pm x-m‘zz “Mp..-”— ,- STUDIES OF ADSORPTION FROM NON-AQUEOUS BINARY AND 'FERNARY SYSTEMS The-sis for the Degree of M. S. MICHiCAN STATE COLLEGE Ruih Frances Hill 194? lull"! Ilil \l l ldxl ..l.| I‘l‘l ln‘w II I l n - t 4. 0". : r '.vt_7..(‘"'. .? -‘, 13;). u, 33‘ ." ~J:~ ‘T ”2". ‘ ‘. v \ 9"..- v. , $‘w‘\.'..~&"\r’ “ 3,“??? \fi Iwo.‘ '.-\3?§i‘§f:,g:)¢ri » " 1 ‘.1I.-.~-«3~<§t" . E ~A‘;f"; 3 ' . 3 a . ‘ 4’ , o; ' '1 a . v' *7! - c c \ 40W {'7' 52"» ¢ ‘V. 7‘ !‘T" )5 5:; #3} ‘L’, 11’ _ ‘o L??? ‘- .«uélc‘gpfi 23’s.. " o s: 33 s 1.“ a? ‘3. 1:! . - .. ail . V A ‘ V" :~. ' ' : .‘7" 7: . W“ . .- A, l. L . "1. 5 I I 9 a». n. ... ,4 " "-. ' 7;. .I' - . ‘ "3- mm ‘r ' v - ‘ ‘ ' ' e? . 4, .4 r ' v _‘ \_ «SJ-r kg“. “’1' 1.5“} 2;: .- ama'?" $3: ._ .l O 5‘ i ' k."--‘ 149?? 4:. l‘. . ‘l “‘2. a; - I~:.:— ' _-k .‘ ‘ 1". l-" . , 1”? fr} T;'?”"?;b° fig“? 7* } .zgf‘ 7" J" '_.. u'lfifi- 2 ~ I ,O. ? .‘~ .1 :1 ‘ 4' -. 5"“ : ‘g... . 'p.‘ ~- 'y -0— n- I» '—.- k -., a”: wavi- 1‘! 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' ~-;-\ ‘5‘- a #5 H Li. ‘f"lfl---q— If“ - ' ‘ ‘ \‘ I‘LA-v' J.“ .H 0 .( “ OJ vv 0 1‘1 L) .L 7'1 _ . .« rPaflCc L'q Law A If ”’nrfnvj-nct‘a ‘ Lv~ Ax.~-l~ u ts for V -. rv n -.L «LA Cu'mittai to the Stat re (3111 re 1" ~ . ~ -‘ 32;.5U “Io Colls~v of A riculture avd Ag; rse Science in partial fulfilment of tn the T;i CF Sch 01 of c lied e d8? Of ) (\ffi". \Vf\“" 1 I}... x ACKTT CTR’LLDGIIZVT The writer wishss to express her sinccre t to Doctor D.T. Ewing for his aid and counsel on various studies unisrtake A. b 148116 ['1 3311{ S the Introduction Nature of the Present Study Aiserytion Isstherms for Cholesterol Chromstagraghic Aisorption of thlesterol Theoretical Aspect A. Nature of the Problem 3. method of Attack if Ft :1) FJ. .J (+- DJ (0 C }J u) C’- *‘b H. *‘J _.--—r. H‘. . . - vteen yes 3, a greet ooCl of uorK has bcen done on Adscrot tion from binary liqui’ systems. ‘3.) ttem t P t: show a cor elation tetteen (L) U rl" . -. f 1v. I 14“ '5' ‘1‘ Variegs “CTASIS _;vc it) the selective Adsorption of one constituent end some iffsren workers have stressed the importance of different properties, certain "acts were oorerved by all. Thus, as Kane and Jetkirl point out, the oreferentiel adsorption of either constituent, degenis to e very large de: es uoon the neture end activit of the adsorpent. I: studying the system, to luene-ecetic eci , they found that to ltlene is edsor ed et all e: icontrut104s, on sugar cher- ! coal, whereas acetic acid is eosorted in this manner on silica :el. For sLimel cnercosl, ho ever, they obtained ‘ 7 Einil-r results were ob sined by K.o. Reo and ‘.s. in studyin: adsorjtion on tale of silica, alumina and . “ ‘.. e‘ _ , ‘ - , ‘7. _ ._\ ,L’ ‘. ..‘,,_-_ . A " ° .3511 Jvlnzenv ’ vill'x-‘ 'ijLij'L-lvpl k—§;;I-l L;2-lllt,.".'l L1 t'st :CL..LOI.L\.: 1.. ' V v " -- -'- -' ,— " .' —.- 5,‘r~ , ~~ ' I,‘ -‘ “ _-\ . ’5 ‘ -‘\ -. 3 l‘ _e-, LUPK;PS neVe stresses toe ip,ortin~e c1 Aenesiui T;nsion as e jeteri nin Jester. ‘urtell :gnu olo.n’, in studyinfi the systems benzene-ethyl alcohol, alpha oromo- nao.tialone-ethyl alcohol :‘d ethyl c rhonate-ethyl alcohol, using a charcoal adsor:ent, found that, in dilute solutions, tne solutes with the fireatest Adhe 'ion Tension a ainst carbon, are adsorbed most. They agree, however, on the i portance of relative concentration, since, if the con >nent of loner Adhesion Tension is present in very s ligh amount, it is preferentiaily adsorsed, anyway. In each case, t 8y ct tainedo urves ov;r the entire range of con'entration. E. Heymann and E. ”fiove4 sungarize these observations by classifying the adsorption curves of binary liquid tive [-1. sys stens into two tyges. in the first, we have cs '(3 f one oomooaent over the whole ran e with a L ’ {.0 L44 ( ) ‘sorotion naximun at some ooint. This is characteristic of mixtures _l in which one component has a high Work of Adncsicn and also of mixtures in which the Surface Tension of one constituent is iarkedly lonered by the addition of the other. In the second, Te have an d-cu;ve thich :nsses through a point of equal alsorption of ooth and moreover, shows an asparent ne etire alsorotion of ore comgonent over a definite co noentr t on r n . This is character- is tic of syste whose components have a small Work of Adhesio-. These worke rs also maie the 1:3 :ortant generalization that, in mixtures of aliphatic and urom tic compounds, O," o i ., Thus 3 aromatic ccn}eu1. tsnrs to 34 s er s; e"t. 1.- ", ‘n ‘ ° W -. ‘ "~ ., _ ..+ z i. : - 1. . - ,-. ,- -. f!~. -h aij~o tiA—fn; llAAJS {Irg {j v.1 3“ L-JIq-d; t0 184:3 Lat-:0; 4“ ‘~ I‘ . v ‘ . J- O 1 --~ ‘." : I . ’ “ ' 4' a stint: in a g- ture CL s iVQHtS. Ina Jeni .Qb H , 1a - .- \ , « . ,-‘ ‘ - ' ".a 1 .As . 4- , -. ‘I ‘- “ >‘. ,e‘ "' :- factor, nere, augeiis to es the eiii-ity ii the sslvcnts. CA - ‘ ~ ~ -\ ~ q I ~ -— -. l ‘ . -- in > . l ’ ." I“! / ~ I“ " ”a armslen.o and LduLHB“ in stui3in_ tne discrctien i .1. . . i -- - 2. z" .. on or“ salIC3.ic and outyric gClQ fro. tne mi tures, ccl4—cnc 3, '3 J P" r~. ': u: I: . " '5‘ U PA ‘ . -_ ;_ -- ir-anren, cQLECn-hg ins Chciv—C2n5cs, mane these servations: .q _ '_ T ‘ .-. n " ~ ‘ ’. V A) ,0 -a -' _ -| __. o 0 A“ l. cri“ ml; ; so /“JLS oi siniiar o0i-iities or . .0 '1 ' 1,, ,3 - _.- . 4. fl 4 ,_ ' .' .— ',~ 4. _v_, .A. ' . I 3 ,: .3 iiiar c~3ait~l niture, nnswrption is assolutcly inacccndent - r ‘0 ~ 3. .-. q, .- \ |,—, J- . . I D I ‘3. N‘ n -O I. ‘ t.J r3 etIVe COJCCUtiiLlOHS :i tae So icnts. p, _ - 4" , .~ _, - A .9 !- , .- ‘ . . 4L V. .. 2. Froi lA‘G 331 cnts i the polar-non solar byovb, ‘ _" ,— _‘ vi ’ ’) V '“ I _ I .0 a _ _ _ _ r‘ A V.' o a y“ ‘ _- '. . ". .' e nis‘rgtion ,1 “alicylic Cid i crcnses LlLH an inciesse J" “~ -' A ‘ " ”’n ' ’ ‘ " f' ‘ 4‘} 1 ' v 7 "\ .~ ." .“ ,.- ‘J-g- t 3". . -' ", '3 Lh3 contentratioq oi the non-solar CQHQUdbdtO “VMSJL , .. . ' .. ,, .1 .." ,‘ 4.1,. - -. . . 1. a \ -‘. .‘ ,- v: "' on yric a,ii, tner -acttgs .ust we COMSL‘CISQ. 6 ‘ r “ - v- " ‘ 4" W ‘ w ‘ \' xx ~ ‘2' . ' w r. . " ‘ 1 In an earlier gassr , these sine torisrs studies the . ‘\ ‘ ‘- J. . " .\ ‘, ‘ 1‘ ..~ ‘ 7' I '-' ‘ " Ifi ‘ ' v“‘ “ ' ‘ ' quLlCU on chuiccal of altnr.nilic :cid from winery vents, and made these observations: in a mixture of two ..J one non-pol; trosily eel r, Adsorption s inversely pricortconal to ' --~. -. . -. 3 '.A9. V Kuhn“, .-- -oludiiit,. In a min are oi Siiil r : etica' nature, CUaflbJS : -" m, '2 1' I\ g' V.’ '- . .- " ‘ l , . ‘- ‘ " r. ' r .' '_‘, . Aisurgtion n;;r13 oirillel has es in 'dlucilit3. here, -. ”‘41. . 4 "L , -,..- ,. o. A,‘ .:~ - A - gluciiity is intriiucea as an luQOPtah -actor ta us cch- ' z 3- A l..va-‘-~7vl O ‘P A "\ 'o'- '7 .' " ' .v ‘ . V ' V 7“ '- r -, '1 _”- . 3" ‘ 1 ‘, l ‘ in enciil tJSJ, ts; lflpOILiSt -dctois iniiuentii ' " ' v 4‘ . "\ ,' F. —‘ v t" J- ' .- I" rm / - L -' -. r". .-. ~ - .— - -. issroti,n Ir». a tWJ-cUmconent liquii SUQtUm, agyBIF to ,e the natu2e an: activity of the mi or eat used, the ielxtive ceicent aticn of the com cuents, the Adhesion Tensions m 4- I". u (*f' (D assorflnrit, tne (unstical trature c; Lure COQgOILilLS. .. ' . - C" 1111 r». . (2' _. — .' ,w. th.’ LA UV H D («+- u I'D >3 ) D (J F—b (+- (L (D I f) O (. _ O (U ‘( cf- \fi Rt 3) (—8- (L. ' ( t) '0 O \ r o 3.1 }_l- P L) S a 1 in a cinary mixture of solvon s, three additional .actsis must be incluied—-the nstur; of the solute, its solutility in both C“; on nts and the oolarit LJ. d) ( I l'14 l" '\ L (.5 O [(-4 C) (v 5.! r—L (J 0 His ggoer aill h; devoted chiefly to a stuiy of the Chromatagra sic and ordinary Adsorptio n from miLud s lxent ginal Fl! systems, ccntainir' ch;1;sterol as the solute. 1h; or purpose wa= t? inv stiqzte the p ctitr"lling 9) C’) F .J ’J. i. .J F}. fl L “ O H the Adsorction and Desorcr M on of cholvst rol on a Twsett mixe d ol.-nts. Throuihout, ‘he adsorbent used is activated bentonito. The cholest rel, in gercolstes and filtiates, was deter iced, colorimetrically, using the Liesermann- urcnar reaction. Special care had to he tajen, often cy .. . :. 4., , M "-,,..\ .- -‘I . ..-.'.‘-_- _. ,—..‘ Cent atid.s t3 brin the JBVUlOJCj colors Litnin a ielcicie . ‘ r . _: 0 .~ , _ t} if 'i '. _. v' ‘ . , ‘ _r' h‘ _: «' , 'f 5 _‘ : ,- — Tue ls”t vection is CCUC3IDcG “its a yJaSlQLd tneor etical approach to the observe. ; eno'ene sod onstitutes "\ s stirting point Ior further theoretical investi_etion. . 1*: Ah —) fi ‘ v ': -'>. _ f w‘:;‘ H... 71' 1- :r‘ -.. ‘1 o’-—4 . up III. £3_-_)‘,-1;I_L IVIJT ..i.-'._.y\) if“. fi‘. U;____L_,‘;._,J r“\ L 4:. =reliminary wirK on the adsorption oi cholesterol n31 consisted of sending solutions of choles erol dissolved in oenzene, t FOL”h Tn.ett columns, 2 cm. long. The s? developing afient, wnicn also eluted the column, vs: a mixture of benzene and Skelly Solve, of varying concentration. Although the quantity of cnole ste rol, appearing in the percolstes, increased with an increase in benzene concentra— sults led to the question of the (L ion, anomalously high r possible negative adsorption of cholesterol or positive edsor ”tic of benzene. The concentration used in this work wesilfiitmn per ml. With this dues tion in n‘.ind, an adsorption isotiert for cholesterol in benzene, was determined over a range in conceztr t: on from 0.197 m . per ml. to 19.73 mg. per ml. Each semole was nixed with 1.1500 g ens of uisor....t. The flasks were swirled frequently and one hour allowed for equili rium to be reached. The samples were then raoidl iy filter d tnriufin oeper, previously Moist n-ed with benzene; The first 2-3 were disourded and the concentration of cholesterol :let r ire2d in the remainder. Tne accomgenying graph and Taole I give the results. 1h To; nature of the S-curve o otzined, indicates 44 U) C. b—J s: *3 Fl (D O H £1: £3 ) C? Li 5.. :5 fl d Rurcn~r1 teet, all filtretee 3nl gelcolate 3 h ‘neee enu tne resiiues >:ic:;~ 3 up in oenzene (C5h5), oercre tce e>ncentr;tione of cholesterol Could he jet “mined. Yoseover, the solubility of cholesterol exceedin“ 10 my. gur ml. couli not :3 3 olqud. Solutien requir,i he tin; in 3 w.t;r path at 35 -40 C. Four isotherms were ”;weter inc—d. The first W‘S for cholesterol in eure benaine. In the others, eclv,nt mixtures were ueed, male up to Cintain 20 ml. of nenzlne :nl 3 ml. of benzene, absolute elcoh 1 Eli ethyl ether, reeg;ctively. The relutlve c-ncentr"tione w2re thus 37} ben"ine to 13} of the minor component. Since the filtr t 3 hwd to be evrprr tei to 3r¢nees and tecen up in Vflfjlfl: luantitiee of benzene for calor- imetric ieter in tion, tne enuili:riu1 concentration C, .3 Ho could not 33 exp eeeed in ms. per al. and given, the gfore, 33 total #31 ht of choleetelol unadecr ed. The 3 initial ccnce ntrition before sis rotion is also xiven The green and Tables II, III, IV, en: V are highly illuminatinfi. Cholesterol is ve‘y hi hly 3330*333 ircn m rkefily r iucei. In orfler cf *3crsisin“ figscrbebiliti, we nfive ethyl ether, sosolmte alcohol ans 0 n23 ne. ihe ourVes for ether enfl elconol have :nsxime, iniic-tin5 that the aisorption of‘ cholesterol increases with incr 33ing c icentrution us to a certain point, beyond which {0 :3 << H.) C: H (A. l * lgtr.3?e in cencentreti on is ac omeenied by e iecres e in actorstL n. :cr all three u'nor constituents, the quantity °;ed is always less than fr01 b nzine alone. IV. SlugiLilT‘A:fi?3 ADS HillfV f? C.OLLSILRLL The rest zlts of t 3 previous study were next ext nW-d to the can; of sissrhtion on a Tv.seit column. With be enzine ". ’0 ,2 ’ .3 ’1 cilctts es the major constituent of thesolv131t mixtuie u r+ :\ (u 3'3 (H ’1 <1 O Q: C 9 a U} C U) (+- i.) 5" O (L U) o; rsrions :inir congonents were omit "p' 1‘ . . 1‘ . rxl’, -'\ ' / ~ -_ ‘ J- ‘ ‘ '; o‘ ~ in " A ,, 1.4 ~10 ‘ n.5- fi’-‘WV*.V H - - if 5 .1 — "L‘5_ l ..—.-. —n —~7 -——————r _——_-~. + 0 O Q ~—_._. a_h_..‘m4 ‘m M l—Q i d an AOSoRm'o‘: hummus “'9': (Hosanna. M Dunn]! “wanna Mo? 0 ~BINZINI «as; . ‘ ' ll aluzml + 3 HL. BINIINI (C‘H‘) .m'. ~. w o BINIINI + 3 M. An. Mum. Jeri x sun-mu + 3 HL. sum «an a”: .. , . .. \ é ~ 2 .o 1- «'7 I C m . 0" '3‘ r 1 4 i t I \ ‘b*L“L‘io"“ 10“‘*Ilo"““to"’ '6o' 119‘“ u 10 ' In . 6. w- Hfiévnt). ,. J L); _- ' “3 ‘4 .1 ”4.3., .3 V‘l—"Ji; '- -' i :4 m- D .1 4--°;-— ,. 1e “7* CDflLalfllfiv also 4 ATVJS 01 3 SI1ULLQM Of Eugen Ill, more 31103-3i t; unjer 311 at suction: tge C) H 0 SJ \J (+- (r! r?‘ W o .1 p:rcolatesv ere coll: ct3d ana t:e columns then 3lwmt i witil 20 ml. of the s'me solvent sixture. Beth percoletes were evaporated to drrneis 333 t3zen ue 1r sufficient benzene, with dilution, if necessary, to insuie a readable color The purpose of the Su: an III 33s to serve as a go siele rial failed to (—4.. . ,— [1.x 1;- 1,. ,‘1 ,_ , ,3. ,. ,1 "— , 4 .-J.V.‘~_, marner ior tie barometafirepn out res aLvd - '\~ , I 'x .» .. 0" ' 3" “ 1.“ " fl 7 ' I-‘Vr E -‘ ‘. r'.‘ projoce nooj 031fl 1~_. :oreover, tde use CI tee -Je must be restricted to an extremely dilute solution since, up to very hijh .ilutioz1s, it will Eive a positive Liebermsnn- Burcherd re3ction. Iue results are summarized in Tesla VI. “The LL h results in tee case of e:so olute alcohol (U 0 gm *1 2.3 (D (+— H I ‘1 f D fl are due to the fact tnet th (13 . .v Ix.-. Lb pv MAL The results for the first three mixtures check very well with the adsorotion iso the rx s for these s::.me mixtures Ref rence to the freon fer tULs reveals that benzene is not as eiii61ent in fiesortius cholesterol, when present Ti; jesarbine oower of isoprooyl alcohzl 6038 not L TADLE If “— .m-Lm—w— -- ‘ ’rfl- 1L Sm. VE~T 5H0 i I g ”IXTURB J _ M13. BENIINE «- Benzene 38:»qu + EYHYL ETHER ' -,.\~nu- IA. .BEw-uve + -—-—- ~—- -—+ A35 . ALOOHoL % 1 i P f. i L Encomwe l jPEBLOLA‘TI'. 2.1 HO NGN * ‘ ' __ . . . a , . .. - ' "'"" l I I l I *mw-ouwhw- Y» '. .-- _ . .. -- .~. . Rfcoveav LisT can. w: w . '3 OUT 0: “Oil—Inn -ao m—fin-u *- —- .9. "or .Ilfi h" ‘ 1 ' ' ’ J ‘ f 3 . I 5 g 3 ‘ ‘; ‘ o i o g x 0 . (, i O ; v D I . 7.60 21.1 35.51 .vr'm""‘u-q _.._.. .. .. ‘ .... i.-- - - ---- n - I. »,u . '-.--q..- .~ . ..-..- -. «p— ‘ 31cc 1 5.4. ! «13.5; :1 BENI WE + 1 150930914 Au; .... — a «Tut-4'“ - ...-....¢. ‘ .— ._ 33.40 ' 5.7. 34.! F". .0 IbfiNZ-IUE +- 9 LA 6M L Assn; ‘Mum-AM‘WWIHJ'hfl-Un .L _. :w-m—u B‘szg q. LHLOROIon H .n- . ~ "-1..-~fih n..-.......~-.-;- rm. --., .4 . -u . ._, («.00 I’LL, - 35.4, .5;.flm..’-~-Ifiq W.-ao - >3 ah.' --. -...Ju....- .—-. .. M ~. .. . «h ,. _.._._- | 1 . .. -31“---H.‘.—-———.—.—w—~—.—3 4 (+ *3 k ('3 .J H 5.) (+ 5.3 t... C J H. D of ti 5 minutes or spout four times as long. In the running of the ai“orotion isotnerm, it was noticed to t swirlin" of the flasxs conteinin: absolute slco {3’ k) H 3, O b (7 Cu 0.: d T} (I) SIT-J t‘ C) 5-5] F'- d O ‘0 'L ( H H F}. S (t "3 ani whit r ani to reouire more time to settle. Ins Si;- ctsczfstion will be discus~ei la ter H. S44 5 Q. 0 F 3 ( (u (I Altnotgn most ”f this study W3s restricp3d to non- L .31 ' , - L1,. .,"-.-“ ,. x- 1.. , ' ',.- _, .-. . .\ _ _. ' v . . .7 aqueous SUlUtljfg, tn. eiie-t oi miter in too so JUUL LlaLUic r ‘— ‘. I : vr \ ‘ ‘ ~---_r ‘ I ~ -' ~-‘w»‘- f“ . ”.7. ‘~ 1%, ~. q " elconol. Two singles Ldid run, usin. tnc can; .etnco. Tne o . . , ,-.. J— . - ‘ - A ., 1-. ‘g \ .J - . . .31 4. _- P n , 7 . - ilTSt o stained 2c ml. 01 the 3enZine s iution Jl cnol sterol, ‘ -‘I A . ‘-‘. r s "' O ,‘1. a" ' K f ' Iv"! . .1 A J” V ' ‘ " ‘ j 1 r‘ 1 mi. Ci alconol in; ; urges of meter tniie tne Seconi Had rt {:4 U ; 3 1% (D O Q '5) O :3 (v :3 F?‘ J) r‘ ,C (7+ :3 O (.3 (7” (l? H .1 o H L B (+ L) \r.‘ 9“ 3) (IV (D o O (—1 0 F5 the cholesterol appeared in the first o rcol te, ,3.C m_. .. ' _/ fl ‘ ‘ . ._~ _ "2le 31? 00 Iglklffo nlt-uOth water. An 3ttenot to uee just benzine and water failed c... C) jesoro ani cholesterol, iue to tn: fact tnat too tater Oes not (1/ {J4 did JCt mix with the bensine. B212ine alon“ 1 oesoro cno esterol wnen 40 ml. are run thr ugh the column. (I) however, the observation meie in the co e of tne mixture containing benzine, alcohol snl water has that the p essure of the weter gr;=tly slosoi uo the percolation. Tie affinity of active ei bentonite for water is a osrently 'rester tna for any otter suofitxnce so that as soon the colu.n, a layer of water )d J) (+ D > < ,‘S H. in ("r S: 1...! ( F“ \J \J (. CU r+ C, surface of tne sis rc3nt. This 9 i fix 3.) O \L 3) (J a) C.) (7+ 0 h; 0 r—J H. LT {v closs uo toe pores so that the other co stituents nevi difficulty gettinfi tnr3ugn. Once the film of water comes , the rate 0; o rcol.tion morxeily increases. A. Nature of the Problem. The entire suoj3ct of adsorption from two and three- v“ ~A"~‘ 4- ,.J_ --. a " >.-‘- J?' . 4-1 n 2' . 3” '3 rufxv” " comooUent syatet. is 1rsuont mica .3ny QUo tions, sowe OI wfiicn n37: seen only 9 rtislly answered and some not at -V v ‘ r1 v‘<\ -.\ l‘ r~ .-‘ I .W , -- " . 'v— "“ " {x v‘ I ' ' _ ."\ 1‘ V .1 .+ .‘1 m {.1 all. u_t suy is a solute s sorted ifwfl one S'l/bnb and ‘ ‘ r A 7 ’ - '1 p w .0 A ‘ I not ‘Io1 eiotnur? Is toe IJ‘UI.Unb lquLL, oi crlm; in- O I.) O 3. 0 ,1 H u ‘— H F). ( J ‘J (1 FJ . Q.- }__J E s E 0 >1 H .M (D \o H ('1; "I *‘5 Q C 0’) 0 >1 H g 1 (C u oetween tne sx";rtent and one or more c goonents oi tne ,. 2. . -.'_ ,. .; 1 .. w, '- ~ .. , - .. .3 , - , . .. .3 , so ution? not 1 r Moos soiuoi-ity .o in oxoleinin. T' (1810:] C;_C): to .Jfi (u 3 —— -~\ . A ~P.r oouervsole site 0 d. U) '0 L ‘ (.1: J] ‘. (I U) H. O H SD 0 (—P‘ C "f Po :3 c. - C ( (L t" ( l ‘ Pi (9 (0 SH @“jOT fs cémgonunt of low tencion is present in hiyn dilution? How much or dence . 4. .-. -., w . " , . .. h ..' ..- 1. .4. ‘ ‘.,-. , . y _ . are We to “1V: exoisnations for a .LVGH SJSLQm, udSGd on It is titn an stte pt to s’molify some of this, tnst this lee section is c ncerned. E. Yethod of Att ck ~.J In; syfitem cool:sterol—henzine-sbsolute alcohol was .‘ ‘ ._ J. .L i”- 3‘ '- "t ._ , 1,- oist. Let us suooOse, ior tne ‘ 1) (D 'r , ( O (L. ( . L- § 7 U) y. ’3') (—1. S ’“5 r+ ’— o D '0 mo ent, tnvt the :xplanstion for tre observed desorption of cool sterol from the solvent mixture of 875 benzine and 1 4 . -‘»‘ "‘ l 7‘! H r“ ‘ " (‘1 ‘ ’5 v-v \ y \ :u.” ' ' ' \ - ! . . > . A‘ '0 ~ to oe niynly ensuroeu fIOn tore ceizine solution, orCVioinb fl tnst 3omo sort Cl attraction exists oatmeen the solid FL (.11 1) '3 PS (7 ._J (+ Pl :3 Q4 (+- .5 (4 U] .olute. Actually, ChClthSTOl is highly a. V .‘__ 1 .J —.~ _‘ 1,.- ._,‘ . —., f, .u. -;~.'J- A‘j..,m_\»‘,‘ 'fi‘._-.A adsoru o irtm pure Uanlne. Pow must “sctuns .Lon ? A small amount 1e.ov&3 o F< VJ alcohol is glued to to; soluti ch; esterol from the sentooite. This can not _e due to to: grexter solubility of cholesterol in alcohol, since J u 1'" I ' \"' ‘~ 'v ,7 V , ‘1 - ,' fl . rm." H I, ' ‘~’ " ‘. ""“‘ 5‘. I" ‘ ,3 \ euloroigrs loes not glfe the same ellect altouumn coolestcrol S'luole in it. is ver ‘1‘ We might assume to't too alcohnl incres es the O H. (“k (U 90 H O O C) H .5 O F" L) 0 CI L__J (u 1)) .0 i»? "S (1 (—f. b k ‘ \U xx: H) O "S (1 L L: H. C) O .0 N v H (L alcohol, after Contact with the sisorocut. The methoj uied was the set.rminltion of isnsity be;ore an: alter adsorption ani comparison with the oeusitics of the pure cup nonts. The satire concentration ran “ was covered. DJHSity pegsureneot: mere male by the Pycnometer method. All mixtures xere set.rmincs at 290C. Croat cue o (0 Ci (E Q L R H (.0 hai to be taken to prevent evaporation sir e" rexely volatile. To) flasks contoinigi adsorbent and solvent mixtur: rare Carefullr stc,§éred on‘ rregged in tinfoil. Raoihity of :anipuletion an; we; hint ani re— L4 *4 N (D d. (L ( F- H O ’1 O petition oi set;rfiostions served to minim’ For*iixtu1's in which the alcohol concentr.ticn is ess than scorchisstelv 13;, the iensity iiter ass roticn is less tags bricre, the shift being is the 3i1:ction o‘ the sure xenzine. Eviieotly, is sucn LiktUYGS, coocl ' ~ "1 - f u. ‘-I _.. — , ‘ J.— . -\ - -‘-. r ‘. .-‘ -. . . .— p -, -. ., '5‘. is as or 31 to e ucs -rester bktcflt than oeuiiue. n . 0 > 1“. q. A \ ?. ‘stioo, to: curv. CTuSSUS toe C: (4‘ (1 C fl F‘J I ) L w 1.4 O Q P O ‘J :3 O (L f.» C’- H w t either Lmfii1 are Quota. :1 to the y | i" 1.. U) P a 1-1. 0 (+- H. :J (.1. o: cure alC“bol, so tuxt we :ey ccncluje tbit benzine I 1 “ -- .-\ r; N \..c ~ ~"‘>.-' ,- - - - -~ .‘1 u 1'- . -'. . .' — I I ’1'. 3'48 'dlUS -118 OCJLI-IS: 5:.LO‘I‘31 1.0 :".11.‘\.4C;.' I it’JI \3;\b‘:t$t. r\ -. ~ ]. u .fi 3- ,- ,a - r\| ,‘ ‘ I' .. . r ' ._ ,fi __ T- 5 ,1. A . f" ‘ c,m-osest sy .ew, Cw01c3t5ICl‘Quflélfl: issclute llCuuo , cholLstsrol 3‘sgro2i. Th-refore, since sen~ioe is not ei“or;el eithir to any great extent, slcoh l ices Lot .£ oeryrine r; .inst ‘e O (—1" {.2 C..- i C) (I, | / w L] t". .I r‘ L 3- K (v F" O ”N w H (L J ' 7) F). J L; O oegtooite. Its o.hsv our is more iirect. so to or toe (I oetur: of .h. solifi-so i} Lsrce of ottrsctio: between TABLE Zn: #— 'fi‘VI-b"- _ ——w a . -. - c ’ I ’0 ALLOHOLE °|o Benny; Dang-W r DE”$\TV ”1‘36; ”V 3 W Bum; AFTER DCW'TV 4 ORIMMAL : OR‘GIUAL. ‘ g Huwunefi mu"! ADfiORPTAms/V AbsoRP-rrv ’4 D -: o 1'. 4:, [6—0 w--. .mwgn ,L. 5.....-- .-1L v--..- cmrmumsmguwhu- I”... ‘15.: 3 262M 3 19.3.9"-.. how? .. ‘_.r- u,mm...r.‘n~m » ‘ :9}‘“ 1"???” “M” h“.1 _ . .Amm-b-urg~m_..i. ..—-.“..-v— . ..'._..—........_.. l..- .1 _.,_ , ___. ”___. _. __ é 9.1 . qo.q .0431 t .6412. -.OO?.o gmem»gga4. .- ‘- 11 “a m-----.»...--.eu.W;..-r-..~ -‘....,--.-...1. h A -_____ tongue-~— . ___" r_____ j” “___“. 4‘- fi- r ‘ L wot J 71.0 ' .9501 .1445: -.oocz i ““"”“h *‘ - i E?'_-r.-t.. 19"]- f “4.05? . ”39""! ,1 179°"? 42.3 512 .4479 i .1041, f.oo14 1 M30 ? 63.0 $131 3 .Lgso 1-.0053 T . _ g a 5L2 Ia“ L1H _ .1114 i .1246 1".0l_2’2. _4 .1526 .11oq hang s. 4 5 3 i" - We -~-~~—-—-...~ -..-4. 1 1043.0 0 .1 5’66. : .1466 +. on M ADI cm: In new Aauurt AL and L- animus, .. . . m xrun I , AF 11!! Autumn-1 dist AmA‘uo , . _ Basra» 17;... ...... ..... i3. 4— -. . _ . - .1- W- \_ ......__.. to 4 in ”bottom” Astana." “'1' i l f 7 ..__, i__.__._.-_ l _ O C) (,I H (L r‘?‘ (‘) -< H 5 "i H I C}, (L 1 3 (a. C) D [.10 r+ (L‘ H ) C‘J 9; k (I) u (—f' {U } c 7') ! (+- rf' *‘5 ‘. I ('+ P O )—l ('2 C‘ f“ F‘ H p— I . \ ‘ . ‘ J —~ - + .a ‘y- ‘0 -— [I — -\ my; \ ‘1 | \ Ir) J ‘1 C 1 . , 1*! A 1‘ JL/j "1:14. tLIIJ --J\./A. L.‘ :lt LC): .J v.3 - .J L.'u .A§k-x.4v ‘Kzn VL.\-J.L\.In ‘ . " ‘ . . '- . u “4.... .. .4. ‘.. "1“..A ' r fi-fi 1'" ,"\y 'N. H. «H m 1-.»~rr. A V. “-x . runnr“ \V' V1 . ‘V 'Wl ~‘ ‘ :3 .i. . 'JL- .L . '1 R. 1,113 V‘ v '..( 1 ‘J L]. _. ‘J "J L'h’ ‘ .nO I H LA ”xv L. L4 ‘4 L '4' L LJK' L' ‘4' xi ‘1 :3 L) ‘v o a - ’ fl ‘ ,- ‘ --|I ‘.- ‘ ‘- ’. ‘ ~V_'._ . . r“ .-‘ _‘ ,l 1 C" 19 -uaorpdd huqfl Lie :LCJJOl CJipdfltLMtlon UACQUJS Lvfl. .‘ I'd - ' '1'- * '3. J-‘4\.4-§. Lil-VL‘xA H k \ A (I) ( Dfi' C! I C) 7‘ ' , J L] ('4‘ £0 (-1- O f L- J O L'J .—1‘ (I? H N H H. {I} C) ( i D L 3 ”I k (l L ..J (4- i '3‘ O (-4 (-9- J" V“ ‘r ’7 ." 4‘ 4 ‘ ‘ W 'V- r~ .‘ "‘. ‘ ' ‘ '1 " " .' " ‘9" I ‘ I' I." 2. F "u j i 7' _.- 2‘ ".' .2 ‘ ' "v' '. ._ LL10 L'AL+1‘\JJ L .‘fihl ,\_, \a’L “— \IsL» QA.LJ: I»; :A¢L(_: la tulk‘l 1? \J-Lvl VLJLJ A;‘.L.js LUaV’ -1 ~ - - - ‘ n - - _ ‘A ‘ ,3 1» ‘ «\u ‘ '\‘ fl . 31 I: {h 3". ,. - f; ‘ ‘ r) t ‘r~ t ' t a , .. . !./-‘ v f .—~ 1 '. f_~. ‘. -_‘A ~ ' C ‘\ l _ l ".- I W 'u '1‘! .‘ LA 1 ”a [A f u LI'J C .1 V .L; J ‘k'v . A .1. H I u nix; . “.1. LA b JUL/1.2 S L.) 'u x; J. W 3 ‘ ‘ \ a -‘ ’ - 4"3‘ i, L ‘_- H: _ .'_ 1" ” ‘-. " amulpr \er .)./Lv.i C'.L Lid-J L. “3? Cum- C r O D Fl r.‘ (I) H (I ( I" E: (u (l I J Fr- \ I 9;; ,\ -o - T T "\"" f‘ -' v ‘. ' . .fi r ‘ 1:. 1', .‘ J— : + 1----. 3“ :1 ‘ ". yOJ:Q 3. Runs 3?, if it is 13pm; tufip LU L43 uyyvz con- , n K '\ I 1 “1 j _ ‘ . v I a L - . ,5 -‘ ‘ - , _ — I ‘ I“ -. , I- r: 4‘ —. r I, ‘ ."_ -. .5 A 4- -: -\ . C-uCJ-lgfiiwgu.~ l 13 49,;3 Vat u on Luv SLmunguuhus LAD Iubibfl (3 ’4’! K i I‘ x’ ( 1' i'—’ (x (—3 5-: (L 1 U U H O (. H. D r (L r: l PC} (L HI I }.1 I , . ( U ( . ( .- L Fl :3 (D H 0) 'l k F- L10 r?- t 1 F I a r: ( h L; O A H C’ d H ) (U H "u \k‘ U ( h (7. O O l l 1 lg .I.L .1. -.I a u 9- J. L; L..'L.A' ._3 .L 'I . V LL]. C Al), LLAV \' _i.--‘U :1 .'_J Lz.’ ‘1' O ‘J‘K u:l.~/..L.L’l it, one would hzve to gsstulets tbs Lormation of ; cuc- - j _ O Q '\ I 1. m1 \‘ F 1 A ”\ '1 ** l “' Lin" ’ ' + “ - _, 1 ~ ' ~— \ 4"] - VIA—:J-L 1‘ \p L41, _Jx. *-\_ " : Jr, y. ‘. V J... | K. L; in.) ‘- _.-_4."- ., — .. 7 ~ '; ,- -. J- -‘.V n.‘ ,_L ,. .. .. 1, LYguL34312 is -c,en.cxu um lutfllq L,o;;rcu. ~fi iflcergdtinfi point to 33 cutervcr about the ;L&uh F" J) r?- P“ (+- r+ (a '_J (I‘ .‘3 I + o r+ 4 "n O L)- ; ’ l \- I ‘4 L I r L J } .1 k L k , \- f l i \ it seems, the explanation is simple. Previous work in this paper nsi mentioned the oose ”rtion that alcohol causes centonit3 to 33:0 5 fin;r uni wLitcr n11 to taxe :uch lon er to settle out. 1his agrees with the work of Ambrose and Loomis7 in which thiey state that "emulscid celleifs grseent in E3nh. IlitB rssg3ni to Chan es in BM of the iisoersion m diun b" Chan es in rate of settling, viscosity in“ is increased, the edsorgent g3rticles become finer. 11 Iising pure alconql, inns :ticles ca £213M1 ough the pores mixture nits the hentonite, is not the density of the alcohol itself out rather the alcoh3l plus these susgended 3 rticles . At the other c3nce ntr .tions used, the osrticlss were coarse enough to be held be 5 by the filter so that no error free this source was introfiuced. The graph can he considered as stertin; at the ori;in Lb on the 13ft, since a 3n sity chane of /.0007 for pure benzine is within the limit of experimental error and can be taken as a chenwe of zero. 1. An S-curve was ieterminsi 1~r the a sorotion of :l-ste rol on aCtiV:'lt d bentonite, from oenzene solution, showing negative aisorption from concentrations less than 2. Aissrotion isotherms were aster inei for cho- lesterol in bentine, benzine-henzene, henzine-ahsolute alcohol and henzine-ethyl ether. Cholesterol is found "iition of l-’ {< £0 ,1) (J O *3 (J ( , LL '"3 "3 O :2 (j :3 E J }-J '3 9. ‘nd r+ rJ I“ (U (U LA to he h'jn the othe componeLts, in the above orier, 0 used in- creasing afiounts to he desoroed. 3. lhe nrom.t3-ra hie assorution of cholesterol was studied, usin: fiifferent solvent mixtures. Benzene, osolute a coh l, ethyl ether, isooro; gl alcoh3l and glacial acetic acid are found to emcee cholesterol from Tusett cslu1ns. Chloroform fioes not. 4. The oresence of water in the eenzine solution of ch:lestero slows up the process of percolation due to the fire t attraction existing -etwee the water and the 5. Density measure; its were m_aoe on oe nnine-ahsolute alcohol mixtures, over the whole concentration range, ~isorption. Alcohol is found to be ai- L (U i a, k) R (D SD ’3 i L.) p—o (—+ C. "S SU sortei to a freater ext:nt from concentrations less than 18% and benzine to he assorhed to a freater extent above 13%. Density measurements are sufijested as one means of laying tie founiation for theoretical explanations of If} aisorption iron three-comgonent systens, containing a solute Missclrej in a binary mixture of Solvents. °r l“"'1*,'T1"'c." ‘r‘ ‘flI “tscsmzniuyo , J.G., and Jo her 5.K.K., Bins ory Systems I A‘scrition from Binary Iigtur,s of Toluene and Acetic icii b1 Charcoal (no Silica ?el. J. Indian Inst. bci., t.) (+ H 4 (0 () d L. L.) m 0 F '7—3' :_' ~ fi ' ' fl r’\ m i gao, K.e., an: Rao, 3.3., comc1r. Selective Aiosrgtion from Binary Fixtures of Liouids on Gels of Silica, Alugins and Ferrous Oxio e. Eroc. Iniian Acad. Sci., fig, 562-70 (1936). C.A., 21, 2062 (1937). .‘ nertell, F.£., and-Sloan, C.K., .fls orotion 0. Euro Carbon I An Interferonetric Investi;ition of Ads irgtion ‘ " ( ‘_‘V\"‘ fi‘,r '5" H, r" ‘Q 1“. -~ .V a , ox :ure C11con Iron ~ n- -Aoueous Jihalf JLDLH180 F‘ 1- a ’3 . ’ n *_ -—.‘ . _ . ‘ ‘1" I ‘ T 11 .1sorwt13n oy rure Vernon fron 1 y \0 -Aoueous Zinerl olstems vs the intire Concentr;tion Range. neymann, 3., 1ni Boye, 1., co1el: e iis’rgtion Iso- Fm \; H her:~ of €insry Liquid 'ixtures. Kolloid—Z., 154-63 (1935). C.A., 22, 375 (1933)- \ 1- ‘ v ’- fi ‘9' “T h - “-w. I.“ 3" I‘ "r" . f D 1rnolenio, 1.:., and Le 1na, Jvo, The Al erotion o1 F1 ..'-.fit " A r» . 3 ‘3 ,A,‘ r? ' ”a ,fi ‘ ~' -. ‘1 1'_‘ ,5 . 4- cr enic “-1 3 iron 41.;13 on: “lied solvents. —-.-—.- Acta Eh.sicoc em., (U.R.S.3.}, 10, 451-64 (1939). C' '9 229 6112 (193;)- O\ 3 gm 3Y1 A ‘T a (-4130. Lt)" r‘ .. Vina ’ D 0 I]; o 7—3.1; a - A Q ,r‘amt- fl _ , 11’131tljn heJ-vr ,3 E f Lun) Solubilitv nnj “ l w ““90n _ J 5." DD VNI-lt P v Ol'tlniJ‘- ,, Li. I l . . . . . I . I , ' I " I . . ' . \ ‘ I I . O ‘ i I '\ I . . . r ' l I i I - U I C I - v I . | l I a , o I c I ' - l 9 I ' I I I A v .' ' ,I . L . Q ' ‘ ' ‘ O ' . ‘- v t I J _ ‘ . D ‘( u \ . . ‘ r I ' ‘ ' I 1 II . t. ‘ I ’ .0 '- I'I I\ . ' l _ , I N " [ 1 [ , . 1 , I JUN 2 m . - . a. I I ' l I ! Q.- .0 I ' 1 | I I I \ O u b ' I i C p .1 1‘: D I I“ ' ' I I k . I l I . L ‘1 ' ' ... U A .' .' l I L ‘. ‘ ' I . ' v z E ' . ~ in ‘ . ‘ . ' I .: I I ,I ~ I 4 ' ‘ ‘ 3 I ,I I l- v I W‘ .1 I- I I '- I I . ' .I I I I . . t ' I . - ‘ I ‘ ' - - i ' f . ' O . o ‘ r " I I. ' . ' '- - o \ I ' . . . _ | ‘ I i I . \ .. .- _‘H- ,D 5‘347 3‘2? ‘ I. . 35’ u' .6 al .- ' . . . ., 4‘ _ ' . I. 1;..1’ 1,} "‘>I~~.—‘)ll'(:lv ’ . f 'q‘ 1'9; *3“ . ' .‘ . § § I - J". , ». ‘ Q51 _ o A» J r ~:>.,; ‘ :3. .'¥"v~(-.I . ‘. . . -l .1 x“- CEBMISTR? £1158?- H647 146116 *——— W‘m—fi T541 H647 146116 H111 Stuflies of adsorption from non—aqueous binary and ternary systems. ammo-213 HICAN w‘TAfE UNIVERSIH UBRAIHES LLLLLL LLLL LLLL LL 31293 02446 8690