INDUSTRIAL AND ENGINEERING CHEMISTRY
140
When the peroxide linkage has split as indicated above, two possibilities for further change are apparent: isomerization to a ketol as described by Morell and eo-workers (11),and removal of hydrogen atoms from the surroundings to give a di-alcohol. The reaction for ketol formation is:
I H H O I l l CaH6-C-C-c-CH3 I l l H O H
Phenyl 1-propenyl ketone and benzoic acid have been isolated as secondary oxidation products which probably result from the decomposition of the a-methylene hydroperoxide of l-phenyl-2butene. Ester formation may result from the decomposition and concurrent oxidation of the polymeric or cyclic peroxides to yield alcohols and acids. H
H
I I I
H
H O O
I /I + Ca,C--C-C-CH3 I H
Vol. 42, No, 1
I
0 0
ACKNOWLEDGMENT
or C8H6-A- -A-A--CHa
H
I
The authors desire to express their appreciation to the Firestone Tire and Rubber Company for the fellowship grant which made this investigation possible. They also wish to thank Hugh Winn, formerly of Case Institute of Technology and now with the Firestone Company, for the numerous helpful suggestions which he contributed in the course of this investigation.
I
H H
The absence of alcohol as noted in Table I11 may result from conversion to ester in the presence of excess acid resulting from oxidation of ketone, ketol, or other intermediates. The formation of large amounts of ester without increase in acid concentration suggests that the decomposition of the polymeric peroxide results in the formation of ester, carbon dioxide, and water as the ultimate products. Further work is in progress on the oxidation of certain of these compounds, It is hoped to obtain more complete analytical data a t various stages of oxidation and thus establish more precisely t,he sequence of reactions involved. SUMMARY AND CONCLUSIONS
1-Phenyl-2-butene oxidized more extensively in the autocatalytic stage a t 100' C. than did 1-phenyl-3-pentene, l-phenyl4hexene, and 1-phenyl-3-vinylbutane. Thus it appears that the double activation of a single methylene group by both the phenyl group and the olefin group produces peroxide more readily than does the simultaneous activation of separate methylene groups by these same structures. The relative order of oxidizability in the subsequent period of slower constant-rate oxygen absorption is: I-phenyl-4-hexene highest; 1-phenyl-2-butene and 1-phenyl-3-vinylbutane about equal; and 1-phenyl-3-pentene slowest. The high rate for the 1-phenyl-4-hexene in this stage may be due to the presence of an additional methylene group available for further oxidation initiated by the decay of the peroxides initially formed. The primary oxidation products of 1-phenyl-2-butene appear to be peroxides. In addition to the formation of a-methylene hydroperoxide, there appears to be some attack a t the double bond to form either polymeric or cyclic peroxides, or both.
LITERATURE CITED (1) Bolland, J. L., and Gee, G., Trans. Faraday Soc., 42, 236 (1946); Rubber Chem. und Technol., 20, 611 (1947). (2) Bolland and Hughes, J. Chem. Soc., 1949,492. (3) Rolland, J. L., Sundralingam, A., Sutton, D. A., and Tristram, G. R., Trans. Inst. Rubber Ind., 17,29 (1941); Rubber Chem. and TechnoE., 15, 72 (1942). (4) Cole, J. O., presented before the A.S.T.M. Symposium on Aging of Rubber, Chicago, Ill., March 2, 1949; abstracted in Rubber Age, 64, 728 (1949); Am. SOC.Testing Materials.
Special Technical Publication No. 89. ( 5 ) Cook, A. H., J. Chem. Soc., 1938,1778. (6) Dornte, R. W., IND. Eso. CHEM.,28,26 (1936).
(7) Farmer, E. H., Trans. Inst. Rubber Ind., 21, 122 (1945); Rubbe7 Chem. and Technol., 19,268 (1946). (8) Farmer, E. H., and Sundralingam, A., J . Chem. Soc., 1942, 121. (9) Farmer, E. H., and Sutton, D. A,, Ibid., 1942,139. (10) George, P., and Robertson, A., Proc. Roy. Soc., A185, 296 (1946). (11) Morell, R. S., J. SOC.Chem. Ind., 50, 27T (1931). (12) Shelton, J. R., and Winn, Hugh, IND.ENG. CHEM.,36, 728 (1944); 38,71, 1052 (1946); 40, 2081 (1948). ENG.CHEX,ANAL.ED., 13, 90 (13) Uhrig, K., and Levin, H., IND. (1941). (14) Wilds, a.L., "Organic Reactions," Vol. 11, p, 200, New York, John Wiley & Sons, 1944. (15) Young, W. G., and Lane, J. F., J . Am. Chem. Soc., 59, 2051 (1937). RECEIVED J u n e 23, 1949.
Volumetric Behavior
of Hydrogen Sulfide H. H. REAMER, B. H. SAGE, AND W. N. LACEY California Institute of Technology, Pasadena 4 , Calif.
YDROGEN sulfide is of increasing importance in petroleum production and processing operations. For this reason it was desirable to determine the thermodynamic properties of this compound over a fairly wide range of temperature and pressure. The present investigation was made at temperatures from 40" F. to the upper limit of thermal stability, which under the experimental conditions was found to be approximately 340" F., and t o a pressure of 10,000pounds per square inch. I n this paper pressures are expressed in pounds per square inch absolute. The re-
sults of the study serve to evaluate the effect of pressure and temperature on the molal volume of this material and include data on the vapor pressure. The properties of hydrogen sulfide have been investigated ( 1 1 ) and its thermodynamic behavior was summarized recently by West (16). This work included tabulation of the enthalpy, entropy, and specific volume as functions of state. The values extend from a temperature of -76" to above 1300' F. but are limited t o a maximum pressure of 1030 pounds per square inch. The limited
INDUSTRIAL AND ENGINEERING CHEMISTRY
lanuary 1950
~
141
~~
TABLE I. VOLUMETRICBEHAVIOROF HYDROGEN SULFIDEIN SINGLE-PHASE REGION Pressure Lb./Sq. I& Absolute Dew point Riihhle point 0 14.696 20 30 40 60
L
60 80 LOO 125 150 200 300 400 500 600 800 1000 1250 1500 1750 2000 2250 2500 2750 3000 3500 2000 2500 5000 6000 7000 8000 9000
10,000 b
6
1
40'
(169.0)' Vb 0.8609 27.32 0.0208 0.6614 1.0000 360.'9 0.9890 264.1 0.9850 174.7 0.9774 130.0 0.9698 103.2 0,9620 85.3 0.9542 62.9 0.9383 49.4 0.9220 48.6 0,9009 31.4 0.8787 0.6611 0.0247 0.6600 0.0369 0.6589 0.0491 0.6576 0.0613 0.6563 0.0734 0,6542 0.0976 0.6521 0.1216 0.6498 0.1515 0.6474 0.1811 0.6452 0.2106 0.6430 0.2398 0.6409 0.2689 0.6389 0.2978 0.6368 0.3266 0.6348 0.3551 0.6309 0.4118 0.6273 0.4679 0.6243 0.5239 0.6213 0.5793 0.6141 0.6871 0.6085 0.7943 0.6037 0.9006 0.5999 1.0068 0.5978 1.1142 Zb
100' F. (394.0) z V 0.7661 11.68 0.0480 0.7313 1.0000 0.9927 406.7 0.9901 297.4 0.9852 197.3 147.2 0.9802 117.2 0.9752 0.9703 97.1 0,9603 72.1 0.9503 57.1 45.1 0.9377 0.9248 37.0 26.98 0.8985 0.8403 16.82 0.7312 0.0487 0.0607 0.7291 0.0726 0.7270 0.0963 0.7230 0.7191 0.1197 0.1487 0.7145 0.1773 0.7099 0,2056 0.7057 0.2337 0.7018 0.2615 0.6980 0.6945 0.2891 0.3164 0.6910 0.3435 0.6878 0.6814 0.3971 0.4499 0.6756 0.6703 0.5022 0.6653 0.5538 0.6560 0.6567 0.7567 0.6493 0.6425 0.8557 0.9545 0.6370 1.0522 0.6320
-
160' F. (778.9) z V 0,6224 5.31 0.1005 0.8581 1.0000 450.2 0.9949 0.9930 330.2 0.9896 219.4 0.9860 163.9 0.9826 130.7 0.9790 108.5 0.9720 80.8 0.9650 64.2 0.9560 50.9 0.9471 42.0 0.9290 30.9 19.76 0.8912 14.14 0.8502 0.8041 10.70 8.33 0.7518 0.8564 0.1030 0.8424 0.1267 0.8266 0.1554 0.8139 0.1836 0.2110 0.8017 0.7909 0.2378 0.2649 0.7831 0.7756 0.2916 0.7688 0.3179 0.7626 0.3440 0.7515 0.3955 0.7416 0,4460 0.7317 0.4951 0.7238 0.5442 0.7100 0.6406 0.6985 0.7352 0.6875 0.8270 0.6780 0.9175 0,6683 1.0049
220' F.
z
v
... ...
...
1.0000 0.9962 0.9949 0.9923 0.9897 0.9872 0.9846 0.9794 0.9742 0.9677 0.9612 0.9480 0.9210 0.8931 0.8636 0.8324 0.7629 0.6783 0.5275 0.2355 0.2451 0.2654 0.2881 0.3112 0.3352 0.3589 0.4063 0.4532 0.4994 0.5446 0.6350 0.7233 0.8088 0,8927 0.9731
49i.x 362.9 241.3 180.5 144.0 119.7 89.3 71.1 56.5 46.7 34.6 21.47 16.29 12.60 10.12 6.96 4.95 3.08 1.1450 1.0216 0.9681 0.9339 0.9079 0.8890 0.8727 0.8468 0.8265 0.8095 0.7945 0.7720 0.7537 0.7375 0.7235 0.7098
. . I
280° F.
340" F.
... ...
v ... ...
... ...
.. .. ..
1.0000 0.9972 0.9962 0.9942 0.9923 0.9904 0.9884 0.9846 0.9807 0.9759 0.9710 0.9612 0.9415 0.9213 0.9005 0.8790 0.8331 0.7830 0.7141 0.6368 0.5501 0.4649 0.4111 0.3950 0.3994 0.4116 0.4435 0.4810 0.5204 0.5606 0.6415 0.7228 0.8017 0.8781 0.9524
538.7 395.4 263.1 196.9 157.2 130.8 97.7 77.8 62.0 51.4 38.2 23.03 18.28 14.30 11.63 8.27 6.22 4.53 3.37 2.495 1.845 1.450 1.254 1.153 1.089 1.006 0.9545 0.9180 0.8900 0.8487 0.8197 0.7955 0.7745 0.7560
1.0000 0.9978 0.9970 0.9956 0.9941 0.9926 0.9911 0.9882 0.9852 0.9815 0.9779 0.9705 0.9556 0.9407 0,9253 0.9097 0.8777 0.8444 0.8017 0.7549 0.7050 0.6569 0.6131 0.5742 0.5476 0.5310 0.5236 0 5400 0.5660 0.5967 0.6635 0.7340 0.8063 0.8778 0.9461
582.7 427.8 284.8 213.3 170.4 141.8 106.0 84.6 67.4 55.9 41.6 27.34 20.18 15.88 13.01 9.42 7.25 5.50 4.32 3.46 2.819 2.339 1.971 1,709 1.519 1.284 1.158 1.080 1.024 0.9490 0.8999 0.8650 0.8370 0.8120
z
Z
V
-
Figures in parentheses are vapor pressures in pounds per square inch absolute. compressibility factor = PV/RT; V molal volume, cubic feet per pound mole.
Z
volumetric data were used Results are presented of measurements of the volu0.15 pound per square inch by West (15) to establish metric behavior of hydrogen sulfide at temperatures from on a change in quality, the constants for the 40' to 340' F. and for pressures up to 10,000 pounds per the fraction vaporized, from Reattie-Bridgeman (3)equasquare inch absolute. The measurements inelude the 0.05 to 0.85. tion of state. The resultmolal volume of the liquid and gas phases, the volumetric Some indication of thering equation was employed behavior of the bubble-point liquid and dew-point gas, mal decomposition was exto describe the volumetric and the vapor pressure. The data are presented in graphiperienced a t 340' F. when behavior for the gas phase. cal and tabular form in terms of the molal volume and the the hydrogen sulfide was in Only limited expericompressibility of the phases. Reasonable agreement was contact with mercury and mental background exists found with earlier studies of the volumetric behavior of a chrome-nickel stainless concerning the volumetric this substance at high pressures. steel. At temperatures behavior of hydrogen sulabove 340 'F. the rate of defide in coexisting liquid and composition was sufficiently rapid to preclude quantitative investigation of the volumetric begas phases (9, 10,26). The specific weight of bubble-point liquid was measured by Baxter, Burrage, and Tanner (1) and also by havior with the equipment available (IS). After a series of measSteele, McIntosh, and Archibald (IC). Although the vapor presurements a t 340" F.,it was found that the vapor pressure of the sample, when measured a t 100" F. and a quality of 0,018, was 39 sure was measured by a number of investigators, only the values cited by International Critical Tables (8) and by West (15) will pounds per square inch higher than it had been originally. At a be used here for comparison. The boiling point was determined quality of 0.18 the increase in vapor pressure was 7 pounds per square inch. Withdrawal of the sample yielded approximately 0.02 by Giauque and Blue (7');their values agree well with those obtained by Clusius and Frank ( 5 ) . The properties a t the critical weight % ' of material which did not condense a t a pressure of 2 x state were reviewed by Pickering ( l a ) ,and the values for critical pound per square inch (0.01 mm. of mercury) and a temperatemperature and pressure appear to be satisfactorily established, ture of -300' F. Probably this latter material was hydrogen which resulted from the thermal decomposition of hydrogen sulfide. whereas more uncertainty exists in the value of critical volume. MATERIALS
PROCEDURES AND EQUIPMENT
The hydrogen sulfide used in this study was obtained by the action of air-free distilled water on a chemically pure grade of aluminum sulfide. The gas evolved was dried over anhydrous calcium chloride and calcium sulfate and collected under acuum a t liquid air temperature. The hydrogen sulfide was stored in a stainless steel weighing bomb (IS). There was no measurable difference in the characteristics of the several samples of hydrogen sulfide prepared by the hydrolysis of aluminum sulfide. It was found that the vapor pressure a t 100' F. changed by less than
The equipment employed for this study has already been described (191,and no significant changes were made in the apparatus or procedure. The calibration of the pressure balance ( 2 , 1 3 ) , by comparison with the known vapor pressure of carbon dioxide ( 4 ) a t the ice point, changed from its original value by less than 0.05oJ, during the decade that it had been in use. The temperature of the working cell was measured by means of a platinum resistance thermometer calibrated against a similar instrument which had in turn been standardized a t the National Bureau of
INDUSTRIAL AND ENGINEERING CHEMISTRY
142
Vol. 42, No. 1!
RESULTS
-_PRESSURE
POUNDS
PER SQUARE INCH
Figure 1. Compressibility Factor of Hydrogen Sulfide
Standards. It is believed that the temperatures were known relative to the International platinum scale within 0.02 F. I n principle the apparatus involved a stainless steel cell whose effective volume was changed by the introduction and withdrawal of mercury, A spiral agitator was provided to assist in obtaining equilibrium. The hydrogen sulfide was introduced prior to and withdrawn after each series of measurements by a weighing bomb technique (13). I n all cases agreement within 0.3% was obtained between the weight of the sample as determined from addition and from withdrawal of the hydrogen sulfide. Seven samples were investigated: three were used in studies a t volumes less than 2.8 cubic feet per mole; two for studies in the critical region; and the other two in measuremefits a t volumes greater than 5.0 cubic feet per mole. Satisfactory agreement among the seven samples was obtained with regard to measurements of vapor pressure and volume, and the extent of the decomposition encountered with each of the several samples was nearly the same. The volumetric measurements were made a t 60" F. intervals in temperature, from 40" to 340" F. Measurements were also made with one sample a t 5" F. intervals from 200" to 220" F., inclusivp, and at 230" F. O
Figure 1 presents the compressibility factor of gaseous hydrogen sulfide for pressures below 1600 pounds per square inch, as determined from one of the four samples investigated. Only a portion of the two-phase region is included in this figure in order that the behavior in the gas phase may be sholvn on a larger scale than rvould otherwise be possible. It is estimated that the average deviation of experimental points shown from the smooth curves of Figure 1is less than 0.1%. The volume is shown in Figure 2 as a function of pressure, primarily above bubble point, for a series of temperatures. The data resulted from two sets of measurements involving different samples of hydrogen sulfide, and it was impossible to distinguish between them. It is estimated that the average deviation of the experimental points shown in Figure 2 from the smooth curves was less than 0.12%. By the graphical use of residual techniques the volume and compressibility factor for hydrogen sulfide were obtained a t evenvalued pressures for each of the temperatures experimentally investigated. These interpolated values are recorded in Table I; sufficient care was taken to avoid irregularities greater than 0.1%. The volume and compressibility factor are recorded to one more significant figure than is justified by the uncertainty of the experimental measurements. This was done to provide adequate consistency when differences between adjacent states are involved. Figure 3 illustrates the influence of pressure on the volume of hydrogen sulfide near the critical state. Most of the data presented in this diagram were taken from measurements made with a sample chosen, as to size, for studies in this region. However. some data from other samples have been included. Table I1 records values of the pressure for a series of evm-valued volumes and temperatures throughout the critical region" This tabulation covers a range of volume from 0.90 to 4.00 cubic feet per pound mole in the temperature interval between 190" and 250 F. The states at which the pressures are independent of t h e volume correspond to the heterogeneous region below the critical temperature. It is probable that the uncertainty in recorded pressures does not exceed 0.4% throughout the ranges of volume and temperature recorded in Table 11. O
TABLE11. PRESSURES FOR HYDROGEN-SULFIDE IN CRITICAL REGION \IoIal Volume Ft./Lb. &Idle 190° F. 200° F. 210° F. 220° F.230' F. 240° F. 250° F. 153sa 1852 0.90 .. 1795 1192 0.95 1480 1550 .. 1272 1.00 lib2 1330 .. .. 1.10 1556 1288 .. 1.20 1462 ,, I .40 .. .. 1410 .. I .60 .. 1389 1270 .. .. 1365 2.00 1256 2.40 .. 1336 1iS4 1227 .. 1288 2.80 1183 1122 3.20 1233 1131 1032 1081 1176 3.60 1080 1036 992 4.00 1120 0 Pressure in pounds per square inch absolute.
&.
. I
OF COEXISTING PHASES IN HYDROGEN TABLE111. PROPERTIES SULFIDE SYSTEM
Pressure, Compressibility Lb ./ Sq Factor Inch Teniperature, Absolute O F. Gas Liquid 0.0246 49.2 0.8475 200 0.0365 0.8056 77.0 300 0.0487 0.7639 101.1 400 0.0614 122.0 0.7250 500 0.0748 137.0 0.6880 600 0.0781 150.1 0.6521 700 0.1037 162.1 0.6154 800 0.1202 174.0 0.5739 900 0.1388 0.5294 184.9 1000 0.1606 194.7 0.4808 1100 0.1901 0.4180 204.0 1200 0,2734 0.3021 212.0 1300 0,2833 0.2833 212.7 1306"
.
~~
i
1
I
" Critical
state.
Molal Volume Cu. Ft./Lb. M16e Gas Liquid 23.14 0.6708 0.7010 15.47 0.7327 11.49 0.7672 9.03 0.7978 7.34 0.8299 6.10 5.13 0.8652 4.34 0.9085 0,9599 3.66 1,025 3.07 1.128 2.493 1.516 1.676 1.565 1.565
INDUSTRIAL AND ENGINEERING CHEMISTRY
January 1950
TABLE IV.
143
COMPARISON OF VALUESOF VOLUME OF HYDROGEN SULFIDE
Temperature,
F. 100 160 220 280 340
Pressure Lb./Sq. I&h Absolute
147.0
147.0 147.0 440.9 734.8 147.0 440.9 734.8 147.0 440.9 734.8 1028.7
Molal Volume, Cu. Ft./Lb. Mole West (16) Authors 37.8 37.9 43.1 42.8 48.2 47.8 14.52 14.59 6.75 7.90 52.9 52.5 16.29 16.44 8.38 9.16 57.4 57.2 17.99 18.20 9.75 10.37 6.07 7.01
OF VAPOR PRESSURE DATAFOR TABLE V. COMPARISON HYDROGEN SULFIDE U
Temperature,
F.
The properties of the coexisting gas and liquid phases of hydrogen sulfide are given in Table 111, where the two-phase pressure, the volumes, and the compressibility factors for the gas and liquid phases have been recorded for even-valued temperatures. Values of the critical pressure, volume, and compressibility factor have been indicated. The values of critical pressure and temperature are the same as those chosen by Pickering (I%?); these agree with .the present measurements. Figure 4 presents the variation with temperature of the residual vapor pressure P"; this quantity is related to the experimentally
-
measured vapor pressure P" and the temperature, t, in following expression:
O
F. by the
N
P
Xn each case the point shown in Figure 4 corresponds to a vapor pressure value experimentally measured a t a quality of 0.5. The corresponding values cited by the International Critical Tables e(8) and by West (15)have been included for comparison. In general, the agreement between the three sets of vapor pressures is satisfactory. Although discrepancies from the present results of a s much as 25.6 pounds per square inch were shown by those of West a t a temperature of 190" F., the agreement with the critical $ables was within 4.5 pounds per square inch. Table IV compares the volume of hydrogen sulfide as computed by West (16)with the present values. States were chosen
Figure 4.
Residual Vapor Pressure of Hydrogen Sulfide
a
Vapor Pressure, Lb./Sq. Inch Absolute International West ( 1 6 ) Critical Tables Authors 169.0
Same critical temperature and pressure used by all.
throughout the ranges of pressure and temperature which were common to both sets of data. For tabulated states a t pressures below 500 pounds per square inch the average deviation between the two sets of data is 0.7%, whereas a t higher pressures the deviation is 10%. The vapor pressures reported by West (15) are compared to present results in Table V. The average difference in vapor pressure between the two sets of data from 4 0 " F. to the critical temperature was found t o be 1.5% or 12 pounds per square inch. ACKNOWLEDGMENT
This paper is a contribution from American Petroleum Institute Research Project 37 located a t the California Institute of Technology. The assistance of Betty Kendall and Virginia Berry in the preparation of the tabular information is acknowledged. BIBLIOGRAPHY
(1) Baxter, Burrage, and Tanner, J. SOC.Chem. Ind., 53, 410T (1934). (2) Beattie and Bridgeman, Ann. Physik ( 5 ) , 12, 827 (1932). (3) Beattie and Bridgeman, Proc. Am. Acad. Arts Sei.. 63, 229 (1928). (4) Bridgeman, J.Am. Chem. Soc., 49, 1174 (1927). (5) Clusius and Frank, 2. physik. Chem., B34, 420 (1936). (6) Cross, J. Chem. Phys., 3, 168 (1935). 5 8 , 8 3 1 (1936). (7) Giauque and Blue, J . Am. Chem. SOC., (8) "International Critical Tables," Vol. 3, p. 213, New York, McGraw-Hill Book Co., 1926. (9) Klemenc, Z. Elektrochem., 38, 592 (1932). (10) Maverick, Batuecas, and Schlatter, J . Chim. phys., 2 6 , 5 4 8 (1929). (11) Murphy, J . Chem. Phys., 5 , 637 (1937). (12) Pickering, Natl. Bur. Standards, Sci. Paper, 541, 597 (1926). (13) Sage and Lacey, Trans. Am. Inst. Mining Met. Engrs., 136, 136 (1940). (14) Steele, McIntosh, and Archibald, Z. physik. Chem., 55, 141 (1906). (15) West, Chem. Eng. Progress, 44, 287 (1948). (16) Wright and Maass, Can. J. Research, 5 , 4 4 2 (1931).
RECEIVED August 16, 1949.
