/ ' v *.. ’*$11 0 * v \ >%,*.’} ,.;J0 'J / The person charging this material is re- sponsible for its return to the library from which it was withdrawn on or before the Latest Date stamped below. Theft, mutilation, and underlining of books are reasons for disciplinary action and may result in dismissal from the University. To renew call Telephone Center, 333-8400 UNIVERSITY OF ILLINOIS LIBRARY AT URBANA-CHAMPAIGN L161— 0-1096 PROPERTIES OF MIXTURES OF NOR- MAL BUTYL ALCOHOL AND WATER; RECOVERY OF NORMAL BUTYL ALCOHOL FROM WATER MIXTURES BY CLARENCE FRANCIS CROSSLEY THESIS FOR THE D E G R E E O F FiAGHE L O R O F S C I E NGE IN CHEMISTRY COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1922 UNIVERSITY OF ILLINOIS May 51, .192 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Clarence Francis Crossley ENTITLED Properties of Mixtures or formal Butyl Alcohol and Water; Recovery of Normal Butyl Alcohol from Water Mixtures IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Bachelor of Science in Chemistry ACTIFGr HEAD OF DEPARTMENT OF -CHEMISTRY-: . %■ Table of Contents. Acknowledgment I. Introduction II. Dehydration of Uormal Buty} Alcohol III. Density of Alcohol-Water Mixtures IV. Boiling Points of Alcohol-Water Mixtures V. Fractional Distillation VI. Summary VII. Bibliography Page . 1 . 2 . 4 . 5 . 8 . 10 . 11 . 12 . . • » 1 . Acknowledgment The writer wishes to express his sincere thanks and appreciation to hr. J.E. Reedy who ren- dered advice and aid at all times and made the completion of this work possible. Digitized by the Internet Archive in 2016 https://archive.org/details/propertiesofmixtOOcros 2 I. Introduction. normal butyl alcohol is becoming more and more important in organic chemistry, especially as a solvent for various substances and the recovery of this solvent promises to develop into an import- ant consideration in commercial use. It was with this idea in mind that the following work was done concerning the physical properties and recovery of the normal butyl alcohol. Until quite recently, very little was to be found in the literature concerning this alcohol and the writer feels that the work is among the first that have been done on this subject. Hereafter in this article the word alcohol will be used to denote normal butyl alcohol only. Uormal butyl alcohol is manufactured by a fer- mentation process in which acetone and alcohol , par- ticularly butyl alcohol, are obtained by fermentation under aerobic or anaerobic conditions of carbohydrate material such as maize, rice, wheat, oats, potatoes, etc., with a culture of the bacteria which are found in soil or on cereals such as maize, rice and flax. The bacteria will also liquefy gelatin and are stated to be probably Bacillus granulobacter pectinovorum. T . 3. The production of this alcohol is now carried on at a comparatively low cost. The price in 1917 was $2.10 for 10 grams and now the cost is only $5.00 per gallon. ' 4. II. Dehydration of Normal Butyl Alcohol. In making anhydrous alcohol, the following pro- ceedure was used. The usual method of treatment with lime was first used. The alcohol refluxdd with fresh lime for several hours and then distilled through an efficient rectifying column. This was then refluxed over metallic calcium and the distillation through the rectifying column repeated until a constant boiling point was obtained. It is believed that alcohol so prepared contains only a small fraction of one per cent of water. This small quantity of waterwould not make an appreciable error in the specific gravity determinations of the alcohol-water mixtures. The partial dehydration by means of lime gives an alcohol of about 99.5 % and for all practical pur- poses this is probably pure enough. However, in or- der to obtain a purer product, the alcohol is reflux- ed over metallic calcium and redistilled. This re- moves all the water. No satisfactory test was found for the detect- ion of slight amounts of water in the alcohol. The copper sulfate test was found to be indecisive while the benzene test could not detect water unless the water was present in an amount greater than 5 %. . . . i 5 III. density of Alcohol-Water Mixtures. The alcohol-water mixtures were ma&e by weighing the water and alcohol in stoppered bottles. The stoppers were then made secure and the solutions thoroughly mixed for several hours by means of a mechanical shaker which insured complete solution of the respective liquids in each other. Then the specific gravity was determined of the solutions in each bottle in which only one layer was present. A Westphal balance was used for the specific gravity determinations. The alcohol will dissolve 19.8 $ of water and v/ater will dissolve 7.25 % alcohol. The results of these determinations are shown below r . Water layer. wt. % alcohol sp. gr 1.62 0.9962 2.29 0.9950 2.21 0.9920 2.97 0.9927 Wt. # alcohol sp, gr 4.71 0.9911 6.22 0.9888 6.98 0.9880 » * t . . . 6 Alcohol layer. YIt.fo alcohol sp. gr 98.1 0.8100 96.6 0.8130 93.4 0.8191 92.2 0.8210 90.8 0.8248 89.3 0.8275 \U.% ale. sp. gr 87.8 0.8298 86.5 0.8322 85.7 0.8345 82.8 0.8390 80.2 0.8445 These results were plotted on cross-section pa$er ( Hates I and II ) so that 0.1 ^cjsald be easily read on the abscissa and 0.0002 sp.gr. on the ordinate. A straight line curve was drawn to connect the points and from these Table I was con- structed, giving the specific gravity for each per- centage by weight of alcohol and the corresponding volume percentage. 7 Table I. Specific Gravity of Normal Butyl Alcohol-Water Mixtures. Wt. % VoT. % Wt. % Vol . °/o ale ohol ale . sp. gr. ale . ale . sp. gr 0 0.0 0.9984 100 100 0.8063 1 1.2 0.9969 99 99.3 0.8082 2 2.5 0.9953 98 98.5 0.8103 3 3.7 0.9939 97 97.6 0.8121 4 4.9 0.9923 96 96.8 0.8140 5 6.1 0.9910 95 95.9 0.8160 6 7.3 0.9895 94 95.1 0.8179 7 8.6 0.9fi£>0 93 94.3 0.8199 7.25 8.8 0.9878 92 93.4 0.8218 91 92.6 0.8258 - 90 91.8 0.8256 89 91.0 0.8275 88 90.1 0.8295 87 89.3 0.8314 86 88.4 0.8333 85 87.5 0.8352 84 86.7 0.8372 83 85.8 0.8391 82 85.0 0.8410 81 84.1 0.8430 80.2 83.2 0.8445 8 IV. Boiling Joints of Alcohol-Water Mixtures. The same solutions that were used for the det- ermination of the specific gravities were also used for the determination of the boiling points of sol- utions of varying concentration. The solution was placed in a flask which was fitted with a condenser in order to keep the concentration of the liquid con- stant. The boiling point was taken and corrections made for pressure differences from 760 mm, for stem exposure, and for calibration of the thermometer used. The thermometer was calibrated with water and a constant correction of + 0.4° found. The observed temperatures were corrected for exposed mercury col- umn by adding IT ( t-t' ). 0)00154, where N is the length of the exposed mercury in degrees, t the observed temperature, and t’ the room temperature. A correction for pressure was calculated from dT = CT-g ( 760 - P ) where dT is the correction, 0 a constant, Tg the boil- ing point of the liquid, and P the observed pressure. Table II shows the data in tabular form and the experimental values were used to construct the boil- ing point curve which is shown on the graph paper f Plate III). 1 . . • ' 9 Table II. Boiling Joints of Alcohol-Water Mixtures. Sp . Gr . ( curve ) o • H +> ca Es B. P. ( obs ) Corr . B. P. ( corr) 0.9984 0.0 98.7 1.30 100.00 0.9960 1.63 97.8 1.27 99.07 0.9947 2.39 96.3 1.24 97.54 0.9935 3.21 95.1 1.28 96.38 0.9924 3.97 94.4 1.20 95.60 0.9915 4.71 93.7 1.18 94.88 0.9891 6.22 92.8 1.16 93.96 0.9880 6.98 92.2 1.16 93 .36 Mixt. both layers 92.1 1.16 93.26 0.8100 98.1 108.0 2.24 110.24 0.8130 96.6 103.0 2.00 105.0 0.8191 93.4 97.0 2.00 99.0 0.8214 92.2 94.8 1.93 96.73 0.8240 90.8 93.6 1.90 95.50 0.8270 89.3 92.6 1.87 94.47 0.8298 87.8 92.0 1.87 93.87 0.8325 86.5 91.8 1.86 93.66 0 . 8340 85.7 91.8 1.86 93.66 0.8395 82.8 91.4 1.85 93.25 0.8445 80.2 91.3 1.94 93.24 0.9984 0.0 98.0 2.00 100.00 10 . VI. Fractional Distillation. I’he alcohol is recovered from the water mixtures by means of fractionation through an efficient rect- ifying column. In a trial run, large amounts of alc- ohol and water were thoroughly mixed and 750 cc of the top layer were taken for the determination. This layer contained 80.2 per cent alcohol. The first portions of the distillate contained 40 per cent of water as conpared to 20 per cent in the original liquid in the flask. This proportion remained con- stant until all the water distilled over and then the pure alcohol was collected. The top layers of each portion were mixed and the fractionation repeated, giveng more of the pure liquid. Then the water layers from each portion were added together and distilled and all the alc- ohol came over quickly in an 80.2 per cent mixture. This was added to the other portions rich in alco- hol and the distillation carried out a third time. The time required for the distillations is not excessive and four distillations yield about 90 per cent of the alcohol in the original mixture in a pure form. . .. . ' . 11 . VI. Summary. 1. The specific gravity of normal butyl alcohol was found to be 0.8064 at 25° 8. Tobin gives 0.8057 and Wad and Gokhale 0.8066. 2. The boiling point was found to be 117.4° at 760 mm pressure, loroshevski and Dvorzhanchik give 117.1°, Kahlbaum gives 117.6°, and Tobin gives 117. 71°, 3. Tables for specific gravities and for boiling points of alcohol-water mixtures are given. 4. The alcohol is only partially miscible with water. Two layers are formed which contain 80.2 per cent and 7.25 per cent of alcohol. 5. Curves for specific gravities and for boiling points of the varying concentrations are given. 6. The alcohol may be recovered from water mixtures by fractionation. 12 VII. Bibliography. 1. Roger 3P. Brunei, J.L. Crenshaw, and Blise Tobin. J. Am. Chem. Soc. 43, 561-77 ( 1921 ). 2. Y. B. Wad and A. G. gokhale. J. Ind. Inst. Sei. 4, 17-25 ( 1921 ). 3. Kahlbaum. Z. physik. ohem. 46, 628 and 646 (1898). 4. Boroshevski and Bvorzhanchik. G. A. 3, 1355 (1909). 5. C. Weizmann. G.A. 13, 1595 (1909). 6. Horace B. Speakman. J. Soc. Chem. Ind. 38, 155-617. 7. Kennedy J. p. Orton and Bavid C. Jones. J. Chem. Soc. 114 . 1194. 8. R. Seligman and P. Williams. J. Soc. Chem Ind. 37, 159-657. 9. Vashburn’s Principles of Physical Chemistry.