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T’ol. 19, No. 2
INDUSTRIAL AXD ENGINEERISG CHELMISTRY
basis. German potash is now turned out by a small number of large chemical refining plants instead of the former large number of small mechanical crushing and sorting plants. The advent of the chemist into the potash industry has effected a revolution which has attracted little attention and is therefore insufficiently appreciated. He has brought about a state of affairs where the economics of potash production is more concerned with the value of the side products obtainable than with the potash content of the raw material. This is most perfectly illustrated by the leading American potash industry, the American Potash and Chemical Company. Here through the ingenuity of American chemists potash almost of the purity of a chemical reagent is manufactured from a raw material containing only 4 per cent KzO and is offered as a fertilizer salt in competition with the European products, by virtue of the equally excellent grade of borax there yielded as a by-product. Here also by the newly developed process for extracting potash from the great New Jersey greensand deposits, containing only 6 per cent Kz0, three side products, ferric oxide, alumina, and activated silica, are yielded, the last named of which i t is estimated can carry all the manufacturing charges and
yield a profit besides, thus in effect placing the potash and the two other products on a basis of zero production cost. Lnfortunately, we Americans do not possess the byproduct type of mind. By-products mean complications both in manufacturing and selling. They are too much trouble. There is more romance in tonnage of output than in cost of production. That is why we are more enticed by the vision of potash mines in Texas than of chemical plants in New Jersey. Both have their function. It is not a plausible assumption that the great, continent-wide agricultural industry of America will ever be supplied with potash from a single source, even should a source large enough ever be discovered. Smaller potash plants, situated strategically with respect to the agricultural areas to be served, and operating on near-by raw materials, each supplying its quota and all producing side products to share the costs of the potash produced, would appear to offer better promise of cheap potash and a stable industry. I n such a scheme Texas potash will play an important role. Only in this way can we hope to effect our complete emancipation from the GermanFrench monopoly.
Significance of the Occurrence of Manganese, Copper, Zinc, Nickel, and Cobalt in Kentucky Blue Grass‘ By J. S. McHargue KENTUCKY AGRICULTURAL EXPERIMENT STATION, LEXINGTON, K Y
R E V I O U S to its inThe soils of the blue-grass region of Kentucky are t r o d u c t i o n into this richer in copper, manganese, zinc, nickel, and cobalt country, Poa pratensis than the soils of other parts of the state. Therefore, (Kentucky blue grass), was Kentucky blue grass makes a more luxuriant growth known by the more common here because it can absorb all the elements that are names of “ E n g l i s h s p e a r necessary for its maximum growth. Hence the blue grass,” “June grass,” and grass of the pastures of this part of Kentucky becomes ‘ g r e e n s w a r d .” However, a more adequate source of all the necessary vitamin with its introduction on the factors for the growth and development of fine livestock fertile soils of central Kenfor which the region has long since attained a worldtucky it was r e c h r i s t e n e d wide fame. “Kentucky blue grass,” preTable I-Analyses of sumably because of the superior luxuriance and development it attained in the soils of this region. Kentucky blue grass is YOUNGBLADES CONSTITprimarily a pasture grass and as such is far superior to any MoistureAsh UENT other grown in this part of the state. When once seeded to free the soils of this region and a good sod is formed, it makes a permanent pasture thereafter and the soil is apparently imPer cent Per cent proved by its continued growth. The grass grows rapidly in Ash Silicon the early spring and undoubtedly contains its maximum Copper nutritional properties when the young blades are 2 or 4 inches Iron Manganese in length. At this stage it presents a beautiful deep green Zinc color to the landscape and affords a rich, succulent food which Nickel Cobalt contains all the necessary elements for the development of Calcium Magnesium some of the world’s finest specimens of livestock. Phosphorus
P
Analysis of Kentucky Blue Grass
For the purpose of determining more definitely the mineral constituents of Kentucky blue grass a t a stage in its growth when it is best suited for grazing, a good-sized sample of the young blades that were about 3 inches long and were 1 Presented before the Division of Agricultural and Food Chemistry at the 72nd Meeting of the American Chemical Society, Philadelphia, Pa., September 5 to 11, 1926.
Sulfur Potassium Sodium Nitrogen Protein
3.83 23.80
... ...
the first to grow in the spring of 1925 were collected, airdried, and analyzed for the various elements contained in the grass. The usual methods of a s h a n a l y s i s were followed,*J but sulfur was determined in the dried grass by the method of Benedict.4 The percentages found are reported in Table I. K e n t u c k y Blue Grass ASH OP ALCOHOLIC
SEEDS
EXTRACT Moisturefree
OF
GREEN
Ash
BLADES Per cent 5.79
Per cent
Per canf
0:315 0.197 0.850 0.201 0.670 0.250 4.35 27.18
4.05 2.79 12.09 2.86 9.47 3.58
o:oii
0.086 0.005 0.086
...
Nine 2.340
0.045
1.770 4.960 2.380
...
... ...
2 Scott, “Standard Methods of Chemical Analysis,” 1917; copper. xanthate method, p. 165; zinc, ferrocyanide turbidity method, p. 487; nickel, glyoxime method, p. 287; cobalt, nitroso-&naphthol method, p. 143. a Willard and Greathouse, J . A m . Chem. Soc., 39, 2366 (1917); manganese. 4 J. B i d . Chem., 6, 363 (1909); sulfur.
February, 1927
INDUSTRIAL AND ENGINEERIiVG CHEMISTRY
It is to be observed from the table that Kentucky blue grass is well supplied with the elements that have important functions in the growth and development of domestic animals. A comparison of the results for some of the most important of these elements with those obtained on another important forage crop, alfalfa, reveals some facts of interest. A sample of alfalfa from the first cutting, May 21, 1924, grown on the Kentucky Experiment Station farm, gave the following analysis on the moisture-free material : Per cent Nitrogen Potassium Phosphorus Calcium Magnesium
2.15
1.91 0.38 1.41 0.27
It is thus seen that Kentucky blue grass contains considerably more nitrogen, potassium, and phosphorus, onethird as much calcium and nearly three times as much phosphorus as alfalfa. Very few analyses have been published showing the amounts of copper, iron, manganese, zinc, nickel, and cobalt occurring in forage crops. Howeyer, an analysis made by the author shows that blue grass contains appreciably more copper, nearly the same amount of iron, more than three times as much manganese, and twice as much zinc as alfalfa flour. The author considers the presence of these elements in blue grass of more significance than mere accidental occurrence, because previous work has shown that manganese is essential for the growth of plants and is concerned in the synthesis of chlorophyl. Kentucky blue grass is particularly rich in manganese and chlorophyl and therefore affords an interesting example of the function of manganese in the development of the beautiful deep green color which is characteristic of the luxuriant blue-grass pastures.
27.5
soluble X factor. For example, the protein matter in normal butter made from whole cream, when separated from the butter fat, was found to contain considerable copper. Copper is also a normal constituent of the yolk of eggs, the germs of seeds, and the livers of animals. The occurrence of copper in Kentucky blue grass and other substances rich in the vitamin A factor suggests the possibility of an important biological function for this element in the normal growth of plants and animals. The writer has previously presented data showing that more than the ten elements, carbon, hydrogen, oxygen, nitrogen, phosphorus, calcium, magnesium, potassium, iron, and sulfur, the so-called essential elements, are necessary for the normal growth and maturation of plants. Evidence has been obtained that manganese is an essential element for the growth of plants and performs an important function in the synthesis of chlorophyl. During the past year results have been obtained which show that small amounts of copper have an additional beneficial effect, as is shown in the accompanying photograph. The plants were grown in purified sand cultures from which all elements except the so-called ten essential ones had been eliminated as carefully as possible. The pot on the left contains adequate amounts of available compounds of calcium, magnesium, phosphorus, potassium, iron, sulfur, and nitrogen; carbon, hydrogen, and oxygen being supplied in the air and in the distilled water added to the pots from time to time during the experiment. All the plants are of the same age and have been treated in a like: manner, with the following exceptions: the pot on the left received available compounds of the so-called ten essential elements only, the second pot received manganese in addition, and the pot on the right received both manganese and copper besides the so-called ten essential elements.
M i n e r a l C o n s t i t u e n t s as V i t a m i n F a c t o r s
Harrow5 asks this very interesting question: “Do plants need vitamins? If animals need vitamins, do plants? And if so, where do the plants get them?” A number of investigators have demonstrated that some of the vitamin factors occur to a much greater degree in the young and tender green leaves of plants than in other parts and that some of these vitamin factors-fat-soliible A, for example-are removed in an alcoholic extract of the green leaves. The following experiment was performed for the purpose of ascertaining what mineral constituents could be removed in an alcoholic extract of the young, tender blades of Kentucky blue grass: One thousand grams of clean, freshly cut, green blades of blue grass were placed in a glass percolator which was fitted with a n asbestos pad a t the lower end. Hot 95 per cent alcohol was poured on the grass until most of t h e chlorophyl had been extracted. The alcohol was later separated from the dissolved matter by distillation in a current of air. The residue containing the chlorophyl extract was dried a t 100” C . in a platinum dish t o a constant weight.
The chlorophyl residue thus obtained weighed 66.7320 grams and upon incineration yielded a n ash weighing 5.7920 grams. Analysis of this ash gave the results contained in column 3, Table I. The chief point of interest in this connection is the fact that quite an appreciable amount of copper was found in the crude chlorophyl extract. iiccording to McCollum, hot alcohol will dissolve fat-soluble A from the tissues of plants that contain it. I n a previous report’ the writer has demonstrated that small amounts of copper are associated with substances that contain the fats “Vitamins,” p. 113 (1921).
“ T h e Newer Knowledge of Nutrition,” p. 265 (1922). ‘ A m . J . Phrsiol., 74, No. 3 (1925). 6
(1) (2) (3) Effect of C o p p e r and Manganese on Plant G r o w t h (l)-Contains 10 essential elements (Z)-Contains 10 essential elements plus M n (3)-Contains 10 essential elements plus M n plus Cu
From the differences in the growth attained by these plants the writer is led to conclude that copper as well as manganese has an important function in the growth of plants and that these two elements, manganese and copper, are two of the vitamin factors which Harrow suggests may be necessary for their growth. The distilled water with which the plants were watered during their growth was condensed
INDUSTRIAL AND ENGINEERING CHEMIXTRY
276
from a quartz tube and did not come in contact with any metal containing copper. I n the writer's earlier experiments with plants, distilled water made with a Barnstead still was used. More recently i t has been shown that water made from this type of still is contaminated with small amounts of copper and zinc. Consequently it was necessary to devise a means of producing a constant supply of distilled water free from metallic compounds. This was accomplished by replacing the metal condenser tube in a Stokes laboratory water still with a quartz tube one inch in diameter. The still has a capacity of about 3 quarts per hour. The distilled water is conducted into a clean, closed acid-proof stoneware storage container, from which it is drawn out as needed. Such precautions are absolutely necessary because plants transpire large quantities of water during a cycle of growth; therefore distilled water containing only slight but constant contaminations of copper or zinc would probably be an adequate supply for the plants' requirements. The other elements, zinc, nickel, and cobalt, whose presence in blue grass is reported in this paper, also offer some interesting possibilities in this connection. Further experiments will be required to ascertain whether or not they have a beneficial effect on the growth of plants. A comparison of the results for copper, manganese, and zinc contained in the blades and seeds of blue grass shows that the largest percentages occur in the seed. The same relationship has been noted in a number of other plants. I n seeds that have germs of sufficient size to permit of their being dissected from the endosperm-wheat and corn, for example-it has been shown that most of the copper, manganese, and zinc occurs in the germs and not in the endosperm. This association of these elements with the vital part of the seed, and also with that part of the seed which contains a number of the vitamin factors, is of particular significance in that it suggests important and necessary functions in the development and growth of the young seedling.
Vol. 19, No. 2
The Vitamin Cycle
It therefore appears that plants obtain such vitamin factors as are necessary for their growth from the mineral elements contained in a fertile soil, taking up small amounts of iron, manganese, copper, zinc, boron, and nickel, with the aid of which there are synthesized complex organic compounds in the plant. These, in turn, are passed on to the animal body, which is incapable of bringing about such a synthesis from the mineral compounds but is capable of assimilating the complex organic combinations and resynthesizing them in such a way as to meet its individual requirements. Just as we feed a plant potassium nitrate and i t synthesizes therefrom organic compounds of nitrogen, such as vegetable protein, which are consumed by the animal and resynthesized into animal protein, so it is possible, and highly probable, that the vitamin factors necessary for the growth of plants also become, upon resynthesis, the vitamin factors necessary for animal growth. Conclusion
After considerable experimenting and study, the writer is more and more convinced of a vitamin cycle in nature, in which small amounts of the elements copper, manganese, and possibly zinc, nickel, and boron, are absorbed from the soil by plants, and with the aid of these elements plants synthesize complex organic combinations which play important functions as catalysts, enzymes, vitamins, etc. When these complex organic compounds which have been synthesized in the plants are consumed by animals they are assimilated and resynthesized into catalases, oxidases, and hormones, or animal vitamins, which function in the secretions of the various organs in a more concentrated form. When the food consists of adequate amounts of green vegetables, eggs, fresh meats, including liver, fresh whole milk, and whole and unaltered cereals, the human body will obtain from such foods all the organic metal vitamin complexes, from which it can resynthesize its own organic vitamin complexes to meet its own peculiar needs and requirements.
By-Products of the Chilean Nitrate Industry' By John B. Faust2 1808 EYE ST., ? W., i WASHINGTON, . D. C.
A
S IT is not generally known that the Chilean nitrate industry produces several by-products of considerable importance, it may be of interest to list these products and outline briefly the processes by which they are made. Analysis of Raw Material
The raw material of this industry varies widely, but the analyses shown below are fairly typical. Caliche is the high-grade and Costra the low-grade material. CALICHE Per cent
Iodates as I2 Perchbrates, as KC104 Magnesium, as MgO Calcium, as CaO
COSTRA Per cent
36.00 30.00 4.50 20.00 5.00 0.10 0.15 0.20 0.70 1.50
57.00
12.50 2.60 16.00 7.50 0.20 0.06 0.30 0.60 2.00
Many of these substances are present in very small amounts, but owing to the large tonnage treated and to the 1
2
Received September 7 , 1926. Formerly chief chemist, Grace Nitrate Co., Iquique, Chile.
method of manufacture they become concentrated in the mother liquors, and so may be extracted. Leaching
The raw material is crushed and dumped into rectangular tanks holding 60 to 70 metric tons each. These tanks are equipped with steam coils for heating and are arranged in batteries of six or eight. Leaching is carried out by the well-known Shanks process, the essential principle of which is that the heaviest solutions come in contact with the fresher material and are thus more rapidly brought to the desired strength. The solutions move from tank to tank until the specific gravity of the solution in the first tank reaches 1.52 to 1.56, the temperature being 110" to 120" C. This solution is then run into a settling tank, where it is replaced with weaker solution from the tanks behind. After settling several hours the solution has a specific gravity of about 1.54 and a temperature of 75" to 90" C. It contains approximately 775 grams per liter of nitrates and 125 grams of chlorides, with varying amounts of sulfates, iodates, borates, and perchlorates. After cooling several days i t deposits crystals containing
