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ARTICLES
AUGUST 1955 .---_.
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IN THIS I S S U E
INDUSTRIAL APPLICATIONS OF MOLYBDENWM CHEMISTRY I&EC-August 1955 This, the first symposium on molybdenum chemistry, emphasizes how complex molybdenum is and also serves to explain why it has generally been considered alinost exclusively within the field of metallurgy. About 90y0 of the total production of molybdenum is used in ferrous alloys. However, the very chemical activity and chameleonlike nature of molybdenum point to a significant potential. Molybdenum is considered in this group of papers as a catalyst, as a pigment in both organic and inorganic pigments, as a metal coating, and as an alloying material for metals to be used in the chemical industries. M o l y b d e n u m Chemistry
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PILOT PLANT Ethylene and Acetylene Production
I&EC-August
,1492
1955
Hydrocarbons are cracked in the Koppers-Hasche furnace by intermittent flow through a mass of hot refractory, alternating with the flow of flame gases in the opposite direction. The over-all process is twostep, cyclic, "heat-make," and regenerative, one heat regenerator alternately preheating combustion air and quenching product gases, the other absorbing combustion heat for subsequent heating of feed gas and supplying the heat of reaction. Fuel gas is fed into a combustion spare between them. The regenerators consist of stacked tile of 99+% alumina, which are shaped to form internal flues, through which the gases flow a t high velocity with low pressure drop. The furnace functions over a wide range of experimental conditions-for example, reaction temparatures have ranged from 1600' to 2650' F. The system is thermally efficient; off gases after removal of ethylene and acetylene more than suffice for all fuel needs. The following listing gives the hydrocarbon feeds used, the principal products, and the yields, in weight per cent of feed at a single pass obtained in the operation of a pilot plant: natural gas, 21% acetylene; ethane, 529i', ethylene; propane, 3470 ethylene 11 ith relatiirely low acetylene, or 27y0 acetylene with relatively low ethylene, or a combination of intermediate yields of ethylene plus acetylene for a total of 45%. J. F. Farnsworth, Milton Manes, G. V. McGurl, and 0. M. B r e t x . . Koppers Co.. Inc., Pittsburgh, Pa.
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ENGINEERING, DESIGN, AND EQUIPMENT Coal Gasification a t Louisiana, Missouri
I&EC-Augwt
,1517
195s
The work on gasification of coal a t the U. S. Bureau of Mines Synthetic Fuels Demonstration Plant at Louisiana, Mo., is reviewed in this article. This review covers the period from construction of the first unit in 1948 to the termination of activities in June 1953. The work on the Koppers-Totzek unit has been previously published, and the present report deals primarily with the various niodifications of the vertical unit. The first of these was a unit lined with monolithic high purity alumina. Coal was fed suspended in oxygen, using the feed system from the Koppers unit. Flame conditions were severe and erosion of the lining was encountered. Results were erratic and inconsistent. A new feed system, using superheated steam for coal transport, new injection nozzle, and refractory brick in the lower section, was installed. A later revision embodying dual feed system with opposed burners and Monofrax K brick in the lower section was successful. H. R. Batchelder a n d 1. L. Hirrt. ......................................................................... Synthetic Fuels Demonstration Plant, U. S. Bureau of hlines, Louisiana, hlo.
August 1955
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
.15ZZ
53 A
Switch to D-4OSF (the dust-free flake form of Detergent D-40) to repackage for car wash or other light duty products-or compound D-40SF for heavy duty use. You’ll discover there is none of the annoying dust so frequently associated with dry detergents.
Other Oronite Surface Active Products: Detergent Alkane (Baric Raw Material1
Detergent Slurry Detergent D-60 Purified Sulfonates Sodium Sulfonate No. Wetting Agents Dispersant NI-0 Dispersant NI-W Dispersant FO
Oronite’s unique classifying system in the manufacturing process eliminates the fine dust particles from D-40SF, providing you a desirable dustfree product. Prove this to your own satisfaction. Write for a free sample of D-40SF and compare it to the product you are now using. Ibu’ll see the difference immediately. And this extra quality feature of D-4OSF is at no premium in cost.
5
(Burner Oil Additive1
Oronite, the world’s largest producer of detergent raw materials, offers Detergent D-40 in three different particle sizes-flakes ID-40SF), granules (D-40) and powder (D-40FG).Write any Oronite ofice for free samples or “use” bulletins showing a variety of fields where D-40 can he successfully used.
ORONITE CHEMICAL C O M P A N Y 2 0 0 Bush S t r e e t , San Francisco 20, C a l i f o r n i a 30 R o c k e f e l l e r P l a z a , N e w Y o r k 20, N e w Y o r k 2 0 N o r t h W a c k e r D r i v e , C h i c a g o 6, I l l i n o i s 714 W. Olympic Blvd., Lor Angeler 15, California M e r c a n t i l e S e c u r i t i e s B u i l d i n g , D a l l a s 1, Texas C a r e w Tower, Cincinnati 2, Ohio ,400
For further information, circle number 54 A on Readers’ Service Card, page 115 A
54 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47,No. 8
-# %,
-*
~~~~
Vapor Liquid Equilibrium Self-Lagging Stills
I&EC-August
1955
A review of previously described equilibrium stills was used to arrive a t a set of principles for still design, and a new equilibrium still, for use a t at'mospheric pressure, was designed on the basis of these principles. The system n-heptane-toluene is proposed as a suitable mixture for testing stills at atmospheric pressure. The self-lagging still permits accurate detern~inttt~ion of the boiling point and incorporates a sanipling device that allows sampling at any pressure while the still is in oper r1 t'Ion,
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Arthur R o a e a n d Edwin T. W i l l i a n u . The Pennsylvania State University, University Park, Pa.
Applications of Matrix Mathematics to Chemical Engineering Problems
I&EC-August
1520
1955
This article presents some of the principles of matrix algeb1.n a,nd calculris auil s h o w s how some problems of a rather complicated nature may be phrased in this language. The matrix method is a particularly useful tool for use in both the steady state and the transient state for niultist'age and multicomponent systems. Methods for solving differential and difference equations defined on matrices are developed. Five illustrative applications to distillation, absorption, a,nd clieniical reactions are made and numerical cases are considered. Matrix methods are useful as computational devices since the large computers now being constructed can handle matrix equations in which the order of the matrix is very large. Suggestions are offered for the evaluation of determinants and the calculation of characteristic roots. It is felt that matrix methods will have wide application in the future, particularly in those problems in which the number of components is large. I n addition, the language of matrices tends to siniplify the manipulation in theoretical investigations and allows the retention of the symmetry which seems to hold in many physical systems. Matrix notation also a l l o ~ xthe generalization from simple to complex with ease.
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Andreas Acrivoa and N e a l R. Amundaon.. Department of Cliemioal Engineering, University of MinneBota, Minneapolis 14. Minn.
A Test for the Validity of Sedimentation Results
I&EC-August
,1533
1455
A mathematical model of a sedimentation experiment is considered in which the particles are assumed to pass freely through one another. The expected number of such transits per particle is proportional to the amount of sedimentary material per unit of cross-sectional area of the settling vessel. The expected time per particle spent in transit is proportional to the concentration of the solution. Both the expected number of transits per particle and the expectetl time per particle spent in transit depend on the size of the particle and the shape of the size distribution curve.
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Walter P. Reid U. S. Naval Ordnance Test Station. China Lake, Calif.
Barrier Systems in Thermal Diffusion Columns
I&EC-Auwst
1541
1955
Thermal diffusion in the Clusius column is a slon process requiring long and precisely constructed columns that handle small quantities per unit time ant3 large energy expenditures. Metal barriers were studied in order to find a way to make the Clusius column more effective, especially under flow conditions. Horizontal plates installed so that annuli remained a t both hot and cold surfaces, and used in conjunction with vertical members, gave a fivefold increase in static equilibrium separation over that observed in the open column. Rates of separation ere five to seven times faster with barriers than without, and up to 35 mole yo separation was realized under flow conditions for the system methane-nitrogen in a 2-foot column with a 270" C. temperature difference. The results reported in this article shon- that harrier systems improve the separatory power of the Clusius coliimn t u such a degree that industrial applications in gas separation and azeotropic separation may be feasible in some cases.
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J . C . T r e a c y and R. E. R i c h . . . . . . . . . . . . . . . . . . Department of Chemical Engineering, University of Notre Dame, Notre Dame, Ind.
August 1955
INDUSTRIAL AND ENGINEERING CHEMISTRY
1544
55 A
from “Royal Water”
Nitric Acid is as modern as tomorrow . . . yet ancient as alchemy. Today, its fuming forms have a vital role as oxidants for rocket propulsion. Yesterday, it was part of the ancients’ gold-dissolving “royal water.” And, across the breadth of present-day industry, it
i’
serves in a host of ways * . .in metals and metallurgy, engraving, explosives, nitrations, etc.
FOR A L L YOUR N E E D S SEE G E N E R A L C H E M I C A L For over 50 years, General Chemical has been one of
..
t h e nation’s leading producers of nitric acid in all its forms . for every type of application. I t was first to develop the special fuming nitrics which have come into prominence in the rocket research program; currently General offers t h e widest selection of grades and strengths on the market. That’s why we say-for all your nitric needs from a carboy to a carload-just phone or write any General Chemical office listed below.
Standard & Diamond 36O,38O,40°, 4 2 O B a u m e ; 95-98%
Reagent, A. C. S.
Photo Engravers
White Fuming
36O,38O,40°,4 2 O B a u m e Red Fuming Technical, Various S t r e n g t h s of
NO, c o n t e n t Reagent,
Sp.Gr. 1.59-1.60
Sp.Gr. 1.42
Technical,
97.5% HNOo Sp.Gr.
Reagent, A. C. S.
1.49- 1.50 Specialized Formulations including Mixed Acids
Natural Convection Bo Cold Cylinders
I&EC-APgast
195s
Despite the fact that much data on heat transfer by natural convection from warm horizontal cylinders to cooler surroundings arc available in the literature, no such data are found for heat transfer in the reverse direction-that is, from warm surroundings to cooler cylinders. By utilizing a simple experimental unsteady-state technique, natura,l convective heat, transfer to room air from single warm horizontal copper cylinders n-as compared with natural convection from room air to similar cold cylinders. KO significant difference could be discerned between the resulting heat transfer coefficients for the warm cylinders and those for the cold cylinders, so that the same generalized dimensionless correlation u-as applicable to both sets of results. Thus, within the limits of the equipment, a change in the direction of heat transfer, together rrith the attendant inversions in temperature and velocity profiles, did not affect' the rate of heat transfer.
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Robert Lemlich a n d Charles S h a r n . . Department of Chemical Engineering, University of Cincinnati, Cincinnati 21, Ohio
Process Design Data
.........1547
....
Rate of Mass Transfer from Gas Stream to Porous Solid in Fluidized Beds
I&EC-August
1955
MaPs transfer studies between a fluid stream and a'porous solid in fluidized beds are needed in elucidating the mechanism of processes such as adsorption and heterogeneous catalytic reactions. In the isothermal adsorption of carbon tetrachloride by activated charcoal in fluidized beds, the over-all mass transfer coefficient decreased as the relative saturation of charcoal increased. This situation can be clearly realized only in fluidized beds in which a uniform composition of solid particles preva,ils. I n a fast process such as physical adsorption, the over-all rate is controlled by mass transfer across fluid film around the solid and the internal diffusion inside the pores within the solid. Therefore, the particle size of the poroiis solid is decisively important on the basis of over-all rate per unit mass of solid. The results presented in this article are expected to be applicable to other adsorbate-adsorbent sy-tems and perhaps to fast heterogeneous reactions. The information is of mlue in t!ie design and operation of commercial processes involving porous solids.
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C. T. Hsu a n d M. C. Molstad Univereity of Pennsylvania. Philadelphia, Pa.
,1550
PRODUCT AND PROCESS DEVELOPMENT Aluminum Borohydride Preparation
I&EC-August
19S5
A method for the preparation of pound quantities of aluminum boiohydride by the reaction of sodium borohydride and aluminum chloride is described. The reaction was carried out in a horizontal, stirred autoclave of 2-liter capacity. Innovations developed in the course of the work included the addition of graphite and mineral oil to the reaction mixture. These materials simplified charging the autoclave, prevented caking of the reaction mass, eliminated bearing wear, and reduced entrainment of finely powdered solids to a minimum. Reaction conditions were developed which consistently gave 65 to 700/, >-ieldsof aluminum borohydride yields using sodium borohydride of higher purity. from crude sodium borohydride and which gave 7 5 to
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J a m e s B. Hinkamp and Vincent Hnizda Ethyl Corporation Research Laboratories, Detroit 20, hlich.
Butyl-Type Polymers Containing Bromine
I&EC-August
1560
19SS
Although butyl rubber has been widely used for inner tubes and ot'her specialty items, the exteiisioii of its uses has been limited by incompatibility with other elastomers with respect to adhesion and cure. Iu an effort to improve these properties of butyl rubber, the effects of broinina,ting the polj-nier were studied. This study revealed some remarkable properties of the brominated h t y l polymer. It was found that an optimum amount of the halogen is required for the best properties and tha,t, this optimum depends on the original unsaturation of the butyl. Both sulfur and metal oxide ai'e applicable as vulcanizing agents for brominated butyl, and both may function in the same compound, t'liereby producing a Faster rate of cure. The modified butyl polymer can be covulcanized with natural rubber find GR-S, and therefore it is noiv possible to impart the excellent properties of butyl (such as lorn air diffusion arid resistance to ozone and flex cracking) to these rubbers. An especially important commercial advantage of the new polymer is tiia t it can easily be adhered to other elastomers and metals. R. T. Morrissey
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1562
The B. F. Goodrioh Research Center, Brecksville, Ohio
August 1955
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
57 A
H
CH,
H
I
I
I
A
I
I
CH,
H
HO-C-C-C-OH
-
Characteristics: Short chain length Symmetrical Reactive
Increased adl~bility
-
Typical Properties: Crystalline Solid White 124°-1300C
Form
Color Melting Point
96% M i n i m
Purity
Potential Uses: ,
Polymeric plasticizer manufacture Polyester resin manufacture Alkyd resin modifier Interest in this isabutyraldehyde derivative has increased to such a degree that additional production has become necessary. A large pilot plant is now in operation at Longview, Texas, and semi-commercial quantities are immediately available. Write to us at Kingsport, Tennessee, for details.
other derivatives of Eastman isobutyraldehydenow available include
isobutyl isobutyrate Coior, APHA Ester Content Boiling Range Spcciflc Gravity, 20°/200C Acidity, as isobutyric acid Available in pilot plant guanfitier
15 moxrmum 98% minimum 146°-1480c~760mm 0.a50.0.860 0.5?& maximum
h ydroxypivaldehyde
mstman CHEMICAL PRODUCTS, INC. KINGSPORT, TENNESSEE subsidlary of EASTMAN KODAK COMPANY
Form Sond Color, APHA 200 maximum 50% minimum Assay (wet basis) 9070 minimum Assay (dry basis) Available in pilot plant quantities, shipped as a wet cake to insure stability.
SALE5 oFncM: Eastman Chemical Products, Inc., Kingsport, Term.! New York-260 Madison Ave.; Fram2,2,4-trimethyl-1 +pentanediol Concord St.j Cincinnati-Corew ingham, Mass.-65 Tower; Cleveland-Terminal Tower Bldg.; ChicagoForm Cryrtalline Solid 360 N. Michigan Ave.4 Houston-412 Main St.; St. Louis Color White -Continental Bldg. West Coast8 Wilson Meyer CO., Sen Francisco-333 Montgomery St.; Lor AngeiesMelting Point 49°-510C 4800 Dirtricf Blvd.; Portland-$20 S. W Sixth Avc.; Purity 95% minimum Solt Lake City-73 5. Main St.; Seattle-821 Second Avc. Available in research quantities For further Information, circle number 58 A on Readers' Service Card, page 115 A
58 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 8
Pinonic Acid Preparation by Ozonolysis of Alpha-Pinene
I&EC-Augwt
19SS
Although the production of pinonic acid by ozonolysis of a-pinene has been reported, the yields obtained were poor and the effects of various reaction conditions on the yield of the acid were not studied. Subsequent workers questioned whether pinonic acid was actually obtained, Since pinonic acid is the precursor of dicarboxylic acids which give esters comparable to the sebacates, improved methods for its production are of interest. I n t h e present investigatioq, pure crystalline dl-phonic acid was obtained by ozonolysis of a-pinene and identified by comparison with a n authentic sample. The yield of pinonic acid obtained under various ozonolysis conditions was determined by a chromatographic technique developed a t this laboratory. Best yields mere obtained by ozonization of the a-pinene in either glacial or aqueous acetic acid solution at about 0' to 10' C., with simultaneous addition of ozone and pinene, followed by decomposition of the ozonide by heating the solution of ozonide at about 90' C., either in the presence of hydrogen peroxide or with aeration. Decomposition under basic conditions of ozonide solutions prepared in alcohols was less satisfactory. Direct ozonolysis of epinene either in basic or acidic mediums gave lower yields.
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a.
5. Fisher and I. S. Stinwn. Naval Stores Station, Olustee, Fla.
1568
Plasticizers for Poly( Vinyl Chloride) Resins Itaconic Acid Derivatives
I&EC-August 19SS
This study of several derivatives of itaconic acid as plasticizers for poly(viny1 chloride) resins was part of a program of research on the use of the acid in the plastics field. A number of the itaconic diesters were prepared and evaluated in a 95% vinyl chloride-5% vinyl acetate copolymer with respect to mechanical properties imparted. The mechanical properties of the diesters were not studied, but rather the mechanical properties of the plasticized compositions. The tetrahydrofurfuryl and octyl esters were the most efficient of those studied, comparing favorably with dioctyl phthalate. The reaction of itaconic esters with 1 or 2 moles of primary amine produced esters and amides of 1-alkyl- or aryl4-carboxy-2-pyrrolidones. The esters are very efficient plasticizers for vinyl chloride copolymer resin. The butyl ester of 1-octyl-4-carboxy-2-pyrrolidone, for example, proved to be appreciably more efficient than dioctyl phthalate. Polymeric liquid plasticizers of promise were prepared by the addition polymerization of dibutyl itaconate. Suitable catalysts include peroxides and air; polymerization temperatures as high as 130' to 150' C . were necessary. Vinyl chloride copolymer compositions containing these polymeric plasticizers possess light color, fair mechanical properties and low-temperature flexibility, enhanced heat stability, and rather poor resistance to oil extraction. Attempts to apply the technique to other esters of itaconic acid were largely unsuccessful.
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Charles J. Knuth and Paul F. B r u i n s . . . . . . . . . Polytechnic Institute of Brooklyn, Brooklyn, N. Y .
Recovery of Catalytic Cracking Stock by Solvent Fractionation
I&EC-August
IS72
1955
Most petroleum residues, normally blended for sale as low profit fuel, are potential sources of additional cracking stock. Recovery of this stock, free of materials deleterious to the cracking operation, however, is difficult. Thus, selective separation processes are important. Cracking stocks low in metals, aromatics, and other detriments have been recovered from residuum by solvent fractionation using propane and isobutane. The choice of solvent is dictated by the light oil content of the residuum ; the heavier residues require the higher molecular weight solvents. Cracking stocks were prepared from residuum by vacuum flashing and solvent fractionation, and comparative cracking tests were made. I n one comparison the solvent-separated oil, compared with the flashed oil, contained 87% less nickel and vanadium, 59% less carbon residue, 48% less carbon in aromatic rings, and substantially less sulfur and nitrogen. Cracking tests showed t h a t the solvent-fractionated oil produced 54% less carbon and over GYo more gasoline than the vacuum flashed oil.
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P a d H. Johnson, K. 1. Mill.. Jr., and B. C. Benedict.. Research Division, Phillips Petroleum Co., Bartleeville, Okla.
August 1955
INDUSTRIAL AND ENGINEERING CHEMISTRY
.lS?B
59 A
For further information, circle number 60 P, on Readers' Service Card, page 115 A
60 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 8
Conversion of Coal to Simple Compounds
I&EC-August 1955
Coals of various ranks have been subjected to thermal and chemical decoinposition under a variety of conditions and with various reagents, but little work has been reported on the action of hydrolytic agents at elevated temperatures. Reaction of a subbituminous coal with aqueous alkali a t 350' C. results in significant yields of simple compounds. I n addition to the phenols, bases, and hydrocarbons found in low temperature carbonization products, significa.nt amounts of the carboxylic acids, acetic, propionic, butyric, and succinic are recovered. This reaction, which is carried out at moderate temperatures and pressures and with low cost reagents, represents a new attack on the old problem of the conversion of coal to simple useful products.
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Franklin 0. Parker, J a m e s P. Fuqassi, and H. C. R e w a r d . . Coal Research Laboratory, Carnegie Institute of Technology, Pittsburgh 13, Pa.
Controlled Enzymatic Synthesis of Dextran
f&EC-AuguSt
.I586
1955
Dextran produced by the customary bacterial fermentation or enzymatic method has very high molecular weight and must be depolymerized and fractionated to yield a product of molecular weight (ca. 75,000) clinically suitable as a blood-plasma volume expander. Yields of clinically useful dextran are low, because dextran of less than 25,000 molecular weight produced by the depolymerization is not permitted in appreciable amounts in clinical products. An enzymatic method for directly converting sucrose to dextran of the desired molecular weight utilizes, as primer for the synthesis, dextran fractions obtained as by-products which are too high or too low in molecular weight for clinical use. Yields of dextran fractions of clinically suitable molecular n eight obtained by the proposed method exceed 25% of the weight of reacted sucrose. N. W. R e l l m a n , H. M. T s u c h i y a , S. P. R e g o v i n 8. 1. Lamberts, Robert Tobin, C. A. Glass, C. 5. Stringer, R. W.'Jackron, and F. R. S e n t i . . Northern Utilization Research Branch, U. S. Department of Agriculture, Peoria 5 , Ill.
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.I593
GENERAL TECHNICAL AND SCIENTIFIC ARTICLES New Polymeric Dispersants for Hydrocarbon Systems
I&EC-August
1955
Tn the course of a search for lubricating oil detergmts that are more effective under low temperature conditions, a new class of surface-active agent for hydrocarbon systems has been discovered. The materials are oil-soluble copolymers containing basic nitrogen. Data are presented concerning the surface activity and the suspending and solubilizing action of these materials. The effect of changes in composition of the copolymers on their performance is discussed. These additives are effective in promoting engine cleanliness under low temperature conditions and in the stabilization of fuel oil. C. P. Biswell, W. E. Catlin, J. F. Froning, and G. B. Robbins. E. I. du Pont de Nemours &- C o . , Inc., Wilmington, Del.
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Styrenation of Alkyds with Controlled Maleic Functionalities
I&EC-August
,1598
1955
Polyesters and oil-modified alkyds containing a small amount of a n a,p-unsaturated dibasic acid, such as maleic, along with a major proportion of a nonreactive dibasic acid, such as phthalic, can be copolymerized with vinyl monomers to yield soluble, homogeneous products. The alkyd must be carefully selected, however, to yield useful copolymers. Several alkyd composition factors-maleic content, degree of esterification, type of polyalcohol, and extent of oil modification-which are interdependent on one another were combined in one parameter, maleic functionality, which was then used to define the operable alkyd composition range for copolymer formation under a given set of conditions. A mathematical formula to calculate this functionality was derived and found very useful in predicting whether a given polyester composition can be expected to yield a gelled or soluble, a heterogeneous or homogeneous product on styrenation. Although empirical and of no exact physical meaning, these functionality values did provide a valuable screening tool in a systematic survey of styrenated maleic-based alkyds.
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Leon S h e c h t e r and John Wynstra. Bakelite Co. 9 I ) ~ \ ~ s i o of n I-nion Carbide and Carbon Corp , 230 Grove Street, Bloomfield. N J.
August 1955
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
.I602
61 A
Announcing t h e 1955 Glycerine Research Awards . . . . . , . . . . $1,000 . . . . . . . . . . $300 . . . . . . . . , . $200
FIRST AWARD Honor Plaque . SECOND AWARD Honor Certificate THIRD AWARD Honor Certificate
The purpose of this group of awards, established in 1952 by the Glycerine Producers’ Association, is to recognize and encourage research leading to new and improved applications of glycerine or glycerine derivatives to products or processes. The work may concern itself with the chemical, Physical O r PhJ’siological Properties of gIYcerine, 01 with Properties of glycerine-containing or glycerinederived materials. It may deal with applications which of themselves are currently or potentially of value to industry or the general public, or it may deal with scientific principles or procedures likely to stimulate future application. Originality in extending the application of glycerine into new fields of usefulness will receive special consideration for awards.
BASIS OF ENTRY These awards are open to any individual in the United Statesand Canada engaged in research, whether employed in indus. try or affiliated with a governmental or educational institution (faculty or college student) except those connected with member companies of the Glycerine Division, Association of American Soap & ciycerine Producers, I ~ ~or , labora, tories which they employ. (joint entries by research teams or associates of or three individuals are also eligible.) P E R I O D O F AWARD First consideration for the 1955 Award will be given to work which has come to a successful conclusion or clear-cut point of accomplishment during the current
year, regardless of the date at which t h e work was initiated. Work carried on in previous years, but the significance of which has been confirmed by commercial application in 1955, will be eligible.
JUDGES Selection of award winners will be made by a committee of three judges of outstanding reputation and appropriate scientific background, having no connection with the Association or its members. DATE FOR NOMINATIONS All nominations for the 1955 awards must be received by November I , 1955. METHOD O F NOMINATION Only nominations made on the official entry blank will be eligible for awards. For a copy of this official entry blank, write to: Awards Committee, Glycerine Producers’ Association, 295 M a d i s o n Avenue, Nezo York 17, N . Y .
For further information, circle number 62 A on Readers’ Service Card, page 115 A
62 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 8
Photographic Study of Boiling
I&EC-August
1955
To make clear the differences among nucleate, transition, and film boiling, a photographic study of these phenomena was undertaken. A set of still photographs was obtained a t 10-6 second, and motion pictures were taken a t 4000 frames per second. These depict methanol boiling a t atmospheric pressure in contact with a 3/8-in~h,horizontal copper tube. The over-all temperature difference varied from 67' to 181' F. Kucleate boiling is typified by the repeated formation of small bubbles from specific, active points on the hot surface. The bubble size is about 0.17 inch and the frequency is about 17 bubbles per second per point. I n transition, boilingexplosive bursts of vapor, lasting about 0.003 second, repeatedly thrust the liquid back about 4 mm. I n film boiling, about 74 ripples per second flow up the tube, forming a gas mass which breaks into rows of bubbles, each about 0.3 inch in diameter. This method for studying boiling may aid in the development of fundamental equations for predicting heat-transfer rates in the different regions of boiling. I. W. Westwater and I. 0. S a n t a n g e l o
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University of Illinois, Urbana, Ill.
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u..oI.I-BP.
Effect of Certain Group IV Oxides on Dielectric Constant and Dissipation Factor of Barium Titanate
1605
I&EC-August
1955
To learn the effects of certain additives on the piezoelectric, dielectric, and elastic constants of barium titanate and thus obtain data for better transducer and capacitor design, the dielectric properties of ceramics prepared from mixtures of barium titanate and the oxides of silicon, titanium, zirconium, cerium, and thorium were first investigated. The addition of these oxides to barium titanate in concentrations up to 50 mole % markedly reduced the dielectric constant of the ceramics over the temperature range from 30" to 170" C. I n general, the dissipation factor is not markedly changed by these additions. Using barium titanate and the oxides and referring to given data it is possible to prepare a ceramic having any desired dielectric constant from about 5000 to less than 100. Thus, capacitors for particular purposes can be designed.
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Graham W. Marks and Lester A. Monson.. U. 8. N a r y Electronics Laboratory, San Dicgo Calif
Sulfate-Bisulfate Equilibrium on Anion Exchange Resins
I&EC-August
.1611
1955
The sulfate form of quaternary ammonium anion exchange resins has been found to possess the acidadsorbing properties of a weakly basic exchange resin, The equilibrium composition of a quaternary ammonium anion exchange resin in a solution of sulfuric acid is a function of the acid concentration. Both the two-step ionization of sulfuric acid and the divalentmonovalent nature of the sulfate bisulfate exchange tend to drive the resin to the sulfate form in dilute solutions and to the bisulfate form in concentrated solutions. This behavior offers an interesting method of removing strong acids from solution without the need for chemical regenerants. The sulfate form of the resin will adsorb the strong acid and in the process be converted to the bisulfate form. The acid can be removed from the resin by rinsing the resin with water. The method can be used for the separation of strong acids from weak acids, water-soluble organic materials, and certain salts.
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R. E. Anderson, W. C. Bauman, and D . F. Harrington Physical ResearchLaboratory, The Dow Chemical Co., Midland, Mich.
Reaction of Artificial Graphite with Carbon Dioxide
I&EC-August
.1620
1955
This investigation was undertaken to study the surface area developed and extent of the reaction occurring in the interior of highly graphitized carbon rods reacting with carbon dioxide a t temperatures between 900" and 1300" C. At temperatures greater than 900" C., the reaction occurs to a greater extent in the outer portion of the rods, from which it is concluded that transport of reactants in and/or products out of the pore system plays an important role in the mechanism of gasification at these temperatures. Partial gasification of graphite rods is accompanied by a large increase in the total surface area as measured by low temperature gas sorption, and the magnitude of the total surface area appears to be characteristic of the reaction temperature. The variation in instantaneous rate at which samples gasify a t constant reactant concentration very closely approximates the variation in superficial particle areas. E. E. Petersen, C. C. Wright, a n d P. L. Walker, Jr..
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,1624
The Pennsylvania State University, Cniversity Park, Pa.
August 1955
INDUSTRIAL AND ENGINEERING CHEMISTRY
63 A
For product improvement
for production efficiency
FIND THE ANSWER
...with Celanese* Chemicals
Even backyard gardeners know how well hormone weed killers attack crabgrass. But the farmer h a s reaped the most from this chemical spray, in time a n d labor saving, a n d in increased crop yields ACETIC ANHYDRIDE-a major ingredient in herbicides-is one of the acetyl chemicals which Celanese produces in volume a n d whose uses Celanese h a s helped to develop over the years.
to a n outstanding industrywide record for performance.
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Today's "horn of plenty" for industry lies deep below the earth's surface, where trillions of cubic feet of natural gas represent a virtually inexhaustible supply of hydrocarbons. Celanese Corporation of America has based its integrated petrochemical operation on this vast storehouse of natural wealth, employing specially developed processes to synthesize orsanic chemicals for use in nearlv everv maior field of pro-
duction. It is a n operation that can supply industrial materials of greater uniformity, higher purity and improved reactivity. It can offer manufacturers the continuity and selectivity they a r e looking for from their basic supplier. When your production problem is chemical-and basic-Celanese organic chemicals can be the answer. Celanese Corporation of America, Chemical Division, Dept. 551-H, 180 Madison Avenue, New York 16. N.Y.
High Temperature Reaction Rates in Hydrocarbon Combustion
I&EC-August
1955
I n the design of high output combustion chambers, maximum possible space heat release rates are desired. The eventual limitation on space heat release is the chemical kinetics of the over-all combustion reaction. This limitation is reached more rapidly a t low combustion pressures; here the reaction rate becomes much slower relative to mixing and large combustion chamber volumes are required. To minimize the volume and optimize design, it is of considerable importance to known the kinetics-limiting rates of reaction of hydrocarbons in air a t usual combustion temperatures. This article describes a study to determine cxperimentally those rates. Combustion was carried out in a flow system, inside 3- and 6-inch insulated spherical reactors. The reaction space was vigorously stirred by incoming jets of homogeneous fuel-air mixture, thus giving nearly homogeneous composition and temperature throughout the reactor. Blowout data were obtained for equivalence ratios from 0.4 to 2.0, pressures from 1 to atmosphere absolute, and mass loadings from 0.6 to 10 gram-moles of air per second per liter of reaction volume. Average residence times varied from about 0.015 to 0.00035 second. The blowout data could be empirically correlated by plotting equivalence ratio against mass flow per unit volume per Blowouts also could be predicted by assuming the spherical reactor to be a perfectly stirred flow system, controlled by the oxygen-combustible reaction rate. Fitting the blowout data to the rate equations yielded an over-all reaction order of 1.8 and an activation energy of 42,000 calories per mole. The maximum observed space heat release rate (near stoichiometric) was 3.0 X lo8 B.t.u. per (hour) (cubic foot) (atm.1.8). Combustion gas samples suggest that, in the final stages of hydrocarbon combustion, the oxidation of carbon monoxide is the slow, controlling step-at least for lean mixtures. The effect of heat loss from the reaction zone is to reduce the flame temperature and thus the rates of reaction and maximum space heat release. Such effects can be of considerable importance.
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John P. Longwell and Malcolm A. W e i u . . Esso R m p a r r h and E n s i n w i i r i s P o , T.indPn. N. .I.
Drying Oil Oxidation Mechanism, Film Formation, and Degradation
I&EC-August
.I634
1955
The work on the autoxidation of drying oil was instituted a t the Naval Research Laboratory in order to gain more insight in regard to the mechanism of oxidation and decomposition of oil-modified film coatings, particularly when exposed to ultraviolet light. Strong evidence was found that under artificial lighting conditions certain definite chemical reactions take place in films of linseed and dehydrated castor oil, such as formation of OH groups, probably hydroperoxide groups, increase in carboxyl groups, shift toward conjugation of double bond systems, and changes involving cis-trans isomerism. There is also evidence that vinyl polymerization may be one of the chief mechanisms of film solidification. Exposure of dried films to intense ultraviolet light results in rapid decomposition and weight loss of the oil films, the infrared spectra indicating that there is a loss in OH groups, CH, groups, and carboxyl group which correlates quite closely with the weight losses. This work has practical significance as a basis for predicting, in advance, the behavior of oil modified air drying films on exposure to ultraviolet light. It is also hoped that knowledge of these oxidation mechanisms will lead to chemical modification of the materials which will enhance their resistance to decomposition brought about by ultraviolet exposure.
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S. B. Creceliur, R. E. Kagarire, and A. L. A l e x a n d e r . . Chemistiy Division, Naval Research I.abor&tory, Washington 2 5 . D C
Thermodynamic Functions of Carbon Dioxide
I&EC-August
.I643
1955
Newly available P-J7-T data for carbon dioxide in the range 200" to 1000" C. and 100 to 1400 bars have been combined with data of higher precision available a t lower temperatures and pressures. From the combined data, enthalpy, entropy, and isobaric heat capacity have been computed for the range of 100" to 1000° C. and 50 to 1400 bars. These values have been compared with others in the region of overlap, but there are no other values for most of the present range. The present values are believed to be most accurate in the region of simultaneously high temperature and low pressure-e.g., 400" to 1000" C. and 50 to 400 bars.
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Donna P r i c e . . . Naval Ordnance Laboratoiy, White Oak, Silver Spring, Md.
August
1955
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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