M a r . , 1914
T H E J O U R N A L O F I N D U S T R I A L AiVD E N G I N E E R I N G C H E M I S T R Y
NOTE ON THE DETECTION OF NICKEL IN FATS B y ROBERTH. KERR
Received November 22, 1913
I n testing samples of cottonseed oil, hydrogenated cottonseed oil, a n d mixtures of f a t s containing cottonseed oil, for nickel b y t h e method of Boemer’ a fugitive red color sometimes appears after t h e addition of t h e dimethylglyoxime and ammonia. This color closely resembles t h a t obtained when a trace of nickel is present, b u t differs from t h a t of nickel dimethylglyoxime, in t h a t it is fugitive, appearing immediately after t h e addition of t h e ammonia, never before, a n d fading away almost entirely within a few minutes. I t s appearance is a p t t o be very confusing, particularly t o one not thoroughly familiar with it. As there is no known inorganic body capable of giving such a reaction with dimethylglyoxime, i t would appear probable t h a t this reaction is due t o some organic base contained in t h e oil a n d extracted from it by t h e hot hydrochloric acid. T h e fact t h a t this reaction has been observed only with cottonseed oil, taken together with th’e well known fact t h a t cottonseed contains numerous basic organic bodies, a p pears t o corroborate this view. This hypothesis leads naturally t o t h e conclusion t h a t t h e trouble might best be prevented by t h e complete destruction of all organic matter contained in t h e acid extract. Experiments have upheld this conclusion. A n u m ber of samples which had previously been found t o show t h e fugitive red color t o a marked degree have been found t o show no trace of it after t h e destruction of all organic m a t t e r in t h e acid extract. As a result of this observation t h e following modification of t h e Boemer method is now proposed for t h e detection of nickel in fats. Ten grams of t h e f a t t o be tested are heated on t h e steam b a t h with I O cc. of hydrochloric acid (specific gravity 1.12), with frequent shaking for 2-3 hours. T h e f a t is t h e n removed by filtering through a wet filter paper, t h e filtrate being received in a white porcelain dish. T h e filtrate is evaporated t o dryness on t h e steam b a t h , 2-3 cc. of concentrated nitric acid being added, after i t has been partly evaporated, t o insure t h e destruction of all organic matter. After t h e evaporation is complete t h e residue is dissolved i n a few cubic centimeters of distilled water a n d a few drops of a one per cent solution of dimethylglyoxime in alcohol added. A few drops of dilute ammonia are t h e n added. T h e presence of nickel is shown by t h e appearance of t h e red colored nickel dimethylglyoxime. The amount of nickel present may be estimated by comparing t h e color developed with t h a t developed in a standard solution of a nickel salt. A considerable number of samples, some of which had previously been found t o give t h e fugitive color mentioned above, have been examined b y this method without a n y instance of t h e appearance of color not due t o nickel. T h e residues from t h e evaporation are also purer a n d more readily soluble t h a n when nitric acid is not used. A larger sample of t h e f a t may Chcm Rei Fell u H a m I n d , Jahr. 19, Heft 9.
207
be taken if desired. If this is done t h e amount of hydrochloric acid used for extraction as well as t h e amount of nitric acid added t o the filtrate should be correspondingly increased. Samples as large as zoo grams have been handled with satisfactory results. BIOCHEXIC DIVISION,BUREAUOF ANIMAL INDUSTRY u. s. DEPARTMENT OF AGRICULTURE WASHINGTON
RECENT ANALYSES OF THE SARATOGA MINERAL. WATERS. IV By LESLIERUSSELLMILFORD
Received December 6, 1913
T h a t t h e restoration of t h e mineral waters t o t h e Saratoga basin is being accomplished, is evident b y t h e d a t a which t h e Reservation Commission has secured since t h e State undertook its protective policy with regard t o t h e springs. A great amount of information is available concerning t h e conditions of t h e springs, t h e influences which cause t h e m t o flow a n d also those which affect t h e flow a n d degree of mineralization of t h e water. A few years will have t o elapse before t h e springs will have adjusted themselves t o all natural conditions which were present before t h e gas companies began pumping t h e gas from t h e wells. Whether or not t h e former degree of mineralization will ever be reached cannot be stated, b u t a uniform head, steady flow and fair degree of mineralization has been obtained. The amount of minerals which these waters held in solution was dependent on t h e quantity of carbon dioxide which impregnated t h e water a n d t h e pressure exerted a t t h e mineral water vein. For over twenty years, as was stated in a previous paper, a n exhaustive pumping of this gas was carried on a n d a great depletion of t h e mineral water basin took place, depriving t h e area of a great amount of energy which nature had furnished for t h e maintenance of her natural fountains. Since April, 1 9 1 1 , weekly chlorine a n d alkalinity tests have been made on these waters, by t h e writer, and these determinations show a fairly constant mineralization varying only with slight physical disturbances. d s t h e main constituents of these waters are the chlorides of sodium, potassium, lithium a n d ammonium and t h e bicarbonates of calcium, magnesium, sodium, and barium, these two determinations, chlorine and alkalinity, gave a quick estimation of over 90 per cent of t h e t o t a l mineralization. If either of these should show a change we would have some idea from week t o week concerning t h e congition of t h e springs. DESCRIPTION O F T H E SPRIXGS
T h e Geyser S p r i n g is situated under t h e old n u t a n d bolt factory near Geyser pond. It was drilled in 1870 with t h e intention of securing a supply of fresh water b u t unexpectedly produced mineral water, t h e vein having been struck a t about 142 feet below t h e surface of t h e ground. This sfiring became very famous a n d was frequently called t h e “spouting spring.” Its discovery first suggested t h e idea of boring artesian wells for mineral water and t h e creation of t h e carbonic
208
T H E J O U R N A L 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 CHEMISTRY
acid gas industry. This spring originally had a large flow a n d would throw a stream 2 j feet above t h e ground. This gradually died out a n d t h e spring failed t o flow for m a n y years, so special attention was given
Vol. 6 , No. 3
a considerable depth with foreign matter. It was therefore reamed t o a uniform size, cleaned a n d explored from t o p t o bottom in order t o locate t h e best mineral water vein. T h e tubing was completed in
IONS, RADICALS A N D OXIDES DETERMINED. RESULTSI N MILLIGRAMS PER LITER Geyser spring
Washington spring
r
D a t e of analysis Formula
SiOz. . . . . . . . . . . . . . . . . . . so1. . . . . . . . . . . . . . . . . . . HCOs. . . . . . . . . . n’o3. . . . . . . . . . . . . . . . . . .
-18.71
2 3 Aug. 12, 1905 July 3, 1912
12.39 3.00 5344.61
20.80 14.80 , 13.08 1.40 4353.20 3540.10 Trace Trace None Trace None None Trace Trace None None 1025.10 1340.06 13.64 11.80 0.76 1 .oo 9.46 (a) 11.83 8.40 4.48 (a) Heavy trace (a) 116.40 426.85 116.02 60.60 4.12 2.60 0.48 Trace 136.04 29.00 2010.90 1386.65 2.76 3.60 14 6 2 11.40 2.11 (a)
(a)
POI . . . . . . . . . . . . . BO*. . . . . . . . . . . . . . . . . . . As0.1.. . . . . . . . . . . c 1. . . . . . . . . . . . . . Br . . . . . . . . . . . . . . . . . . I...................... Fe. . . . . . . . . . . . . . . . . . . . F e and A i . , . . . . . . . . . . .
(a) Trace Trace None 6030.43 29.92 3.59 5.26 (a)
A120s... . . . . . . . . . . . . . . .
Trace
Mn . . . . . . . . . . . . . . . . . . .
(a)
C a . . . . . . . . . . . . . . . . . . . . 2913.70 hIg . . . . . . . . . . . . . . . . . . . 424.42 18.24 Ba . . . . . . . . . . . . . . . . . . . . 3.04 Sr . . . . . . . . . . . . . . . . . . . . . 222.35 4123.56 12.35 hyH4. . . . . . . . . . . . . . . . . . . (a) Oxygen t o form AlzOa, Trace Oxygen t o form Fez03. . . ... Trace F.....................
..
...
4
- 1843 Sept.
25, i o 0.69 2192.15 (a) (a) (a)
(a) (a) 1909.64 5.42 32.54
(a) 20.44 Trace (a)
357.47 190,98 (a) (a)
2.65 1277.15
(a) (a) Trace
...
,..
New red spring
. --
5 4, 1912
Old red spring 6
__ a-
41.25 19.96 1618.84 0.09 Trace None Trace None 468.55 2.39 0.19 36.60 66.46 56.31 iYone 231.93 100.28 1.41 Sone 78.20 386.49 0.80 2.25 26.45
I 8 9 10 Aug. 14, 1912 July 17, 1912 ---a- Apr. 9, 1913
51.75 5.35 1138.64 Trace Trace &-one Trace gone 226 24 2.39 0.46 10.72 24.82 26.58 Trace 190.12 53.96 2.82 Trace 32.83 222.68 1.35 2.27 12.48
...
...
Columbian spring c___-
.
79.40 6.39 1463.22 Trace Trace None Trace None 541.87 8.18 0.30 12.56 19.99 14.02 Heavy trace 281.95 73.71 2.70 Trace 38.88 400, 07 1.41 3.45 6.59
35.12 (a)
1818.80
(a) (a) (0)
(a) (a)
2774.28 Trace 37.12 29.96
(a) (a)
(a)
...
47.80 40.13 1315.08 1.77 Trace Xone Trace Pione 225.34 8.05 0.07 9.18 10.85 3.14 h-one 217.28 74.17 1.06 0.10 47.47 234.39 0.61 1.64 1.47 , . .
HYPOTHETICAL FORM O F COMBINATION NHiCl . . . . . . . . . . . . . . . . . (a) LiCl ....... 74.91 KC1. . . . . . . . 395.23 NaCl, . . . . . . . . . . . . . . . . . 9528.76 KBr. . . . . . . . . . . . . . . . . . . 43.88 KI.............. 4.71 NazSOi . . . . . . . . . . . . . . . . 4.44 Trace
............... NaNOz . . . . . . . . . . . . . . . .
Mg(HC03)2. . . . . . . . . . . . Ca(HC0s)s. . . . . . . . . . . . . Fe(HC0a)i. . . . . . . . . . . . . MnsOa. . . . . . . . . . . . . . . . . FezOs. . . . . . . . . . . . . . . . . . AhOs. . . . . . . . . . . . . . . . . . SiO? . . . . . . . . . . . . . . . . . . T o t a l solids in solution dried at 105’ C . . . . . . . Temperature, . . . . . . . . . .
( a ) , not given.
(a) (a)
1363.26 34.44 7.27 2553.77 2913.70 16.74 (a)
33.80 39.40 (a) 21.80 16.75 (a) 43.90 246.84 (a) 1588.80 1951.08 3148.23 17.50 20.00 8.07 1.30 1.00 ( b ) 42.65 2.10 19.36 1.02 Trace Trace (a) Trace Trace (a) None Trace (a) 5058.30 2238.22 139.62 4.90 7.78 (a) Trace 1.14 (a) 364.90 704.24 1149.15 471.40 1728.78 1445.41 26.70 30.08 65.09 (a) Heavy trace (a)
....
Trace 12.39 16953 3 0
(a) 7.8OC Trace
...
26,58 51.75
14.02 79.40
35.12
3.14 47,80
1968.16
2928.22
6994.73
2227.28
1266.50 11.l0C.
2138.00 11.6OC.
20.80
56.31 41.25
7656.20
7023.92
6014.83
3045.54
(a) (a)
5232.00 10.00
...
....
( b ) , equivalent of NaBr reported.
(c),
(a)
7.Z°C.
...
(a)
5.15 3.70 82.93 295.59 12.00 0.10 59.34 Trace 2.43 Trace 358.76 2.00 0.23 446.29 878.58 29.34 None
...
Trace 25. i o
c.
10.23 8.53 66.66 817.85 12.00 0.40 9.46 Trace Trace Trace 275.32 5.10 Trace 447.42 1141.89 39.94 Heavy trace
...
4.48 14.80
(a)
6.74 8.19 60.22 307.12 3.50 0.60 7.91 Trace Trace Trace 362.63 5.33 Trace 324.70 768.75 34.14 Trace
6.68 5.00 146.89 643.05 3.50 0.25 29.52 Trace 0.12 Trace 452.54 2.67 None 603.38 937.82 116.56 None
2175.00 9.5”C.
...
4379.88
(a) (a)
...
...
...
(a)
(a)
(a)
10°C.
...
...
1471 . 0 0 8 O C.
equivalent of N a I reported
1 = C. F. Chandler. Hydrotherapy a t Saratoga by J. A . Irwin. 1872. 2 = Winera1 watersof the U. S. U. S. Dept. of Agric., Aug. 12, 1905. 3,5,7,8,10 = Files N. Y.State Dept. of Health, 1912 and 1913. 4 = J. R . Chilton. Hydrotherapy a t Saratoga b y J. A . Irwin, 1892. 6 = Prof. Appleton Bulletin No. 32, U . S. Geological Survey. 9 = J. E.Steel. “An Analysis of the Mineral Waters of Saratoga, etc.,” 1838.
OTHERR E F E R E N C E S Advertised analyses in various circulars. Therapeutic Saratoga-American Medical Association, June, 1902. hlineral waters of the.U. S . and their therapeutic uses by J. H. Crook, 1899. T h e mineral springs of Saratoga, N. Y.S t a t e Education Dept. Museum. Bulletin No. 159 b y James F. Kemp, 1912.
this bore by t h e Reservation Commission in order t o restore t h e flow. It was found upon careful investigation t h a t t h e bore was very crooked a n d irregular a n d was filled t o
June, 1912, a n d a n excellent spring, spouting many feet above t h e level of t h e flow, was secured. This revival was brought about b y placing water columns on t h e two Champion springs which were wasting about
Mar., I914
T H E J O U R N A L O F I , V D r S T R I A L A N D ENGIA%TEERINGCHEMISTRZ‘
zoo gallons per minute a n d seemed t o be t h e key t o t h e control of t h e mineral water basin. This spring was cleaned again in -4pri1, 1913,a n d now has a flow of about one gallon per minute. The water is strongly mineralized, being low in chlorides b u t high in sodium a n d magnesium bicarbonates. T h e water is a n excellent table water and is served at t h e spring. Old Red Spriizg-This spring is situated on Spring Avenue a n d was discovered in 1 7 j o or about as soon as t h e locality was visited by white men, being t h e next spring Eound after t h e discovery of t h e famous “High Rock.” I n 1784, the first b a t h house was erected 3n the property. From t h a t time up t o t h e acquirement of the spring by t h e Reserration Commission several b a t h houses had been built on t h e site of t h e old one a n d various improvements were made in t h e spring. The flow for many years was sufficient t o maintain t h e baths and allon- t h e water t o be bottled. T h e spring h a d a reputation for thegreat curative properties of its water a n d was a famous resort in the days of Saratoga’s popularity. When t h e state took over this property t h e b a t h houses. bottling house a n d equipment were old. crude a n d unsuitable for continuance under S t a t e ownership so the buildings were taken down. T h e spring itself was also in bad condition, t h e wooden tubing being neither sanitary nor permanent. I n July, 1912, it was GEYSERSPRING decided t o retube t h e spring, a n d t o avoid excavating a n eight inch steel casing was inserted into t h e m-ooden tubing, and t h e space between t h e two packed with concrete. After retubing, t h e natural flow was slightly greater t h a n before b u t was not enough t o meet t h e demands for bathing or bottling without resorting t o pumping. The spring is 2 2 feet deep a n d has a flow of about one quart per minute. The water is moderately mineralized averaging with t h a t of t h e Columbian. I t is one of t h e famous iron springs a n d derived its name from the red coloration due t o iron which t h e water contained. The lVew Red Spring is situated on this same property about I O O feet southeast of t h e Old Red Spring. I t was drilled in 1885 a n d is 60 feet deep. T h e water of this spring is high in iron content a n d is served t o t h e public. I t has a flow of about two quarts per minute and in mineralization it approaches t h e TVashington. W u s h i i z g t o n Spriitg-This spring is situated on South Broadway just above Congress Park in t h e old Clarendon Hotel property. I t was discovered in 1806 a n d is 1 7 0 feet deep. The water does not flow a t t h e surface of t h e ground b u t is obtained b y pumping. T h e spring
209
h a d a celebrated reputation for its iron content and was used t o a great extent. The property does not belong t o t h e Commission b u t is owned b y t h e St. Peters Catholic Church. Various scientific observations, which have been taken, show an improrement in this spring. T h e Columbiuit Spring is located in t h e famous Congress Park, just west of t h e park entrance and on Broadway. I t is one of t h e oldest mineral springs having been opened by a pioneer, Gideon P u t m a n , in 1806. This is also a chalybeate water being closely connected with t h e T a s h i n g t o n Spring as like changes in water levels are recorded simultaneously in both springs. I n April, 1913,t h e uooden tubing mas cleaned and a n iron casing inserted i n it so as t o insure sanitary conditions. The spring is eleven feet deep and its waters are moderately mineralized. STATE
HYGIEXIC LABORATORY
ALBANY.A-Ew YORK
THE DETERMINATION OF HARDNESS IN NATURAL WATERS By C L A R E K C E
BAHLMAhs
Received December 1, 1913
Lime hardness, magnesium hardness, and total hardness constitute t h e three primary determinations in industrial water analyses. -4n allcalimetrical method for total hardness b y use of soda reagent is described in t h e American Public Health Association’s Standard Llethods of TTater Analysis. Mention is made t h a t errors due t o solubility of t h e precipitated calcium and magnesium salts are not entirely obviated in this method, and t h a t t h e most accurate figure for total hardness is t h a t computed from t h e results for calcium a n d magnesium. This is true when these bases are determined gravimetrically, b u t when t h e magnesium is determined by Pfeifer a n d Wartha’s lime water method as described in t h e 190j edition of Standard AIethods, t h e results are unsatisfactory. For this reason undoubtedly, this method has not been inserted in t h e 1912 edition of t h e above publication; in fact no volumetric method is given for either calcium or magnesium. For many industrial purposes, rapidity in arriving a t results is preferred to extreme accuracy, and simple volumetric methods are entirely satisfactory for ordinary purposes provided t h e deficiencies and limits of accuracy of t h e method are known. This paper is a summary of a n investigation t o ascertain t h e accuracy of results obtained by certain volumetric procedures for calcium, magnesium a n d total hardness. The tests were made upon fifteen samples of natural waters obtained from nearby rivers, springs and wells. a n d showing wide ranges in calcium a n d magnesium content as well as in organic matter. C A LCI L-11 H A R D N E S S
The ease of manipulation and accuracy of t h e permanganate titration of calcium oxalate suggests its applicability in water analysis. Depending upon t h e hardness of t h e water, volumes of I O O cc. t o joo cc. will give workable precipitates. Fifteen waters ranging
