Printed on: Fri May 19 2023, 10:05:55 PM(EST) Status: Currently Official on 20-May-2023 DocId: GUID-FD3BF9F2-0F57-499F-90BD-FD48B2ECB094_1_en-US
Printed by: Van Huynh Le Thu Official Date: Official Prior to 2013 Document Type: GENERAL CHAPTER @2023 USPC
Do Not Distribute DOI Ref: 4wrk1 DOI: https://doi.org/10.31003/USPNF_M98960_01_01
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á211ñ 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 equivalent 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.
PROCEDURES
Apparatus
The apparatus (see illustration) consists of an arsine generator (a) fitted with a scrubber unit (c) and an absorber tube (e)
with standard-taper or ground glass ball-and-socket joints (b and d) between the units. However, any other suitable
apparatus, embodying the principle of the assembly described and illustrated, may be used.
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Arsenic Test Apparatus
Arsenic Trioxide Stock Solution: Dissolve 132.0 mg of arsenic trioxide, previously dried at 105° for 1 hour and accurately
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.
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Printed on: Fri May 19 2023, 10:05:55 PM(EST) Status: Currently Official on 20-May-2023 DocId: GUID-FD3BF9F2-0F57-499F-90BD-FD48B2ECB094_1_en-US
Printed by: Van Huynh Le Thu Official Date: Official Prior to 2013 Document Type: GENERAL CHAPTER @2023 USPC
Do Not Distribute DOI Ref: 4wrk1 DOI: https://doi.org/10.31003/USPNF_M98960_01_01
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Standard Arsenic Solution: Transfer 10.0 mL of Arsenic Trioxide Stock Solution to a 1000-mL volumetric flask, add 10 mL
of 2 N sulfuric acid, then add recently boiled and cooled water to volume, and mix. Each mL of Standard Arsenic
Solution contains the equivalent of 1 µg of arsenic (As). Keep this solution in an all-glass container, and use within
3 days.
Method I
Standard Preparation: Pipet 3.0 mL of Standard Arsenic Solution into a generator flask, and dilute with water to 35 mL.
Test Preparation: Unless otherwise directed in the individual monograph, transfer to the generator flask the quantity, in
g, of the test substance calculated by the formula:
3.0/L
L = limit of arsenic (ppm)
Dissolve in water and dilute with water to 35 mL.
Procedure: Treat the Standard Preparation and the Test Preparation similarly as follows. Add 20 mL of 7 N sulfuric acid,
2 mL of potassium iodide TS, 0.5 mL of stronger acid stannous chloride TS, and 1 mL of isopropyl alcohol, and mix.
Allow to stand at room temperature for 30 minutes. Pack the scrubber tube (c) with two pledgets of cotton that have
been soaked in saturated lead acetate solution, freed from excess solution by expression, and dried in vacuum at room
temperature, leaving a 2-mm space between the two pledgets. Lubricate the joints (b and d) with a suitable stopcock
grease designed for use with organic solvents, and connect the scrubber unit to the absorber tube (e). Transfer 3.0 mL
of silver diethyldithiocarbamate TS to the absorber tube. Add 3.0 g of granular zinc (No. 20 mesh) to the mixture in
the flask, immediately connect the assembled scrubber unit, and allow the evolution of hydrogen and the color
development to proceed at room temperature for 45 minutes, swirling the flask gently at 10-minute intervals.
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Disconnect the absorber tube from the generator and scrubber units, and transfer the absorbing solution to a 1-cm
absorption cell. Any red color produced by the Test Preparation does not exceed that produced by the Standard
Preparation. If necessary or desirable, determine the absorbance at the 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,
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palladium, and silver, may interfere with the evolution of arsine. Antimony, which forms stibine, produces a positive
interference in the color development with silver diethyldithiocarbamate TS; when the presence of antimony is
suspected, the red colors produced in the two silver diethyldithiocarbamate solutions may be compared at the
wavelength of maximum absorbance between 535 and 540 nm, with a suitable colorimeter, since at this wavelength
the interference due to stibine is negligible.
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Method II
[CAUTION—Some substances may react with explosive violence when digested with hydrogen peroxide. Exercise safety
precautions at all times]
[NOTE—If halogen-containing compounds are present, use a lower temperature while heating the test specimen with
sulfuric acid, avoid boiling the mixture, and add the hydrogen peroxide with caution, before charring begins, to
prevent loss of trivalent arsenic.]
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[NOTE—If the test substance reacts too rapidly and begins charring with 5 mL of sulfuric acid before heating, use instead
10 mL of cooled dilute sulfuric acid (1 in 2), and add a few drops of the hydrogen peroxide before heating.]
Standard Preparation: Pipet 3.0 mL of Standard Arsenic Solution into a generator flask, add 2 mL of sulfuric acid, mix,
and add the total amount of 30 percent hydrogen peroxide used in preparing the Test Preparation. Heat the mixture
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 peroxide. Cool, and dilute with water to 35 mL.
Test Preparation: Unless otherwise directed in the individual monograph, transfer to a generator flask the quantity, in
g, of the test substance calculated by the formula:
3.0/L
L = limit of arsenic (ppm)
Add 5 mL of sulfuric acid and a few glass beads, and digest in a fume hood, preferably on a hot plate and at a
temperature not exceeding 120°, until charring begins. (Additional sulfuric acid may be necessary to wet some
specimens completely, but the total volume added should not exceed 10 mL.) Cautiously add, dropwise, 30 percent
hydrogen peroxide, allowing the reaction to subside and again heating between drops. Add the first few drops very
slowly with sufficient mixing, in order to prevent a rapid reaction. Discontinue heating if foaming becomes excessive.
When the reaction has abated, heat cautiously, rotating the flask occasionally to prevent the specimen from caking on
glass exposed to the heating unit. Maintain oxidizing conditions at all times during the digestion by adding small quantities
of the hydrogen peroxide solution whenever the mixture turns brown or darkens. Continue the digestion until the organic
matter is destroyed, gradually raising the temperature of the hot plate until fumes of sulfur trioxide are copiously
evolved, and the solution becomes colorless or retains only a light straw color. Cool, add cautiously 10 mL of water,
mix, and again evaporate to strong fuming, repeating this procedure to remove any trace of hydrogen peroxide. Cool,
add cautiously 10 mL of water, wash the sides of the flask with a few mL of water, and dilute with water to 35 mL.
Procedure: Proceed as directed for Procedure under Method I.
Interfering Chemicals: See Interfering Chemicals under Method I.
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