sand, now used as filler, the acidity produced by these mixed Company, F. S. Royster Guano Company, and the Virginia-
fertilizers could easily be neutralized. Those manufacturers Carolina Chemical Corporation.
who use limestone or produce base-forming fertilizers would
then get credit for the added value of their products and the LITERATURE
CITED
farmer would be protected in that he would know the acid- (1) Britton, H. T. S., Hydrogen Iong, Van Kostrand, 1929.
or base-forming properties of the fertilizers. Moreover, (2) Burgess, P. S.,Rhode Island Agr. Expt. Sta., BUZZ. 189 (1922).
(3) Frear, D. E., J.Bid. Chem., 88, 675-81 (1930).
economy would result fro& the saving of freight on the sand (4) Lipman, J. G., Blair, A. W., and Prince, A. L., Soil Sci., 19,
or inert material now used as filler in mixed fertilizers. 57-75 (1925).
(5) MacIntire, W. H., and Shaw, W. M., IND. ENG.CEIW., 24,
1401-9 (1932).
ACKNOWLEDGMENT (6) MacIntire, W. H., and Shuey, G . A., Ibid., 24, 933-41 (1932).
(7) Parker, F.W., Am. Fertilizer, 76, 2, 13 (1932).
The author wishes to express his appreciation for the (8) Pierre, W. H., J. Am. SOC.Agron., 20, 254-69,269-79 (1928).
cooperation given by T. B. Leith, State Chemist, and the (9) Pierre, W. I-I.,Ibid.,in press (1933).
following fertilizer companies in furnishing many of the RECEIVED April 17, 1933. Publiahed with the approval of the Director of
samples of fertilizer used in this study: Armour Fertilizer the West Virginia Agrioultural Experiment Station as Scientific Paper 128.
Works, The Baugh and Sons Company, Gulf Manufacturing Contribution from the Department of Agronomy and Genetics.
COLORIMETRIC method for the determination of larger quantities. Under the present condition, however,
fluoride in water, recently described ( I ) , is based on the iron withdrawn from reactivity with thiocyanate-that
the fact that the intensity of the color produced with is, the bleaching effect of a given amount of fluoride-is
thiocyanate by a given amount of iron in the presence of definite and reproducible although not a straight-line function.
fluoride is less than that produced in the absence of fluoride, I n the presence of 0.45 mg. of fluoride the color is more
by an amount depending on the quantity of fluoride present yellow than red and it is inadvisable to extend the curve
if there is an excess of iron. By determining colorimetrically beyond this point.
the excess of iron reacting Kith ammonium thiocyanate,
the quantity withdrawn by the fluoride from a given amount TABLE
11. DETERMINATION
OF FLUORIDE
IN ARTIFICIAL
WATERS
of iron may be found by difference and its equivalent in ---so4 AS--- TOTAL -C1 AS-- TOTAL FLUORIDE
Cas04 MgSO4 NazSOa SO4 CaClz MgCh NaCl C1 Added Found
fluoride read from a curve which has been made by plotting Mg. Mg. MQ. Mg. Mg. Mg. Mg. MQ. Mg. MQ.
definite amounts of fluoride against the iron they withdraw 7.0 .. .. 7 . 0 26.5 16.5 2 . 0 45.0 0.35 0.32
0.20 0.20
from the amount of iron used in the determination. 0.025 0.026
In a volume of about 75 cc. 0.375 mg. of iron (5 cc. of a 0 . 0 0 0.00
standard ferric chloride solution containing 0.075 mg. of
iron per cc.) produces about as deep a color as can be read .. 1.5 8.5 10.0 2.5 .. 17.7 20.2 0.35 0.32
0.20 0.20
in a Schreiner colorimeter and was taken as the amount of 0.025 0 . 0 2
0.00 0 . 0 0
iron to be used. On this amount of iron 0.25 mg. of fluoride
produces a marked fading and even as little as 0.025 mg. .. 3.0 1.0 4.0 16.0 ,. 4.0 20.0 0.35 0.35
0.25 0.24
produces a fading that can be detected in a colorimeter. 0.025 0.025
0.00 0.00
This degree of sensitivity permits the use of small volumes
of water, 50 or 100 or even 25 cc,, if the fluoride content .. 3.1 16.8 19 9 9.2 .. 16.5 25.7 0 . 3 5 0.325
0.20 0.20
of the sample is more than 4 parts per million. 0.025 0.025
0.00 0.00
TABLEI. FLUORIDE
FOUND BY SUBTRACTINQ
IRON
WITHDRAWN ... .. 20.0 20.0 1.4 1.2 29.6 32.2 0.35 0.33
BY SULFATE
FROM TOTALIRONWITHDRAWN 0.20 0.20
0.025 0.020
Fe 0.00 0.00
SO4 AS TOTAL Fe WITHDRAWNFe LEFT FLUORIDE
NaaSO4
MO.
WITHDRAWNBY S 0 r
Mg . Mo.
FOR F
Mg .
Added
Mo .
Found
Mg.
4.0 1.5 .. 5.5 6.3 2 . 0 27.5 35.0 0.35 0.34
0.20 0.20
5.0 0.049 0.020 0.029 0.025 0.03 0.025 0.026
10 0.049 0.030 0.019 0.025 0.02 0.00 0.00
25 0.082 0.065 0.017 0.025 0.02
50 0.115 0.105 0.010 0.025 0.01 16.4 13.5 2.6 32.5 13.0 .. 7.6 20.6 0.35
0.20
0.31
0.18
100 0.170 0.160 0.010 0.025 0.01
0.025 0.02
50 0.175 0,105 0.070 0.10 0.08 0.00 0.00
75 0.191 0.140 0.051 0.10 0.06
100 0.212 0.160 0.052 0.10 0.06 .. ,. 2.5 2.5 10.6 3.2 7.6 21.4 0.35
0.20
0.36
0.21
10 0.159 0.03 0.129 0.20 0.17 0.025 0.03
25 0.195 0.065 0,130 0.20 0.17 0.00 0.00
0.14
50
75
0.217
0,212
0.105
0.140
0,112
0.072
0.20
0.20 0.075 4.7 4.4 10.9 20.0 3.2 .. 2.2 5.4 0 . 23 05 0 . 23 04
0.025 0 . 0 3
I n Figure 1 fluoride is plotted against iron withdrawn. 0.00 0 . 0 0
The amount of iron withdrawn does not increase directly
with increase in fluoride. Smaller quantities of fluoride
cause, proportioDately, a much greater bleaching than
July 15, 1933 INDUSTRIAL AND ENG INEERING CHEMISTRY 235
used has no effect on the color; 100 mg. effect a fading which
can just be detected in the colorimeter and which is equiva- 400 4C
lent to only 0.01 mg. of fluoride. For this reason nitric acid
was chosen to neutralize the alkalinity of the water sample. 3 5 0 , I5