guohui Yuan, Dewei Chu, Rihui Shen, Hongwei Pan, Cuifen Zhang

Journal of Electrochemistry

A modified electrolytic manganese dioside doped with Bi (Bi-EMD)wasprepared and examined by XRD and XPS. It is predominantly γ-mnO₂ and the Bi exists as Bi₂O₃ in the modified material. The content of Bi in Bi-EMDs increased with the increasement of Bi³⁺ concentration in electrolyte, and reached 14.3(wt)% from the bath of 0.008 mol·L^-1 Bi³⁺ used. Some Zn/Bi-EMD prototype batteries of AA size were assembled, and which cycle life tests showedthat the Bi-EMD has better reversibility.

Influence Of O-Phenylenediamine On The Catalysis At Hrp Enzyme Electrode In 1,4-Dioxane, Hong Chen, Hui-Huang Wu

Journal of Electrochemistry

Horseradish peroxidase (HRP) was immobilized by crosslinkage on the glassycarbon electrode to prepare the enzyme electrode, where the reduction of H₂O₂ was studied in 1,4-dioxane media. It was shown that HRP electrode can catalyze the reduction of H₂O₂ without anymedintor, however, as an activator, o-phenylenediamine can promote the bio-catalysis. In thepresence of the activator, the parallel reactions occurred on the enzyme electrode. The workingcondition of the HRP electrode was investigated as the sensors for H₂O₂ and o-phenylenediamine, also the influence of water content in organic phase was discussed on the performance …

Size-Dependent Adsorption Models In Microporous Materials. 2. Comparison With Experimental Data, Manuela Giustiniani, Massimiliano Giona, Douglas K. Ludlow

Chemical and Biochemical Engineering Faculty Research & Creative Works

In This Article, We Complete the Study of Size-Scaling Effects and of the Keller Model, presenting a Detailed Analysis of the Application of This Model to a Broad Range of Experimental Data on Microporous Materials (In Particular, Activated Carbon and Zeolites). Particular Attention is Focused on the Temperature Dependence of the Freundlich Exponents Αi, on the Functional Form of the Adsorption Energies, and on the Application of Keller Adsorption Isotherms in a Predictive Way to Generic Multicomponent Mixtures. © 1995, American Chemical Society. All Rights Reserved.

Equilibrium Phase-Behavior Of Nematic Mixtures, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

A phenomenological model for predicting phase diagrams of a binary nematic mixture containing side chain liquid crystalline polymers and/or low molar mass liquid crystals has been proposed by combining Flory-Huggins free energy of isotropic mixing and Maier-Saupe free energy for nematic ordering of the nematogens. Two orientational order parameters, s(1) and S-2, Of the two components in the mixtures having two different clearing temperatures are taken into consideration in the calculation. The Flory-Huggins interaction parameter, chi, and the nematic interaction parameter of the Maier-Saupe theory, nu(1) and nu(22), are assumed to be functions of inverse absolute temperature. Further the cross-nematic …

Removal Of Vocs From Air By Absorption And Stripping In Hollow Fiber Devices, Tarun K. Poddar

Dissertations

Large volumes of exhaust air streams contaminated with volatile organic compounds (VOCs) such as toluene, xylene, acetone etc. are discharged into the atmosphere by various industrial facilities. Common technologies for VOC emission abatement e.g., activated carbon adsorption, absorption in a liquid, incineration and catalytic oxidation, have many strengths as well as considerable limitations. In this study, a regenerative absorption-based removal of VOCs from N₂ in an inert, nonvolatile, organic liquid flowing in compact hollow fiber devices has been developed. The process eliminates flooding, loading and entrainment encountered in conventional absorption devices.

Contaminated air/N₂ stream was fed through the …

Computer-Aided Process Design For Waste Minimization, Konstadinos Abeliotis

Dissertations

Problems related to process design with environmental considerations have been studied in this dissertation. A new heuristic design methodology has been formulated with the objective of minimizing the adverse environmental impact of chemical processes.

This hierarchical methodology starts with the definition and analysis of a process flowsheet followed by quantification of the process environmental loads. The quantification of environmental loads is an essential aspect of this methodology, because it serves as the comparative measure for environmental performance.

If the calculated environmental loads do not satisfy the environmental constraints (e.g., regulatory limits), waste minimization is investigated in the following order:

• Pollution …

The Effect Of Chlorine, Sulfur And Phosphorus Compounds On Deactivation Of Palladium Catalysts, Tai-Chiang Yu

Dissertations

The effects of HCl, H₂S, tributyl phosphate (TBP), P₂O₅, and zinc dialkyldithophosphate (ZDP) as catalyst poisons for methane oxidation over palladium catalysts supported on γ-alumina were investigated in this study. The overall reaction rate of methane oxidation over palladium catalysts can be simplified into a pseudo first order reaction under excess oxidation conditions.

The deactivation of the catalyst poisoned by HCl is attributed to the loss of active sites due to volatilization of PdCl₂. H₂ treatment at 200 °C can reactivate the catalyst poisoned by HCl at temperatures of up to …

Removal Of Vocs From Waste Gas Streams By A Hollow Fiber Permeator, Varinder Pal Malik

Theses

Removal of various VOCs from air/nitrogen feed streams using a novel hollow fiber membrane was studied. Hollow Fiber Module (HFM) used had composite silicone membranes wherein an ultrathin (~ 1μm), nonporous silicone rubber membrane layer had been plasma polymerized on a porous (porosity: 0.4) polypropylene substrate. VOCs studied were toluene, methanol, acetone, methylene chloride and hexane. Primary focus was on single VOCs, although separation of VOC mixtures was also briefly studied. HFM was found to be extremely effective in removing various VOCs from feed streams. Removal of 90-99 % of various VOCs was achieved at low feed flow rates and …

Diffusion In Inhomogeneous Polymer Membranes, Sameer Suresh Kasargod, Farhad Adib, Partho Neogi

Chemical and Biochemical Engineering Faculty Research & Creative Works

The dual mode sorption solubility isotherms assume, and in instances Zimm-Lundberg analysis of the solubilities show, that glassy polymers are heterogeneous and that the distribution of the solute in the polymer is also inhomogeneous. under some conditions, the heterogeneities cannot be represented as holes. a mathematical model describing diffusion in inhomogeneous polymer membranes is presented using Cahn and Hilliard's gradient theory. the fractional mass uptake is found to be proportional to the fourth root of time rather than the square root, predicted by Fickian diffusion. This type of diffusion is classified as pseudo-Fickian. the model is compared with one experimental …

Interphase Mass Transfer From Bubbles, Drops, And Solid Spheres: Diffusional Transport Enhanced By External Chemical Reaction, Leonid S. Kleinman, X. B. Reed

Chemical and Biochemical Engineering Faculty Research & Creative Works

Interphase mass transfer has been analyzed for a reactant being transferred from a sphere into a quiescent, infinite continuous phase where it undergoes a chemical reaction. Ranges of the diffusivity ratio D, the distribution coefficient H, and the Damköhler number Da have been delineated, within which the overall resistance to mass transfer may be reasonably ascribed to the sum of the individual resistances in each of the two phases. Outside these parameter ranges, the resistances for two decoupled mass transfer problems may not be added to give the overall resistance to the coupled mass transfer problem. An alternative procedure for …

Perfusion Chromatography: Performance Of Periodic Countercurrent Column Operation And Its Comparison With Fixed-Bed Operation, G. A. Heeter, Athanasios I. Liapis

Chemical and Biochemical Engineering Faculty Research & Creative Works

Simulation studies using mathematical models that describe the single-component adsorption of bovine serum albumin into spherical bidisperse perfusive and spherical bidisperse purely diffusive anion-exchange porous adsorbent particles in a single-column fixed-bed system and in a two-column periodic countercurrent system in which the adsorbent is equally distributed over two beds are presented. The total length of the two-column periodic countercurrent system is equal to the length of the single-column fixed-bed system, and studies are performed for different values of the intraparticle Peclet number, Peintra, and of the microsphere diameter, dm. In the single-column fixed-bed system, the percentage utilization of the adsorptive …

The Oxidation Of Hydrogen Absotbing Alloys And Its Inhibition, Suqin Wang, Baojia Xia, Geping Yin, Pengfei Shi

Journal of Electrochemistry

This paper introduces the method to judge: 1)the possibility of oxidation of themetal hydride electrode in an anode process by cyclic voltammetric curves, 2)the oxidation pattern ofmetal hydride electrode in oxygen atmosphere in various charged states, and 3)the inhibition ofoxidation of hydrogen absorbing alloys by certain surface treatment.