2480
M. A. ROSANOFF, JOHN F. W. SCHULZE AND R. A. DUNPHY.
CORRECTION. In the article on “Leakage Prevention by Shielding, Especially in Potentiometer Systems,” by Walter P. White, which appeared in the October number of this year, on page 2018, 7th line from the bottom of the page, instead of: “arrangement described in connection with Fig. 7 of the previous paper on potentiometers,” it should read : “arrangement described in connection with Section 4, (a) of the previous paper on potentiometers, page 1875.”
THE PARTIAL VAPOR PRESSURES OF TERNARY MIXTURES OF TOLUENE, CARBON TETRACHLORIDE AND ETHYLENE BROMIDE. BY M. A. ROSANOQP, JOHN F. W.S C H U LAND Z ~ R. A. D ~ P E Y . Received August 17. 1914.
The measurements reported in this paper were carried out in connec-
tion with a study of frac‘tional distillation with regulated stillheads. In the case of binary mixtures, F. D. Brown’ has shown that, if a saturated
Fig I. 1
F. D.Brown, Trans. Chem. SOC.,37,49 (1880)and especially Ibid.,39,517 (1881).
TERNARY MIXTURl3S OF TOLUENE, CARBON TETRACHLORIDE, ETC.
248 I
vapor is partially condensed in a stillhead maintained a t a constant temperature, the residual vapor escaping from the stillhead has a constant composition, viz., the composition of the vapor given off by that liquid mixture which boib a t the temperature of the stillhead. The effect of the regulated stillhead on vapors containing more than two components has never been investigated, and before such an investigation could be undertaken it was necessary to take two preliminary steps: (I) to work out a method by which consecutive fractions of a ternary distillate could be rapidly and accurately analyzed; (2) with a view to discovering the law involved, to determine the partial pressures of the ternary mixtures of a suitable set of three substances, a t the boiling points of the mixtures under ordinary atmospheric pressure. G%C&
Fig 2.
Toluene, carbon tetrachloride, and ethylene bromide were chosen, because, on the one hand, their ternary boiling point surface is not complicated by either a maximum or a minimum; and because, on the other hand, they differ widely in their physical properties, so that their mixtures could be accurately analyzed by a physico-chemical method. The needed analytical method was worked out by one of us and fully described
2482
M. A. ROSANOFF, JOHN F. W. SCHULZE AND R. A. DUNPHY.
in a separate communication.’ We next undertook to determine the required partial pressures or, what is the same, the composition of the vapors in equilibrium with various mixtures of our three substances. As to the method to be employed, there could be c; hesitation. Von Zawidzki’s2 method, in which I cc. is distilled off from about 125 CC. of mixture, could not be used; our analytical procedure called for about IO cc. of the liquid to be analyzed, and to obtain such a quantity of distillate without greatly affecting the composition of the original mixture, we should have had to use, in each single run, as much as I to I .5 liters of mixture;
Fig. 3 .
which was impracticable. The method of Rosanoff, Lamb, and Breithuta could not be used as it would have been exceedingly difficult to produce a ternary saturated vapor of constant composition. There remained the method described by Rosanoff, Bacon and White,4 and this we found to work as well with ternary as it does with binary mixtures. 1 Schulze, THIS JOURNAL, 36, 498 (1914). Von Zawidzki, 2.physik. Chem., 35, 129 (1900). Rosanoff, Lamb and Breithut, THIS JOURNAL, 31, 448 (1909);Z.physik. Chern., 66,349 (1909). 4 ~osanoff, Bacon and White, THISJOURNAL, 36, 1803 (19x4). 2
a
TERNARY MIXTURES OF TOLUENE, CARBON TETRACHLORIDE, ETC.
2483
As in the case of binary mixtures, the method consisted simply in preparing a set of different mixtures of exactly known composition, subjecting each to distillation without reflux condensation, and analyzing consecutive fractions of the distillates. The amount of mixture employed each time was only 100 cc. The analyses were made by determining both the index of refraction and the density of each separate distillate. The treatment of the results was more laborious than with binary mixtures, owing to the fact that three-dimensional coordinates could not be conveniently employed. The method involves, namely, plotting the com-
Fig. 4.
position of the first fraction against the weight of that fraction, the composition that would result by mixing the first and second fractions, against the combined weight of those two fractions, then the combined composition of Fractions I 2 3 against the combined weight of the three fractions, etc., and extending the resulting curve to where the weight of distillate is zero. The point thus attained by the curve would indicate the composition of the first infinitesimal amount of vapor evolved by the given mixture. In the case of ternary mixtures the composition would require two coiirdinate axes for its representation, while the corresponding weights require a third axis. To obtain the desired result with the aid
+ +
2484
M. A. ROSANOFF, JOHN'F. W. SCHULZE AND R. A. DUNPHY.
or ordinary cross-section paper, we had to resort to an indirect procedure, and it is this that involved some additional labor. We proceeded as follows: Having calculated the combined composition of Fractions I 2 , Fractions I z 3, etc., we ascertained, from Schulze's curves, the indices of refraction and the densities that these combined distillates would have. The indices and the densities, were separately plotted against the weights. In this manner two separate plane curves were obtained, which, extended to where weight equals zero, indicated respectively, the refractive index and the density of the first infinitesimal quantity of distillate. The two physical properties revealed the composition of that first injinitesimal distillate or, what i s the same, of the vapor in equilibrium with the given ternary mixture.
+
+ +
Fig. 5 .
The measurements, as already stated, were undertaken as preliminary to a study of the regulated stillhead. For the purposes of that study it was necessary to learn what vapors are in equilibrium with the various ternary liquids boiling a t least a t some one temperature. We did this for five different temperatures, viz., for 8 3 O , gr O, g g o , 1 0 7 O , and I 15'. And for each of these temperatures we studied five different ternary mixtures and the two binary mixtures, all boiling at that temperature. The re-
TERNARY MIXTURES OF TOLUENE, CARBON TETRACHLORIDE, ETC.
2485
sults, tabulated below, are graphically reproduced in Figs. I to 5. The system of coordinates used is an isosceles right-angled triangle, which is by far the most convenient for practical purposes. The length of each of the equal sides is 100. Each vertex represents one of the components in the pure state. Every point on a side represents a binary mixture. Any point within the triangle represents a ternary mixture : its perpendicular distance from each of the two equal sides measures the percentage of the component represented by the vertex opposite to that side; its distance from the hypothenuse, measured alone a line parallel to either of the two equal sides, represents the percentage of the third component. In each of our figures, the heavier curve is an isothermal, showing the compositions of the various mixtures boiling a t the stated temperature; the lighter curve represents the composition of the vapors in equilibrium with those various liquids, the point for each liquid studied being connected by a tie-line with that representing the corresponding vapor. The very same substances were used again that had been prepared and purified in working out the analytical method.' In the tables below all percentages are by weight.
Numerical Results. OF THE MIXTURE: TABLEL-FIRST MIXTUREOF BOILINGPOINT83O. COMPOSITION
83.00% CCL f 17.00% CBH&Hs Distillate NO.
I.......
Weight of distillate.
22.745
z....... 22.647 3...... . 21.283 4 . . . . . . . 21.367 5 . . . .. . . 20.345
Spec. vol.
0.6693 0.6740 0.6827
0.6948 0.7171
Refractive angle.
+
0%
% CCI.
44.442 44.358 44.192 43.958 43.567
92.35 91.45 89.8 87.5 83.3
CzHdBrz. % CtHrCHa. % CaHcBr:.
7.65 8.55
0
10.2
0 0
12.5
0
16.7
0
Hence, composition of first infinitesimal amount of distillate: 92.7% CCld f 7.3% CsHsCHs f 0% C ~ H I B ~ Z . TABLEII.-sECOND MIXTURE OF BOILING POINT 83 O.
81.26% CCh Distillate NO. I 2
.......
...... .
3 ...... . 4..... . . 5 ..... . .
Weight of distillate.
21.498 24.456 23.146 23.951 20.611
COMPOSITION OF THE MIXTURE:
+ 14.34% CsHsCHa f 4.40%
Spec. vol.
0.6610
0.6644 0.6713 0.6815
0.7006
Refractive angle.
44.417 44.342 44.158 43.900 43.433
yo CCh.
91.25. 90.45 88.7 86.1 81.3
CzHdBrr. yo C6HsCHa. % CaHcBn. 6.75 2 .O
7.4 8.8
2.15
10.85 14.8
3.05 3.9
2.5
Hence, composition of first infinitesimal amount 9f distillate: 91.8% CCll GHsCHa -k 1.9% CtH4Bra, 1 Wulze,
loc. cit,
+ 6.3%
M. A. ROSANOFF, JOHN F. W. SCHULZE AND R. A. DUNPH.Y.
2486
TAEILEIII.-THIRD MIXTUREOF BOILINGPOINT83'. TURE: 77.76% CC4 Distillate
Weight of distillate.
NO.
...... . 2 ..... . 3 .. . . . . . I
22.152
21.829 20.959 4.......22.748 s . . . . . . . 21.876
+ 8.64%
CsHoCHs
Refractive angle.
Spec. vol.
0.6423 0.6437 0.6457 0.6487 0.6545
COMPOSITION OF THE MIX-
+ 13.60% C&LBra.
% C~HICH,. % CsHcBra.
% ' CCIc.
44.433 44.367
91.3 90.65 88.9 86.5 82.45
++.zoo
43.967 43.577
3.95 4.35 5.1
6.1 7.85
4.75 5 .O 6.0 7.4 9.7
Hence, composition of first infinitesimal amount of distillate: 91.8% CCL +3.75% C6H6CHs 4.45% CZHaBra.
+
TABLEIV.-FOURTH MIXTUREO F BOILINGPOINT 83'. Turn: 76.04% CClr Distillate No. I
Wei ht of distilate.
. . . . . . . 24.000
..... . ,
23.463 23.548 23.516 5 . . . . . . . 23.181
2
3 ...... . 4... . . . .
COMPOSITION OF THE M U C2H4Bm.
+ 6.16% CsHoCHs + 17.80%
Spec. vol.
Refractive angle.
% CCIc.
0.6342 0.6345 0.6352 0.6366 0.6385
44.425 44.350 44.150 43.867 43.350
91.0 90.2 88.3 85.5 80.1
% OILCHI. % CrHcBrt. 2.8 6.2 3.1 6.7 3.6 8.I 4.5 10.0 6.I 13.8
+ 2.6%
Hence, composition of first inlinitesimal amount of distillate: 91.470CC4 CsHoCHs 6.0% CzH4Brz.
+
TABLEV.-FIFTH MIXTUREOF BOILINGPOINT 83 '. 74.67% Distillate No.
Weight of distillate.
..... . . 2 ..... . .
25.734 25.779 3....... 24.891 4....... 27.162 5 . . . . . . , 23.929 I
cc14 + 3.93% Spec. vol.
0.6268 0.6265 0,6255 0.6241 0.6210
CsH6CHs
COMPOSITION OF THE MIXTURE:
+ 21.40%
Refractive. angle.
% ' CClc.
44.450 44.350 44.117 43.750 42.958
91.1 90.0 87.8 84.1 76.3
CZH~B~Z. % OHbCHa. % CaHcBra. I .8 7.1 2 .O 8.0
9.7
2.5
3.1 4.5
12.8
19.2
+ 1.8%
Hence, composition of first infinitesimal amount of distillate: 91.4% CC4 GHsCHs 6.8% CzH4BrZ.
+
TABLE VI.-SIXTH MIXTUREOF BOILINGP O I N T 83 '. 73.42% CCld Distillate No.
Weight of distillate.
I ......
. 23.056
..... . . 3. . . . . . . 4 . . . . .. . 5 ...... . 2
24.124 24.481 24.350 24.129
COMPOSITION OF THE MIXTURE: CZHIB~Z.
+ 1.88% GHsCH3 + 24.70%
Spec. vol.
0.6198 0.6190 0.6169 0.6137 0.6079
Refractive angle.
44.417 44.350 44.150 43.850 43.283
c/o CCIc.
90.5 89.8 87.9 85.1 79.4
CsHsCHa.
% CaHcBra.
8.7 9.2
0.8 I .o 1.1
I 1 .o
1 .3
13.6 18.7
1.9
Hence, composition of first infinitesimal amount of distillate: 90.8% CCld CsH6CHa 8.4% CZHIB~Z.
+
+ 0.8%
TERNARY MIXTURES OP TOLUENE, CARBON TETRACHLORIDE, ETC.
TABLE VII.-sEVENTH TURE: Distillate
MIXTUREOF BOILINGPOINT 83'. COMPOSITION O F THE MIX72.30% cc14 0% CeHSCHa 27.70% CzH4Br2.
Weight of distillate.
NO.
2487
...... . 2 ..... . .
24.046 24.461 3.. . . . . . 24.109 4... .. . . 24,539 5 ...... . 24.389 I
+
+
Refractive angle.
Spec. vol.
0.6136 0.6120 0.6087 0.6037 0.5941
% ' CClr.
% C6H6CHa.
90.4 89.8 87.7 84.8 79.2
44.425 44.358 44.150 43.858 43.250
% CzHaBr;.
0
9.6
0
10.2
0 0
12.3
0
20.8
15.2
Hence, composition of first infinitesimal amount of distillate: 90.7% ccl4 f GHKCHSf 9.3% C Z H ~ B ~ Z .
TABLEVII1.-FIRST MIXTUREOF BOILINGPOINT 91'. TURE: 59.40% ccl4 Distillate NO.
Weight of distillate.
..... . . 2 ...... .
20.514 20.846 3....... 18.603 4..... . . 19.676 5 ...... . 16.854 I
+ 40.60%
Spec. vol.
0.7473 0.7632 0.7895 0.8276 0.8931
CsHsCHa
Refractive angle.
0%
COMPOSITION OF THE MIX0% GH4Br$.
+
% cct.
% CIHrCHs. % CzHaBrz.
77.6 74.6
4.083 42.841 42.467
69.6
42.000
62.2
41.283
50.0
22.4
0
25.4 30.4 37.8 50.0
0 0 0 0
Hence, composition of first infinitesimal amount of distillate: 78.6% CClr f 21.4% C A C H 3 f 0% CzH4Brz.
TABLEIX.-sECOND
MIXTUREOF BOILINGPOINT 91'. TURE: 59.16% CCla 39.44% CeHsCHa
Distillate
Weight of distlllate.
NO.
20.816 2 ...... . 20.026 3..... . . 18.790 4...... . 17.957 s....... 16.585 I.......
+
COMPOSITION O F THE MIX-
+ 1.40% CZHdBr2.
Spec. vol.
Refractive angle.
0.7431 0.7582 0.7862 0.8175 0.8727
43.100 42.867 42.483 42.067 41.383
YoC c h . 77.5 74.6 69.3 63.3 51.9
% CIH8CH3. % GHiBr;. 0.6 21.9
24.8 30.0 36.o 46.7
0.6 0.7 0.7 1.4
Hence, composition of first infinitesimal amount of distillate: 78.7% CC4 f 20.8% CsHrCHs 0.5% CzHdBrz.
+
TABLEX.-THIRD MIXTUREOF B~ILING POINT 91 '. COMPOSITION OF THE MIXTURE: 54.67% CCI4 23.43% CeH6CHa 21.90% CzH4Brz.
+
Distillate
Weight of distillate.
NO.
21.867 2.. .. . . . 21.606 3.... . . . 21.513 4.......20.527 5 . .... . . 19.911 I.,.....
Spec. vol.
0.6855 0.6926 0.7048 0.7218 0.7475
+
Refractive angle.
43.150 42.900
42,433 41.800 40.650
% CClr
78.2 75.4 69.5 61.6 46.3
% CaHsCHa. % CtHaBrz.
I3 4 15.1
18.2 22.5
29.8
Hence, composition of first infinitesimal amount of distillate: 79.1% CCl, CeHbCHa 8.T % C2H4Br1.
+
8.3 9.5 12.3 15.9 23.9
+ 12.8%
2488
M. A. ROSANOFF, JOHN F. W. SCHTJLZE AND R. A. DUNPHY.
TABLE XI.-FOURTH MIXTUREOF BOILINGPOINT 91'. TURE: 50.88% CCl4 Distillate No.
+ 12.72%
CsHsCHs
Weight of distillate.
Spec. vol.
Refractive angle.
22.860 z . . . . . . . 23.822 3.... . . . 23.250 4.....,. 23.362 5 ..... , . 21.540
0,6448 0.6467 0.6494 0.6528 0.6541
43.150 42.883 42.275 41.392 39.783
I.....
..
COMPOSITI~N OF THE MIXCzHdBrS.
+ 36.40%
% CaHCH:. % CrHrBrz.
% CCh.
78.25 75.5 68.9 59.3 41.9
7.5 8.4
14.25 16.1 20.6 27.5 40.5
10.5
13.2 17.6
Hence, composition of first infinitesimal amount of distillate: 79.0% CsHsCHl 13.8% C2HdBr2.
+
cc14 f
7.2%
COMPOSITION OF THE MIXMIXTUREOF BOILINGPOINT 91'. TURE: 49.22% CCh 8.68% GHsCHI 42.10% CZHrBra.
TABLEXII.-FIFTH Distillate No.
Wei ht of disdlate.
I
24.234 24.755 23.758 23.339 23.739
. . ., .. .
z.......
3 ....... 4...... .
s.......
+
+
Spec. vol.
Refractive angle.
% CClr.
0.6289 0.6287 0.6274 0.6245 0.6150
43.117 42.825 42.183 41.217 39.300
77.8 74.8 68.5 58.9 40.4
% CsHsCHa. % CtHrBn.
5.3 6.I 7.4 9.4 12.4
16.9 19.I 24.I 31.7 47.2
Hence, composition of first infinitesimal amount of distillate: 79.0% CCll C R H ~ C H ~15.9% C2HrBrt.
+
TABLEx I I I . s I X T H MIXTUREOF BOILINGPOINT 91'. TURE: 47.88% CClr Wei ht of distfflate.
Distillate
No.
24.777 2 ....... 24.602 3 ..... , , 24.453 4..,.... 24.320 5 . . , . . . . 24.511 I.......
+ 5.32%
Spec. vol.
0.6155 0.6138 0.6092
0.6011 0.5814
GHgCHa
COMPOSITION OF THE MIXCzHhBrr.
+ 46.80%
Refractive angle.
% CCL.
43.150 42.850 42.200 41.133 38.842
78.3 75.3 69.1 59.1 39.0
% GHICHJ. % CaHrBn.
3.3 3.7 4.6 5.8 8.0
18.4 2 1 .o
26.3 35.1 53.0
Hence, composition of first infinitesimal amount of distillate: 79.4% CCI, GHsCHa 17.6% GH4Br2.
+
TABLE XIV.-SEV&NTHMIXTUREOF BOILINGPOINT 91 '. TURE: 45.80% CClr
+
0%
CaHsCHa
+ 5.1%
+ 3.0%
COMPOSITION OF THE MIXCsHJ3r2.
+ 54.20%
Wei ht of cdlate.
spec. vol.
Refractive angle.
% CCh.
% CsHsCH:.
28.555 2 . . . ,. 25.441 3 ....... 25.965 4....... 26.374 5 ..... 28.389
0.5933 0.5878 0.5759 0.5551 0.51og
43.200 42.833 42.033 40.517 36.800
78.5 75.2 68.3 56.0 30.I
0
21.5
0
0
24.8 31 * 7
0
44.0
0
69.9
Distillate
No.
I.......
.. ..
70CrHdBrl.
Hence, composition of first infinitesimal amount of distillate: 79.7% CCL 4G H ~ C H I 20.3% CnHrBrz.
+
0%
TERNARY MIXTURES OF TOLUENE, CARBON TETRACHLORIDE,ETC.
2489
TABLE XV.-FIRST MIXTUREOF BOILING POINT99 O. COMPOSITION OF THE MIX-.: 35.40% CC4 Distillate
No.
I...... . 2.......
3.. ..... 4.......
s.......
+ 64.60% CsHsCHa 4-
CzH4Bra.
0%
Weight of distillate.
Spec. vol.
Refractive angle.
17.197 16.973 16.153 16.029 14.152
0.8610 0.8852 0.9281 0.9796 1.0410
41.600 41.367 40.967 40.533 40.067
% CCL. 56.0 51 .5 43.5 33.8 22.3
% QHKCH:. % CiH4Bri.
44.0 48.5 56.5 66.2 77.7
0 0
0 0
0
Hence, composition of first inlinitesimal amount of distillate: 57.7% CC4 CaHpCHa 0% CZHIB~S.
+
TABLEXVI.-SBCOND MIXTUREOF BOILING TURE: 34.64% CCl4 Wei ht of dirthate.
Distillate NO.
I....... 2
.......
3....... 4.......
s.......
18.596 18.019 17.841 17.161 16.080
POINT
99'.
COMPOSITION OF THE MIX-
+ 51.96% GHsCH8 + 13.40% C Z H ~ B ~ ~ ,
Spec. vol.
Refractive angle.
0.8125 0.8333 0.8636 0.8994 0.9385
41.617 41.300 40.850 40.333 39.750
% ' CCh. 57.2 51.8
44.1 34.0 22. I
% CeHbCH:.
% CzH4Brr.
36.5 40.8 47.0 54.8 63.1
6.3 7.4 8.9 11.2
14.8
Hence, composition of first infinitesimal amount of distillate: 59.1% CCld WWHa 5.9% CnK4Brz.
+
TABLE XVII.-THIRD MIXTURE OF BOILINGPOINT 99'. TURE: Distillate
No.
...... . 2 ..... . . 3 ...... , I
4.......
s.......
33.50% CCI4
COMPOSITION OF THE MIX-
Weight of distillate.
Spec. vol.
Refractive angle.
19.716 20.311 18.853 18.791 18.188
0.7313 0.7443 0.7606 0.7778 0.7907
41.683 41.275 40.675 39.950 39.033
% cct.
59.9 54.4 46.1 35.3 22
.o
% CIWCH~. % CsH4Br:.
24.3 27.5 31 - 9 36.9 42.0
15.8 18.1 22
TABLE XVIII.-FOURTH MIXTURE OF BOILINGPOINT 99'. M~xrunrt: 32.16% CCh NO.
...... ...... . 3. .. . .
Wei ht of distfllate.
I.
21.482
2
22.122
*
*
4.......
5
.......
.453 21.343 21.138 21
4-21.44%
CsHsCHa
+
23.2%
COMPOSITION OF TEE GHdBi-2.
+ 46.40%
Spec. vol.
Refractive angle.
% CCLC.
% CaHrCH:.
0.6776 0.6832 0.6892 0.6932 0.6860
41.675 41.200 40.367 39.333 37.875
61.5 55.9 46.1 34.0 17.9
16.2 18.4 21.6 25 .o 27.8
% CsHaBn.
Hence, composition of first M t e s i m a l amount of distillate: 64.1 % ccl4 QHICH, 20.8% C*H,Brr.
+
.o
27.8 36.0
+
Dirtillate
+ 35.0%
+ 33.50% CeHsCHa + 33.00% CS4Brl.
Hence, composition of first M t e s i m a l amount of distillate: 62.5% CCl4 14.3% CZHIB~Z.
CaHdXa
+ 42.3%
22.3 25.7 32.3 41 .o 54.3
+ 15.1%
2490
w.
M. A. ROSANOFF, JOHN F.
SCHUWE AND R. A. DUNPHY.
TAB^ XIX.-FIFTH MIXTUREO F BOILINGPOINT 99'. COMPOSITION OF THE MIX. TURE: 31.15% c c b -k 13.35% CeH6CH3 f 55.50% C Z H ~ B ~ . Distillate No. I.......
Weight of distillate.
23.196 2 . . .... , 23.519 3.......23.195 4....... 23.467 5..... . . 24.275
Spec. vol.
Refractive angle.
% CCh.
0.6398 0.6399 0.6388 0.6303 0.6108
41.692 41.083 40.142 38.600 36.683
63 . o 56.7 47 .o 31.8 14.8
% CIHSCHX. % CtHtBn.
26.5 31.3 39.0 51.6 67.3
10.5 I2 .o
14.0 16.6 17.9
+
Hence, composition of first infinitesimal amount of distillate: 65.0% cc14 CeH,CHs 25.0% C2H4Br2.
+
TABLE&.-SIXTH TuRE: Distillate
COMPOSITION OF THE MIX. MIXTUREOF BOILINGPOINT 99'. 29.67% CC14 5.23% CsHsCH3 65.10% GH4Br2.
+
+
Weight of distillate.
Spec. vol.
Refractive angle.
25.959 z . . . . . . . 26.007 3 ..... . . 26.686 4... .. . . 26.811 s . . . , . . . 26.210
0.5987 0.5920 0.5792 0.5559 0,5265
41.650 40.875 39.517 37.200 34.617
No. I
..... . .
% Cclc
% CtHbCH:.
% CsHdBn.
64.3 57.2 45.6
4.3 5 .o 6 .o 7.3 7.1
31.4 37.8 48.4 65.6 82.7
27.1 10.2
Hence, composition of first infinitesimal amount of distillate: 66.7% CClr CsHaCHJ-I- 29.3% C2H4Brz.
TABI,EX X I . - , % $ V B N T H
MIXTURE OF
MIXTURE: 28.55% CC14 Distillate No.
10.0%
Weight of distillate.
I
...... . 2 ...... . 3 ..... , .
26.418 26.960
....... 5 . . ... . .
28.091
4
28.907 31.107
Spec. vol.
+
BOILINGPOINT 99'. CQMPOSITION OF THE GHsCHa 71.45% C Z H ~ B ~ Z .
0%
+
Refractive angle.
% CCh.
% CsHsCH:.
41.650 40.650 38.900 35.817 32.667
65.3 57.2 44.1 23.9 6.7
0 0
0.5709 0.5571 0.5350 0 . 5 6
0.4707
+ 4.0%
% C:HqBn.
0 0 0
34.7 42.8 55.9 76.I 93.3
Hence, composition of first infinitesimal amount of distillate: 67.6% CClr CEHSCHS 32.4% CPHIB~I.
0%
+
TABLEXXLI.-FIRST
MIXTWE OF BOILINGPOINT 107'. MIXTURE: 9.90% CC14 90.10% CeHrCHs
Distillate No. I
..... , . z....... 3 ...... . 4 ...... . 5 . ......
Weight of distillate.
14.30 13.999 14.195 14.029
14.762
+
+
Spec. vol.
1.0549 1.0760 1.0941 1.1144 1.1368
Refractive angle.
39.967 39.850 39.733 39.600 39.483
% CCk.
19.6 15.7 12.3 8.5
4.2
cQMPOSITION 0%
% CsH6CHs. % CnHtBn.
80.4 84.3 87.7 91.5 95.8
Hence,composition of first infinitesimal amount of distillate: 21.5% CClr CEHSCH~ 0% QH4Brl.
+
OF THB
GH+Brt. 0 0
0
0 0
4-78.5%
TERNARY MIXTURES OF TOLVENE, CARBON TETRACHLORIDE, E'J!C.
TABLEXXIII.-sECOND
2491
MIXTUREOF BOILINGPOINT 107'. COMPOSiTION OF THE MIXTURE: 14.32% CCl4 57.28% C B H ~ C H ~28.40% CsHrBrz.
Distillate
Weight of distillate.
NO.
. 16.873 z...... . 17.085
+
Spec. vol.
I......
0.8820
3 ....... 4 .......
0.8964 0.~99 0.9175 0.9126
5 . . . ....
16.437 16.921 15.999
+
Refractive angle.
40.017 39.742 39.400 39.050 38.633
% cch.
% CaHsCHa. % CzHdBrz.
53.2 56.5 59.9 62.5 63.4
30.0 24.7 18.2 12.0
5.5
Hence, composition of first infinitesimal amount of distillate: 32.1% CCl4 GHsCH; 16.4% CzH4Brz.
+
TABLEXXIV.-'I"IRD
16.8 18.8
21.9 25.5 31.1
+ 51.573
MIXTUREO F BOILINGPOINT 107'. COMPOSITION OF THE MIXTURE: 16.32% CC14 38.08% CBHsCHa 45.60% C Z H ~ B ~ Z .
Distillate No.
...... . ....... 3 ....... 4....... I 2
5.......
+
+
Weight of distillate.
Spec. vol.
Refractive angle.
19.324 19.358 19.413 19.227 19.264
0.7752 0.7841 0.7904 0.7874 0.7698
40.017 39.583 39.017 38.350 37.683
% CCh.
36.4 30.5 22 .O
13.o 5.8
% CsHsCHa. % CzHIBn.
36.2 39 .O 41.9 43.5 42.8
Hence, composition of first infinitesimal amount of distillate: 38.6% cc14 CsH6CH8 26.6% C2H4Br2.
+
27.4 30.5 36.1 43.5 51.4
+ 34.8%
TABLE XXV.-FOURTH MIXTUREO F BOILING POINT 107'. COMPOSITION MIXTURE: 17.12% cc14 25.68% CsHsCH3 57.20% CzH4Brz.
+
Distillate
No.
I..
.. . . .
2.... . . .
Weight of distillate.
21.184 20.802
3....... 21.126 4....... 21.185 5.......
21.820
+
Spec. vol.
Refractive angle.
0.7042 0.7079 0.7067 0.6994 0.6780
39.967 39.358 38.592 37.700 36.750
% CClr.
% CsH6CHa. % CzHrBm.
40.6 33 ' I
25.0
27.3 29.3 30.5 29.7
24.0
15.1
5.9
Hence, composition of fmt infinitesimal amount of distillate: 43.9% cc14 CsH&Ha 32.4% C Z H ~ B ~ Z .
+
TABLEXXVI.-FIFTH MIXTURE MIXTURE: 17.58% CCl4 Distillate NO.
...... , ...... . 3 ..... . . 4 .. .. . . I
2
*
5.......
OF BOILINGPOINT107'.
+
11.72%
CsH6CHs
+
34.4 39.6 46.7 54.4 64.4
+ 23.7%
COMPOSITION OF TH& C2H4Brz.
+ 70.75%
Weight of distillate.
Spec. vol.
Refractive angle.
% CCh.
24.002 24.133 24.510 24.710 25.360
0.6211 0.6153 0.6039 0.5860 0.5607
39.850 38.858 37.600 36.117 34.733
45.2 35.9 24.7 12.9 4.6
% CsHtCHa. % OHrBn.
12.2 13.5 14.6 14.9 13.3
Hence, composition offirs$ infinitesimal amount of distillate: 49.3% CC14 39.I % GH4Br2.
GH (CHI
OF THE
42.6 50.6 60.7 72.2
82.I
+ 1k.6%
M. A. ROSANOFF, JOHN F. W. SCHULZE A N D R. A. DUNPHY.
2492
TABLEXXVII.-SIXTH MIXTUREOF BOILINGPOINT 107'. MIXTURE: 17.84% CCh Distillate No.
Weight of distillate.
......
......,
27.001
0.5756 0.5622 0:5433
5.......
28.328 29.894
0.4986
2
3. . . . . . , 4 ..... . .
COMPOSITION OF THE C ~ H S C H ~77.70% C Z H ~ B ~ Z .
Refractive angle.
Spec. vol.
26.187 25.844
I.
+ 4.46%
39.817 38.500 36.708 34.650 33.067
0.5201
+
% Cch.
48.5 38.0 24.7 11.5
3.3
7% CaHsCHa. % CtHdBrr. 4.8 46.7 5.4 56.6 6.0 69.3 5.9 82.6 4.8 91.9
Hence, composition of first infinitesimal amount of distillate: 53.1% CCl4 CIH~CHS 42.3% CzH4Brz.
+
TABLE XXVIII.-sEVENTH
+ 4.6%
MIXTUREOF BOILINGPOINT 107', COMPOSITION OF THE MIXTURE: 18.00% CClr 0% C'HSCHI 82.00% CzH4Brr.
Distillate
Weight of distillate.
NO.
28.039 2 ..... . . 26.919 3....... 28.723 4 , . . . . . . 29.234 5 ...... . 3 1 ~ 1 7 2 I.,,.,..
+
Spec. vol.
Refractive angle.
0.5459 0.5256 0.5007 0.4769 0.4637
39.750 38.083 35.817 33.375 31.850
+
% Cch.
% CeHCHs. % CzH4Br:.
50.5
49.5 61.3 76.0 89.9 97.6
0 0
38.7 24.0
0
IO. I
0
2.4
0
Hence, composition of first infinitesimal amount of distillate: 55.5% cc14 f GHICH: 44.5% C Z H ~ B ~ Z .
+
0%
TABI,~XXIX.-FIRST MIXTUREOF BOILINGPOINT 115'. COMPOSITION OF THE MIXTURE: 0% CCL 50.40% CsH6CHs 49 60% C2HIBra.
+
Distillate
Weight of dilltillate.
NO.
.. .. . . 2 ....... I,
3 ....... 4..... 5..
..
.....
'
17.144 18.419 17.651 23.047 18.346
+
Refractive angle.
Spec. vol.
0.8920 0.8763
38.175 38.083 37.950 37.750 37.392
0.8587
0.8307 0.7881
yo Cad.
% QHrCHa.
0 0 0 0
Hence, composition of f i s t infinitesimal amount of distillate: CsHbCH: 37.1% CZHIBTZ.
+
TABLEx x x . - - s B C O N D
% C~HIB~S.
61.9 59.6 57.1 53.1 47 .O
0
0%
38.I 40.4 42.9 46.9 53.0
CCL
+ 62.9%
MIXTUREOF BOILINGPOINT 115'. COMPOSITION OF THE MIXTURE: 3.81% CCl4 34.29% GHICHa 61.90% GHdBra.
Dintillate
Weight of dhllate.
No. I
..... . .
z.......
..... . . 4..... . . 5 ....... 3
x8.ogo 19.274 18.998 21.530
21.960
+
+
Spec. vol.
Refractive angle.
% CClr.
0.7744 0.7667 0.7540 0.7340 0.7016
38.083 37.792 37.467 37.1m 36.600
10.6 7.6 5 .O 3 .O I .o
% CsHCH:.
Hence, composition of k s t infinitesimal amount of distillate: GHsCH: 45.6% C Z H ~ B ~ Z .
+
% Cd-LBrz.
42.3 4r .9 40.6 38.3 34.2 IZ.S%
47.1 50.5
54.4 58.7
64.8
cck
+
42.1%
TERNARY MIXTURES OF TOLUENE, CARBON TETRACHLORIDE, ETC.
TABLExx.xI.-?'%IIRD
2493
MIXTUREOF BOILINGPOINT 115'. COMPOSITION OF THE MIXTURE: 6.00% CCI, 24.00% CeHsCHs 70.00% CnHdBrt.
Distillate No. I.....
..
. .... . 3 ...... . 4 ...... . 2,
5
......,
Weight of distillate. 21.171
21.543 21.509 21.668 23.061
+
+
Spec. vol.
Refractive angle.
0.6995 0.6921 0.6792 0.6599 0.6315
37.983 37.450 36.908 36.333 35.683
% CCL. 17.5
% CsHsCH;. % CzHdBn.
29.9 31.5 29.4 27.6 24. I
11.1
7.6 3.9 1.4
52.6 57.4 63 .o 68.5 74.5
+ 28.5%
Hence, composition of first infinitesimal amount of distillate: GHrCH, 50.3% CaHdBi-2.
21.2%
TABLE XXXII.-FOURTHMIXTUREOF BOILINGPOINT 115'.
COMPOSITION GH4Bi-t.
+
MIXTURE: 7.44% CC4 Distillate
No. I
.......
2.......
3 ...... . 4 ....... 5..
....,
CC4
+ 17.36% G H ~ C H B+ 75.20%
Wei.ght of Qsttllate.
Spec. vol.
Refractive angle.
20.857 21.763 22.558 22.841 23.669
0.6530 0.6437 0.6316 0.6134 0.5887
37.983 37.233 36.517 35.758 35,017
% CC4.
% CaHbCH;. % CIH4Brr.
22.8 15.8
22.0
55.2
22.4
IO. I
22
61.8 67.9 74.3 80.1
5.0 2 .o
.o
20.7
17.9
Hence, composition of f i s t infinitesimal amount of distillate: 25.7% CCL GHsCHI 52.5% CnHdBrz.
+
+ 21.8%
TABLEXXXIII.-FIFTH MIXTUREOF BOILINGPOINT 115'. COMPOSITION MIXTURE: 8.88% CC14 8.87% C B H ~ C H ~82.25% CsH4Br2.
+
+
Distillate No.
Weight of distillate.
Spec. vol.
Refractive angle.
I
24.412 25.717 25.136 26.253 27.417
0.5880 0,5756 0.5601 0.5422 0.5219
37.750 36.600 35.425 34.367 33.467
....... ..... . . 3 ...... . 4 ...... . 2
5.......
% CCh
28.1 19.1 11.0
4.9 1 .4
% CsH&!H& 11.5 11.9 11.6 10.6 8.5
+
+
MIXTUREOF BOmNG P O I N T 115'. COMPOSITION MIXTURE: 9.66% CCL 4.14% C6H&Hs 86.20% CSHdBi-2. Weight of distillate.
Distillate
No.
I.......
26.402 2....... 27.329 3 . . . . . . . 28.942 4 . 28.855 30.973 5
..... . .......
+
+
Spec. vol.
Refractive angle.
0.5517 0.5351 0.5171 0.5006 0.4870
37.567 36.067 34.525 33.250 32.450
% CCL.
30.9 20.5 11.4 4.5 0.8
11.2%
OF THE
% C~HKCHI.% CzHdBrz.
5.6 5.8
5.4 4.7 3.7
63.5 73.7 83.2 90.8 95.5
Hence, composition of first infinitesimal amount of distillate: 36.5% CClr GHICHI 58.0% c34Br:.
+
O F THE
yo CzHdBr:. 60.4 69.0 77.4 84.5 go. I
Hence, composition of f i s t i w t e s i m a l amount of distillate: 32.7% CC4 GHrCH: 56.1 % CZHIB~Z.
TAFILE XXXIV.-sIXTH
OF THE
+ 5.5%
2494
M. A. ROSANOFF, JOHN
TABLE XXXV.-sEVENTH MIXTURE: Distillate No.
F. W. SCHULZE AND R. A. DUNPHY.
MIXTURE OF BOILINGPOINT I I5 O .
10.00%
CC4
+
0%
CaHaCHs
Weight of distillate.
Spec. vol.
Refractive angle.
28.588 z....... 29.331 3...... 29.414 4 ....,. . 31.646 5 ....... 31.456
0.5160 0.4956 0.4780 0.4665 0.4611
37.233 35.333 33.508 32.200 31.583
I,...,..
.
COMPOSITION OF
+ gam% CzH,Bre.
% CClr.
THE
% CsHrCHa. % CnH4Brn.
32.7
67.3 78.9 88.5 95.4 98.7
0 0 0
21.1
11.5 4.6 1.3
0 0
Hence, composition of first infinitesimal amount of distillate: 40.0% CClr GHoCH$ 60.0% CZHIB~Z.
+
+
0%
TABLEXXXVI.--SUM~~ARY. Composition of liquid. Temp.
Mixture.
% CClr.
% CiHa.
83 O 83' 83 O 83 O 83 O 83' 83 O 91 O 91 O 91' 91 O 91 O 91 91 O 99O 99' 99' 99' 99 99O 99 107O 107' 107O 107O
I
83.00 81.26 77.76 76.04 74.67 73.42 72.30 59.40 59.16 54.67 50.88 49.22 47.88 45.80 35.40 34.64 33.50 32.16 31.15 29.67
17.00 14.34 8.64 6.16 3.93
107'
107' 107 O I150
2
3
4 5 6 7 I 2
3 4 5 6 7 I
2
3 4 5 6 7 I 2
3 4 5 6 7
28.55
9.90 14.32 16.32 17.12
17.58 17.84 18.oo
I
0
1150
2
115'
3
1150
4 5
3 .SI 6.00 7.44 8.88 9.66
1150
1x50 1150
6
7
10.00
I .88 0
40.60 39.44 23.43 12.72 8.68 5.32 0
64.60 51.96 33.50 21 .44 13.35 5.23 0
go.IO 57.28 38 .OS 25.68 11.72
4.46 0
50.40 34.29 24.00 17.36 8\87 4.I4 0
Composition of vapor.
% C2HdBrs'. 0
4.40 13.60 17.800 21.40 24 * 70 27.70 0
1.4 21 .go 36.40 42.IO 46.80 54.2 0
13.40 33.00 46.40 55.50 65.IO 71 a45 0
28.40 45.60 57.20 70.75 77.70 82 .o
49.60 61.90 70.00 75.20 82.25 86.20 90.00
% CCll
92.7 91.8 91.8 91 $ 4 91.4 90.8 90.7 78.6 78.7 79.1 79.0 79.0 79.4 79.7 57.7 59.1 62.5 64.I 65 .o 66.7 67.6 21.5 32.1 38.6 43.9 49.3 53.1 55.5 0
12.3 21.2 25.7 32.7 36.5
40.0
% CrHs. % CaHaBr;.
7.3 6.3 3.75 2.6 I .8
0.8 0
0
1.9 4.45 6.0 6.8 8.4 9.3
21 .4
0
20.8
0.5
12.8
8.1 13.8 15.9 17.6 20.3
7.2
5.1 3.0 0
0
42.3 35 .O 23.2
5.9 14.3
15.1 10.0
20.8 25 .O
4.0
29.3 32.4
0
78.5 51.5
34.8 23.7 11.6 4.6 0
62.9 42.1 28.5 21.8
0
16.4 26.6 32.4 39.1 42.3 44.5 37.1 45.6 50.3 52
.s
11.2
56.I
5 -5
58.0
0
60.0
SUBSTITUTION IN THE BENZENE NUCLEUS.
2495
In conclusion, it is a duty to state that the cost of this investigation has been defrayed out of a grant from the Rumford Fund of the American Academy, for which we express our thanks to the Rumford Committee. MELLON INSTITUTE
OF INDUSTRIAL RESEARCH, UNIVERSITY OF PITTSBURGH.
SUBSTITUTION IN THE BENZENE NUCLEUS. BY A. F. HOLLEMAN. Received September 23, 1914.
A few years ago, I showed‘ that none of the hypotheses proposed to explain the phenomena of substitution in benzene nucleus are able to give a satisfactory explanation of the facts. Since then, H. S. Fry, in a series of papersY2published a new hypothesis and was able to explain some of the phenomena observed by means of it, e. g., the fact that, in the rearrangement of phenyl acetyl nitrogen chloride C6H5NCl.COCHa and similar compounds, the halogen enters only in positions ortho or para to the nitrogen atom. However, on studying this hypothesis more closely it seems to me that there are so many objections against it, that it cannot be accepted. I venture to present the most important ones in the following lines: I. Fry admits that benzene has the structure of Fig. I , based on Thomson’s electronic theory of linking of the atoms. As he observes, this formula H’ indicates the possibility of two isomeric compounds CsHX, whereas no such isomers have been found thus far. In order to explain this, he assumes either * that one of the two isomers (“electromers”), e. g., of HHf t f chlorobenzene is unstable under ordinary physical conditions, or that monochlorobenzene is an equilibrium mixture of two tautomeric electromers. It seems f jg.1. to me that serious objections may be made against both of these auxiliary hypotheses. With regard to the first one; ad-
$+)
-
+
mitting C,&C1 to be stable, CeH5C1 would be unstable. But in o-C&Cl* and p-C6H4C12,where one C1-atom is negative and the other positive, we have perfectly stable compounds. On the other hand, if mono-
-
+
chlorobenzene is a mixture of C&C1 and C6HsC1, the nitration of such a mixture ought to give a mixture of 0- and p-chloronitrobenzene (derived -
+
from C6H5C1)and of m-chloronitrobenzene (derived from CaH6C1),sinceaccording to Fry-“substituents of the same sign occupy positions which “Die direkte Einfiihrung von Substituenten in den Benzolkern,” p. 203. THISJOURNAL, 34, 664 (1912);36, 248, 262 (1914);see also Z. physik. Chem., 76,385 (19x0). 2
