T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
IO1 2
exposed required jo cc. of t h e tenth-normal acid, i t is evident t h a t t h e one-hour exposure does not introduce a n appreciable error. I n view of t h e foregoing results, t h e writers propose t h e following modification of t h e Albert method: T h e air-dried soil is prepared according t o t h e method of t h e Association of Official Agricultural Chemists.’ Place 2 j grams of t h e soil in a Jena Kjeldahl flask. Cover with jo cc. boiled distilled water a n d a d d 50 cc. tenth-normal hydroxide solution. Digest in a briskly boiling water b a t h for one hour with occasional shaking. Remove from t h e water b a t h , a d d 1 5 0 cc. distilled water a n d 5 grams solid ammonium chloride. Connect t h e flask with a nitrogen distillation apparatus, a n d distil. Collect t h e distillate ( 1 5 0 cc.) in tenthnormal acid a n d t i t r a t e , using methyl orange as indicator. T h e strength of t h e barium hydroxide is determined by titrating directly j o cc. of t h e solution, using methyl orange as indicator. The difference between t h e two titrations, therefore, represents t h e amount of barium hydroxide absorbed by t h e soil. T h e soil has a slight decomposition effect on t h e ammonium chloride. It is necessary t o correct for this in each case b y distillation of 2 j grams of soil with j grams ammonium chloride, omitting t h e barium hydroxide solution. T h e ordinary Kjeldahl apparatus may be used, b u t care must be taken t h a t stoppers a n d connections are free from alkali, which may have been left from previous use in t h e ordinary Kjeldahl distillations. This method has been compared with t h e Veitch method on several samples of different types of soil a n d t h e results are given in t h e following table: TABLE111-LIME t a b . No. 2619 2620 2621 2623 2624 2625 3749 3752 3754 3755 15405 15407 15409 15413 15425 15427 15430 15432 15443 15445 15449 13151
REQUIREMENTCALCULATED AS MILLION DnY SOIL
CAO. PARTSPER
Description of soil Veitch Dunkirk clay loam. . . . . . . . . . . . . . . . . . . . 1100 Dunkirk clay loam. . . . . . . . . . . . . . . . . . . . 1100 700 Dunkirk clay loam.. Dunkirk clay loam. . . . , , 1100 Dunkirk clay l o a m . . . . . . . . . . . . . . . . . . . . 1000 Dunkirk clay loam.. . . . . . . . . . . . . . . . . . . 900 Dunkirk clay l o a m . , . . . . . . . . . . . . . . . . . . 900 Dunkirk clay loam.. . . . . . . . . . . . . . . . . . . 900 Dunkirk clay loam.. . . . . . . . . . . . . . . . . . .1000 Dunkirk clay l o a m . . . . . . . . . . . . . . . . . . . . 500 Volusia loam
..
..
Volusia loam.. ....................... 1434 1434 Volusia loam.. ....................... Volusia silt l o a m . , . . . . . . . Volusia silt loam.. . . . . . . . . . . . . . . . . . . . . 2390 1673 Volusia silt l o a m . . .................... Volusia silt l o a m . . .................... 2629 Dunkirk clay l o a m . . . . . . . . . . . . . . . . . . . . 1673 Dunkirk clay loam . . , . . 717 Dunkirk clay loam. . . . . . . . . . . . . . . . . . . 1195 Volusia silt loam. ..................... 1195
Modified Albert 963 940 694 1187 896 694 694 1290 985 761 1836 1321 1749 1344 . 2531 2620 2307 2352 1768 1232 1456 1344
The results obtained by t h e new method agree very well with those obtained by t h e Veitch method, a n d since there is no apparent method of standardizing either, it may be assumed t o be just as correct. T h e new method possesses t h e great advantage of rapidity, and if t h e details are carefully observed, i t is very easy t o obtain concordant results. N. ‘II. STATE COLLEGE O F AGRICULTURE CORNELL UWIVERSITY, ITHACA 1 U. S. Dept. of Agric., Bureau of Chemistry, Bull. 107, 14.
Vol. 5 , No. I 2
AN INTERESTING SOIL WATER QUESTION IN BRITISH GUIANA By MAURICEBIRD^ Received September 15, 1913
Some years ago, Harrison2 first called attention t o t h e markedly alkaline condition of t h e soil water underlying t h e sugar estates fringing t h e coast of British Guiana, and its pernicious effect upon t h e growth of t h e sugar cane; a n d since this interesting problem is one t o be very appropriately recorded in t h e pages of THIS J O U R N A L , t h e writer has prepared t h e following brief account of it. The appended analyses are typical of t h e sugar soils of British Guiana, a n d indicate their wonderful fertility from a standpoint of plant food. T h e yield a n d quality, however, of t h e cane grown upon t h e m is very often disappointing, a n d this is due t o t h e fact t h a t , many of these lands lying below sea level, deep a n d thorough drainage is well nigh impracticable, with t h e results t h a t as t h e soil slowly a n d continuously decomposes, t h e surrounding a n d underlying water becomes charged with alkaline mineral matter, t h e product of this decomposition, a n d this alkaline material entering through t h e roots, acts in. a very deleterious manner upon t h e juice of t h e cane.
Water and volatile matter.. Insoluble matter
....
Soil from Pln. Albion, Berbice (Coastal estate) 18.050 66.250
0,345 Lime. ....................... 0.629 Magnesia. . . . . . . . . . . . . . . . Potash. . . . . . . . . . . . . . . . . . 0.458 0.148 Soda.. ....................... Phosphoric acid.. . . . . . . . . . . . . . 0.248 Nitrogen.. . . . . . . . . . . . . . . . . . . . 0.172 NOTE-Though weighed as ferric oxide is in the ferrous form.
Soil Soil from Pln. from Pln. Hampton Court, Friends, Berbice Essequibo (Coastal (River estate) estate) 19,660 14.503 65.609 66.915 14.503 17.496 0.134 0.316 0.431 0.504 0.495 0.501 0.110 0.112 0.256 0.224 0.351 0.196 some of the iron in these soils
The excess of magnesia over lime in t h e above is very noticeable, and this appears t o be t h e case throughout in t h e alluvial soils of t h e colony. Coming now t o t h e soil waters, t h e writer examined a great many under varying conditions of rainfall etc., finding t h e alkali, a s determined by titrating with decinormal sulfuric acid, t o range from a trace t o 480 parts per million of water, when calculated as sodium carbonate; while t h e total mineral matter, determined by evaporation of t h e water rose t o over one per cent of t h e water. This saline material entering t h e roots of t h e growing cane was found t o produce from three t o five times t h e quantity of ash in t h e juice t h a t is found in t h e juice of cane grown on well drained soils. This ash, or mineral matter, of t h e juice concentrating in t h e molasses from t h e process of t h e sugar factory was found (as so lucidly described by Geerligs)3 t o form uncrystallizable compounds with t h e sucrose, whereby much sugar is lost. I n order t o break up these compounds a n d render t h e sugar available i t becomes’ necessary t o employ some I 2
Chemist t o the New Colonial Co., Ltd. West Indian Bullelin, 9, I. 1-39. “Cane Sugar and its Manufacture,” by H. C. Prinsen Geerligs.
Dec., 1913
T H E J O U R N A L O F I N D U S T R I A L AiVD E N G I N E E R I N G C H E M I S T R Y
such method, as osmosis or t h e Steffen process, as is in use in t h e beet sugar industry. Since t h e soil water contains a large proportion of magnesia, which in t h e cane juice exercises a n especially deleterious effect in restraining t h e crystallization of sugar, t h e experiment suggested itself t o t h e writer of precipitating t h e magnesia from t h e soil water with a solution of hydrate of lime. As this proved highly successful, large quantities of lime (from two t o three tons per acre) were applied t o a large tract of sugar lands, with t h e result t h a t t h e juice of t h e subsequently grown cane was very markedly improved. SUMMARY
One of t h e chief obstacles t o profitable sugar production in British Guiana is t h e highly saline character of t h e soil water, t o overcome which every effort should be made t o achieve deep a n d thorough drainage, which can be most advantageously supplemented b y heavy applications of slaked lime t o t h e land. Where these remedies are not practised a large loss of sugar i n t h e factory can be obviated only b y employing a special process, such as either of those indicated above, t o separate t h e sugar from t h e abnormal quant i t y of mineral matter present. PLN.ALBION,BERBICE BRITISHGUIANA
MICROORGANISMS IN COMMERCIAL LIME-SULFUR' By C. A. PETERS A N D A. W. BROOKS Received October 13, 1913
Manufacturers of commercial lime-sulfur have been troubled for some time b y t h e occasional thickening of their product when stored in barrels. As far as can be ascertained second-hand, wooden barrels of about 5 0 gallons' capacity are used in handling t h e product, a n d of a large number of barrels filled a t t h e same time with t h e same material only a n occasional one will develop t h e thickened material. T h e nature of t h e thickened product has not been understood. I n consistency i t resembles a thin ketchup. I n color i t is nearly white, although seeming t o be tinted red b y t h e lime-sulfur mother liquor. T h e solid matter of t h e mixture remains in suspension settling b u t slightly if a t all. A qualitative examination, made b y t h e writers, of a sample of this thickened material revealed a number of things which m a y be listed as follows: ( I ) When such lime-sulfur ketchup was filtered a n d dried t h e residue was largely sulfur soluble i n carbon disulfid. (2) No sulfids, sulfites, or thiosulfates were present in t h e washed residue. (3) When thickened lime-sulfur containing t h e suspended material was heated, a clear solution was obtained which was evidently t h e original concentrated lime-sulfur solution. These results indicated t h a t t h e precipitate was largely, if not entirely, sulfur. This idea was confirmed b y t h e approximate quantitative conversion of t h e residue from portions of t h e thickened limesulfur mixture into barium sulfate. Such residues filtered on asbestos or paper were washed with water 1 Material and funds for this work were furnished by the Bowker Insecticide Company of Boston, Mass.
I 013
until t h e filtrate was colorless a n d either dried about ~j hours in a n electrically heated oven a t 65-70", a n d weighed, or converted into barium sulfate a n d weighed. The results are given in Table I. TABLEI-CONVERSIOY
NO.
Weight of residue on asbestos Gram
1
0 0365
2
0.0431
OF RE5IDUAL
SULFUR INTO
Sulfur calculated from BaSOa Gram 0,0384 0.0474
B 4504
Difference Gram +0.0019 +O
0033
The amount of sulfur registered in Experiment 0.0365 gram, was transferred t o a beaker with
I,
he asbestos on which i t was filtered. The whole mass was boiled I j minutes with j o cc. of a I O per cent solution of caustic potash, and t h e sulfur oxidized b y 50 cc. of ordinary 3 per cent solution of hydrogen peroxide. T h e mixture was then made acidic with hydrochloric acid, filtered through paper and washed, a solution of barium chloride added t o t h e filtrate, a n d t h e precipitate of barium sulfate dried, heated, a n d weighed. I n Experiment 2 , a 5 cc. portion of t h e thickened lime-sulfur mixture was filtered on asbestos, t h e residue was washed until t h e filtrate was colorand weighed. less, dried about 1 5 hours at 65-70' A duplicate portion was filtered on hardened paper, t h e washed residue separated from t h e paper was treated in a beaker with caustic potash, a n d precipit a t e d a n d weighed as barium sulfate, as just described. T h e figures as given are multiplied by two before insertion in t h e table so t h a t they m a y be compared directly with those of Experiment I . The results are vitiated b y t h e occlusion of potassium salts by t h e barium sulfate, a n d in Experiment I, in addition, probably, b y t h e silica from t h e asbestos, b u t they show a n approximately quantitative conversion of t h e sulfur into barium sulfate. It seeming t o be established t h a t t h e precipitate in t h e lime-sulfur ketchup was due t o a mass of suspended sulfur, ineffective a t t e m p t s were made t o reproduce this characteristic ketchup substance b y heating various lime-sulfur solutions until precipitation took place. None of t h e concentrated mixtures resulting resembled a t all t h e original ketchup substance a n d microscopical examination of t h e residues showed masses of crystals which could have been only sulfur. When, however, t h e original ketchup mixture was examined under t h e microscope t h e first real light was shed on t h e problem. The material consisted of masses of long threads, a n d motil rods were in abundance. T h e threads separated from t h e limesulfur liquid b y filtering a n d washing, and, viewed in a water medium magnified 480 x, developed in a few minutes cross striations, a n d in t h e course of a n hour or so some of t h e threads divided at t h e cross lines. I n a few hours, after further changes, in place of t h e threads only spherical cells remained, t h e position of some of t h e threads being definitely marked on t h e microscope slide by a row of these spherical bodies. This description indicates t h a t t h e solid matter in this lime-sulfur ketchup is due t o microorganisms of a group closely allied t o Beggiatoa.
