44s
CLIFFOKII D. HOLLEI'.
arated melting a t 3 3 O , the melting-poiiit of methyl cinnaniate. This product was then distilled, and the boiling-point also agreed with that of inethyl cinnaniate. T h e yield after all this treatment was found to be 1 5 grains or 60 per cent. of the calculated. T h e di6~0~72in'c,f7~0~1t z,~-rZiizitl-osfiZ6e)zE( I j grams), -when boiled with alcoholic potassiiiin thiocyanate, gave 6 grains of pure 2,.~.di1iitro';til~~eiir or 64 per cent. of the calculated. The dibi-niizidc j j v i i i thc )iifi-i/f clf' flhe)zyZ ci)zuainic acid (60 grains) gave 24 grams of the unsaturated product or 7 0 per cent. of the calculated. These yields do not reprezent the total aniount of unsaturnted material formed, sincc no special effort \vas made to obtaiii the entire ainounts. ?-I:\v
!r.*vl;s, cosx.,
Dehriinsy
IO. 1 w 2 .
LIQUID MIXTURES OF M l N l i l U M BOILING-POINT. Hv CLII.'POKn D. H O L L X Y . K c c c i . e r l Jnndnr!
1 1 , t'i
..
N 1899, Ilr. Garnett Rylaiid' reported the results of an investigation of So pairs of the more coni~nonliquids. H e found that 4j furnished mixtnres which distilled in the same proportions with a constant boiling-point below the boiling-points of the constituent liquids ; one which presented no relative depression or elevation of the boiling-point ; and 3 which were of an uncertain character. During the same year, E. 12. Thayer? and J. K . Haywood' investigated several of the same niixtures, but instead of following the method of Ryland. and determining the minimumpoint by repeated distillations, they determined the boiling-points of several mixtures of the liquid constituents, and plotted the resulting boiling-point curve. From a comparison of the two methods it is seen that the proportion in mhich two liquids give a minimum point on the boiling-point curve is the same in which they distil with a constant boiling-point which lies below that of either liquid constituent, and the boiling-points are the same in both cases. But little having been done along this line during the past two years, it seemed desirable to add to our knowledge of such phenomena, and continue the itivestigations of such systems as would be likely to furnish mixtures of minimum boiling-point.
1
A m . Chrni.J.. a i , X o . 5. 2Jour. Phys. Chem.. a, 382; 3, 1
3
fbid.,2 , 3 1 : .
32
LIQUID ,MIXTURES O F XINIMUM BOILING-POINT.
449
I n this paper are presented the results obtained with amyl compounds as one of the liquid constituents. T h e boiling-point method was chosen as the more preferable, as in the distillation of bromides and iodides the formation of tarry residues towards the close of the distillation renders the thermometer readings inaccurate. A slightly modified form of Hite's apparatus was used. Instead of a differential thermometer,
0
Amyl bromide.
one of the ordinary type was provided. It was graduated to fifths of a degree centigrade but with a scale so large that twentieths could be readily estimated. A weighed amount of the lower boiling constituent was introduced into the bulb of Hite's apparatus, boiled for several minutes and the boiling-point and barometric pressure recorded. Weighed amounts of the other constituents were added, the successive boil-
450
CI.IFFOXD D . HOLLEY.
ing-points noted, aud this procedure was continued until the liquids were present in nearly equal proportions. The flask was then emptied and the process reversed, weighed portions of the first being added to a weighed ainount of the second constituent. T h e results obtained are shown in the form of a plot. No corrections were applied to the curves because of variations of barometric pressure, as the error thus introduced is believed to be inappreciable. The liquids used were purified by redistillatiou, usually the first and last fourth being rejected. The portions reserved distilled at a very nearly uniform temperature. I n experimenting with mixtures of amyl iodide the bulb of Hite's apparatus was covered, and the investigation carried on in very subdued light, but even with these precautions the mixtures were noticeably colored towards the close of the operations from the separation of free iodine. TABLE I.--AMYL SO.
I 2
3 4 5 6
7 8 9 I0
I1 I2
Amyl bromide Per ceut. Ioo.00
9 7.68 95.04 97.39 87.33 83.40 79.22 73.12 65.58 59.38 53.95 47.44 43.00 43.29 37.91
BROhfIDE AND ;\MYL ALCOHOL
Amyl alcohol. Per cent.
Temperature.
0.00
I 17.9 117.2 116.8 116.35 116.15 116.3 I 16.4 116.8
2.32 4.96 S.61
12.67 16.60 20.78 26.88 34.42 40.62 46.02 52.56
C
117.25
117.9 I 1S.4 I
1S.9
j7.00 56. 7 1
I 19.j
120.;
22
26.86 21.03 17.32 13.28 9.02 4.23
62.09 67.60 73.14 78.97 S2.65 86.72 90.93 95.77
23
0.00
100.00
I3 I4
15 16 I7 18 '9 20
21
32.40
119.0 121.j 122. j
124.0
124.9 I 26.0 127.0
128.1 129.0
Barometer mm.
764. I 764. I 764. I 764.0 764.0 764.0 764.0 764.0 763.9 763.9 763.9 763.8 763.8 763,s 763.8 763.5 763.7 763.7 763.7 763.6 763.5 763.5 763.4
451
L I Q U I D MIXTURES O F M I N I M U M B O I L I N G - P O I N T .
TABLE II.-ISOBlJTYL h-0. I
Isobutyl alcohol Per cent. IOO.00
ALCOHOLAND AMYL BROMIDE.
Amyl bromide. Pel cent. 0.00
5.12
21
94.88 89-50 84.33 79.92 76.35 72.96 69.36 66.63 63.63 60.70 57.48 54.56 51.37 48.10 44.32 38.08 31.28 25.55 20.56 16.55
22
12.22
23
7.89 6.01 2.73
23.65 27-04 30.34 33.37 36.37 39.30 42.52 45.44 48.63 51.90 55.68 61.92 68.72 74.45 70.44 83.45 87.88 92.11 93.99 97.27
0.00
100.00
2
3 4 5 6 7 8 9 IO
I1 I2
13
14 15 16 17
18
'9 20
23
25 26
10.50
15.67 20.08
'1'empwature. C. 105.0
104.3 104.0 103.8 103.65 103.6 103.55 103.5 103.45 103.4 103.45 103.5 103.6 '03.7 103.75 103.8 104. I 104.6 105.4 106.2 107.4 109.0
111.2
112.9 115.0 118.1
Barometer.
mm.
757.8 757.8 757.8 757.8 757.8 757.8 757.5 757.5 757.5 757.4 757.4 757.5 757.5 757.4 757.4 757.4 757.4 757.3 757-3 757.3 757.3 757.3 757.2 757.0 757.0 757.0
Table 1. Amyl Alcohol and Amyl Bromide.--In the axompanying plot the left-hand ordinate represents 100 parts amyl alcohol. Amyl bromide (117.9') and amyl alcohol ( 1 ~ 9 . 0 'C.) furnish a mixture with a minumum boiling-point of I 16.15" C. in the proportion of 12.7 parts amyl alcohol, and 87.3 parts amyl broniide. The minimum point is definitely defined. T h e first additions of amyl alcohol cause a rapid lowering of the boiling-point followed by a gradual rise nntil the niaxinium is reached. T h e curve exhibits a distinctly wavy tendency. TabZe 1% Isoburfyl Alcohol and AmyZ Bromide.-Isobutyl alcohol (105') and amyl bromide(118.1") in the proportion of 63.6 parts isobutyl alcohol to 36.4 parts amyl bromide, gives a mixture having a minimum boiling-point of 103.4~ C. T h e major portion of the curve is very flat, and the minimum point is not sharply marked. From the curve it is seen that isobutyl alcohol can be diluted with amyl bromide until it contains nearly 43 per cent. of
45 2
CLIFFORD D . HOI.LEY.
the latter before the boiling-point of the mixture is raised above that of isobutyl alcohol. Table 111. Propyl Alcohol aizd Aniyl Brotttide.--A mixture of propyl alcohol (95.5'), and amyl bromide ( I 18.2'), in the proportions of 70.7 parts propyl alcohol to 29.3 parts amyl bromide, gives
A m y l iodide
a minimum point of 94'. The curve descends in a nearly straight line to the minimum, then rises very gradually at first, but at last with great abruptness to the maximum. Propyl alcohol may contain as much as 65 per cent. of amyl bromide without raising its boiling-point. Table 1V. Amyl Alcohol aiid Amyl lodide.--Amyl alcoho;
LIQUID MIXTURES OF M I N I M C M BOILING-POINT.
453
(128.9') and amyl iodide (146.5') furnish a mixture having a minimum boiling-point of 127.3' in the proportion of 52 parts amyl alcohol to 48 parts amyl iodide. The minimum point is
6:
O!/
20
30
80
70
50
60
40 Amyl acetate.
50
70
30
80 20
90 /D
/OO Q
fairly well defined ; the major portion of the curve is quite flat, and it is evident that amylalcohol may contain as much as 65 per cent. of amyl iodide and still have a boiling-point below that of pure amyl alcohol, TABLEIII.-PRoPYL No. I
Propyl alcohol. per cent. 100.00
2
94.42
3 4 5 6 7 8 9
8S.05
IO
I1 I2
I3 14 I5 16 *7 18
19
83.78 79.55 74.81 70.70 66.99 63.69 59.85 55.98 52.09 47.91 46.60 43.01 40.50 35.35 29.02 23.24
ALCOHOL AND A M Y L BROXIDE.
Amyl bromide. per cent. 0.00
5.58 11.95 16.22 20.45 25.19 29.30 33.01 36.31 40.15 44.02 47.91 52.06 53.40 56.99 59.50 64.65 70.98 76.76
Temperature. 0C.
95.5 95.2 94.8 94.6 94.4 91.2 94.0 94. I 94.15 94.2 94.25 94.3 94.4 94.4 94.5 94.7 95.2 95.9 96.9
Barometer, mm.
762.8 762.8 762.8 762.8 762.8 762.8 762.8 762.8 762.8 763.0 763.0 763.0 763.0 763.0 763.1 763. I 763.1 763.3 763.3
454
C L I F F O R D D . HOLLET h'0. 20 21
22
23 24 25
Propyl alcohol. Amyl bromide. Per cent. Per cent.
18.23 14.81 11.38 8.77 6.49 4.36
26
2.14
27
0.00
TABLEIV.--AMYL No.
Amyl alcohol. Per cent.
81.77 Sj.19 88.62 91.23 93.51 95.64 97.86 Ioo.00 .$I.COHOL Amyl iodide. Per cent.
Temperature CC.
Barometer nim.
98.3 99.6 101.6
763.3 963.4 763.4 763.4 763.6 763.6 763.6 763.6
103.85
106.2 109. I 112.6 118.2 AKD .$MYI,
IODIDE.
Temperature. 0 C.
Barometer.
758 6 755.6 758.6 758.6 758.6 758.7 7jS. j 758.7 75K6 758.6 758.6 758.7 7j8.0 758.0
I
100.00
0.00
I 28.9
2
I1
51.93
I2
48.89 45. 84
6.43 12.53 1S.Sr 25.20 29.81 32.54 36.74 39.92 43.82 48.02 51.11 54.16 59.52 64.40 69.68 78.72 81.88 87.36 89.90 92.57 96.84 97.96
128.6 128.4
IO
93.57 87.47 81.19 74.80 70.19 67.46 63.26 60.08 56.18
3
4 5 6 7 8 9
13 14
40.48
15
35.60
16
30.32
'7
21.28
I8 I9
18.12 12.64
20
10.10
21
7.43 3.16
22
23
2.04
24
0.00
I00.00
128.3 128.2
128.18 128.0j '27.9 127.7 127.4
127.j
127.4 I2j.G
I2S.O
128.6 '29.3 130.6 132.0 133.7 135.2 136.j
mm.
j55.0
755. I 755. I j jS. I 7j5.1 75s. I
140.5
758.3 758.3
142.3
jj5.3
146.5
158.3
TABLE V.-ISOBUTYI. ALCOHOLAND XMVL IODIDK SO.
1 2
3 4 5 6 7
Isobulyl alcohol. Per cent. Ioo.00
94.88 83.36 S2.3j 74.99 67.56 59.67
Aniyl iodide.
Temperature. CC
Barometer
0.00
104.8
717.4
5.12
104.7 104.7
747 4
Per cent.
11.64
17.65 25.01 32.44 40.33
104,s
105.0 105.3 105.j
1nn1
747.4
147.3 747.5 747.5 747.5
LIQUID MIXTURES OF MINIMUM BOILING-POINT. NO.
8
9
Isobutyl alcohol. Per cent.
Amyl iodide. Per cent.
53.87 47.88 43.40 36.86 29.92 25.39 19.20 14.48
46.13
105.8
52.12
106.1 106.2 106.9 107.8 108.7 110.4 112.6
16 I7 I8 '9
I 1.00
2.32
56.60 63.14 70.08 74.61 80.80 85.52 89.00 92.27 94.74 97.68
20
0.00
IOO.00
IO
I1
I2
I3 14 15
7.73 5.26
Temperature.
455
Barometer.
mm.
OC.
747.5 747.5 747.5 747.8 747.8 747.8 747.8 747.8 747.8 748.0 748.0 748.0 748.1
115.0
IIi.8 121.0
126.0 146.5
Table V. Isobutyl Akoltolaitd AmylIodide.--Isobutyl(104.8~) alcohol and amyl iodide I 46. j O ) do not give a mixture having a definite minimum boiling-point. The first two additions of amyl iodide caused a lowering of the boiling-point of 0.I O C. This was followed by a gradual rise until the mixture contained about 7 0 per cent, of amyl iodide, when the boiling-point rose with great abruptness to the maximum. TABLEVL-PROPYL ALCOHOLAND NO.
Propyl alcohol. Per cent.
I
100.00
2
93.36 89.94 79.9' 73.06 66.16 59.90 54.38 46. I5 41.08 36. 50 30.27 24.90 19.19
3 4 5 6 7 8 9 IO
I1 I2
'3 14
I5 16 17 18 '9 20
Amyl iodide. Per cent. O.(K)
11.48 8.64 5.95 3.07
6.64 I 0.06 20.09 26.94 33.84 40. IO 45.62 53.85 58.92 65.40 69.73 75.10 90.81 85.22 88.52 91.36 94.05 96.93
0.00
700.00
14.78
. h I Y I , IODIDE.
Temperature. 0 C.
Barometer. mm.
95. 7 95.6 95.65 95.7 95.8 95.9 96. I 96.3 96.6 96.9 97.6 98.4 99.7 101.4 103.4 105.6 I 08.2 110.8 115.6 146.5
753.8 753.8 753.8 753.8 753.8 753.8 753.8 753.7 753.4 753.4 753.4 753.4 753.4 753.4 753.5 753.5 753.2 753.2 753.2 753.2
. l l , l Y l 3!COllO! h*O.
I 2
3 4
5 6 7
Per cent
129.1
bi). I O
10.90
14.55
11
67.62 64.16 60.08 56.87 50.04
21
42.88 35.21 27.53 20.85 I 7.80 7.45,
22
0.00
17
18 ‘9 20
c.
2.64 5.42 8.16
71.27
15 16
0
97.36 91.55 91.84
9
I3 I4
’Teniprratlirr I 29. j
IO
I2
Percent 0.UO
I00.C’O
s5.42 82.06 78.48 71.%
S
iyl 2L ~ ~ acetate.
‘29.3
130. I 130.2
j 70.0
130.5 131.3 132.0 133.0 133.8 134.55 135.5 136.2 137.5
jj0.0
17.94
I 30.0
21.52
120.
