1
Liquid liquid equilib ia o sys ems glyce ol +
sa dine oil + e -alcohols
Ángela Ga cía Solaesa, Sil ia Liliana Bucio, Ma ía Te esa Sanz
∗
, Sag a io Bel án, Sa a
Rebolleda
Depa men o Bio echnology and Food Science (Chemical Enginee ing Sec ion),
Uni e si y o Bu gos, 09001 Bu gos. Spain
Abs ac
Monoacylglyce ols (MAGs) can be p oduced by lipase-ca alyzed glyce olysis o oils and
a s a a mosphe ic p essu e and low empe a u e. The use o o ganic sol en s as eac ion
media helps o c ea e a homogeneous eac ion sys em be ween he immiscible eac an s
glyce ol and oil. In his wo k liquid-liquid equilib ium a wo di e en empe a u es (303.2
and 323.2 K) and a a mosphe ic p essu e has been de e mined o wo sol en -sys ems in
he glyce olysis o ish oil (sa dine oil): glyce ol + sa dine oil + e -bu anol and glyce ol +
sa dine oil + e -pen anol. F om he expe imen al solubili y (binodal) cu es and ie-lines,
i could be obse ed ha he sys em mu ual solubili y does no signi ican ly inc ease by
inc easing empe a u e om 303.2 o 323.2 K. The O hme -Tobias co ela ion was used o
∗ Co esponding au ho . Tel.: +34 947 258810. Fax: ++34947258831. E-mail add ess
[email p o ec ed]
2
analyze he consis ency o he ie-line da a. The expe imen al liquid-liquid da a we e
co ela ed sa is ac o ily by using he NRTL model o he ac i i y coe icien calcula ion.
Keywo ds: Liquid-liquid equilib ia; Fish oil; glyce olysis; e ia y alcohols.
1. In oduc ion
Fish oil is one o he main sou ces o omega 3 polyunsa u a ed a y acids (n-3 PUFA),
specially eicosapen aenoic acid (20:5 n-3, EPA) and docosahexaenoic acid (22:6 n-3, DHA).
These compounds ha e been epo ed o ha e bene icial e ec s on ca dio ascula diseases,
educ ion o blood p essu e and plasma iglyce ide le els, and con ol o o e ac i e immune
unc ions [1]. Glyce olysis o a s and oils is o en ca ied ou o concen a e hese PUFA in
hei na u al monoacylglyce ides o m (2-MAG). The enzyma ic ca alysis in non-aqueous
media using lipases is a usual me hod o syn hesizing s uc u ed lipids. Lipase-ca alyzed
glyce olysis o oils using 1,3-speci ic lipases has been shown as an in e es ing al e na i e o
he chemical me hods due o he mild eac ion condi ions o eac ions in ol ing he highly
uns able n-3 polyunsa u a ed a y acids [2]. Fo his biocon e sion i is necessa y o
in oduce a sol en in he eac ion sys em o imp o e he solubili y o he eac an s, oil and
glyce ol. Since he wo k o Zaks and Klibano [3], o ganic sol en s ha e been employed
ex ensi ely in enzyma ic eac ions. Among he di e en sol en s conside ed in he li e a u e
o glyce olysis sys ems, alcohols wi h mo e han i e ca bons a e one o he bes op ions
since hey con ain a pola –OH g oup and a nonpola ca bon chain. Since alcohols a e
compe i o s o glyce ol, e ia y alcohols a e conside ed because o i s e ia y s uc u e ha
makes hem o ha e a s ong s e ic hind ance o he enzyma ic eac ion [4]. Acco ding o
Dams up e al. [5] he ela i e low log P alues o e -bu anol and e -pen anol indica e
3
bo h hyd ophilic and hyd ophobic cha ac e is ics, wi h p edominan hyd ophilic
cha ac e is ics. This ac makes hem sui able sol en s o bo h, oil and glyce ol.
Knowledge o he phase beha io o sys ems con aining ish oil, glyce ol and he sol en
added as eac ion media is impo an o a co ec design o he glyce olysis p ocess since
his can in luence he eac ion pa hway as well as he u he pu i ica ion s eps [6].
Composi ion o he oil om indi idual ish species a ies, depending on i s die , ime o he
yea and loca ion in he same way as do he oils om ege able sou ces [7]. Fish oil is a
mul icomponen mix u e. In he e ined p ocess, pola lipids, mainly phospholipids, ee
a y acids, and o he mino compounds a e emo ed. A neu al lipid analysis o he sa dine
oil used in his wo k shows ha nea ly 99.5 % o he sa dine oil a e iacylglyce ols (TAG).
In spi e o di e ence in TAG composi ion among sa dine oil species, de e mina ion o
phase equilib ium da a on na u al mix u es is impo an o es ima e he p ope p ocess
condi ions. In li e a u e, phase equilib ium s udies conce ning ege able oils a e mo e
abundan ; howe e phase equilib ium s udies in ol ing mammals o ish oil a e sca ce.
This wo k p esen s liquid-liquid equilib ium da a o wo e na y sys ems in he glyce olysis
o sa dine oil: glyce ol + sa dine oil + e -bu anol and glyce ol + sa dine oil + e -pen anol
a 303.2 K and 323.2 K. Binodal cu es we e ob ained by he cloud-poin me hod. Tie-lines
ha e been di ec ly de e mined by using a high empe a u e ch oma og aph capilla y column
(HT-GC). The esul s we e compa ed wi h indi ec measu emen s o ie lines h ough
densi y measu emen o he wo phases. The O hme Tobias equa ion was applied o
con i m he eliabili y o expe imen ally measu ed ie line da a. The expe imen al da a we e
co ela ed by he non andom wo-liquid (NRTL) ac i i y coe icien model, using he
simplex minimiza ion me hod wi h a weigh composi ion-based objec i e unc ion.
4
2. Expe imen al sec ion
2.1. Ma e ials
Glyce ol was pu chased om Sigma Ald ich wi h a pu i y o ˃ 99.5% and a wa e con en
o 0.04%. Te -bu anol and e -pen anol we e pu chased om Me ck wi h a pu i y o
≥99% and a wa e con en o 0.298 ± 0.033 % and 0.065 ± 0.023 % espec i ely. Re ined
sa dine oil was kindly p o ided by Indus ias A ines S.L.
Densi ies o he compounds we e measu ed by using an An on Paa DMA 5000 and a e
p esen ed in Table 1 oge he wi h some alues ound in he li e a u e [8, 9].
2.2. Appa a us and p ocedu e
Binodal cu es
The binodal cu e o he wo e na y sys ems s udied in his wo k was de e mined a
303.2 ± 0.5 K and 323.2 ± 0.5 K and a mosphe ic p essu e by u bidime ic analysis using
he i a ion me hod. Di e en bina y mix u es o sa dine oil + e ia y alcohol and glyce ol
+ e ia y alcohol ha e been p epa ed a a ious concen a ions by using an analy ical
balance (Sa o ius Basic, accu a e ± 0.0001 g). These bina y mix u es we e i a ed wi h he
hi d componen (glyce ol o sa dine oil) by using a sy inge needle un il a change om
anspa en o u bid was obse ed by using a u bidime e (Eu ech Ins umen s TN-100).
The unce ain y o he d op has been es ima ed o be ± 0.005 g o glyce ol and ± 0.0018 g
o sa dine oil. The liquid mix u es ha e been igo ously agi a ed by a magne ic s i e .
Expe imen al poin s wi h a high con en in glyce ol, due o i s high iscosi y, we e s i e
o mo e han 15 minu es o assu ance a su icien mix u e o he compounds a he
ope a ing empe a u e. The empe a u e was con olled by a he mos a ic ba h wi h a
5
p ecision o ± 0.5 K. To de e mine he mass added o he hi d componen , he mix u e was
weighed again. The amoun o he hi d componen was also de e mined om he mass
change o he sy inge be o e and a e i a ion. The same esul s we e ob ained by hese wo
measu emen s. The cloud poin was conside ed o be a binodal cu e poin . Samples we e
collec ed o densi y analysis. This way an exp ession o densi y as a unc ion o weigh
ac ion o he h ee componen s can be ob ained. Each expe imen al poin was eplica ed
a leas wice.
Tie lines de e mina ion
Expe imen s we e ca ied ou in equilib ium cells o 20 cm3. A mix u e o sa dine oil,
glyce ol and e ia y alcohol, a a gi en composi ion, was p epa ed di ec ly inside he
equilib ium cell by weighing known quan i ies o each componen in an analy ical balance
(Sa o ius Basic, accu a e ± 0.0001 g). The equilib ium empe a u e was con olled by a
he mos a ic ba h (± 0.5 K). The e na y mix u e was hen igo ously s i ed o a leas 3 h
o allow con ac be ween he wo liquid phases. A e ha , he mix u e was allowed o s and
o a leas 24 h a cons an empe a u e o ensu e equilib ium was eached and wo
anspa en liquid phases wi h a de ined in e ace could be clea ly obse ed. The uppe
phase was he oil- ich phase and he lowe phase was he glyce ol- ich phase. Samples o
bo h phases we e collec ed and composi ion was de e mined by HT-GC and densi y
measu emen s. Tie line expe imen s we e eplica ed wice.
2.3. Analy ical me hods
The sa dine oil used in his wo k was analyzed by gas ch oma og aphy o de e mine he
a y acid p o ile by he AOAC me hod [10]. The a y acid me hyl es e s we e i s ly
p epa ed and hen analyzed by gas ch oma og aphy (GC) in a Hewle Packa d gas

6
ch oma og aph (6890N Ne wo k GC Sys em) equipped wi h an au o-sample (7683B
se ies) and a lame ioniza ion de ec o (FID). A used silica capilla y column
(OmegawaxTM-320, 30m×0.32mm i.d.) was used. Mos o he a y acid me hyl es e s
we e iden i ied by compa ison o hei e en ion imes wi h hose o ch oma og aphic
s anda ds (Sigma Chemical Co.). Fu he de ails o he gas ch oma og aphic me hod can be
ound elsewhe e [11]. Table 2 shows he a y acid composi ion o he sa dine oil. Banda a
e al. [12] analyzed he seasonal change in lipid composi ion o sa dine oil in e ms o a y
acid p o ile. Al hough di e ence can be ound among he indi idual a y acids, a simila
a y acid p o ile as he epo ed in his wo k (Table 2) is ob ained when compa ing he o al
sa u a ed (SFA), monounsa u a ed (MUFA) and polyunsa u a ed (PUFA) a y acids (SFA =
27 ± 1; MUFA = 23 ± 2 and PUFA = 43 ± 3; [12]). Based on he a y acid p o ile ob ained
in his wo k, a molecula weigh o sa dine oil o 879 g·mol-1 has been es ima ed.
The ee a y acid (FFA) con en o he sa dine oil has been de e mined acco ding o AOCS
O icial Me hod Ca 5a-40 [13]. An au oma ic i a o Me h om, model Ti ando 905 was
used. The FFA con en o he e ined sa dine oil was 0.2 ± 0.1 % exp essed as pe cen age
o oleic acid. Due o he low ee a y acid con en , he s udied sys ems ha e been
conside ed as a pseudo e na y mix u e as i will be explained in sec ion 3.2.
The composi ion o he ie lines has been de e mined by using High-Tempe a u e Gas
Ch oma og aphy (HT-GC). A Hewle Packa d (HP 6890 Se ies GC Sys em) gas
ch oma og aph equipped wi h a lame ioniza ion de ec o (FID), a used silica capilla y
column o 30m×0.25mm i.d. coa ed wi h a 0.25 mm ilm hickness o 65% Phenyl
Me hylpolisiloxane (65HT) as a s a iona y phase and Agilen Technologies 7683B Se ies
au oma ic injec o was used. The ini ial o en empe a u e was 120 ºC o 2 min, and was
7
hen aised o 340 ºC a a a e o 15.0 ºCmin−1. Then i was aised again o 365 ºC a a a e
o 1.5 ºCmin−1 and held iso he mally o 4 min. The injec o empe a u e was kep a
380 ºC, while he de ec o empe a u e was 400 ºC. Helium (1 mLmin−1 column cons an
low) was used as ca ie gas. Spli injec ion mode was used wi h a a io o 1:40.
Te ia y alcohols and oil ha e been success ully quan i ied; howe e quan i ica ion o
glyce ol was no e y eliable due o he bad esolu ion o he glyce ol peak by using his
kind o columns. In he las yea s HT-GC has been p o ed o be an a ec i e echnique o
cha ac e ize TAGs om di e en ege able sou ces. Howe e , HT-GC could he mally
deg ade iacylglyce ol species ha con ain polyunsa u a ed a y acids, as in ish oils [14].
Ne e heless, in his wo k, he objec i e is he quan i ica ion o sa dine oil in e ms o o al
amoun o oil and i is no expec ed o cha ac e ize he di e en TAGs o sa dine oil. To
quan i y o al amoun o sa dine oil a con enien calib a ion has been pe o med, as well as
o he o he componen s o he mix u e. Al hough deg ada ion o some TAGs species
could ha e been aken place du ing he HT-GC analysis, his ac would be con enien
co ec ed by using he calib a ion cu e. To show he eliabili y o HT-GC o quan i y
sa dine oil, composi ion o he h ee componen s in he ie line was also de e mined by
densi y measu emen s. Acco ding o Madu o and Azna [15], a densi y calib a ion cu e
was ob ained om he cloud poin de e mina ion as a unc ion o he composi ion o he
h ee componen s, al hough he composi ion o he hi d componen can be ob ained by a
simple mass balance; he e o e, o ie line measu emen s, densi y and only one
composi ion, in his wo k e ia y alcohols composi ion, mus be known o de e mine he
composi ion o he o he componen s h ough a densi y exp ession o he h ee componen s
o he mix u e and by ma e ial balance.
8
3. Resul s and discussion
3.1 Expe imen al da a
The binodal cu e and he densi y da a a 303.2 K and 323.2 K o wo sys ems: glyce ol +
sa dine oil + e -bu anol and o glyce ol + sa dine oil + e -pen anol a e p esen ed in
Tables 3 and 4, espec i ely. In his wo k, a di ec i o he densi y da a, simila o he
app oach used in he co ela ion o he boiling poin s o e na y mix u es wi hou using
bina y da a sugges ed by Tami [16], has been used. The exp ession is:
( ) ( )
[ ]
...wwCwwBAwww 2
jiijjiijij
1N
1i
N
1ij jii
N
1i i+−+−++ρ=ρ
∑∑∑ −
= +==
[1]
The coe icien s o he empi ical Eq. 1 we e de e mined by using he Ma qua d algo i hm.
Table 5 lis s he alues o he adjus able pa ame e s o each sys em a he wo s udied
empe a u es.
Figu es 1 and 2 show he binodal cu es o he sys ems s udied in his wo k. The la ge
wo-phase egion shows high immiscibili y be ween glyce ol and sa dine oil e en in he
p esence o he e ia y alcohols. The in o ma ion p o ided by he binodal cu e is
necessa y o op imize he amoun o sol en used o c ea e a homogeneous sys em
con aining he eac an s, glyce ol and sa dine oil, aking in o accoun he co esponding
eac an mola a io o he glyce olysis sys em. I can be obse ed ha , in he empe a u e
ange co e ed in his wo k (303.2–323.2 K), he e ec o empe a u e is no signi ican on
dec easing he biphasic egion. This beha iou has been also obse ed o e na y mix u es
in ol ing biodiesel and glyce ol oge he wi h di e en alcohols [17-19]. This means ha
he eac ion empe a u e o he glyce olysis sys em can be de e mined in e ms o kine ic
9
pa ame e s a he han in o de o inc ease he mu ual solubili y o eac an s. Addi ionally, i
can be obse ed ha a a gi en empe a u e, he miscibili y egion is bigge o e -pen anol
han o e -bu anol (see Figu es 1 and 2).
The ie line da a o he sys em glyce ol + sa dine oil + e -bu anol (o e -pen anol) a e
p esen ed in Tables 6 and 7 espec i ely. Composi ion o he ie lines was de e mined by
HT-GC as well as by densi y calib a ion using he e ia y alcohols as key componen s. By
using he pa ame e s om Table 5, composi ion o sa dine oil and glyce ol could be also
de e mined. Composi ion o sa dine oil and glyce ol calcula ed by densi y calib a ion and
by HT-GC we e simila . De ia ions be ween bo h me hods a e lowe han 2 % o he majo
compound in he equilib ium phases. Howe e ela i e de ia ions ound o he mino
compound in he equilib ium phases a e no iceably highe . F om he shape o he binodal
cu es o bo h sys ems i can be obse ed ha he amoun o oil and glyce ol in he
glyce ol and oil phases espec i ely is e y small. This ac can be clea ly obse ed in he
composi ion o oil in he glyce ol- ich phase, since o mos expe imen al ie lines, oil
con en in he glyce ol- ich phase is lowe han 1 %. The e o e, ela i e de ia ions be ween
he wo analy ical me hods o oil and glyce ol composi ion in he glyce ol- ich phase and
in he oil- ich phase, espec i ely, a e highe . Rela i e de ia ion can each alues up o 50
%, o e en highe , specially o oil con en in he glyce ol- ich phase. Values epo ed in
Tables 6 and 7 co espond o he alues ob ained by HT-CG analysis.
Tie lines ha e been plo ed in Figu es 3-4 and 5-6 o he sys ems glyce ol + sa dine oil +
e -bu anol and glyce ol + sa dine oil + e -pen anol espec i ely. Tie lines show ha o
he e -bu anol sys em, he glyce ol phase is iche in e -bu anol han he oil phase.
Howe e o he e na y sys em wi h e -pen anol, he oil phase is iche in he e ia y
16
[12] N.M. Banda a, I. Ba is a, M.L. Nunes, J.M. Empis,W.W. Ch is ie, 62 (1997) 40-42.
[13] AOCS, O icial Me hods and Recommended P ac ices o he Ame ican Oil Chemis s'
Socie y, Champaign, 1990.
[14] T.W. Lee,C.I. Has ilow, 76 (1999) 1405-1413.
[15] R.M. Madu o,M. Azna , (2008)
[16] A. Tami , 36 (1981) 1467-1473.
[17] F.M.R. Mesqui a, A.M.M. Bessa, D.D. de Lima, H.B. de San 'Ana,R.S. de San iago-
Aguia , 318 (2012) 51-55.
[18] M.B. Oli ei a, S. Ba bedo, J.I. Sole i, S.H.V. Ca alho, A.J. Queimada,J.A.P.
Cou inho, 90 (2011) 2738-2745.
[19] B.B. F anca, F.M. Pin o, F.L.P. Pessoa,A.M.C. Ulle , 54 (2009) 2359-2364.
[20] J.A. González, I. Ga cía De La Fuen e, J.C. Cobos,U. Domańska, 119 (1996) 81-96.
[21] h p://www.ohma ega.com/en/dielec ic_cons an s.h m.
[22] D. O hme ,P. Tobias, 34 (1942) 693-696.
[23] C.E.C. Rod igues, P.A.P. Filho,A.J.A. Mei elles, 216 (2004) 271-283.
[24] M. Lanza, W.B. Ne o, E. Ba is a, R.J. Poppi,A.J.A. Mei elles, 53 (2008) 5-15.
[25] C.E.C. Rod igues, E.C.D. Reipe , A.F. De Souza, P.A.P. Filho,A.J.A. Mei elles, 238
(2005) 193-203.
[26] A.E. Da Sil a, M. Lanza, E.A.C. Ba is a, A.M.C. Rod igues, A.J.A. Mei elles,L.H.M.
Da Sil a, 56 (2011) 1892-1898.
[27] C.B. Gonçal es, E. Ba is a,A.J.A. Mei elles, 47 (2002) 416-420.
[28] J.A. Reyes-Laba a, M.M. Olaya, R. Velasco, M.D. Se ano,A. Ma cilla, 278 (2009) 9-
14.

17
Table 1. Densi y o he pu e componen s. a
ρexp./kg·m-3
ρli e a u e/kg·m-3
Componen
303.2 K
323.2 K
Glyce ol 1252.11 1240.28 1255.12303.15 [8]
Te -bu anol 775.48 754.03 775.45303.15 [8]
775.85303.15 [9]
Te -pen anol 801.33 783.30 805.0298.15 [8]
Sa dine oil 922.18 908.42 ---
a S anda d unce ain y u is u(ρ) = 0.05.
18
Table 2. Fa y acid composi ion o he sa dine oil and o he wo phases (oil and glyce ol
phases) o a ie line a empe a u e T = 303.2 K o he sys em glyce ol (1) + sa dine oil (2)
+ e -bu anol (3).a
Tie line
Fa y acid Sa dine oil, % OP, % GP, %
My is ic C14:0 7.6 7.7 10.7
Palmi ic C16:0 18.1 19.1 22.1
Palmi oleic C16:1 8.9 8.9 11.3
S ea ic C18:0 3.6 3.8 2.2
Oleic C18:1n-9 10.0 10.1 11.7
Vaccenic C18:1n-7 3.8 3.9 2.2
Linoleic cis (LA) C18:2n-6 2.5 2.5 nd
α-Linolenic (ALA) C18:3n-3 1.1 1.1 nd
S e iadonic C18:4n-3 3.6 3.4 2.9
Eicosa ienoic C20:3n-3 1.7 1.7 nd
Eicosapen aenoic (EPA) C20:5n-3 25.9 25.0 26.3
Docosapen aenoic (DPA) C22:5n-3 2.7 2.7 nd
Docosahexaenoic (DHA) C22:6n-3 10.6 10.3 10.6
GP: glyce ol phase; OP: oil phase
a S anda d unce ain ies u a e u(pe cen age) = 0.5.
19
Table 3. Expe imen al (liquid + liquid) equilib ium weigh ac ions w (binodal cu e da a) o
he sys em glyce ol (1) + sa dine oil (2) + e -bu anol (3) a empe a u e T = 303.2 K and
323.2 K.a
w
1
w
2
w
3
ρ/ kg·m-3
303. 2 K
0.0016
0.0069
0.0256
0.0365
0.0521
0.0586
0.0717
0.1044
0.1271
0.1649
0.2076
0.3122
0.3330
0.4244
0.7361
0.9967
0.9984
0.8648
0.7163
0.6056
0.5144
0.4809
0.4039
0.2851
0.1953
0.1149
0.0689
0.0153
0.0168
0.0039
0.0006
0.0000
0.0000
0.1283
0.2581
0.3579
0.4335
0.4605
0.5244
0.6105
0.6776
0.7202
0.7235
0.6725
0.6502
0.5717
0.2633
0.0033
923.48
903.29
884.94
870.28
864.06
861.47
854.94
849.67
845.95
851.99
858.72
887.25
903.10
934.64
1092.49
1244.91
323. 2 K
0.0043
0.0100
0.0302
0.0378
0.0471
0.0612
0.1037
0.1480
0.1844
0.2542
0.3361
0.9769
0.9048
0.6840
0.6298
0.5743
0.5293
0.3825
0.2437
0.1713
0.0723
0.0285
0.0188
0.0852
0.2858
0.3324
0.3786
0.4095
0.5138
0.6083
0.6443
0.6735
0.6354
906.54
897.25
867.26
862.68
856.39
853.12
843.60
841.47
846.82
855.92
888.24
20
0.4725
0.4995
0.8011
0.0047
0.0042
0.0019
0.5228
0.4963
0.1970
942.45
954.57
1095.16
a S anda d unce ain ies u a e u(T) = 0.5 K, u(x) = 0.0005, u(ρ) = 0.05.
21
Table 4. Expe imen al (liquid + liquid) equilib ium weigh ac ions w (binodal cu e da a) o
he sys em glyce ol (1) + sa dine oil (2) + e -pen anol (3) a 303.2 K and 323.2 K.a
w
1
w
2
w
3
ρ/ kg·m-3
303. 2 K
0.0027
0.0025
0.0045
0.0021
0.0159
0.0523
0.0683
0.1105
0.1635
0.2192
0.3038
0.4170
0.4700
0.6544
0.9056
0.8665
0.8247
0.7361
0.6315
0.5175
0.4783
0.3756
0.2539
0.1589
0.0640
0.0199
0.0101
0.0033
0.0917
0.1310
0.1708
0.2618
0.3526
0.4302
0.4534
0.5139
0.5826
0.6219
0.6322
0.5631
0.5199
0.3423
909.61
905.46
900.43
893.52
885.58
881.25
879.86
881.20
888.48
893.66
914.05
953.34
973.88
1058.99
323. 2 K
0.0051
0.0066
0.0223
0.0854
0.1561
0.1843
0.2155
0.2817
0.3124
0.4948
0.7151
0.8462
0.8414
0.8074
0.6274
0.4406
0.2969
0.2490
0.2005
0.1179
0.0885
0.0147
0.0043
0.0017
0.1535
0.1860
0.3503
0.4740
0.5470
0.5667
0.5840
0.6004
0.5991
0.4905
0.2806
0.1521
886.88
883.61
868.91
865.18
869.77
874.89
881.34
893.46
902.49
969.68
1076.68
1143.25
a S anda d unce ain ies u a e u(T) = 0.5 K, u(x) = 0.0005 , u(ρ) = 0.05.

22
Table 5. Pa ame e s o equa ion 1
Sys em
T /K
Pa ame e s
2
Glyce ol (1) + sa dine oil (2)
+ e -bu anol (3)
303.2
A
12
= 562.24
A13= -181.51
A23= -77.64
B
12
= 606.77
B13= 8.20
B23= 70.33
0.9997
323.2
A
12
= -828.77
A13= -168.48
A23= 19.24
B
12
= -989.29
B13= -199.14
B23= -68.10
0.9986
Glyce ol (1) + sa dine oil (2)
+ e -pen anol (3)
303.2
A
12
= -370.85
A13= -163.54
A23= 57.31
B
12
= 334.08
B13= -11.81
B23= -85.09
0.9998
323.2
A
12
= -386.53
A13= -160.66
A23= 39.15
B
12
= 37.75
B13= -36.12
B23= -78.65
0.9998
23
Table 6. Expe imen al (liquid + liquid) equilib ium da a o he sys em glyce ol (1) + sa dine
oil (2) + e -bu anol (3) o weigh ac ions w a empe a u e T = 303.2 K and T =
323.2 K.a
O e all composi ion
Glyce ol- ich phase
Oil- ich phase
w
1
w
2
w
3
w
1
w
2
w
3
w
1
w
2
w
3
303.2 K
0.2503
0.3003
0.3504
0.4002
0.4485
0.2504
0.2998
0.3499
0.3999
0.4500
0.4993
0.3999
0.2997
0.1999
0.1015
0.3470
0.4412
0.5690
0.7280
0.8594
0.0397
0.0223
0.0191
0.0020
0.0191
0.6133
0.5365
0.4119
0.2700
0.1215
0.0125
0.0169
0.0161
0.0075
0.0055
0.7508
0.7930
0.8243
0.8487
0.8744
0.2367
0.1901
0.1596
0.1438
0.1201
323.2 K
0.2502
0.2998
0.3499
0.3984
0.4500
0.2504
0.3003
0.3501
0.3963
0.4501
0.4994
0.3999
0.3000
0.2053
0.0999
0.3673
0.4843
0.6070
0.7491
0.8944
0.0238
0.0095
0.0076
0.0066
0.0004
0.6089
0.5062
0.3854
0.2443
0.1052
0.0245
0.0185
0.0106
0.0062
0.0051
0.6994
0.7323
0.7539
0.8299
0.9044
0.2761
0.2492
0.2355
0.1639
0.0905
a S anda d unce ain ies u a e u(T) = 0.5 K, u(x) = 0.0005.
24
Table 7. Expe imen al (liquid + liquid) equilib ium da a o he sys em glyce ol (1) + sa dine
oil (2) + e -pen anol (3) o weigh ac ions w a empe a u e T = 303.2 K and T =
323.2 K.a
O e all composi ion
Glyce ol- ich phase
Oil- ich phase
w
1
w
2
w
3
w
1
w
2
w
3
w
1
w
2
w
3
303.2 K
0.3506
0.4002
0.4199
0.4492
0.3502
0.3907
0.4203
0.4433
0.2992
0.2091
0.1598
0.1075
0.7451
0.8470
0.8776
0.9182
0.0027
0.0121
0.0158
0.0085
0.2522
0.1409
0.1066
0.0733
0.0303
0.0108
0.0123
0.0074
0.6238
0.7155
0.7729
0.8476
0.3459
0.2737
0.2148
0.1450
323.2 K
0.3505
0.3797
0.3994
0.4492
0.3501
0.3803
0.4003
0.4486
0.2994
0.2400
0.2003
0.1022
0.7922
0.8545
0.8914
0.9411
0.0007
0.0048
0.0054
0.0015
0.2071
0.1407
0.1032
0.0574
0.0389
0.0257
0.0105
0.0121
0.6117
0.6622
0.7110
0.8317
0.3494
0.3121
0.2785
0.1562
a S anda d unce ain ies u a e u(T) = 0.5 K, u(x) = 0.0005.
25
Table 8. NRTL pa ame e s o he sys ems: glyce ol (1) + sa dine oil (2) + e -bu anol (3)
and o he glyce ol (1) +sa dine oil (2) + e -pen anol (3)
Pai
A
ij
/K
A
ji
/K
α
ij
RMS
Sys em: glyce ol (1) + sa dine oil (2) + e -bu anol (3)
12
13
23
2781.9
620.6
-155.6
1365.1
941.1
1649.8
0.5
0.5
0.5
0.58
12
13
23
5382.9
720.0
614.5
3825.9
1045.3
1506.2
0.309
0.429
0.501
0.48
Sys em: glyce ol (1) + sa dine oil (2) + e -pen anol (3)
12
13
23
4219.8
840.1
48.1
6102.6
1010.3
1744.1
0.4
0.4
0.4
0.48
12
13
23
5012.5
841.1
439.4
2523.4
964.56
1626.4
0.362
0.408
0.454
0.31
32
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00 0.00
0.25
0.50
0.75
1.00
Te -pen anol
Sa dine Oil
Glyce ol
Figu e 6. Liquid-liquid equilib ium o he sys em glyce ol + sa dine oil + e -pen anol a
323.2 K: ---, binodal cu e; ♦ ie lines;  NRTL (α = 0.4).

33
Figu e 7. O hme -Tobias plo o he sys em glyce ol (1) + sa dine oil (2) + e -bu anol (3)
a 303.2 K (●, 2 = 0.9683) and 323.2 K (○, 2 = 0.9704) and o he sys em glyce ol (1) +
sa dine oil (2) + e -pen anol (3) a 303.2 K (■, 2 = 0.9775) and 323.2 K (□, 2 = 0.9701).