Industrial Applications of Fumaric Acid Production of fumaric acid by a new fermentation process has lowered costs and made it available for many new uses. In many ways it is similar to its isomer, maleic acid, and in some fields may either supplement or replace the latter. However, the two isomers are by no means completely interchangeable. As a raw material for synthetic resins, coating compounds, plasticizers, etc., fumaric acid shows great promise. Its esters polymerize readily forming either thermoplastic or thermosetting resins according to conditions. They also copolymerize with other plastic-forming materials to produce clear, stable resin compositions of desirable physical and chemical properties.
C. K. DOSCHER, J. H. KANE, G. 0.CRAGWALL, AND W. H. STAEBNER Chas. Piker & Co., Inc., Brooklyn, N. Y,
UCH work has been done on the synthesis of fumaric acid, and many laboratory methods for its preparation are given in the literature. For example, it may be made by heating halogen-substituted succinic acids (11), by condensing malonic with glyoxylic acid in the presence of pyridine (19), from tartaric acid by reduction (55), by conversion from maleic acid (61, 68), and by boiling maleic acid with sodium hydroxide solution (91). Industrially it has been prepared from maleic acid which is produced by the catalytic oxidation of benzene (91, $8, 67, 71, 79), and also as a by-product in the manufacture of phthalic anhydride. Recently the commercial production of fumaric acid from starch and other carbohydrates by a new and efficient fermentation process has so lowered its cost as to make it an inviting raw material for the chemical and allied industries. Pure fumaric acid crystallizes in small white prisms having a very slight acid taste and no odor. The acid melts a t 290" to 295' C. in a sealed tube. If heated carefully a t 200" C., the acid will sublime without decomposition; a t higher temperatures it forms traces of maleic anhydride. There is no anhydride of fumaric acid. Published data (46, 69) show that fumaric acid has only a limited solubility in cold water, but is considerably more soluble in hot water. The alcohol solubility is somewhat greater, 5.75 grams of acid being dissolved by 100 grams of cold absolute alcohol. The more usual salts, esters, and derivatives of fumaric acid have been studied and are described in the literature (57, YO). I n addition to these compounds, fumaric acid has been used for the synthesis of such substances as aspartic acid (26, 29, 60), trans-trans-muconic acid (SO), racemic acid (49, 50), succinic acid (41, 52), and many others (2). I t s use as the acid constituent of a leavening agent has been patented in Germany (15, 20,39). Although there is evidence that its toxicity is low (34, 44, 53, 56, 73), more conclusive clinical tests would appear desirable before i t is accepted for food uses. Snell (59) found it efficient as a laundry sour. It also has considerable possibilities as a process material in making thermoplastics (23, $4, 38, 64, 66, 66) and varnish-type resins (63, 66), and for condensation with polyhydric alcohols to make casting resins (9, $6, $1, 7 4 ) . A coating for wrapping paper that is tasteless and odorless was prepared by Bremer (8) by reacting hexahydric alcohols of straight-chain type with fumaric or other acids. Resins with an odor are formed with lower alcohols. Lacquer resins are formed by esterifying glycolic or lactic acid with a polyhydric alcohol and condensing with fumaric, among other acids (37). Jaeger (40) prepared a wetting agent of good detergent properties from 2-ethylhexanol, fumaric acid, and sodium bisulfite, among other materials. Because of its activated carbon-to-carbon double bonds, fumaric acid may react with unsaturated compounds in a manner similar to the Diels and Alder (18) diene synthesis.
M
*
For example, Carothers and Collins (14) caused /3-substituted a,y-dienes (e. g., CH,=CH-CC1=CH2) to react with ethyl fumarate and other compounds having activated carbon-to-carbon linkages. Clocker (16) condensed maleic anhydride or substances yielding it under the conditions of the process, such as fumaric acid, with nonconjugated, unsaturated, nonhydroxylated fatty acids of 10 to 24 carbon atoms, such as linseed oil or oleic acid, to form a paint base; he claimed it to be harder, more water resistant, and of greater wetting ability for pigment than the original linseed oil. Morrell and others (61) heated /3-eleostearic acid derived from tung oil with maleic anhydride or its equivalent, such as fumaric acid, to form a material which can be mixed with linseed oil in air-drying paints. This resin may be copolymerized with glycols and may be mixed also with nitrocellulose or other resins if desired. Haroldson (33) combined similar condensation products with phenol-formaldehyde resins for a paint base. McGill (48) treated fire-resistant materials to get a high exudation temperature and good adhesiveness by coating with the reaction product of castor oil and halogenated fumaric acid or other polycarboxylic acids. Isobutylene has been polymerized with diethyl and diallyl fumarates to make glass-clear solids or in emulsions t o make compounds suitable for insulating cables, p,riming leather, coatings, and adhesives (36). Peterson claimed (54) that terpene hydrocarbons which have no conjugated system of double bonds can be condensed with maleic anhydride to form resinous products. Maleic acid or fumaric acid may be substituted for the maleic anhydride. Inasmuch as there are various technical processes in which it may be economically desirable to supplement or replace maleic acid with fumaric acid, the essential characteristics of these two will be compared briefly. The physical and chemical properties of the two stereoisomeric acids are to an extent quite different. Maleic acid is purely a synthetic product and has never been found in na315
316
INDUSTRIAL AND ENGINEERING CHEMISTRY
ture. It melts a t 130" C., compared to 290" for fumaric, and is much more soluble in water (70): Temp., C. 25 40 60 100
Soly., G./100 G. Water) Fumaric acid Maleic acid 0.70 78.8 1.07 112.5 2.4 148 7 9.8 392.6 (at 9 7 . 5 ' C . )
Maleic acid is a stronger acid than its isomeride. The relative p H values as determined by electrometric titration are as follo~vs( 4 ) : Fumaric Acid 0.005 0.0001
Concn., moles/l. p H value
0.01 2.42
Concn., moles/l. p H value
0.01 2.06
2.62
Maleic Acid 0.006 2.36
3.10
0.0005 3.33
0.0001 3.90
0.0001 2.95
0.0005 3.24
0.0001 3.76
The constants (4, 3%)of primary dissociation are 9.50 X l o T 4 for fumaric and 1.42 X lo-* for maleic acid. From the configuration of its molecule, fumaric is obviously the more stable of the two acids. This configuration also accounts for the ease with which maleic acid forms an anhydride whereas fumaric acid does not. As the industrial consumption of fumaric acid has heretofore been limited by its high price, the literature contains relatively little information on its commercial utility. A few specific uses based on its unique chemical and physical properties have been suggested. Clues to additional industrial applications can be found by a study of the existing demand for maleic acid and anhydride. The United States Tariff Commission reports for the year 1939 (3) a domestic production of over 6,000,000 pounds of synthetic resins derived from maleic anhydride and used chiefly for paints and varnishes. This substantial increase over the approximately 3,500,000 pounds produced in 1938 is evidently due to the recent development of new resinous products of the maleic acid type. As reported in the literature (7, 27, 62),resins of similar structure and properties may be obtained from fumaric acid. The present shortage of natural drying oils should increase the demand for these resins and consequently for their raw materials. Data released by the Tariff Commission are reproduced in the following table which shows the relative importance of maleic anhydride to the synthetic resin industry in 1939 (3): Resins Deiived from: Maleic anhydride Phthalic anhydride Cresols or cresylic acid Phenol (casting) Phenol (molding) Phenol (other uses) Xylenols Urea
Production, Lb. 6,263,542 70,208,098 10,515,557 8,617,368 19,421,778 27,785,891 442,889 16,569,343
Sales, Lb 4,929,403 33,161,064 7,893,863 8,252,263 17,396,556 25,766,207 14,'556,232
Value
0 925,048
6,925,898 1,063,772 3,152,444 2,571,930 3,738,052
.....
5,288,767
Until recently there was no evidence in the literature of the maleic-type resins being used alone commercially for molded articles. The work of Bradley et al. (5, 6, 7 ) and of Vincent (62) on the air-drying properties of hybrid polymers derived from the condensation of glycols and maleic or fumaric acid furnishes considerable evidence as to the structure of these resins. Together with Carothers ( I @ , Kienle (42, 43), and others (16, 51, 74), the above investigators have clearly shown that synthetic resins of the thermosetting type can be produced from either of these unsaturated acids and polyhydric alcohols. That these resins have found commercial use chiefly in the paint and varnish industry, rather than as plastics or molding preparations, has been attributed to the slowness with which the resin is converted to the insoluble and infusible stage. This difficulty seems readily obviated by suitable selection of copolymerizing agents.
Vol. 33, No. 3
Supplementing this work, Dykstra ($7) showed that additive polymerization of maleic esters containing only one unsaturated linkage, in particular those formed from monohydric saturated alcohols, results in strictly linear polymers. These linear polymers are thermoplastic in nature, whereas the three-dimensional polymers produced by Bradley from glycols have thermosetting properties. The maleic-type resins are said to blend successfully with vinyl compounds (10, 27, 68), styrene (vinylbenzene), acrylic acids and esters, methacrylate resins, cinnamic and crotonic esters, adipic esters (38), conjugated diolefins, cellulose esters and ethers (1,28, 37, 62), phenol-formaldehyde resins ( 1 , S6), terpene-maleic resins (47, 6 4 , urea resins ( I ) , zein coatings (17), and other polybasic carboxylic acid-polyhydric alcohol resins (1, 24, 36). Maleic-type resins may be modified by the addition of monocarboxylic acids (28).
Formation of Resinous Products DIETHYLFUMARATE. Fifty grams of diethyl fumarate were heated on the steam bath for 24 hours with 1 gram of benzoyl peroxide, using a reflux condenser. The unpolymerized ester was distilled off under vacuum, lea\ ing a residue of 23 grams or 46 per cent of resinous material. The polymer softened to a viscous liquid when heated, but a t room temperature the semisolid mass flowed with difficulty. The soft gummy resin had a turbidity which was not present in the unpolymerized ester, believed to be caused by separation of benzoic acid in the polymer. The easy solubility of the polymer in the usual lacquer solvents suggests its use in coating compounds. Dykstra (27) formed tack-free films of good color stability and excellent characteristics by heating to 150' C. for 24 hours. Products obtained by copolymerizing with other materials, such as vinyl derivatives, were found superior to those made from diethyl fumarate alone. DIALLYLFEWIRATE. One half gram of benzoyl peroxide was dissolied in 25 grams of diallyl fumarate, and the solution maintained at 50' C. in a drying oven. Three hours later an exotheimic reaction occurred in which the ester x a s reduced to a charred mass with the evolution of considerable smoke and irritating fumes. To reduce the violence of the reaction, the experiment was repeated a t room temperature. After standing overnight the solution was transformed to a clear water-white solid which, while perfectly rigid, was soft to the touch and could be easily crumbled between the fingers. h portion of the polymer stored a t 50" C. for 3 weeks gradually hardened but became brittle rather than tough. A yellow color appealed after several days and slowly deepened. Another portion kept a t room temperature for one month became only slightly harder but remained colorless. The properties of this ester suggest its use in copolymerization with other substances ( 1 ) . Britton, Davis, and Taylor (10) claim to have produced a copolymer with vinylidene chloride and diallyl fumarate that is highly resistant to attack by strong acids and alkalies. A process for copolymerization of diallyl fumarate with vinyl acetate to obtain infusible resins was recently patented ( I ) , covering also polymerization of diallyl fumarate mixed with drying oils to obtain coating compounds. POLYMERIZATION CATALYSTS.I n the polymerization of diethyl fumarate with the aid of benzoyl peroxide as a catalyst, a turbid product is formed by the precipitation of benzoic acid, Because clarity is generally an important quality in resinous materials, other catalysts were sought which did not have this undesirable effect. Samples of oleyl peroxide, stearyl peroxide, and linseed peroxide were obtained, and comparable polymers prepared with them, using 50 grams of diethyl fumarate to 1 gram of peroxide. After 24 hoursjon
INDUSTRIAL AND ENGINEERING CHEMISTRY
March, 1941
the steam bath the unpolymerized portions were removed by distillation, and the residues were weighed and compared: Peroxide a8 Catalyst Oleyl Linseed Stearyl
Yield of Polymer, % 32 32 22
Appearance Clear brownish Clear' darker than the preceding Turb:d, light brown
From these results it appears possible to prepare a clear polymer from diethyl fumarate by selecting the proper catalyst. The brown color of the polymer was presumably due to impurities in the catalyst, since no color developed when c. P. benzoyl peroxide was used. From the standpoint of activity, however, benzoyl peroxide is superior to the fatty acid peroxides, yielding 46 per cent polymer under similar conditions.
Condensation of Fumaric Acid with Glycols Fumaric acid (116 grams) was reacted with 110 grams of diethylene glycol a t 200" C. in a three-neck round-bottom flask equipped with a short air condenser, a mechanical stirrer, and an inlet for carbon dioxide; it was designed to effect the esterification under oxygen-free conditions according to the method of Bradley (6). After 6 hours the reaction appeared complete, and the mass was cooled. The product was still liquid after standing overnight, but was extremely viscous and flowed with difficulty. Upon heating, the viscosity was reduced sufficiently to permit easy pouring. The brown turbid product was soluble in benzene and dioxane. The acid number of the glycol fumarate, determined by titrating with 0.1 N potassium hydroxide and using phenolphthalein as an indicator, was found to be 53. Carothers (IS) prepared ethylene fumarate similarly as a transparent, slightly yellow, moderately tough mass. After drying it became insoluble in the common solvents. Vincent (68) found that triethylene glycol fumarate is a viscous balsam which crystallizes slowly on standing without solvents.
317
His resin was oxygen convertible. Bradley (7)found that the hybrid polymers of condensation of glycols and fumaric acid are both heat and oxygen convertible, and are therefore suitable for a series of air-drying lacquer resins. Carothers and Arvin (13)showed that linear condensation polymers are formed by the esterification of dibasic acids with glycols. If the reactants are used in molecular proportion, the resultant polymer may be expected to contain three types of molecules; some of them are dihydroxy and dicarboxylic esters, while others are balanced molecules with terminal carboxyl and hydroxyl groups. By titrating the total acidity, the degree of condensation and the average molecular weight can be calculated (7). As an experiment in polymerization, 0.5 gram of benzoyl peroxide was dissolved in 2 grams of benzene, and the solution added to 20 grams of diethylene glycol fumarate. After stand,ing overnight on the steam bath, the mixture solidified to a hard tough resin, insoluble in the ordinary organic solvents and infusible. This was the most encouraging resin yet produced from fumaric acid and appeared t o possess desirable properties. I n an experimental attempt to improve the color and clarity, 7 moles of recrystallized fumaric acid were reacted with 7 moles of commercial diethylene glycol under oxygenfree conditions. The temperature was raised to 200" C. as rapidly as possible, and heating was continued until water was no longer evolved; 13 hours were required for the complete run. The progress of the reaction was observed by refractive index measurements. The resulting product was almost water-white. The acid number was found to be 24, making the average molecular weight 2337, calculated according to Bradley (7); the refractive index was 1.5044. When cold, the product was extremely viscous but could be easily manipulated when warmed. A portion of the ester was treated with 2 per cent benzoyl peroxide dissolved in 10 per cent benzene; contained in a stoppered test tube, it was put in the drvina oven a t 100" C. for- i 2 hours, At'the end of that time ihe material had solidified to a hard resin which had cracked during the process of polymerization. A light yellow color had also developed. Another portion, containing the same proportion of catalyst, was maintained a t 50" C. for 24 hours but was not completely cured. However, after further heating a t 50" C. for 72 hours, the resin became extremely hard and tough. Shrinkage was just enough to permit easy removal from the test tube. The ends were ground flat with a grindstone and took on a high luster when polished with a buffing wheel. Other samples prepared in the same manner showed excellent machining qualities and could be turned on a lathe, drilled, and cut with ease (Figure 1). A casting made in the shape of a bent rod showed the resin to have the property of bending light in the same manner as methyl methacrylate resins (Figure 2). Since the experiments of Rust (46,68) in polymerizing and copolymerizing maleio esters suggest interesting possibilities, somewhat similar tests were made with the glycol esters of fumaric acid. Benzoyl peroxide (1.1 grams) was dissolved in 10 grams of vinylbenzene, and the solution added to 100 grams of warm (50" C.) diethylene glycol fumarate. After thorough mixing, the mass was poured into a Petri dish. Upon standing a t
318
INDUSTRIAL AND ENGINEERING CHEMISTRY
room temperature for several minutes, the liquid gelled and its temperature increased rapidly. Within a few seconds the gel hardened to a glasslike resin, became extremely hot, cracked in many places, and yellowed slightly. The resin was examined after cooling and appeared harder than the straight diethylene glycol fumarate resin. This interesting result indicated a strong possibility of using this copolymer for compression molding, the curing time being comparable to that required by ordinary urea and phenolic molding compounds. I n order to reduce the violence of the polymerization and its consequent discoloration and cracking, the experiment was repeated with smaller quantities of catalyst. It was not until the benzoyl peroxide was reduced to 0.1 per cent by weight that the mixture could be cast and cured a t 50" C. without cracking. Under these conditions a hard clear resin was obtained after curing for 24 hours. However, even with 0.1 per cent of catalyst the resin could be cured in a few minutes by heating to 100" C. The rate of cure of diethylene glycol fumarate polymers may be substantially accelerated by the addition of vinylbenzene (styrene). On the other hand, with only 1 per cent of vinylbenzene the resin required almost as much time to cure as the plain glycol fumarate resin. When increased to 50 per cent, a cloudy resin was produced which indicated incompatibility. According to Kropa and Bradley (&), in the case of maleic resin this difficulty may be avoided by the addition of a terpene-maleic adduct. The previous experiment was repeated using vinyl acetate in place of the vinylbenzene. The effect on the rate of polymerization, the amount of catalyst required, and the resulting products were essentially the same as when vinylbenzene w&s used as copolymer. Diallyl fumarate was also tried as a copolymer and produced results similar to those obtained in the two preceding experiments. In addition it had the advantage of being compatible in all proportions. The hardness of the cured resin increased with the proportion of diallyl fumarate, higher concentrations making the resin brittle. This particular combination of copolymers is of value because it represents a resin containing only esters of fumaric acid. Copolymerizations were also made with itaconic acid esters, but in general the itaconates were less compatible, particularly a t high concentrations, than the vinyl esters or the diallyl fumarate. When 15 per cent of dibutyl itaconate was added to the glycol fumarate, a flexible but slightly cloudy resin was produced. With less than 10 per cent dibutyl itaconate, the cured resin was clear but lacked the flexibility of the 15 per cent mixture. Copolymerization with 10 per cent of dimethyl itaconate resulted in a hard clear resin. The results of these experiments on copolymerization indicate that, by varying the quantity and type of copolymer, resins can be made from diethylene glycol fumarate having a wide range of properties.
Coating Compounds Using acetone as a solvent, a coating compound was developed having the following composition: 50.0 per cent diethylene glycol fumarate, 48.9 acetone, 1.0 benzoyl peroxide, and 0.1 cobalt acetate. When coated on paper, glass, or metal and dried a t 100" C. for 10 minutes, a hard tough film was produced having excellent properties. A mixture of diethylene glycol fumarate containing 5 per cent vinyl acetate and 0.1 per cent benzoyl peroxide was used to cement together two microscope slides. After curing for 24 hours, the slides could not be separated, and when a knife blade was forced between them and twisted, the glass splintered off but the bond remained unbroken. When frac-
Vol. 33, No. 3
tured by cross bending, the glass shattered, which indicated that the bond lacked sufficient flexibility to be of use in the making of shatter-proof glass. However, it is possible that by suitable modification with plasticizers or by the use of itaconate copolymers, the bonding medium may be made sufficiently rubbery to be of value in this field. Similar experiments on the bonding of fabric, paper, cardboard, and wood showed the resin to have characteristics excellently suited to the laminating industries. When incorporated with various fillers such as gypsum, paper pulp, or asbestos, and polymerized a t 100' C., the fumarate resins yielded an interesting series of synthetics. A linoleumlike product was obtained from the following: 55.0 per cent diethylene glycol fumarate, 5.0 diallyl fumarate, 39.9 gypsum, and 0.1 benzoyl peroxide. Replacing the gypsum with the same quantity of asbestos resulted in an unusually hard and tough substance, extremely resistant to impact. From experimental work so far reported it appears likely that the most immediate large-scale use of fumaric acid may result from its ability to take part in the formation of polymers having properties variously suitable for paints, varnishes, molding, and casting resins. However, this hitherto little-known dibasic acid, with its unsaturated structure and low molecular weight, has an unusual combination of properties and should prove useful in many industries.
Literature Cited (1) (2) (3) (4)
American Cyanamid Co., Brit. Patent 513,221 (Oct. 6, 1939). Anonymous, Oil, Paint Drug Reptr., 137,38 (March 4, 1940). I b i d . , 137, 59 (June 17, 1940). Ashton, H. W., and Partington, J. R., Trans. Faradau SOC.,30,
698-614 (1934). (5) Bradley, T. F., IKD. ENG.CHEX.,29, 440-5 (1937). ( 6 ) Ibid., 29, 579-84 (1937). Bradley, T. F., Kropa, E L., and Johnston, W. B., I b X , 29, (7) 1270-6 I193T). (8) Bremer, C. ( t o Atlas Powder Co.), U. S. Patent 2,176,415 (Oct. 17, 1939). (9) British Thompson-Houston Co., Ltd. (assignee of A. J. Sherburne), Brit. Patent 407,914 not accepted (application June 23, 1932). (10) Britton, E. C., Davis, C. W., and Taylor, F. L. (to Dow Chemical Co.), U. 8. Patent 2,160,940 (June 6, 1939). (11) Brunner, H . , and Chuard, E., Be?., 30, 200-1 (1897). (12) Carothers, W. H., Cham. Rev., 8, 353-426 (1931). (13) Carothers, W. H., and Arvin, J. A., J. Am. Chem. Soc., 51, 2560-70 (1929). (14) Carothers, W. H., and Collins, A. hZ. (to E. I. du Pont de Nemours & Co.), U. S. Patent 1,967,862 (July 24, 1934). (16) Carpenter, J. H., IND.ENG.CHEM.,13, 410-13 (1921). (16) Clocker, E. T., U. S. Patents 2,188,882-9 (Jan. 30, 1940). (17) Coleman, R. E. (to Zein Corp. of Am.), I b i d . , 2,185,122 (Deo. 26, 1939). (18) Diels, O., and Alder, K. (to I. G. Farbenindustrie Akt.-Ges.), I b i d . , 1,944,731-2 (Jan. 23, 1934). (19) Doebner, O., Ber., 34, 53-5 (1901). (20) Downs, C. R., IND. ENG.CHEM.,26, 19 (1934). (21) Downs, C. R., J . SOC.Chem. I n d . , 46, 383-6T (1927). (22) Downs, C. R. (to Barrett Co.), U. S. Patent 1,374,720 (April 12, 1921). (23) Downs, C. R., and Weisberg, L. (to Barrett Co.), Ibid., 1,489,744 (April 8, 1924). (24) I b i d . , U. S.Patents 1,667,197-9 (April 24, 1928). (25) Dunn, M. S., and Fox, S. W., J . Biol. Chem., 101, 493-7 (1933). (26) Du Pont, E. I., de Nemours & Co., Brit. Patent 394,000 (June 19, 1933). (27) Dykstra, H. B. (to E. I. du Pont de Nemours & Co.), U. S. Patent 1,945,307 (Jan. 30, 1934). (28) Ellis, C. (to Elli6-Foster Co.), Ibid.. 2,195,362 (March 26. 1940). (29) Enkvist, T., Be?., 72, 1927-32 (1939). (30) Erlenmeyer, H., and Schoenauer, W., Helv. Chim. Acta., 20, 1008-12 (1937). (31) Fichter, F., and Dreyfus, C., Ber., 33, 1452-5 (1900). (32) German, W. L., Vogel, A. I., and Jeffery, G., P h i l . Mag., [7] 22, 790-800 (1936). (33) Haroldson. A. (to Continental-Diamond Fibre Co.). U. S. Patent 2,185,081) (Dec. 26, 1939).
INDUSTRIAL AND ENGINEERING CHEMISTRY
March, 1941
e
(34) Herniann, S., Neiger, R., and Zentner, M., Arch. ezptl. Path. Pharmakol., 188,526-32 (1938). (35) Hijnel, H.(to Beck, Koller and Co., Inc.), U. 8. Patent 1,870,455 (Aug. 9, 1932). (36) Hopff, H., and Steinbrunn, G. (to I. G. Farbenindustrie Akt.Ges.), Ihid., 2,182,316(Dec. 5, 1939). (37) I. G. Farbenindustrie Akt.-Ges., Brit. Patent 508,016 (June 21,1939). (38) I. G. Farbenindustrie Akt.-Ges., French Patent 841,521(Feb. 6, 1939). (39) I. G.Farbenindustrie Akt.-Ges., German Patent 437,154 (Nov. 11, 1926). (40) Jaeger, A. 0.(to Am. Cyanamid and Chemical Corp.), U. 9. Patent 2,176,423(Oct. 17, 1939). (41) Jaeger, A. 0.(to Selden Co.), Ibid., 1,844,394(Feb. 9, 1932). (42) Kienle, R. H., IND. ENG.CHEM.,22,590-4 (1930). (43) Kienle, R. H., and Schlingman, P. F., Ibid., 25, 971-5 (1933). (44) Krebs, H. A., Salvin, E., and Johnson, W. A., Biochem. J . , 32, 113-17 (1938). (45) Kropa, E. L., and Bradley, T. F., IND. ENQ.CHEM.,31, 1512-16 (1939). (46) Lange, N. A,, and Sinks, M. H., J . Am. Chem. Soc., 52, 2602-4 (1’930). (47) Littman, E. R., IND. ENO. CHEM.,28, 1150-2 (1936). (48) McGill, J. H.,and Imperial Chemical Industries, Brit. Patent 509,711 (July 19, 1939). (49) Milas, N.A.,J. Am. Chem. SOC.,59,2342-4 (1937). (50) Milas, N.A., and Terry, E. M., Ibid., 47, 1412-18 (1925). (51) . . Morrell. R. 8.. Marks, S.. and Samuels, S., Brit. Patent 407,957 (March 19. 1934). (52) Norris, J. F., and Cummings, E. O . , U. S. Patent 1,457,791 (June 5, 1923). (53) Orten, J. M., and Smith. A. H.. J . Biot. Chem.. 117. 556-67 (1937).
319
(54) Peterson, E.G. (to Hercules Powder Co.), U. S. Patents 1,993,026-7, 1,993,031,1,993,034(March 5, 1935). (55) Phelps, I. K.,U. S. Patent 974,182 (Nov. 1, 1910); German Patent 254,420 (Dec. 2,1912). (56) . . Ponstord, A. P., and Smedles-Maclean. Ida, Biochem. J . . 26, 1340-4 (1932). (57) Richter, Victor von, “Organic Chemistry”, Vol. I, Philadelphia, P Blakiston’s Son & Co., 1934. (58) Rust, J. B., IND.ENQ.CHEM.,32,64-7 (1940). (69) Snell. F. D.. Ibid.. 29. 560-4 (1937). (60j Tanatar, S.,‘ Ber.,’29,’1477-9‘(1896). (61) Term. E. M., and Eichelberger. L., J . Am. Chem. SOC..47, 1402-12 (1925). (62) Vincent, H. L.,IND. ENG.CHEM.,29, 1267-9 (1937). (63) Weisberg, L. (to Barrett Co.), U. S. Patent 1,413,144-5(April 18. 1922). __.~.~~ (64) Ibid., 1,443,935(Jan. 30, 1923). (65)Ibid., 1,443,936(Jan. 30, 1923). (66) Weisbern. L.. and Potter, R. S. (to Barrett Co.), Ibid., 1,424,137 (July 25, 1922) (67) Weiss, J. M. (to Calorider Corp.), Ibid., 2,206,377(July 2, 1940) and 2,209,908(July 30, 1940). (68) Weiss, J. M., and Downs, C. R., J . Am. Chem. Soc., 44,1118-28 (1922). (69) I&., 45, 1003-8 (1923). (70) Ibid., 45,2341-9 (1923). (71) Weiss, J . M., and Downs, C. R., J. INDENGCHEM.,12,228-32 (1920). (72) Weiss, J. M., and Downs, C. R. (to Barrett Co.), U. S. Patents 1,318,631and 1,318,633(Oct. 14, 1919). (73) Weiss, J. M., Downs, C. R., and Corson, H. P., IND ENG. CHEM.,15, 628-30 (1923). (74) Zwilgmeyer, F. (to National Aniline and Chemical Co.), U. S. Patent 1,950,468(March 13, 1934)
EVAPORATION NOMOGRAPH
W
D. S . DAVIS
HEN dealing with evaporators it is frequently necessary to calculate the amount of water evaporated per 100 pounds of thin liquor. Let s = solids in thin liquor, % ’ S = solids in thick liquor, yo W = Ib. water evaporated per 100 lb. thin liquor
Wayne University, Detroit, Mich.
F’
Then 100 - s = percentage of water in the thin liquor, and 100 S = percentage of water in the thick liquor. The number of pounds of water evaporated per pound of solids is
so
100 s - - 100 - s _ ___ S S
20
L
-
and the number of pounds of water evaporated per 100 pounds of thin liquor is W: per
Lbs
Water Removed Thin Llquor
100 Lbs
The expression
W
= 100 (1
-;)
is solved conveniently by the nomograph in which the broken line indicates that 84.7 pounds of water are evaporated from 100 pounds of thin liquor in changing the concentration from 2.60 to 17.0 per cent solids. The chart can be used for values of s and S below the range of the scales by moving the decimal point in these values one place to the left without changing the W scale in any way. Thus the broken line also shows that 84.7 pounds of water are removed from 100 pounds of thin liquor in increasing the concentration from 0.260 to 1.70 per cent solids. What is W for s = 60 and S = 801 Sixty is beyond the range of the s scale but W can be found to be 25 by connecting 6 on the 8 scale with 8 on the S scale. d
t
---
-----I--
