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Translation Series No. 633
The relationship of fish-odour reversion to the
isomerization and polymerization of fatty acids
in whale fats
By T. A. Khorin
_
•
•
`:-_-)C 0-\
•
Original title: Zavisimost' reversiya rybnogo zapakha
ot izomerizatsii i polimerizatsii zhirnykh kislot
V kitovykh zhirakh.
From:
Izvestiia Vysshikh Uchebnykh Zavedenii,
Pishchevaya Tekhnologiya for 1965, No. 1, pp. 114-117.
Translated by: G. Phillips,
•
Bureau for Translations, Foreiàn Languages Division,
Department of the Secretary of State of Canada
Fisheries Research Board of Canada
Technological Research Laboratory,
Halifax, N. S.
S
1965
I
I
BUREAU FOR TRANSLATIONS
FOREIGN LANGUAGES - .wwiee
men
DIVISION
/
FeY
-T
D'É 1" A
BUREAU DES TRADUCTIONS
DEPARTMEN.T OF THE SECRETARY OF STATE
CANADA
SECRÉTAI
;-)
DIVISION DES LANGUES
ËTRANGÈRES
TRANSLATED FROM - TRADUCTION DE
Russian
English
SUBJECT - SUJET
Food.technology
AUTHOR - AUTEUR
T.A. Khorin
TITLE IN ENGLISH - TITRE AN?LAIS
h)
.
The dePendunce of fish-odour reversion.on the isomerization and
polymerization of fatty acids in whale fats.
TITLE IN FOREIGN LANGUAGE - TITRE EN LANGUE gTRANGbIE
Zavisimoste reversiya rybnogo zapakha ot izomerizatsli
polimerizatsil zhirnykh kislot v kitovykh zhirakh.
REFERENCE - RdFeRENCE (NAME or 13001A OR PUBLICATION - NOM DU LIVRE OU PUBLICATION;
,
(Index No 70372)
Food Technology, No. 1, 1965.
Id,
PUBLISHER - elDITEUR
Mini str y of higher and intermediate special education
of the USSR
CITY - VILLE
DATE
Moscow
REQUEST RECEIVED FROM
REqufS PAR
DEPARTMENT
MINISTRE
PAGES
January, 1965
Mr. Larose
Fisheries
4
‘ri■ .11
r i le
Wii
„ ii
(Russian)
10 (English)
OUR NUMBER
NOTRE DOSSIER NC)
TRANSLATOR
TRADUCTEUR
r0
•)
5
G. Phillips
.11•10
YOUR NUMBER
VOTRE DOSSIER N 0
DATE RECEIVED
REÇU LE
riOs-300-11>
DATE COMPLETED
REMPLIE LE
(Circa 17.9.65)
2 Nov. 65.
-
.411,
74'/''
M.
-1
Proceedings of high'er educational establishments
(Izvestiya Vysshikh Uchebnykh Zavedenii)
FOOD TECHNOLOGY
No. 1.
1965
n
The dependence of fish-odour reversion'on the
isomerization and polymerization of
•
fatty acids in whale fats.
"
T.A. Khorin
Troitsk Fat- Combine.
The aim of this work is to determine in liquid
whale fat (of Antarctic origin) and its products, the
fractions of fatty acids which govern the reversion of
fishy taste and smell in deodorates of this fat and in
whale tallows.
The liquid, solid and polymerized
fractions were separated by the Twitchell process,
using the - property of insolubility of • lead salts of
polymerized fatty acids in boiling ethyl alcohol acidified
with acetic acid (1).
• Liquid whale fat - loses its unpleasant . fishy smell
when deodorized, and is not susceptible to reversion if
its fatty acid content includes at least 10 - 13% by weight
of polymerized acids.
This quantity is formed in the
first 45 minutes of deodorization at 275-285 °C (Table 1),
whereas during the bext 45 minutes their growth rate is
diminished by a factor of 8 or 9, for example. However,
in the first 45 minutes of deedorizing (raw) linseed oil
at the same temperatures we separated 98O% of the total '
0 04112
weight of acids as polymerized flAtty acids, and in the
next 45 minutes, 31.90%.
In linseed oil and in liquid whale fat the fatty
acids polymerized first are those having not less than
three double bonds in the chain. These acids of whale
fat form in the first 45 minutes 10 to 13% of the
polymerized fraction, which.consists mainly,of high
molecular weight fatty acids.(clupanodonic and the like) :
(Table 1, experiments 1-6).
Due tothe-conversion of the
latter into polymer, reversion of the fishy taste and
. odour of the fat is not transmitted to the produàts. . •
With further deodorizing of . whale fat, when the . acids . .
having not less than three double bonds in the dmdn are._
exhausted, the growth of the Tolymerized fraction Slows
down abruptly (Table 1, experiments 7.84 8).
We demonstrated that the quantity of solid acids
in deodorized liquid whale fat rises initially to a
maximum (Table 1, experiment 4), .and falls with further
_
. _
deorizatn.
In accordance with the.foregoing,. the molecular
weights, coefficients of refraction end iodine numbers
of the solid fractions increase initially and their. diminish (Experiments 1-6). This'is attributable to - the
fact that during the first Minutes Of deodOrization, the
high molecular weight, unsaturated fatty' acids of the
liquid fraction of the raw fat, isomerizing, become
solid, raising its mean moledular weight and other
indices. With further deodoriZatien they go from the
solid fraction into the polymerized fraction, while the
indices of the solid fractions of the fatty acids diminish.
We demonstrated such transitions in deodorizing the
liquid fraction of the fatty acids of raw liquid whale
fat (Table 2).
In the first minute, isomerization and transition
to the solid fraction are experienced by nearly all those
unsaturated fatty acids which subsequently formthe-
•
polymerized fraction of the fatty acids . (Experiment 2).
This is confirmed by the constant melting points of the
liquid and solid fractions respectively in ail deodorates,
and by the fact that the coefficient of refraction of the
raw fatty acids at the beginning of the process falls and.
remains constant in the liquid fractions of all deodorates
(Experiments 2-6). Moreover, the polymerized fraction
grows and the solid fraction diminishes concurrently, but
the sum of both is approximately constant (20080-22.23%),
i.e. the solid fraction is converted into the polymerized
fraction (Experiments 2-6).
The coefficients of refraction
of the solid fractions intreased, evidently, at . the
expense of the increasingly greater nUMber of fatty atid
double bonds in the combined state (2).
With more protracted deodorizing of whale . fat,
the solid acids of the raw fat also become polymerized,
copolymeriZed and partially enter the polymerized fraction
of the deodorate. As a result of this transition and
thanksoigptumnbers(coquntplw
molecular weights), they raised the acidity of the
polymerized fraction (Table 1, experiment 8).
Reversion of fishy taste and odour in liquid
whale deodorates depends ° on the quantity of.solid-fraction
fatty acids which they contain.
It appeared particularly
quickly, for example, in those deodorates where the
difference between the solid fraction content in the
deodorate and in the raw fat was greatest, I,e. in the
range 9 to 13% (Table 1, experiments 2-5). Reversion
did not occur if this difference was under 3% (Experiment
6). Evidently in this case reversion in the deodorate
will not occur if high molecular_weight,:_isomerized,
unsaturated fatty acids have gone from its solid fraction
into its polymerized fraction.
-
•
-
In studying.the solid fractions of fatty acids
•
extracted from whale tallows, we established that the
change in properties of solid acids in the process of
hydrogenating liquid whale fat. at 200-220 °C is identical
with the change in properties of these acids in deodorization (Table 1) of the same whale fat.
The co e fficients -
of refraction, iodine numbers and molecular, weights of.
.
the solid acids of tallows also,increase at the beginning of
hydrogenatioù • of whale fat, but diminish at the end of
hydrogenation.
quantitative
At the same time, the solid fraction grows
(Table 3). .
•
•
Thus, in the hydrogenation of liquid whale fat
also, high moleCular weight, unsatUrated fatty acids are
first isomerized and go from the liquid fraction into the
solid fraction, then they are hydrogenated and remain in the
solid fraction or they are polymerized and go' int °. the
polymerized fraction, while the - -iodine numbers and
coefficients of refraction of thé solid fractions of
the tallows diminish (Table 3).
•• ./5
The falling of melting points and the increase
in the molecular weights of the solid fractions at the
beginning of hydrogenation of the fat is attributable to
the fact that high molecular weight, isomerized fatty acids
have a low melting point (Table 2), and, going into the
solid fraction of the raw fat, they lower its melting
point and raise the mean molecular weight of the solid
acids (Table 3).
•
Subsequently the melting point of the
solid fraction increases at the expense of the hydrogenated,
high molecular weight, isomerized acids, whereas the mea.n,
molecular weight of the fraction diminishes due to the
partial transition of high molecular weight, isomerized
fatty acids from the solid into the polymerized fraction,.
and at the expense of dilution of the solid fraction with
hydrogenated, low molecular weight, fatty acids.
Reversion of fishy odour in the solid fractions of
whale tallows does not occur if the difference between
the coefficients of refraction of the solid fractions of
the fatty acids of the whale .tallow and the raw fat does
not exceed 0.0010 - 0.0015 (10-15 units), or if the
difference in iodine numbers is 10-15, i.e. when the
isomerized, high molecular weight, unsaturated fatty acids
contained in the solid fraction are subjected to hydrogenation.
- CONCLUSIONS 1.
Reversion of fishy taste and smell in
deodorized liquid whale fat does not occur if its fatty
acid content includes at least 10 to 13% of polymerized
acids which were formed from high molecular weight a c- ids
having not less than three double bonds in the chain.
9
../6
At the commencement of deodorization these unsaturated
acids become isomerized, go into the solid fraction and
then into the polymerized fraction of the whale fat
deodorate.
2.
In the hydrogenation of liquid whale fat, '
high molecular weight, unsaturated fatty acids also
become isomerized, and go out of the liquid fraCtion'into
the solid fraction, whereupon a large part of these
isomerized acids becomes hydrogenaeèd and'reMains in . the
solid fraction, and only a small part of them becomes
polymerized and leaves the solid fraction, forming the
polymerized fraction of whale tallow.
Laboratory of physicochemical
Received 2 March 1964
production control.
- BIBLIOGRAPHY ,
1.
Tyutyunnikov, B.N.,
Bogdan,
The Oil and Fat Industry, No. 9, 20, 1960.
(Masloboyno-zhirl;kaya promyshlennost'
2.
Zinov'ev, A.A.,
The Chemistry of (organic) Oils, 46o, 528,
Pishchepromizdat (Food InduStry- Publishing House),
Moscow, 1952.
. •
.../
•
7
Table 1.
_
.
Fractions of fatty acids
p o 1 yra eri zed
Solid
(h)
(a)
.(e)
I (d)
(c)
(f
(g)
)
(h)
(1)
Raw fat
-
29,36 •
I
44
I
276
I
1,4430
I
62
I
0,38
176,40
0,93
160,80
160,90
164,00
179,80 •
180,60
185,00
189,80
Fat deodorates
2
3•
4
5
6.
7
.8
1
5
10
20
45
90
300 .
38,40
38,90
42,96
38,60 f'
32,12
32,00
27,07
277
294
303
280
282
279
270
39
39
38
39
41
42
42
1,4450
1,4453
1,4500
1,4458
1,4446
1,4440
1.4427,
70 •
64
67
65
62 r
62
56
16 .
.
4,10
12,57
14,00
17,50
Raw oil
9
-
18,60
I.
---
I
298
j
-
I
0,26
Oil deodorates
10
12
• 13
14
15
(a)
(1))
(e)
(d)
(e)
(f)
(g)
(h)
(1)
1
5
, 10
15
45
90
21,64
22,20
24,57
28,57
22,01
10,76
0,39
0,50
1,06
1,53
9,80
31,90
Experiment (Serial number).
Duration of deodorization, minutes.
Content, %.
Melting point, °C.
Molecular weight by Rust's method.
Coefficient of refraction at 60°C.
Iodine number by HUbeles method.
Content, %.
Potassium number, milligrams KOH.
Qe
(18
Table 2.
t(b) › (0_1(d) 17 (e) l(f)
Raw liquid fatty acids
-5,5 1 1,4590
HAI< a a
,
Deodorates of liquid fatty acids
H(11.1141Ca SI
••
•
T Be Fula st
If Me p1130 Bamian
)1(11,aita 13
Taepng
flomime pH 30 II a 11u 313
>I<iuu<a n
TBepÂao
nommepx 30 BanHan
n OJI
3
(a)
(b)
(o)
(d)
(e)
(f)
5
10
5
>I<H,aing
15
6
TnepttaR
Flomimepnottaintam
>Kul< an
Tnep2ta n
11 oil 1-1,1 e pFt 36 s tula
25
79,20
19,50
1,30
79,17
14,20
6,63
79,00
11,70
9,30
-5,5
19,0
1,4571
1,4565
-5,o'
19,0
1,4572
1,4591
19,0
1,4571
1,4594
78,70
7,10
14,20
77,77
1,03
21,20
--5,0
19,0
-5,5
19,0
,
1,4571 .
1,4611
1,4578
•1,4645
Experiment (Serial number).
Fractions of fatty acids.
Duration of deodorization, minutes.
Ratio of fractions, %*
Melting point, ° C.
Coefficient of refraction at'60 °C.
)1fm,gxasi
-
TrlepAast
- Solid
rforivnviepma 013aiilia51
-
Liquid
Polymerized
• •./ 9
*,
*if
.1,1.1•Ce.M
Solid fraction of fatty acids'
(f )
(g)
I
(h)ft
Raw fat
1 35,52
I
45
1
280
1 1,4430
48
1,4449
1,4460
1,4443
1,4140
62
- 71
60
Whale tallow
-
2
3
4
5
(a)
(b)
(c)
(d.)
(e)
(f)
(g)
(h)
1
2
3
4
42,54
59,42
60,46
62,03
39
• 32
36
37
299
311
302.
289
sa
Experiment (Serial number)
Duration of hydrogenation, hours°
Content s %.
Melting point, ° C.
Molecular weight by Rust's method.
Coefficient of refraction at 60°C.
Iodine number by Hilbel's method.
Reversion.
A I Did not occur
2. Occurred
3
4 Did not occur
1
t
.5
1
i
. .. / 1 0
• 10
-
TRANSLATORS NOTES 1. The spellings of the surnames in the
translation, i.e. Twitchell, àbel and Rust, are
conjectural.
2. The comma is used as a decimal point in
the tables.
(This notation has not been used in the
translation).
3. As the distinction between whale oil and
liquid whale fat is a subtle one, the Russian "zhir"
•
has been rendered by "fat" in every instance, and the
Russian "maslo" (which appears only in the Tables) by
t
oil".
The word "blubber" has been avoided as unscientific.
4. The word "deodorate" has been coined to
mean "deodorized product" after the Russian "dezodorat"
by analogy with hydrate, filtrate etc.
5. Further research indicates that bibliographical
reference #1 should read:
"Butter and Fats Industry,.
No , 9, 20, 1960" (Maslozhirovaya promyshlennost , )
Vide index number 70510 in the Soviet catalogue
"Newspapers and Magazines of the USSR for 1966".