26
T H A J O U k N A L O F I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
readjustment of the polarized particles of iron and theiiorientation t o the direction of earth magnetism a t t h a t point.’ When, after the drill is magnetized, i t is repeatedly passed (in the process of drilling) up and down through the easing in the same position and direction of movement, i t gradually imparts its magnetism to the casing. Sometimes in driving the casing, by means of a heavy weight, vibrations are set up much the same as those in the drill and induce more or less magnetism. Opposite the Peerless and Magnetic Springs and about one hundred (100)feet south of the celebrated High Rock, is situated the Emperor Spring. This spring was cleaned and retubed t o a depth of I I 7 feet in April and gives a water twice as strongly mineralized as the water showed before retubing. It is just back of this spring where the escarpment of the geological fault, which gave birth t o the mineral springs, is best displayed. This rocky cliff in now exposed a s the buildings with their attendant refuse and rubbish heaps, which formerly concealed it, have been removed. The water of the Emperor Spring flows freely a t the surface of the ground and resembles very closely that‘ of the Peerless. It has a good supply of gas and is suitably mineralized. The water is drunk a t the spring, free service being maintained. The excess or overflow from the bowl is piped across the road to the Magnetic bath house, where i t is used for bathing. The Putnam Spring was discovered in 1890 and is about 2 0 0 feet deep. This was known as the Levingston Spring and is north of the Patterson Spring and separated from it b y Phila Street. This Spring is situated in the Congress Park group and belongs to the milder class. The Putnam has not been exploited commercially, except in connection with the mineral water baths at the Levingston bath house, which stands upon the same lot and under which the waters of the spring emerge. This spring does not flow a t the surface of the ground, so the sample for analysis was obtained b y pumping. The analysis is given for its scientific interest and completeness of the series. The water is high in sulfates. It is not used a t the bath house at present, as a n arrangement has been made whereby the surplus water from the Hathorn Spring No. I is pumped to the baths and used for bathing. A few feet south of the Putnam Spring is the Patterson Spring. This Spring was discovered in 1888 and is 2 5 0 feet deep, 190 feet being through solid rock. This spring is in the Congress Park area on property north of and adjoining the Hathorn Spring No. I . I t s relations t o the latter spring are intimate, as have been shown in recent experimental work on the pumping of this spring and noting the effect on the mineral content, flow, and other physical conditions of the Hathorn No. I , This water is also high in sulfates and is very similar to the Putnam. The waters of the Patterson have been deemed valuable for certain disorders of the human body, but they have not had the reputation of some of the other 1 Underground-Water Papers 1910. Supply Paper 258.
U. S . Geological Survey Water-
Jan.,
I913
waters. The Patterson used t o appear on the market as a bottled water, but the spring is not being exploited now. SANITARY ANALYSES
I n order to insure the wholesomeness and purity of the waters, sanitary and bacteriological analyses of the springs have been made from time t o time. The sanitary analyses have shown small amounts of free and albuminoid ammonia, low nitrates, and nitrites. The bacteriological examinations showed a very low count and absence of B . Coli, which indicates high sanitary purity. STATEHYGIENIC LABORATORY STATE DEPARTMENT O F HEALTH ALBANY, NEWYORK
THE QUANTITATIVE SEPARATION OF MIXTURES OF CERTAIN ACID COAL TAR DYES’ By W. E. MATHEWSON Received January 22, 1912 INTRODUCTION
The use of immiscible solvents for separating mixtures of acid coal t a r colors is discussed in most standard works on the subject. Loomis’ gives data concerning the solubility of a large number of common dyes, and Seekers has published qualitative separations of Orange I and Naphthol Yellow S from certain other dyes depending on the use of amyl alcohol. In such procedures any variation made in the acidity has been attained by using acids of different degrees of dissociation, as acetic acid and a mineral acid, and not by adding varying amounts of the same acid. Chiefly with the object o making a quantitative separation of the colors permitted in foods (Naphthol Yellow S, Ponceau 3 R, Orange I, Amaranth, Light Green SF Yellowish, Erythrosin and Indigo Carmin) , 4 their ratios of distribution between dilute hydrochloric acid of different concentrations and certain immiscible solvents were determined.5 The data indicated a method t h a t gives good results in practice and is of quite general applicability. Some figures have also been obtained for other similar colors that will show where separations can be made and can also be applied for qualitative differentiations. DATA OBTAINED
I n the accompanying table the figures given show the percentage of color remaining in the aqueous layer after shaking with a n equal volume of the immiscible solvent. A solution containing a quantity of dye equivalent to 0.1000gram of pure color was diluted t o 50 cc. with water and standardized hydrochloric acid, sufficient of the latter being taken t o give the solution exactly the acid normality desired. I t was then shaken out with 50 cc. of the solvent. (This shaking was continued for five minutes with dichlorhydrin, two minutes with the ot’her solvents.) Published by permission of the Secretary of Agriculture. U. S. Dept. Am., Bureau of Chemistry, C h c . 63. 3 “Allen’s Commercial Organic Analysis,” 4th Ed., Vol. V. 1 U.S. Dept. Agr., Office of the Secretary, Food Inspection Decision ‘76. 5 Distribution ratios of the permitted dyes betweeq dilute hydrochloric acid and amyl alcohol were sent out by the writer in April, 1911, in a circular letter in connection with the cooperative work of the Association of Official Agricultural Chemists. 1
2
Jan., 1913
T H E JOURNAL. OF I N D U S T R I A L A N D ENGINEERIhrG CHEMI’STR Y
TABLEI-PERCENTAGEOF COLORIN THE WATERSOLUTION AFTER SHAKING WITH AN EQUALVOLUME OF IMMISCIBLE SOLVENT Normality of hydrochloric acid in water layer SOLVENT: AMYLALCOHOL before shaking A
4
2
1
x
--
V8
‘/a
1/18
1/32
Percentage of color in water solution after shaking COLORS 7 11 17 27 43 Naphthol Yellow S No. 4.. . . . . 4 4 2 .. 0.5 1 Orange I No. 8 5 . . . . . . . . . . . . . . . 78 7 21 43 64 .. 1 3 Ponceau 3 R No. 5 6 . . . . .. .. 15 52 82 93 Amaranth No. 107.. ..... 5 .. .. .. 99 99 Light Green S. F No. 435. 9 0 95 97 0 . . . . . . . . . . .. .. Erythrosin No. 5 1 7 . . .. .. .. Indigo Carmin No. 692.. 34 51 89 96 99 .. .. 61 . . . . .. .. 36 Fast Yellow No. 8 . . 2 Crocein Orange G No. 13 . . . . .. 1 .. .. . . . . 18 Orange G No. 14.. 58 . . .. .. Ponceau 2 R No. 5 5 . . . . 2 . . 14 . . . 39 .. Crystal Ponceau No. 64.. . . . . . . . .. 8 . . 62 . . 2 Fast Red B No. 6 5 . . ..... . . . . . 16 .. 11 17 Resorcin Yellow No. 84.. . . . . . . .. 5 .. 2 3 . . . . . . Orange I1 No. 86.. .. .. Brilliant Yellow S No. 89. . . . . 73 . 90 . . .. .. 47 Tartrazin No. 9 4 . . . . . . . . . .. 88 1 Metanil Yellow No. 9 5 . . . . . . .. 1 1 .. 0.2 Fast Red A No. 102.. .. .. .. 1 .. 4 Fast Red C No. 103.. . . . . . . . . .. 68 Fast Red E No. 105.. .... . . . . 1 .. 17 .. New Coccin No. 106.. . . 15 . . 75 .. Scarlet 6 R No. 108.. . . . . 4 1 80 95 . . . . .. . . .. . . 20 Resorcin Brown No. 137.. .. 8 . . 10 .. Cotton Scarlet 3 B No. 146. 2 .. Congo Red No. 2401.. .... . . . . . . .. . . . . . . . . . . .. .. Azo Blue No. 2872.. .. 1 2 Chrysophenin No. 3 2 9 . . .. 25 Guinea Green B No. 4 3 3 . . . . . . 4 8 32 .. Acid Magenta No. 462.. .. 93 .. .. 75 SOLVENT: DICHLORIN. .. 15 .. . . Naphthol Yellow S No. 4.. . . . . Ponceau 3 R No. 5 6 . . 37 . . . . . . .. . . .. Orange I No. 8 5 . . . . . . . . . . . . . 4 . . . . .. .. .. Amaranth No. 107.. ..... 95 .. . . . . 15 . . 17 . . Light Green S F No. 435 Indigo Carmin No. 692.. , . . . . 91 . . . . . . .. . . .. Acid Magenta No. 462,. . . . . 86 . . . . . . SOLVENT: AMYLACETATE. .. Naphthol Yellow S No. 4.. 22 33 48 .. . . .. Ponceau 3 R No. 56.. 95 96 97 .. SOLVENT: ETHER. Naphthol Yellow S. No. 4. 94 97 .. .. 97 97 Orange I No. 8 6 . . Color acid nearly insoluble in both layers. 2 Similar to Congo Red but color acid more soluble in alcohol.
....
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After separation of the liquids, which takes place very rapidly with strongly acid mixtures but more slowly with low acid concentrations, the lower layer was drawn off and the percentage of dye remaining in the water layer estimated. All color determinations were made by Knecht and Hibbert’s method,I a standard solution of pure amaranth being used to titrate back any excess of titanium chlorid added. The extractions were made a t room temperature, z 7 O to 30° C. Of the coloring matters used, the permitted colors were from analyzed commercial samples of excellent grade. The others were commercial samples of good quality, their examination, however, being limited in most cases to a determination of total color and a comparison of their reactions with the description given in Heumann and in Schultz and Julius (transated and enlarged by A. G. Green, 1904). The serial numbers used in the latter work are given with the names of the dyes. New Reduction Methods in Volumetric Analysis, 1910.
2’1
D I S C U S S I O N OF RESULTS
In applying the data given in the table for effecting the quantitative separation of two colors the following procedure, or some simple modification of i t , has been practiced: The solution containing 0 .z to 0.4 gram of color (depending on the nature of the dyes) is treated with sufficient water and hydrochloric acid of known strength t o bring its volume to about 5 0 cc. and its acid concentration t o that point for which the difference in percentage of color extracted for the two dyes is near its maximum. The solution is then shaken out with the immiscible solvent, being passed in succession through three or four separatory funnels each containing 50 cc. of the latter. The portions of the solvent are washed with 50 cc. of hydrochloric acid of the same normality as the solution, being passed successively through the separatory funnels in the same order as was the original solution, and this operation is repeated with one or two fresh amounts of the hydrochloric acid. The dye relatively more soluble in water is determined in the combined washings and extracted solution. The second dye is removed from the solvent by shaking with water, very dilute caustic soda, or, more quickly, with dilute caustic soda after the addition of some gasoline, or similar substance in which the color is insoluble. Assuming the distribution ratios to remain constant, this procedure using four funnels and making three washings gives for a pair of colors whose “distribution numbers ” (as the percentage numbers given in the table may be called) are 80 and 2 0 , respectively, a separation of 9 8 . 3 0 per cent. for each color. With distribution numbers 90 and IO four funnels and three washings give a calculated separation of 9 9 . 7 3 per cent., and the same is obtained with distribution numbers 8 1 . 8 and 5 . 3 if the solvent in which the dyes are relatively more soluble be taken in portions one-half the volume of those of the other liquid. If the second, third, and fourth funnels be given a fifth washing, the third and fourth funnels a sixth, and the last funnel a seventh washing, the calculated loss for the color more soluble in the solvent layer is 0 . 7 6 per cent., while the percentage of the other dye removed is relatively much increased (to 9 9 . 9 9 per cent ) . I n most mixtures the progress of the separation is always apparent. In practice, because of incomplete extraction and separation, and especially on account of uncertainty due to small amounts of subsidiary dyes always present, i t is necessary to increase the number of successive extractions. The distribution ratios change somewhat with varying dye concentrations, the color being relatively more soluble in the non-aqueous layer a t very high dilutions. The formation of esters of the color acids is a possible source of difficulty, but it is not believed to take place. With amyl alcohol as solvent it is almost always desirable to make the original solution more strongly acid than is indicated by the distribution data and use relatively more portions of the washing liquid. Of the permitted colors, Naphthol Yellow S is best
28
T H E J O U R N A L OF INDUSTRIAL. A N D E N 6 l h l E E R I N c C H E M I S T R Y
separated from Orange I b y washing the amyl alcohol solution of the color acids with strong salt solution, care being taken t h a t not too much color is present. With a solution containing 20 grams of salt and 0.04 gtam Naphthol Yellow S per IOO cc. and shaken with a n equal volume amyl alcohol, 97 per cent. of the color is retained by the water. With a similar solution containing 0 . 0 7 gram Orange I, the water layer contains 1 . 5 per cent. of the total color. With higher concentrations some color may be salted out in solid form, b u t this does not interfere if the amount is small. Erythrosin being quantitatively removed from slightly acid solutiona b y amyl acetate, ether, or amyl alcohol, its separation' from sulphonated colors presents no difficulty. 1
Jan., 1913
cc. concefitrated hydrochloric acid and passed through four funnels containing each 60 cc. of amyl acetate. The amyl acetate portions were washed with 3 portions of 30 cc. each of four-normal hydrochloric acid, a fourth washing given t o the last three funnels, a fifth t o the last two, and a sixth t o the last one. From the extracted solution and washings, the Ponceau was taken up with amyl alcohol, the latter diluted with gasoline, the color removed with dilute caustic soda and determined. Total color Was determined and yellow estimated by difference. Ponceau, found 0.1132 gram = 97 per cent. Yellow, found 0 , 1 0 8 9 gram = 100.5 per cent. AMARANTH AND ORANGE I
I
ANALYSES O F MIXTURES
Analyses of a number of mixtures were made with the following results. In all cases the last washings were free or practically free from colors. As the determination of total color is convenient and ac'curate, i t was in most cases made, together with t h a t of t h e dye reacting wit'h the lesser amount of titanium trichlorid. NAPHTHOL YELLOW S AND LIGHT G R E E N S F YELLOWISH
Twenty cc. of a solution containing, in this volume, gram green and 0.1083 gram yellow was treated with 20 cc. five-normal hydrochloric acid a n d diluted t o 50 cc., then shaken out with three portions of amyl alcohol of 50 cc. each. The amyl alcohol wag washed with two portions (50 cc. each) of two-normal hydrochloric acid. Green was determined in the extracted solution and washings, total color in another aliquot of the original solution. Green, found 0.0975 gram = 9 7 . 5 per cent. Yellow, found 0.1085 gram = IOO per cent. 0.1000
NAPHTHOL YELLOW S, O k A N G E I, AND INDIGO
CARMIN
Thirty cc. of solution containing 0.1000 gram orange, 0.1000 gram blue, and 0.1083 gram yellow was treated with 2 cc. five-normal hydrochloric acid and shaken through three funnels containing each 60 cc. amyl alcohol. The latter was then washed with two portions of dilute hydrochloric acid (2 .cc: 2 8 cc. water, or onefive-normal hydrochloric acid third normal). The second and third funnels were then washed with a third portion of acid (30 cc.) and the third funnel with a fourth portion. The blue was determined directly in the extracted solutions and washings. The amyl alcohol was then washed with four portions of 1 2 0 cc. each sodium chlorid solution (zoo grams per liter). The second and third funnels were washed a fifth time and the third a sixth time. Blue, found 0.099 gram = 99 per cent. Orange, found 0.0985 gram = 9 8 . 5 per cent. Total color was determined and yellow estimated by difference. Yellow, found 0.1080 gram = 9 9 . 5 per cent.
+
PONCEAU 3 R AND NAPHTHOL YELLOW S Twenty cc. of solution containing 0.1083 gram yellow and 0.1168 gram Poaceau was treated with 20
Twenty cc. of solution containing, in this volume, ofange and 0 .I 723 gram Amaranth was treated with 2 cc. five-normal hydrochloric acid and 28 cc. water and passed through two funnels containing 50 cc. each of amyl alcohol. The latter were then washed twice with 50 cc. volumes of eighth-normal hydrocliloric acid. Amaranth was determined directly in the extracted solution and washings. Total color was determined in a n aliquot of the original solutio&. Amaranth, found 0 . 1 7 3 1 gram = 100.5 per cent. Orarige, found 0.0995 gram = 9 9 . 5 per cent. 0.tooo.'gram
LIGHT G R E E N S F YELLOWISH, AMARANTH, PONCEAU
3
R,
AND ORANGE I
Thirty-seven cc. solution containing, in this volume, gram green, 0.1000 gram Ponceau, 0.1000 gram orange, and 0 . I 162 gram Amwanth was treated with 2 0 cc. of concentrated hydrochloric acid a n d shaken through three funnels containing each 50 cc. amyl alcohol. The latter was washed with three portions (50 cc.) of four-normal hydrochloric acid. Green was determined in the extracted solution and washings. Two more funnels containing 50 cc.-'portiond of amyl alcohol were now added and the series washed with five 5 0 a. amounts of fourth-normal -hydrochloric acid. The ,first washing was colorlessan coming from the fourth funnel and was discarded, The second, third, fourth, and fifth,funnels were given a sixth additional washing, the last three a seventh, the last two a n eighth, and the last one a niqth. The extracted solutipn afld washings were combined, nearly neut r a l j z d with two-normal ammonium hydroxid, evaporated t o about 150 cc., and Amaranth determined. , A second portion of 37 cc. of the original solution was treated with 2 cc. of five-normal hydrochloric! acid and made up t o 75 cc., then shaken out with dour 2 5 ac. portions of amyl alcohol. These were washed with five portions (75 cc. each) sixteerith-normal hydrochloric acid. The last three funnels were given a sixth washing, the last two a seventh, and the last one a n eighth. Each of the last three amyl alcohol portions was diluted with I O cc. of light gasoline before shaking out with its final portion of washing liquid. After further addition of gasoline, the orange was removed with dilute caustic soda, and estimated. Total color was determined in a n aliquot of the origi0.1000
Jan., 1913
T H E J O U R N A L OF I N D U S T R I A L A N D EiVGINEERING C H E M I S T R Y
nal solution and the Ponceau found by difference.' Green, found o 098 gram = 98 per cent. Amaranth, found o 116 gram = IOO per cent. r r Orange, found 0 . 1 0 2 gram = 1 0 2 per cent. Ponceau, found o 098 gram = 98 per cent. POXCEAU
3
R A X D INDIGO. C A R M I X .
29
it must be remembered that the relative intensity of the coloration of the two layers is usually somewhat different from their relative concentration and may be very much so. NEWYORKFOODAND DRUG INSPECTION LABORATORY
-
Twenty-eight cc. of solution cbnpining o . 1000 THE ALCOHOL REQUIREMENT OF THE PURE FOOD AND gram Ponceau and o 1000gram blue was treated with DRUG LAW AND THE ACCURACY OF ALCOHOL ASSAYS 2 cc. five-normal hydrochloric acid and shaken with OF PHARMACEUTICAL PREPARATIONS . " four 50 cc. portions of amyl alcohol. Three portions B Y c. n. BRIGGS (50 cc. each) of third-normal hydrochloric acid were Received Aug 19, 1912 then passed through the series of funnels, a fourth Before the Pure Food and Drug Law went into washing given to the last three, a fifth'iQ the last two, eff%ct i t is doubtful if manufacturing pharmacists and a sixth t o the last one Blue was determined paid very much attention to the accurate determinadirectly in the extracted solution and washings Total tion of the alcohol in their preparations. They were color was estimated and the Ponceau obtained b y in position to know how much alcohol went into each difference. pkparation and whether this amount of alcohol Blue, found 0 . 1 0 2 gram = 1 0 2 per cent. could be actually recovered was a matter of little Ponceau, found 0.099 gram = 99 per cent. momept. However, on the advent of the Pure Food and Drug Law, i t became necessary to state on the LIGHT G R E E S S F YELLOWISH A N D INDIGO CARhlIN Twenty-three cc. solution containing 0.1000 gram label the percentage of alcohol in every preparation, blue and 0.1000 gram green was. treated with 2 cc. and, the problem of determining this exactly began five-normal hydrochloric acid and shaken out with to. assume serious proportions. It is doubtful if the six 2 5 cc. portions of dichlorhydrin (satuyated with framers of the Pure Food and Drug Law had any water), The dichlorhydrin portions were passed suc- thought of requiring a statement of the alcohol concessively through four funnels containing each 2 5 cc. tent of ordinary galenicals such as are put out by the of fourth-normal hydrochloric acid saturated with manufacturing pharmacist, but it is probable that dichlorhydrin. They were then combined, diluted their real intention was to require the alcohol content with benzol, the color removed with water, and titra- o f . those medicines sold directly to the laity. In ted Total color was determined and blue found by order to do this it was necessary to include all pharmaceutical preparations containing alcohol. difference. The first interpretation of the Law, that the maxiGreen, found 0.099 gram = 99 per cent. mum amount of alcohol could be stated on the label, Blue, found 0 . I O I gram = I O I per cent. was a very practical one and did not cause any undue X A P H T H O L Y E L L O W S A N D AMARANTP hardship to pharmaceutical manufacturers. I t was A I O cc. solution containing 0.1273 gram Amaranth only necessary to know the amount or alcohol which and 0.1083 gram yellow was treated with a n equal went into a n elixir, or in case of a fluid extract the volume of concentrated hydrochloric acid and' shaken amount which was usually obtained, to be able to through three funnels each containing 40 cc. amyl fix upon a maximum percentage for a label claim which acetate. The amyl acetate portions were then washed would not only be safe from the manufacturers standwith 20 cc. of six-normal hydrochloric acid and the point but would also not deviate excessively from the last two funnels given a second washing. The Ama- actual alcohol content. ranth was determined in the extracted solution and The later belief, however, that the actual perwashings The Naphthol Yellow S was removed centage of alcohol must be stated on the label, is a from the amyl acetate by washing with a little dilute matter of grave concern to the manufacturing pharmacaustic soda solution and determined direct1y.z cist. To meet this requirement two courses are Amaranth, found 0.128 gram = io1 per cent. open : Yellow, found 0 . 1 0 8 gram = I O O per cent. I. To assay every preparation for 'alcohol and - I n using the table to distinguish qualitatively bestamp t h e actual content on the label. tween such colors as Amaranth and ' t h e other fast 2. To have the label printed with a standard conreds, or Guinea Green and Light Green S F Yellowish, tent of alcohol for each preparation and to adjust 1 The separation of Orange I from Ponceau 3 R by means of hydroeach individual lot to the standard. chloric acid and amyl alcohol alone gives high reiults for the orange, due The first method requires the special stamping of to the fact that the distribution ratio of the Poncequ changes rather markedly with varying dye concentration Instead of the Drocedure given every bottle and is expensive It also shows variaabove. involving the use of gasoline, the Amaranth, green, and most of the tion in the alcoholic content in the individual lots Ponceau may be removed with surteenth-normal acid, and the remainder of a preparation which is a p t to cause distrust on the of the Ponceau with five per cent sodium chtoride solution Four funnels are required. Four washings are given with the hydrochloric acid, part of the pharmacist and require an undue amount then three with 5 per cent salt, and the last funnels washed with one, two, of explanation on the part of the manufacturer. Anyand three additional amounts of salt solution, respectively Amyl alcohol, acid, and salt solution are taken in 50 cc. portiotls, and the amount of one who has had anything to do with the manufacOrapge I present should not exceed 0 0 4 g ture of fluid extracts, for example, knows that i t is 2 Naphthol Yellow S is conveniently titrated in tartrate solution, a impossible to make several lots of the same kind little Light Green S F Yellowish being added to serve as mdroator.
