Chapter 8

In a recent number of the _Journal des Usines à Gaz_ appears a note by M. Chevalet, on the chemical and physical purification of gas, which was one of the papers submitted to the Société Technique de l'Industrie du Gaz en France at the last ordinary meeting. This communication is noticeable, apart from the author's conclusions, for the fact that the processes described were not designed originally for use in gas manufacture, but were first used to purify, or rather to remove the ammonia which is to be found in all factory chimneys, and especially in certain manufactories of bone-black, and in spirit distilleries. It is because of the success which attended M. Chevalet's treatment of factory smoke that he turned his attention to coal gas. The communication in which M. Chevalet's method is described deals first with chimney gases, in order to show the difficulties of the first class of work done by the author's process. Like coal gas, chimney gases contain in suspension solid particles, such as soot and ashes. Before washing these gases in a bath of sulphuric acid, in order to retain the ammonia, there were two problems to be solved. It was first of all necessary to cool the gases down to a point which should not exceed the boiling-point of the acid employed in washing; and then to remove the solid particles which would otherwise foul the acid. In carrying out this mechanical purification it was impossible, for two reasons, to make use of apparatus of the kind used in gas works; the first obstacle was the presence of solid particles carried forward by the gaseous currents, and the other difficulty was the volume of gas to be dealt with. In the example to which the author's attention was directed he had to purify 600 cubic meters of chimney gas per minute, or 36,000 cubic meters per hour, while the gas escaped from the flues at a temperature of from 400° to 500° C. (752° to 932° Fahr.), and a large quantity of cinders had frequently to be removed from the main chimney flues. After many trials a simple appliance was constructed which successfully cooled the gases and freed them from ashes. This consisted of a vertical screen, with bars three mm. apart, set in water. This screen divided the gases into thin sheets before traversing the water, and by thus washing and evaporating the water the gases were cooled, and threw down the soot and ashes, and these impurities fell to the bottom of the water bath. The gases after this process are divested of the greater part of any tarry impurities which they may have possessed, and are ready for the final purification, in which ammonia is extracted. This is effected by means of a series of shallow trays, covered with water or weak acid, and pierced with a number of fine holes, through which the gas is made to bubble. The washing apparatus is therefore strangely similar in principle to that designed by Mr G. Livesey. M. Chevalet states that this double process is applicable to gas works as well as to the purification of smoke, with the difference that for the latter purpose the washing trays are filled with acid for the retention of ammonia, while in the former application gas liquor or water is used. The arrangement is said to be a practical success.--_Journal of Gas Lighting._

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DETERMINATION OF NITROGEN IN HAIR, WOOL, DRIED BLOOD, FLESH MEAL, AND LEATHER SCRAPS.

BY DR. C. KRAUCH.

Differences obtained in the estimation of nitrogen in the above substances are frequently the source of much annoyance. The cause of these discrepancies is chiefly due to the lack of uniformity in the material, and from its not being in a sufficiently fine state during the combustion. The hair which is found in commerce for the manufacture of fertilizers, is generally mixed with sand and dust. Wool dust often contains old buttons, pieces of wood, shoe pegs, and all sorts of things. The flesh fertilizers are composed of light particles of flesh mixed with the heavier bone dust.

Even after taking all possible precautions to finely comminute these substances by mechanical means, still only imperfect results are obtained, for the impurities, that is to say, the sand, can never be so intimately mixed with the lighter particles that a sample of 0.5 to 0.8 gramme, such as is used in the determination of nitrogen, will correspond to the correct average contents. In substances such as dried blood, pulverization is very tedious. A very good method of overcoming these difficulties, and of obtaining from the most mixed substances a perfectly homogeneous mass, is that recommended by Grandeau[1] of decomposing with sulphuric acid--a method which as yet does not seem to be generally known. From a large quantity of the substance to be examined, the coarse stones, etc., are removed by picking or sifting, and the prepared substance, or in cases where the impurities cannot be separated, the original substance, is treated with sulphuric acid; after it is decomposed, the acid is neutralized with calcium carbonate, and the nitrogen is determined in this mass.

[Footnote 1: _Handbook d. Agrict. Chem. Analyst._, p. 18.]

In order to operate rapidly, it is best to use as little sulphuric acid as possible. If too much sulphuric acid is used, necessarily a large amount of calcium carbonate is essential to get it into proper condition for pulverizing. Under such circumstances the percentage of nitrogen becomes very low, and a slight error will become correspondingly high.

20 c.c. of concentrated sulphuric acid and 10 c.c. are sufficient for 30 to 40 grammes of material. After the substance and liquid have been thoroughly stirred in a porcelain dish, they are warmed on a water bath and continually stirred until the mass forms a homogeneous liquid. The sirupy liquid thus obtained is then mixed with 80 to 100 grammes of pulverized calcium carbonate (calcspar), dried for fifteen minutes at 40 to 60° C., and after standing for one to two hours the dish and its contents are weighed. From the total weight the weight of the dish is subtracted, which gives the weight of the calcium sulphate and the calcium carbonate, and the known weight of the wool dust, etc. This material is then intimately ground, and 2 to 3 grammes of it are taken for the determination of the nitrogen, which is then calculated for the original substance.

Although the given quantities of water and sulphuric acid hardly appear sufficient for such a large quantity of hair or wool, still in the course of a few minutes to a quarter of an hour, after continual stirring, there is obtained a liquid which, after the addition of the calcium carbonate, is readily converted into a pulverized mass. Frequently a smaller quantity of sulphuric acid will suffice, especially if the material is moist. The chief merit of this process is that in a short time a large quantity of material, having a uniform character, is obtained. Its use is, therefore, recommended for general employment.

When the coarser stones, etc., are weighed, and the purified portion decomposed, absolutely correct results are obtained, and in this way the awkward discrepancies from different analysts may be avoided.--_Chemiker Zeitung_, v. 7, p. 703.

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TESTING WHITE BEESWAX FOR CERESINE AND PARAFFINS.

BY A. PELTZ.

The method which is here recommended originated with Dr. M. Buchner, and consists in preparing a concentrated solution of alcoholic caustic potash--one part caustic potash to three of 90 per cent. alcohol--and then boiling one to two grammes of the suspected wax in a small flask with the above solution. The liquid is poured into a glass cylinder to prevent solidification of the contents, and it is then placed for about one half hour in boiling water. With pure wax the solution remains clear white; when ceresine and paraffine are present, they will float on the surface of the alkali solution as an oily layer, and on cooling they will appear lighter in color than the saponified mass, and thus they may be quantitatively estimated. The author likewise gives a superficial method for the determination of the purity of beeswax. It depends on the formation of wax crystals when the fused wax solidifies. These crystals form on the surface on cooling, and are still visible after solidification when examining the surface from the side. The test succeeds best when the liquid wax is poured into a shallow tin mould After cooling another peculiar property of the wax becomes apparent. While the beeswax fills a smaller volume, that is, separates from the sides of the mould, the Japanese wax, without separating from the sides, becomes covered with cracks on cooling which have a depth corresponding to the thickness of the wax.--_Neuste Erfindungen und Erfahrungen_, viii., p. 430.

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THE PREVENTION OF ALCOHOLIC FERMENTATION BY FUNGI.

BY PROF. E. REICHARD.

The manager of a well directed brewery, which was built according to the latest improvements and provided with ice-cooling arrangements, found that the alcoholic fermentation of lager beer did not advance with proper regularity. The beer did not clarify well, it remained turbid and had a tendency to assume a disagreeable odor and taste. Microscopic examination of the yeast, however, showed the same to be bottom yeast. After some time its action apparently diminished, or rather, the fermentation, which began well, ceased, and at the same time a white foam formed in the center of the vat. The manager observing this, again submitted it to microscopic examination. The instrument revealed a number of much smaller forms of fungi, similar to those of young yeast, and some which were excessively large, a variety never found in bottom yeast. Fully appreciating the microscopic examination, and aware of the danger which the spread of the fungi could cause, the manager resorted to all known means to retard its pernicious influence. Fresh yeast was employed, and the fermenting vats throughly cleaned, both inside and out, but the phenomena reappeared, showing that the transmission took place through the air. A microscopic examination of a gelatinous coating on the wall of the fermenting room further explained the matter. Beginning at the door of the ice cellar, the walls were covered with a gelatinous mass, which, even when placed beneath the microscope, showed no definite organic structure; however it contained numerous threads of fungi. Notwithstanding the precautions which were taken for cleanliness, these germs traveled from the ceiling through the air into the fermenting liquid and there produced a change, which would ultimately have caused the destruction of all the beer.

For a third time and by altogether different means, it was demonstrated that the air was the bearer of these germs. The whole atmosphere was infected, and a simple change of air was by no manner of means sufficient, as has already been shown. In addition, these observations throw considerable light on the means by which contagious diseases are spread, for often a room, a house, or the entire neighborhood appears to be infected. It must also be remembered how, in times of plague, large fires were resorted as to a method of purifying the air.

With the infinite distribution of germs, and as they are always present in all places where any organic portions of vegetable or animal matter are undergoing decomposition, it becomes, under certain circumstances, exceedingly difficult, and at times even impossible, to trace the direct effect of these minute germs. The organism is exposed to the destructive action of the most minute creation; several changes in this case give to them the direct effect of the acting germs. The investigation of the chemist does not extend beyond the chemical changes; nevertheless these phenomena are directly explained by the microscope, without which, in the present case, the discovery of the cause would have remained unknown.--_Arch. der Pharm._, 214, 158.

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NEW REACTION OF GLYCERINE.

If two drops of phenic acid are diluted with three thousand to five thousand parts of water, a distinct blue color is produced by one drop of solution of perchloride of iron.

The addition of six or eight drops of glycerine entirely removes the color, and if any glycerine was present in the liquid the reaction does not take place at all. By this test the presence of 1 per cent. of glycerine can be detected. It may be applied to the analysis of wines, beers, etc., but when there is much sugar, extractive or coloring matter, the test can only be applied after evaporating, dissolving the residue in alcohol and ether, evaporating again, and then redissolving in water. Alkaline solutions must be first acidulated.--_Pharm. Zeit. für Russ._

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LYCOPODINE.

While the phanerogams or flowering plants annually contribute to the list of newly discovered alkaloids, with the exception of muscarine and amanitine, no alkaloid has as yet been definitely recognized among the cryptogams.

Karl Bödeker, of Göttingen, has opened the road in this direction, and gives in a paper sent to Liebig's _Annalen der Chemie_, August 15, 1881, the following account of an alkaloid, which, from the name of the plant in which it occurs, he calls lycopodine.

The plant yielding the alkaloid, _Lycopodium complanatum_, belongs to the group of angiospermous cryptogams. It is distributed throughout the whole of north and middle Europe, and contains the largest proportion of aluminum of any known plant. Its bitter taste led the author to suspect an alkaloid in it.

To prepare the alkaloid the dried plant is chopped up and twice exhausted with boiling alcohol of 90 per cent. The residue is squeezed out while hot, and the extract, after being allowed to settle awhile, is decanted off, and evaporated to a viscid consistency over a water bath. This is then repeatedly kneaded up with fresh quantities of lukewarm water until the washings cease to taste bitter, and to give a reddish brown coloration when treated with a strong aqueous solution of iodine. The several washings are collected and precipitated with basic lead acetate, the precipitate filtered off, and the lead in the filtrate removed by sulphureted hydrogen. The filtrate from the lead sulphide is evaporated down over a water bath, then made strongly alkaline with a solution of caustic soda, and repeatedly shaken up with fresh quantities of ether so long as the washings taste bitter and give a precipitate with iodine water. After distilling off the ether, the residue is treated with strong hydrochloric acid, the neutral or slightly acid solution filtered off from resinous particles, slowly evaporated to crystallization, and the crystals purified by repeated recrystallization. To prepare the pure base a very concentrated solution of this pure hydrochlorate is treated with an excess of a very concentrated solution of caustic soda, and pieces of caustic potash are added, whereupon the free alkaloid separates out at first as a colorless resinous stringy mass, which, however, upon standing, turns crystalline, forming monoclinic crystals similar to tartaric acid or glycocol. The crystals are rapidly washed with water, and dried between soft blotting paper.

Thus prepared, lycopodine has a composition which may be represented by the formula C_{32}H_{52}N_{2}O_{3}. It melts at 114° to 115° C. without loss of weight. It is tolerable soluble in water and in ether, and very soluble indeed in alcohol, chloroform, benzol, or amyl alcohol. Lycopodine has a very pure bitter taste.

The author has formed several salts of the base, all of a crystalline nature, and containing water of crystallization.

The hydrochlorate gives up a part of its water of crystallization at the ordinary temperature under a desiccator over sulphuric acid, and the whole of it upon heating.--_Chemist and Druggist._

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CONCHINAMINE.

Some years ago, O. Hesse, when preparing chinamine from the renewed bark of _Cinchona succirubra_, found in the mother liquid a new alkaloid, which he then briefly designated as conchinamine. He has lately given his attention to the separation and preparation of this alkaloid, and gives in Liebig's _Annalen der Chemie_, August 31, 1881, the following description of it:

_Preparation._--The alcoholic mother lye from chinamine is evaporated down and protractedly exhausted with boiling ligroine, whereby conchinamine and a small quantity of certain amorphous bases are dissolved out. Upon cooling the greater part of the amorphous bases precipitates out. The ligroine solution is then first treated with dilute acetic acid, and then with a dilute solution of caustic soda, whereupon a large quantity of a resinous precipitate is formed. This is kneaded up with lukewarm water to remove adherent soda, and then dissolved in hot alcohol. The alcoholic solution is saturated with nitric acid, which has been previously diluted with half its volume of water, and the whole set aside for a few days to crystallize. The crystals of conchinamine nitrate are purified by recrystallization from boiling water. On dissolving these pure crystals of the nitrate in hot alcohol of 60 per cent., and adding ammonia, absolute pure conchinamine separates out on cooling.

_Composition._--Conchinamine may be represented by the formula C_{19}H_{24}N_{2}O_{2}, without water of crystallization.

_Properties._--Conchinamine is easily soluble in hot alcohol of 60 per cent., and in ether and ligroine, from which solutions it crystallizes in quadrilateral shining prisms. It is extremely soluble in chloroform, but almost insoluble in water. It melts at 121° C., forming crystalline stars on cooling.

_Salts._--The salts of conchinamine, like the base itself, have much in common with chinamine, but are, as a rule, more easily crystallizable. They are prepared by neutralizing an alcoholic solution of the base with the acid in question.--_Chemist and Druggist._

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CHINOLINE.

The valuable properties of which chinoline has been found to be possessed have led to its admission as a therapeutic agent, and the discoverer of these properties, Jul. Donath, of Baja, in Hungary, in a paper sent to the _Berichte der deutschen chemischen Gesellschaft_, September 12, 1881, gives the following further details as to this interesting substance.

_Antiseptic Properties._--Chinoline appears to be an excellent antiseptic. The author found that 100 grammes of a Bucholze's solution for the propagation of bacteria, charged with 0.20 g. of chinoline hydrochlorate, had remained perfectly clear and free from bacteria after standing forty-six days exposed to the air, while a similar solution, placed under the same conditions, without chinoline, had turned muddy and contained bacteria after only twelve days' standing.

_Antizymotic Properties._--Chinoline, even in the proportion of 5 per cent., does not prevent alcoholic fermentation, while in as small a quantity as 0.20 per cent. it does not prevent lactic acid fermentation.

_Physiological Effects._--The author gave a healthy man during several days various doses of chinoline tartrate, which in no way affected the individual operated on, nor was any trace of chinoline found in his urine. The author, therefore, considers that the base is oxidized by the blood to carbopyridinic acid, which is a still more powerful antiseptic than chinoline itself. Chinoline taken internally would, therefore, be a useful and safe agent in cases of internal putrid fungoid or other growth.

_Chemical Reactions._--Chinoline yields very characteristic reactions with a number of chemical reagents, for a description of which we refer to the original paper.--_Chemist and Druggist._

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PREPARATION OF CONIINE.

Dr. J. Schorm, of Vienna, the author of this paper, after remarking that in spite of the increase of the consumption of coniine, the methods hitherto in vogue for preparing it yielded an article which darkened on exposure to the air, and the salts of which crystallized but badly, gives the following method for preparing pure coniine and its salts:

_PREPARATION OF CRUDE CONIINE._

A.--100 kilogrammes of hemlock seed are moistened with hot water, and after swelling up are treated with 4 kilogrammes of sodium carbonate previously dissolved in the requisite quantity of water (caustic alkalies cannot be used). The swollen seed is worked up uniformly with shovels, and then placed in an apparatus of 400 kilogrammes capacity, similar to that used in the distillation of ethereal oils, and charged with steam under a pressure of three atmospheres. Coniine distills over with the steam, the greater part separating out in the receiver as an oily stratum, while a part remains dissolved in the water. The riper the seeds, the greater is the percentage yield of oily coniine, and the sooner is the distillation ended. The distillate is neutralized with hydrochloric acid, and the whole evaporated to a weak sirupy consistence. When cool, this sirup yields successive crops of sal-ammoniac crystals, which latter are removed by shaking up the mass with twice its volume of strong alcohol, and filtering. This filtrate is freed from alcohol by evaporation over a water bath, the approximate quantity of a solution of caustic soda then added, and the whole shaken up with ether. The ethereal solution is then cooled down to a low temperature, whereby it is separated from conhydrine, which, being somewhat difficultly soluble in ether, crystallizes out.

B.--The bruised hemlock seed is treated in a vacuum extractor with water acidulated with acetic acid, and the extract evaporated in vacuo to a sirupy consistence. The sirup is treated with magnesia, and the coniine dissolved out by shaking up with ether.

The B method yields a less percentage of coniine than A, but of a better quality.

_RECTIFICATION OF THE CRUDE CONIINE._

The solution of crude coniine in ether obtained by either of the above processes is evaporated over a water bath to remove the ether, mixed with dry potassium carbonate, and then submitted to fractional distillation from an air bath. The portion distilling over at 168° C. to 169° C. is pure coniine, and represents 60 per cent. of the crude coniine.

Coniine thus prepared is a colorless oily liquid, volatile at the ordinary temperature, and has a specific gravity of 0.886. At a temperature of 25°C it absorbs water, which it gives up again upon heating. It is soluble in 90 parts of water. It is not altered by light.

The author has formed a number of salts from coniine thus prepared, and finds them all crystallizable and unaffected by light.--_Berichte der deutschen chemischen Gesellschaft._--_Chem. and Druggist._

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STRONTIANITE.

Since it has been shown by Professor Scheibler, of Berlin, that strontium is the most powerful medium of extraction in sugar refining, owing to its capacity of combining with three parts of saccharate, the idea suggests itself that the same medium might be successfully employed in the arts, and form a most interesting subject of experiment for the chemist.

Hitherto native strontianite, that is, the 90 to 95 per cent. pure carbonate of strontium (not the celestine which frequently is mistaken by the term strontianite), has not been worked systematically in mines, but what used to be brought to the market was an inferior stone collected in various parts of Germany, chiefly in Westphalia, where it is found on the surface of the fields. Little also has been collected in this manner, and necessarily the quality was subject to the greatest fluctuations.