Translation Series No. 3600

gee*
FISHERIES AND MARINE SERVICE
Translation Series No. 3600
Upper limit of complexing of urea with ethyl esters
of normal C 8 to C 12 monocarboxylic acids
by E.I. Salmonova
Original title:
Verkhnii predel kompleksoobrazovaniya karbamida
s etilovymi efirami normal l nykh monokarbonovykh kislot C 8
12
-C
From:
Khim. Tekhnol. Topl. Masel (4): 29-31, 1975
Translated by the Translation Bureau(JW)
Multilingual Services Division
Department of the SecreLary of State of Canada
Department of the Environment
Fisheries and Marine Service
Halifax Laboratory
Halifax, N.S.
1975
8
pages typescript
)Y)
rà
DEPARTMENT OF THE SECRETARY OF STATE
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BUREAU DES TRADUCTIONS
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INTO
'17RANSLATED FROM - TRADUCTION DE
EN
English
Russian
AUTHOR - AUTEUR
E.1. salmanova
TITLE IN ENGLISH - TITRE ANGLAIS
Upper limit
of normal
of
complexing
of urea with ethyl esters
C8 to C 12 monocarboxylic acids
TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS)
TITRE EN LANGUE ÉTRANGÉRE (TRANSCRIRE EN CARACTÉRES ROMAINS)
Verkhnii predel kompleksoobrazovaniya karbamida s etilovymi
efirami normalinykh monokarbonovykh kislot C8-.C 12
REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHARACTERS.
RÉFÉRENCE EN LANGUE ÉTRANGÉRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACTÈRES ROMAINS.
Khimiya i tekhnologiya topliv i masel
REFERENCE IN ENGLISH - RÉFÉRENCE EN ANGLAIS
The Chemistry and Technology of Fuels and Oils
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29 - -31
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USSR
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4 1975
From: Khimiya i tekhnologiya topliv i masel (The Chemistry and
Technology of Fuels and Oils), no. 4, pp. 29--31, 1975 (USSR).
Upper limit of complexing of urea with ethyl esters
monocarboxylic acids uw -rm ril
of normal C 8 to C
• •
I... .z.rifk- iejlATtot,1
12
ioa onl yFe.:r
by
TRADOcTICN NON RZVISEE
inktrmeion scuiern cent
E. I. Salmanova and others
UDC 541.49:547.27
Esters of normal monocarboxylic acids are used as fragrant
29*
substances in the perfumes and cosmetics industry [1].
These compounds are significant with regard to the method
of determining the upper limit of complexing of the hydrocarbons
with urea, since they contain more or less long, normal hydrocarbon chains and should behave like n-alkanes [2, 3].
The only thing that is known about the complexing of esters
with urea is that they form crystal complexes at normal temperatures [4].
For our specimens of the present study we chose ethyl esters
of n-monocarboxylic acids with 8 to 12 C atoms per molecule.
*
SO5-200-10-31
The numbers in the right-hand margin indicate page numbers
of the original (Tr.).
/30
2
We also used analytically pure urea, and as an activator we used
redistilled ethyl alcohol.
The experiments in determining the
temperatures of the upper limit of complexing of individual esters
and of their binary and multicomponent mixtures were conducted
according to the method discussed in [2].
These tests resulted in the establishment of the temperature
of the upper limit of complexing (in C') for ethyl esters of the
following acids:
Caproic acid (n=8) . . . . 65.9
Caprylic acid (n=10) . . . 79.7
Pelargonic acid (n=11) . . 86.8
Capric acid (n=12) . . . . 98.8
where n is the number of C atoms in an ester molecule.
Accordingly, the dependence of the temperature of the upper
limit of complexing of the first members of the series of ethyl
esters, which form complexes with urea, on the number of C atoms in
their molecules can be described by the same general linear equation
which was obtained earlier for the similar first five members of
the n-alkane series [2].
The constant a is numerically equal to1e=0,,--0
I :that is to say,
to the difference in temperatures of the upper limit of complexing
of two individual ethyl esters which differ from each other in
the number of C atoms (by one) in the molecule.
The difference in
the number of C atoms n and the whole number quotient obtained by
dividing the experimentally obtained temperature of the upper limit
of complexing by a is the constant b, and the remainder from the
division is the constant v. Thus:
AO
3
where ip is the integral qudtient;
b =
The constants a, b and v for n-alkanes correspond to 10, 4
and 8, respectively, and for the esters under study they amount
.
to 7, -1 and 2.8 respectively. Thus equation 1 with respect to the
esters in question can be written as follows:
0.-- 74-1)1-2.8.
(2) 1
An analysis of the binary mixtures of the esters referred to
above established that the dependence of the temperature of the
upper limit of complexing of the main mixture constituents on the
concentration of secondary constituents, which varied from 0--99 mass. 70, can
eso be
precisely described by the equation which was obtained earlier
for the binary mixtures of n-alkanes [2].
1- • --06u
where G
• - • .• •
.(3)
is the temperature of the upper limit of complexing (C ° );
o6. m H
is the temperature of the upper limit of complexing of
the same compound in a binary mixture at concentration c of the secondary component (C°);
.
c is the concentration of the secondary component in the
binary system (mass %);
At is the constant gradient of decrease in the temperature of
the upper limit of complexing per unit of concentration
increase of the secondary constituent (C ° /mass %).
An analysis of the values of the gradients6. t for various
binary mixtures of esters revealed another rule, which we could
establish in similar experiments with binary mixtures of n-alkanes.
4
Tab le I
T A 11:111U A 1
flociosifint,te rpaRne07i.t Lit ypanne000 (3)
700 600apilhix
aqiiipors
-CMCCCii 3111,110BI,IX
tIncno yrneromnax a -romon
n 1,:onthy.-e ocromioro
nomnoncura
e
:0e
coe
yrarpoinmx nio,on n MO le) yle
oporo ho , rioneura
7
0, 080
0,130
0,180
0,230
0,280
8
9
10
11
12
C8—C12
rilantlell
I
8
I
9
I
10
I
11
0.080
0, 130 0,0s0
0,180 0,130 0,080
0,230 0, 180 0,130 0,080
Table 1: Constant gradients Qt of equation 3 for binary
ethyl esters.
mixtures of
C8--C12
a - number of C atoms in a molecule of the main
constituent;
b - constant gradients of the number of C atoms
in a molecule of the secondary constituent.
According to the data presented in Table 1, the least gradient
t = 0.080 ° C/mass.% characterizes the binary mixture consisting
of esters which differ from each other in the number of C atoms
in the molecule by
of Zlt.
n = 1.
The more
the higher the value
An increase ingn by one increases
t by 0.050 C ° /mass.%.
The dependence of At on 4 n can be expressed as follows:
1
At .. 0,080 A- OMO (An -- 1).
(4)
1
This dependence as well as the results of analyzing the binary
mixtures of ethyl esters are shown graphically in the illustration
(see illustration) in which the solid lines indicate experimental
curves and the broken lines indicate curves obtained by calculation.
To verify equations 3 and 4, we analyzed a series of multicomponent mixtures resembling industrial mixtures of untreated esters.
The composition of these mixtures as well as the results of the
experimental determination of the temperature of the upper limit of
5
comp1exing of the main constituent and the computed figures for
the upper limit of complexing are shown in Table 2.
•ra bTe 2 -
T A li Jill 11. A 2
1
Pe3yJIbTaill flCCaCROflaUUT mitoroxomnonettrimix cmccen
Cs—C12
ST11:10131,IX
®
Komnoitrunt cwcrl [.1-1 ■ !--0;)
macc. n-voron -IPCotioum>:
Uà
TCM'1?yp ft
BFIK.
K tC1OT
àOcm . °C
,,-z
'0.
rc
.0
,----
c.e
'.'
00
-
5
ii
0 e,
0
Y a
5
5
50
-48
50
-20 . 20
-55
15
10
10
10
1,5
70
8,5
50 20
0
=
c
re:
2 e
10
2
60
30
70
20
30
no
`,3
30
82,0
89,5
78,4
82,5
75,6
83,4
79,8
■•■■•■•
V-
83,8
88,6
78,4
83,0
76,8
83,2
78,9.
+1,8 --0,9
0
+0,5
+1,2
—0,2
-0.6
-
.
.
•
Table 2: Results of a study of multicomponent mixtures of
ethyl esters.
C --C
8
12
a - constituents of the mixtures of esters (in mass.%)
of n-monocarboxylic acids;
al - capric acid;
a2
pelargonic acid;
a3
caprylic acid;
a4 - caproic acid;
a5 - valeric acid;
b - temperature of upper limit of complexing (C ° );
bl - computed;
b2 - experimental;
The temperatures of the upper limit of complexing for the
multicomponent mixtures of esters were calculated on the basis
of the equation which was obtained earlier for triple mixtures of
n-heptane [4]:
(5)
6
95
4-)
•
M
0 ki
ci
k
•90
e4O 0)
x>1
4-) -P
1
E 4-) ci 8 5
M
—C
0
L 0 t" 8 0
5
›
N2
0
• c
m ô 75
0
.c 0
4J .r
4J
4-
■, 1 3
\
\
6
70
\
8
oq
-
0
0
L 0)
D C
/0
9-5
Y 12
N
ro X w
L 0
0-- k
0. a
E E
O 0
h- U
-
13
•
'111,t
60
15
551
0
I
I
I
20
1#0
CO
Kongellmpagan
&ream
80
MO
go,iffionewma,macc.LY0
Concentration of sec. constituent
38B8C1INIOCTb
TemnepaTyptA
OT ;t1i1C.00110r1 RonnenTpannil
Bill<
octionitoro
nToporo
(ç%uleâil.Ty.à )
(«laptibtx cmecnx 3Titaont,ix D(Impon n-monotcap6onoubtx KIIC;10T.
Ipiinble ((ocnonnoii -- ni opoil KomnonenTht») 6llnapubtx
cmcceil atimpon:
I — Ranpnuonnro-taviaprononoro:
2 — xanpuunnorod:rinpn.innorn:
WOMO011ellTa 8
3 — neaaprminnoro-Kalipit lonnro;
9 -- tialiplirion)ro-3univrounro:
a — Kanpnlonqro-'9itair ronoro;
5 — ne:lam- oft ,, tioro-Nanimionorce;
7 — Kattputronoro•eartpolionoro;
8 — ne:Inprollounro.b:nlipounlilt O.
9 — Ranpliaonoro-Kpiiponowiro;
/ 0 — F:aiiptilionnro•nancptiatinnoro:
/1 — «ItaliTour?ro xnupottnivno:
12 -- Tle.lap11111•111110 11a.9Cp11111InnOr0;
13— lianpueo8Oro.n1nepitaitonoro,
11 — Dienwronoro-uanep8a8000ro;
15 — Kaiipolionoro-BaaepnalLonoro.
Illustration: Dependence of the temperature of the upper limit
of complexing of the main constituent on the mass
concentration of the secondary constituent in binary
mixtures of ethyl esters of n-monocarboxylic acids.
Curves ("main--secondary constituents") of binary
mixtures of esters:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
-
capric-pelargonic;
capric-caprylic;
pelargonic-caprylic;
capric-enanthic;
pelargonic-caprylic;
caprylic-enanthic;
capric-caproic;
pelargonic-caproic;
caprylic-caproic;
capric-valeric;
enanthic-caproic;
pelargonic-valeric;
caprylic-valeric;
enanthic-valeric;
caproic-valeric;
7
where
lip
1 for the investigated esters, and the equation takes
.
the form:
(6)
According to the data in Table 2, the convergence of the
calculation and experimental methods of determining the temperature
of the upper limit of complexing for multicomponent mixtures of
ethyl esters of n-monocarboxylic acids is entirely satisfactory,
which suggests that the above relationships are valid and accurate.
The absolute average error amounts to
cm
Conclusions
•
1.
We have experimentally investigated the dependence of the
temperature of the upper limit of complexing of individual ethyl esters
of normal
C8--C12
monocarboxylic acids on the number of C atoms in
their molecules.
The relationships of the temperatures of the upper
limit of complexing of the main constituent of binary and of multicomponent mixtures of these esters to the concentration of the
secondary or other constituents of the mixtures correspond.
2. It has been established that all the relationships investigated can be described by linear equations obtained earlier for
individual
C6--C10
n-alkanes, binary mixtures of C --C n-alkanes
9
6
and triple mixtures of n-heptane respectively, with an absolute
average error not exceeding 0.8 C ° .
3. We have obtained a new linear dependence of the variation
of the constant gradient of the equation of binary mixtures of ethyl
esters on the number of C atoms in the molecules of the main and
secondary constituents of the mixtures.
8
References
1. Bolyanovsky, D.M. and others.
no.5, p.39, 1969.
"Oil refining and petrochemistry,"
2. Matishev, V.A. "The chemistry and technology of fuels and oils,"
no.11, p.18, 1966.
3.
.
"The chem. and tech. of fuels and oils," no.8,
p.6, 1970.
4. Truter, E.V.
"J. Chem. Soc," vol.9, pp.2416--2419, 1951.
I.M. Gubkin Institute of the
Petrochemical and Gas Industry,
Moscow
.1-../■■•■••■■■••■
1114TEPATYPA
L B o .i ii o n c i u
t. M., (I) It .1 11 nnon II. A., B nIC II X E. 11.. 3 a n it B. II. «11c(IncncpcpatIo .ma
TCNIIN11151s>, 1969. j\.:2 5, c. ;.:".9.
TCX1I0.1. TOIL-Inn II MaCC.1"),
2. M i T II III II B. A. eXum.
11, c. 18.
1966,
MaCC.1»,
3. M T II Ill C n 13. A.
. 0.M 8. C. 6
197
4. Truter E. V. J. Chem. Soc,", 1951. v. IX, p. 2416—
2419.
WILLY u