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Dispersometric coefficients of high-boiling hydrocarbons of mixed structure
DISPERSOMETRIC COEFFICIENTS OF HIGH-BOILING HYDROCARBONS OF MIXED STRUCTURE* A. A. PETROV, O. YE. :BATALIN, A. A. MIKHNOVSKAYA, YU. A. BEDOV, M. I. KRASAVCHENKO and S. D. PUSTIL'NIKOVA Institute of Geology and the Exploitation of Mineral Resources; U.S.S.R. State Committee for th~ Fuel Industry; A. A. Zhdanov Leningrad State University (Received 13 December 1962)
TO CHARACTERIZE aromatic hydrocarbons and to determine their concentrations in mixtures, Ioffe and Batalin [1-3] proposed a 0aodified relative dispersion method which consisted in determining the so-called "dispersometric coefficient":
DFC: nF--nc-. 104.
(1)
nc--1.04 In the same papers, on the basis of experimental data for a large number of individual lower hydrocarbons, a numerical formula for the dispersometric coefficient having the following form was proposed; DFc---- 194+
A + 1.5n • 10a , molecular weight
(2)
where 194 is the mean dispersometric coefficient for paraffinic-naphthenic hydrocarbons, A is a factor characterizing the type of aromatic nucleus, and n is the number of substituents in the aromatic rings. It was of definite interest to check values of the dispersometric coefficient for high-boiling hydrocarbons of various structures containing several benzene or naphthalene nuclei and also different numbers of naphthenic rings in the molecule. As experimental material we used the C19-C32 hydrocarbons synthesized in the Laboratory of High-Molecular Weight Petroleum Compounds in 1957-1961 [4]. The investigation showed that the dispersometric coefficients of any hydrocarbons not containing aromatic units (in particular, the hydroaromatic analogues of the hydrocarbons listed in the Table) vary between 192 and 194 units, regardless of their molecular weight and structure. At the same time, the dispersometric coefficients of the aromatic hydrocarbons were well described * Neftekhimiya 3, No. 6, 922-927, 1963. 365
A. A. PETROV et al.
366
DISPERSOMETRIC COEFFICIENTS OF INDIVIDUAL HYDROCARBONS
S t r u c t u r a l formula
Formula
Dispersometric coefficient
2o ~D
Found *
()
- C ~ C~ \C+
0-i:'-
Calculated
C19H32
1.4805
253
255
CI~H3o
1'4973
257
256
C24H4~
1"4800
240(241)
242
C2,H4~
1"4910
257
256
C24H4o
1'5040
251
247
C24H4o
1'4990
242
243
C2~H4o
1"4971
244(243)
243
C~H~o
1"4915
240
243
C2.1H4o
1"5000
256
252
C~Hzs
1'5081
244
243
C24H38
1'5158
246(247)
243
C21I-I38
1"5125
243
243
C32Hse
1.4947
242(239)
237
c ,~1~, -c -
c
C.
O-i:O ~, /\-c
--
c_/\
c
c- .l%l/ l c o c l \ / p-c .
.
.
.
.
-c-C~c c-c -
-II
C-C-O
~-c-c-c-c-c-c-c-,/~ --C~
-- e l I
Dispersometric
coefficients of high-boiling
hydrocarbons
367
Continuation of the Table Dispersometric coefficient
Formula
Found *
( Calculated $
292(292)
293
292(292)
293
1.5412
290
294
1.5392
290
294
1x5257
305
302
1.5300
304
1.5347
312(313)
312
1.5269
299
302
1.5678
314
313
1.5119
279
279
1.5143
288
286
1.5248
299
299
1.5280
311
309
1.5219
302
A . A . IOETROV et al.
368
(Continuation, of the Table) Structural formula
Dispersometric coefficient
Formula
Found *
Calculated
C2sH38
1.5276
305
300
C28H38
1.5540
302
293
C3~H4e
1.5480
289(288)
287
C12H12
1.6120
512(511)
514
CI~H12
1.6070
514
514
C23H34
1.5310
350
350
Ca2Hs2
1.5200
305
305
C3~Ha8
1.5962
418
423
O0-r-nO
C32Ha8
1.5989
442(448)
(A = 105)
~--%_z--% c.
C18H22
1.5682
418
(A = 52)
C2~H34
1-5383
360
(A=52)
C26H3o
1.5661
333
334
C~lHs0
1.5921
374
374
c
c
~
--\_~--%
c_~--%_/--
I
C5
\~
c. I II I C
i
I
I II J I
C C
c/%/\//
0(; ;? 0
j;? '
I
I
?\/%,-c-c,-c-7%/% [
~
I fi
t
-~--%-c-c C
I£~-C-C-C-C-C-C-C-~
'
I
-c-c-?%
?\
*
* The values of the dispersometric coefficients obtained on a precision refractometer of the IRF*23 Pulfrich type are given in brackets. t The hydrocarbons were kindly provided by M. A. CheFtsova and Ye. P. Koplan (Institute of Organic Chemistry, U.S.S.R. Academy of Sciences). I)ispersometric coefficients calculated by means of formula (2).
Dispersometric coefficients of high-boiling hydrocarbons
369
by formula (2}, the mean value of the factor A obtained from the experimental data being 14.5 for hydrocarbons of the benzene series, 29 for a,w-diphenylalkanes, 31 for hydrocarbons of the diphenylmethane series, 52.0 for alkylbiphenyls, 47 for hydrocarbons of the naphthalene series, and 94 for ~,wdinaphthylalkanes. For compounds containing different aromatic nuclei in the molecule, the factor A is an additive magnitude. Thus, the factor A is a characteristics of the nature of the aromatic nuclei in complex hydrocarbon molecules. Consequently, a determination of the dispersometric coefficient can be recommended in the chromatographic separation of hydrocarbon mixtures. This relates particularly to hydrocarbons derived from petroleum, where the presence of a large number of naphthenic rings in aromatic compounds frequently casts doubt on analytical results based only on a determination of the refractive index (Figure).
DFCD 400
?
,4=47 l
35O ,
250
1.55
¢/
150
I A=O
I
0
25
1.60
A =14.5 ~ ~ /
208 -
150
1.65
2
A =29
300
n~°
i
50 %
I
75
1.45 . lot?
Dispersometric coefficients and refractive indices obtained in the chromatography of hydrocarbons of the 350-420° fraction of Giurgill petroleum. Along the axis of abscissae are plotted the percentages by weight of the fractions separated. 1--DFcD; 2--n2DO The determination of the dispersometric coefficient of hydrocarbons was carried out on a standard refractometer of the I1~F-22 Abb6 type. In some cases, precision measurements were carried out similarly on a refractometer of the I R F - 2 3 Pulfrich type. The agreement of these measurements was completely satisfactory (Table). The accuracy of the determination of the dispersometric coefficient on the I R F - 2 2 refractometer was =[=2% (relative). In view of the closeness of the values of n D and n c [5] in the formula D~c~-- n F - n c .104 n c - 1.04
370
A. A, PETROVet al.
the refractive index for the hydrogen line in the numerator can be replaced b y the refractive index for the sodium D line. On an average, for various aromatic hydrocarbons: DFC= DFCD+(0"5 + 1.5)%. However, the use of the D line makes it possible to carry out a determination of the dispersometric coefficient on a standard Abbd type refractometer (IRF-22). I t must also be added t h a t the data in the literature with respect to the dispersion 09FCD can be approximately recalculated to give dispersometric coefficients by the following relation: DFc D ~--CgFCD" 10" 9 ± 2 %
(relative).
The experimental data on the dispersometric coefficients of the hydrocarbons investigated are given in the Table. The column "calculated dispersometric coefficient" gives the values of the dispersometric coefficient obtained by using formula (2) and the average experimental values of the factor A mentioned above. The authors thank B. V. Ioffe for his attention to the present work.* SUMMARY 1. The dispersometric coefficients of a large number of high-boiling hydrocarbons of various structures have been determined. 2. I t has been confirmed t h a t the experimental values of the dispersometric coefficients of aromatic hydrocarbons are satisfactorily described by the formula:
A + 1.5n DFC--~ 194+
molecular weight
' 10a
where A is a factor characteristic of the chemical nature of the aromatic nuclei (benzene, naphthalene, and so on), and n is the total number of substituents in the hydrocarbon rings. 3. I t has been proposed to use dispersometric coefficient determinations in the chromatographic separation of high-boiling hydrocarbon mixtures. Translated by B. J. H.A.ZZl~AD
REFERENCES
1. B. V. IOFFE and O. Ye. BATALIN, Zh. prikl, khim. 34, 603, 1961 2. B. V. IOFFE, Refraktometricheskiye metody v khimii. (Refractometric Methods in Chemistry.) Goskhimizdat, Leningrad, 1960 3. B. V. IOFFE and O. Ye. BATALIN, Nefteldfimiya 1, No. 2, 156, 1961 4. L. N. KVITKOVSKII and A. A. PETROV, Zh. prikl, khim. 34, 613, 1961 5. F. D. ROSSINI, B. J. MAIR and A. J. STRIFE, Uglevodorody nefti. (The Hydrocarbons of Petroleum.) 1957, p. 198 * The following scientific colleagues of the Laboratory for High-Molecular-Weight Petroleum Compounds took part in the synthesis of the hydrocarbons: A. L. Tsedilina, L. N. Kvitkovskii, N. V. Zhdanova, Ye. I. Bagrii and L. N. Stukanova.
TO CHARACTERIZE aromatic hydrocarbons and to determine their concentrations in mixtures, Ioffe and Batalin [1-3] proposed a 0aodified relative dispersion method which consisted in determining the so-called "dispersometric coefficient":
DFC: nF--nc-. 104.
(1)
nc--1.04 In the same papers, on the basis of experimental data for a large number of individual lower hydrocarbons, a numerical formula for the dispersometric coefficient having the following form was proposed; DFc---- 194+
A + 1.5n • 10a , molecular weight
(2)
where 194 is the mean dispersometric coefficient for paraffinic-naphthenic hydrocarbons, A is a factor characterizing the type of aromatic nucleus, and n is the number of substituents in the aromatic rings. It was of definite interest to check values of the dispersometric coefficient for high-boiling hydrocarbons of various structures containing several benzene or naphthalene nuclei and also different numbers of naphthenic rings in the molecule. As experimental material we used the C19-C32 hydrocarbons synthesized in the Laboratory of High-Molecular Weight Petroleum Compounds in 1957-1961 [4]. The investigation showed that the dispersometric coefficients of any hydrocarbons not containing aromatic units (in particular, the hydroaromatic analogues of the hydrocarbons listed in the Table) vary between 192 and 194 units, regardless of their molecular weight and structure. At the same time, the dispersometric coefficients of the aromatic hydrocarbons were well described * Neftekhimiya 3, No. 6, 922-927, 1963. 365
A. A. PETROV et al.
366
DISPERSOMETRIC COEFFICIENTS OF INDIVIDUAL HYDROCARBONS
S t r u c t u r a l formula
Formula
Dispersometric coefficient
2o ~D
Found *
()
- C ~ C~ \C+
0-i:'-
Calculated
C19H32
1.4805
253
255
CI~H3o
1'4973
257
256
C24H4~
1"4800
240(241)
242
C2,H4~
1"4910
257
256
C24H4o
1'5040
251
247
C24H4o
1'4990
242
243
C2~H4o
1"4971
244(243)
243
C~H~o
1"4915
240
243
C2.1H4o
1"5000
256
252
C~Hzs
1'5081
244
243
C24H38
1'5158
246(247)
243
C21I-I38
1"5125
243
243
C32Hse
1.4947
242(239)
237
c ,~1~, -c -
c
C.
O-i:O ~, /\-c
--
c_/\
c
c- .l%l/ l c o c l \ / p-c .
.
.
.
.
-c-C~c c-c -
-II
C-C-O
~-c-c-c-c-c-c-c-,/~ --C~
-- e l I
Dispersometric
coefficients of high-boiling
hydrocarbons
367
Continuation of the Table Dispersometric coefficient
Formula
Found *
( Calculated $
292(292)
293
292(292)
293
1.5412
290
294
1.5392
290
294
1x5257
305
302
1.5300
304
1.5347
312(313)
312
1.5269
299
302
1.5678
314
313
1.5119
279
279
1.5143
288
286
1.5248
299
299
1.5280
311
309
1.5219
302
A . A . IOETROV et al.
368
(Continuation, of the Table) Structural formula
Dispersometric coefficient
Formula
Found *
Calculated
C2sH38
1.5276
305
300
C28H38
1.5540
302
293
C3~H4e
1.5480
289(288)
287
C12H12
1.6120
512(511)
514
CI~H12
1.6070
514
514
C23H34
1.5310
350
350
Ca2Hs2
1.5200
305
305
C3~Ha8
1.5962
418
423
O0-r-nO
C32Ha8
1.5989
442(448)
(A = 105)
~--%_z--% c.
C18H22
1.5682
418
(A = 52)
C2~H34
1-5383
360
(A=52)
C26H3o
1.5661
333
334
C~lHs0
1.5921
374
374
c
c
~
--\_~--%
c_~--%_/--
I
C5
\~
c. I II I C
i
I
I II J I
C C
c/%/\//
0(; ;? 0
j;? '
I
I
?\/%,-c-c,-c-7%/% [
~
I fi
t
-~--%-c-c C
I£~-C-C-C-C-C-C-C-~
'
I
-c-c-?%
?\
*
* The values of the dispersometric coefficients obtained on a precision refractometer of the IRF*23 Pulfrich type are given in brackets. t The hydrocarbons were kindly provided by M. A. CheFtsova and Ye. P. Koplan (Institute of Organic Chemistry, U.S.S.R. Academy of Sciences). I)ispersometric coefficients calculated by means of formula (2).
Dispersometric coefficients of high-boiling hydrocarbons
369
by formula (2}, the mean value of the factor A obtained from the experimental data being 14.5 for hydrocarbons of the benzene series, 29 for a,w-diphenylalkanes, 31 for hydrocarbons of the diphenylmethane series, 52.0 for alkylbiphenyls, 47 for hydrocarbons of the naphthalene series, and 94 for ~,wdinaphthylalkanes. For compounds containing different aromatic nuclei in the molecule, the factor A is an additive magnitude. Thus, the factor A is a characteristics of the nature of the aromatic nuclei in complex hydrocarbon molecules. Consequently, a determination of the dispersometric coefficient can be recommended in the chromatographic separation of hydrocarbon mixtures. This relates particularly to hydrocarbons derived from petroleum, where the presence of a large number of naphthenic rings in aromatic compounds frequently casts doubt on analytical results based only on a determination of the refractive index (Figure).
DFCD 400
?
,4=47 l
35O ,
250
1.55
¢/
150
I A=O
I
0
25
1.60
A =14.5 ~ ~ /
208 -
150
1.65
2
A =29
300
n~°
i
50 %
I
75
1.45 . lot?
Dispersometric coefficients and refractive indices obtained in the chromatography of hydrocarbons of the 350-420° fraction of Giurgill petroleum. Along the axis of abscissae are plotted the percentages by weight of the fractions separated. 1--DFcD; 2--n2DO The determination of the dispersometric coefficient of hydrocarbons was carried out on a standard refractometer of the I1~F-22 Abb6 type. In some cases, precision measurements were carried out similarly on a refractometer of the I R F - 2 3 Pulfrich type. The agreement of these measurements was completely satisfactory (Table). The accuracy of the determination of the dispersometric coefficient on the I R F - 2 2 refractometer was =[=2% (relative). In view of the closeness of the values of n D and n c [5] in the formula D~c~-- n F - n c .104 n c - 1.04
370
A. A, PETROVet al.
the refractive index for the hydrogen line in the numerator can be replaced b y the refractive index for the sodium D line. On an average, for various aromatic hydrocarbons: DFC= DFCD+(0"5 + 1.5)%. However, the use of the D line makes it possible to carry out a determination of the dispersometric coefficient on a standard Abbd type refractometer (IRF-22). I t must also be added t h a t the data in the literature with respect to the dispersion 09FCD can be approximately recalculated to give dispersometric coefficients by the following relation: DFc D ~--CgFCD" 10" 9 ± 2 %
(relative).
The experimental data on the dispersometric coefficients of the hydrocarbons investigated are given in the Table. The column "calculated dispersometric coefficient" gives the values of the dispersometric coefficient obtained by using formula (2) and the average experimental values of the factor A mentioned above. The authors thank B. V. Ioffe for his attention to the present work.* SUMMARY 1. The dispersometric coefficients of a large number of high-boiling hydrocarbons of various structures have been determined. 2. I t has been confirmed t h a t the experimental values of the dispersometric coefficients of aromatic hydrocarbons are satisfactorily described by the formula:
A + 1.5n DFC--~ 194+
molecular weight
' 10a
where A is a factor characteristic of the chemical nature of the aromatic nuclei (benzene, naphthalene, and so on), and n is the total number of substituents in the hydrocarbon rings. 3. I t has been proposed to use dispersometric coefficient determinations in the chromatographic separation of high-boiling hydrocarbon mixtures. Translated by B. J. H.A.ZZl~AD
REFERENCES
1. B. V. IOFFE and O. Ye. BATALIN, Zh. prikl, khim. 34, 603, 1961 2. B. V. IOFFE, Refraktometricheskiye metody v khimii. (Refractometric Methods in Chemistry.) Goskhimizdat, Leningrad, 1960 3. B. V. IOFFE and O. Ye. BATALIN, Nefteldfimiya 1, No. 2, 156, 1961 4. L. N. KVITKOVSKII and A. A. PETROV, Zh. prikl, khim. 34, 613, 1961 5. F. D. ROSSINI, B. J. MAIR and A. J. STRIFE, Uglevodorody nefti. (The Hydrocarbons of Petroleum.) 1957, p. 198 * The following scientific colleagues of the Laboratory for High-Molecular-Weight Petroleum Compounds took part in the synthesis of the hydrocarbons: A. L. Tsedilina, L. N. Kvitkovskii, N. V. Zhdanova, Ye. I. Bagrii and L. N. Stukanova.