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
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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
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Hempel-Dennis, “hIethods of Gas Analysis,” 1906. a Sutton. “Volumetric Analysis” (Mohr’s method), 1901.
596
TNE
10 URA’AL
O F i,VDC/‘STRIAL A N D E I V G I ~ I - E E R I N GC H E M I S T R I ‘ .
Chemistry’ became apparent. By consulting the literature a n d various solubility tables2 and studying the methods of Gooch,3 Treadwell,4 K e n n i ~ u tFrenkel,6 ,~ and Rammelsberg, the following procedure was adopted whereby a larger volume of water could be used and a residue obtained which would give, when treated, a lithium salt containing only a spectroscopic trace of sodium and potassium. hlethod.-Two hundred t o five hundred cc. of the water are evaporated to dryness in a large platinum dish with the occasional addition of small amounts .of concentrated hydrochloric acid. After all of the water has been evaporated t o dryness the dish and contents are heated a‘t 1 2 0 ’ C. for about 30 minutes t o dehydrate the silica. The residue is then treated with a little dilute hydrochloric acid, just enough to moisten the contents of the dish. Then about 2 5 cc. of 9 5 per cent. alcohol are added and the residue is rubbed up with a. small pestle until all lumps and crystals are crushed. The alcoholic extract is then poured on an I I cm. quantitative filter and the filtrate caught in another platinum dish. The residue is washed with 95 per cent. alcohol until i t shows no lithium line when examined in the spectroscope. The alcoholic filtrate and washings are united and evaporated on the water bath. When all of the alcohol has evaporated some dilute hydrochloric acid is added t o the contents of the dish, and the whole evaporated t o dryness and then the residue rubbed up with absolute instead of g j per cent. alcohol. The filtrate is caught as before in a platinum dish and the residue on the filtrate washed with absolute alcohol until no lithium line is seen when tested from time t o time with the spectroscope. The alcohol is evaporated and the dry residue taken up with a little dilute hydrochloric acid. Calcium hydrate is added until the solution is alkaline. The magnesium is precipitated as the hydrate and the solution is filtered. To the filtrate add ammonium hydrate and ammonium oxalate t o precipitate the calcium. This is allowed t o stand twelve hours or over night when it is filtered off. The calcium oxalate precipitate must be thoroughly washed (usually about I O O cc. of water is sufficient) as lithium is held relatively fast by the precipitate and does not wash out easily. When the residue no longer shows lithium, as verified by the spectroscope, the solution is evaporated to dryness and the excess of ammonium salts driven off by first heating the dish on a radiator, then over the free flame. The residue in the dish is taken up with a little dilute hydrochloric acid, heated and ammonia and ammonium oxalate are again added t o precipitate any calcium which might be present. I n any case the solution is filtered from any calcium or magnesium t h a t precipitates on concentrating the solution. The filtrate 1 and 3 “Mineral Waters of the United States.” U. S. Dept. of Agriculture, Bureau of Chemistry, Bzclletilz 91, 1906. 2 Atherton Seidell, “Solubilities of Inorganic and Organic Substances,” 1907. 4 and 7 Treadwell-Hall, “Analytical Chemistry,” 191 1. Chamot-Redfield, “Analysis of Water for Household and Municipal Purposes,” 1911. 6 M. Frenkel, D.Sc., “Extract from the Records of Medical Hydrology and Climatology,’’ Paris, Dec., 1903.
Aug., 1 9 1 2
is evaporated to dryness and all ammonium salts are driven off by heating in platinum t o a little below redness. The residue is again taken up with water, filtered, and washed (using as little wash water as possible), then evaporated t o dryness and heated in platinum to a little below redness t o drive off any ammonium salts. All of the calcium and practically all the magnesium have now been removed, and there is left a residue containing lithium chloride with traces of sodium and potassium chlorides. If we have iodides and bromides present, this residue will contain small amounts of these substances because they are more soluble than the chlorides. I n order t o insure a residue consisting of chlorides only we treat the contents of the dish with a little dilute hydrochloric acid and chlorine water, evaporate to dryness, and gently ignite. By this we have replaced the iodine and bromine with chlorine. The residue is now taken up with a little water and treated with a few drops of dilute hydrochloric acid and transferred to a large platinum dish. About 30 cc. of amyl alcohol are added and the contents of the dish brought t o boiling with constant rapid stirring when heating t o minimize the bumping caused by the escape of the water. When all of the water has evaporated, the dish is placed on the steam bath and a drop of dilute hydrochloric acid added t o reconvert small amounts of lithium hydrate t o the chloride. The evaporation is continued until the volume reaches about I j cc. The amyl alcohol is then filtered into a platinum dish and evaporated to dryness. Water and a few drops of dilute sulphuric acid are now added and the contents of the dish again evaporated to dryness. The excess of sulfuric acid is removed by heating the dish over a radiator and then over the direct flame t o dull redness. The dish is cooled, the contents dissolved in water and a few drops of ammonium hydrate are added t o precipitate the last trace of magnesium which is invariably present a t this stage. Filter, wash with boiling water, evaporate t o dryness, free from ammonium salts, and repeat previous process till no more magnesium precipitates on addition of ammonium hydrate. Finally filter into a weighed platinum dish, evaporate t o dryness, burn, cool in a desiccator, and weigh as lithium sulfate. From this result we subtract o.oo17 gram to correct for the solubility of the sodium and potassium chlorides in amyl alcohol, their presence having been verified by the spectroscope. The contents of the filters containing the NaCl, KC1, etc., which were taken out by the 9 5 per cent. alcohol and absolute alcohol together with the contents of the platinum dish and filter from which the amyl alcohol has been driven off,are all dissolved in water, united, freed from other salts and made up t o a definite volume. By using aliquot portions we can determine sodium and potassium by Gooch’s method. Or the usual procedure, using a small portion of the silica filtrate, can be followed. .1dr,nntnges Given by this Modification: ( I ) Waters high in chlorides can be handled with ease with no danger of loss of lithium by decrepitation.
Aug., 1912
T H E JOURiVAL OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y .
( 2 ) Large volumes of water can be used, thus reducing the error when computing to milligrams per liter. (3) The results can be found to check and can be obtained much more quickly by having a residue free from a n excess of sodium and potassium chlorides. (4) The method involves the use of calcium hydrate instead of barium hydrate for the precipitation of magnesium. This procedure does not introduce another substance which has to be removed by ammonia and ammonium oxalate because we have our calcium in common and have a precipitate of calcium oxalate which is less soluble and more easily washed than barium oxalate.
STATEHYGIENIC LABORATORY, STATE DEPARTMENT O F HEALTH, ALBANY,N.Y.
A NEW VOLUMETRIC METHOD FOR TIN. B y WILLBURTV. PATRICK AND G C. WILSNACK.
Numerous methods for the determination of tin have been tried out in this laboratory with various degrees of success. Gravimetric methods giving results of the required accuracy are too lengthy and tedious for ordinary use in laboratories where it is required t o complete a large number of determinations in a short time. Shorter schemes, such as weighing the combined oxides of antimony and tin, determining antimony in a separate sample, and calculating tin b y difference, cannot be used for alloys containing lead, copper, or numerous other metals which are t o be found in some commercial alloys, unless the amount of these impurities contaminating the oxides be determined and taken into consideration. The volumetric methods proved t o be rather unsatisfactory, especially if the titrating solution was standardized against a standard reducing solution in preference t o C. P. tin. The authors found t h a t determinations on quantities as small as 57' were unreliable, and t h a t on high percentages it was almost impossible t o obtain consistently accurate results even if the oxidizing solution was standardized against a n equivalent amount of metal treated in a n exactly similar manner. Endeavoring t o overcome these difficulties, the following method was finally adopted. The results obtained are consistent and correct t o within 0 . 2 per cent. on amounts of 50 per cent. or over and considerably more accurate on smaller percentages. As large percentages of copper, lead, nickel, and perhaps other metals not experimented with, interfere, it has been found expedient t o modify the method somewhat in the presence of these elements. Both determinations will be described. REGULAR METHOD.
The following scheme of analysis is available where no more than j per cent. of either lead or copper is present in the alloy. Where the percentages of these elements exceed this limit a modification of the method is necessary. Place an amount of sample corresponding to 0.5 gram or less of tin in a j o o cc. Jena Erlenmeyer flask
5Q7
and add 0 . 1 5 gram C. P. metallic antimony if as much or more is not already present in the alloy. If the sample contains less than this amount i t is necessary to make up the deficiency. -4dd I O cc. of concentrated sulphuric acid and heat to effect solution. Remove from the hot plate and cool. Dilute the cold sulphuric acid solution with I O cc. of water, add 60 cc. of concentrated hydrochloric acid, and then 40 CC. more of water. Prepare a four-hole rubber stopper that fits the neck of the flask. Through one hole pass a glass tube bent a t right angles reaching to the bottom of the flask and through the hole diagonally opposite insert another tube bent in a similar manner but extending only a short distance below the bottom of the stopper. Through the third hole pass a long thin glass rod fitted with a 2'' piece of platinum wire. This rod should fit rather snugly without, however, giving any difficulty t o the operator in raising or lowering it during the determination. The platinum wire is now bent into the shape of a hook and a piece of very nearly C. P. iron wire attached. Swedish iron in plates of I/~'' thickness cut
I-
Volumetric Zn ~ppuprotus C
-B
7I
J
into strips of I / / in width and four inches in length, curled up in the form of a spiral, will suit the purpose well. Through the fourth hole pass a 1 1 ~ ' ' tube 4" long and drawn out a t the lower end to a n opening small enough t o enable the operator t o introduce iodine solution in sufficiently small quantities to obtain the starch iodide reaction within one drop of titrating solution. The tapered end is bent slightly in the di-
