ABSORPTION ISOTHERMS 0F “SHE ALPHA;- GAMMA, AND DELTA ISOMERS OF HEXACHLOROCYCLOHEXANE; AND INSTABHJTY OF THE GAMMA ISOMER Thesis {or the Degree of M. S. MECHBGAN STATE COLLEGE Paul Frankiin Biefsld 1951 125:5 ‘ o I “L at _~ ml“ , L I B RA R Y - ~ {7. , jg“; . « ”Ilichigan State ‘ .‘ ‘ University :.E.=.F.3'C.RI‘TIL.\I Ia<.-I'a:;:.s-;::3 (.1: "25:; mm. (mm... ”w ' “3..“ In. 1.1. - "and (J? Hitl'LinEix:xL‘CYCZ Cliisl‘T‘GU'S, D l‘TQTiuili I?! L? 1'11; (1. {3.61 I-i.i"’2.R ’1 PM): }¥'t‘L~’a?iK;I.‘-E {EIRLPELD A TBELIS Submitted to the Lchool of Graduate Jtudies of rich141n State College of fifiriculture and nanlied Science in martial fulfillment of the rogulrewenta for the degree of “ "I'w." ~~3 '-‘1“"“.‘ L" A.- .ns -. ." )4»! .‘4- Qt: Department of Chemistry 1951 The author wishes to thwnk Dr. D. T. Ewing for his aid and guidxnce, without which this work would nut have been nossible. 1. . .iii.‘ i'fli~‘§-‘:l.~* fifi‘fi‘ifi' t2“. Stimtim} lntroduction...................... ChemicalBOOCOO000000000000too...-o ADD&P&tUBoooo..o..o............... Procefiure......................... RGBUltSCooooooooooocoooo00000.00.u Aaaorptlon data tables....... Adsorption 150therm8......... Separation curves of isomers. Ganmu conversion table....... Discussion........................ Pure isomer adsorption....... Gamma isomer conversion...... Summ'ré'ry.........6.fliI............. Bibliography-0000000000000000000000. O... f‘aj :1- " L '('.' C: #9 \fl \fl Q Inrfi:DUCTI;V The commound Hexachlorocyciohoxono was first prenared by Faraday, per Banach (1) in 1825.. In 183 feunier, oer Slade (2) showed the exist nce of two isomers of this com- pound, the alpha and beta isomers.. In 1912 Van der Linden, oer Daaoch (1) showed the existence of two ndditional iso- moru, the gamma and deita isomcr3.. Huuar, huVall and nlquist (3) in 1947 found another isomer, the epsilon iso- mer, which until now 13 the final isomar to he discovered. In this paper only the aloha, gonna and delta isomers were studied. smart, oer Zauer. DuVall and Alquict (3) in 1943 ico- luted tha gamma isomer and foundit to be more toxic to weeviia than was any other cutotunce.. The insacticidul action of hexacblorocyclohexane. benzene hexachioride, or 666 18 due to the gamma isomer. wh ch rfiprescnts 10-12% of the crude material. According to Jlafle (2) less than one part of the gamma isomor will kill groin weevils as effect- ively us fifteen narto of D. D. To. when mixad with the grain. One theory of the insecticidal mechanism is that the structure of gamma icomcr 13 similar to inositoi, and may be absorbed from outside of tho insect, distritutod through- out so;e nortion of the organism to the cells, where a vitwl reaction is blocked, anfi th organism dies. Hexachlorecyclchexano is Drenarud by Dgfiflinfi chlorine gas through bantene i Luminated Ky ultra-violet lights (5). The structure of only the beta is mor has been deter incd, ("‘3 ‘4 J ‘55 I but theisomors ore nrobnbiy similar in structure t: of hexuhydroxycyclohexnno (inocitol) (5). The nurnoce of this work is to otudy the adsorotion isotherms of the alpha, gamma, and deitn isomers of hexa- chiorocyclonexane, with the View of checking and extending Gilbert's (4) work, and examining tho iootbermo at higher concentrations.' Also, some work was done on tho chromo- toaranhic separation of mixtures of tre isomers naing Sauor'a (5) method. The last hart of this work is con- cerned with evidence of tho instability of the gamma iso- mer, and a discussion of the poasibiiity of conversion from this isomer to tho ainha and delta Forms. I ‘l. , I ‘-o 4 " l i .1 VL'I... .J‘I, ‘ Lean n0 - re‘ rah and 30.. ctuformiag ta A. J. a. gtngiris. Alumina - aluminum Co. at L: erion t-xc griia, Cc-fifln was: activate eat, 7777;457:737. f'c‘)!‘ “5:23.22" ‘t"1"-u:"':e “-7.52”: {3.31 com- 03 in a QSEJICitCP main: CELCEJT czisvifla a flryin9 a;nnto "1 .3": 33.3131 :.(7(‘ c- 324 513:0“1‘1‘ t. :Ee-uf"-3.€:".;.l } (:‘-;":i.:7€§vl"f-‘I- 1:35.: tn‘! .2. Ci. _. ..;LS?‘.:,:'IJ'.;”(7€3. Ffix::c3:3.r:~rwcy .1~>!:I’-?x.u.:m Isazrar‘g (.--.1733;f9 =.i'1‘--' "mm. 363‘ ind bu T13 urn J?0Wicu1 bivigigu, fiv;d .‘~~.'......r3; 5.11332"; 11;}..‘1 “737:1". if: Z'iui‘fi., T153114?'~.-"‘>:.‘t. '7'- 7‘1. . ‘6‘! E‘friti‘.) - _.,‘ '£($t.? 2:..“" ?(3’? - I}: k: f“ . Pi ‘ fir fan?! fluent:fixt'LV-iiv- {’mté=l“’iifl L _‘ J .3 #5 U "a. «1‘ fi ‘.. 7;: 1|? 9" o. J .1 I‘ 2" n . ... 7 . ... “ ., . 1., . .,-. ° ‘\ .. ucaw¢n ;21’v~r~i ,Wrfltznw.utfi~atuv. sJ-a Wis Lied. “"- -; .‘Ww‘ ..,_ m 0' . '1 w- '7 " 7 .I .7 " as" ’9;'.-. .' 773’.) h'v... ." i;u.,'\ 2... $123.33 :3 7} g .l L. ”u u )sl.}.&.cj.' 4 o". \ .a \. r. h. L . L,‘ A J “1 l I ' ‘6 L. " J ‘ .,. ‘ r v ya] I p. ' 3‘ .aa. . ‘- -\ ‘. ~ ' -. L.d, rm. 3m Pbil?~,u) twig Jfliu wwn usa »‘.. Vt- O .. .“-~ .“_ I v. » .-..~'n. I ; -n._' ‘. ’.‘ . - . “QC .‘ - r ~1-.‘- ESE) 7. -7£.?‘7-}:t‘127~--4.v"72 U 1 ‘5 5.7Ir “(in .» u..:.'f'$.%‘.l £11. “ L3 5: 1" ELL}: U 11337 . “)7 P Hp 325131.511; The method used for collecting udeorotion dove fol- lows: A saturated solution of each of the «are isomers in hexane was made with an excess of the isomer oresent, suspended in a constant temoerature both For at n ure, 1hxn decanted off. The saturated solution thue otteined was diluted with three milliliters of hexane to 500 milliliters of solution to orevcnt any solid from ecnarating out due to evaporation of the hexane. A weiéhed amount of alumina was oiaced in a weighed Creex enpoule, then 5 to 7 milliiiters or tne orepured soi- ution was nlcced into this amnouie and it was sealed oy on oxy;en torch unfi weighed to determine the weight of solu- tion. at the same time a ocrtion 0’ this solution was placed in c weighed 10 ml. are uated flask, weighed, and analyzed on the infrared enectroohotometor. (This was a control sample. from which the correct concentration of eumoie pieced in the amooule woe detaroined.) The cmnoule was then placed in an under water stirrer and revolved for 72 hours in a constaat tomoerature bath at 2A. 03. The amooulo was then broken coon, and the supernatant eoiution filtered through r0. 1 achleee fiLtcr oaoer into u weighed 10 ml. graduated flank, stococred Lad immediateiy wci;tod to prevent any 1053 due to evanoration. The calvent was then evauoreted, the residue woo taken no in 10 mi. of carbon difiulfide, and analyzed hf the beckmen IR-Q Infrared Spectroohotomotor. §y Conn ring the amount of isomer after ab- adsornticn and before adsorption, the amount adsorbed could be determined. The method of snulyzin; the sunnies was that doveloned by Banach (l), and subsequently used ty Slur (5). The mathematical onersti no used to derive the adsorption hits were those used by Gilbert (A). To obtain adsorption data by using a chromatoarsnhic column. the Following, method was used: The chromLtOgrsohic column was premered by first piecing u plug of cotton in the constricted end of an 8" x 5" tube. Lluminn was placed in this column. a little at n time. and tanned down with a n 1___ n x g was obtained. glass rod. until an alumina column 6 To nrovide s canstnnt flow from the tune, a vacuum was spoiled at the lower end by means of a water acnirstor. The column was wot by a solution of one hurt hoxune and one hart csrbcn disulrids, than the solution of comer mixture dis- solved in the solvent was poured through. To remove the last traces of isomer from the column more soqunt was poured through. All liquid coming free the column (except the first wash solvent) was col.ected in 25 n-. arsduatsd flasks, evseorstod, and the residue token up in carbon disulfide and analyzed by the Bockmsn IR-Q. Two chromatogrsnhic analyses were made with the germ isomer alone, end the dstn are given on page ll. fil" .t ‘l. Q1. :1 '1) VL L. J. gdsorntion d§+n tables The following data are recorded, where: w - grams of isomer in confisct with m grams of alumina. y - grams of isomer left in saiution at the equilibrium point. x - grams of isomer adsorbed by m grams of adsorben Q m ~ grams of stumina. m/w . grams of uluminn par gram of isomer. -conc. - equilibrium concentration in grams of isomer per gram of solvsnt. x/m - amount of isomer adsorbed oer gram of adscrbent. while plotting the sdsorrtiun isothsrms for the sam- piss. it was observed that some of tho uoints on the curves were non-reproducible. The grams of aLumins per gnam of isomer for these samolss, 1.8., m/w, shotofi tkst these oointa reoressnt a lower uni unpor limit of alumina con- centration. No m/w Vulufis for gamma are given boosuse all the gamma points fall along the ideal curve. The non-repro- ducible samples have an asterisk to the right of tho m/w values. w grams 075700 0.0920 0.0880 0.0012 0.0904 0.1041 0.0913 0.1014 000970 0 o O 3 '3 O.C8l2 0 . C704 O .():T:- 52 0.0971 0.0531 0.0320 0.0835 0.0873 0.0841 0.0913 0.0970 0 .C’75O 0.0743 0.0559 0.058 0.0233 0.0539 sisszniisn_2wi Y grams 0 00700 0.0933 0.0977 0.0599 0.0810 0.0090 0.0974 0 .089 '2‘) 0.0547 0.0725 0 no '33!" 0.0630 0.0545 0.0393 0.0533 0.0423 $00372 000499 0.0504 0.0194 0 .089 :5 0.0234 0.0240 0.0280 0.0127 0.0223 0.0008 0.000 x grams 0.0000 -0 o 001 3 -0.0097 0.0013 0.0094 ~0.0027 0.0015 0.0040 0.0030 0.00% 0.0087 0.0130 0.0222 0.0025 0.0105 0.0202 0.0412 0.0305 0.0004 0.0537 0.0719 0.0000 0 o 05]- 13 0.0470 0.0378 .0410 0.0“}? 0.0235 s x a," Job-.1339 0 f' the: m {Pd {.6 1 6 0.0035 0 .03. 3".) 0.02287 0.0328 0.0533 0.0729 0.01:0 0.00h4 0.1153 0.0328 0.29C5 0.3931 0.2571 0.3398 0.4305 0.3913 0.7887 0.1155 O 07 JAI- 0.8927 0.9074 0033.37 1.1133 0.1029 1.f¥fl19 alpha Iyomfir n/w EZI‘J’IE 8/ tram J o.0§;0. 0.5350« 0.5095“ 00700.03“ 0.7.395 0.0;23 1.181 1.302 1.002 2.432 5.410 4.100 4.425 4.870 5.515 5.730 00101 8.310 "3 1791': a.) n U.) 9.252 10.19 12.01‘1 13.79“ 14.29 1 1.515% 23.02 t) (3/ 2:.) o (“:2 X /ID EthS/ cm LL- _ O o {.5000 ‘0 o if 370 O 003‘” ) O 017 35 I”. ‘N' ' .I‘ -‘-4-' .(J'j \) 0.0225 0.0076 0.0500 (1.1030 0.0549 0.07154 0.1070 0.0720 0.0705 0.0095 0.0779 0.0758 0.0739 0.0912 0 .0 )90 O .0 £7 5 0.0587 0.0410 0 o 0349 0.0391 0 0035‘" 0.0347 C. NC 0 L PH. Iii/f ."—- '94“; 1 fix - ' u : i . .l 0.0105 0.0145 0.0145 0 0009 J 0.012% 0 001.354 0.013: 0.0137 0.0131 0.0:05 0.0118 0.0113 0.0037 0.0035 0 .C‘O J7 0.0085 0.0074 0.00? J 0.0055 0.0040 0.0131 0.0043 0.0049 0.0048 0.002 0.0008 0.0000 001019 0.1710 Oil-3&9 O a l 3 JO 0 .1009 0.1245 (3.1570 0.1550 0.1082 0.1047 0.1120 0.1085 1022221190,R&12_9t_119-010m4 Y $470 -001 01.1 00143) 001440 001454 0.1131 0.0077 0.0412 0.0078 0.1237 0.1.21.5 0.1552 0. i 0.135 0.1105 0.1124 00030-4 0.0743 0.0311 00L]. )1 0.00128 0.0233 0.023732 -511 Li&' W X LEETQ 0.0043 0. 005 S O. O 797 0.0038 0.0157 0.0407 0007JS 0.1371 .0993 0.0038 OoCEl} (3 .(V‘\ 7 0.0095 000%.84 0. 04); 0. 0485 0. 0902 0127 0.1195 .3921 0.0979 000399 O o C 1‘ “)4 [[0 m 0.074.}. 000952 0.0540 0.1092 0.2379 0.4505 0.7779 1.0149 0.0520 0.1138 0.0729 O.(‘UC’I‘ O. 441/30 0.2750 0.03.115 Coil-70835 M48 0:32:29 00917.} ‘1.2072 G C :) :5_|,7 0.577“ Isomer ix/m .._0:’9 .C75'} .C19 0.07::4 0.1433 0.179J 0010573 0.17;"' c. 9939 0.0731 0.1790 0.09.233 0.0’3‘35 O o '1"? Q9 0.1700 0.1150 0.1300 00.1 )i-‘IG 0.1420 0. .I'i' 0:- 0.(li L1 0.1304.) p o 1:30 )FJC1CL' 3"”4» h..." ". uno- -‘I: . r... 1;.-- C'\' no. ,3 CV“ U OCLZ‘U 0.-C 233 O. 0234 0.0244 0."223 0.0;?) 0.0.25 *1 .C\r‘_):3 0.0033 0.0245 0.0210 0.0239 0.0233 0.0222 0.0105 0.0160 0.0095 0.0.20 0.0035 0.002; 0.0012 0.0040 0.0051 ’1'?" 7 0 1-« I. 4""- ~ fi’“ -;-'. ‘ ~. ‘1 s.- L\.*‘ EV P’IU tu‘ ‘ u _..- 10V? . . . ;.'J | " if ,A - ‘3 . ,‘ I O . -.,......- “Mac. _.8...'.._...)"§ ,.. g. .-r\ ¢ ‘¢~:1"..I'L~¢' ‘rt‘ 1..., ‘- ‘ 4......wv. 5-..... —-—_..-'.l on. '. . v r -r cu -—- I- i l . ~ J M; . v.” :-«~ . r‘ :h - a. .2...” ... . .-._,-..1 - £- v.,”. A“ n O. J‘. v: ~ ‘ N - ’ P.‘ ~O'T- r]; I; . 1 A 1., at , . 1 - . .-~. . -. as r .—. v: 93 A ‘ ‘J’ . ‘ l ,4 I " I ' 1"" . : \.§ . -. I, 1‘ 1" - 'fi . . a |.’. f . "I". M. " 1’. . “ .I _ q \— O ‘ ‘ ' ’ on. 1 u.“ ,. ...'9 ,.. . Q » ._(7 u ’. \‘. I“) J . . .' c .9. l. . I‘ \l t '1" 1: 1": hi 1, .k , ‘ - I“ 5- . v‘ . .-' . ‘ , .(.--. F . : ~~. \ / 0 our... 9 ‘ o .-..a. ~ n:- ' ‘3 \ ‘3 . ‘1 o *' ’- o - 1* c r ‘ I. u ’ ‘ . f {.1 V, '7 ' (fi' . ' 7 0 ~.' ' . l~ ,.- u. :v' ") b" v: \q.‘ . '\ ”A ‘va 0‘ f' ‘ 1. J a} o .A c _ ‘ l n - t a ‘L .24 doouovdo-oooooto ‘ a." L '1» l i wt ',."~.,\"V" . 'lt‘ :9 {-3 ..-} 1-; I i .4 K.“ -J '.J .adsorbent p H o w //,/1F‘ 8 30.05 A c. / o a D d ‘1 ‘P ‘3000 Q 0.000 0.305 0.Cl0 0.015 Equilibrium conc. — s. isomer/5. solvent Fig. 1 Adsorption isotherm of pure alpha isomer of hexschlorocyclohexane a 0.15 c 8 L. o O 3 . 0.10 to \\ U B m 8 u 0.05 x u) I s \\ “ L 0.0C c.300 0.005 0.010 0.015 0.020 Equilibrium conc. - 8. isomer/g. solvent Fig. 2 Adsorption isotherm of pure delta isomer of hexachlorocyclohexane 9 8 é x/m - 5. adsorbed/5. adsorbent 010 ./H’ ' o 005 000 0.000 0.005 0.010 0.015 0.020 0.025 Equilibrium cone. - 8. isomer/5. solvent Fig. 3 Adsorption isotherm of pure gamma isomer of hexschlorocyclohexane Sens'etiqn curve? of isomers In order to vsriPy Jour‘s (5) work with I order of elution of isomers in a mixture, were senarsted chromfitogranhically. and verify his order of elution, next, anfi delta romaining on the column. corded for chromatograohis analysis of t slone, Table 4. Figure 4: Isomer alpha delta gamma "igure 5: alpha delta gamma Silt??? pl 8 mg. L‘- 229 341 207.5 230.h Hf bra J o 3: ogard to a few mixtures The results follow, 1.0., aloha first. \ 1'20 Eluted DUPB CDC-Q O 0CDU: gamma hata is ulso re- ma isomer Eluted mixed WJ 207.5 0.0 272.5 5'! vi {1.} L‘ CDC C (DOC) tui L: I! 80 milligrams 2., i I V 2 4 6 8 10 12 No. of 25 m1. fractions containing hexschlorocyclobexans Fig. 4 (1) Alpha Isomer (2) Gamma Isomer lilligrtll / / 7 9 ll 3 5 No. of 25 m1. fractions containing hexachlorocyclohexsno Pig. 5 (1) Alpha loo-er (2) Gamma Isomor TS? B 4 Chromatogrsohic analysis of the gamma isomer of hexachlorocyclohexflne. .1. Fraction gr as of grams of grnms of _..__...--....._ fish». .99.? be... 1......1-.. JuntrOl 000 (2.0 0.1.5130 l 0.0 0.0 0.0850 2 0.0 0.0 003775 4 0.0 0.0 Oglifiiéb 5 0.0 0.0 0.1400 6 0.0 0.0 0.1173 7 ‘0.0 0.0 0.0975 8 0.0 0.0 0.0450 9 0.0 0.0 0.030 10 0.0 0.0 0.0225 11 0.0 0.0 0.0175 12 0.0 0.0 0.0150 13 0.0 0.0 0.0100 14 0.0 0.0 0.0 15 0.0 0.0 0.0 1'5 0.0 000 9.0 original sample...... 1.6158 g; l 0.0 0.0 0.0025 2 0.0 0.0 0.0075 3 0.0 0.0 0.0150 4 0.0 0.0 0.2050 5 0.0 0.0 0.1475 6 0.0 0.0 O.C800 7 0.0 0.0 0.1125 8 ‘0.0 0.0 0.0075 9 0.0 0.0 0.0400 11 0.0 ' 0.0 0.0350' 13 '0.0 0.0 0.0150 14 -c.o 0.0 0.00a5 15 0.0 0.0 0.0L75 17 0-0 0.0 £i::_-..C‘:é:2:5 ‘\ 1 .h""‘: M,‘ 3'- O.LJ\ICI _) (rifinfll Bumble...... 0.3393 Cunt” c --' -.vcr£‘. 1-3 t. in. f._2 The cvn‘rol samnlaa of gamma isomer Showed 100% 3% as did Lhe chrom.t032t~hic ans lyses of {"ma isom3r s.lono, whereas the equiiitrium samples showed the foliowing analyses: 2.22.... r: .5 Sample .2lnns 1302? :r delta isomer guw.m2 isomer _. Wt. 4"” ()th j.) Wt} J l 0. 0.1.4 905 Doc. )3 4.505 0.1.4.]. 7500 2 0.003 2.4 0.000 0.0 0.123 97.5 3 0.004 J05 O. C'()O 0.0 00115 9.).5 4 0.013 8.7 0.083' 15.4 0.115 75.9 5 0.007 503 0.013 9.9 0.111 84.8 7 0.003 4.1 0.014 18.9 0.057 77.0 3 0.000 0.0 0.012' 30.3 0.027 09.2 9 0.000 0.0 0.011 22.5 0.033 77.5 10 0.01 5.7 0.020' 15.8 0.090 75.5 11 0.005 5.3 0.010 9.5 0.033 54.5 12 0.025 15.1 0.048' 23.9 0.093 53.0 13 0.008 ' 7.0 0.017 14.9 0.039 73.1 14 0.005 5.7 0.015 14.2 0.005 80.1 17 0.000 0.0 0.0C7 28.5 0.024 77.4 .18 0000.1 200 0.007 L403 0001*]- {'30 19 0.002 7.4 0.022 40.7 0.024 51.9 21 0.00 14.} 0.004 57.1 0.002 AB.0 22 0.002 7.7 0.010 38.5 0.024 53.8 2) 0.000 0.0 0.007 29.2 0.017 70.8 171.501.55.512: N [urn 19;. :34? 2." 1390123333 The adsorption curves, Figures 1, 2 and 3 verify Gilbert's (4) wurk up to his concentr: tion 11m its The curves represantcd hare hzva higher x/m vu.u05 nredumgbly becuun2 o? a higher eguilibrium temperature For 011b0rt'3 work. vein; 8m3;10: umounfis 0? atumina, the":by izdcr: asing the cancefitration a? isonzr in soluti3n, it wig 902sible to anew nevrtiva adaornLien in each 0323. fhis zher omenon ..r is deacribed by Lewis and 313103 (7) :GL&t& that if the ” u2rbau than tha salute, me 5:41: solvant 12 more hi3h Ly 2 Q tiva “do rp..i;.n 1:3 003' swerved :lt haugh true u.L‘"BC.‘.L.1.IIE’JLLJ still be considerable. Tor dilute concentrations, 7r0undlich'a equaticn is almost 8:10 2, but as the canoantrmtion in- 0103302, the adsorntiun b002300 ;e~:u than that indicated. Cumm3 ' m::r finnvevai n :15 It. should be mated that. tin: adscr 1.1011 133’ hm m 7‘0: the gfing 1.0.: 13 Ccnsidarably highs: thfig it should be accerding to chromatographic results. Thin may 03 0:0101n- ed by rarembaring that besides adsorption or the gamma iso- mar 1‘20: 0 seems to b8 0 naiflerttlo c nvcr813n 0” this ino- mer into thw alpha and delta isamars, Table 5. although there aspears to ba 20 ru;e as to ‘he amount of alpha and daita idcrnera formed fr.m thz gumn.u iscmer in cannection with tr: amount of adsorbent 02 concentrati;n 0? Solution, it can dafiniteiy be 3‘ut0d that the canvsrnien is fffectod ti-.Y time and c ntact of a unina. Lone of the c ntrcl samnles "I VI .'.l r, ShOWQd Siflna 0f 0 nvorslon nor did any Spmfilcfi of M‘mma 1aomer a;on¢ on a ChromfitOdrflhhic coiumn (wage ll). ;ow- ever. after allowln, tLe fiamolem to IBRCh equ1;1vr1um in Contact “lth alumina the Large amounts of converfilon noted occurred. This inataVility may be the cutoume of several of the preportiea of the gamma isomer. as hointed out by fiaur (5) structures of greatest aymmetry tend to have g-eater heats of vaoorizution, indicating {pewter intermolaculur attr.c- tion. Therefore, tho isomor with the greateat aymmatry would tend to be afiaorbed th; most. 39th the ainho and damua isomora are adaorbed the least, and so hava boon tentatively asshned the 1.2.4 or 1.3 fcma of structure (5). The recordad melting voint of the ago a looner, 112-112.8°3. which is the lowest of the isomers, indicates lees mo-ecu- lar attraction than the other isomers. Lind, Hobbs and Cross (8). f und the electric moments of the loomera in benzene to be: aloha iwnmer 2.12-2.gau gamma 152m r 2 delta isomer 2.22-2.93; Beta rad, as expected because 0? 1&8 symmetry, 0 moment. (It has been found by other loveetlgatora (8) that delta may huva a moment of O.) This data indicates that gamma has the hi heat olaoLrlc mom nt, indicating the least symmetrical structure. lo 20 3. 3'1". Jr The order of adsorption by activated alumina o? haxa- chlorocy o3oh3>z3na 13omers is delta the most stror 51y adsorbed, 83333 the max t strum; st, and almha 33 least atronnly 3rlsozbedo at the higher ccncer tratl‘na o” iaomzr her gram of solvent negative adsormtion occurs. Th3 53333 isomar while in c ntact with a‘umina in a c" ‘ "3.11 if! ion of hexane 13 unst able and forms the alwhu and delta isomers. l. m a ‘V J. (‘4. A " Y“ .' ”1"" 9.“, f...) "").’!.r:; 7‘ -’ ‘J""'“l“" ' ' ‘0' 3.1033}. 'MU-b «duo! 3.4.3. .19 r-'~~‘!’9o 1" -. 1 _‘ .. m! .s __ ,9 r ‘ 3 . .2‘5 ~ I't‘tf.‘ “'"U‘Ol . 3434,43,; “"“3‘ “V313" 4t. LI" .0 “14;. 3 NIH“. 4.." J "#de (194?). u-( o :- .‘ 'Q‘at. . '1'.I- -‘ V. -y.‘ ‘--"\ _-‘-—_§-. .- .‘19‘ ‘v- .I. UL‘LbItO M. "'2 “"vh‘ir‘wh‘ «Maw: 'a.;.L;U\;.‘J’ 2.. u. glawd 43 (L923). .. _ I,- ' ' :3. - ,P. , -. "I .. " 4-; ' ., ... 'fi‘x‘ v my“, ,3. ,.- ' ‘3. 1 (N- ,4: “3‘5““ . 'l. I O. 1' $37.1...1-L “batik: ‘V‘Ugé ,“', ‘3', £15.: . ;_".‘. 'L- I.’~’ (J."z}9) . E 'l 3 r ‘r ‘ .. - '5‘ if‘ q I: 1 fl ’ 1 '9‘ j. 3‘! $.--¥V.Lt,$. 4, a .j-f.. t 5.2.... (_ a ,- I. '0 ' - _.., “‘4‘, J, . . .4. O «c v x O ' __ v j a- .) ‘ j 9 ‘ . " I J " ‘. . ‘ 5 l. 1 " . ‘Q ‘ '_ ~'-. - .- - _'—'- " ’fl . 'u "3' ‘- '. L1 VIL‘L). ", . ‘a .. 4.1‘.;.Al: 5135... . ..-._- . {voila} "rti‘d ; ,AJ. 5 . \1 . ‘ ‘-‘lijl‘b9tx int], !-,'~..AO; 3;. —l. 4‘._1-, 1.: .. ~ 0 . '3. . x.- 1 a“. 1: .1 ~‘ k!:‘.w":"atz u L" -' ~i'«';h.t.c {fit-51 £11.15; "5 33 1’}‘.'i“'-.i¥fi3 . ' Mute)? '31.»).3. i "If“: ilk-“:1 h]. ‘l. . ‘m' H91 9‘ H‘Y'“ C‘ .{\:") -5...)qu u. I‘LI') k ”BERT"? CT? SCTETJ‘J’S '3’ T773 L..I31C.’L::"£A:TD DELTA IS~“"“S 50F V”XAC'quO"Y"LU”" TE, ATV IfiSTAEIL TY OF T?“ GA? A ISCULR by P:1ulF.3iofold, 1951 The compoun6 raincoloroovcioroznno was first rrepar06 by Forodny in 13 ,. nnvl «p to t s Sflute. fivnr 0.finito isomoric forms hav' boon isolateF, of which one. tho canua isonor, was fauna to be toyic to insects. . T13 purpose of this invnatigntion,has boon to establish RPSOrjtion isot1“r13 of three isoflors of hexabh.orocyclohexane on alumina, to confirn certain chromatographic adsorption 6336133, an6 to proonnt ovi60nce for instability of the finn“a isomer when in contact with tho fiflSCrC e nt n;nninn. To obtain the ndsorytion isotkorms, about five milliliters of a sli Zitly diluto6 noxzne solution of the 330 or was rloood n a weijnnéc orox a“'; 0119 no'fni.‘v~ a knoqufimount of alumina. The nnponlo was 333136, and the ornct avount of solution was obtained by woifihinn. Simultaneously, a portion of this solution was adaed to a woixho6 flasr, an? its woi~wt latrrrinoé This was a control Q sanplo. from unicb tho concentrotion beforo equilibrium was deter- mined. The ampoalo was pbacod nn6or vat"? at 34. 9 00., revolved for vonty—two hours. then brchn ornn and the solution filtered and weighed. The solvent in ho equilibrium niftnre, on well as in the ontrol sample, was than oVnporatpd, the res d"e tn”on no in carbon 6isu7fide, nn6 annlyzofi in the Eocfimon IR-3 Spnctrophotomoter. 3y c03norinr the amount of isomor boforo and nftor adsorption, the amount adsorbed was dotarminoi. To obtain the isotherms. the amount of isoopr adsorbod For rrnn of adsorbnnt was plotted arainst thP 1.3—- J C ocuil isriun concontration. To confirm rotorto6 orfivrs of tie {souors on aluminn, a 6" I L" 311.1236er (‘1'.I‘fi’l"t0ff“"f"i?’llfi hols-inn 2'33 1.1306. A voow'n was 63:31 .‘ed at tzls lowrr or 6 of tbo column to Proc‘6e a constant flow.' Tbis colun. Ln.: wet b" a solwflt on of one n’rt 1(3350 nn6 ona fiart carbon 6isulfido, thsn the isomsr so l'tin:t was toured trrcugb, followed by successive anoints of solvent to remove traces of isomers from the column. Twenty—five milliliter fractions were ccllectnd, tho solvsnt was ovarorotsl. and tho rssi6ue was toren up in carbon disulfido n6 or: 266 in the -sC‘"3; 13-2. Tbn ants shows the orJor of adsorption to co delta th no o