Parte II. SOCIOLOGÍA DEL ORGANIZAR EN CLAVE CONSTRUCTIVA
4.2. Fundamentos constructivos de la sociología del organizar
lati-Gduction ,
Oné problem assooieted'with'the study of seed oils Is the quantitative dëterminàtiOB of the oompohent ■acids, This is
aohieyed hy oonyertiiig'the mixed acids i‘esultihg on hydrolysis (usually & complex mixture) into a large number of fractions
eaoh simple enough,to he characterised hy the iodine value,
saponification equivalent, etc,. The conversion of the initial] complex mixture into a number of simple fractions requires a number:,of separate teohuiques, of■ which-loW*temperatutfe
Cfystailisation,and fractional ,distillatldn are now the moat frequently used, fhe former separates'aoids mainly on the,basil of .the - degree of .ùasa.turàt-ion}. the,.-latter separates asters
miniy. on .the-.basis of .cîmin-lôhgth-,
fhe above prooedure though satisfactory for-most of the
seed oils is Unsatisfactory for oils containing hydroxy or
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epoxy-acids. Attempts, by'.Guutà* ,.Ëi-lâitch' and.'Rlley, to
separate rioinoleic. aoid from other unsatùfàted acids of eastoJ oil by low*tempefature orÿstaillsation from èolVants were
Uneuocessiful, Detefmlhatkon'''of ricinoleic .held as 'hydro'xy#t#r' aoid (after hydrcgenation) gave unsatisfactory results and the oil m e ultimately analysed without subieoting the mixed acid# to loWftemperature orystallisatioA or frabtlohal distillation. The ricinoleic acid content was calculated from the acetyl
yalue determined by,.Hiley'-'-s method-'after inakirig^allowance
content-of ldnoielO“',aç,i:d7Was;:deteraineti:;froifi, the nïtra-Tiolet
absorption ,after.,aikall, l.so^ Oielo- aold. tms' : "
oalCUlatéa.ffcm--:thè,:lodfn@..#lné,,a#df the
, iinoîeio-.and. niclnploio,açiâjSJ,.. thC-contcnt,. of ^,gs,twate.ct,,,aoids
, was, detcffflthèd:' as - ,fhtf ^.wethod,,,is..chvlonsly ..dependant
on satisfactory.détermina,t.i.o.n.of.iodine:,value. . . '. .
Thro'Cghout. his work, on .Stroèhàîithns... sferme'ntosus seed ollt IS
Gunst.oae.. .encountersd dlfficnitF .in .determining, the ■ iodine ynlue:; o,f. fra.çtioa#.: cçntai.niiig.,the ..h.ydro.xy,'.aoid.» :E.#. difficulty was., met - .with .in ' .the.-.ToW-tejiperaturs - orystallis&.tioa, ■ probably ; .due,- to ..the, ; lot. oontent ;.cf . the:' hydroxy ' aoid] , . - The iodine yaluss
werè.:,hlgher'. .than ..expeo.ted. and,. ICBS--,..CoacOrdant.- than usual. This effect’tas-reduced, or .eiirai.n&ted. hy acetylatio'n of the esters
.- n / . ' ' " . ' ' "" .
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. :. and, in tlife' Btronhànthus o,ilç.,exainineâ,■.■.fràotions. containing-- : 'the.,hyaboxy...aoia;.:tcrc.pBethyla.ted,.^ad,.Acatylateîi .h'sforé .
distllla.ticn.an.dithe proportion.of’,.■methyl,.ucetoscyoo-fcadecenoate was ,:eoB®uted, solely, from, the eapoiâfICation. équivalent.- This .- : method.'dS;. .dépendent' on thé .thermal,-.: stability of- the Çsetoxy ' ' .ester--'and,.-it : is .pëxhaÿè..; on .aoQ'ount - of:-this. .factor that, fiuptn»- ‘
,BilditCh;/and:,|lley;r.^di^ , : - ,
.., ',.yidya.rthi.:'.'aha,Ma-llya m v e .i».de.:.simi,laf'-rem^ the ..
unsati'sfadtdry .icdine value of -Vernonia.. a.hthelaintioa .sëed:.o.ll .'ccneidered .,hy;.them; :tc;:qontain 'll^hydroxyo.ctadecis-enciq. acid,;, ' ,hut.-'lateripycved ..hyiaunstcne'' to he : ig: iST-j^-'e'pdxyoieio acid.
. .. 1 # :
a o id has ,b,e# ;d@ $orib
6
&. b y .Aohsya a . ■ S a tu ra te d :;;.aold8: %èr8{first.;rëmqv#y^ Bepafation ànâ the . :
r8ïîm4niïsg,,.a.oiçlë ;wei;e • then.;; separated:! iatq;'tw & ;: fra e ti'o n s - by & V; te ‘ctoi.Q «è;:ln,::\thicïi.:,o'iëi'c ,;acid;':ato^ a v .little j lîn o lé ie ' a d d formed’.
i' , ' ’ '. . '
a xixea., co.mpl.eX'- w h ils t..rl^ u o fe io ' .aM. iuodt o f;th é .’iit o le lc . a ô ld . ; : , .d.i d .no t ,. .This : : la s t;.-f ràQ.tioo:
m.s‘
subHeqçe;nilÿ.;.')néthylat.ëdj ■ ■ .à ostyl& te A . s M a ifî’tille d ;,'- ■The, m orm il pro.oedure needed :y.ét. fu rth e r n io d ïfio a t.lo » fo r :. th e .exâm inatida o f V.arnonife: a a th e là in t!lo & '’a è e d 'é il ahown tg ' co n ta ia - ÎS l;iS '” .epoxyolel.o ao.id.-by' Glms.toûê.' ; The mixed aoids
c o u ld n o t be e a s ily e è te r ifted; by ih s afe’M l methods as th e
epoxide rs a c te d re a d ily w ith ' the ’rçagéata»:' 'Thto ' d l i f im ilty wae. • . s'sroldefi. by, c o iite rtin g ■ the ; epoxy.;'act'd' ' to ■'f :b,e' ■ o o f f o'Sp'onxling.' ■ , ;
d ih y iiro x y a o id 'by.treat'raent 'f lt h , dcet'iC a e id ; fo llo w e d by. .a ik a ll; h yd ro lye is*. T he-aihydrozy; a c id ta s :'th e n sépà-ràtéd: from th e non* hydroxy: .dotd© .by p a r titio n ■'betweeii •
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# [email protected]■ and lig h tpetroleum-;Ci>,ip* -■40-S0)j the aon*iiydxosy doidâ being- ôonôe-ntratôd
in .the -la .tte r *. The aoii-hytbroky aoids'-'were siib se g u e n tly a a te r 'ifi a n d - d is tille d and thé c'om po'sl'tion o f th e ' d is tille d 'frc u c tio n e ." • #)i#utcd.-.:.in. th e u s m 'l-'te y * .T h e .ffn o tio n ' in '? h ie h ' th e dihydroxy
h o ld wus .'opno.ent.rat@d. w&e . .m@thyl&t@d dud 'hC etylated and. th© opntant' - o f dihydroxy gqiç ùàlé.uiatôd 'ffom -ths: '8#onii'i'omtlon
0Q-U:l-yëiïéÙ't .bifoïô - and ,4f .-tér -r ace.tyia.tiôüà.- The- 'S ità ll amount of
aOn*hÿàr,oxy .aoids..in -'th is fr a c tio n .w .s as'Cimod"'to.'ha-ye -the â'ami oom-cosi-tion-'aB' -.tim t.'of'-idle' 'd i'stiiië 'd ;.-f-ra c.tio h . !in -''a irp ro xiim te :,';
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ooBtpositlenoi th© oil w»a thus determined.
In the nereent work a method has been developed for
anaiyeing oils oontalning epokyy mono- or dlhydioxy aoids base* largely on the method just described and depending on the
separation of hydroxy from non*hydroxy acids by partition between suitable solvents.
After the present work was oonoluded, a paper was publish;
107
by Sreenlvasan .gt.ai. on the analysis of castor oil. The methyl esters were resolved quantitatively Into hydroxy and nom-hydroxy esters by reaotion with suooinlo anhydride in toiu; The composition was then oaloulated from the weight of each fraction.(ricinoleic)* the ultra-violet absorption after alkali
isomérisation (linolelo)* the Iodine Value (oleic v saturated), and from periodate oxidation (dlhydroxystearic). Surprisingly the non-hydroxy fraotlon showed conjugated unsaturation and accordingly these Workers used the Woburn procedure for
determining iodine value, in view of our experience with the glycol value {see page lo2.) we do not oonsider this method to
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' Method of Analysis
-greoarâtion of Mixed''HydfokV Aoiae"Free of Unsapohifiable .,.OÙs,,wîiioh;,.4o,.hot; eontà'in.any,;,epoxy aoid,are .hydrolysed dire,ot.ly.iby,.refInxlng with -.ethaholio,potaS%inm hydroxide, .eolution..,fot, 1-8. honrdi,Gonerally iscs-soo g. of the oil are hydrolysed %ith '75?.l#. ■©.,;■ of .potae.itum-.hydroxide.:.in 759-1000, a'
of ethanol, ,ljhen. the''oil,;oontains.-.an-.'.epoxy, aoid* - this., i e -. .co.nyer ted, to the -■ .oorr.eapo.ndlng- aoetoxy*"hydroxy.. a.oia- - prior.. to
the ; alkaline, hydrolysis, hy : ref luxing the, oil with five-;, volmei .,of....ela.oial'i.aoe.tio. adid.-.f©» &.T.;.-hdnr.s,,-.. After...- distilling .off ; the
a;ee.tie,,aôid:,;(the:.iahh traoea7nnder;:,ya.ontn!i);,..-the.;-pro.auot is . sapohif ied with alhpholio potasslina,.hydroxide solution; as aboyi After,- hydro.lysis,, a'hout : half,. of the., aioohol - .is.-, distilled off .an -the -pT©duot ; - diluted ( Wi.th water,» The,'- unsaponifiahle . ma,ter ial is. '..then-.rewey.edi-hy. extraetion with^ether. ..(4-5 times with 500 ml.
per iSp-S# g,-of fat). fhè OQmbinèd ather extracts are washed With;Wa.t.er-.,.!(2-S.-times.-With; SO0 .ml),.and-th.é7wa.shi-ng.s are added
to thai,..extra.©ted,soap.:-Solution whioh is then aoidified with ,, 25# sulphuric acid. The fatty aoids so liberated are extracted with ether, the ether solution is washed free of mineral aoid and dried over sodium sulphate. Removal of the solvent affords
the mixed hydroxy acids.