Principles and practice of agricultural analysis. Volume 2 (of 3), Fertilizers

224. Introduction.—The potash present in unfertilized soils has been derived from the decay of rocks containing potash minerals. Among these potash producers feldspars are perhaps the most important. For a discussion of the nature of their decomposition and the causes producing it the first part of volume first may be consulted. Potash is quite as extensively distributed as phosphoric acid and no true soils are without it in some proportion. Its presence is necessary to plant growth and it forms, in combination with organic and mineral acids, an essential part of the vegetable organism, existing in exceptionally rich quantities in the seeds. It is possible that potash salts, such as the chlorid, sulfate, and phosphate may be assimilated as such, but, as with other compounds, we must not deny to the plant the remarkable faculty of being able to decompose its most stable salts and to form from the fragments thus produced entirely new compounds. This is certainly true of the potash compounds existing in plants in combination with organic acids. The potash which is assimilated by plants exists in the soil chiefly in a mineral state, and that added as fertilizer is chiefly in the same condition. That part of the potash in a soil arising directly from the decomposition of vegetable matters may exist partly in organic combination, but this portion, in comparison with the total quantity absorbed by the plant, is insignificant.

It is then safe to assume that at least a considerable part of the potash absorbed by the plant is decomposed from its original form of combination by the vegetable biochemical forces, and is finally incorporated in the plant tissues in forms determined by the same powerful forces of vegetable metabolism.

The analyst is not often called upon to investigate the forms in which the potash exists in plants, when engaged in investigation of fertilizers. It is chiefly found in combination with organic and phosphoric acids, and on ignition will appear as phosphate or carbonate in the ash.

225. Forms in which Potash is Found in Fertilizers.—The chief natural sources of potash used in fertilizer fabrication are: First, organic compounds, such as desiccated mineral matters, tobacco waste, cottonseed hulls, etc.; second, the ash derived from burning terrestrial plants of all kinds; third, the natural mineral deposits, such as Stassfurt salts.

All of these forms of potash may be found in mixed fertilizers. While the final methods of analyses are the same in all cases the preliminary treatment is very different, being adapted to the nature of the sample. For analytical purposes, it is highly important that the potash be brought into a soluble mineral form, and that any organic matters which the sample contains be destroyed. If the sample be already of a mineral nature, it may still be mixed with other organic matter and then it requires treatment as above, for it is not safe always to rely solely on the solubility of the potash mineral, and the solution, moreover, in such cases, is likely to contain organic matter. In some States, only that portion of the potash soluble in water is allowed to be considered in official fertilizer work. In these cases it is evident that the organic matter present should not be destroyed in the original sample, but only in the aqueous solution. Since, however, the potash occluded in organic matter becomes constantly available as the process of decay goes on, it is not just to exclude it from the available supply. It may not be so immediately available as when in a soluble mineral state, but it is not long before it becomes valuable. Experience has shown, moreover, that phosphorus, nitrogen, and potash are all more valuable finally when applied to the soil in an organic form. This fact is a corroboration of the theory already advanced that all mineral compound bodies are probably decomposed before they enter as component parts into the tissues of the vegetable organism.

It is highly probable, therefore, that the potash existing in organic compounds, finely divided and easily decomposed, is of equal, if not greater value to plant life than that already in a soluble mineral state. The organic matter, when present, is destroyed, either by ignition at a low temperature, or by moist combustion with an oxidizing agent before the potash is precipitated.

ORGANIC SOURCES OF POTASH.

226. Tobacco Stems and Waste.—Until within a few years tobacco stems and other waste from factories, were treated as a nuisance in this country, and burned or dumped into streams. By burning and saving the ash the potash contained in the stems and waste would be recovered in a form suitable for field use. The nitrogen, however, contained in these waste materials, both in the form of nicotin and of albuminoids would be lost. Ignition of this waste, therefore, should not be practiced. It should be prepared for use by grinding to a fine powder. Applied to the soil in this condition the powder may be useful as an insecticide as well as a fertilizer. Tobacco stems contain from twelve to twenty-seven per cent of moisture, and from twelve to twenty per cent of ash. The composition of the stems from two celebrated tobacco growing regions is subjoined:[185]

The ash calculated to the original substance had the following composition:

It is thus seen that about half the ash of tobacco stems is composed of potash. The stalks of the tobacco have almost the same composition as the stems, but the percentage of ash is not quite so great. In three samples analyzed at the Connecticut station the percentages of ash found in the water-free substance were 6.64, 7.00, and 7.46 respectively. The pure ash of the stalks was found to have the following composition:[186]

The leaves of the tobacco contain more ash than the stalks or stems, but the percentage of potash therein is less. In eighteen samples analyzed at the Colorado station the percentages of moisture in the leaf varied from 6.08 to 28.00, and those of ash from 22.60 to 28.00.[187] The percentages of potash in the ash varied from 15.20 to 26.30. In these data the carbon dioxid, sand, etc., are included, while in those quoted from the Connecticut station they were excluded.

227. Cottonseed Hulls and Meal.—A considerable quantity of potash is added to the soil in cottonseed meal and hulls. The practice of burning the hulls cannot be recommended, although it is frequently practiced, for the incineration does not increase the quantities of phosphoric acid and potash, while it destroys the availability of the nitrogen. Nevertheless the analyst will often have to deal with samples of the raw materials above mentioned, as well as with the ash of the hulls, in which the potash can be determined by some one of the standard methods to be described. In general it is found that the hulls of seeds and the bark and leaves of plants have a greater percentage of ash than the interior portions. In the case of cottonseed however, an exception is to be noted. The cottonseed meal in the air-dried state has about seven per cent of ash, while the hulls have only about three. When it is remembered, however, that the greater part of the oil has been removed from the meal it will be seen that in the whole seed in the fresh state the discrepancy is not so marked.

In the crude ash of the hulls the percentage of potash varies generally from twenty to twenty-five per cent, but in numerous cases these limits are exceeded. In twelve samples of cottonseed hull ashes examined by the Connecticut station the mean percentage of potash in the crude sample was 22.47, and the extremes 15.57 and 30.24 per cent respectively.[188] In determining the value of the ash per ton the content of phosphoric acid must also be taken into account.

Cottonseed meal contains about 1.75 per cent of potash. Since the mean percentage of ash in the meal is seven, the mean content of potash in the crude ash is about twenty-five.

228. Wood Ashes.—Unleached wood ashes furnish an important quantity of potash fertilizer. The composition of the ash of woods is extremely variable. Not only do different varieties of trees have varying quantities of ash, but in the same variety the bark and twigs will give an ash quite different in quantity and composition from that furnished by the wood itself. In general the hard woods, such as hickory, oak, and maple, furnish a quality of ash superior for fertilizing purposes to that afforded by the soft woods, such as the pine and tulip trees.

The character of the unleached wood ashes found in the trade is indicated by the subjoined analyses. The first table contains the mean, maximum and minimum results of the analyses of ninety-seven samples by Goessmann.[189]

In sixteen analyses made at the Connecticut station the data obtained are given below:[190]

In fifteen analyses of ashes from domestic wood-fires in New England stoves, the following mean percentages of potash and phosphoric acid were found:

In leaching, ashes lose chiefly the potassium carbonate and phosphate which they contain. Leached and unleached Canada ashes have the following composition:

In the wood ashes of commerce therefore, it is evident that the proportion of the potash to the lime is relatively low.

The number of parts by weight of the chief ingredients of the ash in ten thousand pounds of woods of different kinds is given in the table below together with the percentage composition of the pure ash, that is the crude ash deprived of carbon and carbon dioxid.

Pounds of the Ingredients Named
in Ten Thousand Pounds of Wood.

The Pure Ashes of the Woods
Contain the Following Per Cents
of the Ingredient Named.

229. Fertilizing Value of Ashes.—Primarily, the fertilizing value of wood-ashes depends on the quantity of plant food which they contain. With the exception of potash and phosphoric acid, however, the constituents of wood-ashes have little, if any, commercial value. The beneficial effects following the application of ashes, however, are greater than would be produced by the same quantities of matter added in a purely manurial state. The organic origin of these materials in the ash has caused them to be presented to the plant in a form peculiarly suited for absorption. Land treated generally with wood-ashes becomes more amenable to culture, is readily kept in good tilth, and thus retains moisture in dry seasons and permits of easy drainage in wet. These effects are probably due to the lime content of the ash, a property moreover favorable to nitrification and adapted to correcting acidity. Injurious iron salts, which are sometimes found in wet and sour lands, are precipitated by the ash and rendered innocuous or even beneficial. A good wood-ash fertilizer therefore is worth more than would be indicated by its commercial value calculated in the usual way.

230. Molasses from Sugar-Beets.—The residual molasses resulting after the extraction of all the crystallizable sugar in beet-sugar manufacture is very rich in potash. The molasses contains from ten to fifteen per cent of ash.

The composition of the ash varies greatly in the content of potash as well as of the other constituents.[191] The content of potassium carbonate varies from twenty-two to fifty-five per cent and, in addition to this, some potassium sulfate and chlorid are usually present.

The following figures give the composition of a good quality of beet-molasses ash:

Thus, in 100 parts of such an ash over three-quarters are potash salts. The molasses may be applied directly to the soil or diluted and sprayed over the fields.

231. Residue of Wineries.—The pomace of grapes after being pressed or fermented for wine production contains considerable quantities of potash as crude argol or acid potassium tartrate. This material can be applied directly to the soil or first burned, when its potash will be secured in the form of carbonate.

The use of the winery refuse for fertilizing purposes has not assumed any commercial importance in this country.

232. Destruction of Organic Matter by Direct Ignition.—The simplest and most direct method for destroying organic matter is by direct ignition. The incineration may be conducted in the open air or in a muffle and the temperature should be as low as possible. In no case should a low red heat be exceeded. By reason of the moderate draft produced in a muffle and the more even heat which can be maintained this method of burning is to be preferred. With the exercise of due care, however, excellent results can be obtained in an open dish or one partly closed with a lid. At first, with many samples, the organic matter will burn of its own accord after it is once ignited, and during this combustion the lamp should be withdrawn. The ignition in most cases should be continued in a platinum dish but should the sample contain any reducible metal capable of injuring the platinum a porcelain vessel should be used. The lamp should give a diffused flame to avoid overheating of any portions of the dish and to secure more uniform combustion. In using a muffle the heat employed should be only great enough to secure combustion and the draft should be so regulated as to avoid loss due to the mechanical deportation of the ash particles.

233. Ignition with Sulfuric Acid.—The favorable action of sulfuric acid in securing a perfect incineration may also be utilized in the preparation of samples containing organic matter for potash determinations. In this case the bases which by direct ignition would be secured as carbonates are obtained as sulfates. In the method adopted by the official chemists it is directed to saturate the sample with sulfuric acid and to ignite in a muffle until all organic matter is destroyed.[192] Afterwards, when cool the ash is moistened with a little hydrochloric acid and warmed, whereby it is the more easily detached from the dish. The potash is then determined by any one of the standard methods. This method has several advantages over the direct ignition. Where any chlorids of the alkalies are present in the ash there is danger of loss of potash from volatilization. This is avoided by the sulfate process. Moreover, there is not so much danger in this method of occluding particles of carbon in the ash.

234. The Destruction of Organic Matter by Moist Combustion.—In the process of ignition to destroy organic matter or remove ammonium salts in the determination of potash, there are often sources of error which may cause considerable loss. This loss, as has already been mentioned, may arise from the volatilization of the potash salts or mechanically from spattering. In order to avoid these causes of error de Roode has used aqua regia both for the destruction of the ammonium salts and for the oxidation of the organic matter at least sufficiently to prevent any subsequent reduction of the platinum chlorid.[193] His method consists in boiling a sample of the fertilizer, or an aliquot portion of a solution thereof with aqua regia. The proposed method has not yet had a sufficient experimental demonstration to warrant its use, but analysts may find it profitable to compare this process with the standard methods. The organic matter may also be destroyed by combustion with sulfuric acid, as in the kjeldahl method for nitrogen. The residue, however, contains ammonium sulfate and a large excess of sulfuric acid, and for both reasons would not be in a fit condition for the estimation of potash.

It is suggested that the organic matter might also be destroyed by boiling with strong hydrochloric acid, to which from time to time, small quantities of sodium chlorate free of potash is added. Subsequently the solution could be boiled with addition of a little nitric acid and the ammonium salts be removed.

POTASH IN MINERAL DEPOSITS.

235. Occurrence and History.—The generally accepted theory of the manner in which potash has been collected into deposits suited to use as a fertilizer has already been described.[194] The Stassfurt deposits, which have for many years been almost the sole source of potash in fertilizers, were first known as mines of rock salt. In 1839, having previously been acquired by the Prussian treasury, they were abandoned by reason of the more economical working of rock salt quarries in other localities.[195] It was determined thereafter to explore the extent of these mines by boring, and a well was sunk to the depth of 246 meters, when the upper layer of the salt deposit was reached. The boring was continued into the salt to a total depth of 581 meters without reaching the bottom. The results of these experiments were totally unexpected. Instead of getting a brine saturated with common salt, one was obtained containing large quantities of potassium and magnesium chlorids.[196] Shafts were sunk in other places, and with such favorable results, that in 1862 potash salts became a regular article of commerce from that locality. At first these salts were regarded as troublesome impurities in the brine from which common salt was to be made, but at this time the common salt has come to be regarded as the disturbing factor. At the present time the entire product is controlled by a syndicate of nine large firms located at Stassfurt and vicinity. Outside of the syndicate properties a shaft has been sunk at Anderbeck, (Halberstadt,) which, however, has produced only carnallit, since kainit has not been found there. Also at Sondershausen, potash salts have been discovered and a shaft is now sinking there.

It is thus seen that the potash deposits extend over a wide area in Germany, and there is little fear of the deposits becoming exhausted in many centuries. In this country no potash deposits of any commercial importance have been discovered; but the geological conditions requisite to these formations have not been wanting, and their future discovery is not improbable.

236. Changes in Potash Salts in Situ.—The deposits of potash salts are not all found at the present in the same condition in which they were first deposited from the natural brines. The layers of salt have been subjected to the usual upheavals and subsidences peculiar to geological history. The layers of salt were thus tilted and the edges often brought to the surface. Here they were exposed to solution, and the dissolved brine afterward separated its crystallizable salts in new combinations. For instance, kieserit and the potassium chlorid of the carnallit were first dissolved and there was left a salt compound chiefly of potassium and sodium chlorids, sylvinit. In some cases there was a mutual reaction between the magnesium sulfate and the potassium chlorid and the magnesium potassium sulfate, schönit, was thus produced. This salt is also prepared at the mines artificially. The most important of these secondary products however, from the agricultural standpoint, is kainit. This salt arose by the bringing together of potassium sulfate, magnesium sulfate, and magnesium chlorid, and was formed everywhere about the borders of the layers of carnallit wherever water could work upon them. In quantity the kainit, as might be supposed, is far less than the carnallit, the latter existing in immense deposits. There is however quite enough of it to satisfy all the demands of agriculture for an indefinite time. In fact for many purposes the carnallit can take the place of kainit without detriment to the growing crops. The relative positions and quantities of the layers of mineral matters in the potash mines, and the depth in meters at which they are found is shown in Fig. 17.[197]

237. Kainit.—The most important of the natural salts of potash for fertilizing purposes is the mixture known as kainit. It is composed in a pure state of a molecule each of potassium sulfate, magnesium sulfate, magnesium chlorid, and water. Chemically it is represented by the symbols:

K₂SO₄·MgSO₄·MgCl₂·H₂O. Its theoretical percentage of potash (K₂O), oxygen = 16, is 23.2.

Pure kainit, however, is never found in commerce. It is mixed naturally as it comes from the mines with common salt, potassium chlorid, gypsum, and other bodies. The content of potash in the commercial salt is therefore only a little more than half that of the pure mineral. In general it may be taken at 12.5 per cent, of which more than one per cent is derived from the potassium chlorid present. The following analysis given by Maercker may be regarded as typical:[198]

Kainit occurs as a crystalline, partly colorless, partly yellow-red mass. When ground, in which state it is sent into commerce, it forms a fine, gray-colored mass containing many small yellow and red fragments. It is not hygroscopic and if it become moist it is due to the excess of common salt which it contains.

According to Maercker kainit was formerly regarded as a potassium magnesium sulfate. But this conception does not even apply to the pure salt much less to that which comes from the mines. If, therefore, the agronomist desire a fertilizer free from chlorin he would be deceived in choosing kainit which may sometimes contain nearly fifty per cent of its weight of chlorids.

Where a fertilizer free of chlorin is desired, as for instance, in the culture of tobacco, kainit cannot be considered. In many other cases, however, the chlorin content of this body instead of being a detriment may prove positively advantageous, the chlorids on account of their easy diffusibility through the soil serving to distribute the other ingredients.

By reason of the presence of common salt and magnesium chlorid the ground kainit delivered to commerce tends to harden into compact masses. To prevent this in Germany it is recommended to mix it with about two and a half per cent of fine-ground dry peat.

Such a mixture is recommended in all cases where the freshly ground kainit is not to be immediately applied to the soil.

238. Carnallit.—This mineral is a mixture of even molecules of potassium and magnesium chlorids crystallized with six molecules of water. It is represented by the symbols KCl·MgCl₂·6H₂O. As it comes from the mines it contains small quantities of potassium and magnesium sulfates and small quantities of other accidental impurities. Existing as it does in immense quantities it has been extensively used for the manufacture of the commercial potassium chlorid (muriate of potash). For many purposes in agriculture, for instance, fertilizing tobacco fields, it is not suited, and it is less widely used as a fertilizer in general than its alteration product kainit. Its direct use as a fertilizer however is rapidly increasing since later experience has shown that chlorin compounds are capable of a far wider application in agriculture without danger of injury than was formerly supposed. As it comes from the mines, the Stassfurt carnallit has the following composition:[199]

Pure carnallit would have the following composition:

Equivalent to

The commercial article as taken from the mines, as is seen above, has less potash (K₂O) than kainit, the mean content being about nine and nine-tenths per cent. Those proposing to use this body for fertilizing purposes should bear in mind that it contains less potash and more chlorin than kainit.

Carnallit occurs in characteristic brown-red masses. On account of its highly hygroscopic nature it should be kept as much as possible out of contact with moist air and should not be ground until immediately before using.

By reason of the greater bulk in proportion to its content of potash and its hygroscopic nature and consequent increased difficulty in handling, the price per unit of potash in carnallit is less than in kainit.

In some localities small quantities of ammonium chlorid have been found with carnallit but not to exceed one-tenth per cent. It has therefore no practical significance to the farmer but may be of interest to the analyst.

239. Polyhalit.—Polyhalit is a mineral occurring in Stassfurt deposits and consisting of a mixture of potassium, magnesium, and calcium sulfates, with a small proportion of crystal water. This mineral, on account of its being practically free of chlorin, would be one especially desirable for use in those cases, as in the culture of tobacco, where chlorids are injurious. Unfortunately, it does not occur in sufficient quantities to warrant the expectation of its ever being found in masses large enough to become a general article of commerce. It is found only in pockets or seams among the other Stassfurt deposits, and there is no assurance given on finding one of these deposits of polyhalit that it will extend to any great distance. The composition of the mineral is shown by the following formula: K₂SO₄·MgSO₄·(CaSO₄)₂·H₂O. Its percentage composition is shown by the following numbers:

The percentage of potash corresponding to the above formula is 15.62. It therefore contains a considerable excess of potash over kainit, and on account of its freedom from chlorids, would be preferred for many purposes.

240. Krugit.—This mineral occurs associated with polyhalit and differs from it only in containing four molecules of calcium sulfate instead of two. Its formula is: K₂SO₄·MgSO₄·(CaSO₄)₄·H₂O. As it comes from the mines it is frequently mixed with a little common salt. Its mean percentage composition as it comes from the mines is given in the following numbers:

The percentage of potash corresponding to the above formula is 10.05. It is therefore less valuable than kainit in so far as its content of potash is concerned. This salt also exists in limited quantities and is not likely to become an important article of commerce.

241. Sylvin.—One of the alteration products of carnallit is a practically pure potassium chlorid which, as it occurs in the Stassfurt mines is known as sylvin. The alteration of the carnallit arises from its solution in water from which, on subsequent evaporation, the potassium chlorid is deposited alone. This mineral is found in only limited quantities in the Stassfurt deposits and it therefore does not have any great commercial importance.

242. Sylvinit.—This mineral has been mined in recent years in considerable quantities. It is, in fact, only common salt carrying large quantities of potassium chlorid together with certain other accidental impurities. It was probably formed by the drying up of a saline mass in such a way as not to permit the complete separation of its mineral constituents. The average composition of sylvinit as it comes from the mines is given in the following table:

This salt is richer in chlorin than any other of the Stassfurt potash minerals, containing altogether 79.14 per cent of chlorids. Its potash content amounts to 23.04 per cent, but in proportion to the potash which it contains, it is relatively poorer in chlorin than kainit and carnallit. On account of its high content of potash the freights on a given weight thereof as contained in sylvanit are lower than for kainit and carnallit.

243. Kieserit.—The mineral kieserit is essentially magnesium sulfate and it does not necessarily contain any potash salts. Under the name of kieserit, however, or bergkieserit, there is mined a mixture of carnallit and kieserit, which is a commercial source of potash. The mixture contains the following average content of the bodies named:

This mixture contains only about seven per cent of potash and would not prove profitable when used at a distance from the mines on account of the cost of freights. It has proved valuable, however, for a top dressing for meadow lands in the vicinity of Stassfurt.

244. Schönit.—Among the Stassfurt deposits there occurs in small quantities a mineral, schönit, which is composed of the sulfates of potassium and magnesium. The quantity of the mineral occurring naturally is very small and therefore it has no commercial importance. When, however, kainit is washed with water the common salt and magnesium chlorid which it contains being more soluble are the first leached out, and the residue has approximately the composition of the pure mineral. This mixture, as prepared in the way mentioned above, has the following average composition:

The percentage of potash corresponding to the above composition is 27.2. This substance being so rich in potash, and practically free of chlorids, is well suited to transportation to great distances and for general use in the field. Since, however, a considerable expense attends the manufacture of the artificial schönit, the advantages above named give it very little, if any, advantage in competition with the other potash salts as they come from the mines. It has, however, an especial value for the fertilization of tobacco and vineyards.

245. Potassium Sulfate.—Several grades of potassium sulfate are found in the market for fertilizing purposes, some of them quite pure, containing over ninety-seven per cent of the pure sulfate. The following data show the composition of a high grade and low grade potassium sulfate of commerce:

Naturally, high grade sulfates of this kind can only be prepared in chemical factories built especially for the work. The result is that the potash per unit is raised greatly in price. When, however, the fertilizers are to be transported to a great distance, the saving in freight often more than compensates for the higher price of the potash. It therefore happens that there are many places in this country where the actual price of potash per pound is less in high grade sulfates than in kainit or carnallit. When, in addition to this, the especial fitness of the high grade sulfates for certain forms of fertilization, especially tobacco growing, is considered, it is seen that at this distance from the mines these high grade salts are of no inconsiderable importance. The percentage of potash in the high grade sulfates often exceeds fifty.

246. Potassium Magnesium Carbonate.—This salt has lately been manufactured and used to a considerable extent, especially for tobacco fertilizing. As furnished to the trade it has the following average composition:

The content of potash, as is seen from the above formula, amounts to from seventeen to eighteen per cent. The compound is completely dry, is not hygroscopic, and is, therefore, always ready for distribution. It is especially to be recommended for all those intensive cultures where it is feared that chlorids and sulfates will prove injurious, especially in the cultivation of tobacco.

247. Potash in Factory Residues.—The residues from the potash factories in Stassfurt and vicinity contain considerable quantities of potash and attempts have been made to recover this waste and put it into form for fertilizing uses. The waste waters of the factories are sometimes collected and evaporated, and the residue incinerated. The content of potash in these residues is extremely variable, usually quite low, and they, therefore, cannot be recommended for fertilizing purposes, especially if they are to be transported to any distance.

248. Quantity of Potash Salts Used.—The total quantity of potash delivered to consumers from the Stassfurt mines in 1891, the last year for which complete statistics are at hand was 413,508 tons of kainit and sylvinit, 39,444 tons of carnallit, 18,078 tons of sulfate, and 12,453 tons of the potassium magnesium sulfate. Of the above quantities, 115,245 tons of kainit were shipped to North America, and of the high grade sulfate mentioned, 13,322 tons were sent to other countries, and of the potassium magnesium sulfate, 11,081 tons were exported.

METHODS OF ANALYSIS.

249. Classification of Methods.—To detect the presence of potash in a mixture the aid of the spectroscope may be invoked. In the scale of the spectrum divided into 170 parts, on which the sodium line falls at 50, potassium gives three faint rather broad bands, two red, falling at 17 and 27, and one plum-colored band, near the extreme right of the spectrum, at 153. Potassium, however, does not give brilliant and well-marked spectral bands, such as are afforded by its associates rubidium, caesium, sodium, and lithium. A convenient qualitative test which, for practical purposes will be quite sufficient, may be secured by dipping a platinum loop into a strong acid solution of the supposed potash compound, and viewing through a piece of cobalt glass, the coloration produced thereby when held in the flame of a bunsen. The red-purple tint thereby produced should be compared with that coming from a pure potash salt similarly treated. If a fertilizer sample give no indication of potash when treated as above it may be safely concluded that it does not contain any weighable quantity of potash.

For the estimation of the percentage of potash present in a given sample it may be safely assumed that all of value in agriculture will be given up to an aqueous or slightly acid solution if organic matter have been destroyed as indicated in a previous paragraph. In the case of minerals insoluble in a dilute acid the potash may be determined by some one of the processes given in the first volume.[200] The potash having been obtained in an aqueous or slightly acid (hydrochloric) solution, it may be determined either by precipitation as potassium platinochlorid or as potassium perchlorate. The former method is the one which has been almost exclusively used by analysis in the past, but the latter one is coming into prominence and by reason of the greater economy attending its practice and the excellent results obtained by some analysts, demands a generous consideration.

250. The Platinic Chlorid Method.—The principle of this method rests on the great insolubility of the potassium platinochlorid in strong alcohol and the easy solubility of some of its commonly attending salts; viz., sodium, etc., in the same reagent. Before the precipitation of the potash it is necessary to remove the bases of the earths, sulfates, etc. Barium chlorid and hydroxid, ammonium oxalate or carbonate, sulfuric acid, etc., are used in conjunction or successively to effect these purposes in the manner hereinafter described. The filtrate and washings containing the potash are evaporated to dryness and gently ignited to expel excess of ammonium salts and in the residue taken up with water and acidulated with hydrochloric acid, the potash is precipitated with platinic chlorid solution. The best methods of executing the analysis follow.

251. The Official Agricultural Method.—This method is based on the processes at first proposed by Lindo[201] and Gladding,[202] and is given below as adapted to mixed fertilizers and mineral potash salts.[203]

(1) In Superphosphates.—Boil ten grams with 300 cubic centimeters of water thirty minutes. To the hot solution add ammonia in slight excess, and then a sufficient quantity of ammonium oxalate to precipitate all the lime present; cool and make up to half a liter, mix thoroughly, and filter through a dry filter; evaporate fifty cubic centimeters, corresponding to one gram, nearly to dryness, add one cubic centimeter of dilute sulfuric acid (1 to 1), evaporate to dryness and ignite to whiteness. As all the potash is in form of sulfate, no loss need be apprehended by volatilization of potash, and a full red heat must be maintained until the residue is perfectly white. This residue is dissolved in hot water, plus a few drops of hydrochloric acid, and a slight excess of platinum solution is added. This solution is then evaporated to a thick paste in a small dish, and eighty per cent alcohol added. In evaporating, special precaution should be taken to prevent absorption of ammonia. The precipitate is washed thoroughly with alcohol by decantation and on the filter, as usual. The washing should be continued even after the filtrate is colorless. Ten cubic centimeters of the ammonium chlorid solution, prepared as hereinafter directed, are run through the filter, or the washing may be performed in the dish. The ten cubic centimeters will contain the bulk of the impurities, and are thrown away. Fresh portions of ten cubic centimeters of the ammonium chlorid are run through the filter several times (5 or 6). The filter is then washed thoroughly with pure alcohol, dried, and weighed as usual. Care should be taken that the precipitate is perfectly soluble in water. The platinum solution used contains one gram of metallic platinum in every ten cubic centimeters. To prepare the washing solution of ammonium chlorid, place in a bottle 500 cubic centimeters of water and 100 grams of ammonium chlorid and shake till dissolved. Now pulverize five or ten grains of potassium platinochlorid, put in the bottle and shake at intervals for six or eight hours; let settle over night, then filter off the liquid into a second bottle. The first bottle is then ready for preparation of a fresh supply when needed.

(2) Potassium Chlorids.—In the analysis of these salts an aliquot portion of the solution, containing a half gram, is evaporated with forty cubic centimeters of the platinum solution and a few drops of hydrochloric acid, and washed as before.

(3) Potassium Sulfate, Kainit, Etc.—In the analysis of kainit, dissolve ten grams of the pulverized salt in 300 cubic centimeters of boiling water, add ammonia to slight excess, then a sufficient quantity of ammonium oxalate to throw down all lime present; cool and make up to half a liter, mix thoroughly, and filter on a dry filter; from twenty-five cubic centimeters, corresponding to a half gram, proceed to remove the ammonia, as in the analysis of superphosphates; dissolve the residue in hot water, plus a few drops of hydrochloric acid, and add fifteen cubic centimeters of platinum solution. In the analysis of high-grade sulfate and of double-manure salt (potassium sulfate, magnesium sulfate, containing about twenty-seven per cent of potassium oxid), make up the solution as above, but omit the precipitation, evaporation, etc.; to an aliquot part equal to a half gram add fifteen cubic centimeters of platinum solution. In all cases special care must be taken in the washing with alcohol to remove all the double platinum sodium chlorid which may be present. The washing should be continued some time after the filtrate is colorless. Twenty-five cubic centimeters of the ammonium chlorid solution are employed instead of ten cubic centimeters, and the twenty-five cubic centimeters poured through at least six times to remove all sulfates and chlorids. Wash finally with alcohol; dry and weigh as usual.

252. Alternate Method for Potash.—Boil ten grams of the prepared sample for thirty minutes with 300 cubic centimeters of water, and, after cooling and without filtering, make up to one liter and filter through a dry filter. If the sample have ten per cent of potassium oxid, use fifty cubic centimeters of the filtrate; if less than ten per cent of potassium oxid (ordinary potash fertilizers), use 100 cubic centimeters of the filtrate. In each case make the volume up to 150 cubic centimeters, heat to 100°, and add, drop by drop with constant stirring, a slight excess of barium chlorid, and, without filtering, in the same manner add barium hydrate in slight excess. Filter while hot and wash until the precipitate is free of chlorids. Add to the filtrate one cubic centimeter of strong ammonium hydrate, and then a saturated solution of ammonium carbonate, until the excess of barium is precipitated. Heat and add, in fine powder, a half gram of pure oxalic acid or 0.75 gram of ammonium oxalate. Filter, wash free of chlorids, evaporate the filtrate to dryness in a platinum dish, and ignite carefully over the free flame, below red heat, until all volatile matter is driven off.

The residue is digested with hot water, filtered through a small filter, and washed with successive small portions of water until the filtrate amounts to thirty cubic centimeters or more. To this filtrate, add two drops of hydrochloric acid, in a porcelain dish, and from five to ten cubic centimeters of a solution of ten grams of platinic chlorid in 100 cubic centimeters of water. The mixture is evaporated on a water-bath to a thick sirup, as above, treated with alcohol of eighty per cent strength, washed by decantation, collected in a gooch or other form of filter, washed with strong alcohol, afterwards with five cubic centimeters of ether, dried for thirty minutes at 100°, and weighed.

It is desirable, if there be an appearance of foreign matter in the double salt, that it should be washed, according to the previous method, with ten cubic centimeters of the half-concentrated solution of ammonium chlorid, which has been saturated by shaking with potassium platinochlorid.

253. Method of Solution for Organic Compounds.—In case the potash is contained in organic compounds, like tobacco stems, cottonseed hulls, etc., weigh ten grams, saturate with strong sulfuric acid, and ignite in a muffle to destroy organic matter. Add a little strong hydrochloric acid to moisten the mass and warm slightly so as to loosen it in the dish. Proceed then as in the lindo-gladding or alternate method.

254. Factors.—The use of the factors 0.3056 for converting potassium platinochlorid to potassium chlorid and 0.19308 for converting it to potassium oxid is advised. The latter number is almost identical with that used by the Halle and Stassfurt chemists viz., 0.1927 and 0.1928 respectively.

255. Methods Used at the Halle Station.—(1) In Kainits and other Mineral Salts of Potash.[204]—Five grams of the prepared sample are boiled for half an hour in a half liter flask with from twenty to thirty cubic centimeters of concentrated hydrochloric acid and 100 cubic centimeters of water, and afterwards as much water added as is necessary to fill the flask about three quarters full, and the sulfuric acid is then precipitated with barium chlorid. To avoid an excess of barium chlorid the solution used is of known strength and is added first in such quantity as would precipitate the sulfuric acid from a kainit of low sulfuric acid content. The mixture is then boiled, allowed to settle and tried with a dropping tube containing barium chlorid. If a further precipitate be given a few drops more of barium chlorid solution are added, again boiled and allowed to settle. This is continued until barium chlorid gives no precipitation. After the barium chlorid gives no more precipitate a drop of dilute sulfuric acid is added to test for excess of barium. The operation is continued with the sulfuric acid until it no longer gives a precipitate of barium sulfate. By the alternate use of the barium chlorid and sulfuric acid the exact neutral point can soon be secured. When this point is reached the liquid is allowed to cool, the flask is filled to the mark, its contents filtered, and of the filtrate fifty cubic centimeters, equal to half a gram of the substance, taken for further estimation.

This quantity is evaporated on a water-bath to a sirupy consistence in a porcelain dish with ten cubic centimeters of platinic chlorid. The platinic chlorid solution should contain one gram of platinum in each ten cubic centimeters. The residue is treated with eighty per cent alcohol and, with stirring, allowed to stand for an hour. The precipitate is then collected on a gooch, either of platinum or porcelain, washed about eight times with eighty per cent alcohol and the potassium platinochlorid dried for two hours at 100°. After weighing the precipitate is dissolved in hot water and the residue washed under pressure, first with hot water and then with alcohol. The crucible with the asbestos felt is dried at 100° and weighed. Any impurities which the double salt may have carried down with it are left on the filter and the weight of the original precipitate can thus be corrected. The weight of potassium platinochlorid is multiplied by 0.1927 and the product corresponds to the weight of K₂O in the sample taken.

(2) Estimation of Potash in Guanos and Other Fertilizers containing Organic Substances.—Ten grams of the substances are carefully incinerated at a low temperature in a platinum dish. After ignition the contents of the dish are placed in a half liter flask and boiled for an hour with hydrochloric acid and a few drops of nitric acid. The sulfuric acid can then be precipitated directly with barium chlorid, or better, allow the flask to cool, fill to the mark, filter and treat an aliquot part of the filtrate with barium chlorid as described above. The filtrate from the separated sulfate of barium is neutralized with ammonia and all the bases, with the exception of magnesia and the alkalies, precipitated with ammonium carbonate; boil, fill to the mark and filter. Of this filtrate evaporate from 100 to 200 cubic centimeters in a platinum dish. After evaporation the ammonium salts are driven off by careful ignition, the residue taken up with hot water and filtered through as small a filter as possible into a porcelain dish; the magnesia remaining in the precipitate. The filtrate is acidified with a few drops of hydrochloric acid, ten cubic centimeters of platinic chlorid added and the further determination conducted as with kainit.

256. Dutch Method.—The process used at the Royal Agricultural Station of Holland is almost identical with that employed at Halle.[205]

A. Method for Stassfurt and other Potash Salts.—The necessary reagents are:

1. A dilute solution of barium chlorid:

2. A solution of platinic chlorid containing one gram of platinum in ten cubic centimeters: It must be wholly free from platinous chlorid and nitric acid, and partially freed from an excess of hydrochloric acid by repeated evaporations with water.

3. Alcohol of eighty per cent strength by the volume:

The methods of bringing the potash into solution and of precipitating the sulfuric acid are the same as for the Halle process described above.

Add then twenty cubic centimeters of the platinum solution and evaporate the mixture nearly to dryness. Add a sufficient quantity of eighty per cent alcohol and stir for some time. Allow to stand and then filter through a gooch dried at 120°. Finally wash with eighty per cent alcohol, dry at 120°, and weigh.

B. Method for Potash Superphosphate and other mixed Fertilizers.—The reagents necessary are the same as under A, and, in addition, a saturated solution of barium hydrate and a solution of ammonium carbonate mixed with ammonia.

Boil twenty grams of the substance with water for half an hour, cool, make up to half a liter and filter. Boil fifty cubic centimeters of the filtrate, and add barium chlorid till no more precipitate forms. Mix with baryta water to strong alkaline reaction, cool, make up to 100 cubic centimeters and filter. Raise fifty cubic centimeters of the filtrate to the boiling temperature and add ammonium carbonate solution till no more precipitate forms: Cool, make up to 100 cubic centimeters and filter. Transfer fifty cubic centimeters of the filtrate to a platinum dish, evaporate and heat the residue, avoiding too high a temperature, till the ammonia salts are expelled. Dissolve the residue in water, filter, and treat the filtrate as described under A.