210
INDUSTRIAL AND ENGINEERING CHEMISTRY
250 in molecular weight gave breaking loads averaging 1.5 pounds over the control. Sodium sulfonates of the lower homologs had little effect. A short series of sodium alkylphenolsulfonates was similarly tested. Sodium sulfonates of alkylphenols above 230 in molecular weight gave a 1.5-pound increase in breaking load while the lower homologs were without effect, The increased cord strength attributable to alkarylsulfonates is realized at relatively high elongations without any significant trend toward lower elongation with higher breaking loads. Under is, conditions of processing favoring low elongations-that greater mechanical stretching in the wet condition-the increase in breaking load is additional to and may be overshadowed by the effects of the wet stretching.
Firestone Research Laboratories for carrying out the experimental twisting, for supplying the physical testing data, and for the discussion of the statistical handling of the latter. The authors' thanks are hereby expressed to W. James Lyons, D. E. Howe: and I. B. Prettyman. LITERATURE CITED (I)
(2) (3) (4) (5) (6)
(7) (8)
ACKNOWLEDGMENT
The interest and encouragement of F. W. Stavely, R. F. Dunbrook, and J. W. Liska in this investigation are gratefully acknowledged. The authors also wish to thank the management of The Firestone Tire and Rubber Co. for permission to publish this report. The authors are deeply indebted to the Textiles Group of the
Vol. 45, No. 1
(9) (10) (11) (12)
Adams and Myers, private communication to the Office of Rubber Reserve (Nov. 20, 1946). Andreev and Petrov, Zhur. Priklad. Khim.,21, 134 (1948). Buckwalter, U. S. Patent 2,297,536 (1942). Kitaigorodskii, Acta Physicochim. U.R.S.S., 21, 1047 (1946). Lippincott and Lyman, IND. ESG. C H m , 38, 320 (1946). hlcCutcheon, Chem. I n d s . , 61, 811 (1947). Petrov and Andreev, Zhur. Obshchet Khim., 12, 95 (1942). Philipp and Conrad, J. Applied PhzJs., 16, 32 (1945). Seyferth and Morgan, A m . Dyestuff R e p t r . , 27, 525 (1938). Snedeoor, "Statistical Methods," pp. 56-9, 71--3, Ames, Iowa, Iowa State College Press, 1940. Tilicheev, Khim. Tzerdogo Toplieu, 7, 181 (1938). Tsukervanik and Terent'eva, Zhur. ObshcheE Khim.. 7, 637 (1937).
(13)
I-oung and Coons, "Surface Active Agents," Brooklyn, Chemical Publishing Co., 1945.
RECEIVED for review May 20, 1952.
pp.
117-52,
ACCEPTED August 20, 1952.
Phase Behavior of the HydrogenPropane System W. L. BURRISS, N. T. HSU, H. H. REARIEK, AND B. H. SAGE California Institute of Technology, Pasadena, Calif.
L
ITTLE experimental information is available concerning the phase behavior a t elevated pressures of binary mixtures containing hydrogen. A study of the carbon dioxide-hydrogen system was reported by Verschaffelt (f7). This work indicated a rapid increase in the critical pressure with a decrease in temperature below that corresponding to the critical temperature of carbon dioxide. Information is available concerning the vaporliquid equilibrium of three binary hydrogen-paraffin hydrocarbon systems at temperatures between 100" and 300"F. and at pressures up to 5000 pounds per square inch ( 5 ) . Kay (8) determined the bubble point and dew point pressures and temperatures for three mixtures of hydrogen in a petroleum naphtha and found a marked minimum solubility with respect to changes in temperature. Frolich and coworkers (6) established the sohhility of hydrogen in ten different hydrocarbon liquids including propane. This latter work represents the only information available at elevated pressures concerning the solubility of hydrogen in propane. Nelson and Bonnell (If) determined the composition of the liquid phase of mixtures of hydrogen and nbutane a t temperatures up t o 250' F. for pressures as high as 1500 pounds per square inch. Except for the measurements of Dean and Tooke ( 6 ) ,none of the data includes information concerning the composition of the coexisting gas phase. The volumetric behavior of hydrogen has been studied in detail by Wiebe and Gaddy ( 1 8 ) and by Bartlett and coworkers ( I ) in the temperature range coveied by this investigation. Johnston and White ( 7 ) recently summarized the compressibility data for hydrogen a t temperatures from its boiling point to about 100 F. The vapor pressure of propane was studied by several investigators ( 2 , 3, I I ) , who also determined the volumetric behavior in the one- and two-phase regions with an accuracy adequate for present purposes. The volumetric and phase behavior of pro-
pane was reviewed in a recent study (19) and these data were employed here. MATERIALS
The hydrogen used in this study was obtained from the Matheson Chemical Co. and was prepared electrolytically. Akspectrographic analysis of the dried hydrogen as received indicated that it contained approximately 0.002 mole fraction of oxygen and negligible quantities of other materials. The hydrogen was passed over heated platinum at a pressure in excess of 1000 pounds per square inch and subsequently was dried over anhydrous calcium sulfate and activated charcoal. The purified gas contained less than 0.001 mole fraction of material other than hydrogen. The propane was obtained from the Phillips Petroleum Co. and it was reported to contain less than 0.001 mole fraction of material other than propane. This hydrocarbon was employed without further purification since such small quantities of inipurities would not alter significant,ly the results obtained. The vapor pressure of the propane employed did not change by more than 0.2 pound per square inch a t 130" F. upon a change in fraction vaporized from 0.2 to 0.9. METHODS
The apparatus used in this investigation TT-as described earlier (16). I n principle, it consisted of a stainless steel pressure vessel within which the sample was confined over mercury. Ports were provided at two different points in the wall of the equilibrium vessel to permit the withdrawal of gas and liquid phases after equilibrium was obtained. Equilibrium between the gas and liquid phases was attained by means of a mechanical spiral agitator located within the vessel. The stainless steel working
~
INDUSTRIAL AND ENGINEERING CHEMISTRY
January 1953
MEASUREMENTS OF COMPOSITIONS OF COEXISTING PHASES IN TABLE I. EXPERIMENTAL Mole Fraction Hydrogen Riihhle ...... Dew point point 40' F. 0,7465 0.7468 .... 0.8404 0.0373 0,8399 0.0383
366.8 646.6 980,l
0.8817 0,8812
0 0500 0.0519
1624.8
0.9135 0.9131
0.0866 0.0877
2584.8
0.9288 0.9265
0 1339 0 1348
0.9373 0.9334 0.9342 0.9334
....
.... ....
4106.7
.... ....
0.2122 0.2138
4681.0
0.9337 0.9352
6032.5 7213.5
3570.7 4106.6
378.8 379.0
0.6182
....
652 6
....
0,0363
1393.3
0,7728
.... 0.0922
.... 0.8025
1E05.2 2701.4
....
0,. 1217
....
2701.8
0.8317
3801.7
0.8405 0.8407
....
3003.1
0.9309 0.9314
0.3010 0.3005
.... ....
0.2403 0.2424
4486.4
0.9261 0.9257
0,3498 0.3513
.... ....
0.3086 0.3080
4489.4
....
5247 1
0,8399 0.8411
....
....
....
.... .... ....
....
.... ....
.... ....
.... .... .... .
.... ....
I
.
.
....
7208.4
.... ....
.... ....
7632.5
0.7390 0.7377
.... ....
7051.9
....
...
....
....
.....
0.0528 0.0531
....
0,1869
2186 4 2649 7
0.5908 0.5952
0.2078 0.2658
....
2804 4
0.5945 0,5944
0,2862 0.2866
3245.0
0.5510 0.5513
0.3663 0.3659
3305.3
0.5287 0.5290
0.3928 0.3924
....
. . I .
.... ....
....
....
.... ....
0.3598 0.3593
....
.... .... ....
7:303,6
0.3727 0.3748
0.0890
0.7827 0.7830
.... ....
....
0.1521
0.4316 0.4322
....
0.2100
0.4780
..,.
....
846 1
....
0.5584
.... ....
....
846 0
HYDROGEN-PROPANE SYSTEM
1167 2
6211.1
....
570 5
THE
Mole Fraction Hydrogen Bubble Dew point point 160' F. 0.0200 0.0204 0.2102 ....
1704 5
0.8332 0.8345 0.8174 0,8176
62311.8
....
.... ..I.
52149.2
570 3
....
652.5
....
....
100' F. 0.0129 0.0155 0,4200 0.4194 ....
1393 5
....
Pressure, Lb./Sq. Inch Absolute
...
1805.0
.... .... .. .. .. .. .... .,..
.... .... ....
Pressure Lb./Sq. I&h Absolute
Mole Fraction Hydrogen Dew point Bubble point
.... ....
....
..,.
....
....
.... .... ....
.... ....
.... .... ....
....
..... ..
.... ...
.... ....
....
....
....
.... .... .... .... ....
0.5739 0.5739
Pressure Lb./Sq. Idch Absolute 719.6 719.7
....
Mole Fraction Hydrogen Bubble Dew point point 190' F. 0 0300 .... 0 0304 0.1282 ..
-
1007.0
.. .. .. ..
1007.1
0.2372
. .
1267.5
.... ....
0 1231 0 1227
1269.5
0,2790 0.2799
1389.0
....
0.1614 0,1527
1389.2
0.2890 0.2881
....
1468.7
0,2855 0,2829
0.1769 0.1758
....
....
....
0.2058 0.2080
1525.6
0.2678 0.2664
....
.... .... ....
....
.... .... .... ....
....
.... .... .... ....
....
....
.... ....
....
1525,5
.... . . . . . .
... ....
....
. . . ....
.... ....
....
.... ....
....
.... ....
.... .... .... ....
....
....
.... ....
....
. . .
.... ....
....
....
0 0775 0 0772
....
....
....
0.5116 0.5125
21 1
. I . .
.... .... ....
....
....
. . I .
....
....
....
9000
r u
8000
z
w
oc
7000
3 6000
a W
5000
m n
z
4000
a
2
3000
3
m
m
;2000 4
1000
0.0
Figure
0.2
0.4 MOLE FRACTION
1.0
0.0 HYDROGEN
0.6
1. Pressure-Composition Diagram Hydrogen-Propane System
for
the
50
Figure
75
100 125 150 TEMPERATURE O F
175
2. Pressure-Temperature Diagram Hydrogen-Propane System
200
for
the
INDUSTRIAL AND ENGINEERING CHEMISTRY
212
T.4BLE
11. SMOOTHED VALUES I X G PH.4SES IN THE
Pressure Lb./Sq. I&h Absolute
Figure 3.
PER SQUARE
INCH
Equilibrium Ratio for Hydrogen
section was immersed in an agitated oil bath, the temperature of which was maintained a t a constant value by means of a modulating electronic circuit controlled by a resistance thermometer (16). The temperature of the samples was measured by means of a platinum resistance thermometer of a strain-free type and was known within 0.02' F. relative to the international platinum scale. Pressures were established by means of a balance (16) which was calibrated against the vapor pressure of carbon dioxide (4). Calibration of this instrument has not changed by more than 0.02% in the past decade. It is believed that the ressures were known within 0.2 pound per square inch or 0.25& whichever measure of uncertainty was larger. Appropriate quantities of propane were introduced into the apparatus to ensure an interface located somewhere between the upper and lower sample ports. The location of the interface was established by means of a movable rod upon which was mounted B short length of platinum wire parallel to the interface. This 1.0
0.0
0 t Q
cr
0.6
0.2
. Mole Fraction Hydrogen Dew point Bubble poinL
Equilibrium Ratio Hydrogen Propane
7000 8000
40° F. 0,000 0,025 0.052 0.07LI 0.1J 0.131 0.156 0.181 0,206 0 231 0.255 0.303 0.350 0.399
188.7" 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 6000 7000 7880b
0.000 0.534 0.717 0.780 0.814 0.829 0.835 0.841 0.842 0.841 0.840 0.822 0.793 0.666
100' F. 0.000 0.024 0.062 0.099 0.136 0.171 0.206 0.241 0.275 0.310 0,346 0.415 0.493 0.666
22.27 11.570 7.880 5,985 4,836 4.053 3.490 3.060 2.713 2.428 1.981 1.609 1,000
383.8" 500 1000 1500 2000 2500 3000 3430b
0.000 0.142 0.437 0,534 0.581 0.593 0.591 0.477
160' E'. 0,000 0,012 0,071 0.128 0.186 0.245 0.319 0.477
11.840 6.150 4.172 3,124 2.420 1.853 1.000
190' F. 0.000 0.075 0.121 0.190 0.244
3.133 2.289 1.463 1.000
6000
POUNDS
FOR COhlPOSITIOS O F COEXISTHYDROGEN-PROPASE SYSTEM
0.000 0.810 0,882 0.909 0.921 0,929 0 932 0.933 0.935 0.936 0.934 0.931 0.925 0,922
79Q 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
PRESSURE
Vol. 45, No. 1
524.W 1000 1260 1500 1580b a b
0,000 0.235 0.277 0.278 0.244 Vapor pressure of propane. Critical state.
. , . .
32.40 16.92 11.506
8.768 I ,094 5.972 5.155 4,539 4.052 3.663 3.073 2,642 2.311
1.000 0.195 0,124 0,099 0,088 0,082 0 081 0,082
0.082
0,083 0,088 0.099 0.115 0.130
....
1 000 0.477 0.302 0,244 0.215 0.209 0,208 0.210 0.218 0.230 0,245 0.304 0,408 1.000
....
1.000 0.868 0.606 0.534 0.515 0.539 0,599 1.000
....
1.000 0.827 0,822 0.891 1.000
wire was maintained slightly above the temperature of the equilibrium vessel by the passage of an electric current. A sudden change in the resistance of this wire occurred when it crossed the interface. After the introduction of propane, the necessary quantities of hydrogen were added to bring the equilibrium nressure to the desired value. The contents of the working section were agitated and the attainment of equilibrium was indicated by constancy of the pressure under conditions of fixed total volume and temperature. Samples of the liquid and gas phases were then withdrawn under isobaric, isothermal conditions. The pressure was kept constant by introducing mercury to compensate the withdrawal of samples of the liquid and gas phases. The composition of the samples withdrawn was determined by measurement of the specific weight of the sample at substantially atmospheric pressure. The system was assumed to be an ideal solution (10) a t these states. At nearly all states duplicate measurements of the compositions of the coexisting liquid and gas phases were obtained. It was found that the standard deviation between values obtained from duplicate samples of the liquid and gas phases was 0.0008 mole fraction hydrogen. EXPERIMENTAL RESULTS
100
200
500
P O U N D S PER Equilibrium Ratio for Propane
PRESSURE
Figure 4.
2000 S O U A R E INCH
1000
5000
Figure 1 is a pressure-composition diagram for the hydrogen-propane system. The experimental points obtained during the course
INDUSTRIAL AND ENGINEERING CHEMISTRY
January 1953
213
TABLE 111. PROPERTIES OF THE HYDROGEN-PROPANE SYSTEM IN THE
Pressure Lb./Sq. Idoh Absolute 1000 2000 3000 4000 5000 6000 7000 8000 1580 3430 5700 7880 1360 2610
... ...
Temp.,
F.
CRITICAL 199 9 182.9 166.8 152.3 139.3 126.0 112.2 98.8 100.0 160.0 130.0 100.0 193.9 172.9
... ...
CRITICAL REGION
Mo1.e Fraction Hydrogen 0.110 0.318 0.439 0.515 0.569 0.611 0.644 0.669 0.244 (5.477 0.600 0.666 0.200 0.400
... ...
Pressure Lb./Sq.* d o h Absolute
200
Temp.,
F.
Mo!e Fraction Hydrogen
MAXCONDENTIXERM 199.0 0.150 1000 187.9 0.322 1500 174.9 0.470 2000 160.0 0.593 2500 143.1 0.697 3000 122.1 0.781 3500 93.2 0.858 4000 4500 40.0 0.036 1400 190.0 0.289 3330 130.0 0.754 3900 100.0 0.842 70.0 0.899 4280 1135 195.0 0.200 1765 181.4 0.400 2520 159.3 0.600 3640 115.9 0.800
of this investigation are shown in this figure and recorded in Table I. The standard deviation of all experimental points from the smooth curves was 0.0064 mole fraction hydrogen. Figure 2 is a pressure-temperature diagram for this binary system. The vapor pressure curve of propane has been included (14). There exists a rapid increase in the critical pressure with a decrease in temperature from the critical state of propane. Such behavior is to be expected for this system because of the widely different critical temperatures of propane and hydrogen. The present behavior is similar to that found in the earlier work of Verschaffelt upon the hydrogen-carbon dioxide system (17). The loci of the critical and maxcondentherm states are shown in Figure 2. The maxcondentherm state is the maximum condensation temperature for a system of constant composition and has often been called the cricondentherm (9). Marked differences in the pressures and temperatures corresponding to these states for a given mixture are evident as would be expected for components having widely separated critical temperatures. From the information presented in Figures 1 and 2 the gasliquid equilibrium ratios for hydrogen and for propane were computed. The product of the pressure and the equilibrium ratio for hydrogen and propane were smoothed with respect t o pressure and temperature. The values of the composition of the coexisting phases and of the equilibrium ratios for the components are recorded in Table I1 for a series of even-valued pressures, The product of the pressure and the equilibrium ratio for hydrogen is presented in Figure 3. The effects of pressure and temperature upon the equilibrium ratio for hydrogen are similar t o those for the more volatile components of binary mixtures of the lighter hydrocarbons, except that the pressures a t which two phases exist are markedly higher than in the case of the methanepropane system (IS). Figure 4 depicts the equilibrium ratio for propane in the hydrogen-propane system. A logarithmic scale was employed for the abscissa in Figures 3 and 4 in order t o present these characteristics of the system with comparable detail a t low and high pressures. The effect of pressure and temperature upon the equilibrium ratio of propane is similar t o that found for binary hydrocarbon systems except that two phases exist a t much higher pressures. Figure 5 presents the critical pressure and maxcondentherm for this binary system as functions of composition. Similar information is recorded in Table 111. The marked effect of composition upon the critical pressure is evident from Figure 5 and Table 111. ACKNOWLEDGMENT
This work was a part of the activities of the General Petroleum Fellowship and the financial support and interest of that organization made the completion of this study possible. Paul Helfrey assisted with the accumulation of a portion of the experimental
I75 LL 0
150
a
3
5a
125
w
e
3
I00
I-
75
50
0 .o
0.2 MOLE
Figure 5.
0.4 0.6 0.8 F R A C T I O N HYDROGEN
I .o
Some Properties of the Hydrogen-Propane System in the Critical Region
results and W. N . Lacey reviewed the manuscript. Virginia Berry and Olga Strandvold assisted with the preparation of the data and the assembly of the manuscript. LITERATURE CITED
(1) Bartlett. E. P., Cupples, H. L., and Tremearne, T. H., J . Am. Chent. SOC., 50,1275-88 (1928). (2) Beattie, J. A., Kay, W. C . , and Kaminsky, J., Ibid.. 59, 1589-
90 (1937). (3) Beattie, J. A., Poffenberger, N., and Hadlock, C., J . Chem. Phgs., 3,96-7 (1935). (4) Bridgeman, 0. C., J . Am. Chem. Soc., 49, 1174-83 (1927). (5) Dean, M. R., and Tooke, J. W., IND. ENG.CHEM.,38, 38993 (1946). (6) Frolich, P. K., Tauch, E. J., Hogan, J. J., and Peer, A. A., Ibid., 23,548-50 (1931). (7) Johnston, H. L., and White, D., Trans. Am. SOC.Mech. Engrs., 72,785-7 (1950). ( 8 ) Kay, W. B., Chem. Revs., 29, 501-7 (1941). (9) Kuenen, J. P., “Theorie der Verdampfung und Verflussigung von Gemischen und der fraktionierten Destillation,” Barth, Leiprig, 1906. (10) Lewis, G. N., J . Am. Chem. SOC.,30, 668-83 (1908). (11) Nelson, E. E., and Bonnell, W. S., IND. ENG.CHEM.,35, 204-6 (1943). (12) Reamer, H. H., Sage, B. H., and Lacey, W. N., Ibid., 41,482-4 (1949). (13) Ibid., 42,534-9 (1950). (14) Sage, B. H., and Laoey, W. N., “Thermodynamic Properties of the Lighter Paraffin Hydrocarbons and Nitrogen,” API, 1950. (15) Sage, B. H., and Lacey, W. N., Trans. Am. Inst. Mining Met. Engrs., 136, 136-57 (1940). (16) Ibid.. 174.102-20 (1948). (17) Versahaffelt, J. E., C o h n u n s . Kamerlingh Onnes Lab. Univ. Leiden, No. 65 (1900). (18) Wiebe, R., and Gaddy, V. L., J . Am. Chem. SOC.,60, 2300-3 (1938). RECEIVED for review Maroh 30, 1952.
ACCEPTED August 18, 1952.
Materials of Construction Review on ‘Elastomers Correction I am indebted t o Glen E. Meyer and R. G. Newton for correcting the second sentence of the second paragraph on technically classified natural rubber in my review on “Elastomers” [IND. ENG.CHEM.,44, 2309-17 (1952)l. It should read, “The current method reduces considerably the variability in rate of vulcanization,” not just “the rate of vulcanization.” HARRYL. FISHER
