As was mentioned in the chapter on Bones, Liebig in the year 1840 discovered that the effect of adding oil of vitriol, or sulphuric acid, to bones was to render the phosphate they contain soluble. This discovery marked an epoch in the history of artificial manures, and laid the foundation of the now enormous manufacture of superphosphate. In 1862 the juries of the London International Exhibition published an elaborate report containing an interesting article on the manure trade of Great Britain, in which it was stated that the annual quantity of superphosphate then made amounted to from 150,000 to 200,000 tons. Now it may be placed not far short of a million tons. Probably that made in the United States is considerably more. In the first instance, superphosphate was manufactured by Sir John Lawes from spent bone-char. This was superseded by coprolites and Estremadura phosphorite, Suffolk coprolites being for many years the chief material employed. This in turn was succeeded by the richer Cambridge coprolites, but of late years coprolites have practically ceased to be a source of superphosphate, the other mineral phosphates mentioned in the previous chapter—such as the South Carolina, Belgian, Somme, &c., phosphates—taking their place.

Manufacture of Superphosphate.

The manufacture of superphosphate is of too technical a nature to permit of discussion in a work of this kind. It is important, however, that the general principles underlying the process of manufacture and the chemical changes in the phosphate taking place during the process be clearly understood. In the first place, great importance attaches in the manufacture of the superphosphate to the fineness of division of the raw material, and much ingenuity has been spent on apparatus designed for this purpose. The difficulty of grinding the phosphate varies, of course, with the nature of the material used—apatite, for example, being much more difficult to reduce to the necessary fineness than phosphatic guano. The finer the state of division, the more complete will be the decomposition of the phosphate by the acid. Mr Warington recommends that for first-class work the powder should be so fine as to admit of it passing through a sieve of eighty wires to the inch. After the phosphate is reduced to powder, it is mixed with acid. This takes place in the mixer, which is generally in the form of an iron cylinder furnished in the centre with a revolving shaft, the sulphuric acid used being the ordinary chamber acid (sp. gr. 1.57). Whatever strength of acid is used, there must be a certain quantity of water present to form gypsum. It is to the formation of gypsum in the resulting product that the dryness of the superphosphate is due. The proportion of sulphuric acid used depends on the composition of the phosphate; and here it may be pointed out that the presence of much carbonate of lime is a most important factor in determining the quantity of acid required. The reason of this is, that where carbonate and phosphate of lime are present together, sulphuric acid first acts upon the carbonate, and it is not till this is wholly decomposed that the phosphate can be acted upon. Hence mineral phosphates with a large percentage of carbonate of lime do not constitute such an economical material for the manufacture of superphosphate as those in which the percentage of carbonate is small.[225] A certain amount of heat is necessary for the purpose of enabling a quick decomposition to take place. For this purpose the sulphuric acid added has been previously heated. In the ordinary manufacture of superphosphate, however, this is not considered necessary, as the heat developed by the chemical action between the phosphate and the acid is sufficiently great. The phosphate, after being thoroughly mixed with the acid, is discharged into what is technically known as the pit, a chamber built of brick or concrete. The mixture, which is in a fluid state when it enters the pit, very soon hardens, and is dug out in a day or two. It is next reduced to powder in a disintegrator, and is then ready for use as a manure.

Nature of the Reaction taking place.

In order to clearly understand the nature of the reaction which takes place when sulphuric acid is added to a phosphatic material, it may be well to say a word or two on the composition of the different compounds of lime and phosphoric acid.

Phosphates of Lime.

In the various phosphatic manures used in agriculture there are four different kinds of phosphates. In the commonest form, popularly called bone-phosphate, which is the form in which lime and phosphoric acid are combined in bones, guano, and the ordinary mineral phosphates, the lime and phosphoric acid are combined in the form of what is known as tribasic phosphate of lime, or tricalcic phosphate—that is to say, for every equivalent of phosphoric acid there are three equivalents of lime. This may be represented as follows:—

Lime }
Lime } Phosphoric acid.
Lime }

Or we may also say that for every 142 parts by weight of phosphoric acid there are 168 parts by weight of lime in this form of phosphate. This is the least soluble form of phosphoric acid,[226] and is the form generally referred to in commercial analyses as insoluble phosphate. When this phosphate is acted upon with sulphuric acid, a soluble phosphate is formed, as Liebig first showed, to which the name superphosphate has been given, and which is also known as monobasic phosphate of lime, or monocalcic phosphate. This compound may be represented as containing, instead of three equivalents of lime, only one, the other two equivalents being replaced by water. This compound may be represented as follows:—

Lime }
Water } Phosphoric acid.
Water }In it, for every 142 parts of phosphoric acid, there are only 56 parts of lime. It is soluble in water, and gives to the commercial article known as superphosphate of lime its value. Intermediate in composition between these two phosphates there is another known as precipitated phosphate of lime, or dicalcic phosphate (the same as reverted phosphate), which contains two equivalents of lime and one equivalent of water as follows:—

Lime }
Lime } Phosphoric acid.
Water }

This compound contains, for every 142 parts of phosphoric acid, 112 parts of lime; and in solubility occupies an intermediate position. Lastly, there is a fourth compound of lime and phosphoric acid, which only occurs in one phosphatic manure—viz., phosphatic slag, in which indeed it was first discovered—which consists of four equivalents of lime to one of phosphoric acid, to which the name tetrabasic phosphate of lime or tetracalcic phosphate has been given. Its composition may be illustrated as follows:—

Lime }
Lime } Phosphoric acid.
Lime }
Lime }

Or, for every 142 parts of phosphoric acid, there are 224 parts of lime. Contrary to what we might expect, this phosphate is less insoluble than the ordinary tribasic or bone phosphate. This may be owing to the fact that, in the tetrabasic phosphate, there is more lime present than that which the phosphoric acid can retain with strong chemical affinity.[227] In the manufacture of superphosphate the tribasic phosphate is converted into the soluble phosphate—the lime, which was formerly in combination with the phosphoric acid, uniting with the sulphuric acid, and forming gypsum.[228] It was till recently supposed that soluble phosphate and gypsum were the only two resulting products of this decomposition. It has been recently shown, however, by Ruffle and others, that this is not, strictly speaking, the case, and that probably a large proportion of free phosphoric acid is formed; in fact, it seems probable that in the first stage of the reaction, only phosphoric acid is produced, and that this subsequently acts upon the undecomposed phosphate, with the production of monocalcic phosphate.[229] The amount of sulphuric acid which experience has shown it is necessary to add for the successful and economical manufacture of superphosphate, depends on the composition of the raw material employed. The larger the percentage of tribasic phosphate, the larger the quantity of sulphuric acid required for its decomposition; but sometimes even a poor phosphate consumes a large amount of sulphuric acid. This is the case where much calcium carbonate or fluoride is present in the raw phosphate, as both of these compounds require a quantity of acid for their decomposition, which takes place before the decomposition of the phosphate. Hence phosphates rich in carbonate of lime are not well suited as economical materials from which to manufacture superphosphate.

Reverted Phosphates.

A change which is apt to take place in superphosphate after its manufacture is what is known as reversion of the soluble phosphate. Thus it is found that on keeping superphosphate for a long time the percentage of soluble phosphate becomes less than it was at first. The rate at which this deterioration of the superphosphate goes on varies in different samples. In a well-made article it is practically inappreciable, whereas in some superphosphates, made from unsuitable materials, it may amount to a considerable percentage. The causes of this reversion are twofold. For one thing, the presence of undecomposed phosphate of lime may cause it. This source of reversion, however, is very much less important than the other, which is the presence of iron and alumina in the raw material. When a soluble phosphate reverts, what takes place is the conversion of the monocalcic phosphate into the dicalcic. Now in the first case, where reversion is due to the presence of undecomposed phosphate, the action taking place may be represented as follows:—

It may be mentioned, however, that reversion from this cause probably takes place to a very slight extent in practice.[230] Where reversion is due to the presence of iron and alumina in the raw material, the nature of the reaction is not well understood, and is consequently not so easily demonstrated as in the former case. Where iron is present in the form of pyrites, or ferrous silicate, it does not seem to cause reversion. It is only when it is present in the form of oxide—and in most raw phosphatic materials it is generally in this latter form[231]—that it causes reversion in the phosphate.

Value of reverted Phosphate.

The value of reverted phosphate is a subject which has given rise to much dispute among chemists. That it has a higher value than the ordinary insoluble phosphate is now admitted; but in this country, in the manure trade, this is not as yet recognised. At first it was thought that it was impossible to estimate its quantity by chemical analysis. This difficulty, however, has been overcome, and it is generally admitted that the ammonium citrate process furnishes an accurate means of determining its amount. Both on the Continent and in the United States reverted phosphate is recognised as possessing a monetary value in excess of that possessed by the ordinary insoluble phosphate. The result is, that raw phosphates containing iron and alumina to any appreciable extent are not used in this country, although they do find a limited application in America and on the Continent.

Composition of Superphosphates.

Superphosphates as manufactured may be divided, generally speaking, into three classes—viz., low class, medium, and high class. The ordinary or medium class contains from 25 to 27 per cent of soluble phosphate; and here it may be pointed out that by soluble phosphate is meant the percentage of tribasic phosphate which has been dissolved—not, as might at first sight be supposed, the percentage of monocalcic phosphate. The lower-class superphosphates are those containing less than 25 per cent, generally 23 to 25 per cent, of soluble phosphate; while the high-class superphosphate may contain from 30 to 45 per cent. For the manufacture of high-class superphosphate only a certain number of raw phosphates are available, such as CuraÇao and Somme phosphates, phosphatic guanos, bone-char, &c. Certain processes have been patented for the manufacture of even more concentrated superphosphates, and by them phosphates containing as much as 40 per cent of soluble phosphoric acid—i.e., equal to 87 per cent of soluble phosphate—have been prepared. To this class belongs the so-called double superphosphate, manufactured at Wetzlar in Germany. Such a concentrated form of manure is naturally very expensive to manufacture, and is hardly to be recommended for home consumption. Where, however, manures have to be conveyed long distances, and the freight is consequently very high, such a concentrated article may be found most economical.

Action of Superphosphates.

When superphosphate is applied to the soil it is converted into an insoluble state. In short, the process of reversion is carried on on a wholesale scale. This is due to the lime, iron, and alumina salts which the soil contains. In all probability the phosphate is finally converted into a hydrated ferric or aluminic phosphate, in which form it is gradually acted upon by the sap of the plant-roots as required. This being the case, it may be asked, Why is superphosphate so much more rapid in its action than insoluble phosphate; or why should we be at the trouble and expense of dissolving the phosphate if it has to become insoluble again in the soil? This question is one of very great importance, for the answer to it furnishes, in our opinion, the key to the whole phosphate question. When superphosphate is added to the soil, being soluble in water, it is soon dissolved and carried down by the rain into its pores, and becomes thoroughly mixed with the soil-particles. It is thus soon fixed in the soil, beyond the risk of being washed away. The result is, that the phosphate is obtained in a state of division infinitely more minute than could ever be obtained by mechanical grinding, and is, further, most intimately mixed with the particles of the soil. It is this intimate mixture of the phosphate with the particles of the soil, and its minute state of division, that constitute the only reason for rendering superphosphate superior in its action to even the most finely ground insoluble phosphates. This opinion is supported by the fact, that although the chemist has imitated nature in this matter so far as to manufacture precipitated phosphate, he has failed, as a rule, in getting as favourable results with it as with superphosphate. Although the mechanical state of division of the manufactured precipitated phosphate is probably as fine as that obtained by nature from the superphosphate, it is impossible to obtain so intimate a mixture with the soil-particles, and hence the results obtained are different. For these reasons it will be easily seen that the rate of action of the superphosphate must always be quicker than that of any other form of phosphatic manure. The phosphate is everywhere distributed in the soil. The plant-roots are thus furnished with a continuous supply throughout their growth, and micro-organisms, which require for their development a supply of this necessary plant-food, are propagated. A regularity in the plant's growth is thus secured, which is of great importance. But while admitting this, there are many cases in which this greater quickness of action does not render soluble phosphate the most economical form. The nature of the crop, as well as the nature of the soil, may in many cases be such as to render the application of the cheaper insoluble phosphate more economical. It is imperative that the early growth of some crops be hastened as much as possible by a ready supply of easily assimilable plant-food, in order to enable them to successfully sustain the attack of certain pests to which they are liable to succumb. This, for example, is notably the case with turnips. In such a case there can be no doubt that the value of soluble phosphate to the young plants is very great, as it enables them to survive this critical period.

Action of Superphosphate sometimes unfavourable.

But even in this case there may be other conditions which render insoluble phosphate a preferable manure. Such a case is where the soil is of a very light nature and is deficient in lime. In this case the acid superphosphate, not having the necessary base to combine with, may prove even hurtful to the young plants. According to the late Dr Voelcker, a concentrated superphosphate may produce a smaller crop than a fertiliser containing only a quarter as much soluble phosphoric acid, when applied to root-crops on sandy soils, greatly deficient in lime. Cases such as the above, however, are extremely rare; and we may say that, in the case of root-crops generally, superphosphate must be regarded as of special value.

Application of Superphosphate.

In any case, superphosphate ought to be applied to a soil some time before it is likely to be assimilated by the plant, in order to allow neutralisation of its acid character to be fully effected before the plant's roots come in contact with it. Thus Professor S. W. Johnson, one of the greatest living American authorities, states it as his opinion that recent investigations tend to show that soluble and reverted (or precipitated) phosphates are, upon the whole, about equally valuable as plant-food, and of nearly equal commercial value. But as Sir John Lawes, in quoting Professor Johnson to the above effect, remarks, this opinion is based on an experience of American agriculture, in which country soluble phosphate is chiefly applied to cereal crops, while in this country it is chiefly applied to turnips. In the case of cereal crops, the importance of a speedy early growth is not so great, as we have already pointed out, as it is in turnips, where the danger to the young plants from the ravages of the turnip-fly is such that the growth of even a day or two may make a very considerable difference.

Value of Insoluble Phosphate.

A consideration of the action of superphosphate, then, throws a good deal of light on the conditions which determine the value of insoluble phosphates when applied to the soil, and shows that the state of division, intimacy of mixture with soil-particles, and the nature of the soil, are the determining factors. Insoluble phosphates, as we shall have occasion to see when discussing basic slag, have their best action on soils poor in lime and rich in organic matter. Tables have been drawn up with a view to furnishing a guide for the value of phosphoric acid in different manures. In the Appendix[232] we give those of Wolff for 1893, and an American table, drawn up for 1892. The comparative values of mineral phosphates, as well as Peruvian guano and bone-dust, will be further referred to in the following chapter.

Rate at which Superphosphate is applied.

The rate at which superphosphate is applied to the soil varies in different parts of the country. In England 2 to 3 cwt. per acre is considered an average dressing; whereas in many parts of Scotland it is applied in as large quantities as 6 to 8 cwt. per acre to the turnip crop. The reason why so much heavier dressings can be advantageously given in northern parts of this country is owing to the much longer period of unchecked growth. In the more southern districts, where the rainfall is less, mildew is almost certain to appear when the sowing is as early as required for a maximum crop. With it, as with other manures, the quantity must be determined by the conditions of its application, and the amount of other manure applied.

FOOTNOTES:

[225] This holds true, it may be mentioned, with regard to the application of certain manures, such as bone-char, to the soil. Bone-char was for a long time used in France as a manure without being dissolved. The action of such a manure, containing a considerable percentage of carbonate of lime, is slower than its action would be were it pure phosphate of lime, as the carbonate of lime is first acted upon (as in the case of superphosphate manufacture) by the soil acids.