632 INDUSTRIAL ,4ND ENGINEERING CHEMISTRY Vol. 22, No. 6

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 unsatura- tion 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.

On this basis the x-ray observations of Debye and Scherrer (Z), which they thought indicated that amorphous carbon con- sists 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 arrange- ment 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 . Chem. , 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. IRD. 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 STATES GEOLOGICAL SURVEY, WASHINGTON, D. C.

N COSNECTION with studies of the hot springs of Arkansas, made a t the request of the Sational Park I Service, analyses of samples from several of the springs,

taken a t different times in the year, were made in the water- resources 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.

tE

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 investiga- tion 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

2 29 19 30 23 24 21 22 2 7

Analyses of Hot Springs and Public Supplies (Numbers refer to analyses in table)

June, 1930 INDUSTRIL4 L Ah'D ENGINEERING CHEMISTRY 633

Analyses of Hot Springs and Public Supplies TOTAL

TOTAL HARD-

SOURCE No. ANALYST TION TURE s o l , I D s Si02 F e Ca h lg K a K HC03 so1 cl Koa CaCOIQ 0 C. P.p.m. P.p.m. P.p.m. P.p.m. P.p.m. P.p.m. P . p . m . P.p.m. P.p,m. P.0.m. P.p.m. P.0.m.

DATE OF TEM- DIS- NESS I,OCATION A N 0 COLLEC- PERA- SOLVED A S

Hot Springs, Arkansas: Spring KO. 25 1 Haywood 5-19-01 , . . 19!1.5 47.31 46.82 5.01 4 . 7 3 1 . 6 9 1 6 6 . 5 7 . 8 2 . 5 Trace 138

2 Foster 3-3-25 . . . 194 43 0:03 45 5 .5 4 . 5 0 . 9 162 8 . 7 2 . 1 0 .05 135 3 Foster 12-5-25 194 45 0 .06 46 5 . 5 3 .8 0 . 6 163 8 . 7 2 . 2 0 . 0 3 138 4 Foster 3-6-26 l4i' 20:3 55 0 . 3 8 46 5 . 2 4 . 3 0 . 7 165 8 . 7 2 . 1 0 . 0 136 5 Foster 9-10-26 146 197 46 0 . 0 7 45 5 . 5 4 . 8 1 . 1 165 9 .2 1.8 0.05 135

Spring S o . 37 6 Haywood 5-19-01 , . . 213 7 Foster 3-3-25 22 1 8 Foster 6-6-25 121' 221 9 Foster 12-5-25 , , . 212

10 Foster 2-4-26 223 11 Foster 3-6-26 109' 205 12 Foster 9-10-26 120 195

~~

4 6 , 6 5 43 46 42 39 43 43

2: 37 0.71 0 . 6 7 0 . 8 3 0 .84 0 .84

49 .93 50 51 48 51 47 43

5.07 6 . 2 5 . 6 4 . 9 5 . 5 5 . 7 5 . 2

5 28 4 1 4 3 4 2 3.8 3 8 4 2

1 .76 0 . 7 1 . 4 0 . 6 1 . 4 0 . 7 1 . 3

169 .6 135 135 138 134 140 143

1 5 . 7 8 35 35 29 41 26 18

2 . 6 7 Trace 7 .6 0 . 0 7 5 . 5 0 . 0 2 5 . 7 0 . 0 3 5 . 2 0 .05 4 . 2 0 . 0 7 3 . 2 0 .07

146 150 150 140 150 141 129

Spring S o . 42 13 Haywood 5-19-01 , , , 203 4 9 . 6 3 45 .93 5 . 1 9 5 . 0 8 1 . 7 2 1 6 6 . 5 8 . 4 2 . 8 3 0 .44 136 14 Foster 3-3-25 , , . 195 44 0:02 45 5 . 4 4 . 8 1 0 157 12 3 . 0 0.05 135 15 Foster 12-5-25 196 45 0 . 0 4 46 4 . 6 4 . 3 0 6 159 11 3 . 0 0 . 0 3 134 16 Foster 3-6-26 139' 195 45 0 .32 46 5.3 4 . 4 0 . 7 159 11 2 . 6 0 . 0 137 17 Foster 9-10-26 141 195 45 0 . 0 7 45 5 . 3 4 . 7 1 . 2 160 11 2 . 6 0 . 0 134

Hot'Springs, Virginia: Hot Sulphur Spring 18 Clarke 1884 9 8 . 5 573

19 Foster 7-5-29 9 7 . 5 582 20 Foster 1-6-30 97 589

Soda Spring 21 Foster 7-5-29 75 423 22 Foster 1-6-30 72 389

Cold Magnesia Spring 23 Foster 7-5-29 6 0 . 3 223 24 Foster 1-6-30 60 170

Falling Spring 25 Foster 7-5-29 7 4 . 5 672 26 Foster 1-6-30 65 3913

Drinking Pool 27 Foster 7-4-29 , . . 52.5 28 Foster 1-6-30 95 52.5

Chicago. Ill. 29 Weinhold 12-5-21 . , . 183 Sioux City. Iowa

(Lowell S a . ) 30 Foster 3-17-22 . . . 589

a Calculated.

Falling Springs, L'irginia:

Warm Springs, Virginia:

Public Supplies:

of two public water supplies that are somewhat like the hot- spring 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 notice- ably 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 tem- perature 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 ( 3 F. The hot springs are practically identical in composi- tion 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 com- position 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 tempera- ture 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

- r o

23 132 33 14 11 463" 127 3 2 465 23 0:Zl 137 37 8 , 9 8 . 4 449 133 3 2 0:O 494 25 0.05 136 37 8 . 6 11 455 $134 3 2 0 0 492 16 O , l 5 102 24 4 . 4 5 .1 330 90 2 . 2 0 . 7 5 353 14 0 . 0 2 9 8 23 4 . 8 4 . 0 320 77 2 . 4 0 . 9 3 339

9 . 9 0.08 62 10 2 . 8 2 . 2 190 42 1 . 6 0 . 9 1 196 8.3 0.08 49 8 . 0 1.5 1 . 3 150 28 1 . 2 0 . 8 9 155

20 0 . 1 3 153 31 7 . 4 6 . 5 310 261 2 . 9 1 7 510 13 0 .04 99 18 4 . 1 4 . 6 226 134 1 . 8 3 0 321

24 0 . 1 1 118 22 6 . 5 z . 4 192 228 2 . 4 0 . 0 385 23 0 . 0 5 114 28 3 . 8 3 .6 196 232 1 . 8 0 . 0 400

18 0 . 4 36 10 4 .6 1 . 6 144 10 6 . 0 1 8 131

16 0 . 4 4 119 34 27 5 . 9 3 i l 174 11 0 16 437

character. The sulfate i- slightly greater than the bicar- bonate, 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 pro- portions of the different constituents remain fairly constant. This indicates that, ahile the hot springs come from a con- siderable 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 Surve 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