INDUSTRIAL AND ENGINEERING CHEMISTRY
102
COMPOUNDING A N D TESTING.The physical properties listed in Tables I V and V were obtained on vulcanizates compounded according to the following recipe: Polymer E P C black ZnO Stearic acid Captax Sulfur
100 50 5 2 1.5 2
The same recipe, with omission of the carbon black, was used for the gum stock vulcanizates. The following vulcanization periods and temperature were used: Polymer B/S 100/0
90/10 80/20 70/30
Polyisoprene
Vulcanization Conditions Min. F. 40/275 501’275 60/275 70/275 40/276
Because of the limited amounts of polymer available, a series of cures could not be run to determine time for optimum cure. The abrasion resistance was measured on the National Bureau of Standards testing machine ( I ) , for which a standard natural rubber stock was given an arbitrary abrasion index of 100. ACKNOWLEDGMENT
The writers are grateful to A. A. Morton for supplying the Alfin catalysts with recommendations as to their use. Dilatometric measurements were made by R. 31. Pierson and E. A. Sinclair. Density and refractive index data a e r e obtained with the assistance of R. W. Schrock. The x-ray diffraction and infrared data were obtained by P. J. Jones and D. E. Woodford. Compounding data were provided by the research testing laboratory and the Compound Development Department. Test tires were compounded under the supervision of J. H. Fielding. The writers wish to express their appreciation to H. J. Osterhof and The Goodyear Tire & Rubber Company for permission to publish this paper. LITERATURE CITED
(1) Am. Soc. Testing Materials Standards on Rubber Products, A.S.T.M. Designation D 394-47, Method B, p. 105, February 1948. ( 2 ) Beu, K. E., Reynolds, W. B., Fryling, C. F., and McMurray, H. L., J . Polgmer Sci., 3, 465-80 (1948). (3) Davis, C. C., and Blake, J. T., “ChemistIy and Technology of
Vol. 42, No. 1
Rubber,” A.C.S. Monograph 74, Chap. 3 and 21, New York, Reinhold Publishing Corp., 1937. D’Ianni, J. D., IND. ENG.CHEM.,40, 253-6 (1948). Eberly, K. C., and Johnson, B. L., J . Polymer S c i . , 3, 283-96 (1948). Field, J. E., Woodford, D. E., and GehinaTl. S. D.. J . A p p l i e d Ph?/s., 17, 386-97 (1946). Firestone Tire and Rubber Co., private cornniunication. Gehman, S. D., Woodford, D. E.. arid Wilkinson, C. S.,1x1). ENG.CHEM.,39, 1108-15 (1947). Hanson, E. E., and Halvorson. G., J . Am. Chem. Soc., 70, 779-83 (1945). Hart, E. J., and Meyer. A . W.. I b i d . , 71, 1980-5 (1949). Hendricks, S.B., Wildman, 9. G., and Jones, E. J., Arch. Biochem., 7, 427-38 (1945) : Rubber Chem. Techno/., 19, 501-9 (1946). Kemp, A. l i . , Proc. Rubber Tech. CoiLf., L o n d o n , 1938, 68-79; Rubber Chem. Technot., 12, 470-81 (1939). Kolthoff, I. &I., and Lee, T. S., J . Polymer S c i . , 2, 206-19 (1947). Kolthoff, I. M., Lee, T. S., and Maiw. M , A . . Ihid., 2, 220-8 (1947). Ibid.,pp. 199-205. Madorsky, I., and Wood, I,. A , , private corninuiiication. Marvel, C. S.,Bailey, W. J., and Inskeep, G . E., J . Polymer Sci., 1, 275 (1946); Rubber Chem. Technol., 20, 1 (1947). Meyer, K. H., and Mark, H., ”Der Aufbau del, hochpolymeren organischen Naturstoffe,” pp. 199, 205, Berlin, Hirschwaldsche Buchhandlung, 1930. Morton, A. A., et al., J . Am. C h ~ m Soc., . 68, 93 (1946) ; 69, 160, 161, 167, 172, 950, 1675 (1947); 70, 3132 (1948); 71, 481, 487 (1949). Natl. Bur. Standards, Circ. C461 (November 1947). Natl. Bur. Standards, private communication. Saffer, A., and Johnson. B. L., IND.ENG.CHEM.,40, 538-41 (1948).
Sckulee: W. A., and Crouch, W. My.,J . Am. Chem. Soc., 70, 3891-3 (1948). Shearon, W. H., McKenzie, J. P., and Samuels, M. E., IND. ENG.CHEM., 40, 769 (1948). Taft, W. K., University of Akron Government Laboratories, private communication, March 11, 1949. Wall, F. T., private communication. Wood, L. A., Proc. Rubber Tech. Conf.,London, 1938, 933-53; Rubber C h e m . Technol., 12, 130-62 (1939). Bakkedahl, N., and Roth, F. L., IND.EXG.CHEM., Wood, L. il., 34, 1291-3 (1942). Yanko, J . A , , J . Polyme? Sci., 3, 576-601 (1948). RECEIVED June 27, 1940. Presented before the Division of Rubber Chemistry, AMERICANCHEXICALSOCIETY,Boston, M a s s . , M a y 23 t o 25, 1949. Contribution 168 from T h e Goodyear Tire R: Rubber Company Research Laboratory. This investigation was carried out under the sponsorship of t h e Office of Rubber Reserve, Reconstruction Finance Corporation in connection with the government synthetic rubber program.
Treatment of Paper astes in Biochemical xidatio Ponds C. C. PORTER AND FRED W. BISHOP Southland Paper Mills, Inc., Lufkin, Ter.
T
HE paper mill with which the authors are connected manu-
factures groundwood, unbleached and bleached kraft pulp using pine as a raw material. The pulps are converted into newsprint, cylinder board, and kraft wet lap. The newsprint furnish includes 20% bleached kraft and SO% groundwood pulp. The cylinder board may be solid unbleached kraft or unbleached kraft with a bleached liner or unbleached kraft with a small amount of groundwood pulp added. The met lap may be either solid bleached or unbleached pulp. Unbleached kraft pulp is made by the selective saponification of lignin in wood b r digestion with rauqtic soda and sodium
sulfide as the active ingredients. The saponification product is collected from a three-stage, countercurrent vacuum washing system, which discharges clean pulp from one end and concentrated liquor from the other. The sodium lignate, commonly called black liquor, is evaporated, ignited to sodium carbonate, and recausticized to sodium hydroxide for reuse in the digesters. Unbleached kraft pulp is bleached in a three-stage system employing direct chlorination, caustic extraction, and sodium hypochlorite addition, in that order. Groundwood pulp is prepared by mechanically pressing 4foot lengths of peeled logs lengthwise against a revolving grind-
January 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
considered as negligible. stone. The wood fibers are The problem was first attorn from the log and disT h e problem is presented as the result of mill waste tacked from the standpoint integrated into very small entering a natural water course which has a very low flow of chemical treatment using during the dry summer months. The total mill effluent is size fibers. different combinations of a combination of wastes from kraft pulp mill, bleach plant, The mill is located in groundwood pulp mill, newsprint machine, and cylinder coagulants to produce coAngelina County a t an eleboard machine. The work in the laboratory soon exagulation and sedimentavation of 310 feet. The hausted the possibilities of chemical or physical treattion or clarification. In combined wastes from the ment from the economic standpoint. Storage tests in the light of the tremendous mill are distributed into a large crocks performed on individual departmental waste background of work by dry creek bed which flows and on the total mill effluent indicated that the best rethe industry as a whole on approximately 8 miles into sults of over-all biochemical oxygen demand (B.O.D.) rethis means of treatment, the Angelina River. The duction could be expected from the latter. Further storit was decided that this elevation a t confluence with age tests were run on the total mill effluent under sterile method had been relegated the river is about 165 feet. conditions, and also under conditions of supplemental t o a position which would Before the mill was built the seeding and feeding. The analysis of these data indicated always be classified as a creek carried run-off water that relatively short periods of storage by impounding last resort measure. The during the rainy season and effected biochemical oxidation by the native bacterial chemical cost and the inwas dry during the summer flora. The problems and results of 2 years of successful season for several months stallation and operating operation with the large retention ponds are presented. except immediately followcosts of equipment would Normally, the B.O.D. on the total mill effluent is reduced ing heavy rains. never be considered as 70% as a result of biochemical oxidation in the retention I n this area the yearly economically feasible proponds before it is discharged into the river. The suppleprecipitation over the last mental measures required for a mill expansion program vided there were other 10 years has averaged 45 are mentioned, and the results of these measures are alternatives. inches. This rainfall is disbrought up to date. tributed unevenly over the LABORATORY year, the wet season extendEXPERIMENTS ing usually from November 1 until June 1, while the summer months are marked by dry spells As the natural topography of the surroundings lent itself t o the construction of impounding reservoirs, it was decided t o of one t o several weeks’ duration. The stream flow of the Anevaluate the effect of storage on the effluent. The nature of gelina River roughly follows seasonal variation in rainfall. I n the wastes was such that the following conditions could be carried winter, the river is out of banks for months with a normal flow on the credit side of the ledger: There would be dilution of the of 6700 cubic feet per second, while in the summertime there are dry spells during which the flow is as low as 55 cubic feet per kraft mill waste by groundwood and newsprint mill effluents; second. Above Lufkin the river drains a basin of approxiby the presence of possible nutrients from the goundwood and newsprint operations; by the presence of septic tank effluent; mately 2000 square miles. The Angelina joins the Neches River and by the partial neutralization of alkaline wastes by acid about 110 miles below the mill site. The rivers flow about 200 effluents. miles from Lufkin to Sabine Lake on the Gulf of Mexico. The first unit of the mills began operating in January 1940 with These credits established a condition which could be favorable the manufacture of groundwood pulp and newsprint. The t o the growth of native bacterial flora and t o the oxidation of substances that would otherwise deplete the oxygen in the river. bleached kraft required in the newsprint furnish was supplied by another mill in this locality. As the wastes from these units With these facts in mind, storage tests in 5- to 10-gallon stoneware were small and had relatively low B.O.D. , their presence in the crocks were started on the individual departmental wastes and river at times of low flow did not deplete the oxygen below a point on the total mill effluent. From the beginning it was apparent that the total mill effluent where aquatic life was adversely affected. The oxygen-demanding would readily lend itself t o some type of over-all B.O.D. reduction materials of this initial effluent comprised wood flour, wood fiber, as a result of storage. The individual departmental wastes and reducing sugars produced by the hot water extraction of followed this trend in very much the same manner, but often in wood. varying degrees of magnitude. Nevertheless, the results obIn 1942 the company initiated a construction program which tained on storage of total mill effluent were considerably better involved the addition of an unbleached kraft pulp mill, bleach than could be expected by determining a weighted average of the plant, cylinder board machine, and two wet lap machines. individual contributing sewers. I n general, B.O.D. plotted Following modern principles of design, the kraft pulp mill was against time in days followed a curve comparable t o that of a specified to operate a t an absolute minimum loss of chemical negative exponential function. The slope varied from a straight in sewage wastes. Experience with the newsprint mill wastes had taught that an line almost parallel to the horizontal t o a curve of high initial additional B.O.D. load in the river could not be tolerated in slope soon leveling out t o approach infinity with the horizontal periods of low water without running the risk of reducing the (Figure 1). These curves are probably general in most respects oxygen below a safe minimum. Accordingly, a program of in any type of storage where an organic material is subjected laboratory research was initiated with the objective of finding t o bacterial decomposition. With this in mind, the bulk of the experimental work was performed with the idea of increasing the ways and means of reducing the oxygen-depleting effect of the initial downward slope of the curve in the shortest possible time. combined total mill effluent. As the kraft mill wastes represented the largest single conStorage tests were continued using first baker’s yeast and tributor, the first attack was directed toward the suitable treatbrewer’s yeast, singularly and in combination with nutrient ment of this. A typical kraft mill waste contains primarily materials in the form of sugar, starch, nitrogen, and metallic salts. Of course, some benefit was derived from many of these sodium lignate, sodium resinate, and complex organo-sulfur compounds, and some fiber in relatively dilute solution. The combinations t o effect an additional B.O.D. reduction against design of the pulp mill inherently prohibited very large losses of time. For instance, as the nitrate content was increased, the reduction rate was accelerated. The same was true in the use these sodium base compounds, and furthermore the fiber loss was ~~
#
103
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104
of some of the other materials, but the use of additives would necessarily increase the cost of operation disproportionately to the results produced. Along the same line the total mill effluent was seeded individually with solutions of fresh feces from horse, cow, goat, and sheep in the presence of nutrient materials mentioned earlier. A11 of the above-mentioned storage tests were performed under both aerobic and anaerobic conditions. As one of the large contributors to the B.O.D. load of the total mill effluent was cellulosic fiber, considerable storage work was performed by the Engineering Experiment Station of the Agricultural and Mechanical College of Texas using the bacteria from a cow's stomach as a seeding material. The results were good, but they failed to show sufficient improvement over straight storage t o warrant further study. No real differentiation could be made on the over-all study of these combinations; however, in the light of performance tests in the initial study, the work resolved itself t o a continuation of storage tests on the total mill effluent alone without any supplemental nutrient or seed.
-
Vol. 42, No. 1
feeding the pilot pond. The pond was designed for a capacity of 50,000 gallons, and the retention rate could be varied over a wide range by regulating the number of cups full of waste picked up from the flume by each revolution of the wheel. A series of storage experiments mas conducted by varying the over-all retention time from 3 to 20 days. Periods of retention in excess of 10 d a y produced only a slight improvement in over-all B.O.D. reduction. The rate of reduction after 10 days' storage was very slow as compared to that of the first 10 days. To compare the operation of the pond nith the laboratory results, parallel storage tests in crocks were conducted on the total mill effluent. In most every instance the crock tests proceeded a t an increased rate over the pilot pond operation. This was attributed in most cases to the elevated temperatures in the crock samples. As the over-all reduction in pond storage amounted to only 3070, secondary storage on the pond effluent was conceived and started in crocks. These results were very promising and indicated the necessity for additional work. The secondary storage tests were performed over a wide range of conditions employing many of the supplemental seeding and feeding principles used in the initial work. In most all cases, apparently sufficient seeding was derived in the process of primary storage t o produce secondary B.O.D. reduction by prolonged storage. With this in mind, a secondary pilot pond was constructed on a still smaller scale to be fed by gravity from the primary pond effluent, and to be operated a t retention times varying from 5 to 20 days. The operation of the secondary pond substantiated all of the previous results to the extent that it affected an additional B.O.D. reduction of 30%, or 60% over-all in both ponds. Based on this work the studied opinion indicated that the conditioning of wastes, as affected in both ponds, could be secured in large reservoirs handling the entire mill effluent. Further studies on the flow characteristics of the river gave reasonable hope that conditioned effluents could be absorbed satisfactorily in periods of low flow.
::k 50
\
..-----
I
0 '
0
2
4
6
8
DAYS
IO 12 STORAGE
14
16
18
Figure 1. Storage Curves Typical of Individually Contributing Wastes Which Make Up the Composite Total Mill Effluent
In an effort to study the mechanism of the results obtained, a series of experiments was run by storing total mill effluent under the following conditions: (1) total mill effluent as control; (2) total mill efluent filtered through a Seitz filter and stored under sterile conditions; (3) total mill effluent filtered through a Seitz filter and heated t o 180' F. to destroy the enzymes, and stored under sterile conditions; (4)total mill effluent with 0.4% potassium fluoride to inhibit the growth of bacteria. This type of test repeatedly indicated that both samples filtered through the Seitz filter practically maintained their initial B.O.D. content throughout the period of time when the control test lost as much as 90%. The specimen treated with potassium fluoride maintained its initial B.O.D. for a number of days, at which time the bacteria apparently became acclimated to the conditions and became active again. Storage experiments were conducted to evaluate the contribution made by suspended materials. Invariably, the filtered samples indicated a faster rate of B.O.D. reduction than the total mill effluent. The suspended material in the form of pulp fiber and wood fiber would naturally lend itself t o bacterial degradation resulting in oxygen consumption. However, since the suspended material increased the over-all load by only about 2075, it was decided that filtration equipment would not be needed provided pilot plant operation would give results comparable t o those obtained in the laboratory. FIELD EXPERIMENTS
To substantiate the laboratory results an earthen dam was built across a small natural depression adjacent t o the outfall of the total mill effluent. As the waste at this point was distributed over a concrete flume a t high velocity, a paddle wheel with sampling cups was installed in this stream and used as a device for
STOR4GE RESERVOIRS
Plans for the construction of large reservoirs a4 ruecuted, called for two 50-ac-reponds t o be built along the stream about a mile below the mill and extending over a distance of 2 miles. The distance from the overflow of the second pond to the river is, roughly, 10 stream miles. The topography was such that a natural fall existed from the mill to the ponds and from the ponds to the river. The volume of each was to be approximately 250 acre feet which uould allow a mean retention time of 13 days when the mill effluent was 5500 gallons per minute or 12 cubic feet per second. The ponds were built by throwing earthwork dams across natural ravines with adjacent spillways above the normal water level to carry the run-off from the flash floods. The normal sewage overflow was handled over a tower in front of the dam which dropped the discharge into a conduit beneath the base of the dam. Gates were installed a t the upstream end of the conduits to facilitate complete drainage of the ponds during the seasons of high flow in the river. OPERATIONAL RESULTS
Full scale operation of the large impounding reservoirs was started in the late spring of 1946. They fulfilled all of the physical design specifications in regard to capacity and operating principles. After the ponds were in operation for a few weeks, the results indicated that the desired benefits might be expected. A typical pattern of B.O.D. reduction on the total mill effluent from the mill t o the river may be listed as follows: mill outfall, 200 p.p.m.; effluent from the first pond, 160 p.p.m.; effluent from the second pond, 120 p.p.m.; effluent a t the river, 90 p.p.m. With the reservoirs in operation and with the river flow a t 400 cubic feet per second, the dissolved oxygen a t the sag point in the river was 4.1 p.p.m. In the year before a t this river flow, only a slight trace of oxygen was found a t this point. The sag point,
INDUSTRIAL AND ENGINEERING CHEMISTRY
January 1950
anaerobic conditions along the bottom were having little effect on the picture of the over-all operation. All of the above results represent average conditions and are comparable for two dry seasons of operation in which the paper mill wastes did practically no damage t o fish life in the Angelina River. Throughout the times of low water, good catches were made of both game fish and bottom-dwelling fish in t h e river reaches below the point where the conditioned effluent entered.
1946 OPERATIONS
280
105
DISCUSSION
40
I
I)
.7
8- I
7-1
9-1
DATE
Figure 2.
One Season's Operation
Top bar line represents tests on total mil! effluent, dottcd bar line is Gltered total mill effluent, third and fourth lines represent effluent from the first and second ponds. respectively, and the hottom line repregents tcfits on eflluent at river
*
aa mentioned above, had been established earlier as the place a t which the dissolved oxygen content would be lowest as the result of introduction of wastes. The river flow continued t o drop until it reached a low of only 55 cubic feet per second, and the dissolved oxygen at the sampling point was 3.4. At this flow the ratio of river water to reservoir effluent was 4.5 to 1. During the months of August and September, the average temperature of the atmosphere and the impounded waste was 89" F. At a time like this the bacterial activity was apparently accelerated t o the extent that the B.O.D. reduction was as follows: total mill effluent, 200 p.p.m.; first pond effluent, 120 p.p.m.; second pond effluent, 90 p.p.m.; effluent a t the river, 35 p.p.m. Figure 2 is a graphical illustration of a season's operation. The B.O.D. drop in the 10 miles of stream bed from the second pond t o the river was very advantageous and was usually evident at the most propitious time. The growth of blue-green algae along the stream banks indicated advanced stages of purification of the effluent. Apparently with the elevated summer temperatures, the wastes were conditioned in such a manner that they were readily subjected t o reoxygenation by aeration along the route. With the earlier stages of oxygen demand satisfied, the introduction of such wastes into the river during the lowest flow periods did not present the demand in such a rapid manner that the over-all reconditioning ability of the river w&s taxed. The actual p H of the waste throughout the system apparently had little effect on the operation, and it only indicated a condition which was favorable t o bacterial growth. Normally it varied from 7.8 to 8.6, and the variation necessarily was governed by any change in the total mill effluent. Normally 4500 pounds per day of sulfates as such were included in the total mill effluent aa a result of conventional loss in the paper and board making processes. I n following the sulfate content through the treatment process, it was found that they were almost entirely reduced and were nonexistent in No. 2 pond effluent. It is indicated that this reduction is brought about by the action of sulfatereducing bacteria, and that oxygen from these sulfates is given up to the surrounding materials. As impounded kraft mill waste inherently has a bad odor, it was difficult t o determine that the sulfate reduction was contributing any more. With the ponds in normal operation, they were sampled in many localities over the surface and in the deeper parts t o a depth of 10 and 20 feet t o check pH, sulfates, and B.O.D. The results indicated that there was very little channeling and that
Definite origin of the bacteria which produces beneficial results is not known. The assumption is that the organisms are native to the soil, the wood, and the air. At any rate, they are always present in the desired quantities and specie combinations to develop a colony capable of producing effective results. As a primary energy food, t h e bacteria utilizes the water-soluble constituents of wood from the groundwood process. As these constituents are primarily wood sugars, their presence along with that of wood flour apparently account for the sustenance and profuse growth of the organisms. The presence of these materials probably play a n important part in the symbiotic system which normally propagates the sulfate-reducing organisms. The sodium lignate in the kraft mill effluent is somehow attacked within the cycle of the system t o the extent that its individual purification is accelerated. An important influence is exerted by these conditions on the oxidation rate of kraft mill waste. This is evidenced by the fact that kraft mill waste without groundwood mill effluent did not oxidize nearly so rapidly on storage. As far as the oxidation rate is concerned, a definite relationship exists between it and strength of the waste, energy food content, and caustic alkalinity.
Figure 3. Aerial Photograph of Presedimentation Pond Showing Dam, Overflow Launder, and Tower Number one and two ponds are in the background
These statements should not be misconstrued as anything other than logical assumptions formulated by continued observation of the reactions and by a study of the materials available t o support this reaction. A pure biological study has not been made exccpt in a very crude form, and the findings would mean very little t o one of this science. They would serve only as an instrument t o provide some insight t o those who were in the midst of the problem. Newer concepts of oxidation and reduction do not necessarily entail oxygen transfer, but conversely the loss or gain of hydrogen
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INDUSTRIAL AND ENGINEERING CHEMISTRY
atoms or electrons. When a substance loses these, it reaches a higher state of oxidation by dehydrogenation. As a result of this reaction, the organic matter is said to be oxidized t o the extent that oxygen consumption is reduced. During 2 years of operation a very large accumulation of suspended material settled in the upper reaches of the first pond. In operation much of this material in the process of decomposition floated t o the top and covered as much as two thirds of the surface. The material was shifted from one end of t,he pond to the other according to wind direction, but apparently it did not impose too much additional load in the liquid effluent from this pond. It was readily apparent that over a period of years the sludge and its subsequent removal would prove a tremendous problem. A mill expansion program started shortly thereafter necessitated an additional consideration for the stream improvement program which would ultimately eliminate this condition. In the spring of 1948 another groundwood mill and newsprint machine and an expanded bleach plant went into operation imposing an additional load of 10 cubic feet per second of effluent on the conditioning ponds. Between the mill and the first pond a pre-sedimentation pond was built with smooth sloping sides to facilitate easy removal of the deposited sludge. The new pond was designed for 16 hours' retention time handling all of the effluent including that from the expanded program. I t discharges over the edge of a launder 200 feet long falling into a trough below and flowing from there to a tower like those on the original ponds (Figure 3). This basin was built with the intention of a complete cleaning program each year during the winter months. This would be accomplished by the use of a dragline to move the material above the water line, or by using a bulldozer and pushing the material from the basin. The pond operations during the 1948 season followed the same general range of efficiency as indicated in the former operations. During the most critical period of low river flow, the B.O.D.
Vol. 42, No. 1
of the effluent entering the river was in a range of from 30 to 40 p.p.m. having dropped during passage through the ponds from approximately 230 p.p.m, The presedimentation pond, which had been installed during the winter of 1947 to 1948, proved of considerable value in taking care of the additional effluent occasioned by the mill expansion. The river conditions were not as good as those indicated in the 1946 figures. This was not due to any lower efficiency of the pond operations, but duc to the abnormally low river flow. -4severe drought was prevalent in the general northeast, east, and southeast parts of Texas, and in many regions rainfalls were lower than in any year since 1917. At one period during the summer the paper mill effluent constituted 40'% of the total river flow. CONCLUSION
The use of oxidation lagoons is not presented as a cure-all for kraft or newsprint effluents, but rather as an abatement procedure which map be utilized when all of the conditions are favorable. ACKNOWLEDGMENT
The authors wish to acknowledge the contributions of Charles C. Carpent,er, former general superint'endent'; the work of Robert J. Speer and George Schnitzer, former research chemists; and that of A. B. Youngblood, field technician. The advice and recommendations of Harry Gehm and fi'illiam Moggio, Sational Council for Stream Improvement, Inc., \\*ereinvaluable throughout the project. Contributions on some phases of the project were made by J. H. Sorrells and E. H. Gibbons through the Engineering Experiment Station of t h P Agricultural and Xechmical College of Texas. RECEIVED March 12, 1949. Presented before the Division of Water, Sewage, and Sanitation Chemistry a t the 1 1 4 t h Meeting of the AMERICAN CHIIIICAL SOCIETY,St. Louis, Mo.
Vapor-Liquid Equilibria inBinary Systems d
d
Water-2-Methyl-3-butyn-2-01 and Water-3-Hydroxy-3-methyl-2-butanone ALBERT Z. CONNER', PHILIP J. ELVING2, JOSEPH BENISCHECK3, PHILIP E. TOBIAS', AND SAMUEL STEINGISER6 Publicker Industries, Incorporated, Philadelphia, Pa. Vapor-liquid equilibrium data at atmospheric pressure are presented for the binary systems, water-f-methyl-3butyn-2-01 and water-3-hydroxy-3-methyl-2-butanone. A minimum boiling azeotrope was found in each system. The isopiestic activity coefficients for the components in the two systems have been calculated and van Laar equations have been fitted to the activity coefficient data. The refractive index-composition relations for the binary systems were determined. The vapor pressure-temperature relations up to 800 mm. of mercury pressure were determined for the 2-methyl-3-butyn-2-01 and the 3-hydroxy3-methyl-2-bu tanone. Present address, Hercules Experiment Station, Wilmington, Del. State College, State College, Pa. 3 Present address, Temple University, Philadelphia, Pa. * Present address, 15 Harvin Road, Upper Darhy, Pa. 6 Present address, University of Connecticut, Storrs, Conn. 1
* Present address, The Pennsylvania
V
APOR-liquid equilibrium data, especially for systems which show deviations from the laws of ideal solutions, are necessary for the design of rectification equipment for the separation of binary and polycomponent, systems. In addition, vapor-liquid equilibria studies can be used to evaluate such factors as the extent of hydrogen bonding and other structural or thermal effects. dct,ivity coefficients can be calculated for the complete composition range of a liquid system and the resulting relations used t o establish the self-consist~encyof t,he experimental data. I n connection with the study of an acetylenic alcohol and its ketone-alcohol hydration product, 2-methyl-3-butyn-2-01 and 3-hydroxy-3-methy1-2-but~anone, the vapor-liquid equilibrium relations in the binary systems formed by each of these two compounds with water were investigated. Minimum constant boiling mixtures were found. In the calculation of the activity coefficients for the evaluation and int,erpretation of the experimental equilibrium data, it vas
