234 ANALYTICAL EDITION Vol. 5 , No.

sand, now used as filler, the acidity produced by these mixed
fertilizers could easily be neutralized. Those manufacturers
who use limestone or produce base-forming fertilizers would
then get credit for the added value of their products and the
farmer would be protected in that he would know the acid-
or base-forming properties of the fertilizers. Moreover,
economy would result fro& the saving of freight on the sand
or inert material now used as filler in mixed fertilizers.
ACKNOWLEDGMENT
The author wishes to express his appreciation for the
cooperation given by T. B. Leith, State Chemist, and the
following fertilizer companies in furnishing many of the
samples of fertilizer used in this study: Armour Fertilizer
Works, The Baugh and Sons Company, Gulf Manufacturing
Company, F. S. Royster Guano Company, and the Virginia-
Carolina Chemical Corporation.
LITERATURE
CITED
(1) Britton, H. T. S., Hydrogen Iong, Van Kostrand, 1929.
(2) Burgess, P. S.,Rhode Island Agr. Expt. Sta., BUZZ. 189 (1922).
(3) Frear, D. E., J.Bid. Chem., 88, 675-81 (1930).
(4) Lipman, J. G., Blair, A. W., and Prince, A. L., Soil Sci., 19,
57-75 (1925).
(5) MacIntire, W. H., and Shaw, W. M., IND. ENG.CEIW., 24,
1401-9 (1932).
(6) MacIntire, W. H., and Shuey, G . A., Ibid., 24, 933-41 (1932).
(7) Parker, F.W., Am. Fertilizer, 76, 2, 13 (1932).
(8) Pierre, W. H., J. Am. SOC.Agron., 20, 254-69,269-79 (1928).
(9) Pierre, W. I-I.,Ibid.,in press (1933).
RECEIVED April 17, 1933. Publiahed with the approval of the Director of
the West Virginia Agrioultural Experiment Station as Scientific Paper 128.
Contribution from the Department of Agronomy and Genetics.

Colorimetric Determination of Fluoride in

Water Using Ferric Chloride
MARGARET
D. FOSTER,
United States Geological Survey, Washington, D. C.

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fluoride in water, recently described ( I ) , is based on the iron withdrawn from reactivity with thiocyanate-that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

The possibility that iron in solution in the sample might

increase the color with ammonium thiocyanate and counter-
act the effect of fluoride is negligible. Examination of more
than 650 analyses of waters from all parts of the United
States indicates that practically all alkaline waters when
analyzed contain in solution less than 0.10 part per million
of iron-that is, less than 0.005 mg. of iron in 50 cc.
The details of the procedure follow:
Neutralize the alkalinity of 50 cc. of the sample of water
contained in a comparison tube with 0.05 N nitric acid. Do
not add an indicator but calculate from the alkalinity determi-
nation the amount of acid necessary t o neutralize the volume
of water used. If the alkalinity is high, use a stronger solution
of nitric acid (0.02 N ) in order t o keep the volume of the neutral-
ized sample within 60 cc. Add 5 cc. of ferric chloride solution
(1 cc. = 0.075 mg. of iron, with 30 cc. of N hydrochloric acid to
a liter) plus the amount necessary (by reference t o the curves)
to counteract the effect of the sulfate and chloride present and
10 cc. of ammonium thiocyanate (24 grams in a liter). Make
the volume up t o about 75 cc. and mix well.
Compare in a Schreiner colorimeter with a standard containing
a known amount of iron (2 t o 5 cc. of ferric chloride solution,
the amount depending on the depth of color of the sample)
and 10 cc. of ammonium thiocyanate solution in the same volume.
Subtract the amount of iron found from 0.375 t o get the amount
withdrawn. Its equivalent in fluoride may be read from the
curve (Figure 1). The ammonium thiocyanate should be
added t o the sample and standard at the same time and the
comparison made immediately. The color of the standard
should not be over 50 er cent greater or less than the color of
the sample. If the cogr of the sample is too weak t o be com-
FIGURE 1. IRON WITHDRAWN FROX REACTIVITY WITH pared with a 2-cc. standard-that is, if the sample contains more
THIOCYANATE BY DIFFERENT QUANTITIES OF FLUORIDE than 0.40 mg. of fluoride-a smaller sample should be taken.
The sample used for the determination should not contain
more than 50 mg. of sulfate or 100 mg. of chloride. If it con-
The iron withdrawn from reaction with thiocyanate by tains less than 2.5 mg. of sulfate and/or 5.0 mg. of chloride,
the other acidic constituents of natural waters was determined iron in excess of 0.375 need not be added.
in the same manner as for fluoride. Most natural waters
do not contain enough phosphate or borate in the volume
used for the determination t o interfere with its accuracy.
Nitrate present in quantities as great as 75 mg. in the volume 450 4:

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

The quantities of sulfate and chloride likely to be found in

water, however, have a decided bleaching effect on the 330 30
intensity of color produced by 0.375 mg. of iron with thio-
cyanate. The effect of sulfate and chloride is the same 2 5 0 ; 25
whether.they are present as calcium, magnesium, or sodium
salts. I n the earlier paper this effect of sulfate and chloride 200 2c
was corrected by subtracting, by reference to the curves,
the iron withdrawn by the amounts of sulfate and chloride
I50 15
in the unknown from the total iron withdrawn. On further
study, however, this was found to give erroneous results
particularly for the larger concentrations of sulfate (as 100 1 9

shown in Table I) because, in the presence of sulfate and

chloride, the effect of the fluoride is not on 0.375 mg. of 50 .5

iron, on which the curve is based, but on 0.375 mg. minus

the amount taken by sulfate and chloride. All three are o <
competing for the iron. If, however, the amounts of iron
withdrawn by the amounts of sulfate and chloride in the FIGURE 2. IRON WITHDRAWN FROX REACTIVITY WITH
THIOCYANATE BY DIFFEREXTQUANTITIES OF OTHER
sample are added to the samplein addition to the 0.375 mg. ACIDICRADICALS FOUND IN WATER
of iron regularly added, the effect of the sulfate and chloride
It is advisable that each
is counteracted and the effect of the fluoride is on 0.375 mg. fluoride, sulfate, and chloride, analyst work out his own curves for
of iron. This was proved by a number of tests in which the The accuracy of the method was checked by adding 0.025,
effect of different amounts of sulfate and chloride in samples 0.20, and 0.35 mg. of fluoride t o artificial waters containing the
containing no fluoride was counteracted in this way (shown sulfate and chloride salts of sodium, calcium, and magnesium
in Table 11). The resultant red color was equivalent, in in different combinations and amounts. The results are shown
in Table 11.
all tests, to 0.375 mg. of iron. If, however, the sample
contains much more than 50 mg. of sulfate or 100 mg. of One hundred and thirty samples of ground and surface
chloride, this does not hold true. So much excess iron must water from 28 states, tested by this method, ranged in
be added that the bleaching effect is on 0.5 or 0.6 mg. of fluoride content as follows: 0 t o 0.5 part per million, 50;
iron and not on 0.375. 0.5 to 1.0 part, 38; 1.0 to 2.0 parts, 25; 2.0 to 3.0, 11; and
236 ANALYTICAL EDITION
more than 3.0, 6. The highest fluoride found, 5.6 parts,
was in a sample from a hot spring in California.
If preferred, standards made by adding known quantities
of fluoride, 0.10 to 0.40 mg., to 5 cc. of ferric chloride solution
and 10 cc. of ammonium thiocyanate in the same volume
might be used, preparing the samples as already described.
This affords a direct determination of fluoride against fluoride
standards,
By using such fluoride standards, and by adding to the
standards the quantities of sulfate and chloride (as sodium
'salts) contained in the volume of sample used, this method
may be applied to the determination of fluoride in sea waters,
brines, or any water containing more than 2500 parts per
million of sulfate or more than 5000 parts of chloride. For
such waters, however, 10 cc. of ferric chloride must be added
to both sample and standard instead of the 5 cc. used when
the effects of sulfate and chloride are counteracted by the
addition of ferric chloride. This is necessary in order to
have enough iron left for the fluoride after the sulfate and
chloride have been satisfied.
Vol. 5, No. 4
This modification is recommended only for highly con-
centrated waters. It is not advisable to use it in preference
to that in which the effects of these constituents are counter-
acted by the addition of ferric chloride for waters containing
less than 2500 parts per million of sulfate or 5000 parts per
million of chloride because (1) if 5 cc. of ferric chloride solu-
tion are used in sample and standard, the iron left for
fluoride after the sulfate and chloride have been satisfied
may be so reduced as greatly to restrict the fluoride range
and sensitivity; (2) if 10 cc. are used the color in water
containing low sulfate, chloride, and fluoride would be too
deep to read; and (3) a different set of standards might be
required for each sample.
LITERATURE CITED
(1) Foster, M. D., J. Am. Chem. Soc., 54, 4464 (1932).
RECEIVED March 7, 1933. Presented before the Division of Water, Sewage,
and Sanitation Chemistry a t the 85th Meeting of the American Chemical
Society. Washington, I). C., March 26 to 31, 1933. Published by per-
mission of the Direotor, U. 8. Geological Survey.

Determination of Fluorides in Illinois Waters

C. S. BORUFF
AND G. B. ABBOTT,State Water Survey, Urbana, Ill.

An adaptation of the volumetric thorium pre-

M OTTLED tooth enamel
is caused by the con-
ingestion of
fluorides during the period the
teeth are being formed (8, 18,
cipitation has been found to be the most
reliable for the quantitative examination of
waters for fluorides. The fluoride content of a
concentration, drying, and dis-
tillation of silicon fluoride from
dry residues in the presence of
sulfuric acid and silica (i7) with
subsequent determination of the
19). Mottled teeth have been number of Illinois waters has been determined by soluble fluoride by one of many
found in p r a c t i c a l l y e v e r y the use of this method. m e t h o d s found in the litera-
country. This condition is en- F~~~ the data obtained it that the tUre, have been found tedious
demic over large areas in the and u n s a t i s f a c t o r y (23,27).
southwestern part of the United waters containing the greater quantities of The technic is exacting. This
States and is frequently found in fluorides are those which are found in and around m e t h o d w a s used in the first
other s e c t i o n s (8, 11, 12, 1.4). the northeastern and northwestern part of the studies r e p o r t e d b y S m i t h ,
Studies already published have Illinois coal basin. All of these waters r u n high Lantz, and Smith (19).
largely l i m i t e d the p r i m a r y in nonincrustingsolids. T~ date the results The method of Fairchild (9)
Sources Of thediet to has been modified and used by
have not shown fluorides to be characteristic of Churchill (r), Hale ( l i ) ,and
that found in drinking waters
(11-13, 18, 19). Bauxite, Ark., any one stratum since they are found in waters Smith (21). This method calls
and Oakley, I d a h o , have dis- associated with rocks of Pennsyhanian, Silurian, for the addition of a ferric salt
carded abundant water supplies and Ordovician age. which f o r m s ferric fluoride or
in favor of others containing less the complex FeF,j--- with the
fluorides ( l a ) , and other cities fluorides present. The excess
are considering similar action. The exact minimum concen- ferric ion is then caused to react with potassium iodide, and
tration of fluorides that will cause mottled teeth is not known. the liberated iodine is titrated with thiosulfate. The re-
It has been reported by some to be about 2.0 p. p. m, (21) liability of the method depends on the stability of the iron-
while others claim it to be about 1.0 p. p. m. (16). fluoride complex and on a quantitative reaction between
Lack of agreement in results obtained in this and other ferric iron and potassium iodide. The reaction
laboratories while analyzing waters for small quantities of
fluorides, using methods reported in the literature, together
+
2Fe+++ 21- = 2Fe++ 1 2 +
with the fact that extremely little is known concerning the is reversible, and, if it is to be used in a quantitative de-
fluoride content of Illinois waters, led the Water Survey to termination, the iodide must be added in large excess (26).
initiate the following investigation. This is strictly a chemi- Fairchild and Churchill have not used sufficient potassium
cal study; no attempt has been made by the authors to iodide. Upon testing the reliability of their methods, the
correlate the presence or absence of mottled teeth with the present writers found that the amount of iodine liberated by
fluoride content of the Illinois waters which have been ex- the reaction of 5.0 cc. of approximately 0.08 M ferric chloride
amined. with the 10 cc. of 5 per cent potassium iodide in distilled
Of the numerous methods found in the literature for the water, according to their procedures, required an amount of
quantitative determination of fluorides, there seem to be only 0.025 N thiosulfate which varied from 13.7 to 15.2 cc. Others
a few which might be utilized to determine the small quan- (6) have noted similar variations in this reaction. Increasing
tities (0 to 15 mg. per 1.) found in waters. Gravimetric and quantities of potassium iodide (iodine-free) required in-
colorimetric methods are fraught with many difficulties and creasing volumes of thiosulfate to react with the liberated
uncertainties (6, 9, 11, 16, 22, 24, 26, 27). Likewise, the iodine. Similar tests made by adding definite volumes (1