948
HERRICK L. JOHNSTON AND EDWARD Fl. GRILLY
tetrachloride, mere not attempted in this study, as previous work (1) indicated that these methods would be unsatisfactory. Tie lines were determined by making up several samples of alcohol, glycerol, and carbon tetrachloride having compositions within the immiscibility region and allowing them to stand 24 hr. in sealed separatory funnels immersed in a water bath maintained at 25.OoC. & 0.1'. The mixtures separated into an upper and a lower layer, which were divided by means of a separatory funnel. The modified form of viscosimeter (1) was used to determine the composition of the samples in the two layers. The weight per cents of alcohol and of glycerol are listed in table 1 and plotted in figure 1. In table 2 are listed the compositions of the conjugate solutions. SUMMARY
The solubility relationships, region of immiscibility, and tie lines for the ternary system ethyl alcohol-glycerol-carbon tetrachloride have been determined at 25.OoC. A viscosimetric method was used to analyze the composition of the conjugate solutions. The authors express thanks to Mr. E. W. Colt, Chief Chemist, Armour and Company, 31st St. Auxiliaries, Chicago, for furnishing the glycerol used in this experiment. REFERENCE (1) MCDOXALD, H . J . : J. Am. Chem. SOC.22, 3183 (1940).
VISCOSITIES OF CARBOK MOXOXIDE, HELIUM, XEOS, A S D ARGOS BETWEES 80" AND 300°K. COEFFICIENTS OF VISCOSITY
HERRICK L. JOHNSTON
AND
EDWARD R . GRILLY
Department of Chemistry, The Ohio State University, Columbus, Ohio Received Augwt 67, 1942
The present paper is a continuation and extension of the program (4) at this laboratory to determine gaseous viscosities as a function of temperature at temperatures below 300°K. The data presented in this paper are for carbon monoxide, helium, neon, and argon in the region 80-300°K. at about 15' intervals. As in the previous work, the viscosities are relative to air at 296.1'K. where the viscosity is taken as 1833.0 X IO-' poises. METHOD AND APPARATUS
The method and apparatus are essentially those of Johnston and McCloskey (4). The chief modifications have been' in the treatment of the suspension
VISCOSITIES OF GASES BETWEEN
80”
AXD
300°K.
949
wire and in the control of Bmperature. According to Johnston and hIcCloskey the minimum wire constant, a correction for energy losses in the wire alone, was about 7 x 10-4 in the logarithmic decrement. We have found that annealing the wire by passing an electric current through it lowers this value to about 2 x 10-4. Furthermore, such treatment eliminates the large variations in the wire constant due to both the normal work hardening with time and the marked increase when glassblowing is done on or near the apparatus. The annealing was done at a faint red glow in high vacuum (about mm. of mercury). Thermostatting to within 0.05” was extended down to 130°K. Additional points at about 78°K. were obtained with a bath of liquid nitrogen. The pressures used were 34 cm. of mercury at 300°K. for helium, neon, and argon and 30 to 70 cm. for carbon monoxide. PREPARATION AND PURIFICATION OF GASES
The carbon monoxide was prepared by dropping formic acid into concentrated sulfuric acid. The gas wm passed through potassium hydroxide solution and through phosphorus pentoxide, collected as a liquid, and fractionally distilled with the aid of “bubblers.”1 Only the middle third was retained. The helium, neon, and argon were “spectroscopically pure” preparations obtained from the Linde Air Products Company. The neon was specially prepared for us at the Tonawanda Laboratory of the Linde Air Products Company and was stated to contain less than 0.25 per cent impurities. The argon was likewise a special preparation sent direct from the Tonawanda Laboratory.* The helium was a stock preparation of “spectroscopically pure” helium which was apparently free from significant amounts of other gases. CALIBRATION
The wire constants used are indicated in table 1. The apparatus constants used are indicated in table 2. THE DATA
Tables 3 to 6 give the experimental viscosities at the temperatures noted.3 Table 7 gives smoothed values of the viscosities read at 10% intervals from large-scale graphs. For each of the four gases, the average deviation of the experimental points from the smooth curve is f 0 . 1 3 per cent, which is the same deviation as Johnston and McCloskey found for the average deviation of all their points on eight gases. The maximum deviations are &s follows: for carbon monoxide, 0.38
Cf.Johnston and Giauque: J. Am.Chem. SOC. 61, 3194 (1929). An earlier stock preparation of “spectroscopically pure” argon, on which initial data were taken, was found to be contaminated with air. We had a somewhat similar experience with another stock preparation of “spectroscopically pure” argon which contained an impurity condensable in a dry ice-ether bath, probably water. 8 In several cases, where the temperatures were slightly different, the viscosities were calculated to common temperatures. 9
950
HERRICK L. JOHXSTON AND EDWARD R. GRILLT
11YP
April 12, 1940 to April 17, 1940... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . July 25, 1940...................... ............... July 30, 1940 to August 9, 1940... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . August 12, 1940 t o August 23, 1940. September 3,1940 t o September 11, 1944........................ January 10,1942 to January 31, 1942............................
APPAPATUS CONSIANT
5.414 5.469 5.444 5.662 5.706 5.386
comparison we have interpolated these earlier data to rounded temperatures with the aid of the temperature coefficients taken from our own work. The interpolations amount, on the average, to about ~t0.35OK.and in no case exceed 1.8"K. Our own values of the viscosities are takenfrom our smooth curve. In general, the values closest to ours have been published since 1929, and of these the work of Trauta and coworkers (average deviation, f0.6 per cent; maximum deviation, 1.6 per cent) agrees better than that of Van Itterbeek and coworkers (average deviation, f 1 . 5 per cent; maximum deviation, 3.9 per cent).
VISCOSITIES OF GASES BETWEEK
80" AXD 300°K
95 1
TABLE 3 Viscosity of carbon monozide
OK.
August 23, 1940 April 15, 1940... . , , . . . . . . . . . . . .
April 12, 1940, . . . . . . . , . , , , , ,
April 15, 1940
80.75
.I
82.43
90.28
April 13, 1940
July 30,1940
August 8, 1940
527.7 535.2 533.0 537.2 538.6 542.7 542.4
536.9
544.6 550.6 546.5 548.5
547.2
598.9 597.7 597.7 598.1 596.8 605.7 608.1 606.5 610.5 612.5 613.3 594.0 602.0 600.6 605.0 600.0
August 6, 1940
September 5, 1940 August 7, 1940 August 16, 1940
117.40
131.47
August 17, 1940... . . . . . .
603.0 613.7 611.1 600.5 601.0 611.0 610.5
604.3
788.4 772.1 779.7
780.1
861.9 864.2 868.9
865.0
949.3 851.9
950.6
952
HERRICK L. JOHNSTON AND EDWARD R. GRILLS TABLE 3-Continued T
DAXE
tl
x
10'
AMPAOK
'K.
August 20, 1940.. . . . . . . . . . . . . August 22, 1940... . . . . . . . . .
..
159.23 173.95 184.17 203.03
August 21, 1940.. , . . . . . . . . . . .
April 17, 194
...............
August 22, 1940.. . . . . . . . . . . . .
April 12, 1940... .
August 9,
.. . . . . .
August 13, 1940... . . . . . . , . . . .
.. . .. . . . . . . .. . .
July 31, 1940. . . . . . . . . . . August 7, 1940.. . . ,
1031.0
1124 1116
1120.0
1176 1177
1176.5
1286
1287
1286.5
1330 1324 1326
1326.7
225.13
1406
1406.0
240.84
1488 1486
1487.0
1501 1502 1502 1501
1501.5
1558 1566 1679
1567.5
1657 1655 1655 1657 1656 1657
1656.2
1710 1708 1708
1708.7
1764 1764 1762
1763.3
211.27
242.34
258.00
273.16
1416... . . . . . . . . . . .
April 13, 1940..... . . . . . . . . . . .
1032 1030
283.70
295.13
296.10
1768 1766 1766 1764
VISCOSITIES OF GASES BETWEEX
80" AND 300°K.
953
TABLE 3-Concluded
I
DATE
nx
T
101
AVEIAGE
'K. September 3, 1940. . . , . . . . . . . , . . September 5, 1940. . . . . . . , . . . . . April 13, 1940 . . .
,
... . . .., ..
.
305.77
.I
August 7, 1940.. . . . . , . , . . . . . . . July 30, 1940
I
1783 1765 1766 1765 1763
1765.1
1806 1811 1813 1809 1811 1816 1811 1813
1811.1
DISCCSSIOX
Van Cleave and Maass (13) fitted experimental data for air, hydrogen, ethylene, carbon dioxide, sulfur dioxide, ammonia, methyl ether, and propylene to five different equations that have been proposed to represent the dependence of viscosity on the temperature. The five equations were as follows: that of Sutherlsnd (9):
that of Chapman (1): 7 =
70
(g)"
that of Jones (5):
that of Cooper and Maass (2): 7 = aT"'
+ bTaiZ
(4)
and an empirical one of their own
, = AT^/^,^^
(5)
In the above equations T Oand 9 0 refer to some reference temperature and the viscosity at that reference temperature, respectively, and C, m, n,S , a, b, A , and B are constants for each gas.
954
HERRICK L. JOHNSTOS AND EDWARD R. GRILLY
TABLE 4 Viscosity of helium 'K. T
DATE
-
September 9, 1940.. , , . . . . . . . . . .
79,24
~
September 8, 1940,. . . ,
.., .....
.I
1
130.55
167.07 180.05 195.70 209.16
1
1 1
224.81 241.03 257.66
296.10 September 9, 1940.
. .
79.92
1132 1126
i
1129.0
1291 1291
I
1291.0
1323 1323
1323.0
1388 1388
1388.0
1476 1476
1476.0
,
i
1510.5
16x1 1620
1
1620.0
1695 1694
1
1694.5
1777 1778
I
1777.5
1872 1871
1 1
1871.5
1969 1968 1973 1972
1
1970.4
1196 1192 1199
'
1195.7
1322 1322 116.93
815.3 884.6
~
i
~
*vEPACE
1
1539 1542
276.40
September 10, 1940.. . . . , , .
815.3 815.3 885.0 884.2
90.04
159.08
September 7, 1940
~
1614 1611
1
1,
1322.0
I
1612.5
1
VISCOSITIES OF GASES BETWEEN
955
80" AKD 300°K.
TABLE &Concluded DAIZ
T
September 10, 1940... . . . . . . . . .
130.57
n
x 10'
AVSRAGE
'R.
147.92 180.00 September 11, 1940. . . . . . . . . . . ,
174,Ol 169.30 204.62
219.40
234.93
249.65
September 11, 1940
265.67
280.16
September 10, 1940
296.13
1741 1741 1741
1741.0
1920 1911
1915.5
2035 2038
2036.5
2151 2151
2151 .O
2277 2275
2276.0
2414 2415 2415 2416
2415.0
2.541 2539 2539 2540
2539.6
2658 2665 2657 2665
2661.2
2783 2764 2790 2766
2765.5
2913 2917 2907 2912
2912.2
3020 3021 3014 3012
3016.7
3145 3144
3144.5
956
HERRICK L. JOHNSTON AND EDWARD R . GRILLY
TABLE 5 Vi'iscosity of arpon T
x 107
AVEIAGE
aK.
January 14, 1942... . . . . . . . . . . . .
January 17, 1942
January 10, 1942... . . .
77.90
90.32
. . . .. ...
January 31, 1942... . . , . . . . . .
,
...
118.17
131.35
140.72
January 25, 1942... . , . . .
. ..,
..
150.15
165.40 182.18 January 14, 1942.. ., . .. . . .. . . . .
192.34 201.37
January 26, 1942... . . . . . . , . . . . .
210.17 224.76 240.43
675.5 671.2 675.5 678.3
675.1
758.4 764.7 764.4 763.8 767.7 767.0
763.6
979.0 977.6 977.6
978.1
1084.2 1084.5 1074.7
1081.1
1153.7 1154.1 1146.6
1151.5
1223.8 1225.7 1225.0
1224.8
1342.7 1344.4
1343.5
1469.2 1477.3
1473.2
1538.9 1537.8
1538.3
1809.2 1605.7 1670.8 1671.2
1607.4 1671 .O
1772.0 1772.2
1772,l
1876.5 1877.9
1877.2
VISCOSITIES OF G.4SES BETWEEN
80"
ASD
300°K.
957
TABLE &Concluded
I
DATE
T
x 107
AVXIAGE
'IC.
January 26, 1942 . . .
255.13
1 1 January 25,1942... . . . . . . . . .
269.34 281.72 296.10
1980.2 1984.1
1982.2
2077.6 2076.5
2077.0
2153.8 2153.8
2153.8
2248.5 2248.1 2246.5 2246.1
2247.3
TAELE 6 Smoothed values of the viscosities T
C A l B O N MONOXIDE
HELIUM
NEON
AICON
OK.
80.0
533.0
90.0
602.0 668.5 733 .O 796.0
100.0 110.0 120.0 130.0 140.0 150.0 160.0 170.0 180.0 190.0 200.0
210.0 220.0 230.0 240.0 250.0 260.0 270.0 280.0 290.0 300.0
273.1 293.1 296.1 298.1
1589.0 1639.0 1688.0 1736.5 1784.5
1343.0 1395.0 1448.0 1496.0 1545.5 1594.5 1643.5 1691.5 1740.0 1788.5 1838.0 1887.5 1937.0 1987.0
1198.0 1320.0 1434.5 1542.5 1646,O 1745.0 1840.5 1934.0 2025.5 2115.5 2204.0 2291.0 2375.5 2460.0 2543.5 2626,5 2708.0 2788.0 2866.5 2943.5 3020.5 3096.5 3172.5
688.0 763.0 839.0 915.5 992.5 1069.5 1146.0 1222.0 1297.5 1372.5 1447.0 1521 .O 1594.0 1666.5 1738.5 1809.0 1878.0 1946.5 2014.0 2080.5 2145.0 2208.0 2269.5
16%. 0 1753.0 1766.0, 1775.5
1863.5 1952.5 1969.0 1977.5
2967.5 3121 .O 3143.5 3158.0
2100.5 2227.0 2246.0 2257.5
858.0
919.0 979.0 1038.0 1096.0 1154.0 1211.5 1268.0 1323.5 1378.5 1433.0 1486.0 1538.0
820.5 881.5 947.0 1009.5 1068.0 1125.5 1181.5 1236.5 1290.0
'
958
HERRICK L. JOHNSTON AND EDWARD R. ORILLY
TABLE 7 Comparison of our values for the viscosity with those of earlier authors CAS
T
__
‘I
x
,x
107
(THIB ESEAPCR)
10’ REFERENCES
(PUBLISHED)
VALUES
O K ,
Carbon monoxide.
Helium
..
80.0
633
195.0
l%O(
235.4 273.1 290.0 296.1
1462 1655 1736 1766
555
;
1477 1672 1738 1780
80.0
I
90.0 195.0 273.1 290.0 293.1
Neon. . , . . . . . . , , .
1953 (11)
1953
77.4 83.4 90.0 195.0
2334
~
2359’
273.1 293.1
Argon. , , . , , . . . . . . ,
80.0
84.6 90.0 140.8 194.3 212.9 232.9 252.9 272.9 286.3 293.1 ~
* Crude neon.
688{ 722 763
720 757
Vogel (17) Vogel (17) Trauta and Trauts and Vogel (17) Trautz and Trauta and
Baumann (12a) Baumann (12a) Baumann (12a) Melster (12d)
Vogel (17) Trauts and Zimmerman (12f) Van Itterbeek and Keesom (14) Van Itterbeek and Van Paemel (16) Trauta and Zimmerman (12f) Vogel (17) Trauta and Zimmerman (12f) Vogel (17) Van Itterbeek and Van Paemel (16) Trautz and Melster (12d) Trauta and Melster (12d) Trauts and Zimmerman (12f) Van Itterbeek and Keesom (14) Van Itterbeek and Van Paemel Van Itterbeek and Van Paemel Van Itterbeek and Van Paemel Trauts and Zimmerman (12f) Trautz and Zimmerman (12f) Trautz and Zimmerman (12f) Trautr and Zimmerman (12f) Trauta and Zimmerman (12f) Van Itterbeek and Van Paemel Trauta and Baumann (12a)
(16) (16) (16)
Van Itterbeek and Van Paemel Van Itterbeek and Van Paemel Van Itterbeek and Van Paemel Van Itterbeek and Van Paemel Kopsch (7) Kopsch (7) Kopsch (7) Kopsch (7) Kopsch (7) Kopsch (7) Kopsch (7) Trauta and Melster (12d) Van Itterbeek and Van Paemel
(15) (15) (15) (15)
(16)
(15)
VISCOSITIES
OF GASES BETWEEN
80"
AND
959
300°K.
Oxygen. . . . . . 100 767.7115.970,9033531.960.9354 69.63 55.3510.21398 61.5022158 Nitrogen. . . . . . . 100 697.5 94.240.85568 34.330.9400 57.39 53.0750.16674 57.3719539 Methane. . . . . . 100 402.8128.410.92751 9.550.7660 17.271 28.2060.12073 31 .SI23483 Nitric oxide . . . . 130 912.7129.920.89821 io LOO0 129.94 55.8580.18608 62.0519591 h'itrous oxide.. 190 948.6226.570.984918.14/0.720020.750 39.2060.15585 47.66~19660 Carbon dioxide. 200 1015.0204.550.955235.27'0.5320-0.435 42.6740.14548 49.6118458 Carbon monoxide. . . . . . . . . . . 90 602.0108.950.9053613.900.8450 30.44 46.1270.19264 51.2823717 Helium., , . . . . . 90 884.5 31.860,66993 9.210.7565-4.00 84.0050.10256 85.26~9941 Neon.. . . . . . . , . 90 1320.0 46.450.7287112.760.83oO 5.01 119.9310.21349 123.3513380 Argon. . . . . . . . . . 90 763.0~110.24,0.90814 8.080.7175 7.99 58.274 0.24617 64.8723878 ~
,
~
concluded that equation 5 gave the best representation of the data in the convex (low-temperature) portions of the curves, and equation 1 in the concave (hightemperature) portions. The data of Van Itterbeek and Van Paemel (16) in conjunction with our own, for neon, give an inflection at about 4OoK. and appear to substantiate the hypothesis of Van Cleave and Maass regarding the inflection point. However, the data of Van Itterbeek and Keesom ( l i ) ,for hdium, in conjunction with the present research, and those of Van Itterbeek and Van Paemel (l5), for argon, give no indication of an inflection. Furthermore, the data of Johnston and McCloskey (4) for carbon dioxide give a concave curve in the same temperature region in which the curve of Sutherland and hIaass (10) was convex. This is substantiated by the data of Johnston and McCloskey (4) for nitrous oxide over the Fame region. Comparison of our own data (for carbon monoxide, neon, argon, and helium) and of tho\? of Johnston and 3lcCloskey (for hydrogen, air, osygen, nitrogen,
980
HERRICK L. JOHNSTON AND EDWARD R. GRILLY
methane, nitric oxide, nitrous oxide, and carbon dioxide) with the five viscosity equations are shown in figures 1 to 5. The data employed are taken from table 13 of Johnston and McCloskey4 and from table 5 of the present paper. The graphs represent deviation of the equations from the smoothed tabular values. For the sake of ready comparison all five graphs use the same scale. Table 7 lists the constants which we used with equations 1 to 5, respectively.
I
I
IW
150
1
I
I
1 I
I
I 2w
I
2w
I 3ca
J
TEMPERATURE '*I
FIG. 1. Deviation of Sutherland equation from experiment
25
1' 1
I
I00
I
I
I50
I
I
200
I
I
250
I
2-30
'rEMPEnATunr,*n
F I G .2. Deviation of Chapman equation from experiment
These constants were determined empirically by fitting the data to the equation at two temperatures (three for the Jones equation). I t is at once apparent that the Jones equation (equation 3) gives by far the best representation of the data, which is perhaps to be expected from the fact that it is a three-constant equation while the others are two-constant equations. Equation 5 gives a rather poor representation for all twelve gases. For the 4 The following changes in their data are t o be made: for air at l a o , 975.1 t o 974.1; for oxygen at IN",999.2 to 989.2, and at 250", 1786.3 to 1787.3; for methane at IN",559.7 to 563.7; for nitric oxide at !2W, 1710.7 to 1720.7, and at 280°, 1837.6 to 1827.6. These were typographical error8 in the earlier paper.
VISCO~ITXES OF GASES BETWEEN
80'
300'K.
AND
961
1EMPERATURL.h
FIG.3. Deviation of Jones equation from experiment
0
g
