cally unaffected by cold permanganate, whereas all terpenes and unsaturated compounds are oxidized, more or less readily, to soluble products. The unattacked eucalyptol can be measured, and its purity confirmed b y physical tests. The assay may be conducted as follows. I O cc. of the oil (eucalyptus or cajeput) are run into a joo cc. flask having a narrow neck, and 5-6 per cent. KMnO, solution added in small portions, with shaking, keeping the flask in ice water, until the reagent is no longer reduced. The amount required will vary from I O O cc. for rich oils to 400 cc. for inferior ones. When an excess of permanganate has been added, the flask is kept cold, with occasional shaking, for 12-18 hours. The precipitated manganic oxide is then dissolved by sufficient sulphurous acid (or sodium bisulphite and hydrochloric acid) and the flask filled with water, allowing the unoxidized oil to collect in the neck. After settling, the oil is transferred by a capillary pipette, t o a graduated tube, washed with a little alkali t o remove traces of sulphurous acid, and the volume read off. All reagents should be perfectly clear, or filtered if necessary. The eucalyptol thus obtained should show : Sp. gr. a t i s 0 , 0.929-0.930. Opt. rotation, i o o . Soluble in 31/2 volumes 60 per cent. alcohol a t 2 5 O. This method has been used for several years with very satisfactory results. Examples: Oil eucalyptus.. , . . . ,
Oil cajeput..
.,
. . .. . . . . . .
S. G. 0 928 @ 1.5’ 0 923 @ 1 5 O 0 915 @ , 15’ 0 908 @ 2.5’ 0 905 @ 2 5 O 0 098 @ 2 5 O 0 913 @ 25’ 0 916 2.5’ 0 914
0.R. +O.O5O +0.550
-3.150 +0.50°
-6.0’ -4.160 -2.100 -I ,450 -1.96’
Per cent. E. byvol. 85 81 52 68
S.
G.
66 74 60 61
of E. 0.929 0.929 0,929 0.929 0.930 0,928 0.929 0.927
56
...
Check assays on known mixtures of eucalyptol, terpenes, and terpineol, have shown the reliability of the method for technical work. The isolation of the eucalyptol in a pure state is a great advantage, as any stable compounds which might be present are immediately manifested by their effect on the physical constants. Thus: Camphor (stable to KMnO,) increases S. G. and shows 0. R. Inactive camphor (stable t o KMnO,) increases S. G. Fenchone (stable t o KMnO,) increases S. G. and shows 4 0. R. Paraffins or petroleum products increased, diminish S. G . and solubility. Borneol (oxidized to camphor). Menthol (oxidized t o menthone). Menthone (slowly oxidized) diminishes S. G. and shows 0. R. Rornyl acetate (stable) increases S. G. and shows 0. R. The method as outlined is, I believe, the only direct method among those applicable to constituents of the
+
+
essential oils, i. E . , one in which the compound to be estimated is isolated in a pure and determinable shape. LABORATORY DODGE& OLCOTTCo., BAYONNE, PIT. .T.
RECENT ANALYSES OF THE SARATOGA MINERAL WATERS. ny LESLIE RUSSELLMILFORD Received February 21. 1912.
G E h-E R.4 L
.
This group of mineral springs is recognized as one of Kew York State’s unique natural resources, and their discovery dates back t o 1767 when, according to tradition, the Indians brought Sir William Johnson to the High Rock Spring t o be treated for gout. The general belief is that the wells and springs in this region have a coninion source far down in the earth and situated along a geological fault, the strata a t the west being many feet above .those corresponding in the east. The minerals are held in solution by the great amount of carbon dioxide which saturates the waters along the mineral stratum. This stratum is supposed t o be the remains of a n extinct volcano or the remnant of a Silurian Ocean. I t was through this geological fault that the springs found their way to the surface flowing by their own gas pressure. The popularity of these springs soon became known, and a water resort of great therapeutic value, resembling, in quality, the famous French 1-ichy, was given to the public. The springs and wells a t Saratoga may be divided into three groups: Geysers Park, Congress Park, and High Rock Park, each of which contains its supply of mineral waters. About fifteen years ago i t was discovered that the carbon dioxide with which these mineral waters were charged could be profitably separated from the waters and sold. A large industry soon became established in Saratoga, companies being formed, generally called “gas companies,” for the promotion of the industry. At first these gas companies extracted the carbon dioxide from what were called “dry wells” or “pockets” and also from the mineral water as i t naturally issued from the ground. But later it was discovcred that by pumping with more powerful and modern machinery a far larger amount of mineral water could be forced from the ground and consequently more gas extracted. This pumping soon began t o have a marked effect on the other springs, causing a diminution in flow and alteration of the minerals in solution. A great amount of litigation was soon begun between the spring owners and the gas companies, the spring owners showing that pumping affected the flow of their springs and the “gas companies” asserting a property in the flow of the mineral waters from the springs on or under their lands. The result of this agitation over the effect of pumping caused an “anti-pumping law” t o be passed by the legislature in 1908. The passage of this act was followed by more lawsuits extending over a period of many months. The need of unified ownership in the springs became apparent
A-YD EAITGIAYEERI!YG CHEJ12STR17.
594
and the legislature in 1909 passed an act appointing the Commissioners of the State Reservation a t Saratoga Springs, who a t once began their duties of preserving the springs and restoring them t o their former natural condition. To aid them in their work special investigations were undertaken by the Division of Laboratories of the State Department of Health a t the request of the Saratoga Reservation Commission. The analyses, and their explanations which follow, represent t h e work which has been recently completed
and a part of the series of the analyses which are t o be made. The writer personally collected and sealed the samples in 5-gallon demijohns so that the analyses are known t o be from true samples of the mineral mater as i t came from the source. An important feature to note with this work is that the State Hygienic Laboratory is only forty miles from the Reservation a t Saratoga so that a great amount of field work was easily carried on in connection with the laboratory examinations. Also a quick
CONSTITUEXTS AS ACTUALLY DETERMINED. Hathorn Spring N o . 1. Coesa (Carlsbad) Spring.
Hathorn Spring No. 2.
-
7-.
Formula.
... ................. HC03. . . . . . . . . . . . . . . . . . . . . . . NO3. . . . . . . . . . . . . . . . . . . . . . . . .
21.58 trace 4354.14 a a 0.05
so
4 . . . . .
NOn . . . . . . . . . . . . . . . . . . . . . . . . .
POa. . . . . . . . . . . . . . . . . . . . . . . . . AsO,. . . . . . . . . . . . . . . . . . . . . . . .
n
trace 5370.03 20.31 2.82 5.95
CI. . . . . . . . . . . . . . . . . . . . . . . . . .
F e and AI.. . . . . . . . . . . . . . . .
7.14 2.24 a 1008.71 826,73 17.54 trace 85.90 3455.29 20.16 a
Mn.......................... Ca . . . . . . . . . . . . . . . . . . . . . . . . . .
...................... Ra.,........................ Sr . . . . . . . . . . . . . . . . . . . . . . . . . .
K..... Na.. . .
Li., . . .
NH,
........................
3. 4. 5. Results in milligrams per liter. 19.60 13.85 8.60 13.50 5.60 21.42 3.77 2 .SO 4746.34 4244.50 3585.60 2219 .OO none a none none a none trace none a nnne none none a none none none trace trace small amount small amount 5150.45 4419.60 3685.50 2293 .OO 2.05 a 40.30 26.90 0.60 a 1 .60 1 .50 18.70 10.08 a a 19.40 a 13.10 9.80 a 1.40 a a a none a a 650,70 499.80 733 .65 628.60 90.00 332.90 298.80 228 80 5.50 12.31 15.93 10.10 trace trace trace trace 304.53 237.80 197.20 471.40 3525.55 3014.50 2430.70 1280.10 3.70 15.18 5.30 0.50 6.00 a 13.40 10.70 ...... 5.70 2.
1.
Oxygen t o form Fea03
F. . . . . . . . . . . . . . . . . . . . . . . . . . .
trace
NHnCl . . . . . . . . . . . . . . . . . . . . . . LiC1. . . . . . . . . . . . . . . . . . . . . . . . . KCI.. . . . . . . . . . . . . . . . . . . . . . . h’aC1. . . . . . . . . . . . . . . . . . . . . . . . KBr. . . . . . . . . . . . . . . . . . . . . . . . KI. . . . . . . . . . . . . . . . . . . . . . . . . . Na&04.. .................... NaN03.. . . . . . . . . . . . . . . . . . . . .
a
Aug., 1912
Hathorn Spring No. 3. 8.
6.
7.
7.70 27.00 3912.50 none none none none trace 4180.00 40.90 1 90 16.10 16.90 1.50 3 60 781.90 288.40 4.70 1 .io 242.20 2556.90 12.20 5.53
8.15 12.60 5677.90 none none none none trace 7044.75 29.84 3.81 4.50 16.30 8.50 trace 974.85 472.40 25.30 6.10 442.80 4369,OO 11.60 18.10
8.50 6.60 5581.60 trace none none none trace 5775.70 16.10 1.26 14.30 17.30 7.60 . none 1057.SO 412.30 13.70 2.70 365.50 3621.90 iz.8n 13.30
16.46 74 20 422.10 6444.70 60.00 2.50 39.90 none none trace 68.19 8.90 4.00 17.50.70 3166.70 2.5.50 5.00 1 .50
53.90 70.50 815.60 10825.90 43.75 5 .oo 18.64 none none trace 362.10 47 . S O 14.60 2867.40 3948.10 37.70 trace 8.50
39.60 76.10 676.40 8957.30 25 .oo 1.65 9.80 trace trace trace 331.80 25.90 6.40 2502.60 4281.40 22.50 none 7.60
HYPOTHETICAL FORM OF COMBINATION. 150.28 164.11 8720.45 c 20.36 d 2.02 e trace b
0 R
NaRO2.. . . . . . . . . . . . . . . . . . . . .
trace 73 ..72 29.70 trace 3017.52 2918.05 19.29 a 1.24
..........
Mg(HC03)z. . . . . . . . . . . . . . . . . . . Ca(HCO3)2. . . . . . . . . . . . . . . . . . . Mn30a . . . . . . . . . . . . . . . . . . . . . .
....................... .......................
A1203.
FezO SiOz. . . . . . . . . . . . . . . . . . . . . . . . . Total solids.. . . . . . . . . . . . . . . . . Residue on evaporation.. . . . . . . Temperature, . . . . . . . . . . . . . . . . Organic matter. . . . . . . . . . . . . Density. . . . . . . . . . . . . . . . . . . . . N a B r . , ,. . . . . . . . . . . . . . . . . . . . NaI, . . . . . . . . . . . . . . . . . . . . . . . . NaF . . . . . . . . . . . . . . . . . . . . . . . .
17.90 22.40 898.80 3253 .80 3 .OO 0.40 31.70 none trace trace 276.10 23.30 trace 556.40 2024.20 29.60 none 1.40
........
........
21.55 15154.82 12663.61
13.85 19.60 10858.60 6152.85 a 6030.00 a lO.5OC
................... ................. ...
31.80 3 .OO 350.70 5762.40 40.00 1.90 8.20 nnne none trace 586.40 10.40 trace 1377.80 2635.30 31.10 none a
.....
(1
trace 1.0115 26.23 2.39 trace p. 10 trace 194.74
a , Not given.
b , Equivalent of LiHCO.3 reported. c , Equivalent of NaBr reported.
d , Equivalent of NaI reported. e , Equivalent of K&Ol reported.
.....
..... .............. . . . . . . . . . . . . . .
.............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
..............
b
a 113.89 574.05 8324.11 a
e
a 5.47 a
a trace 898.61 30.10 tracc 2020.71 2971.30 32.15 a a
..... 8.60 14978.99 a a
.....
......
......
...... ......
..... 6.84 147.40
39.67 31.80 415.60 6873.50 60.00 2.10 4.10 none none trace 1126.70 19.10 trace 1798.90 2545.80 U U
!i8.sn)
........
.., ., , . .
13 S O 12949.70
7.70 12098,05 10570.00
a
a
........
11oc.
.......
........ ........
.......
....... ........
.......
.......
........ ........
....... ....... ....... .......
........
........
8.15 18764.59 16220. O O 10.5oc
8.50 16640.75 13830.00 10.4’C.
....... ....... ....... .......
....... ....... .......
...... .......
....... . . . . . . .......
1, C. F.Chandler, The AnieruaTz Chemist. 2, No. 6.(1871). 2 and 5,“Mineral Waters of the U. S.,” Dept. of Agriculture, Bulletin No. 91. 3,6,7 and 8,Files of New York State Department of Health, January, 1912 4, Analysis by E . E. Smith, Ph.D., M.D., August, 1901.
A u ~ . 1, 9 1 2
T H E JOUK.\7AL
OF I N D C S T R I - 4 L A N D EZ;GIlYEERIJYG C H E M I S T R Y .
delivery of the samples for mineral analysis is to be had. The methods given in Bulletin 91, 13ureau of Chemistry,’ except for the determination of lithium, were followed. For lithium a new method w a s adopted which is described by the author in another paper. The waters of the Hathorn Spring No. I and the Coesa Spring (formerly known as the Carlsbad) have been analyzed by other chemists and the results of the analyses have been published in the literature, but for the sake of comparison these older analyses have been inserted beside the new ones. Where the results have been combined in a different way than was adopted by the Bureau of Chemistry and followed by the New York State Department of Health, the writer has computed them to a comparable equivalent. The hypothetical forms of combination have been computed as milligrams per liter. From the data we can see t h a t great changes have taken place in the springs from time t o time. The water of the Hathorn Spring No. I when analyzed by Prof. Chandler forty years ago was over twice as strongly mineralized as it is now. I t was also less mineralized when the sample was taken last July than i t was when analyzed by the Bureau of Chemistry of the U. S. Department of Agriculture. The water of the Coesa Spring contained less minerals in solution when the sample was taken in November, 1911,than i t did when analyzed by Dr. Smith or the U. S. Department of Agriculture. The amount of lithium found in the last analyses is higher than t h a t reported in the results published in Bulletin 91,because of a new method employed which now gives more complete results. The Hathorn Spring No. I is situated in the village of Saratoga, while the Coesa is situated a t the Geysers. These two waters have a n abundant supply of gas and are suitably mineralized. The Hathorn Spring No. 2 and Hathorn Spring No. 3 have never been analyzed by other analysts, so that no data for comparison are available. These two, springs are situated in the Geysers district about 300 feet apart and were found in the early part of 1 9 1 0 by drilling. Hathorn No. z is the most highly mineralized spring in Saratoga and its waters are pronounced by eminent physicians to be of great therapeutic value. Hathorn No. 3 is of the same general nature as Hathorn No. 2 . As seen from the analyses these springs contain the important constituents-magnesium, sodium, lithium and carbon dioxide. A N A L Y S E S O F T H E GAS.
The supply of carbon dioxide being great, it was thought advisable to analyze the gas from some of the important springs where the sample could be easily collected. S .I R.\ T 0 GAk S P R I .V G W A T E R S . The gas was collected in a five gallon demijohn by first filling i t with the charged water, issuing from the spring, then inverting and displacing the water by the gas from the spring. The apparatus of Hempel “Mineral Waters of the Vnited States Bureau of Chemistry, Bullefztt 91, 1905
”
U S Dept of Agriculture.
595
was used for measuring the sample, then it was estimated by the ordinary absorbents in the absorption pipettes. Hydrogen sulphide was determined by passing the gas through a measured amount of standard arsenious acid solution and titrating back with iodine, using starch as a n indicator.2 GAS FROM COESA (CARLSRAD) SPRING. Sample of gas taken July 14, 1911: Sample for analysis corrected Carbon dioxide. . . . . . . . . . . . . Oxygen. . . . . . . . . . . . . . . . . . . . . . . . 0.0 Combustible.. . . . . . . . . . . . . . . . . . . 0.0 Nitrogen and non-combustible. , , . 2.5 Hydrogen sulphide. . . . . . . . . . . . . . 0 . O When three liters of the gas were tested. GAS FRO31 HATHORN SPRING S O . 3. Sample of gas taken July 13, 1911: Sample for analysis corrected.. . . . 100 cc. Carbon dioxide.. . . . . . . . . . . . . . . . 9 8 . 1 Oxygen. . . . . . . . . . . . . . . . . . . . . . . . 0.0 Combustible. . . . . . . . . . . . . . . . . . . . 0.0 Nitrogen and non-combustible 1.90 0 .O When three liters of the Hydrogen sulphide., . . . . . . . . . . . . gas were tested. No samples of gas were taken from Hathorn Springs Nos. 1 and 2. I3 ACT E R I O LO G I C 4I,
EX A M I N A T I O N S .
The xaters of these springs have been examined bacteriologically from time to time, and the results showed a t the time these samples were taken t h a t the bacterial count was very low; no organism of the B. coli type was isolated. This proves that the springs are of a high sanitary purity. I n the near future other analyses will be made, and the results will be published from time to time. The writer wishes to express his gratitude to the State Department of Health and the Saratoga Reservation Commission for the permission to use their data and information. STATE HYGIENICLABORATORY, STATE DEPARTMENT O F HEALTH, ALBANY, S. Y.
DETERMINATION O F LITHIUM. By LESLIE RUSSELLMILFORD. Received February 21, 1912.
I n the work with the first samples of the Saratoga mineral waters, which the writer has been analyzing, the determination of lithium was found t o be difficult and the results obtained were not satisfactory because of the fact that parallel determinations would not check and too small volumes of water had to be used. The waters of these springs are highly mineralized, the chlorides ranging from I O O to 11,000 parts per million. Therefore, a great deal of trouble was experienced in volatilizing the ammonium salts when working with large volumes of water. Mechanical loss, due to decrepitation and splitting apart of the crystals, m-as a constant source of error. On the other hand, if one took a small volume of water the chlorides could be dried and the ammonium salts driven off more easily, but the possibility of multiplying errors would be great because of the relative small amounts of lithium present. The need of a n improvement or change of the method given on page 29, Bulletitt 91, of the Bureau of
’
Hempel-Dennis, “hIethods of Gas Analysis,” 1906. a Sutton. “Volumetric Analysis” (Mohr’s method), 1901.
