Dec., 1913
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c Effect of Soluble Sulfates. Richardson, J. Am. Chem. SOC., 1314 (1907). 13. Use of Tartaric Acid to Prevent Separation of F e a n d Mo, by Juptner. Chem. Centralblatt, 2, 1813 (1894). 14. Neumann’s Method. 2. phys. Chem., 87, 115 (1902). (Boils yellow then cools and titrates back precipitate with K O H to remove “3, with acid.) 15. Reaction of Phenolphthalein with PtOa Thompson, Chemical News. 47, 127, 186 (1883). 16. Amount of Phenolphthalein Necessary t o Use. Long. Am. Chem. J., 11, 84 (1889). 17. Direct Weighing of Yellow Precipitate‘. Gladding, J. Am. Chem. SOC., 18, 23 (1896); U. S. D. A,, Div. of Chemistry, Bulletin 61, 47 (1898); 49, 60 (1897). 18. Purification of Yellow Precipitate by Double Precipitation and Estimation of PzOI b y Weight of Yellow Precipitate, with S t u d y of Effect of Iron a n d Various Substances. Woy, Chem. Ztg., 21, 442 (1897). Translation in Treadwell & Hall, Anal. Chem.. 11, 344. Well washed a n d 19. Finkner’s Method. Berichte. 11, 1640 (1878). dried a t 160-180, factor, 0.3794. Hundeshagen’s factor for same is 0,3753. 20. Estimation of P2Os b y Weight of Yellow Precipitate, Wash with Acetone D r y in Vac. Lorenz method, Chem. Abstracts, M a y 20, 1912, First paper 1266. Original in Z. anal. Chem., 61, 161-175. I b i d . , 46, 193. Estimation of PzOs b y Weight of Yellow Precipitate. Chem. Abst., 21. Original in Oesterr. Chem. Ztschr., 14, 6, 584 (1912), M a r c h 10. 1-5 a n d abstract in J. Chem. SOC., 100-11, 11, 1028. 22. Lorenz Method Direct Weighing of Yellow Precipitate after Drying. Landw. Vers.-Stat.. 66, 183. 23. Ignition of Yellow Precipitate to P z O ~(MoOs)zr, Effect of Various Sherman & Hyde, J. Am, Salts a n d Adding M o Solution ?dually. Chem. SOC., 22, 652 (1900). 24. This is essentially Woy’s method. Chem. Ztg., 21, 441, 469 (1897). 25. Pre-ipitate Ignited below Red Heat and Weighed. Factor = 0,3946 for PzOs (Mo0a)r. Berichte. 11, 1640 (1878). b y Weight of Yellow Precipitate, after Heating 26. Estimation of P z O ~ till Blue. Factor, 0,0396. Double Precipitation Used t o Get Pure Precipitate. Auld, Analyst, 37, 130 (1912). 27. Use of BaClz to Get Correct E n d Point in Titration. THISJOURNAL, July, 1912, p. 520. 28. Volumetric Determination of PzOa, Use of BaC12. t o Improve E n d Point. Chem. Abst., M a y 20, 1912, p. 1265. Original in J. Wash. Acad. Sci., 2, p. 114. 29. Colorimetric Determination of Pzos. Chem. Abstracts, March 10, 1912, p. 662. 30. Colorimetric Detrrmination of PzOs. Prep. Sodium Molybdate, Etc. Expt. Station Record, 26, 406 (1912, April). 31. Silver Phosphate as Standard for PzOa. Dumas, Chem. Eng., 11, 185 (1910). 32. Preparation of Pure AgsPO4. Baxter and Jones, J. Am. Chem. SOC., 82, 298 (1910). 33. NaNHtHPO4,HzO a s Standard Phosphate. Jorgensen, Z. anal. Chem.. 46, 273 (1906). 34. Hundeshagen’s Work on Yellow Precipitate. Etc. 2. anal. Chem., 28, 141. Trans. in Chemical News, 60, 168, 177, 188, 201,215. 35. Comparison of Several Methods for P2Oa Determination b y D. J. Hissink. Chem. Weekblad, 116, (1905). 36. Influence of Al, M g , C a on PzO6 Determination. Neubauer. Landw. Vers.-Stat., 63, 141 (1905-6). 37. Citric Acid to Prevent Contamination of MgNHdPO4 with MgO. Lorenz, 2. anal. Chem., 32, 64 (1893). 38. Use of MgO for Incinerating Material for Pi06 Determination. Chem. Abstracts, 6, 1416 (1912, June). From 2. physiol. Chem., 76, 426. 39. Same subject in Experiment Station Record, 28, 20 (1913, Jan.). Loss of PZOSin Burning Wheat. Leavitt and LeClerc, J. Am. Chem. 40. SOC.,SO, 391, 617 (1908). 41. Direct Titration of Phosphate Solution b y Molybdate Solution Containing Gelatin. B y -4.Grete, in Koenig/iUnters. Landw. a n d Gewerblich Stoff. 42. Same subject in Experiment Station Record, [3] 28, 203 (1913). 43. Neumann’s Method for PzOs, Use of Formaldehyde. Experiment Station Record, 26, 406 (1912, April). 44. Loss of Phosphorus on Ignition of MgiP20,. Neubauer, J. Am. Chem. SOC.,16, 289 (1894). 45. Composition of Yellow Precipitate, Etc. B y Baxter, Am. Chem. J., 28, 298 (1902). 46. Same by Baxter and Griffin, Am. Chem. J., 34, 204 (1905). 47. Use of HzSOd t o Obtain Constant Results. B y Lagers, 2. anal. Chem., 47, 561 (1908). 12.
&RTnIZER CONTROL LABORATORY UNIVERSITY OF CALIFORNIA BERKELEY
THE COMPOSITION OF SEDIMENTS FROM THE POTOMAC AND SHENANDOAH RIVERS B y JOSEPH G . SMITHA N D WILLIAMH. FRY> Received October 13, 1913
This investigation was undertaken t o ascertain whether or not the sediments from t h e two rivers showed a n y marked chemical a n d mineralogical differences, with a view t o using t h e results i n t h e s t u d y of soil erosion. Samples of water were collected b y t h e Weather Bureau in five-gallon lots, a t various times during a n interval of two years. The sediments were allowed t o settle, t h e water siphoned off and t h e residues dried. I n most cases t h e amount of sediment was so small t h a t a chemical analysis was impossible. Mineralogical examinations, however, were made of each sample. The particles, generally, were of extremely small size; a n d were very much weathered a n d coated with iron oxides, hydroxides, organic matter, a n d possibly other material. Consequently, t h e character of t h e larger percentage of t h e grains was wholly indeterminable. T h e mineralogical analyses represent simply t h a t p a r t of t h e material which was in large enough particles a n d fresh enough for determination. This determinable m a t t e r probably never amounted t o more t h a n t e n per cent of t h e total sample. It is not t o be concluded t h a t t h e minerals cited in t h e following tables were t h e only ones present. T h e y are t h e more prominent ones which could be positively identified, a n d i t is quite probablf: t h a t other mineral species were present which defied identification. T h e lithology of t h e two river basins seems t o be very similar as will be seen from t h e following r6sum6: The Potomac River above Cumberland comes into contact with sandstones, shales, limestones, etc. F r o m Cumberland t o Harper’s Ferry it flows over or in close proximity t o sandstones, shales, limestone, a n d unconsolidated sands a n d clays.* T h e Shenandoah River above Riverton flows over limestone-shale a n d sandstone-shale formations. The headwaters rise in a sandstone-shale-limestone formation, a n d flow over a narrow band of sandstone-shale. Below Riverton i t flows over limestone and shale, a n d touches a sandstone-shale-quartzite f ~ r m a t i o n . ~ DETAILEDMINERALOGICAL ANALYSES(W. H. F R Y , ANALYST) MD. (POTOXAC RIVER) SEDIMENTSFROM CUXBERLAND, No. 1. Hornblende, biotite, quartz, feldspar [labradorite(?)I, orthoclase. T h e doubtful labradorite showed twin structure and the determination was made by the extinction of the twins in conjunction with the refractive index. However, the particle was very small; but it is certainly one of the plagioclase group. There were present very small fragments of what appear t o be silicious tests of spicules of some form of microscopic animal or plant life. No. 2. Quartz, biotite. animal o r vegetal spicules, plagioclase, a doubly refracting grain with a high index of refraction which may be zircon (the small size of the particle prohibited its determination), hornblende(?), small amount of magnetic particles. No. 3. One rather large grain of what appears t o be a glass. It is isotropic with an index or refraction very near 1.54. It is probable t h a t this is a fragment broken from a glass vessel. Magnetic particles, quartz, hornblende. No. 4. Magnetic particles, muscovite, quartz, isotropic particles with index of refraction near 1.54, plagioclase. No. 5. Largely organic matter, The organic material masks the mineral constituents so a s to make them indeterminable. 1Scientists in Soil Laboratory Investigations, Bureau of Soils, U. S. Department of Agriculture. 2 Maryland Geological Suruey, 3, P1. 6 (1899). 3 T. L. Watson, “ A Geological M a p of Virginia,” Va. Geol. Survey.
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Vol. 5 , No.
12
I
h-0. 6. Quartz, some indeterminable lerromagnesian mineral, hornblende, animal or vegetable tests. No. 7. Muscovite, biotite, quartz, animal or vegetable tests, hornblende. X o , 21. Magnetic particles, quartz, muscovite, plagioclase. animal or vegetable tests, biotite, microcline. No. 29. Magnetic particles, quartz, muscovite, hornblende, biotite, animal or vegetable tests, orthoclase. No. 34. Quartz, hornblende, biotite. All of the particles in this sample are of very small diniensions. No, 36. Slight amount of magnetic particles, quartz, orthoclase, hornblende, mica(?). No. 39. Magnetic particles, quartz, muscovite, biotite, hornblende, animal or vegetable tests. N o . 41. Magnetic particles, quartz, hornblende, muscovite, orthoclase, biotite. Very much vegetable matter present. N-0, 43. Slight amount of magnetic particles, quartz, biotite, hornblende. SEDIMENTS FROM RIVERTON,V A . ( S H E N A N D O A H RIVER)
KO, 14. Quartz, garnet, muscovite, biotite, orthoclase. No. 15. Magnetic particles, quartz, biotite, orthoclase. N-0. 16. Quartz, muscovite, animal or vegetable tests, biotite. KO. 20. Quartz, muscovite, biotite, plagioclase ( ? ) , garnet, hornblende. No. 27. Quartz, plagioclase. This material is extremely fine and is very much coagulated. N-0. 31. Slight amount of magnetic particles, quartz, biotite, orthoclase, hornblende. No. 32. Isotropic particles with index of refraction about 1.54, probably glass, quartz, orthoclase, biotite, hornblende. No. 37. Quartz, calcite. This material is extremely fine. N o . 38. Quartz, hornblende, mica(?). Material is very fine.
SEDIMENTS FROM HARPER’SFERRY (POTOMAC RIVER) No. 8. Quartz, biotite, muscovite, labradorite, orthoclase, few vegetable or animal tests, chlorite(?). Nro. 9. Quartz, hornblende, biotite, plagioclase, muscovite. No. 10. Quartz. muscovite, particles deeply coated and impregnated with some coloring matter, probably iron oxides. No. 11. Magnetic particles, quartz, hornblende, muscovite, animal or vegetable spicules, biotite, plagioclase. No. 12. Magnetic particles, quartz, zircon, hornblende, calcite plentiful. tourmaline, biotite, Orthoclase, muscovite. No. 13. Magnetic particles, quartz, very much altered biotite, plagioclase, hornblende, muscovite. No. 18. Magnetic particles, quartz, muscovite, garnet, biotite, orthoclase. Y o . 19. Magnetic particles, quartz, biotite, garnet, hornblende, plagioclase, orthoclase. No. 22. Magnetic particles, quartz, biotite, muscovite, microcline, plagioclase, orthoclase, hornblende. A fair amount of this material consists of grains of about the dimension of very fine sands, thus differing from the usual silty or clayey character of the sediments. These large grains are mainly quartz. Iio. 23. Very small amount of magnetic particles, quartz, biotite. small amount of animal or vegetable tests, labradorite, some ferromagnesian mineral, muscovite, orthoclase. Practically all the particles are very small. No. 24. Quartz, animal or vegetable tests, microcline, labradorite, biotite, muscovite, orthoclase, hornblende, calcite. No. 25. Small amount of magnetic particles, quartz, plagioclase, biotite, muscovite, hornblende, orthoclase. KO. 26. Magnetic particles, quartz, muscovite, tourmaline, orthoclase, plagioclase, biotite, hornblende. A-0. 28. Quartz, biotite, animal or vegetable tests, rutile, garnet, muscovite, hornblende. No. 30. Very slight amount of magnetic particles, quartz, biotite, orthoclase, plagioclase, rutile, microcline, muscovite, shell fragments which effervesce with hydrochloric acid. X o . 33. Very slight amount of magnetic particles, quartz, muscovite, hornblende, biotite. No. 35. Very slight amount of magnetic particles, quartz, hornblende, biotite. orthoclase, plagioclase(?), muscovite. No. 40. Quartz, orthoclase, biotite, hornblende, muscovite, plagioclase. Iio. 42. Magnetic particles, quartz, microcline, biotite, muscovite, calcite, plagioclase. No. 44. Magnetic particles, quartz, labradorite, biotite, muscovite, orthoclase. S o . 45. Small amount of magnetic particles, quartz, muscovite, biotite, hornblende. Iio. 46. Small amount of magnetic particles, quartz, hornblende, some mineral which appears to be a n amphibole other than hornblende, muscovite, biotite, X o . 47. Magnetic particles, quartz, hornblende, muscovite, plagioclase, biotite. S o . 48. Quartz, muscovite, biotite(?), calcite(?). No. 49. Quartz, hornblende. Particles extremely fine.
TABLEI-SUMMARY
THE MINERALS FOUND I N THE
OF
SEDIMENTS FROM
THE DIFFERENTS T A T I O N S
CUMBERLAND
RIVERTON
HARPER’S FERRY
Hornblende Biotite Quartz Orthoclase Plagioclase Magnetite Muscovite Labradorite(?) Zircon(’) Microcline Femic mineral(?)
Hornblende Biotite Quartz Orthoclase Plagioclase Magnetite Muscovite
..........
Garnet Calcite
Hornblende Biotite Quartz Orthoclase Plagioclase Magnetite Muscovite Labradorite Zircon Microcline Femic mineral(?) Garnet Calcite Tourmaline Rutile Chlorite(?)
......... ..........
..........
.......... .......... .......... ..........
.......... ..........
..........
As can be seen from Table I , the sediments from Riverton do not show the presence of microcline, t h e doubtful femic mineral, labradorite, a n d zircon, which are present in the sediments from Cumberland, while t h e Riverton sediments contain garnet a n d calcite in addition t o t h e minerals found in t h e Cumberland sediments. The sediments from Harper’s Ferry, where t h e two rivers join, contain all of the minerals found in the sediments from the other two stations, a n d tourmaline, rutile, a n d doubtful chlorite in addition. However, it should be remembered t h a t only a relatively small proportion of t h e minerals were determinable and t h a t t h e composition of t h e indeterminable material, were it known, might or might not considerably modify this table. TABLE11-CHEXICAL ANALYSESOF SEDIMENTS F R O M CUMBERLAND C. F. Miller, Analyst
No. 1
6 34
SiOn A1203 52.03 48.97 55.23
+ FezOa
27.78 24.88 25.50
CaO 0.65 1.15 1.07
MgO 1.70 1.16 1.37
PzOj 0.30 0.40 0.24
NazO 1.92 1.41 0.67
Kz0 3.28 2.36 2.91
TABLE111-CHEMICAL ANALYSESOF SEDIMENTS FROM RIVERTON R. F. Gardiner, Analyst No. Si02 AlnOa FezOa CaO MgO PzOj Nan0 KzO
+
14 27 38
63.00 67.07 50.51
22.56 21.06 27.34
0.48 0.46 0.63
0.90 1.12 1.27
0.52 0.34 0.63
0.72 0.90
1.36 2.42
. . . . . . . .
TABLEI v - C H E M I C A L
ANALYSESOF SEDIMENTS FROM HARPER’SFERRY Average of Duplicate Analyses b y R . F. Gardiner and C. F. Miller No. 12 22 23 28 35 48
Si02 A1203 58.91 67.05 63.33 64.73 62.53 53.73
’
+ Fez08
22.70 18.05 20.95 20.54 21.08 25.00
CaO
MgO
P20;
NazO
Kn0
1.33 0.50 0.71 0.86 1.12 1.07
0.94 0.91 1.00 1.07 1.23 1.44
0.43 0.46 0.30 0.28 0.29 0.31
0.76
1.93
. . . . . . . . 1.70 0.78 0.48 0.90
2.18 2.26 2.05 2.16
The soda a n d potash determinations were made by the J . Lawrence Smith method, t h e others by fusion with sodium carbonate. Samples 2 2 from Harper’s Ferry and 38 from Riverton were so small t h a t only a partial analysis could be reliably made. The analyses do not show any definite relation between chemical composition and t h e amount of sediment carried in the streams when the samples of water weredaken. This was to be expected, since unequal rainfall over the varying geological formations of these large river basins would carry into t h e streams material of varying composition. The results are in harmony with the well-known
T H E J O U R N A L O F I N D U S T R I A L A N D ELVGINEERING CHE-WISTRY
Dec., I913
fact t h a t t h e finer particles of soils such as would be carried b y stream waters are high i n potash, phosphoric acid, lime, organic m a t t e r , etc. BUREAUO F S O I L S U. S. DEPT. AGRIC., WASHINGTON
ESTIMATION OF THE LIME REQUIREMENT OF SOILS' BY J. A. BWZELLAND
'r. .I
LYON
Several methods have been proposed for t h e estimation of soil acidity, b u t none is entirely satisfactory. T h e difficulty is t h a t t h e t r u e n a t u r e of t h e acidity is not understood. T h e problem is further complicated b y t h e fact t h a t lime m a y be beneficial t o a soil i n other ways t h a n b y simply correcting a n acid condition. T h e nearest approach t o a quantitative determination of t h e lime requirement of a soil, therefore, would seem t o be a n estimation of t h e t o t a l absorptive power of t h a t soil for lime. This is t h e principle upon which t h e well-known method proposed b y Yeitch* is based. T h e most serious objection t o this method from t h e analyst's standpoint is t h e large n u m b e r of determinations which must frequently be made before t h e alkaline point is reached. T h e writers have also frequently found i t difficult a n d sometimes almost impossible t o determine t h e saturation point. This is t r u e particularly oi soils containing a large q u a n t i t y of organic m a t t e r yielding highly colored extracts, a n d of those containing a large percentage of clay. M a n y clay soils will n o t settle sufficiently, el-en after very long standing, a n d the clay particles in such cases are so fine as t o defy filtration b y t h e ordinary methods. With a view t o overcoming these difficulties t h e writers have examined a method described by R. Albert3 a n d propose certain modifications which seem t o render i t suitable for estimating t h e lime requirement of soils. I n brief, t h e method as proposed b y Albert is as follows: To 2 j grams of air-dried soil a d d 2 0 0 cc. boiled distil'ed water, j o cc. of a s t a n d a r d solution of barium hydroxide, a n d j grams solid ammonium chloride. Distil t h e mixture! collecting t h e a m monia formed in tenth-normal acid. T h e a m o u n t of ammonia found i n t h e distillate is assumed to be proportional t o t h e free barium hydroxide not required t o saturate t h e soil. Barium hydroxide was found TABLE I-LIME
REQCIREMENT CALCULATED A S C.40.
PARTS
PER b ~ I L L I O N
DRYSOIL Lab. No. 2333 2619 2620 262 1 2622 2623 2624 2625
Veitch method
Albert method
Lab. No.
1500 1100 1100 i00 0 1 100 1000 900
930 67 24 0 0 156 201 0
2626 3749 3750 3751 3752 3753 3754 3755
Veitch method 0 900 0 0 900 1400 1000 5 00
Albert method 0 0 0 0 134 560 0 0
preferable t o calcium hydroxide, since t h e latter seems t o form with t h e soil certain easily decomposed compounds which effect decomposition of a m m o n i u m chloride. Paper presented a t the 48th meeting of the A . C. S., Rochester, September 8-12, 1913. 2 J . A m . Chem. SOC.,24, 1120. Z. angew. Chem., 1, 533.
IO1 I
This method was compared with t h e Veitch method on a number of samples of soil a n d subsoil of t h e Dunkirk clay loam t y p e , obtained from t h e experiment field. T h e results are given in Table I . T h e results b y t h e t w o methods were widely differe n t , a n d in view of t h e field results obtained b y t h e use of lime an this soil, indicated t h a t t h e figures obtained b y t h e Albert method were much t o o low. This discrepancy appears t o be due chiefly t o t w o factors which apparently were not recognized b y t h e author. I n t h e first place solid ammonium chloride undergoes slight decomposition when boiled with water, a n d appreciable quantities of ammonia are given off. When boiled with some soils ammonium chloride gives u p enough ammonia t o very materially affect t h e results, rendering t h e figures for acidity much t o o low. T h e a m o u n t of ammonia given off was diRerent for each soil. Twenty-five samples were examined a n d t h e ammonia formed expressed in equivalent of tenth-normal acid varied from 0.4 cc. t o j . 6 cc. It becomes necessary, therefore, t o determine this factor for each soil a n d t o make a correction accordingly. T h e second error consists in assuming t h a t t h e absorption of barium hydroxide is immediate. This assumption was found t o be incorrect. I t was found t h a t fixation of barium hydroxide b y a soil was complete when t h e mixture mas heated i n a water b a t h for one hour a t t h e temperature of boiling water. T h e effect of this t r e a t m e n t is shown in t h e following table: TABLE11-BARIUM HYDROXIDE~BSORBEDEXPRESSED AS
I,I'*IE (CAO).
PARTS PER MILLION DRY SOIL
Lab. No. 2619 2620 2623 2624
Absorbed immediately
Ahsorbed during one-hour standing in boiling water
425 425 403 425
9 63 940 1187 896
Absorbed immediLab. 5-0. ately 3i4Y 37.i2
3i54 3755
313 515 268 224
Absorbed during one-hour standing in boiling water 694 1209 985 i61
T h e higher figures obtained b y t h e longer contact of t h e b a r i u m hydroxide a n d soil might be ascribed t o t h e removal of t h e base from solution b y t h e carbon dioxide of t h e air, in which case t h e longer exposure would introduce a n error. T o test this point jo CC. of t h e s t a n d a r d barium hydroxide solution a n d jo cc. of water were placed i n a j o o cc. Kjeldahl flask. T h e unstoppered flask mas t h e n placed i n a water b a t h maintained ai; t h e boiling temperature a n d allonTed t o remain one hour. T h e flask was t h e n removed, ~ j cc. o water a n d j grams solid ammonium chloride added, a n d t h e mixture distilled in t h e ordinary Kjeldah1 a p p a r a t u s with t h e following results : Ammonia expressed in equivalent of S , 10 acid Cc. 5 1 .4 50 cc. barium hydroxide 5 grams ammonium chloride. . . . 5 grams ammonium chloride.. . , , . , , , , , . , , , , , , . , , . , . . . . . . 1.6 Formed b y barium hydroxide., . , . , , , . , . . . . , . . . . . . . . . . . , . 49.8
+
As direct titration of jo cc. barium hydroxide u n -
