12 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 9, NO.

I n ea,ch method the effect of slowing down the rate of stretch
was to increase the value for distensibility, as is the case for
metals and other materials. This indicates that, as more time
is allowed for stretching, an opportunity for internal flow
within the finish coating is provided, by means of which the
finish can partially accommodate itself to the applied stress.
This effect was particularly noticeable in the case of finishes
that have aged not more than about one month. The effect
diminished rapidly with age with thin-finish coatings, and
slowly as the coating thickness was increased. The fact that
the distensibility values are influenced by rate of stretch means
that with either test a constant rate of extension should be
used. The authors have found the rate of 15 seconds for the
complete bend in the mandrel test and 0.6 inch per minute
for the extension test satisfactory.
Summary
Two methods of measuring distensibility of organic finishes
are described.
I n order to be able to express results in per cent elongation,
methods for either calculating an approximate per cent
elongation value or determining actual elongation of mandrel
specimens are described. A correction for thickness of finish
is given.
A direct-extension method for coated specimens is described
which has the advantage of permitting any degree of disten-
sibility up t o rupture of the supporting base material to be
measured.
The factors that affect the distensibility of an organic
finish are discussed and the relative importance of these
factors is illustrated by experimental values.
Literature Cited
(1) Gardner,H. A., Am. Paint Varnish Mfrs. Assoc., Circ.240 (1925).
(2) Hunt, J. K., and Lansing, W. P., IND. E m . CHEM.,27, 26 (1935).
(3) Nelson, H. A . , Proc. Am. SOC.Testang Materials, 21, 1111 (1921).
(4) Ibid., 23, Part I, 290-9 (1923).
(5) Nelson, H. A,, and Rundle, G. W., Ibid., 23, Part 2, 356-68
(1923).
(6) Rundle, G. W., and Norris, W. C., Ibid., 26, Part 2, 546-55
(1926).
R I D C ~ I VSeptember
~D 14, 1936. Presented before the Division of Paint and
Varnish Chemistry a t the 92nd Meeting of the Amerioan Chemical Society,
Pittsburgh, Pa., September 7 t o 11, 1936.

A Photoelectric Method for the Determination

of Phosphorus’
C. W. EDDY AND FLOYD DEEDS
Bureau of Chemistry and Soils, U. S. Department of Agriculture, a t the Department o f Pharmacology, Stanford
University School of Medicine, San Francisco, Calif.

W I T H existing quantitative methods for detecting phos-

phorus it is not possible to determine with a high degree
of accuracy quantities as small as 0.001 mg. The device
vanometer scale, since by its use compensation for battery
depletion is regulated.
A number of precautions in the use of this photoelectric color-
herein described was constructed to give a sensitive, simple imeter are essential, when great accuracy is desired. Cleanliness
and rapid, yet accurate, method for phosphorus determina- of Nessler tubes, light bulb, photoelectric cell, and the apparatus
tions when applied to the methods of Fiske and Subbarow in general is necessary. The effect of finger marks is appreciable
( I ) , Kuttner and Cohen (6),or Kuttner and Lichtenstein (6). and, unless the Nessler tube is kept clean, is reflected in deflec-
tion of the galvanometer to the extent of 1 to 2 mm. It is cus-
The apparatus has been entirely satisfactory when applied tomary, prior to making a determination, to clean the tube with
t o the determination of blood sugar by Folin’s method (a),the chromic acid solution, followed by washing with distilled water.
study of phosphatase activity by Jenner and Kay’s (4) modi- Before each reading is made, the outside of the tube is wiped dry
fication of the Kuttner and Cohen procedure, and the deter- and free from finger marks.
The resistance RI must be capable of carrying 10 amperes;
mination of yeast population by turbidity measurements. otherwise tem erature changes of the resistance will cause fluctua-
The use of the photoelectric cell for colorimetric and tur- tions in the gafhnorneter, producing erroneous results.
bidity estimations is not new, It has been applied by Osborn It is essential to use the same Nessler tube for all determina-
(7), Greene (a), and Samuel and Shockey (8). tions, since the authors have not found two tubes characterized
by the same calibration curve. This will be seen by comparing
The apparatus described makes use of the circuit outlined Tables I, 11, and 111with Figure 2, three different Nessler tubes
by Samuel and Shockey (8) modified to permit the use of a having been used.
sensitive galvanometer, and a smaller light source.
The modified circuit of the apparatus is given in Figure 1. TABLEI. REPRODUCIBILITY
OF CALIBRATION
CURVE
A single light source of low intensity directed vertically up- 0,00093 0.001868 0.00467 0.00934
Phosphorus Blank mg. mg. mg. mg.
ward through a 50-ml. flat-bottomed Nessler tube containing Readingso 42.2 37.6 30.6 19.6 10.4
the solution to be tested, and impinging on the photronic cell, 43.2 37.6 31.6 20.2 10.6
42.0 36.4 31.4 19.9 10.0
causes a deflection of the galvanometer, the amount of the 43.2 36.2 30.4 19.6 10.2
deflection being a function of the quantity of light allowed to 43.6 37.0 30.8 ... 10.8
Mean 42.84 36.86 30.98 19.78 10.62
pass through the solution. Photronio cell No. 9. Nessler tube No. 3.
The circuit used in the apparatus described has two de-
cided advantages over previously described photocolorimeters : Photronic cells vary appreciabl in the current output relative
to a given change in depth of c o h . Therefore, each photronic
The use of a light source of small intensity eliminates tempera- cell must have its own calibration curve.
ture effects, the solutions can remain in the apparatus for ex- Because of the sensitivity of the e uipment to minute changes
tended periods without being influenced by temperature. in depth of color, it is always essenti3 to follow the identical pro-
The use of a variable resistor (Ea) instead of a fixed resistor cedure in developing the color in a series of determinations that
was employed in establishing the calibration curve. The same
makes it possible to maintain a constant spread on the gal- precaution applies to turbidity measurements.
a Since presentation of this method a similar photoelectric colorimeter has The characteristicsof the photronic cell are such that colorimet-
been described (9). ric methods involving transmitted light of yellow or orange color
JANUARY 15, 1937 ANALYTICAL EDITION 13

ing by the use of the resistor R+ The greater the spread, the
7

i
0 greater will be the sensitivity of the apparatus, and the more
accurately the unknown substance can be determined. The
double-pole double-throw switch is then placed in position 2,
and R1 is adjusted until the galvanometer again gives the
same reading as selected in the first operation. It may be
r- necessary to readjust RI again, until both positions give the
I same desired deflection. If the current source is constant
there is no further need of adjustment.

I Procedure for Determination of Phosphorus

I I The method for the determination of phosphorus as finally
I I R2 modified by Kuttner and Lichtenstein (6) was used. The
following reagents are necessary:
I I STOCKSOLUTIONS.(1) Sodium molybdate (NazMo04.2Hz0)
I I 7.5 per cent; (2) 10 N sulfuric acid, 282 cc. of concentrated acid
I (sp. gr. 1.84) per liter; and (3) stannous chloride, 40 per cent in
I concentrated hydrochloric acid.
I--+ I--i I STANDARD SOLUTTONS. Dissolve 0.0879 gram of dried mono-
potassium phosphate (KHzP04) in 1 liter of distilled water, and
add a few drops of chloroform. One cubic centimeter of this
solution contains 0.02 mg. of phosphorus. Make five standard
solutions by placing 1.0, 2.5, 5, 7.5, and 10 cc. of the above solu-
tion in each of five 100-cc. volumetric flasks, and filling to the
mark with distilled water. These standards contain 0.001,
0.0025, 0.0050, 0.0075, and 0.010 mg. of phosphorus in 5 cc., re-
spectively.
The color of the standards is produced as follows:
FIGURE1. SCHEMATIC
DIAGRAM
A molybdic acid solution is freshly prepared by adding 20 cc.
N . Nessler tube, flat bottom of distilled water to 10 cc. of 7.5 per cent sodium molybdate
B . 6-volt storage battery
5. Single- ole single-throw switch (solution l), and then 10 cc. of 10 N sulfuric acid (solution 2).
L. 3-candg power 6-volt automobile bulb A dilute stannous chloride solution is freshly prepared by diluting
A . Reflector 0.25 cc. of 40 per cent stannous chloride (solution 3) to 50 cc.
D . Double-pole double-throw switch
P . E . Weston 594 photronic cell with distilled water. To 5 cc. of each standard, 4 cc. of the
G. L.N. box galvanometer (0.025 microamp. per mm.), scale replaced molybdic acid solution are added and, while stirring constantly
by scale 70 mm. long graduated in 1 mm. and regularly, 1cc. of the dilute stannous chloride is added. One
Ri. %ohm, 10-amp. variable resistor serially connected t o %ohm, 10-
amp. fixed resistor hour is allowed for the maximum color development.
Rz. 1.5-megohm fixed radio resistor After the apparatus has been adjusted for the desired sensi-
Ra. 200,000-ohm variable radio resistor tivity the blue colored standards are transferred successively to
--- Light-tight box with two separate light-tight compartments' a
the Idessler tube and made up to the mark. After placing the
round 3.75-om. (1.5-inch) diameter opening is made between
N and L t o allow light to pass through Nessler tube tube in the apparatus and closing the light-tight box, the gal-

l--

\
are less satisfactory than methods based on changes in blue. A .O'
spectrally pure blue-green filter inserted between the light source
and the solution to be tested will be found helpful in the case of
yellow solutions.
If it is desired to reduce the sensitivity of the instrument, a
shunt can be placed in the galvanometer circuit, or a 0-100 micro-
ammeter can be substituted, in which case it becomes necessary
t o reduce the amount of resistance in Rz and Ra. 00 7

Operation of Colorimeter
Five minutes before a determination is t o be made the
switch. is closed, allowing the apparatus to attain equilibrium.
,005 & \
A clean Nessler tube filled with distilled water is placed in
position. With switch D open, the galvanometer is set a t 0.
With the double-pole double-throw switch in position 1, the
deflection on the galvanometer is set at some arbitrary read-

IN BONEAsn
11. PHOSPHORUS
TABLE
Variation "o"= Omm.
Experi- Age Weight of
ment of of Dilution Sca!e Duplicate

I
No. Rat Ash Factor Readinga PhosDhorus Readinab
Dags Mg. Mm. Mg. % %
98 24 11.2 1000 33.0 0.00199 17.76 1.51
32.8 0.00202 18.03 1.50
102 39 6.8 500 22.2 0.00422 31.03 0.47
22.0 0.00424 31.17 0.47 .Ool
,000
107 50 16.7 1000 23.4 0.00395 23.65 2.28
23.8 0.00386 23.12 2.33
113 62 38.9 2000 23.5 0.00394 20.25 1.78 Scab Reading mm.
23.0 0.00401 20.61 1.75
Photronic cell No 9 Nessler tube No. 2.
2. STANDARDIZATION
FIGURE CURVEFOR PHOSPHORUS
b Difference in mg.' X' 100. DETERMINATION
mg. Photronio cell No. 9, Nessler tube No. 2
14 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 9, NO. 1
vanometer deflection is noted. Five standards suffice to plot a Table I1 were obtained with photronic cell No. 9 and Nessler
calibration curve, as shown in Figure 2, which automatically tube No. 2 and fit the calibration curve shown in Figure 2.
eIiminates any error due to traces of impurities in a given set of
reagents. The data in Table 111, using a different photronic cell and
Analysis is accomplished by taking 5 cc. of a solution in which Nessler tube, furnish additional evidence of the applicability
the amount of phosphorus lies within the range of 0.001 t o 0.010 of the method.
mg. The color is developed and the galvanometer deflection ob- The variation in phosphorus content of bone ash in differ-
tained as in the case of the standards. From the position of the
galvanometer reading on the calibration curve the quantity of ent experiments is due to the fact that bones from rats of
phosphorus present may be read off. different ages, as well as poisoned and unpoisoned rats, were
used. These variations are of no significance for this paper
TABLE
111. PHOSPHORUS
IN BONEASH and will be discussed in a subsequent publication.
Variation
Experi- Age Weight of
ment
No.
of
Rat
of
Ash
Dilution Scale
Factor Readinga Phosphorus
Duplicate
Readingb
Summary
Days Mg. Mm. Mg. % % A simple photoelectric colorimeter employing a Weston
61 10 2.4 100 32.9 0.00115
0.00112
4.79 2.61 photronic cell is described, and its application to the deter-
33.3 4.67 2.68
62 6 1.4 50 24.1 0.00206 7.32 8.29 mination of phosphorus between the limits 0.001 and 0.01
26.7 0.00188 6.71 9.06 mg. is demonstrated.
64 20 15.6 1000 32.4 0.00120 7.69 1.67
32.2 0.00122 7.82 1.65
66 11 6.1 200 15.2 0.00395 16.49 1.26
15.4 0.00390 16.29 1.28 Literature Cited
a Photronic cell No. 1, Nessler tube No. 1.
b Diterence in mg. X 100. (1) Fiske, C. H., and Subbarow, Y., J . Biol. Chem., 66, 375 (1925).
mg. (2) Folin, O., “Quantitative Clinical Chemistry, Vol. 11, Methods,”
by Peters, J. P., and Van Slyke, D. D., p. 462, Baltimore, Wil-
The character of the calibration curve is conditioned by the liams & Wilkins Co., 1932.
(3) Greene, C. H., J. Am. Chern. SOC.,56, 1269 (1934).
particular photronic cell, Nessler tube, and set of reagents (4) Jenner, H. D., and Kay, H. D., Brit. J . Ezptl. Path., 13,22 (1932).
employed. With these three factors constant, the reproduci- (5) Kuttner, T., and Cohen, H. R., J. Biol. Chem., 75, 517 (1927).
bility of the calibration curve for photronic cell No. 9, tube (6) Kuttner, T., and Lichtenstein, L., Ibid., 86, 671 (1930).
No. 3, was determined by noting the galvanometer reading of (7) Osborn, R. A., J . Assoc. Official Agr. Chem., 17, 135 (1934).
(8) Samuel, 13. L., and Shockey, H. H., Ibid., 17, 141 (1934).
five sets of standards. Table I lists the mean and individual (9) Yoe and Crumpler, IND. ENG.CHEM., Anal. Ed., 7, 281 (1935).
galvanometer readings for the blank and four solutions con-
taining known concentrations of phosphorus. RECEITED July 8, 1936. Presented before the Division of Agricultural and
Food Chemistry a t the 89th Meeting of the American Chemical Society,
The results of a number of typical analyses for phosphorus New York, N. Y., April 22 t o 26, 1935. Food Research Contribution No.
in bone ash are given in Tables I1 and 111. The data in 297.

Sodium Chlorite as a Volumetric Oxidizing Agent

DONALD T. JACKSON AND JOHN L. PARSONS
Hammermill Paper Company, Erie, Pa.

Sodium chlorite of high purity is now
available in quantities which permit it to
be considered as a laboratory reagent, par-
ticularly as an oxidant in volumetric analy-
sis. A sodium chlorite solution is easily
prepared and standardized, and is stable
over a period of several months if kept in a
dark bottle. Standard sodium chlorite
solutions have been successfully used in the
determination of sulfur dioxide, sulfites,
and bisulfites, and preliminary work indi-
cates that their use can be extended to the
quantitative oxidation of other reducing
substances.
acid, and sulfites can be satisfactorily determined by oxida-
tion with sodium chlorite. Preliminary work indicates that
it can probably be applied to the volumetric determination of
certain other reducing substances.
There are but few references in the literature t o the use of
chlorites (1, 3 , 4 , 5 ) and only one to their use as a quantitative
analytical reagent. Levi and Ghiron (4) made use of the
reaction between calcium chlorite and a permanganate in a
neutral solution to determine the permanganate.
The sodium chlorite as obtained is a white, finely crystalline
material. Being slightly hygroscopic, it takes up some moisture
when exposed t o air. The salt dissolves readily in water, its
solubility being 91.3 parts in 100 parts, of water at 30‘ C. (6).
The freshly prepared solutions are entirely clear and colorless.
The more concentrated solutions gradually turn yellow and
yellow-green if allowed to stand exposed to light.
An analysis (8) of a sample of sodium chlorite showed the
following percentages: NaC102, 97.6; NaCl, 0.7; NaOH, 1.5;
NaClOs, 0.0; and HzO (by difference), 0.2.

S ODIUM chlorite of high purity has recently been made

available (The Mathieson Alkali Works, Inc., 62 East
42nd St., New York, N. Y.) in quantities which permit it to be
Preparation and Standardization of Solutions
considered as a laboratory reagent. The stability of sodium The equivalent weight of sodium chlorite (as an oxidizing
chlorite solution and its smooth and easily controlled oxida- agent in an acid solution) is one-fourth of its molecular
tion reactions suggested that it might prove of use as an oxi- weight :
dizing reagent in volumetric analysis. The authors’ investi-
gations have shown that dissolved sulfur dioxide, sulfurous ClOz- + 4H’ + 4 (-) +C1- + 2Hz0