1052
it) and wrapping the wick around this metal tube, the authors have
been able to burn methylnaphthalene without smoking.
Attempts have been made to burn bottoms samples in this lamp. So
far they have been unsuccessful, and the results have indicated that
more radical lamp modifications would be needed.
SUMMARY
A modified lamp design is presented, allowing analysis of high-
boiling organic liquids Accuracy of the determination of hy-drogen is
of the order of *0.02 to 0.037, hydrogen, absolute. Variations in this
design are suggested, which should permit the use of only one lamp
for the determination of the hydrogen and carbon contents of all
organic liquids from those volatile at room temperature to those of
boiling point greater than 500" C.
Determination of Phosphorus Pentoxide in Phosphate Rock
JAMES L. KASSNER, HOWARD P. CRAMMER, AND 3IARY ALICE OZIER
School of Chemistry, Metallurgy, and Ceramics, University, Ala.
Perchloric acid may be used for the dehydration of silica in
phosphate rock, prior to the determina-tion of phosphorus
pentoxide. A new mixed indi-cator comprised of phenol red
and bromothymol
blue gives a sharp color change at pH 7.5. When this mixed
indicator is used, the phosphorus pent-
I N THE determination of phosphorus pentoxide in phosphate
rock, it is customary to separate the phosphate from the
interfering substances by precipitating it as ammonium molybdi-
phosphate (9). The most common procedures for the treatment of the
ammonium molybdiphosphate are the alkalimetric method, in which
the nitric acid-free precipitate is dissolved in an excess of a standard
solution of sodium hydroxide and the excess caustic is titrated Kith
standard nitric acid in the presence of phenol-phthalein; and the
gravimetric method, in which the ammonium molybdiphosphate is
dissolved in dilute ammonium hydroxide, citric acid is added, the
phosphate is doubly precipitated with magnesia mixture, and the
resulting magnesium ammonium
phosphate hexahydrate is ignited to the pyrophosphate. Hillebrand and
Lundell (3) have shown through the co-
operation of representative analysts that the results obtained by the
alkalimetric method when phenolphthalein is used as the indicator are
approximately 0.3% higher than those obtained by the double
precipitation as magnesium ammonium phosphate. In order to avoid
this error, it is common practice among com-mercial laboratories to
determine the titer of the alkali empirically by analyzing a Bureau of
Standards phosphate rock rather than by using its stoichiometrical
measurement.
An improved procedure developed in this laboratory eliminates the
empirical nature of the present alkalimetric method. A
mixed indicator has been developed which gives a sharp color change
at the stoichiometric end point; the molybdate solution has been
stabilized; and the conditions for precipitation have been established
which give an ammonium molybdiphosphate precipitate of uniform
composition. Data are presented which show that the precision and
accuracy of the improved procedure are both very good. The
maximum deviation in thirty con-secutive samples mas 0.1 mg., and
the average deviation 0.05 mg. of phosphorus pentoxide.
REAGENTS AND STANDARD SOLUTIONS
Indicator. Prepare the phenol red and bromothymol blue solu-tions
by triturating 0.1000 gram of each of the indicators in an agate mortar
with an excess of sodium hydroxide. When the
A N A L Y T I C A LC H EMIS TR Y
ACKNOWLEDGMENT
The assistance of J. Grider with most of the experimental work is
gratefully acknowledged. W. T. Harvey of the Sun Oil Company,
Marcus Hook, Pa., very kindly contributed the results of the carbon-
hydrogen train analyses.
LITERATURE CITED
(1) Am . SOC. Testing Materials, D90-46T.
(2) Hindin, S.G., and Grosse, A . V., IND.ENG:CHEM.ANAL,.ED.,
17, 767-9 (1945).
(3) Javes, A. R., J. Inst. Petroleum Tech., 31, 129-53 (1945) .
(4) Simmons, M . C., ANAL .CHEM.19, 385-9 (1947) .
RECEIVEDMarch 16. 1948.
oxide titer of the alkali may be determined with potassium
acid phthalate. Free molybdic acid does not separate at the
boiling point when molybdate solutions containing citric
and nitric acids of pre-scribed composition are used. At the
boiling point, the yellow precipitate separates almost
immediately.
indicator has dissolved completely, adjust the pH with nitric
acid to 7.5 and dilute the solution to 250 ml. in a volumetric flask.
Prepare the mixed indicator by mixing 40.0 ml. of the bromo-
thymol blue solution with 25.0 ml. of the phenol red solution. Use
0.5 ml. of this indicator for each 100 ml. of solution at the
end point.
Citromolybdate Solution. SOLUTIONA. Dissolve the following
reagents in 1360 ml. of water, without heating: 54 grams of
ammonium nitrate, 52.6 grams of citric acid, and 68 grams of
ammonium molybdate, (r\rH,)&10&.4H20.
SOLUTIONB. Dilute 253 ml. of concentrated nitric acid (specific
gravity 1.42) with 310 ml. of water.
Prepare the citromolybdate solution by pouring solution A into
solution B. Clear it as follows: Bdd filter paper pulp or a few drops of
diammonium hydrogen phosphate solution, boil for about 5 to 10
minutes, allow to stand overnight; then siphon off the clear solution.
(Such a solution remained clear 7 years and is still clear.)
Sodium Hydroxide Solution. Prepare a carbonate-free sodium
hydroxide solution (approximately 0. 3 N ) by diluting a
saturated solution of sodium hydroxide with carbon dioxide-free distilled
water. Standardize the solution with a Bureau of Standards sample of
potassium acid phthalate (4) using_ phenol_-phthalein indicator.
Nitric Acid Solution. Standardize the nitric acid solution
(approximately 0.1 N ) with the sodium hydroxide solution, using
phenolphthalein or the mixed indicator.
PROCEDURE
Wet a 1-gram sample of phosphate rock with 15 ml. of water; add
5 ml. of concentrated nitric acid and 10 to 20 ml. of 60 to 70y0
perchloric acid and heat to copious fumes of perchloric acid. Cover
the container and boil gently for 20 minutes to dehydrate
the silica. Cool somewhat, add 75 ml. of water, heat to boiling, and
filter into a 250-ml. volumetric flask. Wash filter with hot
dilute nitric acid solution and then with hot water. Add any
phosphate remaining in the silica to the original solution after treating it with hvdrofluoric
and nitric acids and fusing it with
-
sodium-carbonate..
To a 25-ml. aliquot of the sample add 80 ml. of the citromolyb-date
solution. Heat the resultant solution to boiling, keep at this
temperature for 2 or 3 minutes, and filter either hot or cold.
By decantation wash the precipitate four or five times with neutral
1% potassium nitrate or cold water, using 20 to 25 ml. for each wash.
Transfer the precipitate to the crucible and wash ten
V O L U M E 20, NO. 11, NOVEMBER 1 9 4 8 1053

To determine how much perchloric acid could be present in the

Table I. Effect of Perchloric Acid on Determination of solution without vitiating the results, solutions of potassium
Phosphorus Pentoxide dihydrogen phosphate (14) were prepared and analyzed after various
Citro-
KHzPOh molybdate PzOa Content of 25-hf1. Aliquot amounts of perchloric acid had been added (Table I).
Solution Solution Calcd. Exptl. In the analysis of samples of phosphate rock, nitric acid waa used
KO. KO. HCIOP value value
M1. M g . Mo. jointly n ith perchloric acid to eliminate the possibility of an
119 explosion (7,16)due to the presence of organic matter (13). Mixed
Indicator. Because sodium molybdate, ammonium
molybdate, and sodium ammonium acid phosphate are formed in the
127 159 6.0 32 . 46 32.43
8.0 32.90 titration of ammonium molybdiphosphate with sodium hydroxide, it
8.0 32.76 seemed advisable to determine the pH curve for the titration of the
60% concentration, added to 25-ml. aliquot before precipitation. yellow precipitate and of each component. The pH measurements were
made with a glass electrode, and the curves are given in Figure 1. A
study of these curves shows that the phenolphthalein end point comes
long after the maximum breaks in the titration of molybdic acid with
times. Place the crucible in the original beaker, and dissolve the sodium hydroxide and with ammonium hydroxide. This finding
precipitate in a 0.3 N sodium hydroxide solution, using about 15-ml.
excess. .4dd 1 ml. of the mixed indicator, and titrate the solution with substantiates the conclusion of Hillebrand and Lundell (4 )that
0.1 S nitric acid until it turns yellow. Remove the phenolphthalein is not an ideal indicator. The curve for the titration of
crucible from the beaker, wash with water, and adjust the volume of the yellow precipitate with sodium hydroxide does not give a sharp
the solution to about 200 ml. In direct sunlight, or in front of an change in pH a t any point, indicating that the solution is rather highly
illuminator equipped with a fluorescent daylight Mazda lamp, back-
titrate the solution with 0.3 rV sodium hydrox-ide to a light permanent buffered. It is therefore necessary for the indicator selected to give a
purple color (Th? solution becomes practically colorless just before the sharp color change within a very narrow pH range.
end point is reached.)
A4ftera great many indicators and mixtures of indicators and dyes
DEVELOPMENT OF METHOD had been tried, it was found that certain mixtures of phenol red and
I n determining the optimum conditions for the recommended bromothymol blue gave a sharp change from colorleH to purple, and
procedure, the method was applied to solutions prepared from reagent that the pH a t which the color change took place could be raised by
quality potassium dihydrogen phosphate (14) and to Bureau of increasing the ratio of bromothymol blue to phenol red.
Standards samples of phosphate rock. (The former gave the theoretical
loss on ignition of 13.32%.) The phosphorus pentoxide values of the The pH a t which the purple color could be seen varied with the
salt were found to be 52.11, 52.19, and 52.1070,whereas the light conditions. When a titration was made using a titration
theoretical value is 52.18%. illuminator fitted with a fluorescent Mazda daylight lamp, or in direct
Use of Perchloric Acid (22,26). Inasmuch as the advantages of sunlight, the color change appeared at a pH of 7.5 and the results
using perchloric acid to remove silica (15) are well recognized, it obtained by the alkalimetric method agreed wibh those reported by the
seemed advisable to investigate the applicability of this pro-cedure to Bureau of Standards.
phosphate rock, prior to the determination of phos-phorus pentoxide. I t was discovered early in this work that successive samples of
The silica was therefore removed from three 1-gram samples of phenol red and bromothymol blue obtained on the open market were
Bureau of Standards phosphate rock 56a by using 20 ml. of 60 to 70% not of the same degree of purity. Further study showed that the desired
perchloric acid. The percentage of phosphorus pentoxide was results could be obtained with any sample of phenol red or
determined according to the method outlined in the procedure, and the bromothymol blue, by determining a new ratio for each sample.
following results were ob-tained: 32.92,32.89, and 32.90 (certified However, through the cooperation of Eastman Ilodak Company, it is
value 32.9070). now possible to prepare the new mixed
indicator from successive batches of these in-
dicators without altering the ratio for each batch.
The mixed indicator has a yellow color up to pH
about 7.2, is practically colorless a t 7.3, and turns a
light purple a t pH about 7.5 when the color change
is observed in direct sunlight or under a fluorescent
daylight illuminator.
In most titrations the end-point color was ob-
served to fade rather rapidly; however, in a few cases
the purple color persisted from 5 to 30 minutes or
even longer. The end-point color will remain 10 days
or more if 0.3 A' sodium hydroxide is added in
excess of that required to dissolve the yellow
precipitate (about 15-ml. excess for a sample
containing approximately 30
mg. of phosphorus pentoxide).
Use of Citric Acid. 4 preliminary investiga-
tion in this laboratory showed that the use of citric
acid and boiling temperature promoted rapid and
complete precipitation of coarse crys-tals of
ammonium molybdiphosphate which had a very
uniform composition.
Lipowitz (6) was the first to show that the
Figure 1. pH Curve inconstancy of composition of the ammonium
A . Yellow precipitate with NaOH C. HiMoOr with "{OH molybdiphosphate precipitate was due to the
B . HzMoOd with NaOH D . HsPO4 with NHIOH t o pH 6.8, then NaOH occlusion of molybdic acid. He proposed the
1054 ANALYTICAL CHEMISTRY

phosphorus pentoxide. Eighty milliliters of citromolybdate solu-tion

Table 11. Effect of Temperature and Citric Acid upon Per Cent cleared with filter paper pulp were used in each run. The data are
Phosphorus Pentoxide"
tabulated in Table 111.

1 .m 2 .i \'one 7.5 35 53 Table 1V. Svnthetic Potassium Acid Phosnhate Solutions

75
-" - - -.. -

2 50 40 None 35 . 55
3 50 103 None 75 49 30a citro - PzOs Content of Aliquot Indicatedm
4 40 103 1 0 90 35 . 22 KHzPOd molybdate Calcd. Exptl.
5 40 103 2.0 115 35 . 19 S o h No. S o h . No. Aliquot value value Deviations
6 40 103 4.0 165 35 . 19 M1. Ma. 30. Mo.
Bureau of Standards sample 120, 35.20% PzOa, b y double pptn. 117 146 10 11 . 64 11 . 71 0 . 07
b Note influence of higher temperature and lack of citric acid. 149 10 11 . 65 0 . 01
10 11 . 60 - 0 . 04
5 5.82 5 . 91 0 . 09
Table 111. Effect of Addition of Nitric Acid and Ammo-nium 118 160 10 12 . 93 12 . 92 -0.01
12.97 0 . 04
Nitrate on Completeness of Precipitation 13 . 03 0.10
Run NHdNO HNOs Added PaOr 5 6 . 47 6.53 0 . 06
No. Added (Sp. Gr. 1.42) Found Error 6 . 54 0.07
Grams M1. Mo. MQ. 125 157 10 12 . 46 12 . 53 0.07
1 None None 31 . 48 -0.04 157 5 6.23 6.23 0 . 00
-
2 Iione None 31 . 59 0 . 07 Total 0.56
3 1.0 None 31.47 -0.05
4 1.0 None 31 . 54 0 .02 Av. 0.05
5 2.0 None 31 . 51 -0.01 a Samples filtered within 1 minute after boiling.
6 2.0 Sone 31.66 0.04
7 3.0 None 31.72 0.20
8
9
3.0
3.0
None
None
31 . 86
31 . 76
0 . 34
0 . 24 Table V. Synthetic Potassium Acid Phosphate Solutions
10 None 6.0 31 . 44 -0.08 Citro- P2Os Content of 25-MI. Aliquota
11 None 6.0 31 . 51 -0.01 KHzPOd molybdate Calcd. Exptl. Devia-
12 None 8.0 31 . 36 -0.16 S o h . No. Soln. No. value value tions
13 None 8.0 31 . 44 -0.08 Mo. Mg. Mo.
118 150 32 . 33 32 . 32 -0.01
32 . 40 0.07
32 . 35 0 . 02
117 149 29 . 09 29 . 06 - 0 . 03
147 29.16 0.07
precipitation of the ammonium molybdiphosphate a t the boiling 146 29 . 11 0 . 02
point from solutions containing tartaric acid. Since that time 29 . 07 - 0 . 02
121 152 31 . 88 31 . 92 0.04
the formation of the yellow precipitate at the boiling point in the 31.87 - 0 . 01
122 155 31 . 68 31 . 75 0 . 07
presence of ammonium citrate has been investigated by Pellet 31 . 67 - 0 . 01
(10) and Graftiau (2)and in the presence of citric acid by Vincent 123 156 31 . 04
31 . 77 0 . 09
31 . 02 - 0 . 02
(18). Pellet claimed that the presence of the ammonium citrate 31 . 06 0.02
31 . 08 0.04
ensured the formation of an ammonium molybdiphosphate 125 157 31 . 13 31 . 03 - 0 . 10
31 . 18 0.05
precipitate of constant composition. MacIntire, Shaw, and Hardin (8) 31 . 13 0.00
have shown that quantitative results can be obtained
-

31 . 16 0 . 03
at 45 a C. in the presence of small amounts of citrates. Total 0 . 73
To show the influence of temperature and citric acid on the results, Av. 0.04
a 0.9560-gram sample of Bureau of Standards phosphate a Samples filtered within about 1 minute after boiling.
rock No. 120 was dissolved as outlined in the procedure and diluted
to 250 ml. A 25-ml. aliquot was used in
each run. The ammonium molybdate solution used
in these analyses contained 25 grams of
ammonium molybdate and 80 ml. of nitric acid
(specific gravity, 1.42) in 200 ml. of water. The
data are given in Table 11.
Phenolphthalein was used as the indicator in runs
I, 2, and 3, and the mixed indicator in runs 4, 5, and
6. In runs 4, 5, and 6 the indicated amounts of
citric acid and ammonium molybdate
solution were substituted for the citromolybdate A Low results
solution as outlined in the procedure. 0 Correct results

Citromolybdate Solution. -1s the composition of

the yellow precipitate is governed by such factors as
the composition of the reagents used and the
presence of other substances in the solu-tion, a series
of citromolybdate solutions were prepared and used
in the analysis of a potassium dihydrogen phosphate
solution which contained an equivalent of 32.72 mg.
of phosphorus pent-oxide for each 25-m1. aliquot.
These data are
shown in the ternary diagram, Figure 2.
To show how the composition of the solu-
tion influenced the results, nitric acid and am-
monium nitrate were added to 25-ml. aliquot8 "0, OOI

of a potassium dihydrogen phosphate solution, Figure 2. Ternary Diagram of Citric Acid, Nitric Acid, and
which contained an equivalent of 31.52 mg. of Ammonium Nitrate Solution
V O L U M E 20, N O . 11, N O V E M B E R 1948 1055

used in this investigation, thus

Table VI. Results Obtained with Bureau of Standards Phosphate Rocks making it possible to repro-
Sample PZOS
Ce tified
PZOK
Exptl.
Other Materials Present
_____ ~ _ _
duce the new mixed indicator
XO. Sample 3afalue Value Fez02 AlzOs F-~ Si02 Ti02 from various batches of these
Gram % % 70 70 % 70 % indicators.
56a 0.1088 32.90 32 . 89 2.18 2.02 3.56 11.01 0.08 This research was sponsored
0.1102 32.90 32.88 2.18 2.02 3.56 11.01 0.08
120 0.1100 35.20 35.18 0.89 0.80 3.76 7.40 0.07 by a grant from the Research
0.0793 35.20 35.23 0 . 89 0.80 3.76 7.40 0.07 Fund of the University of
0.0560 35.20 35.22 0.89 0.80 3.76 7.40 0.07
Alabama.

Table \-II. Synthetic Potassium Acid Phosphate Solutions Containing Impurities

- LITERATURE CITED
P*Osin 25-M1. Aliquot
Calcd. Exptl. Impurities Present in 25-111. .Iliquot (1) Assoc. Official Agr. Chem.,
Sample value value CaO Fer01 -41~0s H~SOI MnO Official and Tentative
M Q . M Q . Gram Gram Gram Gram Gram Methods of Analysis. 5th
A 31.18 31.14 0.03 0.005 0 . 005 0.1 ,.. ed., p. 23 (1940).
31.16 (2) Graftiau, F., Atti V I Congr.
B 20.92 20.94 0.03 0,005 0.005 0.1
20.95 0.03 0.010 0.010 ... 0.OOSo intern . chim. applicata,
20.92 0.06 0.005 0.005 ... 0 . 0005 Rome, 1 , 64 (1906).
C 10.10 10.03 0.03 0.005 0.005 0.1 I..
Hillebrand, W. F.,
(3) and
10.12

D 5.53 5.52 0.03
5,82
Wash Solution. Either potassium nitrate or cold water may be
used for xashing the yellow precipitate. According to Kolthoff
and Sandell (5), water peptizes the precipitate and causes it to
run through the filter; however, for the volumetric procedure,
cold water is recommended (1). Experiments show that iden-
tical results are obtained when either potassium nitrate or cold
water is used as the wash solution, provided the amount of
wash solution when water is used is kept a t a minimum.
APPLICATION OF METHOD
A number of synthetic potassium acid phosphate solutions,
ranging from 32 to 6.0 mg. of phosphorus pentoxide per 25-ml.
aliquot, were analyzed (Tables IV and V). The data show that
the results are independent of the amount of phosphorus pent-
oxide in the sample. The maximum deviation was 0.1 mg. and
the average deviation 0.05 mg. of phosphorus pentoxide.
Two Bureau of Standards samples of phosphate rock were
analyzed, along with several synthetic solutions that contained
certain impurities (Tables VI and 1’11).
ACKNOWLEDGMENTS
The authors are indebted to the Eastman Kodak Company,
Rochester, S . Y., for standardizing the purity of the indicators
0.005 0,005 0.1 ... Lundell, G. E. F., “Ap-
plied Inorganic Analysis,”
p. 563, New York, John
Wiley & Sons, 1929.
(4) Ibid., p. 568.
(5) Kolthoff, I. M., and Sandell, E B., “Textbook of Quantitative
Inarganic Analysis,” p. 371, New York, Macmillan Co., 1937.
(6) Lipowitz, Pogg. Ann., 119, 135 (1860).
(7) Lundell, G. E. F., and Hoffman, J. I., “Outlines of Methods of
Chemical Analysis,” p. 46, New York, John Wiley & Sons,
1938.
(8) MacIntire, W. H., Shaw, W. M., and Hardin, L. J., INDENG. .
CHEM.AXAL , .ED.,10, 143 (1938).
(9) Pauling, L . , J. Am. Chem. Soc., 51, 2863 (1929).
(10) Pellet,, H., Bull. assoe. belge chim., 3, 51 (1888-89).
(11) Smith, G. F., “Pzrchloric Acid,” 4th ed., Columbus, Ohio, G
Frederick Smith Chemical Co., 1940.
(12) Vincent, V.,Ann. fals., 23, 475 (1930).
(13) Wiley, H . W., “Principles and Practice of -4grioultural Analysis,
Vol. 11, Fertilizers and Insecticidea,” 3rd ed., p. 63, Table
VII, Easton, Pa., Chemical Publishing Co., 1931.
(14)Ibid., p. 186.
(15) Willard, H. H., and Cake, W. E., J. Am. Chem. SOC42,. 2208
(1920).
(16) Willard, H. H . , and Diehl, Harvey, “Advanced Quantitative
Analysis,” p. 8, New York, D. Van Nostrand Co., 1943.
RECEIVEDOctober 4, 1947. Presented before the Division of Physical and
Inorganic Chemistry, at the 100th Meeting of the AMERICANCHEMICAL
SOCIETY,Detroit, Mich. Report on citromolybdate aolution presented be-
fore the Division of Physical and Inorganic Chemistry, at the lOlst meeting
of the AMERICANCHEMICALSOCIETY,St. Louis, AVO.A part of this work
was presented by Howard P . Crammer in partial fulfillment of the reqoire-
ments for the degree of master of science, 1941.

CHEMISTRY OF THORIUM
Quantitative Estimation of Thorium by a Titrimetric Iodate Procedure
THERALD MOELLER AND NANCY DOWNS FRITZ, University of IEZirwis, Urbana, I l l .

T HE lack of rapid methods for the accurate estimation of thorium

in the presence of yttrium and the rare earth elements has been emphasized
repeatedly (1, 5, 8). Of the recorded reac-
tions of the thorium ion, that involving its precipitation as iodate from
solutions containing nitric acid appears most promising as a basis for a
direct and potentially rapid method for estimating the element under
these conditions. Not only does this reaction yield a thorium salt
containing an ion that may be determined by familiar oxidimetric
procedures, but it also effects complete separation of thorium from
yttrium and the tripositive rare earth
elements, the iodates of which are soluble in nitric acid solutions
(6) .
While iodate precipitation is an established procedure for freeing
thorium of yttrium and the rare earth elements prior to its esti-mation
by gravimetric means (8), reports on its adaptation to a direct
titrimetric method have been fragmentary. Chernikhov and
Uspenskaya (5)described a procedure in which thorium was
precipitated from nitric acid solution by excess potassium iodate, and
the precipitate was washed with nitric acid containing po-tassium
iodate, treated with 95% ethanol, dried, and dissolved in