Equilibrium Conceptsin Natural WaterSystems

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A Comparison of Three Reactor Models in the Prediction of First- and Second-Order Reactions. Presents nonideal reactor flow data involving both linear and nonlinear kinetics. Interprets data in terms of several possible flow models. Presents some more generalized models than those in the literature.

R. M . Dipert, J . E. Parrish, T. E. Corrigan, and E. E. Smith, Ohia State University M s . 68-81 28 pages (7figfigures,2 tables)

Subscribers 83.00 Nonsubscribers $6.00

Design Methods for Countercurrent Flow with Backmixing.

1. Distillation with Constant Molar Enthalpy. Presents method for design of distillation columns using manual calculation, which allows for finite transfer rates and backmixing in both phases but retains assumption of constant molar enthalpy.

J . C. Mecklenburgh and S. Hartland, University of Nottinghan, England

Ms. 68-82 23pages (3jgures, 1 table)

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Design Methods for Countercurrent Flow with Backmixing. II. Solvent Extraction with Partially Miscible Solvents. Presents a method which permits extractors to be designed when solvents are partially miscible and there are backmixing in both phases and finite transfer. Calculations can be done manually,

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Noncatalytic, Fluid-Solid Reaction in Single Porous Pellets. Existence of a product layer surrounding an unreacted core has been investigated. I t appears that a reaction zone of finite thickness exists except when reaction rate constant approaches infinity. Implications for interpretation of reaction mechanisms are discussed.

J . H. Bowen and C. K . Cheng, University College of Swansea, Wales, United Kingdom Subscribers 83.00

Ms. 68-95 23 pages (5jgures)

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Kinetics and Mechanism of Thermal Reaction of Ethylene. From studies a t atmospheric pressure and temperatures from 703 to 854’ C, a mechanism was proposed based on kinetic evaluation of relevant elementary reactions and verified by experimental results.

Taiseki Kunugi, Tomoya Sakai, Kazuhiko Soma, and Yoichi Sasaki, University of Tokyo, Japan Subscribers $7.00

M s . 68-99 62 pages ( 1 8 j g u r e s , 10 tables)

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J . C. Mecklenburgh and S. Hartland, University of Nottingham, England

Fuel for the Supersonic Transpori. The Effects of Deposits on Heat Transfer to Aviation Kerosine. Fuel stability deduced from heat transfer measurements correlates with breakpoint temperature measured with ASTM-CRC Fuel Coker. Behavior of smooth cylindrical bore tubes and tubes containing turbulence promoters is compared. Effects of varying mass flow rates are evaluated.

MS. 68-83

J . D . Smith, Shell Research Ltd., Thornton Research Centre, Chester,

29 pages (djgures, 2 tables)

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England

MS. 68-102

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35pages (ldjgures, 3 tables) Design Methods for Countercurrent Flow with Backmixing. 111. Distillation with Variable Enthalpy. Design method is presented which permits distillation columns to be designed using a manual calculation which accounts for finite transfer, backmixing in both phases, and variable molar enthalpy.

Nonsubscribers $8.00

J . C. Mecklenburgh and S. Hartland, University of Nottingham,

Meaning and Use of the Dimensional Constant g, with Engineering Units Based on Force, Mass, Length, and Time. A systematic analysis of prevalent misconceptions in the interpretation and use of the constant go, with guidelines for remedial action.

England

A . Klinkenberg, University of California

Ms. 68-84 24pages (SJigures, 7 table)

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M s . 68-704

Subscribers 13.00

23 pages

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Liquid Holdup in Packed Towers. The Effect of Gas Flow. T h e effect is most easily taken into account by multiplying local gravitational acceleration, ft/sec2 by a factor which may satisfactorily describe the available experimental data without considering any drag by the gas flow on the liquid film.

Linear Multistate Chemical Systems. Mathematical continuity of separations, thermodynamics, and kinetics is shown. Five concepts form the basis of the theoretical and conceptual description. T h e theoretical expressions are placed in dimensionless form, then applied to five examples of multistate systems.

J . Buchanan, University of New South Wales

Peter R. Rony, Monsanta Company

MS. 68-88 7 pages

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MS. 68- 105

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40 pages

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Structure and Properties of Paper. Quality and performance are determined largely by a combination of physical properties, with structure the link between what the papermaker has and wants. It is shown that structure can be described in quantitative detail by means of statistical geometry.

Heinz Corte, Wiggins Teape Research &? Development Ltd., Beaconsfield, England

MS. 68- I I 7 36 pages (16figuresj

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The SettIing of Flocculated Suspensions. Reports and correlates data for two systems markedly different from kaolin suspensions. I t is concluded that the Michaels and Bolger equations are valid in design calculations for settling of industrially important flocculated materials.

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Two-Point Practical Control of a Class of Distributed Processes. Control of tubular processes using proportional action at a n intermediate point and integral action a t the exit is proposed and investigated theoretically and experimentally. Significant improvement results over control based on exit response only.

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Equilibrium Concepts in Natural Water Systems ADVANCES IN CHEMISTRY SERIES NO. 67 Natural waters are open, dynamic systems with variable inputs a n d outputs of mass and energy. Their chemistry is complex and involves many variables. Simplified, manageable models are used t o overcome this complexity and t o help understand a n d predict real systems. Sixteen papers represent the collaboration of aquatic chemists, analytical chemists, geologists, limnologists, and sanitary engineers. Among the topics covered are: Thermodynamics of water systems Limitations of trace metal analysis 0 Gibbs phase rule and marine sediments Water-solute interactions Heterogeneous equilibria Coordination chemistry of the oceans Equilibrium models of the Great Lakes

344 pages with index cloth bound (1967) $8.50 postpaid in U.S.and Canada, plus 20 cents PUAS and elsewhere. Set of L.C. cards free with library orders.

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A General Process Controller. Derived to minimize a timeweighted integral-square-error criterion for process models containing time constants and time delays. Performance as tested on a real process i s superior to that of conventional controllers tuned for the same model.

Lowell B. Koppel and Philip M . Aiken, Purdue Uniuersity M s . 68-176

321 pages ( I I figures)

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Dynamic Effects of Recycle Elements in Tubular Reactor Sysiems. Methods for determining local asymptotic stability of reactor-recycle systems are presented. I t is shown that heat exchangers and mixing tanks do not have a n adverse effect on system stability, and may even improve it.

G. Pareja and .M. J . Reilly, Carnegie-.Wellon University MS. 68-7 I9 26 pages (4Jgures)

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Electrical Resistiviiy and Cross-linking in Thermosetting Resins. Measurements on unsaturated polyester resins crosslinked with styrene were correlated with changes in infrared absorption spectrum of the resin. T h e method is convenient to study reaction rates of resins. As expected, a relationship exists between resistivity and modulus-dependent expressions.

George S. Learmonth and Geoffrey Pritchard, University o j Aston in Birmingham, England Subscribers $2.00 MS.68-720 77pages (5figures)

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Novel Electrolytic Cells. 1. Sodium Dithionite Production at a Swept Mercury Cathode, Diffusion limitations restrict yields

a t economic current densities in a 200-A cell because of further reduction to thiosulfate. Oscillating sweepers a t the cathode/catholyte interface raise current efficiency of dithionite formation from below SOYOto over 8070.

M . S. Spencer and W. J. Skinner, Imperial Chemical Industries, Limited, Billingham, England M S . 68-72? Subscribers $3.00

24 pages (Gfigures) I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

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Lowell B. Koppel, Daniel T . Kamman, and John L. Woodward, Purdue University

Ms. 68- 7 7 5

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R E S E A R C H RESULTS Novel Electrolytic Cells. II. Sodium Dithionite Production at Wiped Solid Metal Cathodes. Most of the diffusionlay er on disk and cylindrical cathodes was mechanically removed by rubber wipers, thus raising yields of sodium dithionite a t economic current densities from 25 to 35% to over 90% current efficiency.

Reactions of Sodium Sucrate in Solution. Preparation of Pure Long-chain Ethers of Sucrose. Surface-active ethers of sucrose were prepared in dimethylsulfoxide, and isolated in a pure state by precipitation with barium hydroxide. Sodium sucrate dissolved in liquid ammonia was alkylated by methyl iodide, but did not react with long-chain alkylating agents.

M . S. Spencer, P. J . Carnell, and W. J . Skinner, Imperial Chemical Industries, Limited, Billingham, England

J . A . Reeder, H . B. Rayner, G. Aitken, D. Bradley, and J . Atkinson,

MS. 68-722

Ms. 68-132

75pages (4figures, 2 tables)

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British Columbia Research Council, Vancouver, Canada Subscribers $3.00

26pages ( 7 table)

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Heal Transfer by Benard Convection, General correlations are obtained for heat transfer between horizontal parallel plates heated from below, using data on Prandtl numbers from that of mercury (0.0244) to silicone oil (3650) and Rayleigh numbers from laminar flow (1708) to about lo7.

Vaporization of liquid Droplets in High Temperature Air Streams. An experimental method for study of rapid vaporization of liquid droplets in high temperature gas streams is described. Data from a prototype model are presented and discussed in terms of data obtained by other methods.

Fernando Villarroel and J . M . Marchello, University of Maryland

George C. Frasier, J r . , and William W. Hellier, Jr., The Johns Hopkins Uniuersity

Ms. 68-723 73pages (4figures)

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M s . 68- 133

Subscribers 82.00

13 pages (dfigures) Flame Resistant Urethane Foams from Adducts of Hexachlorocyclopentadiene and Castor Oil. Adducts obtained by heating mixtures of castor oil and hexachlorocyclopentadiene a t 150' C contained 25 to 36% C1, had low acid contents, and good storage stability. Rigid urethane foams prepared from these adducts had excellent flame resistance, high strength, and low shrinkage.

Nonsubscribers $4.00

Electrolytic Preparation of Pure Basic Aluminum Fluorides. Results of work reported indicate that it is possible to obtain any desired F:A1 mole ratio in solid aluminum hydroxy fluorides by electrolysis of a solution containing the aluminum and the fluoride in the desired ratio.

C. K. Lyon and G. Fuller, Western Regional Research Laboratory

D. B. Vanderheiden, J . T . Dumler, D . R . Allen, and A. S. Allen, Wichita State University

Ms. 68-124

M s . 68- 134

9 pages ( 1 figure, 5 tables)

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Subscribers 81.00

7pages ( 2 tables)

Nonsubscribers 62.00

Alkylation of lsobutane with Various Olefins in the Presence of Sulfuric Acid. Isobutane was alkylated with Ca and C4 olefins and mixtures of olefins using HnS04 as catalyst. Information was obtained on importance of operating variables, character of emulsion, and on secondary reactions in continuous flow stirred tank reactors.

Polymer Reactors and Molecular Weight Distribution. The Role of Viscosity and Recycle in Reactor Systems. A polymer reactor model has been developed and used to simulate transient and steady state behavior of a system of reactors. Recycle of dead polymer may be used to increase polymer production rate and to control molecular weight.

R. J . Shlegeris and L . F. Albright, Purdue University

A. W. T . Hui and A . E. Hamielec, McMaster University, Hamilton, Ont.

Ms. 68-125 27pages (?figure, 7 tables)

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Cbntrolling Mechanisms In the Catalytic Vapor Phase Elhylation of Aniline, Indian bauxite has been found to be a good catalyst for selective ethylation of aniline to monethylaniline, with only small quantities of the diethylated product and ethylene being formed as by-products. A detailed report on the complete kinetics of the system is presented.

P. Goyal and L. K. Doraiswamy, National Chemical Laboratory, Poona, India M s . 68-129 5 4 pages ( I 4 figures, 6 tables)

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Axial Dispersion of Gas in Bubbling Fluidized Beds. Theoretical equations predicting extent of axial dispersion of flowing gas in fluidized beds are derived from a recently proposed bubbling bed model. Theory agrees satisfactorily with experiment, indicating general correctness of the model.

K. Yoshida and D. Kunti, University of Tokyo, Japan, and 0. Levenspiel, Illinois Institute of Technology M S . 68-130 20pages (7figures, I table)

Subscri bers $2.00 Nonsubscri bers 84.00

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M s . 68-137 47pages (74figures, 6 tables)

Nonsubscribers 810.00

Correlation of Diffusion Coefficients for Paraffin, Aromatic, and Cycloparaffin Hydrocarbons in Water. Diffusion coefficients for all hydrocarbons investigated (five paraffins, three aromatics, three cycloparaffins) can be correlated over a temperature range of 2' to 60' C using the Wilke-Chang empirical equation.

P. Witherspoon and L. Bonoli, University of California Subscribers 8 1.OO

MS.68- 7 38

7pages (2jgures, 2 tables)

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Delayed Coking of Low-Temperature Lignite Pitch. Investigation was over an 800' to 1200' F range. As expected, increased coking temperature resulted in increased yield of coke and gas and a decrease in oil yield. Several promising uses for the three products are discussed.

John S. Berber, Richard L. Rice, and Robert L. Lynch, Morgantown Coal Research Center

MS. 68- 139

Subscribers 82.00

21 pages ( 7 7 figures, 2 tables)

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Hydrocracking of Gas Oil. A mechanism involving simultaneous and consecutive cracking reactions is followed by rapid isomerization and hydrogenation of the products. T h e over-all kinetics fit first-order rate equations for gas oil hydrocracking, desulfurization, and denitrogenation.

Residence Time Distribution Theory for Unsteady, Stirred Tank Reactors. The classical analysis of reactor kinetics in terms of residence time distributions has been extended to unsteady, stirred tank reactors. This allows treatment of unsteady or cyclic reactors within the same theoretical framework used for steady, continuous flow reactors.

S. A. Qader, W . H . Wiser, and G. R. Hill, Uniuersity of Utah

E. B. Nauman, Union Carbide Corporation

Ms. 68-137

Ms. 68-141

24pages (74figures, 2 tables)

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14 pages

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R E S E A R C H RESULTS The Thermodynamics of Water Interaction with a Crystalline Surface of a Secondary Explosive. Based on the thermodynamics of water adsorption, surface properties of a n organic explosive are characterized. T h e manner in which the polar nature, degree of heterogeneity, and distribution of energy sites change with grinding is revealed.

Dextrose-Based Polyurethane Fsams. Polyether polyols were conveniently made from dextrose using aqueous 70% hydrofluoric acid as oxypropylation catalyst. Physical properties of rigid polyurethane foams prepared from these low viscosity polyols are similar to foams made with commercial polyether polyols.

Thomas C. Castorina and Jerome Haberman, Picatinny Arsenal

C. D . Roth, R. G. Short, and C. S. Nevin, A . E. Staley Manufacturing Company

Ms. 68-142

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23pages (7jigures)

Ms. 68- 152

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lopages ( 3 tables) Compressional Behaviors of Polymeric Foams with Isolated Cells. Dynamic Compression in Some Simplified Gases. An empirical relationship between viscosity coefficient and compressive modulus was obtained on artificial double-structured foam substances perforating relatively large cells in commercially available foams in which small spherical cells were randomly dispersed.

Vapor Phase Noncatalytic Oxidation of Olefins. Describes behavior of ethylene, propylene, and butenes in a countercurrent flow of fine particulate solids. Major products are carbonyls and epoxides. Solids help maintain a uniform reaction temperature, but do not prevent addition of oxygen to the double bond.

Jenning H . Jones, Thomas E. Daubert, and hierrell R. Fenske, The Pennsj lvania State University

KRLUO Mihira, Tadashi Ohsawa, Akira Nakayama, Gifu University, Japan Ms. 68- 146 Subscribers $3.00 27pages (Q)gures, 2 tables) Nonsubscribers $6.00

MS.68-753

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N e w Methods of Testing Thermodynamic ConsiSlency of Isobaric, Multicomponent Vapor-liquid Equilibrium Data. Proposed methods are especially useful for systems with large temperature gradients and complcrnent conventional methods based on the Gibbs-Duhem equation. Illustrations for a binary and a quaternary system are given.

Thomas E. Corrigan, John D. Corrigan, and William 0. Beavers, Mobil Chemicals Corporation MS.68-148 Subscribers $2.00 77pages (5jigures, 3 tables) iVonsubscribers $4.00

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Data for ImperFectly Mixed Vessels with Dead Space Interaction. T h e Corrigan equation for dead space interaction is verified by experimental data obtained on the transient response behavior of continuous stirred vessels under conditions of imperfect mixing.

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