USP 36 Chemical Tests / 〈211〉 Arsenic 145

APPENDIX 2: OLIGOSACCHARIDE STRUCTURES (Continued)

∆IIA-IVSglu

∆IIA-IISglu

1,6-Anhydro ∆IS-IS epi or

〈211〉 ARSENIC
This procedure is designed to determine the presence of
trace amounts of arsenic (As) by converting the arsenic in a
substance under test to arsine, which is then passed
through a solution of silver diethyldithiocarbamate to form a
red complex. The red color so produced is compared, either
visually or spectrophotometrically, to the color produced
similarly in a control containing an amount of arsenic equiv-
alent to the limit given in the individual monograph. Limits
are stated in terms of arsenic (As). The content of arsenic
does not exceed the limit given in the individual
monograph.
Two methods are provided, the methods differing only in
the preliminary treatment of the test substance and the
standard. Generally, Method I is used for inorganic materials,
while Method II is used for organic materials.
Apparatus—
The apparatus (see illustration) consists of an arsine gener-
ator (a) fitted with a scrubber unit (c) and an absorber tube
(e) with standard-taper or ground glass ball-and-socket Arsenic Test Apparatus
joints (b and d) between the units. However, any other suit-
able apparatus, embodying the principle of the assembly
described and illustrated, may be used. Arsenic Trioxide Stock Solution—Dissolve 132.0 mg of
arsenic trioxide, previously dried at 105° for 1 hour and ac-
curately weighed, in 5 mL of sodium hydroxide solution (1
in 5) in a 1000-mL volumetric flask. Neutralize the solution
with 2 N sulfuric acid, add 10 mL more of 2 N sulfuric acid,
then add recently boiled and cooled water to volume, and
mix.
146 〈211〉 Arsenic / Chemical Tests USP 36

Standard Arsenic Solution—Transfer 10.0 mL of Arsenic stead 10 mL of cooled dilute sulfuric acid (1 in 2), and add
Trioxide Stock Solution to a 1000-mL volumetric flask, add a few drops of the hydrogen peroxide before heating.
10 mL of 2 N sulfuric acid, then add recently boiled and Standard Preparation—Pipet 3.0 mL of Standard Arsenic
cooled water to volume, and mix. Each mL of Standard Arse- Solution into a generator flask, add 2 mL of sulfuric acid,
nic Solution contains the equivalent of 1 µg of arsenic (As). mix, and add the total amount of 30 percent hydrogen per-
Keep this solution in an all-glass container, and use within 3 oxide used in preparing the Test Preparation. Heat the mix-
days. ture to strong fuming, cool, add cautiously 10 mL of water,
and again heat to strong fumes. Repeat this procedure with
another 10 mL of water to remove any traces of hydrogen
METHOD I peroxide. Cool, and dilute with water to 35 mL.
Test Preparation—Unless otherwise directed in the indi-
Standard Preparation—Pipet 3.0 mL of Standard Arsenic vidual monograph, transfer to a generator flask the quantity,
Solution into a generator flask, and dilute with water to in g, of the test substance calculated by the formula:
35 mL.
Test Preparation—Unless otherwise directed in the indi- 3.0/L
vidual monograph, transfer to the generator flask the quan-
tity, in g, of the test substance calculated by the formula: in which L is the arsenic limit in ppm. Add 5 mL of sulfuric
acid and a few glass beads, and digest in a fume hood,
3.0/L preferably on a hot plate and at a temperature not exceed-
ing 120°, until charring begins. (Additional sulfuric acid may
in which L is the arsenic limit in ppm, dissolve in water, and be necessary to wet some specimens completely, but the
dilute with water to 35 mL. total volume added should not exceed 10 mL.) Cautiously
Procedure—Treat the Standard Preparation and the Test add, dropwise, 30 percent hydrogen peroxide, allowing the
Preparation similarly as follows. Add 20 mL of 7 N sulfuric reaction to subside and again heating between drops. Add
acid, 2 mL of potassium iodide TS, 0.5 mL of stronger acid the first few drops very slowly with sufficient mixing, in or-
stannous chloride TS, and 1 mL of isopropyl alcohol, and der to prevent a rapid reaction. Discontinue heating if foam-
mix. Allow to stand at room temperature for 30 minutes. ing becomes excessive. When the reaction has abated, heat
Pack the scrubber tube (c) with two pledgets of cotton that cautiously, rotating the flask occasionally to prevent the
have been soaked in saturated lead acetate solution, freed specimen from caking on glass exposed to the heating unit.
from excess solution by expression, and dried in vacuum at Maintain oxidizing conditions at all times during the digestion
room temperature, leaving a 2-mm space between the two by adding small quantities of the hydrogen peroxide solution
pledgets. Lubricate the joints (b and d) with a suitable stop- whenever the mixture turns brown or darkens. Continue the
cock grease designed for use with organic solvents, and digestion until the organic matter is destroyed, gradually
connect the scrubber unit to the absorber tube (e). Transfer raising the temperature of the hot plate until fumes of sulfur
3.0 mL of silver diethyldithiocarbamate TS to the absorber trioxide are copiously evolved, and the solution becomes
tube. Add 3.0 g of granular zinc (No. 20 mesh) to the mix- colorless or retains only a light straw color. Cool, add cau-
ture in the flask, immediately connect the assembled scrub- tiously 10 mL of water, mix, and again evaporate to strong
ber unit, and allow the evolution of hydrogen and the color fuming, repeating this procedure to remove any trace of
development to proceed at room temperature for 45 min- hydrogen peroxide. Cool, add cautiously 10 mL of water,
utes, swirling the flask gently at 10-minute intervals. Discon- wash the sides of the flask with a few mL of water, and
nect the absorber tube from the generator and scrubber dilute with water to 35 mL.
units, and transfer the absorbing solution to a 1-cm absorp- Procedure—Proceed as directed for Procedure under
tion cell. Any red color produced by the Test Preparation Method I.
does not exceed that produced by the Standard Preparation. Interfering Chemicals—See Interfering Chemicals under
If necessary or desirable, determine the absorbance at the Method I.
wavelength of maximum absorbance between 535 and
540 nm, with a suitable spectrophotometer or colorimeter,
using silver diethyldithiocarbamate TS as the blank.
Interfering Chemicals—Metals or salts of metals, such as
chromium, cobalt, copper, mercury, molybdenum, nickel,
palladium, and silver, may interfere with the evolution of
arsine. Antimony, which forms stibine, produces a positive
interference in the color development with silver dieth- 〈221〉 CHLORIDE AND SULFATE
yldithiocarbamate TS; when the presence of antimony is
suspected, the red colors produced in the two silver
diethyldithiocarbamate solutions may be compared at the The following limit tests are provided as general proce-
wavelength of maximum absorbance between 535 and dures for use where limits for chloride and sulfate are speci-
540 nm, with a suitable colorimeter, since at this wave- fied in the individual monographs.
length the interference due to stibine is negligible. Perform the tests and the controls in glass cylinders of the
same diameter and matched as closely as practicable in
other respects (see Visual Comparison under Spectrophotome-
METHOD II try and Light-Scattering 〈851〉). Use the same quantities of
the same reagents for both the solution under test and the
NOTES— control solution containing the specified volume of chloride
(1) Caution—Some substances may react with explosive vio- or sulfate. If, after acidification, the solution is not perfectly
lence when digested with hydrogen peroxide. Exercise safety clear, pass it through a filter paper that gives negative tests
precautions at all times. for chloride and sulfate. Add the precipitant, silver nitrate TS
(2) If halogen-containing compounds are present, use a or barium chloride TS as required, to both the test solution
lower temperature while heating the test specimen with sul- and the control solution in immediate sequence.
furic acid, avoid boiling the mixture, and add the hydrogen Where the individual monograph calls for applying the
peroxide with caution, before charring begins, to prevent test to a specific volume of a solution of the substance, and
loss of trivalent arsenic. the limit for chloride or sulfate corresponds to 0.20 mL or
(3) If the test substance reacts too rapidly and begins less of 0.020 N hydrochloric acid or sulfuric acid, respec-
charring with 5 mL of sulfuric acid before heating, use in- tively, apply the test to the solution without further dilution.