Results and Discussion Literature Cited

Experimental measurements of the solubility of C02 and H2S

Deal, C. H., Dunn. C. L., Hill, E. S., Papadopoulous, M. N., Zarker, K. E.,
in a Sulfinol solution have been made at 40 and 100 O C . Partial Proceedings of the 6th World Petroleum Congress, Section IV, Paper 32,
pressures of C02 ranged from 2.4 to 5688 kPa while partial Frankfurt, 1963.
Dunn, C. L., Freitas, E. R.. Goodenbour, J. W., Henderson, H. T., Papado-
pressures of H2S ranged from 4.6 to 3862 kPa. The results are poulos, M. N., Hydrocarbon Process., 43 (3),150 (1964).
presented in Tables I and I1 for C 0 2 and H2S, respectively. No Fisher, P. W., lngenieur (The Hague), 78 (19), 45 (1966).
comparisons with data from the literature are possible for this Goar, 8.G.. OilGas J., 67 (26),117 (1969).
Isaacs, E. E.,Otto, F. D., Mather, A. E., J. Chem. Eng. Data, 22, 71
solution, but comparisons with a 2.5 kmol m-3 DlPA solution are (1977).
shown on Figures 2 and 3 for H2S and C02, respectively. The Klein, J. P., OilGas Int., 10 (9).109 (1970).
Lee, J. I., Otto, F. D., Mather, A. E., J. Chem. Eng. Data, 17, 465 (1972).
amount of DlPA in the Sulfinol solution is equivalent to that in a Lee, J. I., Otto,F. D.. Mather, A. E., Can. J. Chem. Eng., 5 2 , 803 (1974).
3.4 kmol m-3 solution so that the somewhat lower solubility in MacNab, A . J., Treseder, R. S., Mater. Prof. Perform., 10 (l), 21 (1971).
the Sulfinol solution is consistent with the effect of amine con- Richardson, I. M. J., O'Connell, J. P., Ind. Eng. Chem., Process Des. Dev.,
14, 467 (1975).
centration on solubility behavior. At high partial pressures, Shoemaker, D. P., Garland, C. W.. "Experiments in Physical Chemistry",
however, the effect of the physical solvent, sulfolane, becomes McGraw-Hill, New York, N.Y., 1962,p 162.
paramount and leads to high solubilities of the acid gases in the
liquid. The present results are consistent with the statement ( 4 )
that Sulfinol solutions are attractive solvents at acid gas partial Received for review November 1, 1976.Accepted February 28, 1977.Work
pressures of 760 kPa or greater. supported by the National Research Council of Canada.

Vapor-Liquid Equilibria at 25 O C for Nine Alcohol-Hydrocarbon

Binary Systems

Shuen-Cheng Hwang and Robert L. Robinson, Jr."

School of Chemical Engineering, Oklahoma State University, Stillwater, Oklahoma 74074

assembly, an equilibrium cell, and a pressure measurement

Solution vapor pressures at 25 " C were measured over the facility. All components other than the degassing assemblies
complete composition range for the nine alcohol- were housed in a constant-temperature air bath where tem-
hydrocarbon binary systems formed among methanol, perature was controlled at 26.0 f 0.2 'C. The equilibrium cell
ethanol, 1-propanol, n-hexane, cyclohexane, and benzene. was further immersed in a liquid (water) bath where the tem-
Vapor compositions and excess Gibbs energies were perature was controlled at 25.0 f 0.01 O C . Temperatures were
calculated from these data by the method of Mixon, measured by mercury-in-glass thermometers which had been
Gumowski, and Carpenter. Heat-of-mixing data from the calibrated against an NBS-certified platinum-resistance ther-
literature were combined with the present data to permit mometer.
presentation of complete information on the excess The equilibrium cell (Figure 2) is patterned after that of Gibbs
properties GE, HE,and SEfor each system. and Van Ness. However, the pressure measurement and liquid
measurement and injection apparatus differed from their design.
Recent interest in predictionof the phase behavior of nonideal Pressures were measured by a mercury manometer with levels
solutions has led to the introduction of numerous models to determined by cathetometer. The manometer was maintained
represent this behavior. To develop and/or evaluate such at a temperature of 28-29 O C to prevent condensation of vapor
models, especially those of the group-contribution type, requires
accurate, systematic data on homologous series of substances
with limited numbers of functional groups. Such data are sur-
prisingly scarce. The present study was designed to produce data
on the behavior of normal alcohols with an aliphatic, a naph- ASSEMBLY 4SSEYsLY

thenic, and an aromatic six-carbon hydrocarbon. The particular

systems were selected, in part, because heat-of-mixing data are
available for each system, thus rather complete excess prop-
erties (G, #, $) could be calculated from the combined
data.

Experimental Section
Apparafus. Detailed description of the experimental work is
given elsewhere (7). Basically, the apparatus is similar in many
i CONSTANT /
features to that used by Gibbs and Van Ness (5).As shown in I ;::FE;E CONSTANT TEMPERATURE AIR B A T H
Figure 1, the major components of the system included a de-
/ / / / / / / / / / / / / / / / / / / / .
gassing assembly and storage bulb for each component of a
binary system under study, a liquid measurement and injection Figure 1. Schematic diagram of apparatus

Journal of Chemical and Engineering Data, Vol. 22, No. 3, 7977 319
Table I. Organic Chemicals Used in This Investigation

Specified Most probable

Compound Manufacturer min purity impurity

Methanol Fisher Scientific Co. 99.9 mole %

Ethanol U.S. Industrial Reagent quality
Chemical Co. 200 proof
I-Propanol Fisher Scientific Co. Certified grade, bp
96.9-97.3 OC
Benzene Phillips Petroleum Co. 99.91 mole % Toluene
Cyclohexane Phillips Petroleum Co. 99.94 mole % 2,4-Dimethylpentane and
2,2-dimethylpentane
+Hexane Phillips Petroleum Co. 99.99 mole YO Methyl cyclopentane

Table II. Pure Component Densities at 26 OC B B

I I
Density, p , g cm+
Compound This work Lit. a

Methanol 0.7857 0.7856-0.7a5a

Ethanol 0.7842 0.7842-0.7844
I-Propanol 0.7989 0.7989-0.7991
Benzene 0.8727 o.a725-o.a727
Cyclohexane 0.7729 0.7728-0.7731
n-Hexane 0.6537 0.6539-0.6542
a Linear interpolation between 25 and 30 OC. Reference 17.

Table 111. Pure Component Vapor Pressures at 25 'C

Vapor pressure, mmHg A - CONNECTIONS TO EQUILIBRIUM CELL

B - CONNECTIONS TO DEGASSING ASSEMBLY
Compound This work Lit. ( 1 7 ) C - LIOUID STORAGE BULBS
D - MEASURING BULB SET
Methanol 127 14 (0 Oga) 125.40-127.18 E - MERCURY RESERVOIR
Ethanol 58.96 (0.09) 58.90-59.80
F - SCREW PUMP
G - HIGH VACUUM SHUTOFF VALVES
I-Propanol 20.96 (0.01) 20.44-20.90
Benzene 95.11 (0 01) 95.03-95.25 Figure 3. Liquid storage, measurement, and injection assembly.
, ,

Cyclohexane 97.69 (0.10) 97.41-98.25

n-Hexane 151.79 (0.11) 15 1.05-152.85
a Average absolute deviation from mean of three measurements. in the manometer. The injection and measurement facility is
shown in Figure 3. The degassed liquids were stored over mer-
cury in the storage bulbs (C) of 200 cm3 capacity. The mercury
ir' was also in communication with a set of calibrated measuring
bulbs (D) and a screw pump. The bulbs had nominal volumes of
20, 4, 2, and 1 cm3 with average uncertainties of 0.004 cm3. A
fifth, uppermost bulb served as an overflow reservoir.
The degassing assembly employed the technique of molecular
sublimation as described by Bell et al. ( 1).
Procedure. The experimental runs were begun by degassing
the pure components. Each component was sublimed and
condensed two or three times to ensure thorough degassing. The
degassed liquid was then allowed to drain into the evacuated
storage bulbs. This degassing technique proved definitely su-
perior to the bulk freezing, evacuation, and melting technique
used previously in this laboratory ( 16).
When the degassed liquids were in place in the storage bulbs,
mercury was injected into each bulb until the bulb was com-
pletely liquid-filled. Components were metered from the storage
bulbs into the equilibrium cell as follows. First, mercury was
injected into the measuring bulb assembly to the desired level,
with valve G (Figure 3) open. The needle valve G (Figure 2) on
the equilibrium cell was then slightly opened, allowing the
mercury level in the measuring bulbs to drop and force degassed
liquid into the equilibrium cell. The decrease in volume of mer-
A- ONNEC I O N S TO L l O U l D STORAGE BULBS
B - CONNECTION TO MERCURY-IN-GLASS MANOMETER cury in the measuring bulbs was then identical with the volume
C - VACUUM CONNECTION of liquid displaced from the storage bulb C (Figure 3) into the
D - CELL COVER equilibrium cell.
E - GLASS CUP
-
F TEFLON-COATED MAGNETIC SPINBAR
Vapor pressure measurements were begun by injecting 25
G - NEEDLE VALVES cm3 of one component and measuring its vapor pressure. A
H - O-RING second injection of 25 cm3 was then made and the pressure
Figure 2. Equilibrium cell. remeasured.This procedure served as a partial test for incom-

320 Journal of Chemical and Engineering Data, Vol. 22, No. 3, 1977
Table IV. Experimental Vapor Pressures at 25 OC

x1 K , mmHg x1 T , mmHg x1 T , mmHg X1 K , mmHg

Methanol (1)-Benzene (2) Ethanol (1)-Cyclohexane (2)

0.000 95.1 0.561 183.05 0.344 139.45 0.924 106.05
0.010 129.1 0.619 182.5 0.4165 139.4 0.944 98.2
0.034 157.55 0.6565 182.4 0.483 139.3 0.9655 87.3
0.0595 168.3 0.699 181.7 0.536 139.05 0.977 79.7
0.0875 173.65 0.747 180.0 0.5565 139.05 0.9885 70.55
0.118 176.35 0.802 177.55 0.579 138.65 1.000 59.05
0.1495 177.8 0.847 173.75 0.615 138.1
0.201 179.3 0.8975 166.35 1-Propanol (1)-Cyclohexane (2)
0.247 180.35 0.9185 161.7 0.000 97.85 0.502 102.0
0.28a5 180.85 0.9405 155.45 0.010 104.65 0.539 101.1~
0.3765 181.95 0.9635 147.9 0.0205 105.8 0.5475 101.0
0.445 182.45 0.977 141.25 0.0505 107.0 0.5735 99.8
0.5005 183.0 0.990 133.95 0.082 107.15 O.60& 99.6
0.5055 183.0 1.000 127.15 0.11& 107.1 0.6695 96.55
Ethanol (1)-Benzene (2) O.l6& lO6& 0.753 90.8
0.000 95.1 0.539 121.35 0.2075 106.6 0.7915 86.45
0.0065 101.9 0.573 120.1~ 0.2475 106.4 0.834 79.95
0.015 107.6 0.590 120.3 0.2845 105.9 0.881 69.8
0.0295 113.1 0.623 118.95 0.3185 105.4 0.9335 55.4
0.0535 117.2 O.68& 116.0 0.391 104.45 0.9625 42.95
0.087 119.95 0.733 112.75 0.450 103.35 0.9855 30.35
0.145 122.45 0.792 108.2 0.450 103.5 1.000 20.95
0.1965 123.3 0.861 99.95 0.4985 102.3
0.242 123.4 0.8905 94.4 Methanol (1)-n-Hexane (2)
0.283 123.4 0.9225 87.1 0.000 151.75 a 265.8
0.370 122.9 0.9565 78.3 0.004 205.65 a 265.85
0.439 122.5 0.976 70.5 0.010 230.55 a 265.85
0.4935 122.1~ 0.990 63.95 0.0185 243.0 a 265.85
0.530 121.1 1.000 58.8 0.035 253.85 a 265.85
1-Propanol (1)-Benzene (2) 0.058 259.8 a 265.85
0.000 95.1 0.5375 87.7 0.092 263.65 0.820 265.9
0.010~ 97.05 0.5635 86.65 0.1305 264.2 0.850 264.95
0.0245 97.25 0.584 85.25 0.1745 265.45 0.882 263.8
0.042 97.8 0.608 84.2 0.2165 265.9 0.9165 259.55
0.0635 97.75 0.660 81.45 a 265.85 0.936 252.9
0.089 97.15 0.722 77.75 a 265.85 0.9545 241.1
0.1175 97.1 0.7965 71.6 a 265.85 0.970 223.3
0.1665 96.75 0.8295 67.6 a 265.85 0.9815 203.7
0.210 96.0 0.8655 61.6 a 265.85 0.9895 183.15
0.2505 95.4 0.904 54.3 a 265.85 0.9955 149.1
0.287 94.7 0.928 47.9 1.000 127.0
0.3655 92.9 0.9535 39.85 Ethanol (1)-+Hexane (2)
0.428 91.35 0.9755 31.8 0.000 151.95 0.5185 188.45
0.480 89.85 0.988 26.6 0.0255 183.25 0.553 188.8
0.525 87.95 0.995 23.7 0.0505 185.7 0.629 187.15
1.000 20.95 0.097 188.9 0.6675 185.65
Methanol (1)-Cyclohexane (2) 0.1395 189.9 0.7105 183.5
0.000 97.65 a 213.65 0.197 190.2 0.760 179.55
0.0095 183.05 a 213.6 0.247 190.25 0.7975 175.1
0.020~ 199.45 a 213.65 0.307 190.25 0.8385 168.0
0.0475 208.95 a 213.65 0.358 189.95 0.884 156.15
0.0855 2 12.65 a 213.65 0.4215 189.85 0.908 145.9
0.1255 213.7 a 213.6 0.4405 190.2 0.9325 132.3
a 213.85 0.828 213.6 0.473 188.95 0.9585 112.8
a 213.85 0.8655 212.85 0.5165 188.95 0.986 82.3
a 213.85 0.906 209.8 1.000 59.05
a 213.85 0.9295 204.5 1-Propanol (1)-n-Hexane (2)
a 213.75 0.9525 193.8 0.000 151.65 0.5245 150.15
a 213.7 0.9765 171.8 0.0065 157.5 0.5485 149.65
a 213.65 0.9905 149.1 0.0245 159.35 0.570 148.1
a 2 13.6 1.000 127.25 0.0525 159.8 0.5935 147.7
Ethanol (1)-Cyclohexane (2) 0.105 159.45 0.646 144.9
0.000 97.6 0.645 138.0 0.1515 158.65 0.709 139.65
0.028 130.9 0.655 137.95 0.194 157.95 0.785 130.55
0.055 134.95 0.6935 137.05 0.2325 157.25 0.819 124.1
0.0815 136.75 0.7365 135.35 0.3165 155.75 0.8565 114.95
0.131 138.85 0.785 132.4 0.3835 154.55 0.897 101.9
0.175 139.45 0.8325 128.1 0.439 153.05 0.941 80.65
0.233 139.55 0.8675 121.5 0.4855 151.75 0.964 63.25
0.284 139.55 0.895 114.9 0.510 150.65 0.987 38.9
a Two-liquid phases. 1.000 20.95

Journal of Chemical and Engineering Data, Vol. 22, No. 3, 1977 321
Table V. Vapor-Liquid Equilibrium Data and Excess Properties at 25 ‘C

cf, #a TSE,
x1 T ,mmHg Y1 Y1 Y2 cal g-mol-’ cal g-mol-’ cal g-mol-’

System Methanol-Benzene (2, 7 1, 78)

0.1 174.9 0.476 6.536 1.061 142.8 136.0 -6.8
0.2 179.25 0.494 3.480 1.179 225.9 167.0 -58.9
0.3 181.0 0.504 2.390 1.334 274.3 171.5 -102.8
0.4 182.0 0.514 1.838 1.534 296.3 166.1 -130.2
0.5 182.9 0.532 1.530 1.778 296.5 148.6 -147.9
0.6 182.7 0.564 1.350 2.072 279.3 126.5 -152.8
0.7 181.3 0.593 1.208 2.557 245.2 100.0 - 145.2
0.8 177.5 0.627 1.095 3.438 189.3 69.1 -120.3
0.9 165.4 0.709 1.026 4.999 108.8 35.8 -73.0

System Ethanol-Benzene (2, 7 1)

0.1 120.4 0.249 5.075 1.054 124.2 161.0 36.8

0.2 123.0 0.283 2.956 1.155 196.5 201.2 4.7
0.3 123.5 0.310 2.167 1.274 238.0 208.0 -30.0
0.4 123.2 0.336 1.755 1.430 260.5 204.0 -56.5
0.5 122.0 0.357 1.478 1.644 263.0 187.9 -75.1
0.6 119.8 0.380 1.289 1.945 248.0 153.0 -95.0
0.7 115.0 0.419 1.169 2.335 215.4 117.4 -98.0
0.8 107.4 0.474 1.08 1 2.962 165.6 80.0 -85.6
0.9 92.8 0.583 1.022 4.059 94.7 39.0 -55.4

System 1-Propanol-Benzene (2, 1 7 )

0.1 97.5 0,090 4.142 1.037 103.4 174.0 70.6
0.2 96.5 0.120 2.753 1.116 171.9 229.8 57.9
0.3 94.4 0.140 2.096 1.219 213.7 248.4 34.7
0.4 91.9 0.156 1.707 1.359 235.9 245.9 10.0
0.5 88.9 0.172 1.455 1.549 240.7 224.5 -16.2
0.6 84.6 0.192 1.288 1.798 229.0 193.1 -35.9
0.7 79.0 0.217 1.165 2.171 201.0 150.5 -50.5
0.8 71.2 0.253 1.070 2.803 154.2 101.0 -53.2
0.9 54.8 0.350 1.017 3.754 87.3 51.6 -35.7

System Methanol-Cyclohexane ( 9 )
0.05 209.2 0.542 17.841 1.018 95.1 65.0 -30.1
0.10 213.2 0.550 9.235 1.074 169.7 90.0 -79.0
0.85 213.4 0.562 1.111 6.281 216.4 115.0 -101.4
0.90 210.5 0.571 1.052 9.095 157.9 95.5 -62.4
0.95 195.0 0.629 1.017 14.599 88.6 63.1 -25.5

System Ethanol-Cyclohexane (6, 78)

0.1 137.8 0.318 7.413 1.064 151.8 108.0 -43.8
0.2 139.4 0.333 3.931 1.184 242.3 141.5 -100.8
0.3 139.5 0.337 2.648 1.347 296.6 153.2 -143.4
0.4 139.4 0.352 2.074 1.535 325.2 156.7 -168.5
0.5 139.2 0.356 1.678 1.825 331.6 153.3 -178.3
0.6 138.5 0.362 1.414 2.249 315.3 142.5 -172.8
0.7 136.5 0.374 1.234 2.904 276.6 125.1 -151.5
0.8 131.5 0.398 1.107 4.033 213.4 99.8 - 113.6
0.9 113.6 0.483 1.032 5.994 122.3 61.2 -61.1

System I-Propanol-Cyclohexane ( 78)

0.1 107.1 0.119 6.043 1.070 142.8 97.3 -45.5
0.2 106.6 0.134 3.381 1.179 222.2 126.0 -96.2
0.3 105.5 0.143 2.384 1.319 269.3 140.1 -129.2
0.4 104.1 0.151 1.867 1.504 293.0 141.3 -151.7
0.5 102.1 0.160 1.547 1.753 295.5 134.0 -161.5
0.6 99.4 0.169 1.329 2.110 278.0 118.7 -159.3
0.7 94.9 0.183 1.178 2.642 240.5 94.9 -145.6
0.8 85.1 0.214 1.080 3.422 182.4 69.3 -113.1
0.9 65.0 0.298 1.024 4.678 104.2 38.0 -66.2

System Methanol-n Hexane ( 13)

0.05 258.2 0.424 17.242 1.017 93.8 73.9 -19.9
0.10 263.7 0.436 9.062 1.072 167.7 92.5 -75.2
0.15 265.2 0.445 6.211 1.122 220.2 106.1 -114.1
0.20 265.5 0.449 4.614 1.204 269.1 115.7 -153.4
0.85 265.3 0.456 1.124 6.235 221.3 98.7 -122.6
0.90 262.4 0.461 1.060 9.170 162.5 77.9 -84.6
0.95 245.1 0.502 1.021 15.868 93.5 46.9 -46.6

322 Journal of Chemical and Engineering Data, Vol. 22, No. 3, 1977
Table V (Continued)

G5 /-/Ea TSE,
x1 T . mmHg Yl Y1 72 cal g-mol- ' cal g-mol-' cal g-mol-'

System Ethanol- n-Hexane (3, 8)

0.1 188.8 0.226 7.204 1.064 149.8 101.5 -48.3
0.2 190.2 0.242 3.890 1.180 239.4 126.4 -113.0
0.3 109.25 0.258 2.762 1.321 295.8 136.4 -159.4
0.4 190.1 0.259 2.081 1.536 326.1 138.0 -188.1
0.5 189.4 0.262 1.679 1.830 332.4 133.0 -199.4
0.6 187.8 0.268 1.418 2.250 316.3 122.0 -194.3
0.7 184.1 0.278 1.237 2.902 277.5 106.0 -171.5
0.8 174.6 0.301 1.113 3.998 214.8 82.0 -132.8
0.9 149.0 0.368 1.032 6.186 124.7 48.0 -76.7
System 1-Propanol-n-Hexane (3)
0.1 159.3 0.084 6.339 1.068 144.4 97.0 -47.4
0.2 157.8 0.096 3.573 1.175 227.4 134.7 -92.7
0.3 156.0 0.102 2.511 1.319 278.5 145.4 -133.1
0.4 153.9 0.107 1.952 1.509 304.8 146.6 - 158.2
0.5 150.8 0.113 1.611 1.765 309.5 137.5 -172.0
0.6 146.9 0.119 1.379 2.134 293.9 120.6 -173.3
0.7 140.4 0.128 1.217 2.695 247.6 99.5 -158.1
0.8 128.0 0.145 1.104 3.614 199.1 72.8 -126.3
0.9 100.9 0.193 1.031 5.397 116.3 40.0 -76.3
a Data sources shown after each system title

O T H I S WORK 0 THIS WORK

A SCATCHARD, WOOD AND MOCHELI 15)
901
0
"
02
' '
04
' "
06
"
08
'
IO 'O
A SMITH AND ROBINSON (I61

' 0.2
I ' 0.4 ' 0.6 ' 0.8
' I 1.0
L l O U l D OR VAPOR MOLE FRACTION METHANOL LlOUlD OR VAPOR MOLE FRACTION E T H A N O L

Figure 4. Vapor pressure at 25 O C for the methanol-benzene sys. Figure 5. Vapor pressure at 25 O C for the ethanol-benzene system.
tem.

plete degassing, since subsequent injections (of a pure com-

ponent) should result in increased pressures if more dissolved
gases were injected into the constant-volume equilibrium
cell.
If degassing was deemed adequate, a small amount of the
second component was injected into the cell. After the pressure
stabilized (usually 20-30 min) a pressure reading was recorded.
This injection procedure was repeated until the equilibrium cell
contained approximately equal volumes of the two components.
The cell was then emptied, cleaned, and leak-tested and the
above procedure repeated with the components injected in re-
verse order.
Materials, The suppliers and purities of the components used
in this study are summarized in Table I. All chemicals were used
as received, without further purification.

Results 0 THIS WORK

A KURTYNINA, SMIRNOVA
Two properties of each pure substance were measured in this
study. In addition to the vapor pressures described above, the 0.2 0.4 0.6 08 IO
densities at 26 OC were determined pycnometrically by the LlOUlD OR VAPOR MOLE FRACTION METHANOL
technique described by Robinson (72). These densities were Figure 6. Vapor pressure at 25 O C for the methanol-cyclohexane
required because the materials were injected volumetrically into system.

Journal of Chemical and Engineering Data, Vol. 22, No. 3, 1977 323
 MlXON METHOD)

A WASHBORN AN0 H A N W R F (19)

0 INTERPOLATED FROM SCATCHARO
AN0 SATKIEWICZ (14)

04 06 (18 I O
LlOUlD OR VAPOR MOLE FRACTION ETHANOL

Figure 7. Vapor pressure at 25 O C for the ethanol-cyclohexane sys-

tem.
0 0.2 0.4 0.6 0.8 I0
LlOUlO MOLE FRACTION METHANOL
Figure 9. Excess thermodynamic properties at 25 OC for the metha-
nol-benzene system.

MlXON METHOD
0 KURTYNINA, SMIRNOVA AND
ANORUKOVICH ( 9 )

I-
Y
3
130- \
v)
Y ) .

w
LL
VAPOR
110-
(CALCU LATEO,
0 MlXON METHOD)
u -
90-

70-
0 THIS WORK IO
A SMITH AND ROBINSON (16)
LlOUlD MOLE FRACTION METHANOL
0.2 0.4 0.6 0.8 1.0 Figure 10. Vapor-liquid composition data at 25 O C for the methanol-
LIQUID OR VAPOR MOLE FRACTION ETHANOL cyclohexane system.
Figure 8. Vapor pressure at 25 OC for the ethanol-n-hexane sys-
tem. These properties were combined with (smoothed) literature data
on heat of mixing (/#) to calculate excess entropies, T$ = /#
the equilibrium cells. The pure component properties are given - G.Table V contains the complete results. Figure 9 presents
in Tables I I and 111. Also shown are the ranges of literature data excess properties for the methanol-benzene system whose
as compiled by Timmermans ( 77). behavior is qualitatively similar to the other miscible sys-
Experimental vapor pressures over the composition range tems.
for each of the nine binary systems are given in Table IV. Total
mole fractions in the equilibrium cell were determined from Discussion
measured injection volumes; liquid mole fractions were calcu- Figures 4-8 show comparisons of the data from the present
lated by an iterative technique (7) which accounted for vapor- study with those of previous authors. The single data point of
ization of a portion of the mixture to fill the vapor space in the Scatchard et al. ( 7 5 ) for methanol-benzene is in excellent
cell. Figures 4-8 show experimental results for the five systems agreement with the present data. The data of Smith and Robinson
for which some literature data are available. Also shown in the (76)for ethanol-benzene and ethanol-n-hexane are also in
figures are vapor compositions calculated by methods described reasonable agreement with the present results but show pres-
below. sures about 3 mmHg lower at 0.9 liquid mole fraction ethanol
Based on the system calibrations, pure component mea- and, for ethanol-benzene, 2 mmHg lower at 0.5 mole fraction
surements, and data replication conducted in this study, uncer- ethanol. For both the methanol-cyclohexane and ethanol-
tainties in the measurements are estimated to be 0.01 OC,0.2 cyclohexane systems, the present data demonstrate higher
mmHg, and 0.0008 mole fraction unit. pressures in the dilute regions than prior studies (9, 74, 79),but
they are significantly lower (for methanol-cyclohexane) in the
Data Reduction midcomposition region.
The experimental K - x data were utilized to determine values Figure 10 shows a typical comparison of the vapor compo-
of y, Cf,and y by the technique of Mixon, Gumowski, and Car- sitions calculated from the vapor pressures of this work with
penter ( 70) using relations described in previous studies ( 16). directly measured values for methane-cyclohexane from the

324 Journal of Chemical and EngineeringData, Vol. 22, No. 3, 1977

Table VI. Azeotrope Compositions at 25 OC molecule (relative to the normal and cycloparaffins). This in-
teraction leads to increased breakage of hydrogen bonds among
Azeotrope composition, mole fraction the alcohols.
alcohol
System This work Lit. Glossary

Methanol-benzene 0.539 NAa @ excess Gibbs free energy

Ethanol-benzene 0.313 0.312 I# excess enthalpy
1-Propanol-benzene 0.080 NA SE excess entropy
Ethanol-cyclohexane 0.340 0.336 T absolute temperature
1-Propanol-cyclohexane 0.121 NA x liquid-phase mole fraction
Ethanol-n-hexane 0.249 0.245 y vapor-phase mole fraction
1-Propanol-n-hexane 0.085 NA y activity coefficient
a Not available in literature.
T system pressure

literature. This figure includes vapor mole fractions of Campbell Literature Cited
and Anad ( 4 ) who did not present T - x data.
Of the nine systems studied, two exhibit partial miscibility. The Bell, T. N., Cussler, E. L.. Harris, K . R., Pepela, C. N., Dunlop, P. J . , J. Phys.
Chem., 72, 4693 (1968).
present data indicate solubility limits of 0.120 and 0.830 mole Brown, I., Fock. W., Smith, F.. J. Chem. Jhermodyn., 1, 273 (1969).
fraction methanol in the methanol-cyclohexane system. , , Brown, I., Fock, W., Smith, F.. Aust. J. Chem.. 17, 1106 (1964).
(4) Campbell, A. N., Anad, S. C., Can. J. Chem.. 50, 479 (1972).
Kurtynina et al. ( 9 )report values of 0.112 and 0.830. For meth- (5) Gibbs, R . E., Van Ness, H. C., Ind. Eng. Chem. fundarn., 11, 410
anol-n-hexane, the present data give solubility limits of 0.210 (1972).
and 0.810 mole fraction methanol while Savini et al. ( 73) report (6)Goates, J. R., Snow, R. L., James, M. R . , J. Phys. Chem, 65, 335
(1961).
values of 0.270 and 0.791 mole fraction from heat-of-mixing (71 Hwang, S.-C., Ph.D. Thesis, Oklahoma State University, Stillwater. Okla..
data. 1975
(8) Jones, H. K. D.. Lu, B. C.-Y., J. Chem. Eng. Data, 11, 488 (1966).
The seven miscible systems studied all exhibited azeotropes. (9) Kurtynina. L. M., Smirnova, N. A., Andrukovich, P F , Khim. Termodin.
Table VI lists the azeotropic compositions, including literature Rustvorov, No. 2, 43 (1968).
data for three systems. (10) Mixon, F. O., Gumoski, E.,Carpenter, E.H.. Ind. Eng. Chem. Fundam.. 4,
455 (1965).
The excess properties of the systems studied in this work are (11) Mrazek,R. V., VanNess, H.C., A I C M J , 7, 190(1961).
similar qualitatively for the miscible systems. Heats of mixing (12) Robinson, Jr., R. L., P h D Thesis, Oklahoma State Unlversitv. Stillwater,
Okla , 1964
are positive and reach maxima in the alcohol-dilute portion of (13) Savini, C G I Winterhalter. D R , Van Ness, H C , J Chem Eng Data, 10,
the composition range. Excess Gibbs energies are positive and 171
,
119651
nearly symmetric in composition. Excess entropies show pos- (14) Scatchard, G.,Satkiewicz, F. G., J. Am. Chem. Soc., 86, 130 (1964).
(15) Scatchard, G., Wood, S. E., Mochel, J. M., J. Am. Chem. Soc., 68, 1957
itive values in the dilute alcohol regions. This behavior is probably (1946).
due to the loss of orientation order that accompanies the (16) Smith, V. C.,Robinson, Jr., R. L., J. Chem. Eng. Data, 15, 391 (1970).
(17) Timmermans, J., "Physico-Chemical Constants of Pure Organic Corn-
breaking of hydrogen bonds in the alcohols. The benzene sys- pounds", Vol. 2, Elsevier, New York, N.Y., 1965.
tems exhibit the highest heats of mixing and excess entropies (18) Vesely, F . , Pick, J., Collect. Czech. Chem. Commun.. 34, 1854 (1969)
due to the favorable interaction energies between hydroxyl (19) Washburn, E. R., Handorf, 6.H., J. Am. Chem. SOC.,57, 441 (1935).
groups and the more polarizable electrons in the aromatic Received for review November 9, 1976. Accepted April 15, 1977

Journal of Chemical and EngineeringData, Vol. 22, No. 3, 1977 325