DETERMINATION OF THE RICHNESS AND PURITY OF INDIGOES.
It is evident that the commercial form and the high price of this drug favor fraud, and the desire to illicitly introduce foreign substances into the paste. It is important, therefore, that the purchaser should carefully ascertain the actual value of the article which he is to use. He should know not only the proportion of indigotine contained, which varies in the commercial indigoes from twelve to seventy-five per cent, but the hardness and density. A good indigo ought to have qualities which can be recognized by the eye and touch alone. The first and the only examination ordinarily made by purchasers is in respect to the physical qualities of the article. Different pieces are selected, and their fresh fracture is attentively observed. The purchaser observes whether the squares are like each other, and if the parts of the same piece present the same tint. He determines the porosity by the simple means of applying his tongue to the fresh fracture. The more rapid the adherence of the tongue, the more porous the indigo. By scratching the piece with his finger-nail, he determines the extent of the coppery reflection, — an important test.
From all these characters, taken together, the purchaser can form quite a correct idea of the value of indigoes in general; and the greater number of dyers, both in Europe and this country, are satisfied to make their purchases with only this physical examination. The most experienced dealers in this country make no other examination than the physical one. An eminent indigo broker in Boston has permitted me to copy the following memoranda for the physical examination of indigo from his notebook.
The chief signs of good indigo are its lightness, feeling dry when touched, and, when broken, appearing of a beautiful violet blue. Good indigo swims in water; if thrown upon burning coals it emits a violet-colored smoke, and leaves but little ashes.
In selecting indigo the large regularly formed cakes should be preferred,—those of a fine, rich blue color, extremely free from the white adhesive mould, [1] and of a clean, neat shape. When broken, it should be of a bright purple cast, of a close and compact texture, free from specks or sand, and when rubbed with the nail should have a beautiful shiny coppery appearance; when burnt in a candle it should fly like dust; that which is heavy and dull colored should be rejected. Indigo is estimated and classed in commercial language, as follows: fine blue, ordinary blue, fine purple, inferior purple, and violet, strong copper, and ordinary copper. It is purchased by the factory maund (74⅔ lbs. The Bazaar maund is 82²⁄₅₀ lbs.), packed in cases containing on an average 2¼ cwt., dammered (pitched) and covered with gunny bagging.
Still, in making large purchases, as a measure of wise precaution the chemical test should be added. This is used to ascertain the proportion per cent of indigotine which a given indigo has. The determination of the quality of indigotine contained is not alone sufficient to fix the value of an indigo. With an equal yield of indigotine, the indigoes are always to be preferred which have a light and soft paste; and for the preparation of the indigo vat the preference should be always given to the violet red rather than to the clear blue indigoes.
The chemical works which treat of this subject give elaborate details of a great number of processes for determining by chemical tests the amount of indigotine, or the coloring material in indigoes. To give these numerous processes would only confuse the reader. In our own confusion upon this subject we submitted the descriptions of these various processes to one of the most eminent and practical of American chemists, Dr. Charles T. Jackson, an official State Assayer for the State of Massachusetts, who has had much experience in testing indigo, with a request that he would describe the process which he approves and practises. He has obliged us by the following communication:—
Boston, Nov. 21, 1872.
No. 47 Court Street, Room 4.
John L. Hayes, Esq.
Dear Sir,—In reply to your inquiry as to the simplest method of analyzing indigo, I would say that I first ascertain the amount per cent of earthy matters and metallic oxides, in the samples brought to me, by burning a weighed quantity in a counterpoised platinum crucible, until all organic matters are removed or consumed, and then weighing the ashes obtained. The ash is then subjected to analysis in the usual way, and lime, alumina, peroxide of iron, and some other earthy impurities are separated.
Then, to determine the amount of coloring matter, or indigotine, I make use of a standard sample of pure reduced indigo, which is dissolved in the most concentrated sulphuric acid, and diluted with water after solution. Then I ascertain how much bleaching powder (chloride of lime) is required to dissolve the solution. This is the quantity required for absolutely pure indigo.
Now, the indigo of commerce does not contain more than say from forty or fifty per cent of pure indigotine, and of course will require a smaller quantity of bleaching powder to decolor it; or the quantity of bleaching powder to decolor a given weight of pure indigo may be weighed out, and the sample to be compared having been dissolved in strong sulphuric acid, and diluted with water, is to be poured in and stirred or shaken well until the point of decoloration is ascertained. In this case it is best to weigh out at least twice as much of the sample to be tested as was used of pure indigo, and to measure the solution in a graduated glass vessel,—an alkalimeter, for example,—so that by measure we may know exactly how much of the sample we add to the solution of bleaching powder. Thus the relative coloring values of the samples may be readily ascertained.
If you have no purified indigo on hand, you can make a good comparative trial of your samples against a perfectly good sample of Bengal indigo, which may be kept for a standard of comparison. Very useful practical results may thus be obtained.
It is well, however, to keep on hand a standard sample of pure indigo, prepared from reduced or white indigo, as directed by Berzelius (vol. vi. page 3, French ed., 1832), and in Muspratt’s Chemistry applied to the Arts (Dyeing, Indigo).
In the analysis by reduction of indigo, the process is simply as follows: Reduce the indigo to fine powder, and weigh it; weigh out an equal quantity of pure quicklime (made from pure white marble). Measure in a graduated vessel a certain volume of water. Slack the lime with a portion of this water. The rest of this water is to be used in rubbing up the indigo in a mortar. Then the slacked lime is to be mixed with the indigo, rubbing the substances well together. Introduce the whole into a large flask; 1½ to 2 litres (about 3 to 4½ pints) of water is required for 1 gramme (or about 15 grains of indigo). The flask and contents are then to be exposed to a heat of from 176° to 190° F. for some hours. This is best effected in a water bath. By this digestion the lime is made to combine with the indigo brown, and the coloring matter is set at liberty. Dissolve in the liquor a little protosulphate of iron, exempt from copper, and reduced to a fine powder. The flask is to be corked and well shaken, and allowed to cool. When the sediment is settled, decant the clear solution by means of a syphon into a graduated glass. The coloring matter oxidizes by exposure to the air; and to favor this oxidation and to keep the lime in solution, add muriatic acid to the liquor. When the liquor has become clear, filter and collect the precipitate on a weighed filter, which wash with hot water, and dry at a temperature of 212° F. Thus we can learn, by weighing the filter again, how much indigotine is contained in the sample.
If we make use of 200 measures of water, and have drawn off 50 measures of the solution to oxidate, and this 50 measures has produced 10 grains of indigo, the whole sample evidently contained 40 grains of indigo blue.
This method serves both for an assay of the sample and the production of a standard sample of pure indigotine. The operation may be carried on upon a larger scale for the manufacture of a standard sample.
Yours truly,
C. T. Jackson.
Dr. Jackson adds the following note:—
In the processes given I have not referred to the qualitative analysis or testing for all the kinds of adulterations, but have given only valuation of the coloring power of indigo.
I have had occasion to search indigo for Prussian blue, an occasional adulterant. This is ascertained by caustic potash, which becomes in part an oxide if Prussian blue is present. This acidulates with muriatic acid, and, tested with sulphate of iron, proves, by formation of Prussian blue, the presence of the ferrocyanide of potash in the solution, and hence Prussian blue in the indigo. Lime and clay are the usual adulterants, and oxide of iron is often present accidentally or from the clay adulterants. Starch and flour are rarely used, as they add little to the weight.
C. T. J.
Many experienced purchasers in this country pay no regard to this mould, as it weighs scarcely any thing.—Ed.