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T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
ADDENDUM-AS s t a t e d above no literature bearing directly on this subject was found by t h e author. T h e following literature will be of interest t o anyone wishing t c undertake work of this kind. Comfit. vend., 132 (19011, 435-437. I b i d . . 141 (1905), 433-445. An abstract in Ex$. Sla. Rec., 13, 534. Landwirtschaftliche Jahrbucher, 41, 7 17-754.
This work was undertaken a t t h e suggestion of Dr. Ernest Anderson of t h e Massachusetts Agricultural College a n d was completed in t h e Department of General a n d Agricultural Chemistry of t h a t college. AGRICULTURAL EXPERIMENT STATION PURDUE UNIVERSITY,LAPAYETTE, IND
DISTRIBUTION OF CERTAIN CONSTITUENTS IN THE SEPARATES OF LOAM SOILS B y L. A. STEINKOENIG Received April 6, 1914 INTRODUCTION
T h e determinations given in this paper were made with a view t o finding t h e distribution of t h e commoner elements in t h e finer separates of a series of loam soils. T h e analyses were made b y fusion methods, so t h a t t h e entire amount of t h e constituent was determined in each case. I n many former experiments in this direction only t h e material extracted by digesting with acid of certain concentration was determined. Previous related work along this line was reviewed b y Failyer, Smith a n d Wade, in Bulletin N o . 54, Bureau of Soils, U. S. Department of Agriculture. Little work has been done along this line since this publication was issued. The bulletin of Failyer, Smith a n d Wade gives t h e determinations of t o t a l lime, magnesia, potash a n d phosphoric acid. The present work covers in addition t h e distribution of silica, iron oxide, alumina, titanium oxide, zirconia and soda. Twenty-seven soils of various types were examined b y Failyer, Smith a n d Wade f o r t h e distribution of phosphoric acid, potash, lime, a n d magnesia among t h e separates. Among other conclusions, t h e y found t h a t these constituents were more concentrated in t h e finqr particles a n d t h e segregation is more marked in soils t h a t have been subject t o extreme weathering. DESCRIPTION O F SAXPLES
T e n soils in all were examined. follows:
They were as
1-Volusia silt loam, soil, 0-8 inches, 31/g miles S. W. Saples, N. Y . Glacial origin. Formed mainly from sandstone a n d shale material, with some brought in b y glacial action. 2-Cecil sandy loam, soil, 0-8 inches, 31/2 miles S. W. Charlotte, N. C. Derived mainly from granite, gneiss a n d t o a smaller extent from other crystalline rocks. A Piedmont Plateau type. 3-Durham sandy loam, soil, 0-10 inches, l3/4 miles N. E. Archer, N. C. Formed mainly of materials derived f r o m light-colored, mediumgrained granite. A Piedmont Plateau type, occurring in the region bordering t h e Coastal Plain. Contains a relatively large percentage of potash feldspar, derived from the parent rock. 4-Hagerstown loam, soil 0-8 inches, 1 mile K. W. Conshohocken, Pa. One pf a group of soils resulting from the weathering of limestone. Sands rich in mineral species. 5-Norfolk sandy loam, soil, C-14 inches, 31./2miles S. W. Laurinsburg, N. C. An important type in the Coastal Plain Province. Derived from unconsolidated marine deposits. 6-York silt loam, soil, 0-10 inches, Bethany, S. C Formed of materials derived from imperfectly crystalline rocks, mainly talcose a n d micaceous schists. Piedmont Plateau Province.
Vol. 6 , No. 7
7-Louisa loam, soil, 0-12 inches, Trevelians, Va. Derived mainly from talcose and micaceous schists a n d imperfectly crystalline slates. Piedmont Plateau Province. 8-Penn silt loam, soil, 0-.9 inches, 11% mile W , Penn Square, Pa. Formed mainly from sandstones of triassic age. Piedmont Plateau Province. 9-Gloucester stony loam, 3 miles E. of Marlboro, N. H., soil, 0-8 inches. A glacial soil derived mainly from granite and mica schist, b u t with some admixture of other materials brought b y glacial action. 10-Carrington loam, 0-1 1 inches, Lawville, Wis. Derived through weathering, from glacial till. Glacial and Loessial Province. PREPARATION O F SEPARATES
The separates of t h e soils were obtained b y sedimentation a n d centrifuging as described in Bulletin 84, Bureau of Soils, Department of Agriculture, 1912.’ T h e diameters of t h e particles making up the separates used were as follows: Diameter in millimeters 0.1-0.05 0.05-0.025 0.025-0
Separates Fine sand Coarse silt Fine silt a n d clay
After t h e samples were ground a n d had reached equilibrium with t h e moisture of t h e air, they were ready for analysis. Moisture lost a t 1 1 0 ’ C. was determined and calculations made on t h e basis of samples dried a t this temperature. METHOD O F ANALYSES
The determinations were made by fusion methods following very closely those given in Bulletin 422 of t h e U. S. Geological Survey, “ T h e Analysis of Silicate a n d Carbonate Rocks.” Silica, iron oxide, titanium oxide, lime, and magnesia were determined first b y fusing a three-quarter gram sample. A 2 gram sample was used for t h e determination of zirconia. Zirconia was, after separation from larger amounts of silica, alumina, etc., taken up in dilute sulfuric acid solution a n d precipitated a s phosphate, fused, a n d again brought into solution a n d precipitated. The weight of t h e dioxide is calculated from t h e amount of t h e phosphate. For t h e determination of phosphoric acid the sample was fused with sodium carbonate. After removing silica t h e phosphorus is precipitated as yellow phosphomolybdate of ammonium, dissolved in ammonia a n d later precipitated as magnesium ammonium phosphate a n d weighed as magnesium pyrophosphate. The alkalies were determined b y t h e J . Lawrence Smith method. Alumina was determined by subtracting from t h e iron group t h e sum of t h e other oxides present. T h e following tables give t h e results of t h e analyses. DISTRIBUTION
O F T H E E L E X E N T S IiX G E N E R A L
T h e order of abundance of silica, alumina a n d iron oxide in these separates is t h a t usually found in soils. I n every separate examined t h e percentage of silica (SiOz) is greater t h a n t h a t of a n y other oxide. I n all cases, except two, alumina is second in order of abundance. I n most cases iron is third. As with soils hitherto examined, t h e percentage of silica decreases from t h e coarser t o t h e finer particles. Zirconia follows t h e same variation except i n t w o cases. Iron oxide, alumina, titanium (with two exceptions), potash (with three exceptions), a n d phosphoric acid 1 T h e mechanical analyses were made b y Messrs. W. B. Page of the Bureau of Soils.
L. A.
Kolbe and
T H E J O L T R N d L OF I N D I T S T R I A L ALVD E N G I N E E R I N G C H E M I S T R Y
J u l y , 1914
577
TABLEPERCENTAGE COMPOSITION OF SOIL SEPARATES No. 1 VOLUSIA SILTLOAM Fine CONSTITUEAT sands Si02 . . . . . . . . . . . . . . . . 9 0 . 0 5 1.89 5.08 0.64 CaO . . . . . . . . , , . . . . . . 0.56 Trace Zr0z . . . . . . . . . . . . . . . 0 . 1 4 NazO. . . . . . . . . . . . . , . 0.79 . KaO . . . . . . . . . . . . . . . , 0.99 PzOa . . . . . . . . . . . , . . . . 0.16
No. 2
CECILSANDY LOAM .-Fine -. Coarse Fine silt Coarse Fine silt silt a n d c l a y 87.78 4 6 . 0 9 1.69 10.51 5 . 6 6 22.52 0.95 0.98 0.47 0.70 0.15 1.03 0.07 0.01 1.06 0.40 1.06 1.66 0.44 0.08
sands 94.79 1.21 2.73 0.87 0.33 Trace 0.11 0.13 0.79 0.10
h’o. 6 YORKSILTLOAM
silt a n d clay 86.89 45.92 1.21 6.46 6.86 28.14 1.05 1.19 0.13 0.26 Trace 0.36 0.06 0.01 0.06 0.20 1.66 1.99 0.12 0.23 No. 7
LOUISA LOAM
r
9 7 . 5 1 75.03 3 8 . 9 7 0.82 2.27 7.13 1.07 15,08 31.33 0.41 0.33 0.45 0.11 0.19 0.36 0 . 0 4 Trace Trace 0.03 0.05 0.02 0.59 0.61 0.06 3.72 5.40 0.22 0.09 0.04 0.12 P205.. . . . . . . . . . . . . . ( a ) Includes both ferric a n d ferrous iron.
.
97.35 1.24 0.92 0.55 0.27 0.06 0.11 Trace 0.02 0.10
89.11 2.79 3.72 2.44 0.34 0.15 0.15 0.24 0.76 0.01
57.07 7.11 18.51 1.70 0.22 0.26 0.04 0.14 1.85 0.24
TABLE 11-AVERAGE, MAXIMUM A N D MINIMUM AMOUNTSO F THE SEVERAL MINERAL CONSTITUEKTS FOUND I N THE DIFFERENT SEPARATES
{$ax. Min Av. Fez03 Max. iMin.
AlzOa Ti02
{A v’ Max. Min. Av. ihlax. (Min.
ikx.
CaO
Min.
PERCEATAGES Fine silt Fine Coarse a n d sands silt clay Constituent 8 8 . 5 0 83.05 45.52 Av. 9 8 . 9 9 95.37 5 8 . 7 1 hIgO Max. 76.23 6 4 . 1 3 22.55 Min. 1.66 1 . 9 6 8.73 2.95 4 80 17.02 ZrOz Max. 0.35 0.52 3.97 Min. 5.48 8 44 22.57 \Av. 12 56 18 28 31.33 NazO Max. 0 . 4 0 1 48 1 6 . 7 6 IMin. 0.72 1.11 1.34 /Av. 1.20 2.44 3.38 Kz0 iMax. 0.41 0.33 0.45 ( Min. 0.59 0 . 4 8 0.64 \Av. 1 . 7 2 0 . 9 7 1.27 PzOs Max. 0.05 0.13 0.22 IMin.
{ jAV’
Fine Coarse sands silt 0.40 0.33 2 . 0 6 1.05 Trace Trace 0.05) 0.11 0 . 1 4 0.20 0.02 0 . 0 3 0.73 0.86 2 . 1 8 1.78 Trace 0 . 0 6 1.58 2.04 5 . 5 6 4.35 Trace 0 . 7 6 0 . 1 1 0.08 0.20 0.14 0.04 0.01
Fine silt and clay 0.54 1.56 Trace 0.02 0.07 0.01 0.35 0.61 0.14 2.15 5.40 0.63 0.29 0.46 0.08
Table I1 of averages a n d maximum a n d minimum results shows t h e general composition of t h e finer separates of loams a n d direction of segregation of constituents in t h e m . BUREAUOF S O I L S
E.
s. DEPARTXENT O F AGRICULTURE %’ASHIXGTON
THE PREPARATION OF “NEUTRAL” AMMONIUM CITRATE’ By
ERMON D. EASTMAX AND
No. 4 HAGERSTOWA LOAM
JOEL H. HILDEBXAND
I n t h e official method for t h e determination of phosphoric acid i n fertilizer, i t is necessary t o use a “neutral solution’’ of ammonium citrate of density 1.09 a t zoo. A n u m b e r of methods have been proposed for preparing this solution, such as those using various indicators,* t h e titration b y c o n d ~ c t i v i t y t,h~e extraction a n d h e a t of reaction method^,^ a n d a n analytical method proposed b y P a t t e n a n d MartiS6 Mention 1 Presented a t t h e 49th Meeting of the A. C. S., Cincinnati, April 4-6, 1914. 2 Bull. Bur. Chem., 107, 1; 132, 11. 8 Hall and Bell, J . A m . Chem., SOC.. 4 (1912), 443. Bell and Cowell, J . A m . Chem. Soc., 35 (1913), 49. THIS JOURNAL, 5 (1913), 567.
No. 5 NORFOLK SANDY LOAM
.?
Fine Coarse Fine silt sands silt and clay 98.99 9 5 . 3 7 58.71 0.35 0.52 3.Y7 0.40 1 . 4 8 18.44 0.57 1.12 3.38 0.05 0.24 0.28 0.01 0 . 0 3 Trace 0.06 0.18 0.07 Trace 0.08 0.26 Trace 0.15 0.63 0.08 0.03 0.08
Fine Coarse Fine silt sands silt a n d clay 7 9 . 4 4 80.53 55.29 1.27 1.05 4.84 11.39 10.08 24.80 0.79 1.11 1.86 0.88 0.68 0.43 Trace Trace Trace 0.14 0.03 0.20 0.24 1.58 1.31 1.62 5.56 4.35 0.12 0.14 0.17
Fine Coarse Fine silt sands silt and clay 76.23 8 2 . 2 6 42.96 2.32 1 . 6 7 11.13 8.01 8 . 1 9 23.80 1.03 1.16 1.01 1.27 1.72 0.97 1.44 2.06 0.84 0.11 0.11 0.01 0.27 0.83 0.37 3.83 2.54 2.02 0.45 0.20 0.03
XO. 8 PENNSILTLOAM
No. 9 GLOUCESTER STONY LOAM . r
(with one exception) increase in percentage composition with t h e fineness of t h e particles. Lime, magnesia a n d soda seem t o follow n o general rule. T h e higher content of potash in t h e coarser separates of three soils is d u e t o t h e presence of coarse crystals of potash feldspar. As a rule potash is segregated i n t h e finer particles.
Constituent
.-
1 7 -
SiOi.. -~~~ , . . . . . . . . . . . . . FezOs. . . . . . . . , . . . . . . Alz03. . . . . . . , . . . . . . . Ti02 . . . . . . . , . . . . . . . CaO. . . . . . , . . . . . . . . . AlgO. . . . . . , , , . . , . . . ZrOz. . . . . . . . . . . . . . . NazO. . . . . . . . . . . . . . . Kz0. . . . . . . , . . . . . . . .
SiOz
NO. 3 DURHAM SANDY LOAM
85.16 2.46 7.52 0.70 0.31 0.35 0.08 2.18 0.58 0.06
84.27 46.05 1 . 8 1 10.09 8.11 23.23 1.14 1.04 0.35 0.98 0.40 1.56 0.11 0.01 1.78 0.41 1.38 2.87 0.02 0.29
.
77.19 6 4 . 1 3 22.55 2.95 4.80 17.02 12.56 1 8 . 2 8 16.76 1.09 1.20 1.15 1.09 0.78 0.74 0.30 0.62 1.05 0.01 0.09 0.08 0.49 1.70 1.52 1.79 1.40 2.60 0.43 0.15 0.13
ivo. 10
CARRINGTOA LOAM
-_
I
88.33 2.07 5.15 0.45 0.59 0.28 0.07 0.56 2.40 0.10
8 5 . 0 4 41.62 1.80 9.02 6 . 9 1 18.14 0.69 0.68 0.67 1.20 0.37 1.21 0.07 0.01 1.12 0.36 2.22 1.67 0.04 0.46
should also be made of t h e recent paper b y Rudnick a n d Latshaw.’ T h e result has been t h a t while one analyst can usually reproduce his own results, t h e results of different analysts have frequently shown wide variations. T h u s LIcCandless,2 while referee on phosphoric acid for t h e Association of Official Agricultural Chemists, found solutions made b y differe n t men t o vary in their ratio of ammonia t o citric acid from I : 3.775 t o I : 4.189. T h e commercial importance of this solution requires t h a t i t should be defined accurately a n d t h a t t h e method for i t s preparation should be simple a n d reliable. Reference t o this problem b y one of us in a n address3 a t t h e Milwaukee meeting of t h e American Chemical Society led t b a request from t h e Fertilizer Division for cooperation i n its solution, resulting i n t h e work which is described i n t h e following pages. DEFIKITIOK
OF A “NEUTRAL
SOLUTION”
I n defining t h e solution it is necessary t o bear i n mind t h e fact t h a t salts of weak acids a n d bases do not necessarily react neutral i n aqueous solution. A saltlike sodium acetate will react alkaline, due t o hydrolysis, while one like ammonium chloride will react acid. When both a weak acid a n d a weak base are involved as with ammonium acetate, considerable hydrolysis will t a k e place, a n d t h e solution will contain a n a p preciable q u a n t i t y of free acid a n d base, though t h e extent t o which t h e solution would depart from neutrality would depend on t h e relative strength of t h e acid a n d base. A solution of ammonium citrate, therefore, shows considerable hydrolysis, a n d contains free acid a n d free base, even when t h e citric acid a n d t h e ammonia are present i n equivalent quantities. F o r this reason i t is folly t o expect t o prepare a neutral solution of ammonium citrate b y one of t h e methods t h a t has been proposed, i. e., t o a d d a n excess of a m monia a n d let s t a n d till t h e excess has volatilized. Any solution of ammonium citrate, whether acid or alkaline, contains free ammonia, which would be gradually removed on standing open t o t h e air a n d more rapidly b y boiling. 1
THISJOURNAL, 5 (1913). 998
2
Bull Buy. Chem., 122, 147. Hildebrand, J . A m Chcm. SOC.,36 (1913). 848, 1538.
3
