June, 1940
METHYLAND METHYLENE PERCHLORIDES [CONTRIBUTIONFROM
THE
1575
BAKERLABORATORY O F CHEMISTRY AT CORNELL UNIVERSITS ]
The Chlorinates. 111. Temperature-Concentration Equilibria in the Systems Methylene Chloride-Chlorine and Methyl Chloride-Chlorine. The Perchlorides of Methylene and of MethyP2 BY J. ALLENWHEAT,11, AND A. W. BROWNE In determining temperature-concentration equilibria in the system methylene chloridechlorine the experimental procedure was identical with that followed in the earlier work with chloroform and chlorine.2 The data obtained are presented in Table I and are plotted in Fig. 1. TABLEI TEMPERATURE-CONCENTRATION OR SOLUBILITY DATAOF THE SYSTEM CHsCla-C12 Temp., =C.
Concn., mole yo Clr
- 97.0
0.0
-
98.0 99.5 -101.5 -104.0 - 108.5 -110,o -113.0 -118.5 -119.5 -120.5 -122.5 - 124.5
1.5 3.1 6.0 7.4 11.5 14.7 16.8 20.5 22.9 23.8 25.1 26.5
-128.0
27.7
Curve (Fig. 1)
A.
- 132.0
55.5
-129.5 -125.5 -123.0 -121.5 - 119.0 -117.5 -119.0 -121.0
56.3 59.1 61.1 63.2 85.8 67.0 68.6 70.2
- 122.0
71.3
-120.0 -119.0 -117.5 -115.5 -110.5 -106.0 -104.0
72.5 74.8 76.2 79.8 85.6 92.3 95.9
- 102.0
100.0
(Solid CHZC12, liq., vapor)
AB. (Solid CHnC12, satd. soln., vapor)
- 100 B. (Eutectic: solid CH2C12, solid (CH&)2.Cls, satd. s o h , vapor)
-127.0 -126.0 -125.5 -125.0 - 125.0 -1128.0 - 127.5 -129.5 -131.5 -134.0
28.5 29.4 30.8 32 2 34.8 37.4 39.4 41.0 42.6 44.5
BCD. (Solid (CH2C12)2C12,satd. s o h , vapor)
- 135.0
45.1
D
-130.5 -127.0 - 126.5 -127.0 - 128.0 - 130.5
46.6 48.9 50.5 51.3 53.0 55.0
1A
F.
(Eutectic: solid CH2Cl*.C12, solid CHzC12.2C12, satd. soln., vapor)
FGH. (Solid CH2C12.2Cl:., satd. s o h , vapor)
H. (Eutectic: solid CH1C12.2Cl1, solid Clp, satd. s o h , vapor)
HI. (Solid Cln, satd. soln., vapor)
I. (Solid Cla, liquid, vapor)
1
L;
.a
-110
u
2 +
g
-120
; U J
-130
- 140
(Eutectic: solid (CH&12)2Cl,, solid CH,Cl,*C12, satd. s o h , vapor)
DEF. (Solid CH?ClyCl2, satd soln., vapor)
(1) This article is based upon the thesis presented to the Faculty of the Graduate School of Cornell University by J. Allen Wheat, 11, in partial fulfillment of the requirements for the degree of Doctor of Philosophy. (2) For the preceding articles in the current series, see Wheat and Browne, THISJ O U R N A L , 68, 2410 (1936); 60, 371 (1938).
20 40 60 80 Molar percentage of chlorine. Fig. 1.-Freezing point vs. composition for system of methylene chloride-chlorine,
For the investigation of the system methyl chloride-chlorine, in which both components are vapors a t ordinary temperatures, a special apparatus, shown in Fig. 3, was used. This consisted essentially of a closed reaction cell immersed in a pentane bath, the temperature of which could readily be controlled between - 1500 and +20° by means of liquid air. Accessory devices facilitated the introduction of measured amounts of either component into the cell. For
1576
J. ALLENWHEAT,11, AND A. W. BROWNE
Vol. 62
- 124
27.8
$ a
- 123 - 121 - 120 - 120 - 121 - 122
- 124
28.3 30.0 34.6 35.1 40.1 41.0 43.2
E: -120
- 125
44.1
- 124 - 122 - 122 - 123 124 - 128
45.2 49.0 51.6 54.5 57.4 62.0
DEF. (Solid s o h , vapor)
- 129
63.3
F.
- 124 - 120 -117 - 113 - 110 - 105 - 104
66.5 69.5 72.0 78.0 82.0 89.6 95.0
- 102
100.0
-90
9 -100 .3
$
-110
F-”
- 130 20 40 60 80 Molar percentage of chlorine. Fig. 2.-Freezing point vs. composition for system of methyl chloride-chlorine.
each concentration studied, the system was cooled well below the freezing point, with constant agitation, until solidification occurred. The bath TABLE I1 TEMPERATURE-CONCENTRATION OR SOLUBILITY DATAOF THE SYSTEM CHsC1-C12 Temp.,
OC.
-
Concn.,
mole % C1z
90
0.0
95 -100 -103 -108 -114 -119
6.5 11.2 14.2 17.5 21.6 25.8
Curve (Fig. 2)
A.
(Solid CHsCl, liq., vapor)
AB. (Solid CH3C1, satd. soln., vapor)
-
B.
(Eutectic: solid CHsC1, solid (CHC1)2.Clt, satd. soln., vapor)
BCD. (Solid (CHaC1)2.C1,, satd. s o h , vapor)
D. (Eutectic: solid (CHsCl)&lr, solid CHSCl.Cl2, satd. s o h , vapor)
CHLY.Clz, satd.
(Eutectic: solid CHsClClZ, solid Clt, satd. s o h , vapor)
FG. (Solid Clz, satd. s o h , vapor)
G. (Solid C12, liq., vapor)
was then allowed to warm slowly, with constant stirring, and the temperature of the bath a t which the last trace of the solid phase disappeared, was taken as the freezing point. Possible error due to temperature lag between bath and cell was elimi-
J Fig. 3.-A, Cylinder of CHsCl; B, gas trap (mercury) ; C, double stopcock; D, E, water-jacketed gas buret and leveling bulb (mercury); F, exhaust stopcock; G, double stopcock; H, glass spiral; I, reaction cell; J, pentane-bath; K, electric motor; L, exhaust stopcock; M, gas drying bottle (concentrated sulfuric acid); N, double stopcock; 0, P, water-jacketed gas buret and leveling bulb (saturated NaCl in water) ; Q,gas trap (saturated aqueous solution of sodium chloride) ; R, cylinder of chlorine; S, liquid air supply; T, copper tubing: U, aspirator pump.
THEHYDROGEN PERCHLORIDES
June, 1940
nated by special calibration of the pentane thermometer with the aid of several pure gases whose (known) melting points were determined in the same way. The data are submitted in Table 11, and are plotted in Fig. 2 . The data in the foregoing tables clearly indicate the formation of three chlorinates of methylene chloride, and two chlorinates of methyl chloride, all with congruent melting points, as follows (1) methylene chloride hemichlorinate, (CHzClt)t.Clt, - 124.5" (2) methylene chloride monochlorinate, CHzClyClz, 126.5" (3) methylene chloride dichlorinate, CH2C1*.2Clz, -117.5" (4) methyl chloride hemichlorinate, (CH&1)2.C12, - 120' (5) methyl chloride monochlorinate, CHsCI*Clz,- 122 '
-
While no evidence concerning the' structure of these compounds has been obtained as yet, it is possible to write their formulas in the manner tentatively suggested for the chlorinates of chloroform and of carbon tetrachloride in the earlier
(CONTRIBUTIONFROM
THE
1577
articles of the current series. The fact that the maximum number of chlorine molecules held in combination by any of the chloromethanes is equal to the number of chlorine atoms in the chloromethane molecule tends, in the opinion of the authors, to confirm the idea that the solvates under investigation are coordination compounds. In conformity with the definition of perchlorides proposed in the second article of this series, the three chlorinates of methylene chloride and the two of methyl chloride may be regarded as perchlorides of methylene, and of methyl, respectively. Their empirical composition could therefore be expressed by the formulas (CH%)zC16, CHZC14, CHZCls, (CH&Cl, and CH3C13.
Summary Two chlorinates of methyl chloride, or perchlorides of methyl, and three chlorinates of methylene chloride, or perchlorides of methylene, have been identified and their congruent melting Points d e t e r m i m i ITHACA,N. y.
RECEIVED APRIL 5, 1940
BAKERLABORATORY O F CHEMISTRY AT CORNELL UNIVERSITY]
The Chlorinates. IV. Temperature-Concentration Equilibria in the System Hydrogen Chloride-Chlorine. The Hydrogen Perchlorides1a2 BY J. ALLENWHEAT,11, AND A. W. BROWNE Since chlorine readily forms solvates with the chloromethanes2 i t has been suggested tentatively TABLE I TEMPERATURE-CONCENTRATION OR SOLUBILITY DATAOF THE SYSTEM HC1-Cl, Temp., OC.
- 112
- 114 -117 - 120 -122 -125 -128 -129
1
Concn., mole % CIz
0.01
19.6 23.0 25.6) 26.3
1
j
Curve (Fig. 1)
- 123 - 122 - 122 - 124
30.6 32.2 35.0 37.6
(Solid HCI, liquid, vapor)
40.4 49.4
AB. (Solid HCl, saturated solution, vapor)
-115 - 116 - 117 120 - 124
B. (Eutectic: Solid HC1, solid (HC1)z: Clt, saturated solution, vapor)
(1) This article is based updn the thesis presented to the Faculty of the Graduate School of Cornell University by J. Allen Wheat, 11, in partial fulfillment of the requirements for the degree of Doctor of Philosophy. (2) For the preceding articles in the current series, see Wheat and Browne, THIS JOURNAL, 68, 2410 (1936); 60, 371 (1938); 62, 1575 (1940).
1'
- 125
- 120 - 116
A.
)
-
1 1
BCD. (Solid (HC1)z: Cln, saturated solution, vapor) D. (Eutectic: Solid (HCl)Z:Cl,, solid HCl:Clz, saturated solution, vapor)
DEF. (Solid HCl: Clz, saturated solution, vapor)
60.0 63.5
- 128
F. (Eutectic: Solid HCI: Clz, solid Clz, saturated solution, vapor)
- 122 - 117 - 112 - 109 - 106 - 103 102
-
72.6
I
77.5 82.5 I 88.9 95.0 J 100.0)
FG. (Solid Clz, saturated solution, vapor)
G. (Solid (211, liquid, vapor)
