RESEARCH RESULTS . . . . . . immediateb available All papers listed are being considered for publication in I&EC or one of the I&EC Quarterlies. They are available in manuscript form, with the requirement that any reference to their content in a publication must have the author's prior approval. Orders are processed within 24 hours of receipt, with shipment by first class mail. Prices for subscribers and nonsubscribers are listed with each manuscript. Please include Davment with order.
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Fluid Mechanical Description of Fluidized Beds. Comparison of: Theory and Experiment. Equations of motion previously
NONSUBSCRIBER
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Synthesis of Amines from Paraffins via liquid Phase Nitration.
proposed for fluidized systems are subjected to experimental test by measuring the propagation properties of instability waves in liquid fluidized beds of glass beads. T . B. Anderson and Roy Jackson, University of Edinburgh, Scotland M S .6 8 - 2 1 4 Subscribers $4.00 3 4 p a g e s (QJgures, 3 tables) Nonsubsnibers $8.00
Describes novel processes for making primary amines and for synthesizing dimethylamino paraffins by direct reductive methylation of nitroparaffins, using moderate temperatures and pressures. Robert W . Rosenthal and Richard Seekircher, Gulf Research t Y Development Company Ms. 68-267 Subscribers $2.00 7 5 p a g e s ( 3 tables) Nonsubscribers $4.00
Further Analytical Solutions for Adiabatic Reactor Problems.
Representative Potentials Using the Dynamic Hydrogen Electrode. Demonstrates stability of a practical and convenient
When an ideal adiabatic tubular reactor is used for certain catalytic reactions of Langmuirian type, it is possible to compute the temperature and composition profiles analytically, using a table of the exponential integral. S. J . W a j c , Lhiversitd Libre de Bruxelles, Belgium Ms. 68-235 Subscribers $1 .00 4 pages Nonsubscribers $2.00
reference electrode in HzSOa and KOH solutions. Gives overvoltage corrections for convenient conversion to standard hydrogen reference electrode system. James R. Maser, Catalyst Research Corporation Ms. 68-271 Subscribers $1.00 7 pages ( 2 tables) Nonsubscribers $2.00 Selectivity Effects in Some Catalytic Oxidation Processes.
Starting with two runs on each of seven variables, and continuing through seven runs if necessary, the experimenter can calculate the effects of the variables a t the end of each run and the possibility of learning more with another run. R. J . DeGray, Standard Oil Company MS. 68-240 Subscribers $2.00 13pages ( 4 tables) ATonsubsnibers $4.00 Sequential Youden Square.
Empirical Virial Equation. Use of Theoretical Temperature Dependence, Expansions in reciprocal temperature are used
for real fluids in tests of the equation. A fifth order expression in density with truncated coefficient expansions (in reciprocal temperature) is used to describe compressibility (methane) factors at 508 points, 0.082% average deviation. B. H . Vernick and K . E. Sfarling, University of Oklahoma Ms. 6 8 - 2 6 0 Subscribers $2.00 7 7 k a g e s (5Jgures, 1 table) Nonsubscribers $4.00 Stress Relaxation in liquids. T h e (complete) linear viscoelastic constitutive equation is used to obtain solutions to equations of motion for two problems involving stress relaxation in liquids. Results are applied qualitatively to the melt fracture phenomenon. E. A . Uebler, E. I . du Pont de Areemours S Campan), Inc. MS. 68-265 Subsnibers $3.00 24 pages ( 2 j g u r e s ) Nonsubscribers $6.00 Multiple limit Cycle in a Continuous Stirred Tank Reactor.
Describes an approximate theory which is sometimes useful for predicting the existence of multiple limit cycles. Discusses the importance of reactors which exhibit this kind of behavior. A'. Y . Gaitonde and J . M . Douglas, University of Rochester Ms. 68-266 Subscribers $2.00 74pages ( Z j g u r e s , 2 tables) Nonsubscribers $4.00
68
INDUSTRIAL AND ENGINEERING CHEMlSTRY
Relative reactivity behavior of species in competing reactions is of paramount importance. Sulfur dioxide as oxidant gives substantial improvement over oxygen in selectivity for several reactions, but no theoretical treatment of differences in catalysts of different compositions is currently adequate. Charles R.Adams, Shell Dezelofiment Company Ms. 68-275 Subscribers $3.00 2Qpages (7Jgures, 6 tables) Xonrubscribers $6.00 Pyrolysis of Coais in a Microwave Discharge. T h e gaseous product type and distribution are influenced by rate of formation or removal of the products. Acetylene is the main hydrocarbon produced. Y u a n C. Fu and Bernard D . Blaustein, Pittsburgh Coal Research Center Ms. 68-277 Subscribers $2.00 78pages (5$gures, 4 tables) Nonsubscribers $4.00 Experimental Technique for Direct Measurement of Crystal Nucleation and Growth Rate Kinetics in a Backmixed Crystal Slurry. A Study of the KzSOi System. Shows how simulta-
neous processes of nucleation and growth can be quantitatively measured in backmixed crystal suspensions, and describes an experimental apparatus which should advance greatly the stateof-the-art for such measurements. A . D. Randolph and K . Rajagopal, L'niuersity of Florida Ms. 68-280 Subscribers 84.00 34 pages ( 8 j g u r e s ) Nonsubscribers 88.00 Sorption of Sulfur Dioxide by Ion Exchange Resins. Uptake of
SOa by macroreticular ion exchange resins is limited by intraparticle diffusion. Equilibrium loadings a t 25 OC compare favorably with other adsorbents, but relatively large heat of adsorption indicates that capacity of resin for SOz will decrease rapidly with increasing temperature. L. Layton and G. R. Youngquist, Clarkson College of Technology M S . 68-287 Subscribers $4.00 3 2 p a g e s (15Jigures, 1 table) Nonsubscrihers $8.00
Rotational Discrimination for Optimization with limits on the Variables. A method for minimizing a general multivariable
function is described. Major advantages are its quadratic convergence properties and its ability to solve difficult problems without modifications. Numerical results are presented to compare the method with other techniques. V. . I Law, . Tulane University and R. H. Fariss, Monsanto Company Ms. 68-284 Subscribers $3.00 29 pages Nonsubscribers $6.00
Selective Chlorination of 2,3-Dichloropropene with fed-Butyl Hypochlorite. Conversion was effected in 60% yield by photo-
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chemical chlorination. Yield increased with decreasing hypochlorite-to-olefin ratio. Reginald F. Roberts, Jr., The Dow Chemical Company Ms. 68-287 Subscribers $7.00 Nonsubscribers $2.00 6 pages ( 7 Jigure)
Elaboration and Extension of Experimental Results through Mathematical Correlations and Fundamental Knowledge. HCN Reactor Studies, Reliable trends of the Andrussow
HCN process in far extended ranges were achieved, and the usefulness and limitations of the mathematical correlations generalized. A practical case is illustrated using the HCN reactor system. Bingham Y . K . Pan, Monsanto Company Ms. 68-280 Subscribers $3.00 27pages ( Z f i g u ~ e s8, tables) Nonsubscribers $6.00
Dense Gas Diffusion Coefficients for the Methane-Propane System. For pure components, good agreement was obtained
between diffusion coefficients calculated from molecular theory and those measured by the N M R spin-echo technique. For mixtures, the observed dependence on composition, temperature, and pressure is in general agreement with theory. D . E. Woessner, B. S. Snowden, Jr., R. A. George, and J . C. Melrose, Mob2 Research d Development Corporation Subscribers $4.00 Ms. 68-297 Nonsubscribers $8.00 34 pages (8Jigures, 4 tab1e.r)
Unleash your copy of CHEMICAL ENGINEERING CATALOG to flush out facts. When you’re hounded for data on equipment, materials of construction or specialized services, CEC puts you hot on the trail and leads you to a brace of ideas. (The 5-way index always “points” the way). Keep CEC right on your desk in hand-reach -where you can use it every working day. It’s a bird-dog. It’s the process man’s best friend when the hunt for facts begins. Good hunting! CHEMICAL ENGINEERING REINHOLD PUBLISHING CORP. CATALOG 430 PARK AVENUE, NEW YORK. N. Y. 10022
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Contraction lasses in laminar Flow through Circular Tuber.
Sudden losses resulting from liquid running through a syphon tube were studied. Experimental results were correlated by two empirical equations, one for R e < 400 and one for R e > 400. There appears to be no definite upper limit for the critical value. Huan-Yang Chang and Vijay Fadia, Lowell Technological Institute Ms. 68-292 Subscribers 97.00 6 pages (ZJigures) Nonsubscribers $2.00
Diffusion Coefficients for He-NZ and Nz-COSat Elevated Temperatures. A diffusion cell was developed and applied to measurement of diffusion coefficients over a 300’ to 900’ Krange. Temperature dependency of observed coefficients was nearly identical to that predicted with intermolecular potential parameters derived from viscosity data for pure components. C. S. Ellis and J . N . Holsen, Washington University Ms. 68-293 Subscribers $2.00 lopages (5jgures, I table) Nonsubscribers $4.00
Similarity Solution to the Diffusion Equation in Presence of Nonlinear Reaction Process. Shows how to obtain an exact
solution to a problem wherein diffusion is coupled with a simultaneous nonlinear reaction process. M . L. R. Murthy, University ofDelaware MS. 68-294 Subscribers $7.00 8 pages (4jgures) Nonsubscribers 82.00 Drying Cellulose Acetate
Reverse Osmosis Membranes.
Describes a method whereby water in the membrane is evaporated under ambient or elevated temperatures after membrane has been soaked in a surface active agent. The membranes, if rewet, show no loss in desalination characteristics compared with undried membranes. K . D. Vos and F. 0. Burris, Jr., Gulf General Atomic Inc. Subscribers 82.00 Ms. 68-295 20pages ( 7 j g u r e , 8 tables) Nonsubscribers 84.00
Automatic SAMPLER lor Water
POLLUTION CONTROL This unit consists of a trouble-free positive displacement tubing pump, adjustable programmer and a 2% gallon composite sample container, in a weather proof case (less than 30 Ibs.). Samples can be drawn up to 18 feet. The natural pulsing action keeps the line clear and flowing. Small fibers and particles do not plug the tubing. Four models are now available, two battery operated units for remote field work and two 110-volt units for A.C. power. This Sigmamotor pump is designed to take samples periodically on a programmed basis.
SIGMAMOTOR, INC. 67 North Main St. See
Us A
t Booth
Middleport, N. Y. * Phone (716) 735-3411
1003,
VOL. 6 0
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Water Pollution Conference, Chicago
NO.
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SEPTEMBER
1968
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RESEARCH RESULTS Fluorocarbon Pyrolytic Graphite. Feasibility of producing pyrolytic graphite from CzF4 is shown. However, deposition rates were as muchas 50% lower than CHa depositions under similar conditions. Densities of deposits from CnFa were also lower. D.H. Leads and Julian Heicklen, Aerospace Corporation Ms. 68-297 Subscribers 52.00 74pages (Z&gures, 2 tables) Nonsubscribers $4.00 Turbulent Mixing of Two Species with and without Chemical Reactions. Product of the concentration fluctuations obtained when two species are mixed is calculated and related to product Of fluctuations obtained with second order stoichiometric reactions. H. L. Toor, Carnegie-Mellon University Ms. 68-298 Subscribers 82.00 1 5 pages (2figures) Nonsubscribers 54.00 Criteria Which Determine the Computational Error of Numerically Calculated Fourier Integral Transforms. Upper frequency
limit is shown to depend on how well the approximating function used in the numerical integration represents the real continuous function. Problems associated w-ith analysis of transient responses and their transformation into the frequency domain are discussed. Charles J . Messa, William L. Luybm, and Gary W. Poehlein, Lehigh Uniuersity MS. 68-299 Subscribers $3.00 22Pages (Zfigures, 3 tables) Nonsubscribers $6.00
POST keeps you up-to-date on research, development, planning, and production activities as reflected i n the current scientific and technical literature. Nearly 450 journals are regularly monitored for you as are patents issued by 25 countries. Concise, d e s c r i p t i v e d i g e s t s are prepared for each paper and patent selected. These digests are i n d e x e d i n d e p t h t o m a k e your searching as easy and as profitable as possible. For flexibility of use, patents and journals are covered i n separate issues of POST published i n alternate weeks. Digests also can be provided i n machine language for use in computer-based information retrieval systems. For details write t o Mr. E. G. Johnson, Subscriber Information Department PST.
PLASTICS INDUSTRY NOTES covers the business and trade literature for you. Write for details.
American Chemical Society
Columbus, Ohio 43216
70
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Hydrodynamic Performance of
a Flooded-Plate Column.
Pressure drop and entrainment data are reported for a 5 l/Z-inch diameter perforated-plate column, without weirs, operated so that the plate liquid level is self-adjusting. Interesting differences are noted when compared with conventional column operation. C . Y . Cha and C . Moreland, University of N e w Brunswick, Canada Subscribers 14.00 M s . 68-303 3 2 p u g e s ( 7 j g u r e s , 3 tables) Nonsubscribers $8.00 Inequality Methods for Computation of Optimal Systems. Problems in Multistage Reactor Analysis. Optimization problems are reduced to solution of sets of algebraic equations by means of a new inequality. A computation method for solving the algebraic form is described and compared with other methods. C. D. Eben and 3.R. Ferron, University of Delaware Subscribers 85.00 M s . 68-304 48Pages ( 7 j g u r e s , 7 table) Nonsubscribers B 7 0.00 Thermal Stability Test for Composite Modified Double-Base (CMDB) Propellants. Time to autoignition (Tai) of solid
propellant samples is a reliable measure of thermal stability. Tai varies regularly with stabilizer content of propellant and with test temperature, and should be useful in determining “safe life.” D . D . Rice, R. J . DuBois, and R. S. Lambert, Herculeslncorporated Ms. 68-305 Subscribers $2.00 76pages (4figures, 7 table) Nonsubscribers 54.00 Catalytic Hydrocracking. 1. Hydrocracking of a l o w Temperature Coal Tor. Hydrocracking over a dual-functional
Ghemical Abstracts Service ~
Glyoxal from Ozonolysis of Benzene. Synthesis in yields over 70% (based on absorbed ozone) was achieved. Yields depend on variations in solvent, temperature, degree of conversion, reducing agent, and gas dispersion; also on presence of Lewis acids and age of ozonized solution prior to reduction. William P. Keaveney, Raymond 8. Rush, and James J . Pappus, Znterchemical Corporation MS. 6 8 - 3 0 0 Subscribers 12.00 79pages ( 7 table) Nonsubscribers 84.00
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
catalyst yielded 7 5 % premium gasoline. T h e catalyst gave better product distribution with respect to gasoline production, higher cracking, isomerization, and hydrogenation activities when compared with conventional cracking and refining catalysts. S. A . Qader and G. R. Hill, Uniuersity of Utah MS. 68-306 Subscribers 82.00 7 8 Pages ( I O j g u r e s , 2 tables) ~Vonsubscribers$4.00
Kinefics of Homogeneously Catalyzed Gas-liquid Reactions. Chlorination of Benzene with Stannic Chloride Calalyst.
Describes a simple method for measuring reaction rates between a liquid and a reactant gas dissolved in it, which should be of general utility for systems with gas solubility high enough to permit moderate reaction. Application to heterogeneous conditions is demonstrated. Bernard Silberstein, Harding Bliss, and John B. Butt, Yale University MS. 68-308 Subscribers $4.00 39 pages (14fgures, 4 tables) Nonsubscribers $8.00
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Induced Oxidation/Precipitafion of Iron from Aqueous Solutions of MnSOa-FeSOe Oxidation rate of iron(I1) is accelerated
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in the presence of magnanese(I1). Results indicate that a threshold set of temperature and oxygen partial pressure conditions must be exceeded within the system before manganese(I1) is activated to a n inductive role. Vance G. Leak and M . M . Fine, T w i n Cities Metallurgy Research Center Ms. 68-309 Subscribers $2.00 73 pages (5fgures) Nonsubscribers $4.00
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amorphous silicas
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Micronized Amorphous Silica:
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Progress in Polymer Engineering. A review of the youngest and
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fastest growing section of the chemical industry, with over 50 references and many examples. Originally presented a t the anniversary meeting of the Societe d e Chimie Industrielle, Paris, on May 30,1968. Norbert Platzer, Monsanto Company MS. 68-310 Subscribers $6.00 52pages ( 2 5 f g u r e s , 1 table) Nonsubscribers $12.00
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Air Floated Amorphous Silica:
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(winding angle, radial pitch, axial pitch) was studied, and measured shell side coefficients of each of six heat exchangers were correlated. Equations are presented which relate the parameters to construction variables. Charles J . Messa, Alan S. Foust, and Gary W. Poehlein, Lehigh University Ms. 68-314 Subscribers $2.00 7Qpages ( d f g u r e s , 5 tables) Nonsubscribers $4.00
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classes of intramolecular reaction products (cyclic ethers, cyclic hydrocarbons, lactones) and many volatile products were detected. A reaction mechanism is reported, based on current knowledge of other systems, the products are identified, and the stoichiometry of the reaction is discussed. B. D. Boss and R. N . Hazlett, Naval Research Laboratory Ms;68-377 Subscribers $3.00 2 5 p a g m ( 7 f g u r e s , 2 tables) Nonsubscribers 86.00
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Low cost, inert filler-extender. High G. E. Brightness. No appreciable viscosity increase with loading. High purity 99+% Si02 low quartz content (less abrasive). Slow settling, anti-packing properties. Extremely low moisture content (not Hydroscopic). Excellent electrical resistance. Proven in epoxy, polyurethane and polyester formulations.
I Oxidation OF Hydrocarbons in fhe Liquid Phase. 1. nDodecane in a Borosilicate Glass Chamber at 200 ‘C. Three
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Desirable Characteristics:
I Shell Side Heat Transfer Coefficienfr in Helical Coil Heat Exchongers. Influence of geometric construction parameters
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criteria can be ranked in order of importance. Formulates a simplified model to maximize total yearly profit and minimize sensitivity of profit to variations in refinery conditions. Presents detailed nonlinear programming results. John H. Seinfeld and Warren L. McBride, California Institute of Technology MS. 68-373 Subscribers $3.00 2 3 pages ( 1 figure, 7 tables) Nonsubscribers $6.00
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0 ‘0’Grade (99.5+% through I 325 mesh) CI 1240 Grade (98.0-99.4% through 325 mesh) I 0 1160 Grade (9698% through 325 mesh) I I 0 54 Grade (90-95% through I 325 mesh) I 250 Grade (9699% through I I 200 mesh) 0 200 Grade (90-95% through I I 200 mesh)
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Opfimizafion wifh Multiple Performance Criteria. Application to Minimization of Paramefer Sensifivifies in a Reflnery Model. Proposes a practical scheme for problems in which
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0 IMSILB A-10 (99% below IO microns) 0 IMSILB A-15 (99% below 15 microns) 0 IMSIL@A-25 (99.9+% through 400 mesh screen)
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R E S E A R C H RESULTS Pressure Drop Studies on a Single Perforated Plate. Proposes an empirical correlation for wet plate pressure drop in terms of gas rate, liquid rate, and surface tension. Pressure drop results obtained with plates of different design characteristics are compared. Durgaprasada Rao and Venkata Rao, Andhra University, Waltair, India Ms. 68-319 Subscribers $2.00 79 pages (IOj'igures, 1 fable) Nonsubscribers84.00
Nozzles mix compressed air and liquid t o give finest possihle atomized spray. Wide selection of interchangeable spray set-ups for flat, round and wideangle round sprays . . . pressure and siphon liquid feed . . . capacities from 0.03 GPH, to over 1,000 GPH . . . 1/4", and 1" NPT connections.
Active Species of Coked Silica-Alumina Catalyst.
Evidence shows that the rapid initial temperature rise attending oxidation of coked silica-alumina catalysts is due to an active hydrogen-rich species on the coked particles, which may be removed or rendered inactive by pretreatment under vacuum or in nitrogen a t high temperature. F. E. Massoth and P. G . Menon, Guy Research t 3 Deuelopment Comfiany Ms. 68-321 Subscribers 62.00 14pages (Zj'igures, 4 tables) Nonsubscribers$4.00
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Technique for Predicting the Thermal Conductivity of Suspensions, Emulsions, and Porous Materials. T h e technique predicts values of thermal conductivity within 18.2% for suspensions, 9.5y0 for emulsions, and 9.9% for porous materials.
SPRAYING SYSTEMS CO. 3255 Randolph Street Bellwood, Illinois 60104
Radiative and convective heat transfers are assumed negligible. S. C. Cheng and R. I. Vachon, Auburn L'niversity M S . 68-329 Subscribers $2.00 Nonsubscribers $4.00 16pages ( 6 tables)
INDEX TO ADVERTISERS IN THIS ISSUE Brooks Instrument Div., Emerson Electric Co Benn Associates, Inc.
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Chemical Abstracts Service. Chemical Engineering Catalog. Persons Advertising, Inc.
69
Engelhard yanovia, Inc., Lamp Division., Keyes, Martin & Co.
Hanovia .............. 8 QHart-Carter International.. ........ OBC Stevenson and Associates, Inc. Haws Drinking Faucet Co.. Pacific Advertising Staff
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REINHOLD PUBLISHING CORP. 430 Park Ave., New York, N.Y. 10022 (Area Code 212) 688-8600
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Robet N. Sillars, Jr. Advertising Sales Manager, IGEC
Philadelphia 19107 Benjamin W. Jones 12 South 12th Street, (Area Code 215f Tulsa 74114 , , Max C. Nelson Roy Mc. Donald Associates Inc 2570 b. Harvard Ave., (Area Code $18 j'724-9961
10
Laurence 0. Roberts Midwestern Regional Manager
Norton Co........................ J. M. Mathes, Inc.
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Clay S. Holden Western Regional Manager
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Preprint Publications of. the Division of Petroleum Chemistry, Inc..
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SALES REPRESENTATIVES
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Chicago 60603 Laurence 0. Roberts, Thomas R. Millerd, Joseph C . Hoopes, D. Steven McLean, 10 South LaSalle St., (Area Code 312) 726-1282
IBC G9
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Great Britain and Western Europe Brayton Nichols, The American Magazine Group, 44 Conduit Street London W. 1, England, Telephone-Reient 4714
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Japan Itsuo Okawa, Nippon Media Repre624 Kamisentatives Gakken Bldg ikegami-cho, Ota.ku, Tokyo)
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Los Angeles 90045 Clay S. Holden 8939 So. Sepulveia Blvd., Suite 528: (Area Code 213) 776-0552
Thomas N. J. Koenver Advertising Sales Director, ACS Publications
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Houston 77006 Frank N. Vickrey, Richard Clothier, Roy McDonald Associates Inc., 3130 Southwest Freeway, (Are; Code 713) 529.6711
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Kay-Fries Chemicals, Inc.. Warner, Bicking & Fenwick, Inc.
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New York 10022 Robert N. Sillars, Jr Edmund B. Sullivan, J. Ronald Dora;: Harqld I. Sheils, Jr., Samuel W. Percy, Denis A Cardone 430 Park Ave., (Area Code 212) 688-86'00
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Salsbury Laboratories. Griswold-Eshleman Co. Shell Chemical Co.. Ogilvy & Mather, Inc. Sigmamotor Inc... Gelia and Wells, Inc. Spraying Systems, Inc.. Advertising Producers-Associated, Inc.
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Adcertising Management for the American Chemical Society Publications
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Illinois Minerals Co.. Jack M.Doyle, Advertising, Inc. Ionac Chemical Co. Rumrill-Hoyt, Inc.
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