INDUSTRIAL ,4ND ENGINEERING CHEMISTRY
632
certain adsorbed or contained impurities), but very high molecular, highly unsaturated hydrocarbons; in other words, they are carbon complexes in which the fields of force between the carbon atoms are unbalanced by an occasional stray hydrogen atom, thus preventing the stable crystallization of the carbon atoms and producing a general state of unsaturation and hence of surface activity. Graphite is thus to be regarded as the only stable crystal form of carbon other than diamond, but amorphous carbon is not to be considered as a physical modification of graphite. This general view is favored by the results of Lowry (i), who has found that all oxygen is evolved from charcoals below 1000° C., but that the hydrogen content is still 0.48 per cent, decreasing to about 0.1 per cent a t 1300" C., while his coefficient of surface activity (cc. COz adsorbed per cm. mm. total pore volume) did not decrease appreciably until above 1000" C. I n view of the high heat of combustion of hydrogen per gram, and the degree of carbon unsaturation which could reasonably be produced by 0.5 to 1.0 per cent hydrogen ( I hydrogen atom per 16 to 18 carbon atoms), it seems quite possible that this can account for the 341 calories per gram increased heat of combustion observed as compared with that for graphite.
Vol. 22, No. 6
On this basis the x-ray observations of Debye and Scherrer (Z), which they thought indicated that amorphous carbon consists of agglomerates of extremely small true crystals of
graphite, would rather be interpreted as showing the local formation of such crystals or minute regions of stable arrangement of carbon atoms a t points where the hydrogen atoms have become too few and too widely separated to prevent this crystallization. That this hydrogen is very firmly held is shown, not only by the temperature observed by Lowry that was required to remove it, and by the temperatures found necessary to produce appreciable graphitization (Roth and Doepke, ci), but also by the data of Table 11. Evidently preliminary oxidation, either during or after manufacture, has no effect on the internal composition or structure as reflected by the heat of combustion after degassing in yacuum a t 1000" C. Literature Cited (1) Asahara, Japan J . C h e m . , 1, 35 (1922). (2) Debye and Scherrer, Physik. Z . , IS,291,(1917). (3) Johnson, IND.E N G .CHEM.,21, 1288 (1929). (4) Lamb, Wilson, and Chaney, J. I R D .E R G .CHEW.,11, 420 (1919). (5) Lowry, J . Phys. Ckem., 34, 63 (1930); J . .am.Citem. Soc., 46, 824 (1924). (6) Roth and Doepke, B e y . , 60, 530 (1927).
Chemical Character of the Hot Springs of Arkansas and Virginia" Margaret D. Foster UNITED STATESGEOLOGICAL SURVEY, WASHINGTON, D. C.
I
N COSNECTION with studies of the hot springs of
Arkansas, made a t the request of the Sational Park Service, analyses of samples from several of the springs, taken a t different times in the year, were made in the waterresources laboratory of the United States Geological Survey. 1 Received April 3, 1930. Presented before the Division of Water, Sewage, and Sanitation Chemistry at the 79th Meeting of the American Chemical Society, Atlanta, Ga , April 7 to 11, 1930 2 Published by permission of the Director, United States Geological Survey.
Some of these analyses are given in the accompaiiying table, together with analyses made by J. K. Haywood ( S ) , of the Bureau of Chemistry of the United States Department of Agriculture, in 1901. Similar analyses of samples from Warm Spring Valley, Va., were made by the United States Geological Survey in connection with a cooperative investigation initiated by the Virginia Geological Survey. Some of these analyses are given in the table, with one analysis from a series made by F. W. Clarke (I), of the United States Geological Surrey, in 1884. The table also includes analyses
tE
2
29
19
30
23
24
Analyses of Hot Springs and Public Supplies (Numbers refer to analyses in table)
21
22
27
633
INDUSTRIL4L Ah'D ENGINEERING CHEMISTRY
June, 1930
Analyses of Hot Springs and Public Supplies
TOTAL
TOTAL
I,OCATION A N 0
SOURCE
Hot Springs, Arkansas: Spring KO.25
Spring S o . 37
Spring S o . 42
Hot'Springs, Virginia: H o t Sulphur Spring
N o . ANALYST
TION
.. . ..
5-19-01 3-3-25 12-5-25 3-6-26 9-10-26 5-19-01 3-3-25 6-6-25 12-5-25 2-4-26 3-6-26 9-10-26 5-19-01 3-3-25 12-5-25 3-6-26 9-10-26
Clarke Foster Foster Foster Foster Foster Foster
1884 7-5-29 1-6-30 7-5-29 1-6-30 7-5-29 1-6-30
98.5 97.5 97 75 72 60.3 60
Foster Foster
7-5-29 1-6-30
7 4 . 5 672 65 3913
Foster Foster
7-4-29 1-6-30
95
Weinhold Foster
12-5-21 3-17-22
AS
TURE s o l , I D s Si02 Fe Ca 0 C. P.p.m. P.p.m. P.p.m. P.p.m.
1 Haywood 2 Foster 3 Foster 4 Foster 5 Foster 6 Haywood 7 Foster 8 Foster 9 Foster 10 Foster 11 Foster 12 Foster 1 3 Haywood 14 Foster 15 Foster 16 Foster 17 Foster
18 19 20 Soda Spring 21 22 Cold Magnesia Spring 23 24 Falling Springs, L'irginia: Falling Spring 25 26 Warm Springs, Virginia: 27 Drinking Pool 28 Public Supplies: Chicago. Ill. 29 Sioux City. Iowa (Lowell S a . ) 30 a
HARDNESS
DATEOF TEM- DISCOLLEC- PERA- SOLVED
,
l4i' 146 ,
..
121' ,,
.
109' 120 ,,, ,,
.
139' 141
,
..
.,. .. .
19!1.5 194 194 20:3 197 213 22 1 221 212 223 205 195 203 195 196 195 195
47.31 43 45 55 46 46,65 43 46 42 39 43 43 49.63 44 45 45 45
573 582 589 423 389 223 170
23 23 25 16 14 9.9 8.3
132 0:Zl 137 0.05 136 O , l 5 102 98 0.02 62 0.08 49 0.08
20 13
0.13 0.04
153 99
52.5 52.5
24 23
0.11 0.05
118 114
183
18
0.4
589
16
0.44
~~
0:03 0.06 0.38 0.07 2: 37 0.71 0.67 0.83 0.84 0.84 0:02 0.04 0.32 0.07
46.82 45 46 46
45 49.93 50 51 48 51 47 43 45.93 45 46 46 45
hlg Ka K HC03 so1 cl Koa CaCOIQ P.p.m. P.p.m. P . p . m . P.p.m. P.p,m. P.0.m. P.p.m. P.0.m.
5.01 5.5 5.5 5.2 5.5 5.07
6.2 5.6 4.9 5.5 5.7 5.2 5.19 5.4 4.6 5.3 5.3 33 37 37 24 23 10 8.0
4.73 4.5 3.8 4.3 4.8 5 28 4 1 4 3 4 2 3.8 3 8 4 2 5.08 4.8 4.3 4.4 4.7
1.69 0.9 0.6 0.7 1.1 1.76 0.7 1.4 0.6 1.4
166.5 162 163 165 165 169.6 135 135 138 134 0 . 7 140 143 1.3 1.72 166.5 10 157 0 6 159 0.7 159 1.2 160
7.8 8.7 8.7 8.7 9.2 15.78 35 35 29 41 26 18 8.4 12 11 11 11
2.5 2.1 2.2 2.1 1.8 2.67 7.6 5.5 5.7 5.2 4.2 3.2 2.83 3.0 3.0 2.6 2.6
14 8,9 8.6 4.4 4.8 2.8 1.5
11 8.4 11 5.1 4.0 2.2 1.3
463" 449 455 330 320 190 150
127 133 $134 90 77 42 28
3 2 3 2 3 2 2.2 2.4 1.6 1.2
31 18
7.4 4.1
6.5 4.6
310 226
261 134
22 28
6.5 3.8
z.4
3.6
192 196
228 232
4.6
1.6
144
10
5.9
3il
174
36
10
119
34
27
Trace 0.05 0.03 0.0 0.05 Trace 0.07 0.02 0.03 0.05 0.07 0.07 0.44 0.05 0.03 0.0 0.0
138 135 138 136 135 146 150 150 140 150 141 129 136 135 134 137 134
0.75 0.93 0.91 0.89
465 494 492 353 339 196 155
2.9 1.8
17 3 0
510 321
2.4 1.8
0.0
0.0
385 400
6.0
11
0:O 0 0
1 8
131
0 16
437
Calculated.
of two public water supplies that are somewhat like the hotspring waters in their content of dissolved mineral matter. The analyses made by Haywood a t Hot Springs, Ark., show that in general the hot springs there are fairly uniform in composition. The dissolved mineral matter is almost entirely calcium bicarbonate and silica. Analyses of seven springs made by the writer in 1925 and 1926 gave for three (Nos. 10, 25, and 29) results practically identical with those reported by Haywood in 1901. Three iSos. 28, 42, and 46) showed slight increases in sulfate, which were consistent in four samples from each spring collected a t different times in the year. The water of spring No. 37 had changed noticeably since Haywood's analyses, and it changed from time to time during the year. The greatest change was in the sulfate. There was no apparent relation between the temperature and the composition. Analyses for a typical spring of each group are shown in the table. Of the springs in Warm Springs Valley, J-a., those a t Hot Springs are the most used. They may be divided into two groups-the hot springs, which range in temperature from 86" to 106" F., and the springs whose temperature is above the mean annual air temperature but not more than about - r o ( 3 F. The hot springs are practically identical in composition and show almost no change from season to season and from year to year. The analyses in the table for the Hot Sulphur Spring represent closely the composition of water from the Spout, Boiler, or Magnesia Spring. The springs that have somewhat lower temperatures are similar in composition to the hot springs, but they contain less dissolved mineral matter and change with the seasons. Analyses of Soda Spring and Cold Magnesia Spring are shown in the table. All the waters a t Hot Springs, T7a., are essentially calcium bicarbonate waters. The water a t Warm Springs has about the same temperature as that of the hot springs a t Hot Springs and, like those waters. is constant in composition throughout the year and from year to year. It is, however, of a somewhat different
character. The sulfate i- slightly greater than the bicarbonate, but the ratios of the basic constituents are practically the same as a t Hot Springs. The water a t Warm Springs and that of the Hot Sulphur Spring a t Hot Springs contain enough hydrogen sulfide to gixe a slight odor, but this has disappeared by the time a sample reaches the laboratory. The quantity is, therefore, of the order of 1 p. p. m. or less. The water a t Falling Springs is intermediate in composition between those at Hot Springs and a t Warm Springs. Its temperature is like that of the cooler springs at Hot Springs, and, like them, it changes greatly in composition from time to time. Analyses indicate that Healing Spring may be grouped with the hot springs at Hot Springs and the Cascade Spring with the Soda and Cold Magnesia Springs. The springs that Vaiy in composition with the seasons appear to change only in concentration. The relative proportions of the different constituents remain fairly constant. This indicates that, ahile the hot springs come from a considerable depth without much mixture with shallower waters, the colder springs have certain proportions of shallow water a t all times. The general characteristics of these J\aters are shown in the figure, which includes for comparison analyses of two public water supplies ( 2 ) . The waters a t Hot Springs, Ark.. are similar in chemical composition to the public water supplies of Spokane, Wash., Pontiac, Mich., Quincy and Chicago, Ill., and almost exactly like the supply of Dover, Del. The waters of the hot springs in Virginia are similar to the public supply of Sioux City, Iowa, and many private supplies in the United States. Analyses of the Chicago and Sioux City supplies are given in the table and shown in the figure. Literature Cited (1) Clarke, U S Geol S u r v e i , Il'aier-Supply Paper 364, 10 (1914). (2) Collins, I h z d , 496 (19231 (3) Haymood, 57th Cong , 1st sess , Senate' Document 282
