the filter drains the edges and sides and the crystals are washed down, with about 5 or 6 cubic centimetres of water, the water serving quite as well for these washings, etc., as the mixture recommended. When drained the filter is closed together and lightly pressed between folds of bibulous paper, and then dried at 100°C. It is better not to put the crystals back into the flask to dry, but to dry and weigh them in the filter, and dry and weigh the flask separately. Then the morphia should be detached from the filter, and the filter be re-weighed, this second weight being subtracted in getting the account of the morphia. The only use in taring and marking the filter before it is used is that the difference in the weight before and after it has been used serves as a good and useful indication of how well the crystals have been washed, because the increase of weight in the filter is from the quantity of the ethereal solution which has dried in it. When it is very much heavier than it was before use, then the morphia also is a little heavier than it should be from some little of this solution having dried it.

It seems somewhat pretentious to call these mere changes in detail a modification of the process of Prof. Flückiger, but they are by no means unimportant, and therefore the writer submits them under the following title, and claims that this is the best process yet offered. He may apologize for giving it in so much detail, but this is done advisedly, as the minutiæ are given in the hope that pharmacists who may be unaccustomed to such work may thus be induced to try it. While, if the Committee of Revision choose to adopt it, they can properly condense it, this pamphlet being always accessible as a process, with a running commentary, which this writer found so rare and yet so useful in his younger days.

OPIUM ASSAY.

FLÜCKIGER'S PROCESS MODIFIED BY E. R. SQUIBB.

Take of Opium in its commercial condition 10 grammes=154.32 grains.

If commercial powdered Opium is to be assayed for morphia, it should not be dried, but should be weighed for the assay in the condition in which it is found in the market, and in which it is to be dispensed.

If commercial moist Opium is to be assayed for morphia, the taking of the sample for assay is a matter of great importance, because it is highly probable that, unless by accident, no two lumps of a

case are of exactly the same morphia strength. Hence it is that assays of moist opium are at best only close approximations, though sufficient for practical purposes.

About every tenth lump of a case should be sampled by cutting out a cone-shaped piece from the middle of the lump, with an ordinary pocket knife. Then from the side of each cone, a small strip is taken from point to base, not exceeding say half a gramme from cones which would average 10 to 15 grammes, and the cone is then returned to its place in the lump. The little strips are then worked into a homogeneous mass by the fingers, and the mass is then wrapped in tin-foil, moist cloth or paper, to prevent drying, until it can be weighed off for assay. When opened to be weighed off, it is best to weigh at once three portions of 10 grammes each. In one portion the moisture is determined by drying it on a tared capsule until it ceases to lose weight at 100° C. 212° F. Another portion is used for immediate assay, and the third is reserved for a check assay if desirable.

Put the weighed portion into a flask, or common wide-mouthed vial of 120 c.c.=4 fluid ounces capacity, tared and fitted with a good cork. Add 100 c.c. 3.3 fluid ounces of water,-distilled water by preference, but this is essential only when common water contains an unusual amount of inorganic matter,—and shake well. Allow it to macerate over night, or for about 12 hours, with occasional shaking, and then shake well and transfer the magma to a filter of about 10 centimetres=4 inches diameter, which has been placed in a funnel and well wetted. As it is the shaking which accomplishes the object here in view rather than the standing, the time of maceration can be easily shortened even to three hours, if the shaking be frequent and active.

As rare exceptions, some powdered opiums will be found which through natural conditions give a magma with water which will not filter, or filter so very slowly that the water solvent becomes impracticable. When this is discovered, the magma is thrown away and a fresh portion of powder is taken. Wash this by agitation in the bottle with 30 c.c.=1 fluidounce of ether (s. g. 728), transfer it to a filter, rinse the bottle with 20 c.c.66 fluidounce more ether, and pour this onto the opium in the filter. When this has passed through, wash the filter and opium with 10 c.c.=33 fluidounce more ether applied drop by drop around the edges of the filter and on the surface of the opium. Then dry the powder on the filter and use it as in the case of opium which does not need to be first washed with ether.

Opium which is adulterated, or standardized by admixture with dextrine, gums, sugar or glucosides yields an impracticable magma with water, and ether washing to such does little or no good. All such samples have to be exhausted with an alcoholic solvent. If

not much adulterated a mixture of equal measures of alcohol (s. g. 820) and water will answer best, but generally a mixture of 2 measures of alcohol (s. g. 820) with 1 measure of water is to be used, instead of water alone, for the exhaustion, and as this mixture is not as good a solvent for the morphia salts in the opium as water, more of it is required, and the washing and percolating should be carried to 250 c.c.-8.33 fluid ounces of solution from the 10 grammes=54.132 grains of opium. The process after exhaustion is the same as where water is used as the solvent.

Filter off the solution into a tared or marked vessel and percolate the residue on the filter with water dropped onto the edges of the filter and the residue until the filtrate measures about 120 c.c.= 4 fluidounces, and set this strong solution aside. Then return the residue to the bottle by means of a very small spatula, without breaking or disturbing the filter in the funnel, add 30 c.c.= 1 fluid ounce of water, shake well and return the magma to the filter. When drained rinse the bottle twice, each time with 10 c.c.33 fluid ounce water, and pour the rinsings upon the residue. When this has passed through, wash the filter and residue with 20 c.c.='66 fluidounce of water, applied drop by drop around the edges of the filter, and upon the contents. When the filter has drained, there should be about 70 c.c.=2,33 fluidounces of the weaker solution. This (120+70=) 190 c.c.=6.33 fluid ounces of total solution will practically exhaust almost any sample of 10 grammes=154,32 grains of Opium. But occasionally a particularly rich Opium, or one in coarse powder, or an originally moist Opium which has by slow drying become hard and flinty, will require further exhaustion. In all such cases, or cases of doubt, the residue should be again removed from the filter and shaken with 30 c.c. fluidounce of water, and returned, and be again washed as before. The filter and residue are now to be dried until they cease to lose weight at 100° C. 212°F. If any residue remains in the bottle, the bottle is also to be dried in an inverted position and weighed. Evaporate the weaker solution in a tared capsule of about 200 c.c.=6.66 fluidounces capacity without a stirrer, on a water-bath until reduced to about 20 grammes=309 grains. Now add the 120 c.c of stronger solution, thereby subjecting this portion to the shortest practicable heating with least injury to the alkaloid— and evaporate the whole again to about 20 grammes=309 grains. Cool the capsule and contents, and when cool add 5 c.c.= fluidounce of alcohol (s. g. 820) and stir until a uniform

1

17

solution is obtained, and no extract adhering undissolved on the capsule. If this solution should contain an appreciable precipitate, as from rare specimens of Opium it will, it must be filtered, and the filter be carefully washed through. Then the filtrate must be evaporated to 25 or 30 grammes. Pour the concentrated solution from the capsule into a tared flask of about 100 c.c.=3.33 fluidounces capacity, and rinse the capsule into the flask with about 5 c.c. of water used in successive portions. Then, if the solution has not required filtering, add 5 c.c.='17 fluidounce more of alcohol. If it has been filtered and evaporated add 10 c.c.= 33 fluidounce of alcohol and shake well. Then add 30 c.c.1 fluid ounce of ether, and again shake well.

This shaking together first of the watery solution and alcohol causes the alcohol to combine with the water before the ether is added. The ether then added, the second shaking saturates the watery solution and combined alcohol with ether, and then the mixture is ready for the precipitation of the alkaloid under the most favorable condition.

Add now 4 c.c.=133 fluid ounce of solution of ammonia, of 10 per cent. (s. g. 960) and shake the flask vigorously until the crystals begin to separate. Then set the flask aside in a cool place for 12 hours, that the crystallization may be completed.

This shaking secures the crystallization in very small crystals, so as to be easily washed and not adherent to the flask. The crystals will then be found partly at the bottom of the flask and partly in the ether at the surface of the lower dark, watery solution. If the shaking be frequent and vigorous, two or three hours' time will be sufficient to complete the crystallization, or if it be continuous, half an hour will be sufficient, but as a general rule it is better to allow the flask to stand over night. When there is no haste, a very good method is to macerate the opium over one night-prepare the solution during the day, and allow the second night for completing the crystallization. Then finish the assay on the second day. If there be haste, however, the assay may be completed in one day by the vigorous and frequent shaking above indicated. Indeed, maceration without agitation or percolation is comparatively useless after the powder to be exhausted becomes completely saturated; and crystallization in a dense liquid like this is very slow if convection or liquid diffusion be depended upon; but agitation brings all parts of the liquid so thoroughly in intimate contact, that an half-hour's vigorous agitation must be fully equal to twelve hours standing without agitation.

Pour off the ethereal stratum from the flask, as closely as possible, onto a tared filter of about 10 centimetres=4 inches in diameter, well wetted with ether. Add 20 c.c.66 fluidounce of ether to the

contents of the flask, rinse round without shaking, and again pour off the ethereal stratum as closely as possible onto the filter, keeping the funnel covered. When the ethereal solution is nearly all through, wash down the edges and sides of the filter with 5 c.c.17 fluidounce of ether, and allow the filter to drain with the cover off. Then pour on the remaining contents of the flask and cover the funnel. When the liquid has nearly all passed through, rinse the flask twice with 5 c.c.17 fluidounce of water each time, pouring the rinsings with all the crystals that can be loosened onto the filter, and dry the flask in an inverted or horizontal position, and when thoroughly dry weigh it. Wash the filter and crystals with 10 c.c. =33 fluidounce of water applied drop by drop to the edges of the filter. When drained, remove the filter and contents from the funnel, close the edges of the filter together, and compress it gently between many folds of bibulous paper. Then dry it at 100° C.=212° F. and weigh it. Remove the crystals of morphia from the filter, brush it off and re-weigh it to get the tare to be subtracted. The remainder, added to the weight of the crystals in the flask, will give the total yield of morphia, in clean distinct small light-brown crystals.

Take a small portion of these crystals, rub them into a very fine powder and weigh off 1 gramme=1.54 grains. Put this in a large test-tube fitted with a good cork and add 10 c.c.=33 fluidounce of officinal lime water. Shake occasionally, when the whole of the powder should dissolve. (Absence of narcotine.) [Flückiger.]

In pouring off the ethereal stratum from the flask as closely as possible, a little of the dark liquid and crystals will pass in with it, but this is of no consequence. The second portion of ether is added to dilute the remainder of the first, so as to get as much of it as possible separated before the watery liquid is poured into the filter, because this first ether contains all the narcotine and oily matters of the solution, and as the ether evaporates off from these they are deposited in the filter and with the morphia, and would be weighed with it. During this ethereal filtration the funnel is kept closely covered to prevent this evaporation and precipitation, but after the edges have been washed down with fresh ether, and the whole has passed through, there is so little of it left with the watery portion, and that little is so diluted that the whole may be poured on together. In adding the last or diluting portion of ether to the flask it is a little better to shake the whole contents together vigorously, but then it becomes necessary to wait a half-hour or more for a complete separation before the ether can be poured off well. In pouring off this second portion, in order to leave as little ether as possible in the flask, it must be done very slowly, and toward the