Vapor Pressure-Temperature Data on Some Organic Compounds R. R. DREISBACH AND S. A. SHRADER The Dow Chemical C o m p a n y , Midland, M i c h . w
I
T
HE present investigation was inaugurated a number of years
ago when it became necessary to know the barometric boiling point of the forward flow on styrene fractionating columns. In order to do this a table of vapor pressure-temperature relations was developed and this required an accurate knowledge of a t least two boiling points a t their respective pressures. It became necessary to set up Cox chart families, and for this purpose data on at least three compounds of the family were required. The only families for which these data were available in the required accuracy were the aliphatic hydrocarbons, benzene hydrocarbons, cyclohexanes, and oyclopentanes. The data on these were determined by the Bureau of Standards (8). In order to set
( O C.) TABLE I. BOILINGPOINTS
Compound Chlorohenocnc m-Diclllorobenzene p-Dichlorobenzene a-Die hlorobcnzene p-Et hylchlorobenzene Bromobenzene a-Isopropylbromobenaene o-Dibromobenzene
760 Mm. 131.70 173.00 174.12 180.48 184.42 156.06 210.24 219.30a
p-Methylvinylbenzene o-Ethylvinylbenzene m-Ethvlvinvlbenzene .u-Ethdvin;lbenzene p-Godropyivinylbenzene p-Isopropyl-a-methylstyrene o-Chlorovinylbenzene p-Chlorovinylbenzono a-Bromovinylbenzene v-Bromovinylbenzene &-Divinylbenzene
171.06" 187.26" 189.95" 192.30" 205.29" 221.50' 186.4" 189.20P 206. 20a 210.40" 210.55=
a
AT
315.52 Mm. 101.85 140.49 141.65 147.64 151.62 124.47 175.83 184.58
123.76 Mm. 75.22 111.49 112.66 118.32 122.33 96,32 145.08 152.79
B.P., e C. 111.16 127.88 157.50 117.48 172.68 205.41 154.94 127.27 129.27 146.81
P,Mm.
B.P., ''2, 98.13 112.09 128.29
Acetone Methyl ethyl ketone Methyl isopropenyl ketone Diethyl ketone Diisopropyl ketone Ethyl alcohol twf-Butyl alcohol n-Butyl alcohol ;IOctyl alcohol Methyl-a-keto butanol' ormic acid Acetic acid Propionic acid n-Butyric acid Chloroacetio acid Ethyl acetate Methyl benioate &Phenyl ethyl acetate o-Chlorobenaaldehyde Propionsldehyde Nitromethsne Nitroprop&e o-Nitrotoluene p-Nitrotoluene
OF
760 Mm. 56.20 79.50 97.71' 101.70 125.25 78.27 82.41 117.40 195.28 189.60 1OE. 70 117.72 140.80 163.25 187.85 76.82 199.10 232.57 212.04 50.29 99.98 131.38 222.15 233.26
127.20 132.45 315.52 78.77 315.30 507.80 315.52 123.76 75.86 123.76
75.86 Mm. 63.05 98.05 99.41 104.94 108.98 83.99 131.66 130.03W.o')
66.39 Mm.
....
.... ....
80. 08
.... ....
P, Mm.
77.64 76.00 123.76 ..,. ..,. 142.13 127.30 315.30 186.89 123.76 124.82 113.76 75,86 66.39 125.60 75.86 132.66 .... ... 121.22 75.86 Boiling point at 760 mm. calculated from infinite point and one of determined values at
Compound
0
VARIOUSPRESSURES OF SATURATED AND UNSATURATED HALOAND HALO-ALKYLBENZENES AND m-DIVINYLBENZENE
507.50 Mm. 117.30 157.37 158.52 164.65 108,136 140.69 193.68 203.16
TABLE 11. BOILINGPOINTS (' C.)
F
up other Cox chart families more accurate and additional data were required than were available in the literature. The accompanying vapor pressure-temperature tables are the result of this work, The boiling point a t various pressures was determined by S. A. Shrader in apparatus elsewhere described (41, except that the Points for Controlling the pressure were placed on the atmospheric side instead of on the pressure side. The results obtained on the boiling points checked the Bureau of Standards' results t o Within *o.olo c. when the compounds used were those furnished by the bureau. The method of preparing the compounds, the purity, and other physical data are as given in the foregoing paper ( 1 ) . The same paper tabulates the A and B values of the Antoine equation and the A* and B* values of the Dreisbach-Spencer ( 2 ) vapor density equation for each compound.
Four tables are given listing the determined boiling point at 760-mm. pressure and seven lower pressures and a table listing the infinite points of 23 Cox chart families.
B.P., O C. 90.98 108.60 114.87
.... 128.23
57.04 Mm. 56.28 90 72 61.99 97.66
47.16 Mm.
76.38
71.76
....
.... ....
.... .... .... ....
....
37.58 Mm.
...
... 87102
... ... ...
P, Mm. B.P., " C . P,Mm. B.P., 37.16 66.41 75.86
i i :64
123.76 157.33 75.86 111.41 66.39 109.97 121.45 57.04 66.39 128.95 66.38 116.98 a lower pressure.
....
104.43 107.30
56:SO 57.04
120.47 143.41 103.57 106.09 116.53 124.71 112.40
5i:i6 75.86 57.04 57.04 47.16 57.04 57.04
....
C. P, Mm.
.... 99.67 ....
44:41
....
... ...
98.51 100.91 110.19 119.51
57:i)4 47.16 47.16 37.58 47.16
.... 135.57 ..
SOMEALIPHATICKETONES, ALCOHOLS, ACIDS, ESTERS, ALDEHYDES, AND NITRO COMPOUNDS 507.50 Mm. 44.81 67.36 84.87 88.91 111.28 68.71(608.58) 72.49 106.46 (698.68) 181.17
....
87.82
....
128.34 150.70 174.44 65.01 183.32 lQ5:42(Ml*8) 39.07 88.23 117.56 205.48 216.17
315.52 Mm. 32.55 54.29 71.00 75.04 96.34 57.47("6.W 61.82 94.52(an.m 166.09 160.2 73.55 91.13 114.62 136.77 159.92 52.34 166.28 197.90
....
....
74,25 102.72 185.48 197.76
Boiling point at 760 mm. calculated from lower pressures.
2879
123.76 Mm.
.... 31.84
47.19 51.24 70.58 38.26 (128.6i) 43.34 73.73 (126.68) 140.27 183.16 48.79 66.07 90.73 112.57 134.67 30.45 136.80 167.24 146,73(127.82)
....
50.85 76.97 156.61 165.98
75.86 Mm.
.... ....
....
36.36 58.66
.... .... .... 128.52
121.08 37.35 55.75 79.68 101.32 123.19
....
123.23 153.10
.... .... ....
65.11 142.43 151.43
66.39 Mm.
.... ....
.... .... .... ....
57.04 Mm. 47.16 Mm.
....
..I.
.... .... .... ....
55.73
52.19
125.42 118.3
121.99 114.0
76: 75 98.35
72:39 95.01
....
.... ....
....
....
115.55 149.41 132.67c77.6')
110.88
62.00 138.75 147.71
58.65 134.51
.... ....
.... .... 48.04
.... .... ....
....
.... .... .... .... 109.6
.... .... .... 90.92
112.30
.... ....
....
129.31
....
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
2880
TABLE111. BOILINGPOINTS ( "
c.)O F SOME ETHERS, KETONES, NITRILES, AND PHENYL ETHYL ALCOHOLS
Compound 760 Mm. 507.50 Mm. 68.27 56.12 Isopropyl ether 141.97 127.73 n-Butyl ether 186.75 171.37 rc-Amyl ether 153.75 Anisole 139.37 170,on Phenetole 155.16 174.31 189.90 n-Propyl henyl ether 210,20 193.97 n-Butyl plenyl ether Diphenyl ether 201.85" l i b : is o-Chloroanisole 211.94 C hlorophenet ole 195.79 ibenzyl ether 2ia:65a 201.32 Propiophenone 220.33 237.00n Chloroacetophenone 306.10 287.23 ensophenone 80.06 67.75 Aoetonitrile 97.35 84.44 Propionitrile 141.25 126.92 a-Valeronitrile 163.65 148.80 a-Capronitrile 189. 76(518.851 203.5n a-Phenyl ethyl alcohol 205.41 190.50 Benzyl alcohol 218.90 202.91 &Phenyl ethyl alcohol 250.0 o-Ethyl-@-phenyl ethyl alcohol 250. l o a p-Ethyl-@-phenyl ethyl alcohol 242:i5 259.35 p-Chloro-@-phenylethyl alcohol 192. 63' Dimethyl phenyl carbinol a Boiling point a t 760 mm. computed from lower pressures. I
.
.
315.52 hlm. 43.09 112.28 154 67 123.77 139.17 157.64 176.51
TABLExv. 760 M m . 181.75 190.95 201.88
507.50 M m . 167.63 176 14
Phenol o-Cresol p-Cresol .... ptcrt-Butyl phenol Aniline 183.93 168.21(507.3' +Toluidine 200.3 184.80 m-Toluidine 203.34 187.87 o-Chloroaniline 208.84 192.71 mi,17~7.8) p-Ethylaminobenzene 217.22 6 5 , 87(50*3.58 n-Butyl chloride 78.44 1,2-Dichloroethane 83.38 P,2-Dichloropropane 98.20 i3:is 113.67 100.34 B,1,2-Trichloroethane Perchloroethylene 121.02 107.17 (501.8 1 Uns m-Tetrachloroethane 130.20 115.99 ibromoethane 131.41 117.21 &!Tribromoprqpane 221.88O 205.20 d a r b o n tetrachloride 76.75 64.02 Wnyl chloride -13.70 -23.35 5 Boiling point a t 760 mm. calculated from lower pre8sures.
....
145.38
57.04 Mtn. 47.16 Mm.
..
73.60 112.86 84.55 98.94 114.83 132.19
81.31 95.60 110.81 127.73
91.89 106.39 123.53
101.00 118,88
123.63 130.90
126.80
119.81
115.13 122.01
13a:i1 152.07 211.16
132:21 147.38 206.42
142 70 200.50
69.07
.... ....
.... ....
169,44 178.38
140.47 148.33
127.27 134.54
183.84 202.05 266,87 54,45 70.45 111.48 132.62 174.08(324.Q) 174.64 186.30 216 ,35(317.0) 216.37(aii.a) 224.31
1k4: 73 170.18 231.57 31.00 45.76 84.59 104.54 147 ,43(133.55i 147.09 157.60 186.38('16.ej 186.18'126.67' 193.20 143.52
140.02 156.31 215.46
66: 84 105.46
....
.. ....
....
....
....
. . I .
73.34
....
....
....
. I . .
....
ROILING POINTS ('
66.39 Mm.
....
85.75 126.06 96,89 111.56
....
B
Compound
....
....
....
75 86 M m .
123.76 Mm.
I
I
6.
Vol. 41, No. 12
....
35.5 72.55 91 98 8 4 , 78(85.861 134.28 144.61 172.75tr8.77j 172.32'78.77) 178 78 130.72
.... ....
:
.... ....
....
....
...
....
81.99C75.95J 130.90 141.10
....
127.12 137.15
122.52 133.05
....
..I.
....
....
175.22 127.09
. I . .
171.00 123.64
165.98 118.68
c.) O F SOME PHER'OLS, AMINES,AND HALOALIPHATICS
315.52 Mm. 152.37 160.17 171.27 l&:io(eifi.ar
168.06 171.18 154.55 183. 88V15.a) 52 .43(315.Zi)
123.76 Mm. 125.95 132.63 143,86
75.86 Mm. 113.81 120.22 131.26
125: i6m7.a! 139.00 142.27 145.30 153.Q6(121.81 29 ,37(128-58)
135.99 129.03 131.54 140.41(
...
57.04 M m . 107.15 113.11
....
....
.. ...
,.
1 1 . .
...
. I . .
122:iz 125.57
.... , . . , .~..
7 6 . ~
...
61.29 66.44(127.Sl 74.47 75.64 155.54 26.03
47.16 hlm.
....
li2:92(77.89,
ii:is
66 .' 00 85.99 9 2 , 21(315.81 100.69 101.94 186.94 50.41 -33.51
66.39 h l m .
..
....
49:97
.... 59.31
....
62.39 63.59 141.15
.
I
.
, . ,
...
. . . ...
.
....
. . , ,
... ....
... I
.
.
I
.
.
.... ....
...
....
.
60.43 137.42
52:5t3 133.11
....
....
....
....
. . I ,
118.46 121.77 124.48
....
127.98
....
,..
TABLE V. INFINITE POINTS OF Cox CHA.RT FAMILIES Factor
( T m +230) T,,
Formula
Tables I to I V of the present paper record the boiling points a t the various pressures as indicated. Table V gives the infinite points of the various Cox chart families, calculated from the data in Tables I to IV. These points were obtained by plotting A against 13 on ordinary coordinate paper and drawing the best average straight lines through thase points. t , and P , were then calculated from the equations,
Benzene family (satd.) Halo benzenes (satd.) Cyclohexanes (very close) Benzene family (unsatd.) Halo benzene family (rinsat Naphthalene Halo naphthalene Aromatic amines Halo aromatic amines Aromatic phenols Halo aromatic phenols Nitrobenzenes Halo nitrobenzenes
CnHzn CnHzn
CnHzn
-(6
LITERATURE CITED
(1) Dreisbach, R. R . , Martin, R. A., IND. ENG. CHEM., 41, 2875 (1949). (2) Dreisbach, R. R., Spencer, R. S., Ibid., 1363 (1949). (3) Rossini, F. D., et al., Natl. Bur. Standards, Circ. C461 (1947).
C.
prn
x
104
x
lo.(&)
-m)Xm
-
CnHzn 8 CnHm - (8 - m ) X m CnHzn 12 CnHzn (11 - m ) X m CnHzn & CnHzn - ( 6 -m)NXm CnHza - S O CnHzn - ( e - m ) O X m CnHzn - ? N o r CnHzn - ( ? -m)SOnXm CnHzn - a 0 CnHzn - (8 - m ) O X m CnHzn - SO CnHzn (a m) OXm Aromatic ketones CnHzn - 1 6 0 Halo aromatic ket,ones CnHm -(la-m)OXm Aromatic-aliphatic ket.ones CnHzn - 8 0 Halo aromatic-aliphatic k e t m e s CnHzn - (8 - m ) O X m Aromatio et,hers CnHzn - 1 4 0 Mixed aromatic-aliphatic ethers CnHzn a 0 Cyclohexyi ethers (all satd. and unsatd .)CnHznO Cyclopentanes CnHzn Aliphatic hydrocarbons CnHzn + 2 Halo aliphatic hydrocarbons CnHm + ( 2 - m!Xm Unsatd. aliphatic hydrocarbons CnHzn %-Primary alkyl amines t o 190° C. CnHm + sN n-Primary alkyl amines, 190-350° C. C n H z n + aN Aliphatic ethers CnHzn .+2 0 Aliphatic ketones CnHznO Nitroparaffins CnHzn + iN0z Aliphatic nitriles CnHzn - I N Aliphatic esters CnHznOz Aliphatic alcohols CnHzn + 2 0 -4liphatic acids t o 1414 C. CnHznOa Aliphatic acids above 142O C. CnHznOz Halo aliphatic acids CnHzn - m O X m
1670
2,320
1063.4
0.910
3985.0
921.5
0.530
3274.6
1750
3,800
7324.0
1937
8.204
8740.0
2022
3,701
8304.0
6621.0
600
0.150
1905.0
3300
20.000
15,550.0
2186
5.186
9263.0
1850 1450 1240 1450 1725 1125 1270 1579 3293 1350 2025 1639 12,150 364
3.400 1.550 1.300 1.698 1.441 1.253 2.525 6.929 2 . on0 3.461 3.800 128.200 0.0596
7597.0 6560.0 4753.0 5693.0 6548.0 4424.0 5029.0 6730.0 13,950.0 5404.0 8250.0 6913.0 64,718.0 1125.0
iiS8
9.060
6881.0
- -
wheret, = " c . p , = pressure in mm.
0
-6
1.860
....
....
J., Pignocco, J. M.and Hossini, F. D., J . Research Natl. Bur. Standards, 35,219 (1945).
(4) Willingham, C . B., Taylor, W.
RECEIVED May
9, 1R49.
