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Based on Remarks made in the Presidential Address to the British Association at Bristol in 1898.

REVISED WITH AN ANSWER TO VARIOUS CRITICS

By SIR WILLIAM CROOKES, F.R.S.
SECOND EDITION.

WITH PREFACE AND ADDITIONAL CHAPTER, BRINGING THE
STATISTICAL INFORMATION UP TO DATE.

With Two Chapters on the Future Wheat Supply of the
United States, by MR. C. WOOD DAVIS, of Peotone,
Kansas, and the HON. JOHN HYDE, Chiet Statistician
to the Department of Agriculture, Washington.

OPINIONS of the PRESS.

"In this bulky volume Sir William reproduces the gist of the sensational Bristol Address, and supplements it with carefully prepared answers to his chief critics and confirmatory chapters on the future wheat supply of the United States."-Morning Post.

"The appearance of the papers in this convenient form will be welcome to everyone who appreciates the importance of the problem."-Scotsman.

"The book is a useful one to all interested in the production of wheat both from the commercial and scientific points of view."-Knowledge.

"Sir William Crookes's statistics seem to make good his alarmist statement."-British Weekly.

"Sir William Crookes . . has propounded a problem which in the next century [written in 1899] is bound to engage the close attention not merely of agricultural experts, but of economists and statesmen."-Speaker.

"The student of economic science and sociology ill find this volume full of interesting material. . . The entire subject is of the profoundest interest, and an excellent purpose has been served by the publication of these papers in a single volume."-The Eagle (Brooklyn, N.Y.).

BICHROMATE OF SODA. BICHROMATE OF POTASH

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THE CHEMICAL NEWS,

16, Newcastle Street, Farringdon Street, NDON, E.G

CITY, N.Y., U.S.A.

CHEMICAL NEWS, Nov. 9, 1917

THE

PROBLEMS BEARING ON RESIDUAL AFFINITY.*

By SPENCER U. PIC KERING, M.A., F.R.S.

THE great majority of known inorganic compounds cannot be represented without attributing to the constituent atoms valency values higher than those commonly ascribed to them. The combination of molecules with each other is sufficient proof that the atoms composing them must possess residual affinity, and therefore additional combining capacity; for the properties of any mass of matter can only be those of its constituent particles. The residual affinity of an atom, A, may be insufficient to attach to it more than one atom, B, but might suffice for the attachment of another B atom if this were already combined, and had only residual affinity available; hence the higher valencies can be expected to come into play only in the formation of complex or molecular compounds, the constituents of which will be united with comparative feebleness.

Oxygen in water, nitrogen in ammonia, and sulphur are conspicuous in forming molecular compounds, and also in polymerising, as is shown by the phenomenal magnitude of the heat absorbed by them on rise of temperature or change of state. On the other hand, carbon and hydrogen appear to have little or no residual affinity, and hence have fixed valency values. As a consequence, compounds of these two elements can be built up in a way that is impossible in other cases. This is also the reason why the substitution of CH3 for H in an organic compound, or of any other single atom such as Cl or O, evolves practically a constant amount of heat, whereas the introduction of a second Cl or O, since it admits of the residual affinity of the two atoms coming into play, results in a larger heat development.

The metallo-compounds investigated by the author necessitate higher valency values for many metals than those generally exhibited by them. They are isomers of the normal organic salts, the metallic atoms forming part of the anion, being unrecognisable by the ordinary tests, and being therefore directly united to the carbon :

Metallo-compound

MIVO

anhydrous. hydrated. They are obtained as emulsions, either by double decomposition or by adding alcohol to a freshly prepared solution of the compounds. They are much more soluble than the corresponding normal salts, and gradually change more or less completely into the latter, with, in some cases, a considerable alteration in colour intensity. In cases where the change is not too rapid they may be obtained as scales or glass on evaporating their solutions. Overy forty pairs of such isomers have been obtained containing thirteen different metals, and five different acids; whilst the colour intensity of the copper salts of other organic acids renders it practically certain that similar isomers must exist in all such cases.

* Prom a paper read before the Royal Society.

223

Their preparation by double decomposition with the organic salts of sodium implies that these too must exist as such in solution, and the sodi-tartrate and sodi-citrate they have been isolated in scale form.

Alkalis or metallic oxides may take the place of the H2O in the hydrated metallo salt, and many such compounds have been isolated, some of them being isomeric with ordinary basic salts, from which, however, they differ by being soluble. But the oxygen atom may be displaced by any basic radicle, hence a salt or an acid may combine with a metallo-compound, M2R" or H2R", taking the place of H2O; such compounds may be termed metallatocompounds; e.g, sulphato, carbonato-, &c.; many of the cupricarbonates originally isolated were carbonatocupricarbonates. If the basic and acid radicle in the salt combining with the metallo-compound are the same as those in metallo-compound itself, the product will be isomeric with the simple metallo-compound, and also with the normal salt.

Metallato compounds are intermediate in solubility between these two; they form jellies or gelatinous precipitates, consisting of minute membranous particles. The formation of them constitutes one of the four or five stages (some of which are often unrecognisable) occurring in double decomposition. When barium chloride is added to con. centrated potassium tartrate solution, an emulsion of the bari-tartrate is first precipitated; this rapidly redissolves forming an ato-compound with the potassium tartrate present, its formula being BaT,K2T; then a bulky precipitate of the ato-compound, BaT, BaT, forms, which after several hours begins to redissolve, and the crystalline normal salt separates from the liquid. With the citrate more than one mixed ato-compound, Ba3Cit2x (K3Cit), is produced, some of which are sparingly soluble.

Such metallato-compounds, since they contain the group OK, not derived from an acid hydroxyl, must be alkaline, and it is owing to their presence in solutions of organic salts that these are alkaline. Such alkalinity cannot be explained by hydrolysis, for it is found that litmus is equally sensitive to acids and alkalis, and hydrolysis would liberate equivalent proportions of each.

The neutralisation of an alkali by an acid is but a special instance of double decomposition, and follows the course indicated above, but the ato-compound formed, instead of being alkaline, will be neutral, except for a slight acidity due to partial hydrolysis. Definite compounds with acids have been isolated in several cases where the metal was one of the metals of the alkaline earths, and where it was one of the alkali metals proof of their existence has been obtained by acidimetric methods. It is owing to the formation of these neutral compounds of acids with organic salts that exact titration of organic acids is generally impossible. The proportion of acid combining with the salt in solutions of decinormal strength varies from 03 to nearly 4 equivalent. A curious result of such combination is that the presence of potassium citrate, &c., prevents the evolution of carbon dioxide when an acid is added to a carbonate.

Ato compounds containing different acid radicles have been investigated. Evidence as to the existence of 2K3Cit,3(K2SO,) has been obtained, and it is owing to the formation of this (or analogous compounds) that the presence of an organic salt interferes with the determination of sulphuric acid, barium, &c., by precipitation. A barium salt added to the above compound results in the formation of a small quantity of a gelatinous or membut contains only the elements of barium sulphate, and branous precipitate, which is evidently an ato-compound,

must be sulphato-sulphate. Other evidence as to the possibility of inorganic salts existing in the metallo condition has been obtained.

With organic compounds acidity is dependent on the presence of hydroxyl side by side with a doubly-linked oxygen. It is inconceivable that a constitution which is essential in this case should not be essential in any other; it is equally inconceivable that this doubly-linked

oxygen, if essential to acidity, should play no part in neutralisation. The acidity of the haloid acids is known to depend on the presence of water; to admit of the true acid containing the group XOOH, the elements two molecules of water must be present, and, as a result, the halogens must be heptads, a value already assigned to them on other grounds. Similarly, sulphur, &c., will sometimes have to be octads, and phosphorus, &c., nonads. That a doubly-linked of oxygen is present in all acids seems to be proved by the fact that all the so-called neutral salts of the alkali metals, and of the metals of the alkaline earths, are really alkaline, just as are the salts of organic acids, though in a much feebler degree; the same explanation must apply in both cases, and this involves the presence of some of the salt in the form of a metallato-compound, and hence the presence of X=O. The alkalinity of these salts is independent of the method of preparation and purification, and is of the order of 5 × 10-4 MOH for a grm.-equivalent of the salt.

Since carbon is incapable of assuming a valency higher than 4, carbonic acid can be monobasic only; the sup posed dibasic acid, H2CO3, is unknown, and the compounds derived from it have certainly no claim to be considered as true salts-the product of the neutralisation of the acid by an alkali-for with alkali metals they are strongly alkaline, and the heat of their formation is much below the normal. All the other seven cases in which the heat of neutralisation is abnormally low are similar. Ortho-phosphoric and arsenic acids must be dibasic only, unless we assign an unacceptably high valency value to phosphorus and arsenic, and the heat of neutralisation shows them to be dibasic, the displacement of the first two hydrogen atoms evolving the normal amount of heat, whereas that of the third evolves little more than half this quantity, and the resulting products are strongly alkaline. The accepted neutralisation equation

XOH+HOM=XOM+HOH

represents a case of double decomposition, which should therefore be reversible, and in which the heat evolution should be 8900 cal. (the heat of condensation of a molecule of water), since the chemical interchange of atoms from combination with one oxygen atom to combination with another should evolve no heat. The fact that the actual evolution is 13743 cal. shows that some affinity not represented by the equation must become satisfied. This must be the residual affinity of the doubly linked oxygen atom, which comes into play on the substitution of hydrogen. which possesses no residual affinity, by a metal which possesses such affinity. With these affinities operating, a normal salt of a dibasic acid will be represented by I.,

and the corresponding metallo-compound by II.; this latter, as will be seen, is now represented as the less saturated compound of the two, which it evidently is, since it changes spontaneously into the normal salt; this agrees also with the heat of neutralisation values, for in the case of organic acids, where the metallo-compounds are the main products, the values are 2 per cent lower than with inorganic acid. Another remarkable feature of the heat of neutralisation, which is quite inexplicable on the dissociation theory, is explained by these views, namely, that the total heat of neutralisation of dibasic inorganic acids is normal, but that the addition of the first equivalent of base develops 18 per cent more heat than that of the second. Formula III. shows that the acid salt need not be, as it thus certainly is not, intermediate between the

AL

neutral salt and the acid. But with organic acids the heat developed on adding successive equivalents of base should be, and is, almost constant, for no acid salt is formed; the first equivalent of base produces the metallocompound, which unites with the rest of the acid left to form the neutral metallato-compound, and the second equivalent converts the acid in this into the normal salt, this remaining combined with the metallo-compound in the form of the slightly alkaline metallato-compound. In many cases there is a development of heat, often considerable, on adding alkali in excess of that required to saturate an acid, and the combination of alkali with normal salts have further been established by alkalimetric methods; the combination results from the conversion of MO-X=O into MO-X = (OK)2, analogues of basic salts. Taking the difference between the heat of neutralisation of inorganic and organic acids as being due to the fact that the normal salt is almost the sole products in the former case, and the metallato-compound in the latter, a rough estimate may be obtained of the heat developed in satisfying the residual affinities concerned, and, applying this to Formula I., the value for the normal heat of neutralisation should be 12419 cal., which is in quite as good agreement with the observed value of 13743 as could be expected under the circumstances.

THE GREAT FOOD PROBLEM. CLEAN CULTURE FARMING. BREAD FROM STONES. By SAMPSON MORGAN.

BREAD from stones the farmers will ask incredulously? But why not? Have I not shown from my articles that it is possible to get it? And this bread will be perfect because it will be made from perfect grain. Granite dust according to recent experiments, inspired by my clean culture propaganda, increases the fluorine and phosphorus contents of roots, fruits, and particularly of wheat grains. This fact alone must eventually induce the legislature to make the use of granite dust by wheat growers compulsory. Perfect health of body and mind without the highest percentage of both these non-metallic elements in foodstuffs is impossible. Fluorine is of the utmost importance for bone, hair, and nails. The percentage of phosphorus is higher in wheat grains than in any other vegetable product. Phosphorus-the great brain, nerve, and health food is higher in wheat grains, or whole wheat meal grown under clean culture granite dust fertilisation, than in wheat grains, or wheat meal grown under any other form of feeding.

"Without phosphorus no thought." As the phosphorus in the brain is derived from the blood, and the blood from the diet, the importance of my clean culture food reform movement is perceptible to everyone. With a knowledge of the agricultural districts all must see that the time has come when the whole industry should be completely changed and put upon a modern business basis. If the present type of fariner cannot effect the transformation then a better class of cultivator must take his place. The existence of the people depends to a very great extent upon the proper development of the food resources of the nation's acres.

We import over 10,000,000 tons of cereals, and raise about 6.500,000 tons. Yet less than one-third of the 16.500,000 tons of grain are eaten by the people. The live stock in the fields are eating us out of house and home. No wonder the representatives of Japanese agriculture who saw our boundless ranges of pastures and hordes of cattle should be astonished, because the simple British people allowed the bulk of the grains they imported and grew to be given to live stock.

The belief that flesh is necessary for health and strength is a very costly one, to say the least,

Wheat 100 Bushels an Acre.

General Cotton, who was prominent in the days of the old London Echo, when I was initiating the fruit growing and fruit eating movements in its columns, claimed to have grown wheat at the rate of 100 bushels an acre-the present acre average is 33. He obtained this remarkable result by deep digging, aeration of soil, and hand planting the wheat grains one and a quarter feet each way. The average yield per plant was 55 ears. An acre thus dealt with would contain nearly 30,000 plants. He summed up the situation by saying, "It is simply giving more air to the soil," and he was right. He grew and exhibited a plant of wheat 6 feet high having 65 ears.

Scientists tell us that of every 100 parts of the wheat crop 95 per cent is derived from air, sunlight, and moisture. In 50 tons of manure there are 40 tons of water. In the residue there is only the most infinitesimal part that can be claimed as worth anything. Manure being a soil sourer and poisoner, as I have shown, its use is as unjustifiable as it is costly.

In experiments some years ago under-drainage alone increased the yield of oats from 30 to 40 bushels an acre, the extra weight of grain alone being 400 lbs. Deep ploughing with green manuring alone assured a yield of 40 bushels of wheat against 30 bushels of oats, and an increase of 650 lbs. of grain to the acre.

It has also been found, as one would naturally expect, that sub-soils contain on an average 30 per cent more of the inorganic elements of plant food than the surface soils and when these soils were dealt with by spade labour the yield from the surface soils was seventeen-fold, and from the sub-soils forty-fold. This was greatly due to deep digging, increased sub-soil aeration, &c., enhancing the supply of available mineral matter, of which the shallow surface soils had been depleted. "I was greatly astonished many years ago," wrote an agricultural reformer, "when I dug up an average of 14 lbs. of potatoes per root, planted 3 feet apart each way, in a rich sandy soil at Tunbridge Wells, equal to 30 tons an acre, simply through aerating the sub-soil by a three-feet deep digging." But with the bonfire ash fertilisation alone I lifted plants

225

bearing 35 fine potatoes to a root, at the rate of over 50

tons an acre.

The farmers cannot by deluging the land with manure m ke up for lack of cultivation, and that the agriculturists of the sixteenth century knew better than do those of the twentieth century.

The national acre average for potatoes is seven tons. It could be made ten easily by the aid of granite and ash. In addition, instead of decreasing the output by a loss of 2,000,000 tons through disease, why should the loss not be turned into a gain by the aid of scientific cultivation. In this way a total wastage of over 5,000,000 tons could be prevented.

There is no reason why the acre average for wheat should not be 10 bushels more than it is. On 2,225,000 acres devoted to that crop the annual wastage exceeds 22,000,000 bushels of bread making grain. Yet legislators have made it a criminal offence to throw the bread crumbs which fall from the table to the birds.

Near where I write a gentleman farmer with labourers of fifty years' experience in farm work has recently deluged land intended for wheat with manure. As a matter of fact every hour spent upon the labour entailed was worse than wasted. The pea crop which preceded the wheat was a most miserable one, and it was grown in a broken up pasture, and that also had been deluged with manure previous to sowing. Every hour also spent in carting and distributing that manure was also wasted. These facts are evident to anyone acquainted with the most elementary principles of soil science.

The broken up pasture with the addition of mineral in the form of ash preferably or of granite dust would have contained ample plant food for peas. The wheat needed nothing but granite dust and gypsum, or a bland form of lime with the former dust. This is but one of thousands of cases in which the land is imperfectly and wastefully treated. Despite all the talk about economy as a nation we do not know what frugality really means. In respect to food production the ordinary agriculturists, from the highest official down to the humblest farmer, appear banded together for the purpose of maintaining methods which are discreditable to the age in which we live. Whilst manufactures have progressed agriculture lags in the rear, and there are actually numerous centres where the lazy methods of the Tudor age are still perpetuated. I could refer to broad expanses of pastures where nothing whatever in the form of mineral plant food has been added possibly for fifty years. There are millions of such acres with their restricted output, an output which is shameful, held by cultivators who are totally unacquainted with a smattering even of soil science, and who are content to jog along on the old lines, devoting their impoverished pastures to low-grade stock, which in hard winters, like the soil they feed upon, are half starved.

It is time the owners and farmers of these run down lands were called to account, and compelled to take a leaf out of the book of progressive and prosperous city industrial concerns.

Miles and miles of these impoverished acres cry out aloud for phosphates, for dust of the vitalising primitive rocks with their fertilising electrical influences, of which the sour and sluggish soil stands so greatly in need.

Amongst the conclusions formed from investigations in the production of food it was admitted that well tilled arable land will supply twenty-seven times as much human food as is now produced by our poorest pastures. And yet year after year the huge loss of foodstuffs through this slovenly system is repeated without any attempt being made by the Government to stop it.

Though I use the term "poorest pastures" I would emphasise the fact that they are poor not because of the nature of the soil but because of lack of mineral plant food and cultivation.

With a great food shortage confronting us it is nothing less than criminal, that with our costly Department of Agriculture and a bulky and highly paid staff of officials,

It is actually suggested that the annual average pro duction of meat from poor pastures is only 20 lbs. per acre, though such land put under the plough could be made to produce an average of 15 tons of potatoes or of 40 bushels of wheat an acre. With the perpetuation of such methods the wonder is not that the four-pouud loaf has been up to a shilling, but that the people have not been brought face to face with actual famine.

Ten Million Extra Acres Needed..

From the first day of the war I have persistently emphasised the necessity for taking 10,000,000 of the 17,000,000 acres of permanent pastures, in which millions of acres of the "poorest pastures" I have mentioned are included, and putting two-thirds of them mainly under wheat and potatoes. Year after year that suggestion has been ignored until this year the Government was compelled by the sheer force of circumstances to do something, and at last they have decided to increase the wheat areas by 3,000,000 acres, and then only next year. The 10,000,000 extra acres I have proved were absolutely necessary should be devoted to wheat, oats, barley, and potatoes.

Under clean culture the pastures, after being broken up with simple dressings of fine dust of the primary rocks and gypsum, or a bland form of lime, would be perfectly fitted to assure bumper harvests of wheat, and of wheat of far higher nutrient quality than any now upon the markets of the United Kingdom. Thus these extra lands could have been dressed to perfection, economically, and with the lowest possible expenditure upon labour. With regard to labour there is ample available, A staff of sturdy farm-hands have been engaged for weeks near where I write, tarring the highways to make motoring more delightful-at such a time too?

The official experts in fertilisation have been recently expressing doubts as to the possibility of farmers getting the necessary supplies of potassic fertilisers. Well, there are the granite rocks about us on every hand, and they contain the very material that they complain may not be available.

In my speech at the opening of the Swanley Horticultural College, which I founded, I exhibited some of these pears, and they were so large and richly coloured that I heard one well known gardening editor whisper to another at his side, "They are foreign." But they were home-grown. Every authority on roses commends manure. But it is the very worst material for the purpose. It induces weak shoot growth, and this in time becomes smothered with aphides, thanks to the manure.

It is easy to get sturdy rose bushes smothered with the largest, cleanest, and most fragrant flowers each year by reliance solely upon wood ashes, brick-dust, or granite dust. All these materials are perfect for grain, fruit, and flower production on clean culture lines. They will double the saccharine content of sugar-beets, mangolds, and similar roots. Through neglectiul cultivation of the broad acres of Britain we are losing millions of money each year, some of which should go into the pockets of the producers, distributors, and landowners, and a goodly part into the National Exchequer,

The politicians have been saying almost daily that we must economise. But what about the continuance of this National waste for neglecting to control which they alone are responsible? We are losing millions of tons of good food also, and yet with the most serious of faces we are continually saying, "We must economise." What sarcasm! Why do we not make a start with the land and make it produce the whole of the grain needed for our daily bread?

CHEMICAL NOTES.*

Nothing but the primitive rocks alone, ground down without any treatment for the production of extracts of a costly nature, are necessary, and such can be had now in abundance for perfectly fertilising wheat, barley, oats, and potato crops to perfection. It can even be supplied to wheat that has already been sown this autumn after the plants are up.

The provision of this powdered felspar will prove one of the greatest boons ever conferred upon agriculture. With it the whole of our run down and impoverished pastures, together with our grain and potato lands, can be well fed, cheaply and easily. In this way the whole of the community next year would enjoy greatly increased supplies of perfect foodstuffs at pre-war prices. Had this method been adopted at the outbreak of hostilities these cheap and abundant supplies would have been enjoyed without a penny rise in the market price of any of them. We could have had the full weight, four pound pure wheaten loaf at sixpence so long as the war should last. The war bas proved that our official departments have failed us lamentably all round. And why? Because they are staffed with political nominees and not with the best brains

obtainable.

We are a nation of spendthrifts so far as agriculture is concerned. In addition to the granite rocks, solidified bonfire ash, there are millions of tons of splendid fertilising material in the dust of burned clay about the brick kilns throughout the four kingdoms. At one brick works I saw immense quantities of this material in heaps covered over with luxuriant weeds. Yet it forms a splendid and true mineral plant food for the crops I have mentioned, and for fruit of all kinds it is invaluable. I could name one large

Corrosion is effected by a weak solution of acetic acid. The corrosion vats are set on an incline, one below the other so that the solution is syphoned from one vat to the other and kept in constant circulation, the content of the

bottom vat being re-pumped back to the top of the series.

These vats are 7 ft. 6 in. in diameter, and hold a ton and a half each of lead and solution. They are made of California red wood, which does not stain the solution. The vats are fitted with false bottoms, The bottom vats are covered to ensure cleanliness and avoid evaporation of the acid. The bottom vat is 10 ft. by 6 ft., and the solution is retained here till it becomes sufficiently dense as shown by test hydrometer readings. The solution is then pumped to the precipitation vat where it is treated with carbon dioxide produced from lime rock and coke, the gas being injected by a blower pump. The gas is purified before use by being passed through a scrubber and waterspray filter, which free it from tar, &c.

From the bottom of the precipitation vat the precipitate is drawn off into the washing vats, of which there are three. The acetic acid is recovered and used over and

* Abstracts reprinted from the Journal of the Chemisal, Metallurgical, and Mining Society of South Africa, May, 1917.