Chemical 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.

Hydrogen-Atom Direct-Entry Mechanism Into Metal Membranes, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

The hydrogen-atom direct-entry mechanism is used to explain why the steady-state hydrogen permeation current density through a metal membrane is directly proportional to the cathodic current density, i_c, and is independent of the membrane thickness when i_c is small.

Proton Diffusion In Nickel Hydroxide Films: Measurement Of The Diffusion Coefficient As A Function Of State Of Charge, Sathya Motupally, Christopher C. Streinz, John W. Weidner

Faculty Publications

Electrochemical impedance spectroscopy (EIS) was used to measure the solid-state diffusion coefficient of protons in nickel hydroxide films at room temperature as a function of state of charge (SOC). A model for the complex faradaic impedance of the nickel hydroxide active material is presented and used to extract the diffusion coefficient of protons from the EIS data. Impedance data over a range of frequencies can be used to extract a constant diffusion coefficient without the knowledge of the initial mobile proton concentration or the form of the charge-transfer kinetic expression. The proton diffusion coefficient is a strong function of SOC …

A Boundary-Layer Model Of A Parallel-Plate Electrochemical Reactor For The Destruction Of Nitrates And Nitrites In Alkaline Waste Solutions, Shailesh Prasad, John W. Weidner, Andrew E. Farell

Faculty Publications

Electrochemical processes appear to be attractive for treating low level nuclear wastes. The development of a simple divided electrochemical-cell model operating in a batch mode, used for the reduction of nitrates and nitrites from nuclear wastes, is presented. This model, based on a boundary-layer approach, is simple and yet encompasses the key features of a previously developed distributed-parameter model that includes diffusion, migration, and convection as the flux components. Because it dramatically reduces computation time, this boundary-layer model is well suited for use in a complex interactive flowsheet model and for optimization studies. The boundary-layer model is used to predict …

Use Of Underpotential Deposition Of Zinc To Mitigate Hydrogen Absorption Into Monel K500, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

Polarization experiments and a potentiostatic pulse technique have been used to show that a monolayer coverage of zinc effectively inhibits the absorption of hydrogen into Monel K500. By depositing a monolayer of zinc on Monel K500, the hydrogen evolution reaction and hydrogen ingress flux rate were reduced by 60%.

A Finite-Difference Method For Pseudo-Two-Dimensional Boundary Value Problems, Z. Mao, Ralph E. White

Faculty Publications

A finite-difference method is presented for solving pseudo-two-dimensional boundary-value problems. The sparse and nearly block tridiagonal properties of the matrices generated by using the finite-difference method for problems of this type are fully utilized and maintained, which yields a method that is highly efficient in the use of storage space and computation. An example shows that the central process unit time required by the method is significantly less than that required by an alternative method.

The Role Of Thallium As A Hydrogen Entry Promoter On Cathodically Polarized Hy-130 Steel, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

Hydrogen permeation experiments were carried out to investigate the effect of thallium on hydrogen entry into HY-130steel. These experiments show that the presence of thallium ions in an electrolyte drastically increase the hydrogen entry rate. The hydrogen entry efficiency and hydrogen surface coverage were increased by a factor of 10 and 6, respectively. In order to fit the permeation experimental data, the Iyer-Pickering-Zamanzadeh (I-P-Z) hydrogen permeation model was modified by including a mass-transfer term in the discharging equation. The relationship between hydrogen permeation and the hydrogen evolution reaction were investigated and new relationships were obtained.

Surface Treatment For Mitigation Of Hydrogen Absorption And Penetration Into Aisi 4340 Steel, G. Zheng, Branko N. Popov, Ralph E. White

Faculty Publications

The effectiveness of underpotential deposition of Pb onto a membrane made of AISI 4340 steel on the reduction of the hydrogen evolution reaction on the membrane and the degree of hydrogen ingress into the membrane was determined. In the presence of a monolayer coverage of Pb on the membrane surface, the hydrogen evolution currents were reduced by a factor of two compared with the values obtained on bare steel, and the steady-state hydrogen permeation flux through the steel membranes was reduced by 71%.

Mathematical Modeling Of A Primary Zinc/Air Battery, Z. Mao, Ralph E. White

Faculty Publications

The mathematical model developed by Sunu and Bennion has been extended to include the separator, precipitation of both solid ZnO and K₂Zn(OH)₄, and the air electrode, and has been used to investigate the behavior of a primary Zn-Air battery with respect to battery design features. Predictions obtained from the model indicate that anode material utilizationis predominantly limited by depletion of the concentration of hydroxide ions. The effect of electrode thickness on anode material utilization is insignificant, whereas material loading per unit volume has a great effect on anode material utilization; a higher loading lowers both the …

Parameter Sensitivity And Optimization Predictions Of A Hydrogen/Oxygen Alkaline Fuel Cell Model, Michael C. Kimble, Ralph E. White

Faculty Publications

A mathematical model is used to predict parameter sensitivities and optimal design parameters for a hydrogen/oxygen alkaline fuel cell. A sensitivity analysis of the various transport and electrode kinetic parameters indicates which parameters have the most influence on the predicted current density and over which range of potentials these parameters affect the fuel-cell performance the most. This information can be used to decide which parameters should be optimized or determined more accurately through further modeling or experimental studies. The effect of various design parameters on the limiting current density are investigated to determine if optimal values exist for the parameters. …

The Self-Discharge Of The Niooh/Ni(Oh)2 Electrode Constant Potential Study, Z. Mao, Ralph E. White

Faculty Publications

Hydrogen oxidation currents at a NiOOH/Ni(OH)₂ electrode were measured directly at constant potentials for various hydrogen pressures and states of charge. It was found that the hydrogen oxidation current is linearly proportional to the hydrogen pressure at all electrode potentials and that the logarithm of the anodic current is a linear function of electrode potential. It was also found that hydrogen oxidation on the nickel substrate material was strongly inhibited by the presence of nickel hydroxide on the substrate surface. By comparing the currents for hydrogen oxidation and oxygen evolution on the NiOOH/Ni(OH)₂ electrode and on a nickel …

Mathematical Modeling Of Cathodic Protection Using The Boundary Element Method With A Nonlinear Polarization Curve, J. F. Fan, S. N. R Pakalapati, T. V. Nguyen, Ralph E. White, R. B. Griffin

Faculty Publications

The distributions of potential and current density around a cathodically protected pipeline in seawater were determined using the boundary element technique. A nonlinear polarization curve for a low carbon steel in artificial sea water was obtained from dc-potentiodynamic measurements and was fitted for use as the boundary condition on the pipe. The program was used to evaluate cases in which one or two aluminum sacrificial anodes are used to protect a low carbon steelpipe in seawater. The results show that the number of anodes, the sizes of the anodes, and the distance between the anodes and the cathode are of …

Hydrogen Diffusion, Solubility, And Water Uptake In Dow's Short-Side-Chain Perfluorocarbon Membranes, Yu-Min Tsou, M. C. Kimble, Ralph E. White

Faculty Publications

Hydrogen gas diffusion coefficients and solubilities as well as water uptake values are reported for Dow's short-side-chain perfluoro-sulfonic and -carboxylic membranes of different equivalent weight (EW). The diffusion coefficients and solubilities were determined with an electrochemical test cell. Hydrogen solubility decreases with increasing EW in the lower EW range and tends to level off at higher EWs for both types of membranes. Both hydrogen solubility and diffusion coefficients of a sulfonic membrane with EW higher than 800 are higher than the corresponding values of a carboxylic membrane of similar EW. An unusual maximum is observed in the diffusion coefficient-EW plot …

A Mathematical Model Of A Cuo/Cu Vaporvolt Cell, Makoto Kawanami, Trung V. Nguyen, Ralph E. White

Faculty Publications

A new battery named "Vaporvolt"^b cell is in the early stage of its development. A mathematical model of a CuO/CuVaporvolt cell is presented that can be used to predict the potential and the transport behavior of the cell during discharge.A sensitivity analysis of the various transport and electrokinetic parameters indicates which parameters have the mostinfluence on the predicted energy and power density of the Vaporvolt cell. This information can be used to decide whichparameters should be optimized or determined more accurately through further modeling or experimental studies. Theoptimal thicknesses of electrodes and separator, the concentration of the electrolyte, and …

Modification Of Newman's Band(J) Subroutine To Multi-Region Systems Containing Interior Boundaries: Mband, D. Fan, Ralph E. White

Faculty Publications

Newman's BAND(J) subroutine, which has been used widely to solve models of various electrochemical systems, is extended to solve a system of coupled, ordinary differential equations with interior boundary conditions. A set of coupled, linear ordinary differential equations is used to demonstrate the solution procedure. The results show that the extended technique has the same accuracy as that of using pentadiagonal BAND(J), but the execution speed is about five times faster than that of pentadiagonal BAND(J). Using sparse matrix solver Y12MAF to solve the same set of equations takes even longer time than pentadiagonal BAND(J).

A Mathematical Model Of Electrochemical Reactions Coupled With Homogeneous Chemical Reactions, Ken-Ming Yen, Taewhan Yeu, Ralph E. White

Faculty Publications

The zinc/bromine (Zn/Br2) flow battery has received considerable
attention in recent years [e.g., (2-4)]. Although it
is agreed that the solution chemistry is important in the
system, most of the work that has been done is concentrated
on the design variables. In this note the basic mass
transfer-solution and surface kinetics are studied to furnish
a better understanding of the system.

A Modified Electrochemical Process For The Decomposition Of Hydrogen Sulfide In An Aqueous Alkaline Solution, Z. Mao, A. Anani, Ralph E. White, S. Srinivasan, A. J. Appleby

Faculty Publications

An electrochemical process for the decomposition of hydrogen sulfide into its constituents in an aqueous alkaline solution is presented. It essentially consists of presaturation of an alkaline scrubber solution with H₂S. Thereafter, partial neutralization of the presaturated solution provides not only the necessary mass balance for electrolysis, but also creates the optimum conditions under which passivation of the anode, as well as side chemical and electrochemical reactions, are minimized. Finally, the electrolysis stage of the process leads to precipitation of crystalline sulfur at the anode and evolution of hydrogen at the cathode. Regeneration of the alkaline solution via …

Effect Of Ohmic, Mass-Transfer, And Kinetic Resistances On Linear-Sweep Voltammetry In A Cylindrical-Pore Electrode, John W. Weidner, Peter S. Fedkiw

Faculty Publications

Extracting quantitative kinetic information from linear-sweep voltammograms (LSV) on porous electrodes is more difficult than on planar electrodes since the electrode surface is not uniformly accessible to the bulk supply of reactant or the counterelectrode. We present here a means to account for the effect of ohmic, mass-transfer, and kinetic resistances on LSV by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne^– <=> R where both O and R are soluble species. Both analytical …

An Algebraic Model For A Zinc/Bromine Flow Cell, G. D. Simpson, Ralph E. White

Faculty Publications

An algebraic model for a parallel plate, zinc/bromine flow cell is presented and used to predict various performance quantities, which are compared to those predicted by using previously published differential equation models. The results presented compare well with previous work. The model is based on the concept of using well-mixed zones and linear concentration and potential profiles for the diffusion layers and the separator. The Butler-Volmer equation is used for the electrochemical reactions, and the homogeneous reaction between bromine and bromide is included.

A Comparison Of Newman's Numerical Technique And Deboor's Algorithm, D. A. Curtis, T. I. Evans, Ralph E. White

Faculty Publications

No abstract provided.

Estimation Of Electrode Kinetic Parameters Of The Lithium/Thionyl Chloride Cell Using A Mathematical Model, T. I. Evans, Ralph E. White

Faculty Publications

A one-dimensional mathematical model for the lithium/thionyl chloride primary cell is used in conjunction with a parameter estimation technique, in order to estimate the electrode kinetic parameters of this electrochemical system. The electrode kinetic parameters include the anodic transfer coefficient and exchange current density of the lithium oxidation, _a,1 and i_0,1,ref; the cathodic transfer coefficient and the effective exchange current density of the thionyl chloride reduction, _c,4 and a⁰i_0,4,ref, and a morphology parameter, . The parameter estimation is performed on simulated data first in order to gain confidence in the method. Data reported in …

Analysis Of Electrokinetic Data By Parameter Estimation And Model Discrimination Techniques, Prosper K. Adanuvor, Ralph E. White

Faculty Publications

An alternative approach to classical methods of electrochemical data analysis is presented. This alternative method is based on nonlinear parameter estimation and model discrimination techniques. The method is used to obtain the relevant kinetic and transport parameters and to elucidate the kinetic mechanism of O₂ reduction at carbon and silver electrodes in alkaline electrolytes.

Modeling The Rotating Disk Electrode For Studying The Kinetics Of Electrochemical Reactions, P K. Adanuvor, Ralph E. White, S E. Lorimer

Faculty Publications

A general mathematical model for studying the kinetics of electrochemical reactions at a rotating disk electrode under steady-state potentiostatic conditions is presented. The model, apart from predicting the net and partial current densities at given values of the applied potential, the ohmic potential drop, and the concentration and potential profiles in the solution, also accounts for homogeneous reactions of any order in the solution and noncharge transfer reactions at the electrode surface. The versatility of the model is demonstrated by the application of the model to a variety of complex reaction schemes.

Simple Models For Diaphragm-Type Chlorine/Caustic Cells Ii. Effect Of Acidic Anolyte On Steady-State Caustic Yield, John Van Zee, Ralph E. White

Faculty Publications

A simple steady-state model of a diaphragm-type chlorine/caustic cell in which the diaphragm is divided into two regions by a homogeneous acid-base reaction is presented. The location of the reaction affects significantly the caustic yield and effluent concentration. The model is used to predict the location of this reaction as a function of the operating variables, the physical constants, and three measurable properties of the diaphragm. These measurable properties are the MacMullin number or resistivity ratio of electrolyte-filled diaphragm relative to the electrolyte, the Darcy's law diaphragmpermeability, and the diaphragm thickness. The model is used to predict a maximum in …

Simple Models For Diaphragm-Type Chlorine/Caustic Cells I. Dynamic Behavior, John Van Zee, Ralph E. White, A T. Watson

Faculty Publications

A simple model of the dynamic behavior of a diaphragm-type chlorine/caustic cell is presented. The model is based upon measurable diaphragm properties and the mass transfer of hydroxyl ion through the diaphragm. The anolyte is modeled simply as a region in which the OH^– ion concentration is fixed, the diaphragm is modeled as a plug-flow reactor with an electrochemical reaction occurring at the catholyte/diaphragm interface where the cathode is placed, and the catholyte is modeled as a completely stirred flow reactor. Analytical integration of the governing equations for thesemodels yields two mathematical expressions: one for the concentration distribution of …

Prediction Of The Current Density At An Electrode At Which Multiple Electrode Reactions Occur Under Potentiostatic Control, Ralph E. White, S. E. Lorimer, R. Darby

Faculty Publications

It is often desirable to be able to predict the total current density at an electrode when multiple electrochemical reactions occur there under potentiostatic control. It is also sometimes desirable to include the effect of ionic migration within the diffusion layer upon the predicted total (1) and partial current densities (2). A procedure for doing this can be illustrated by considering the rotating disk electrode (RDE) system and the associated potential distribution near the RDE as shown in Fig. 1 and 2.

Electrochemical Reduction Of Molybdenum(Vi) Compounds In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen

Faculty Publications

Molybdenum (VI) oxide reacts with molten LiCl-KCl eutectic at 450° to form MoO₂CI₂, which probably is present as an anion MoO₂Cl₄⁼, and pyromolybdate, Mo₂O₇⁼. Both of these species are electrochemically reduced to MoO₂, which can be reoxidized to MoO₂Cl₂ by current reversal. A second reduction step, observed whether MoO₃ or Mo₂O₇²⁻ is added to the melt, can be attributed to the reduction of MoO₄⁻⁻, formed as a secondary reaction product in the first …

Electrochemical Reduction Of Chromate In The Presence Of Nickel Chloride In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen

Faculty Publications

Chronopotentiometry of chromate in the presence of NiCl₂ in molten LiCl-KCl eutectic reveals a diffusion controlled, three electron reduction step. In the presence of excess NiCl₂, chromate is reduced at −0.35V vs. Pt(II)/Pt reference electrode and the electroactive species responsible for the chrono-potentiometric wave is estimated to have a diffusion coefficient of 1.06 · 10⁻⁵ cm² sec⁻¹ at 450°C. The stoichiometry of the reduction product depends mainly on the temperature at which the deposit is formed. At 500°C the deposit approaches the composition LiNi₂CrO₄. X-ray powder diffraction shows the deposit …

Electrodeposition Of Cellulose And Carboxy-Methylcellulose, Charles Edward Driesens Jr.

Theses

The previous work done by Frank Cozzarelli on the eleotrodeposition of cellulose from a sodium zincate-urea-cellulose system has been verified, except that zinc was found to deposit on the cathode at all voltages and current densities within the range of the optimum conditions for deposition. The optimum conditions are: voltage - 1.10 to 1.28 volts; current density 0.13 to 1.10 amperes/square foot; electrode material - copper. Current efficiencies range from 0.80 to 5.53%.

A chelate-like complex formed from the sodium zincate and urea which couples with the cellulose has been proposed as a possible explaination of the mechanism governing the …