THE USE OF ESTER FRACTIONS IN DE- TERMINING THE PURITY OF FATS BY CARL BECKER THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE TN CHEMICAL ENGINEERING COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1922 Digitized by the Internet Archive in 2015 https://archive.org/details/useofesterfractiOObeck / S22 B3S UNIVERSITY OF ILLINOIS __Llay__8^ i 92 _ 2 ._ THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Carl Becker ENTITLED__Tli9__Uj3.8-jDf--EL3.tiai2-£r^c4>.i-o»it--iTi-IIai.Qrjiiinin^__tha. _?_? _ IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF BajchaLar — oi'--Sc.i32ac-e--in._CLi.e.Piica.l — Sn-gi^^ie-e-rA-n-e^ Instructor in Charge HEAD OF DEPARTMENT OF CHEMISTRY 3 .- Vf ' **' W^" "" 1 ^ •„ s.'- i*W»j . ■'w-.V- 's ^,= ,, „ ■ 210V1UJI no yTI 8 J? 3 V|V'y ■ * '■ -i 3:,3 ' in n?'V •i til .:^ i?? « V . V. 'ft' t □ '' - T V- ■'*»•;’« . ’'m- , , I, a , ..;=’■■'•■ f , ■ ■■ . ir Xii ’ t- . i-- 1 ‘ , m # 3 *" ' ._ » ■ "• ftif 1 1 B Ci _ jii. .-tlu' i-i '.ia « /" I .»*«. MiSX..A%Wn& '..'^r-:j .•t-iv - * I r f riBir'p ' ■J ■ ' 5 : '•■■ V '^‘ - JLv '-' * ^ " M , 4 *'; -•i Th©- writer wishes to express his;appre..- ciation to Ur, GUD.Beal fort? the suggesi»ion of: this:; method! and for? the helpfull guid- ance which made its* solutioaipossible . A .. . \ 'fh » t l^p ■ ^ «v.'.:/-s;. . 1 1, ■ ., “ -V->>ir':s »■'!-' rr:.)i H' >f-‘ "(' } 1 • A r- :ri ''■ 4 • tV- ' ' . Wr • i- ' ■“ • '■ ■'''' ^ •■ *-4 I """ ' ' •*■ ' . V.i ; ■ ■ ' ■; :; -'mm ' 0 *’v» ^ 'if ;■, ' ^ ■ 'f'" ♦ -*\!j Ik • . *^^ ' . " y f ' ■ . H., * ; « . ii-v ■f^A. " S| -■'4 ■ I-. '■„ ' '- -jn .v'*i J-- ilf S >p 4 ■ -■ • .... ,i' •'*" :, ^ f - - ■ ' 1 ^. ■'■ ,.ii* % l-x. ? -VlT' « ip^'W' . ■ ’S ... ..«.'*4'.;’ < 1( :-^ ;i»<,-.-ir ■■' - «' ' ' ‘?fs!Pf»F l^ . Trf.’ i of Contents I IntrocLuction. II Method’ (si) Conjjtints for Cotton Seed OIX, Linseed Oil, and- Soy Be An Oil . (b) Muiterition Tests, III A^psiratus and Details IV Solutions V Conclusion VI B1 b li o^u ^hy 1 . Ti^Use of Ester Fra.ctions in Determining Tile P.urity of Fats. I Introduction. It is obvious that fhere is an urgent need for a short, reliable method for the detection of adultei*ants in fats and oils. There are thousands of manufacturing concerns that use great quantities of various fats and oils without any definite information as to their purity. Of course, if It were known that a certain oil, say olive oil, was packed and shipped directly from the olive orchard, then it would be safe to say that the oil was pure. But there have been so many cases and types of oil and fat adulteration, that a concern using any quantity of oil cugiit to take avery precaution to determine its pur- ity . At present the methods of testing oils are by means of the Iodine Humber, So.pcnif ication Humber, Index of Refraction, and other similar physical and chendcal constants, or by repeated fractional crystallization of the acids as a qualitative measure. They are not of much value, hov/ever, because an oil, by the use of two adulter- ants, can be adulterated so that it will e:±iiblt the same balanced physical and chemical properties as the pure oil. For example, an oil like olive oil (Iodine Humber 90) can be adulterated with two cheap oils, one having a higher iodine number and the other a lov/er iodine num^er than 90 . By regulating the proportions in which they ar® added, an if ,r jgFaiT--- ii i /■ i; ’ i . ■ K-Sy)^ ''¥i ’ V' '■■ . ' **'''^ t ^-■ 4 U'iC.r ^ 1 * % 4 * !Vn^HB :.*1 ’ ' atfH . --r . ■*^ '.'W l '3 W' , «^f •• rjiUA-i! ^^ 7^. 3 yP • ' ■'■ ^’’ • ■/ l’' . r’'" I'l™ ., ’,■'. .» , . ■"' ,,'.. 1 - • ■■ •g. ;•* -cij tr,i 4 - 4 ^-' ^?.•J^rfiS► &l 4- 2 ' j 0 ^' fli. i' ^ . 4uC^;s*-J .Dultf 15P ,JiW:9Lj&h ' <«»X-cr0;t£#*^ 14 J " j ’'’V ' - ,S9 . , "^Klr ‘ H - ' V ■ • ' • ' ’ ' T ■ ' > \ •JSS " 1 V ^ - '^ ‘ ■ --■ ■ ^ Q ‘'i ^ W|i. «a*“ ’ ' jff \ t ^ ■.' -t V i- ,.,.ri ^-'' ^ D •^'^Biis -li' f --‘ -**' .♦ti!k ,r «<«uiaosJQ*. '. ^ ij* *^l^‘fc4iin ^ .^*’ • • /» ■•. - ^ '- X •? ’ft -i ss- ; liX ??■ .: ' ■<*' •' ^ ■ * ' y' ^ ^ ‘•. r •: . jfr< ■ ■•* ♦ Equiil Volume Fractions of Cotton Seed Oil--Cont 6 Table 4. Second Run Fraction I II III IV V lod , No . 81.0 95 .2 111.0 122.9 133.9 Sap . No. 198 .0 194.9 193 .0 191.3 189 .0 Index Ref . 1 .4543 1.4571 1.4583 1 .4594 1.46 Pres . mm. 26 .0 - - - - T emp . ^ C . -216 216 -20 220-22 222-23 223-50 Table 5 . P_ure Soy Bean Oil Equal Volume Fractions First Run Fraction I II III IV V I od . No . 112 .0 124 .0 136 .0 144.5 136 .3 Sap . No. 192 .0 191.0 190 .0 189 .5 139 .0 Index Ref . 1 .4566 1 .4585 1 .4594 1 .460 1 .465 Pre s . mm . 17 .0 - - - - T emp . ® C . -210 210 -13 213-14.5 214 .5 -17 217 -25 Table 6 . Second Run Fraction I II III IV V lod. No. 113.0 124 .7 134.2 143.9 135 .6 Sap . No . 195 .0 191.6 190 .6 190 .0 189 .0 Index . Ref . 1 .4570 1 .4588 1 .4595 1.4596 1 .4648 Pres . mm . 17 .0 - - - - T emp . ® C . -211 211-12 212 -13 .5 213 .5-18 218 -24 -'T ■ 7,. Pure Linseed Oil Equal Volume Fractions Table 7 . Fraction I First Run II III IV V lod. No. 166 .0 178 .0 185 .0 192 .1 191.0 Sap , No. 195 .0 L83 .5 181 .5 178 .5 173 .0 Index Ref . 1.465 1 .4652 1 .4665^ 1 .4667 1.4675 Pres . mn . 14 .0 - - - - T emp . C . -209 209 -10 210-11 211-12 212-14 Table 8 . Fraction I Second Run II III IV V lod . No . 166 .5 173 .5 184.8 192 .4 191.1 Sap . No. 193 .6 184.0 132 .0 178 .0 173.8 Index Ref . 1 .465 1 .4653 1 .466 1,4869 1 .4678 Pres . mm . ‘ 14.0 - - - - Temp . ® C . -208 206-10 210-11 211-12 212 -16 Table 9 . Fraction 25? Cotton I Seed Oil a: II nd 75? Linseed Oil III IV V lod . No . 142 .8 157 .2 164.4 177 .4 178.8 Sap . No. 194 .5 186 .0 134.2 180 .2 177 .0 Index Ref . 1 .46 o5 1 .462 1 .464 1.465 1.466 Pres . nm . 20 .0 - - - - Temp C . -215 215-16 216 -17 217-18 218-24 8 5^ Gotten Seed Oil and 96^ Linseed Oil Table 10. Fraction I II III IV V lod . Ko . 161.8 173.2 178.8 188 .2 189 .0 Sap . No, 193.9 184.5 182 .9 179 .0 174.6 Index Ref . 1.4627V 1 .4640 1.4650 1 .4660 1 .4670 Pres . mm . 18 .0 - - - - _ Temp C . -214 214-16 216-17? 217 -18 218 -25 2^ Cotton Seed Oil and 98^ Linseed Oil Table 11. Fraction I II III IV V lod. No. 16 3 .0 175 .2 180 .9 190 .3 190 .6 Sap .No. 193 .7 164 .4 182 .9 179 .0 174 .6 Index Ref . 1 .4635 1 .4647 1 .4655 1 .4664 1 .4675 Pres . mm . 18 .0 - - — . Temp .° C . -214 214-16 216 -18 216-19 219 -24 5^ Linseed Oil and 95$^ Cotton Seed Oil Table 12. Fraction I II III IV V lod. No. 86 .0 100.6 116 .4 127 .3 137 .2 Sap . No . 196 .4 193 .1 192 .0 190 .2 189 .9 Index Ref , 1 .4560 1 .4589 1.4-596 1 .4619, 1.4641 Pres . mm . 16 .0 - — — — • Temp C . -208 208-12 212-14 214-15 215 -20 A ’■ • , « ,. '‘^- " BS , , Lia, 4,10 .1 t' !'■ ^r lii ' ] B V !( I'tt ’ * fwS'*“ s. mi ' a* dtjL ii' n o.ierti; “O, ->i otat*. X ■3i >a l'; . 'X (j 59 >. X o^ai*. X jrs-^fS 59 ■'^1. , ^ 01 - rxii s 'VX- SIS ax- i ixi 0 .xax a.?;^ I .jjK TS^i^.I 0 . i in V ^• :A ■'K *j* .* ^Ai 2 .® 0 ax .a 9id»t. "'&• I . ^ -aoXX^rin^ ©5. ± . la ' ± i''/. ^ ^ e. oaf gvV_ - . 8. sat «'• lit'Jt;- s.-ftW .o4 ?89S.I '^’ aeoi-.x, ' aiJiX ■ ' ^. #5)- ,■ . ** 5i' - ' t3f A ^ ^ ^0. KX < 5^: ,gi'!. . - .. , Hi E'-5' - ' ;■’ #^ t m X !( IT-' Q ■ ..^ . E'-5 -- ^ £t 0 2 «eB i*i‘A XiO t; ' tC ^ '’' ffi W, - • ■ ’B »I. ■• J ' . ■ .-?• a. ■' ’V« J^ is . SX ^XUaT ; #x m/ 4 « j-i?. 'v ■ t ' \, ^ s.atx' ■ ' ' 0, aa oB ># itol 'ifie>.x n ’ '■■'•■- ’"J^' ■''" ’ I.: - ^1 “Tit': .: • \ ‘ '>5» ^ ’M-^XI^' ‘^^’>- -X-TOS ;5*^ , ,^(,0. m :j^ ■S7 ■ ^^.30--, 'U. r V -Ja * 'JP.! *: •■ .Lj b.y ? . -a;-]* -.li* -r , ''/'A « -.' ' 5 :iH £ •1 '.. ■h. . 4 ^^ , V ,■ -T ^-™?l ■• :,? -.i -Vi ,S ■'> t - ''’I'i ii'j ^,■1 J ■i t c '•rr-vsfc'Wfta-r; 9 5^ Soy Bean and 95^ Cotton Seed Oil Table 13. Fraction I II III IV V I od . No. 63.1 99 .8 113 .2 124.2 135 .2 Sap . No. 198 .0 185 .2 194 .0 190 .2 189 .9 IndeM Ref . 1 .4548 1 .4576 1.4587 1 .4596 1.4638 Pre s . mm . 16 .0 - - - - 0 Temp . C . -207 207 -12 212-15 215-16 216 -20 • Cotton Seed Oil and 95^ So^' ' Bean Table 14. Fraction I II III IV V lod . No . 109 .6 122 .1 133.2 141.9 156 .0 Sap . No . 192 .6 191.9 189 .9 189 .5 189 .6 Index Ref , 1.4558 1 .4560 1 .4590 1 .4598 1 .4643 Pres . mm . 16 .0 - - - Temp . ° C . -210 210-12 212 -15 215 -17 217 -23 Crude Soy Bean Oil Table 15. Fraction I II III IV V I od . No. no .3 118 .9 133.9 142 .7 137 .9 Sap . No. 193 .0 190 .2 190 .0 189 .5 189 .0 Index Ref . 1 .4565 1 .4582 1 .4585 1 .4605 1 .4620 Pres . mm . 21 .0 - - - - Temp . ® C . -209 209 -11 211-12 212-13 213-31 . .. . 1 . .■ 'n I . -u? ,rVi * r,i^ ■ '•''.!^ --fa .' : < 10 Description of Apparatus' In. the Diagram (1; Jena, Clalssen flasK with an indented side neck. 1 liter. («^) Ordinary 90 cm. condenser tube. i'6j Adapter welded to ^ in. stopcock .(4) . (5 Stopcock. . (6) liln^ test tube. W:"' -V t i t' k =: f;'. F- ■ I « 'I \ { ! f 4 k * ir « •• ^ • 11 III Apparatus and Details Cutting the ester fractions at constant, definite temperature ranges was found difficult and inaccurate, and was abandoned for the equal v olune -fraction method. The diagram show the set-up for this method. At first, the absolute methyl alcohol v;as prepared by refluxing it v^itii chemico^l lime (8 liters of alcohol to 1600 grams of lime) and then distilling off the alcdiol. Then it was found that by using the ordiisary methyl alcohol with calcium chloride, excellent results could be obtained. To 500 grams of oil and 1 liter of alcohol, sat’orated with hydrochloric acid gas, were added 100 grams of anhydrous calcium chloride; this was then refluxed in tiie usual way for fifteen or twenty hours. Sometimes at the end of this period the ester layer would fail to separate, but by add- ing 25-50 grams more of calcium chloride and refluxing for thirty minutes, a perfect separation was obtained. Before distilling a batch of esters, the volume must be determined and then fractions taken so that the entire distillate will be divided into five equal parts. From 500 grams of oil the yield of esters is usually about 500 grams having a volume of about 430 cc . From this volume of esters about 21 cc , are lost in volatilization and residue as a result of the distillation. This loss is appr Oyd.mately proportional to the initial volume of the esters, thus making it easy to calculate the volume of the fractions to be taken for any oil. I W- ‘ ■■• ’ i^rli i| i». . • . ' ii ^ ' - £v A r.-J'.C •« . p* ’-rf/ • — . . : -y. 1 . c e o - - . - -' j: :;v . ' r-** . f! •. ? *S 0 '' .'"f c ’'. •. ..• . ...,; • "'I'l ',-\ I '7 ia'’' ■i ^ . , ik , o . ►<9 ,VI* . . " r\- ' ' ■'■' ■ ./ /-<. Jv .: 'j ^ Vkv > ., ■; ,^v; •a.' i '-■ ' .< :'V'v ' ■ ' ' •■;;• ■•; \::P^ ■ c\iTA:l v ■ • Ak. "■ ' ■ ^ ■ . • • -yf- ',J ! . 'ij ’X^,' V • *>..■ , . ,. VwA' ■ , - i . -■ .' i - ' ■ ‘ -■" * -‘-v ■■‘' . . I* , -..1 . ': '■ I- I ,. !w /V . ..... ■ ■',•-%■■-. r i "► - I >v ‘•.“'■)- < i ,_.., 4 .V.^ '•. 5 * V •. ■ ■ i '■■■?. 'I ' • jv i ‘1 M»Vj' •i ; - . ^j. ‘ .1 . j. *• ■ ^ ■ i j-- . ' ■ j , ?. .41 .1. 41' - .• • *" ' J. \ ? . ^ J 12 . Test tubes of ordlnciry glass were used to collect tile fractions. They are calibrated accurately enough for this work by a pencil mark on a gummed label glued to the outside of the tube, A pressure of 15-20 mn. of mercury was obtained by the use of an ordinary water suction pi^P • No difficulty was encountered with leaks. Rubber stoppers were used, protected with tin foil. If leaks occur, they can be easily stopped with a paste of glycerine and lead oxide, or with shellac . Wlien the distillation is ready to proceed, stopcock #4 is open and #5 closed, Wiien the desired volume has passed over #4 is closed and #5 opened to release the vacuum. Then the test tube is remo\’’ed and another put in place. Then suction is applied to #5 and vdien the tube is evacuated, #5 is closed and #4 opened. In this way the distillation proceeds uninterruptedly, A Raikow receiver was used at first, but this was found to be very troublesome and was replaced by the method described. V-* 13 IV Solutions and Determination of Constants 2 Eanus Solution 13.2 grams of iodine and 3 cc . of bromine were dissolved in 1 liter of glacial acetic acid, and kept in a brown, glass-stoppered bottle. Iodine lumbers were determined as follows: 0.250 grams of tlie oil are vifeighed into a ^lass stoppered flask and dissolved in 10 cc . of chloroform. Then 25 cc , of Hanus solution is added. The stopper is moistened with 15^ potassium iodide solution and the groove betv/een the stopper and the edge of the flask, filled Vifith the same solution. The solutions are allowed to stand for 2 hours in the dark and then titrated v;ith sodium thiosulfate, after the addition of 10 cc . of a 15^ solution of potas- siumt iodide and 150 cc . of water. The absorbtion of iodine by the unsaturated esters depends upon the mass action law, and unless a large ex- cess of iodine is present, poor results virill be obtained. For oils with Iodine Numbers up t o 135, use 25 cc . of Hanus solution for a 0.2500 gram sample; above 135, use 40 cc . Alcohol Potash Solution Dissolve 52 grams of potassium hydroxide in a very small amLOunt of waiter and filter if necessary. Add this to 1 liter of ethyl alcohol and also ^ gram of sodium peroxide Slriake, and allow to stand for several hours. Then filter and keep it in a glass stoppered bottle. 14 Saponification iJimiticrs v;ere detertiined as follows’^: 0 .2 y?ams of tiie ester are weighed into a 250 cc . flask and dissolved in 25 cc . of alcoholic potash solution. The solution is the refluxed for hour and titrated hot vilth N ■^hydrochloric acid, using phenolphthaleln as an indicator. Cork, and not rubber, must be used to connect the condenser and flask for the refluxing, because the alcohol dissolves some of the rubber and discolors the solution, masking the end-point. Sodium Thiosulfate N Ajq solution of sodium thiosulfate was made up and allowed to stand several days before indirect stand- ardization against arsenous oxide. The solution was protected with a soda -lime tube against carbon dioxide. This solution vnus used for titrating the excess Hanus solution in determining the Iodine numbers. Hydrochloric Acid n A solution of hydrochloric acid was made up and standardized against sodium carbonate, using methyl orange as an indicator, 4 Index of Refraction The Indeces of refraction were determined with an Abbe Refractometer at 24® C , These values for 24° can be reduced to the usual standard of 20® by using the factor 0,00038 for each degree Centigrade, remembering that the refractive index decreases with an Increase in temperature. f 4' 1 » V . -’■V ,' ’ 4 '' ■’ 'i-t, yp^Tv^ ^ • ' . V* • '' ^ ■ > ’ * .' ' , ■ ' • ' ’ i^v.",' ' tv > -;■ ' - * "it: ' ■ ' •:.'''* ^‘/* ’ v"' ■.' '• ’ . iuV- -UA>ifu &cJ ni 4p-iV*i'l£>«: I*. *■ ' ■ . 5i ‘ '■ ■y 111 , \ . • . J , '*lf ' ■ ^ |», ' , *. ^ ’ j ® 'bs-*-' . .^ »|i ' ■' ^'t’"''- ' ,, . ’*/. : * ■ V ■' ■ ■ •. ■'■ ‘ <-^‘- ffi,{,,Uit^i»^ ,5Xi'fc?i.r^ien u<»X'r . i' '■■\^t%0:£^ti^^ -iSru; •'jv-di;^, ct^",^’ ifto. j.xii silrtft l\ c' **'i--,iS J , ■ ' ■ '■> ' ■ ■ 'W : i. ,i #■• .'■^J^'-'-* .- ' . .■' **,.^ t5 ' ' ■% ' ' ;'- -v. V"!'^ ‘ ■ -^0'^\«i?XLvXfci;0a , ., ^ «■'■' ' ‘;-*j^a#ifcti4a&.''*i!^ 4a0i.^ a ?"■;■ J. 15 V C one Ivis ions In Uie writers opinion tliis iiietiioci is reliable and can accurately detect adulteration in fats and oils as low as 5^, and in a goed many cases as low as 2^. Tlie detemination of the Saponification Numbers and Refractive Indices is not necessary. The Iodine Number is sufficient to determine whether or not the oil is pure. The Saponification Nvimber is not of much value, be- cause the range of its values is so small that even a ± 0 $ adulteration would not cause an appreciable difference in the Saponification numbers of the corresponding fractions of the pure and the adulterated oil. The Index of Refraction is also unreliable, because there seems to be other factors, besides the degree of un- saturation, and the number of carbon atoms, that effect its value . By a study of the tables given, it can be readily seen that the iodine Number immediately reveals ai^y appre- ciable adulteration. The degree of adul tei>ation, of course, cannot be determined, but can be reasonably estimated. This method should be practical, because it re- quires no apparatus e::cept that which is found in any com- mercial laboratory. The ordinary water vacuum pump supplies sufficient suction, jt is not necessary that the pressure be constant, because the fractions are cut by volume and not temperature. b»V U -.C^ i£^ * ^ 1 Jki! #- t .^.^tv '. > " 'V ■ 5 ^' \ . n ![' >;C t* fi-A*- ^:>4.'>‘fi'x<»v iij Qio^- ■ : ^ ^1 > « >;■ , fffl'' »■«- ;t«.C4»v' • V^ ■ .# . ^ 410,;.;. .’ \ ■ '‘O Jt ^ 0;tl tn^ .» ^k. t !|» i;' , ■ " .: .... "M V.V ojtJf^<.*J t '■ . "’fwk'ii •-*'■* i f . * \ A #nl J ' 1^?. aj> /cff »}it: /ti>;t.'r»-.^ j4i.i‘i% ; *i! oi- ; # T v * ’■■* ‘ ' f J.. g ' ■ ^/p^' * » n/T '«j.<^» :« y it ' fc j,rt til ^ ae' r“ ■» * ■ " '** I , J*: 4* T ■ ■^ .•, * A*’ - .•'’ ^ K i *J» i ' '•■ ' ' » '" i ■■;/ ■frt' »■ - ' !T.* .»-3 " ii ■ ‘ ■" ' ■ ' • '* .% ' 16 VI Blbiio^^rcApliy (1) Compt. rend., 1906(143), 657. (2) Zeits. f. Unters , d. Nahrgai-u. Genuaem., 1901, 913, (3) Levskowltsch vol. 1 p,380, (4) Lewkowitsch vol. 1 p.328.