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A study of two component systems, sulfur dioxide and caprylene Hodnett, Lisle 1934

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A STUDY OP TWO COMPOUND SYSTEMS SULEUR DIOXIDE AID CAPRYLSNS. BY l i s l e Hodnett, B. A. Sc. A t h e s i s submitted to the Chemistry Department of the U n i v e r s i t y of B r i t i s h Columbia, as part requ-irements f o r the degree of Master of Applied Science. A p r i l , 1934. TABLE- OP uOHTMTS. In t r o d u c t i o n Page 1 Object of I n v e s t i g a t i o n " 1 Experimental a. D i f f i c u l t i e s " 2 b. Test f o r peroxides " 3 c. P u r i f i c a t i o n of the caprylene " 3 cc. P r e p a r a t i o n of the n i t r o g e n " 5 d. Prep a r a t i o n of the s u l f u r d i o x i d e " 6 e. Prepa r a t i o n of the c a p r y l e n e - s u l f u r d i o x i d e mixtures " 6 f• f r e e z i n g point of pure caprylene " 8 g. F r e e z i n g p o i n t s and c r i t i c a l s o l u t i o n temperatures " 1 1 h. S t a n d a r d i z a t i o n of the pentane thermometer " 13 1. Accuracy of the readings " 13 3. A d d i t i o n a l observations " 1 4 Summary " 1 7 Diagrams and graphs P i g . I To face " 4 P i g . I I " " " 4 P i g . I l l » " " 6' P i g . IT " " " 8 P i g . Y " " 5 P i g , VI " " " 15 P i g . V I I " " " 12 P i g . V I I I " " " 12 (1) A STUDY OF TWO COMPONENT SYSTEMS. SULFUR DIOXIDE AND CAPRYLSNS. INTRODUCTION. Among the numerous processes used to r e f i n e l u b r i c -a t i n g stock, i s one patented by L. Edeleanu ( 1 ) . In t h i s process, l i q u i d s u l f u r d i o x i d e i s used as the solvent f o r the separation of the aromatics, unsaturated c y l i c s and unsatur-ated a l i p h a t i c s from the p a r a f f i n s and naphthenes. Since t h i s time, a number of other l i q u i d s u l f u r d ioxide processes have been developed, such as the s u l f u r d i o x i d e - s u I f u r i c a c i d process (2) and the s u l f u r dioxide-benzene process. (3) OBJECT OF INVESTIGATION. In order to gain a c l e a r e r understanding of the mechanism of the d i f f e r e n t processes, i t i s necessary to know wnat r e a c t i o n s may take place between the solvent or s o l v e n t s , and the members of the d i f f e r e n t hydrocarbon s e r i e s present i n the stock. In t h i s connection, Dr. W.F. Seyer, a s s i s t e d by Dunbar ( 4 ) , Huggett ( 5 ) , G i l l ( 6 ) , Peck ( 7 ) , Todd ( 8 ) , B a l l (.9), Gallaugher (10), King '(11), Lawley (12), Martin ( I K ) , and Hodnett (14), has made a s e r i e s of studies on the solub-i l i t i e s of the d i f f e r e n t members of v a r i o u s hydrocarbon s e r i e s , In l i q u i d s u l f u r d i o x i d e . The main object of t h i s research i s the t a b u l a t i o n of more data regarding the s o l u b i l i t i e s of the members of the o l e f i n s , C^I^n» s e r i e s , i n l i q u i d s u l f u r d i o x i d e . The members of t h i s s e r i e s , which have been studied up to the present time are, cetene C^H^g, (5) and pentene C5H-LQ (15). A f t e r (2) a study of the shape of the curves obtained from these i n -v e s t i g a t i o n s , i t was thought that the t r a n s i t i o n -noint of the s e r i e s would occur at the compound caprylene, I.e., i t would be the f i r s t of the s e r i e s to show any signs of i m m i s c i b i l i t y , and that only over a l i m i t e d range of concentration. F. de C a r l i (16), i n an a r t i c l e on the s o l u b i l i t i e s of a number of hydrocarbons i n l i q u i d s u l f u r d i o x i d e , stated that caprylene was only s l i g h t l y s o l u b l e i n the s o l v e n t , any s o l u t i o n s obtained, having a s l i g h t y e llow c o l o r a t i o n . This c o l o r a t i o n , he thought, might be due to compound formation, but owing to the incomplete nature of the work, could not make any d e f i n i t e statements. EXPERIMENTAL. a. D i f f i c u l t i e s . The main d i f f i c u l t y , encountered during the f i r s t stages of the i n v e s t i g a t i o n , was the r a p i d d i s c o l o r a t i o n of the c a p r y l e n e - s u l f u r d i o x i d e mixtures a f t e r reaching room temperature, the extent of the d i s c o l o r a t i o n being so great, that i t was impossible to use the mixtures f o r s o l u b i l i t y det-erminations. In a previous i n v e s t i g a t i o n (11), i t was found that the presence of minute q u a n t i t i e s of a i r i n cyclohexene-s u l f u r d i o x i d e mixtures, caused immediate polymerization of the cyclohexene, the oxygen apparently a c t i n g as a c a t a l y s t . For t h i s reason, i t was decided, that a l l work was to be done i n an Inert atmosphere, n i t r o g e n being chosen f o r the purpose. This d i s c o l o r a t i o n of the c a p r y l e n e - s u l f u r d i o x i d e (3) mixtures, i s probably the same as was n o t i c e d by de C a r l i (16) and may be due to the p o l y m e r i z a t i o n of the caprylene i t s e l f , r a t h e r than the formation of a d d i t i o n compounds w i t h s u l f u r d i o -x i d e , since the f r e e z i n g point curve obtained shows no I n d i c -a t i o n of compound formation. Because .the,.same c o l o r a t i o n was n o t i c e d when caprylene was r e f l u x e d i n the presence of a i r , i t was thought that the presence of peroxides i n the m a t e r i a l might be the cause of the r e a c t i o n , and to a s c e r t a i n whether any were present, s p e c i a l t e s t s were made on the r e f l u x e d and o r i g i n a l m a t e r i a l s , b. Test f o r peroxides. The t e s t used, suggested by J.B. Conant and W.E. Peterson (17), consisted of pouring a 10fo s o l u t i o n of ammon-ium thiocyanate, i n which a c r y s t a l of f e r r o u s ammonium s u l -f a t e had been d i s s o l v e d , through the m a t e r i a l to be t e s t e d ; a deep red c o l o r , due to the formation of f e r r i c thiocyanate, being produced i f peroxides were present. The o r i g i n a l mat-e r i a l gave t h i s c o l o r a t i o n immediately, as d i d a sample of the f r e s h l y d i s t i l l e d m a t e r i a l that had not been r e f l u x e d , but the r e f l u x e d m a t e r i a l , which had been standing i n an i n e r t atmosphere f o r over a week, gave no c o l o r a t i o n , even a f t e r i t had been shaken w i t h the reagent f o r a period of ten minutes. This t e s t proves the presence of peroxides, which were only e l i m i n a t e d by r e f l u x i n g ; these peroxides, probably having a marked i n f l u e n c e on the polymerlzatioia of the m a t e r i a l , c. P u r i f i c a t i o n of the caprjrlene. The caprylene used throughout t h i s i n v e s t i g a t i o n was (4) obtained from the Bast/nan Kodak Go. Rochester, I.Y., and acc-ording to t h e i r s p e c i f i c a t i o n s , b o i l e d between 124 and 126 degrees Cent, c i t 760 nun. The f r e e z i n g point of the m a t e r i a l was not foiind i n any t a b l e of p h y s i c a l constants consulted. The f o l l o w i n g t a b l e gives the b o i l i n g 'points av.6 r e f r a c t i v e i n d i c e s of the m a t e r i a l and I t s component p a r t s : caprylene being a mixture of the two isomeric compounds, 1- and 2-octene. TABIE I Compound B.P,. Deg. C. Temp. Refer. 1-octene 122 760 mm 1.40 4 19°C (18) 2-oct fine l*i o - 126 760mm 1.415 20° C (18) caprylene 749mm 1.41315 20°C (19) caprylene 124 -126 760mm 1.41378 20°C , Pound A comparison of th-e' r e f r a c t i v e i n d i c e s of the pur-i f i e d m a t e r i a l used and that used by B r u h l (19), shows a s l i g h t v a r i a t i o n , which i s probably accounted f o r by a d i f f -erence i n the percentage of each isomer present, since the m a t e r i a l s were procured from d i f f e r e n t sources, the m a t e r i a l used by B r u h l being of German o r i g i n (Kahl baum) and that used here of American, With t h i s f a c t i n mind, i t was decided that the m a t e r i a l was pure enough f o r the purpose of t h i s i n v e s t i g -a t i o n . The a c t u a l p u r i f i c a t i o n was c a r r i e d out In the type of apparatus shown i n P i g . 1. The m a t e r i a l , along w i t h met-a l l i c sodium f o r the removal of water, was introduced Into the •f^ask through the side arm G. The o u t l e t from the nitr o g e n apparatus was then connected to the f l a s k at G and a steady (5) stream of gas allowed to sweep through the apparatus, the gas flow being continued throughout the e n t i r e p u r i f i c a t i o n . The time allowed f o r p u r i f i c a t i o n depended upon the amount of d i s c o l o r a t i o n produced when the m a t e r i a l was f i r s t heated. IThen p u r i f i c a t i o n was complete, the side arm G was bent at D and the m a t e r i a l d i s t i l l e d over, the middle f r a c t i o n , of the d i s t i l l a t e being r e t a i n e d . A second d i s t i l l a t i o n , over m e t a l l i c sodium and i n an i n e r t atmosphere, was consid-ered a d v i s a b l e , the middle p o r t i o n of t h i s d i s t i l l a t e being condensed i n 3? and running d i r e c t l y i n t o the container E, from which, a f t e r being connected to the apparatus i n P i g . 2 i t was f o r c e d over i n t o the b u l b s , cc. P r e p a r a t i o n of the n i t r o g e n . The method of p r e p a r a t i o n , suggested by Mel l o r (20} was done w i t h the use of the apparatus i n P i g . 5. A i r , the f l o w of which could be regulated to s u i t requirements, was passed through a wash b o t t l e A containing concentrated amm-onia. The vapors were passed through a Pyrex tube B f i l l e d w i t h copper tu r n i n g s and heated by means of the g a s - f i r e d combustion furnace C. The o x i d a t i o n of ammonia to n i t r o g e n and water takes place In the tube, the copper a c t i n g as a c a t a l y s t . During the o x i d a t i o n , the oxygen i s removed from the a i r , and as long as an excess of ammonia i s present, the copper w i l l appear b r i g h t and shiny, showing that no oxygen i s present to o x i d i z e the copper. These passes, c o n s i s t i n g of water vapor,fi!trogen and excess, ammonia, were then passed through the other wash b o t t l e s D, E and P, the b o t t l e D (6) a c t i n g as a safety t r a p , preventing the flo w of any l i q u i d i n t o the hot combustion tube. The excess ammonia was removed from the gas stream wh i l e passing through S, which contained d i l u t e s u l f u r i c a c i d , while the l a s t t r a c e s of water vapor and ammonia were removed by the concentrated s u l f u r i c a c i d i n P. Since the gas produced by t h i s method caused no d i s c o l o r -a t i o n of the m a t e r i a l , while being r e f l u x e d , i t . was consider-ed pure enough f o r t h i s work. d. Preparation of the s u l f u r d i o x i d e . The s u l f u r d i o x i d e was prepared, when necessary, by the a c t i o n of concentrated s u l f u r i c a c i d on sodium b i s u l f u r i t e . The b i s u l f i t e was placed In the f l a s k A, F i g . 25, and the a c i d allowed to d r i p from the separating funnel B, upon i t . The s u l f u r d i o x i d e generated, passed through the concentrated s u l f u r a c i d In G, to remove any tra c e s of water present, and was condensed i n D, fehlch, during the preparation, was imm-ersed i n a bath G, kept at - 20°C. While the s u l f u r dioxide was condensing, the bulbs E, were evacuated. 'When s u f f i c i e n t s u l f u r d i o x i d e had condensed, stopcocks R and Z were closed and the one at Y opened, a l l o w i n g the s u l f u r d i o x i d e , with the bath G removed, to vaporize i n t o the evacuated bulbs. When the bulbs were f i l l e d , stopcocks S, V, W, X and Y were closed and the apparatus was ready f o r use. e. Prepa r a t i o n of s u l f u r dloxide-caprylene mixtures. The bulb method, described by Seyer and Dunbar (4), was used f o r the determination of the f r e e z i n g p o i n t s and' C r i t i c a l S o l u t i o n Temperatures (C.S.T.) of the mixtures. (7) F o r t h i s p u r p o s e , a number of g l a s s b u l b s were blown, each a b l e t o h o l d about 10 oc of m a t e r i a l , and f i t t e d w i t h a item about 12 cm l o n g . S i n c e t h e a p p a r a t u s i n F i g . 3 was made of P y r e x , i t was n e c e s s a r y to make the b u l b s o f t h e same g l a s s . The-bulb was f i t t e d w i t h a r u b b e r cap and a c c u r a t e l y weighed. The cap was removed, and t h e b u l b f i t t e d over t h e tube T, P i g . 2, and h e l d t h e r e by t h e rubber s l e e v e S. The stopcock a t A was opened and t h e a i r i n t h e b u l b D, "swept out by a stream of n i t r o g e n . The s t o p c o c k at B, was then opened and t h e one a t A c l o s e d l o n g enough .to f o r c e t h e r e q u i r e d amount of m a t e r i a l f r o m 0 i n t o t h e b u l b . The b u l b was removed, r e -capped and reweighed. T h i s gave th e weight of c a p r y l e n e used. The b u l b was then immersed i n a b a t h of l i q u i d a i r II, F i g . 3, and s e a l e d to t h e a p p a r a t u s at Q. With stopcock T c l o s e d , the l i q u i d a i r b a t h removed, and t h e m a t e r i a l i n P a l l o w e d to l i q u i f y , t h e 1 1 q u i f a c t i o n of t h e m a t e r i a l under;.:thisereduced p r e s s u r e , f r e e i n g i t of a l l d i s s o l v e d g a s e s . The bulb was a g a i n immersed i n the b a t h and w h i l e f r o z e n , was evacuated f u r t h e r . W i t h s t o p c o c k s S, W and Y open, th e p r e s s u r e on t h e manometer and t h e temperature of the a i r s u r r o u n d i n g the bulbswere r e c o r d e d . Stopcock R was c l o s e d and the one a t T then opened l o n g enough t o a l i o ? / a p o r t i o n of the s u l f u r d i o x i d e t o condense. A f t e r s t o p c o c k T was c l o s e d , the bulb P, was s e a l e d o f f at Q, c a r e b e i n g t a k e n d u r i n g t h i s o p e r a t i o n , t h a t no a i r e n t e r t h e b u l b . A f t e r a p e r i o d o f about 15 .. m i n u t e s , d u r i n g w h i c h t i n e "he b u l b s E a t t a i n a c o n s t a n t temp-e r a t u r e , t h e manometer r e a d i n g and t h e temperature were a g a i n (8) recorded. From these readings, the.-volume of. the bulbs... which .had been p r e v i o u s l y determined,, and the p e r f e c t gas law, the weight of s u l f u r dioxide i n the bulb was c a l c u l a t e d . Thus, with the composition of each bulb known, a l l that r e -mained to be done, was to determine the f r e e z i n g point and c r i t i c a l s o l u t i o n temperature of each mixture, f. F r e e z i n g point of the pure caprylene. In order to complete the study, i t was necessary t o . f i n d the f r e e z i n g - p o i n t of the p u r i f i e d m a t e r i a l , which was done i n the apparatus shown i n F i g . 4. The tube 0 was f i t t e d w i t h a s i d e arm f i l l e d w i t h t i g h t f i t t i n g oofks, through which the crank D passed. To insure a constant r a t e of s t i r -r i n g , the crank, which was attached to the platinum s t i r r e r S at G, was turned by a r e d u c t i o n gear attavhed to a const-ant speed motor. S u f f i c i e n t m a t e r i a l ifco cover the bulb of the thermometer, about 20 cc, was put Into the tube and the metal cap F, through which the platinum r e s i s t a n c e thermom-eter T passed was sealed i n t o place w i t h DeEhotinsky cement. The tube was immersed i n a bath B, f i l l e d w i t h a low b o i l i n g g a s o l i n e , and cooled w i t h l i q u i d a i r u n t i l the m a t e r i a l s t a r t e d to f r e e z e . The temperature was then r a i s e d s l o w l y u n t i l the c r y s t a l s s t a r t e d to melt, t h i s point being the approximate f r e e z i n g point of the m a t e r i a l . The bath was cooled again u n t i l the m a t e r i a l s t a r t e d to f r e e z e and t h i s time, the temperature was r a i s e d to w i t h i n 1.5°C of the approximate f r e e z i n g p o i n t . This temperature was held f o r a p e r i o d of about one hour, no v a r i a t i o n s over 0.4°C i n the bath temperature being allowed. The reading of the (9) p o t e n t i o m e t e r was r e c o r d e d f o r t h e l a s t 20 minutes of t h i s p e r i o d , and t h e r e s u l t s a c c e p t e d , o n l y i f t h e r e a d i n g s showed a maximum w a r i a t i o n of l e s s t h a n 0.000 ohms. The t h r e e a c c e p t e d s e t s of r e a d i n g s showed t h e f o l -l o w i n g c h a r a c t e r i s t i c s r e g a r d i n g v a r i a t i o n s i n the amount of c r y s t a l f o r m a t i o n . D u r i n g t h e o b s e r v a t i o n s , t h e f i r s t showed s l i g h t d e c r e a s e i n t h e number of c r y s t a l s p r e s e n t , t h e second no change, and the t h i r d an i n c r e a s e . The mean of these t h r e e t e m p e r a t u r e s was t a k e n as the f r e e z i n g p o i n t of t h e compound w i t h i n Q.35°C s i n c e t h i s mean v a l u e i s w i t h i n t h i s a l l o w a b l e v a r i a t i o n of e i t h e r of the two o u t e r v a l u e s , one of which i s too low and t h e o t h e r too h i g h . The- appended t a b l e s g i v e t h e r e a d i n g s for" each de t e r m i n a t i o n . TAB IB I I T e s t Bo. B a t h Temp. Time l o r m . M g . Time Rev. Rdg. 1 max. 1:35 1.4721 .1:37 1:4614 - 105.4 1:40 • 1.47 26 1:42 1.46 19 min. 1:45 1.4721 1:47 1.4610 — 106 .0 1:50 1.4721 1:53 1.4613 TABLE I I I T e s t l o . B a t h Temp. Time Iform.Edg. Time Rev. Rdg. S smax. 3:30 1.4702 3:32 1.4594 - 105.8 3:35 , 1.4707- 3:38 1.4600 3:40 1.4702 3:42 1^4593 min. 3:45 1.4705 5:47 1.4603 - 106.4 5:50 1.4709 3:53 1.4598-(10) 0 TABU IV Test No, Bath. Temp. Time Norm. Rag. Time Rev, Rdg. 3 max. 4:40 1.4676 4:42 1.4556 - 106.0 4: 45 1.4676 4; 48 1.4556 4:50 1.4676 4:52 1.4554 min. 4;55 1.4676 4:57 1o 4o 5 X - 106,6 5:00 1.4672 5:02 1.4560 The f r e e z i n g point of the m a t e r i a l was c a l c u l a t e d 'with the use of the f o l l o w i n g equations, (1) Tt = 10.0 (R - R') (2) t - P t * d(-0.997 t -1) 100 ^' 100 where the symbols have the f o l l o w i n g meanings; t - a c t u a l f r e e z i n g point of the m a t e r i a l , p^ =• constant connecting the two equations, R r average potentiometer reading i n ohms, R' ~ reading at 0°C 2.546 ohms, E . fundam.ent-a.il E100~ R 0 0.997 ohms, and d * 1.500 Table V, below, gives the average readings f o r each determination and the f r e e z i n g point c a l c u l a t e d from each reading. Test No 1 2 TABLE V Average Reading Pt 1.46681 - 108.244 1.46519 - 108.406 1.46153 - 108.77 3 f r e e z i n g point - 105,01 - 105.17 - 105.52 The average value, - 105.23, i s taken as the correct f r e e z i n g point of the p u r i f i e d caprylene. (11) g. F r e e z i n g p o i n t s and c r i t i c a l s o l u t i o n t e m p e r a t u r e s . The b u l b was p l a c e d i n a b a t h of low b o i l i n g p o i n t g a s o l i n e and t h e b a t h c o o l e d w i t h l i q u i d a i r u n t i l the mat-e r i a l s t a r t e d to f r e e z e . n The temperature was a l l o w e d to r i s e s l o w l y u n t i l o n l y a few c r y s t a l s were l e f t i n the mix-t u r e . T h i s t e m p e r a t u r e was h e l d f o r a p e r i o d of t e n minutes and i f t h e amount of c r y s t a l l i z a t i o n had not d e c r e a s e d , t h e b a t h t e m p e r a t u r e was r a i s e d 0.1°G. The above procedure was r e p e a t e d , t h e b a t h t e m p e r a t u r e b e i n g r a i s e d 0.1°C. each t i m e , u n t i l t h i s r i s e caused t h e c r y s t a l s t o m e l t . The l a s t r e a d i n g at w h i c h t h e r e were s t i l l some c r y s t a l s p resent was taken as t h e f r e e z i n g p o i n t . The whole proc e d u r e was a g a i n r e p e a t e d and t h e average of t h i s and t h e p r e v i o u s r e s u l t , t aken as t h e c o r r e c t , f r e e z i n g p o i n t of t h e m i x t u r e i n t h e b u l b . S i n c e t h e amount of m a t e r i a l used was s m a l l , i t was n e c e s s a r y t o keep th e amount of c r y s t a l f o r m a t i o n q u i t e s m a l l , as.any a p p r e c i a b l e degree o f c r y s t a l l i z a t i o n would change t h e c o m p o s i t i o n o f the mother l i q u o r so t h a t a decrease in. t h e f r e e z i n g p o i n t would be t h e r e s u l t , making the temperat-u r e s r e c o r d e d , t o o low. A s i m i l & r procedure was f o l l o w e d i n t h e d e t e r m i n a t i o n of t h e C.3.T. The b a t h was c o o l e d s l o w l y u n t i l the m i x t u r e , when shaken, formed an e m u l s i o n , showing t h e presence of two m u t u a l l y i n s o l u b l e l a y e r s . The b a t h was t h e n allowed t o warm s l o w l y u n t i l t h e two l a y e r s d i s a p p e a r e d l e a v i n g one homogeneous l a y e r . The average o f . t h e temperatures at which t h e two l a y e r s appeared and d i s a p p e a r e d was t a k e n (12) TABLE VI Bulb to. Weight caprylene Weight se 2 Weight #30302 Mol 70 SO g r • c* m U © W • X » Deg.G. Deg. C. 0 21 100.00 100.00 - 75.43 C 57 0).O588 6.6579 99.12 99 .50 - 75.85 C 58 0.0461 4.5568 98.78 99.31 - 76.25 0 54 0.0707 5.5639 98.05 98.88 .. - 6 2.70 - 75.60 (j 36 0.1734 3.6490 95.46 98.68 - 36.00 C 59 0.2787 3.9 589 93.42 96.13 *~ *5 X«9 5 - 75.60 C 47 0.3826 3.5519 90.30 94.22 - 25.60 c 44 0.3989 2.3408 85.44 91.13 - 20.55 - 75.80 0 43 0.4600 1.7847 79.51 87.17 - 17.30 - 75.80 c 49 0.9442 2.8030 74.80 83*86 - 16.95 - '.•'"S55-."©0 c 42 • 0,5940 1.4227 70.61 80.79 - 16.45 - 75,60 G 45 0.7164 1,6657 69,92 80.27 - 16.70 - 75.80 C 46 0.6926 1.2766 64.84 76.35 - 16.95 - 76.00 C 62 1.0661 l.ysio 64.43 76.01 - 16.80 -0 63 0.9368 1.4487 60.73 73.02 - 17.00 - 75.50 G6 4 0.9599 1.2572 56.70 69.62 - 17.85 - 76.10 G 35 1.1335 1,1410 50.16- 63.80 - 18.80 G 65 . 0,7039 0.6166 46.57 61.81 - 20.00 - 75.80 C 33 1.5431 0.930.3 37.61 51.34 - 25.20 0 61 0.4026 0.5709 28.93?;;: 41.61 - 32.80 - 76.00 G 40 2.0771 0.5234 20.13 30-* 63 - 47.10 - 75.80 G 53 3.7764 0.4998 11,69 18.81 - - 88.40 C 31 3.6818 0.4000 9.8 0 15.98 - 89.50 G 38 3.7910 0.3138 7 .64 12.65 - 97.75 C 30 0.00 0.00 - 105.23 (13) as the c r i t i c a l s o l u t i o n temperature f o r that mixture, h. S t a n d a r d i z a t i o n of the pentane thermometer. The pentane thermometer used, was graduated i n 0.2 degrees Gent, and could "be estimated to 0,05oC, The stand-a r d i z a t i o n was done by determining the f r e e z i n g point of pure s u l f u r d i o x i d e and also of pure 'calrylene, as read by the thermometer. By using the correct values f o r each mat-e r i a l , - 7 5.43°C f o r s u l f u r dioxide and - 105.23°G f o r cap-r y l e n e , a c o r r e c t i o n can be found which may be used to f i n d the c o r r e c t f r e e z i n g p o i n t s of the v a r i o u s mixtures. By determining t h i s c o r r e c t i o n , any time lag i s almost el i m i n a t e d as the c o n d i t i o n s under which the s t a n d a r d i z a t i o n and f r e e z i n g p a i n t s are done are i n d e n t i c a l . i . Accuracy of the readings. Prom the curve p l o t t e d , caprylene i s only s o l u b l e i n s u l f u r d i o x i d e up t o ifo w h i l e s u l f u r d i o x i d e i s soluble i n caprylene up t o about 3$. Prom the f i r s t f a c t i t i s seen that the amount of two l a y e r formation of mixtures over'90$ s u l f u r d i o x i d e i s very s l i g h t and f o f t h i s reason I t i s only p o s s i b l e to o b t a i n a s l i g h t milkyness i n the bulbs, and the point at which t h i s appears and disappears can only be found w i t h i n about 1.0°C. Over the r e s t of the curve the p o i n t s can be found to w i t h i n 0.1OC, except f o r the f r e e z i n g p o i n t s of those mixtures showing two layer form-a t i o n . These p o i n t s are probably only accurate to w i t h i n 0.4°Q, the cloudiness of the mixtures, due to the e m u l s i f i c -a t i o n of the two l a y e r s , preventing more accurate work. (14) j. A d d i t i o n a l Observations. A check of the c r i t i c a l s o l u t i o n temperature was made two weeks a f t e r the o r i g i n a l readings had been taken, and a d i s t i n c t r i s e i n temperature was n o t i c e d , t h i s being anywhere from 0.2°U to 0.9°0, The r i s e i s apparently independ-ent of the composition of the mixtures, as approximately equal r i s e s are n o t i c e d f o r v a r i o u s mixtures. A f t e r n o t i c i n g t h i s f a c t , i t was decided to repeat these determinations two weeks l a t e r , which was done. Another r i s e was n o t i c e d , but was not n e a r l y so pronounced, being smaller and more i r r e g u l a r than the previous one. The i r r e g u l a r i t y i s probably due to the f a c t that the each mixture i s approaching a d e f i n i t e maximum f o r that composition,. Those bulbs, l y i n g on the maximum of the o r i g -i n a l curve a l l approach a maximum temperature of - 15.8°C. The cause f o r these changes i s probably due to polymerization of the hydrocarbon, induced e i t h e r by a minute t r a c e of a i r or by the s u l f a r d i o x i d e present. I t i s more probably the 1 l a t t e r , as the bulbs are a l l colored to a c e r t a i n degfee, the amount of c o l o r being p r o p o r t i o n a l to the percentage of s u l f u r d i o x i d e i n the mixture. Table V I I I gives the order of increas-ing s u l f u r d i o x i d e content and the order of i n c r e a s i n g c o l o r , the 81ose agreement being quite n o t i c e a b l e . (15) TAB IS V I I Bulb IIo. Per cent SQ)g Reading Mar. 13 Reading Mar. 27 Reading Apr, 11 0 61 28.93 - 32.80 •™ *32 © £«5 C 33 37,61 - 26.20 - 25.40 - 25.40 G 65 46.57 - 20.00 - 19.40 - 19.40 G 64 56 . 70 - 17.85 - 17*25 G 63 60.73 ~ 17.00 - 16.40 - 15.85 GO 62 64143 - 16.80 - 16.00 - 15.85 G 46 64.84 - 16.95 - 16.20 - 15.85 0 45 69.92 - 16.70 - 16.10 *"* X 5«9 5 G 42 70.61 » 16.45 — - 15.85 C 49 74,80 - 16.95 - 16.50 - 15.85 C 43 79,51 - 17.80 - 17.10 - 16•35 044 85.44 - 20.55 - 18.70 - 18.70 C 47 90 .30 - 25.60 - 21.00 - 21.00 (16) TABLE V I I I Bulb ifo. Per cent Order of so 2 Color 0 38 7.64 C 38 C 31 9.80 C 31 C 53 11«69 G 53 G 40 20.13 0 40 C 61 28.93 G 61 0 33 37.61 C 65 G 65 46.57 e 33 G 64 56.70 G 63 0 6 3 60.73 0 64 G 46 64*84 • 0 46 0 45 69.92 0 42 0" 42 70.61 G 43 G 49 74.80 0 49 G 43 79 .51 0 45 G 44 85,44 C 44 G 47 90.30 0 47 C 59 95.42 G 59 C 36 95.46 G 58 C 54 98.05 0 54 C 58 98.78 C 3 6 C 57 99.12 0 57 (17) SUMMARY $1) The f r e e z i n g point of pure caprylene has been obtained, being, - 105.23°C. w i t h i n 0.35°C. (8) The f r e e z i n g point and c r i t i c a l s o l u t i o n temp-erature curve f o r caprylene and s u l f u r d i o x i d e has been determined and no i n d i c a t i o n s of compound formation are found. (3) The t e s t s made upon the m a t e r i a l showed the ease w i t h which I t u n i t e s w i t h oxygen to form peroxides, these peroxides r e a c t i n g again, aided e i t h e r w i t h heat or the pres-ence of s u l f u r d i o x i d e to form polymers. (4) The m a t e r i a l on standing i n the presence of s u l f u r d i o x i d e , undergoes a change i n character, probably polymeriz-a t i o n , causing a r i s e i n the s o l u t i o n temperatures of the va r i o u s mixtures, the values approaching a maximum f o r each composition,, (5) The degree of d i s c o l o r a t i o n of the s u l f u r d ioxide mixtures agrees w i t h the percentage of s u l f u r d i o x i d e i n the bulbs, Increasing s u l f u r d i o x i d e per centage g i v i n g an increase i n d i s c o l o r a t i o n . ( i ) BIBLIOGRAPHY. (I) X. Edeleanu, B r i t . Pat« 11,140. May 22, 1908. L. Edeleanu, U. S. Pat, 911,553. Feb. 2, 1909. L. Edeleanu, E. P f e i f f e r , K. Gress & P. Jo-deck, U. S. Pat. 1,666,560. 1928, (2) E. A.Starke, U. S. Pat. 1,109,187. S e p t . l , 1914. (3) J. M. Treneer & G.S. Benjamin, B.P. 164,325. 1914. (4) W.F. Seyer & V. Dunbar, S o l u b i l i t y of oyclohexane i n s u l f u r d i o x i d e . T.R.S. Can. 16 ( I I I ) 307-10 (1922) (5) W.F. Seyer & J.L.Huggett, S o l u b i l i t y of cetene i n s u l f u r d i o x i d e . T.R.S. Can. 18 ( I I I ) 213-16 (1924) (6) W.F. Seyer & A.F? G i l l , S o l u b i l i t y of normal hexane i n s u l f u r d i o x i d e . T.RS S. Can. 18 ( I I I ) 209-11 (1924) (7) W.F. Seyer & W.S. Peck, The e f f e c t of temperature on the molecular surface energy of b i n a r y mixtures. J.A.G.S. 52 19 (1930) (8) w'.F. Seyer & E. Todd, O r i t i c a l s o l u t i o n temperatures of hydrocarbons. l a d . Eng. Chen. 23 325-7 (1951) . (9) W.P. Seyer & R.W. B a l l , S o l u b i l i t y of c e t y l a l c o h o l i n s u l f u r d i o x i d e . T.R.S. Can. 19 ( I I I ) 149-51 (1926) (10) W„P. Seyer & A,P. Gallaugher, The system of s u l f u r d i o x i d e and n-octane. T.R.S. Can. 20 ( I I I ) 593-5 (1926) ( I I ) u.P. Seyer & E.G. King, The systems of s u l f u r dioxide and the hydrogen d e r i v a t i v e s of benzene. J.A.G.S. 55 3140. (12) J.R. Lawley, M.A. Sc. Thesis, 1953. (13) K.A. M a r t i n , B.A. Sc. Thesis, 1932. (14) L.Hodnett, B. A. Sc. Thesis, . 1935, ( i i ) (15) A.F. G i l l , M.A. T h e s i s , 1925. (16) P. de C a r l i , G&zz. chim. i t a l . 57 34t~55 C.A. 21 3097. (17) J.B. Qonant & T?.R. Peterson, P o l y m e r i z a t i o n r e a c t i o n s under h i g h pressures. I I . tl.A.C.S. 54 628 (1932) (18 ) M. Bourgeul, B u l l . Soc. Uhim. 41 1475-8 (19) J.Vi. I r t f h l , Untersuchung tjber die M o l e k u l a r r e f r a k t i o n organ i s cher f l u s s i g e r JS.8rper yon grossem Part enzerstreuungs-vermtfgen. Annal en 235 11. (20) J.W. M e l l o r , A Comprehensive t r e a t i s e on t h e o r e t i c a l and i n o r g a n i c chemistry. V o l . V I I I page 48. T o P o tenhomete«r> fMk\fmifr/j\rss/Ars/nvrs/A Fio. 4 

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