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The solubility of dotria-contane (nC32H66) in propane and butane 1936

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THE SOLUBILITY OF DOTRIA-CQNTANE (n H 6 6) ' . .In . PROPANE AND BUTANE by REID GEORGE FORDYCE. A THESIS SUBMITTED FOR THE DEGREE o f MASTER OF APPLIED SCIENCE i n the DEPARTMENT OF CHEMISTRY, TABLE OF CONTEHTS. Page. Introduction© 1. Preparation of dotria-contane. 3. M e l t i n g Point. 3. F i g . 1 Condensing Apparatus diagram, opp. 4. Pl a t e 1, P i c t u r e of Apparatus, opp, 5. Apparatus. 4, P u r i t y of M a t e r i a l s . 4. Experimental procedure, 4, Corrections to r e s u l t s . 6. Treatment of corrected r e s u l t s , 7, Conclusion. 8, Acknowledgement. 3 . Thermometer C a l i b r a t i o n , Table 1, Tabulated Experimental Results. Butane Dotria-Contane. Table 2. Propane Dotria-Contane. Table 3, Butane Dotria-Contane S o l u b i l i t y curves. P i g 2 & 3, Propane Dotria-Contane S o l u b i l i t y Curves.Fig.4 & 5 . C a l c u l a t i o n of Latent Heat of Fusion, Table 4, Bibliography, THE SOLUFtBILITY OF DOTRIA-CONTANE (n C 3 2 H 6 6) IN PROPANE AND BUTANE. I n t r o d u c t i o n . In 1932 So v. P i l a t and M.G o d l e w i c z 1 repeating the work of K„ Kli n g 2 t r e a t e d a P o l i s h petroleum v;ith a propane butane f r a c t i o n instead of the low b o i l - i n g point gasoline used by K l i n g . This treatment p r e c i p i t a t e d most of the asphalt in. the crude. By intr o d u c i n g methane up to a pressure of 30 atmos- pheres the remainder of the asphalt was p r e c i p i t a t e d as a dark semi-fluid^product. Further increase of • the methane pressure caused the p r e c i p i t a t i o n of a heavy o i l and by gradually i n c r e a s i n g the pressure to 130 atmospheres s t i l l l i g h t e r o i l s were p r e c i p i - t a t e d . I n v e s t i g a t i o n s by F. Fischer-and Zerbe^ and P.K, F r o l i c h 4 i n d i c a t e that the s o l u b i l i t y of petro- leum hydrocarbons i n methane depends upon t h e i r molecular weight and chemical nature. Therefore i t i s assumed that the methane p r e c i p i t a t e d those con- s t i t u e n t s which are i n s o l u b l e . Many i n v e s t i g a t i o n s s i m i l a r to the above have been c a r r i e d out by other researchers i n t h i s l i n e , A commercial process has been developed by the Union O i l Co, of C a l i f o r n i a ^ u s i n g t h i s p r i n c i p l e . The asphalt base o i l i s extracted f i r s t with propane then with sulphur dioxide and f i n a l l y with sulphur d i o x i d e and benzene. The Standard O i l Development Go^ f r a c t i o n a t e o i l s u s i n g the hydrocarbons from methane to pentane. By a l t e r i n g conditions of temperature and solvent composition lube o i l s of various c h a r a c t e r i s t i c s are obtained. In view of the importance of these processes i t was decided to determine the s o l u b i l i t y - t e m p e r a t u r e curve f o r a high molecular weight hydrocarbon^ dotria-contane, i n the solvents propane and butane, A s e r i e s of such i n v e s t i g a t i o n s u sing various hydrocarbons w i l l undoubtedly give an i n s i g h t i n t o the chemical nature of the products produced using these solvents. F u r t h e r ? t h i s data together with c e r t a i n thermal measurements may be used to check the s o l u b i l i t y equation derived by J , H. Hildebrand and S. B. Wood?, In t h i s d e r i v a t i o n the p r o b a b i l i t y f u n c t i o n of Menke^ i s applied to a re g u l a r s o l u t i o n to obtain the poten- i a ! energy change on mixing. This expression enables one to c a l c u l a t e the s o l u b i l i t y when c e r t a i n thermal constants f o r both substances are known, Hildebrand and Y/ood define a r e g u l a r s o l u t i o n as one i n which the randomness, of d i s t r i b u t i o n of both kinds of molecules i s complete and i n which the molecules are both symmetrical and non-polar. Since the molecules of both our components f a l l w i t h i n t h i s category and since we may s a f e l y assume random d i s t r i b u t i o n , our s o l u b i l i t y data may be used to check t h i s equation© „3~ PREPARATION OF DQTRIA-CONT ANE. The hydrocarbon dotria-contane was synthesized from c e t y l a l c o h o l according to the method of K r a f z t ^ . The c e t y l a l c o h o l used was of a p u r i t y supplied by the Eastman Kodak Co, By repeated leading of hydrogen i o d i d e gas through the a l c o h o l which i s melted i n a water bath, c e t y l i odide was prepared. The hydrogen Iodide used was prepared by the a c t i o n of water on an intimate mixture of phosphorous and i o d i n e . The gas was lead through a s e r i e s of traps and f i n a l l y washed with concentrated h y d r i o d i c a c i d . The crude c e t y l iodide a f t e r washing and r e c r y s t a l l i z i n g from e t h y l a l c o h o l gave a product which melted at 23°G. By treatment with sodium i n ether s o l u t i o n the iodide e a s i l y y e i l d e d dotria-contane. By r e c r y s t a l l i z i n g f i v e times from ether the pure product was obtained i n the form of g l i s t e n i n g f l a k e s . The l a s t c r y s t a l l - i z a t i o n gave no change i n the melting p o i n t . MELTING POINT. A search of the o r i g i n a l sources shows the f o l l o w - in g values f o r the melting p o i n t of d i - c e t y l , ar- ranged i n c h r o n o l i g i c a l order;- 7 0 1 0 , 70.0 1 1, 68-70 1 2, 69.8,13, 7 1 1 4 , 7 0 ^ 7 0 . 5 1 6 , 74-75 1?, 70.5 1 8. As J.H. Hildebrand and A. V/achterl9 p o i n t out, the true melting p o i n t of dotria-contane i s i n the neighbourhood of 70°, r a t h e r than 74-75° l i s t e d i n the " I n t e r n a t i o n a l C r i t i c a l Tables". Our melting l 1 point, .determination was made using a mercury ther- mometer c a l i b r a t e d against a standard r e s i s t a n c e thermometer'and the value obtained was 6 9 , 9 ° , Table 1 gives the c a l i b r a t i o n 'figures... / APPARATUS. The apparatus used to condense the required amounts of butane and propane i s shown i n P l a t e 1 and represented diagrammatically i n f i g . 1. Two f i v e l i t r e bulbs are contained In a thermal insulating, asbestos box which also contains an e x t e r n a l l y , con- t r o l l e d heating c o i l and c i r c u l a t i n g fan. . By t h i s means the butane i s kept at a constant temperature during condensation and thus, knowing the constant of the apparatus the pressure drop© observed on the manometer, for, a given weight .of butane I s e a s i l y c a l c u l a t e d . As shown i n f i g 1. the apparatus i s evacuated by means of a mercury d i f f u s i o n pump operating with anc.oir vacuum for e pump, the pressure being measured by means of a c a l i b r a t e d McLeod, Ci uage. I t was found that pressures of the order, of. :„00i mm0 of mercury were required-not only to Insure the absence of a i r from the f r e e z i n g p o i n t bulbs but also to insure the condensing of l a r g e r amounts of butane, u s i n g l i q u i d a i r as the cooling-agent. PURITY OF MATERIALS. • The propane and butane used were the commercial proau c t s supplied i n small pressure tanks. EXPERIMENTAL PROCEDURE. A f t e r considering various procedures i t was  decided to use the more p r a c t i c a l f r e e z i n g p o i n t bulb method. Thick walled uniform bulQS, 2 cm, i n diameter* were blown and sealed to 9,5 cm, stems of 2 mm, g l a s s tubing, For the l a r g e r amounts of butanf bulbs 3 cm, i n diameter were used. Varying amounts of dotria-contane determined by weighing, were i n t r o - duced i n t o the bulbs by melting the hydrocarbon and running i t through a funnel made by drawing' down lar g e diameter g l a s s tubing. The bulbs were then sealed to the apparatus, evacuated, and the required amounts of butane or propane condensed i n each. Each bulb was then i s o l a t e d from the main system, by t u r n i n g stop cocks shown i n f i g 1,, the butane frozen and the tubes sealed o f f at c o n s t r i c t i o n . I n t h i s manner bulbs containing v a r y i n g percentage composition mixtures of propane- d i - c e t y l and butane-* d i - c e t y l were obtained. The f r e e z i n g p o i n t s were determined by immersing: the bulb i n a water bath equipped with an automatic s t i r r e r and two properly c a l i b r a t e d thermometers, A t h i r d a u x i l i a r y thermometer was used i n order to make stem c o r r e c t i o n s . The bath was heated u n t i l the c r y s t a l s of dotria-contane were d i s s o l v e d i n the butane. The bath was then allowed to cool slowly while the bulb was constantly a g i t a t e d to Insure e q u i l i b r i u m . The temperature & % j t i i c h c r y s t a l s , of dotria-contane appeared was c a r e f u l l y read on both thermometers. The bath was then slowly heated and the temperature of the disappearance of the crystals.; noted. This procedure was repeated and the mean tem- perature taken as the s a t u r a t i o n p o i n t f o r that composition. The p o i n t of appearance and the p o i n t of disappearance of the c r y s t a l s was extremely sharp and d i d not vary more than t ,02° i n any case. The spread between the appearance temperature and the disappearance temperature was never greater than ,05° thus d e f i n i t e l y p recluding any i d e a of compound formation or s o l i d s o l u t i o n . A f t e r obtaining the s a t u r a t i o n p o i n t the stem of each bulb was scratched with a f i l e and the bulb accurately weighed. The bulb was then immersed i n l i q u i d a i r to reduce the vapour pressure of the s o l - vent, q u i c k l y removed and the stem broken at the sc r a t c h , care being taken to catch any g l a s s p a r t i e l e s on glazed papero The whole was then placed i n an oven and heated at 80° f o r t h i r t y minutes,removed, desiccated, and again weighed. This d i f f e r e n c e i n weight a f t e r c e r t a i n c o r r e c t i o n s , given l a t e r , were appl i e d , gave the weight on* the propane or butane i n the mixture. As a check on the o r i g i n a l weighing of dotria-contane and to detect any l o s s of d i - c e t y l during the heating, the hydrocarbon was removed from the bulb by d i s s o l v i n g i t i n ether, the bulb d r i e d and weighed. Our r e s u l t s show tha t l o s s of d o t r i a - contane during heating i s n e g l i g i b l e . CORRECTIONS TO RESULTS. Since the volume of dotria-contane used i n each determination never exceeded one cubic centimeter, no buoyancy c o r r e c t i o n was made f o r i t s weight. Because the butane or propane was weighed* as pre- v i o u s l y described i n a sealed tube, a p o s i t i v e c o r r e c t i o n was made to allow f o r the buoyant force of the a i r on the volume occupied by the l i q u i d and vapour phases of the butane or propane, A f u r t h e r c o r r e c t i o n was made to the weight of the butane or propane i n the vapour phase at the satur- a t i o n temperature. This i s , of-, course, a negative c o r r e c t i o n since the vapour i s not e f f e c t i v e i n d i s s o l v i n g the di - c e t y l , , Since t h i s c o r r e c t i o n i s very small c a l c u l a t i o n s were made usi n g the P e r f e c t Gas Laws, The values f o r the vapour pressure of butane at the various temperatures were c a l c u l a t e d from the f o l i o w i n g ; - l o g 1 0 p m 7.3948 - ^ j j j 4 " 5 given i n the " I n t e r n a t i o n a l C r i t i c a l Tables'*, The best values f o r propane pressures over our pem- perature range were those of A. W. F r a n c i s and G.'.iu B o b b i n s 2 0 whose equation l o g P= 4.375 - was used. The volume was obtained by measuring the amount of water required to f i l l the vapour space i n each bulb. TREATMENT OF CORRECTED RESULTS. The corrected r e s u l t s are tabulated i n tabl e s 2 and 3, From these r e s u l t s the temperature s o l u b i l i t y curves f i g . 2,3,4 and 5 have been constructed. In t a b l e 4 c a l c u l a t i o n s f o r the l a t e n t heat of f u s i o n -8- of dotria-contane are given. CONCLUSION. The s o l u b i l i t y - t e m p e r a t u r e curves of d o t r i a - contane i n butane and propane have been obtained. I t i s expected that c a l c u l a t i o n s made using t h i s data together with measurements to be made at t h i s l a boratory w i l l enable a f u r t h e r t e s t of the s o l - u b i l t y equation o f Hildebrand and Wood to be made. ACKNOWLEDGEMENT. F i n a l l y , the w r i t e r wishes to express h i s appreciation of the valuable help and guidance given him by Dr. W.F. Seyer. TABLE 1. THERMOMETER CALTERATION. Formulae f o r Standard Resistance Thermometer.- R * R L ± i • .Bo - 2 . 5 1 0 4 F « . 9 7 2 7 G = 1 . 5 0 4 p , o R - RQ T - b+ - G ( T - 1 ) -JL . -̂ t - ^ 1 0 0 1 0 0 (1) Thermometer Reading (Mercury) = 2 1 . 4 9 ° C Resistance Thermometer N s 2 . 7 1 5 9 R , » 2 , 7 2 2 9 •'- T » 2 1 . 2 6 8 ° C . AT m - . 2 2 ° ( 2 ) Thermometer Reading (Mercury) c 7 0 , 7 9 ° ° Resistance Thermometer, R , s 3 . 2 0 7 6 •'. T s 7 0 . 8 0 0 /• Z\ T - , 0 1 ° Note.Assume v a r i a t i o n of c o r r e c t i o n term f o r intermediate temperatures i s l i n e a r . Experimental Results. Tabulated.^ (Butane). Weight v/t.bulo V.'t. of Mean Corrected Corrected of and dotria- d o t r i a - C r i t i c a l Mean Wt, of bulb. contane. contane.Demp. C r i t i c a l Butane, ; t Temp, 1 0 , 9 9 6 3 1 1 . 0 8 9 1 ^ 0 9 2 2 1 7 . 4 9 1 7 , 2 6 5 . 7 8 6 9 H © 9<^57 1 2 . 0 2 1 6 © 0 9 5 9 2 0 . 2 4 2 0 . 0 2 4 , 2 9 6 2 1 I L « 3 2 2 7 1 1 . 4 4 6 8 2 0 . 7 0 2 0 . 4 8 4 © 9 9 0 2 7 , 3 2 9 2 7 . 3 6 9 0 . 0 3 9 8 2 4 . 2 9 2 4 . 0 9 1 . 0 6 2 3 7 , 0 2 7 8 7 . 0 7 2 5 . 0 4 4 7 2 7 . 6 8 2 7 . 4 9 ;: v686§ 7 , 0 2 0 0 7 . 1 4 6 7 . 1 2 6 7 3 0 . 6 5 3 0 . 4 7 1 . 2 0 8 0 7 , 3 2 0 9 7 . 4 8 6 8 . 1 6 5 9 3 4 . 4 9 3 4 & c>4 . 8 9 0 5 ' 6 . 6 1 2 9 6 . 8 3 5 4 . 2 2 2 5 3 6 . 7 5 3 6 . 6 0 6 . 6 3 8 1 7 , 0 1 9 0 , 3 8 0 9 3 8 , 0 0 3 7 , 8 6 1 • 1 5 5 7 6 . 4 6 1 3 6 . 8 5 4 7 ® 3934L 4 0 . 4 4 4 0 . 4 1 . 8 0 6 9 5 . 5 6 2 4 5 , 8 9 9 8 . 3 3 7 4 4 2 . 1 0 . 4 1 , 9 8 . 6 1 3 3 7 © 7 , 5 2 2 6 . 4 0 9 7 4 2 . 2 5 4 2 e 1 3 , 6 7 8 9 5 , 4 4 2 2 5 . 9 3 8 0 . 4 9 5 8 4 3 , 5 2 4 3 , 4 0 , 6 9 8 3 6 . 8 0 4 3 7 , 2 7 3 8 . 4 6 9 5 4 6 . 6 1 4 6 . 5 1 , 4 6 3 0 6 , 7 6 8 8 7 , 4 1 0 9 . 6 4 2 1 5 3 « 1 3 5 3 . 0 6 • 3 1 0 0 5 . 2 2 2 4 5 . 9 1 2 0 . 6 8 9 6 5 3 . 2 2 5 3 . 1 5 , 3 0 5 2 5 , 7 4 5 1 6 . 4 8 7 3 . 3 4 2 2 5 4 . 6 3 5 4 . 5 6 9 27-L4 5 , 6 4 6 0 6 , 4 0 9 0 , 7 6 3 0 6 0 . 9 5 . 6 0 , 9 1 ® JLO2S 7 © 7 . 5 9 3 3 . 4 7 6 4 6 7 . 8 0 6 7 . 7 8 , 0 1 1 6 Experimental Results Tabulated, Weight Wt,bulb V/t. of Mean Corrected Corrected of and d o t r i a - d o t r i a - C r i t i c a l Mean Wt, of bulb, contane. contane .Temp. C r i t i c a l Propane.. Temp. 8.2303 8.3498• ,1195 3 5 © 35 35,70 1,0181 6,2360 6,5467 © 3107 42,25 42.13 ,6688 7.4447 7.3108 $ 3C3*ol 44.24 44 & 13 .5374 5.9286 6,4055 ,4769 .44.40 44,30 .6309 5.9671 6,6059 .6388 49,69 49,60 .4033 6.3794 7,0377 ,6583 52.98 52,90 @ 311<^ 7,0426 7.8875 . 8449 57.95 57,90 , 2272 7,6031 8,4818 ,8787 62,45 62.42 .1015 TABLE 2, BUTANE - DOTRIA-CONTANE Wt, of Corrected C r i t i c a l y/t. per Mol.per d o t r i a - Wt.. of Temp, °c cent of cent contane. Butane. d o t r i a - d o t r i a - contane. contane. -135,0 0 0 .0922 5.7869 17.26 •/ 1.57 ,206 .0953 4.2962 20,02 Cj « 13 .288 . 1241 4.9902 20.4.8 2.43 • 321 . 0398 1,0623 24,09 , 3.56 .482 ,,0447 X ,6866 27.43 6.11 ,832 ,1267 1 02080 30,47 9.49 1,335 ,1659 ,8905 34.34 1 5.7 2«347 «y £!t225 ,8332 36.60 21 ̂  1 O © OO ,3809 1 <9 1557 38,00 24,8 4,08 ,3934 ,8069 40,40 32,8 5,92 «o374 # S.L.t->3 41,98 3 5«5 6,63 ,4097 .6789 13 37.7 7,23 ,^4958 . 6983 43,40 4 1 . 6 8,41 .4695 .4630 4G e 51 50 a 3 11.56 ,6421 . 3100 53.06 67,3 21.10 ,6896 © 3052 53.15 (33» 3 22 , o5 ,7422 o 27-1.4; 54,56 73 ® 2 26,10 • 7630 a 1328 6 0 . 9 1 85.2 42,55 .4764 • . 0116 67,80 95.8 81.00 69.90 100. 10.0 Wt. .of d o t r i a - contane. Corrected Wt. of propane. C r i t i c a l Temp °C. Wt, per cent of d o t r i a contane. Mol, per cent d o t r i a contane. -189.9 0 0 # 1195 1 © 0 l o l 35.70 10.5 1, lci6 ,3107 . 6688 42 013 319 i 4,35 .3661 ,5374 44.13 <L3 9 © 35 © 27 ,4769 ,6309 44.30 43.20 6,91 .6338 ,4083 49,60 61.00 13,29 ,6583 .3113 52,90 68,0 17.15 .8449 e 22*72 57,90 78.70 26.70 .8787 . ,1015 62.42 89,50 45,80 69,9 . 100 100,  [ \ ' 1 t > I J s \ — 1 _ — L 1 Si s \ I \ — .1—Ihl.. 1 1 \ i 1 \ s \ * \ 5 \ N \ : • • • ; k 1 I l — 1 M - N : i > 1 1 rs ( \ <0 5 <\ i i i v V   Table 4. Since the s o l u b i l i t y curve of* both propane and butane approximate a s t r a i g h t l i n e over the range from 40 mol. per cent to 100 mol, per cent dotria-contane , we may assume t h a t Raault ! s Law holds over these values. Thus the f o l l o w i n g equation; - l o g K = (-1- " - i - j which depends on Raoult' s Law can be applied to c a l c u l a t e the l a t e n t heat of f u s i o n of d o t r i a - contane. C a l c u l a t i o n s ; - T m (Melting p t . of dotria-contane) » 343°A. When N = .40.T (from f i g , 2 or 4) - 333°A. whence L f = 2 1 , 0 0 0 c a l . men.11 = ,70, T (from f i g . 2 or 4) s 339,5 °A. Whence L-p ~ 23,500 c a l . Bibliography . 1. P o l i s h Pat. 1029; G erman Pat, 362458, 2. S, v . P i l a t : Oel u. Kohle, E r d o l v. Teer, 11,665 (1935), P o l , Pat. 20607, of 6.2.33, Prezeml, Chem 18,376, 1934, 3. Brennstoff - Chemie, 4, 17, (1923). 4. Jour. Ind, Eng. Chem. 23,548 (1931). 5. U l r i c Bray U.S. Pat. 1, 988,713 (1932) Chem. Z e n t r a l b l 11, 314, 1935, 6. French Pat, 770,903, (1934); U.S. p r i o r June 10,1933, 7. Jour. Chem. Phy, 1, 12 Dec, (1333). 8. H. Menke, Phy, Z e i t s 33, 533 (1932). 9. K r a f f t Ber. 19,2219 (1886). 10. S o r a b j i , J . Chem. Soc. 47, 39 (1885). 11. K r a f f t (Ber, 19,2219 (1886) 12. Liabery (a) Jour. Amer. Chem, Soc. 27 R35 (1905). 13. K r a f f t i b i d 40,4783 (1907) 14. Meyer and Soyka, Monatsh. 34,1163 (1913). 15. Spath i b i d . 34,1987 (1913). 16. Gascard . Compt. Rend. 159,258 (1914). 17. Levene West and and van der Schur.J. B i o l . Cham. 20,521 (1915). B i b l i o g r a p h y continued, 18. Gas card <j . Chem. Soc. 106,1045, (1914). 19. J.II. Hildebrand and Wachter. J , Chem. Soc. 51.2487, (1929). 20. A l f r e d "iy. F r a n c i s and G. W. Bobbins J.Chem Soc. 42, 4339, (1933).

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