Arsen.01 Imprimir

ARSEN.
01-1
ARSENIC
PRINCIPLE
Arsenic is determined by the silver diethyldithiocarbamate method (Note 1).

Arsenic in the reaction solution is converted to arsine, which is evolved and then
complexed with silver diethyldithiocarbamate. The intensity of the color of the
complex is determined with a spectrophotometer or colorimeter. Arsenic
concentration is ascertained by reference to a calibration curve prepared with the
aid of standard arsenic solutions.
SCOPE
The method is applicable to corn sugar, corn syrup and corn starch.
SAFETY
Because of the use of hot concentrated acids and the extreme toxicity of arsine,
assemble all apparatus and perform reaction in a well-ventilated fume hood.
Operate behind a shield and wear protective gear in the handling and disposal of
reagents and reaction products according to Good Laboratory Practice. Consult
Manufacturer's Safety Data Sheets (MSDS) of all reagents.
SPECIAL APPARATUS
1. Arsenic Apparatus: Consisting of three parts: generator flask, 125-mL

Erlenmeyer flask with a Ts24/40 interchangeable joint, a scrubber tube with
a Ts24/40 joint, connected to an absorber tube by means of a ball and
socket joint. Absorption tubes used with standards and samples must have
the same dimensions to insure equal arsine recoveries (Fisher Scientific
Company, Catalog No. 1-405 or equivalent). Alternative arsenic apparatus,
without the ball and socket joint is available also (SGA Scientific Inc.,
Catalog No. JA-9540, without ball and socket joint).
2. Spectrophotometer: An instrument having a continuously-variable

wavelength control in the visible spectrum and equipped with matching 1.0
– cm cuvets is recommended (Note 2).
Analytical Methods of the Member Companies of the

Corn Refiners Association, Inc.
ARSEN.01-2
3. Water Bath: Temperature-controlled at 25 ± 1°C.
REAGENTS (Note 3)
1. Standard Arsenic Solution, 1 microgram arsenic per ml:
Stock Solution: Dissolve 0.132 g of National Bureau of Standards

arsenious oxide (As2O3) dried 1 hr. in a vacuum oven at 105 ° C) in 10 ml
of 10% sodium hydroxide solution. Neutralize with 1N sulfuric acid
solution, and add 20 ml in excess; dilute to 1-liter volume with distilled
water and mix.
Standard Solution: Pipet 10 ml of the stock solution into a 1-liter

volumetric flask, add 20 ml of 1N sulfuric acid, dilute to volume with
distilled water and mix. Prepare fresh daily.
2. Hydrochloric acid, Concentrated: Reagent grade (37% HC1, sp g 1.19).
3. Lead Acetate Trihydrate Solution, 10%: Dissolve 10 g of neutral lead

acetate trihydrate (Pb(C2H3O2)2•3H2O) in distilled water, dilute to 100-ml
volume and mix.
4. Potassium Iodide Solution, 15%: Dissolve 150 g or reagent grade

potassium iodide (KI) in distilled water, dilute to 1-liter volume and mix.
5. Silver Diethyldithiocarbamate Solution, 0.5%: Dissolve 1.0 g of silver

diethyldithiocarbamate [AgSCSN(C2H5)2] (Fisher Scientific Company, No.
S-666 in 200 ml of reagent grade pyridine (C5H5N) to mix. Store in a
nonactinic bottle.
6. Stannous Chloride Dihydrate Solution, 40%: Dissolve 40 g of reagent

grade stannous chloride dihydrate (SnCl2•2H2O) in concentrated
hydrochloric acid and mix.
7. Zinc Metal: Granular, 20 mesh.
8. Ammonium Oxalate Monohydrate Solution, Saturated: Add 50 g of

reagent grade ammonium oxalate monohydrate [(NH4)2C2)4•H2O] to 1 liter
of distilled water and heat to dissolve. Some solid should crystallize as the
solution cools to room temperature. Allow crystals to settle and use the
clear supernatant.
ARSEN.01-3
9. Sodium Hydroxide Solution, 50%
10. Bromophenol Blue Indicator, 1%
11. Nitric Acid, Concentrated: Reagent grade (70% HNO3, sp g 1.42)
12. Sulfuric Acid, Concentrated: Reagent grade (96% H2SO4, sp g 1.84)

PROCEDURE (Note 4)
A. Standardization: Pipet 2.0, 5.0, and 10.0 milliliters of standard arsenic

solution into separate generator flasks and reserve one empty flasks and
reserve one empty flask as a blank. Add 5 ml of concentrated hydrochloric
acid, 2 ml of 15% potassium iodide solution, and 0.5 ml of 40% stannous
chloride solution to each flask. Dilute the contents of each flask to 40 ml with
distilled water, mix, and allow to stand in a water bath at 25 °C for 15 mins.
Fill each scrubber tube with glass wool moistened with 10% lead acetate
solution, avoiding excess. Pipet 4.0 ml of silver diethyldithiocarbamate
solution into each absorber tube. When the 15-minute standing period has
elapsed, remove the generator flask from the bath, add 4 g of granular zinc
(Note 5), and immediately attach the scrubber tube and absorber tube.
Immerse the apparatus in the water bath at 25 °C for 30 mins. Repeat the
above with each assembly.
Using the reagent blank as a reference solution at 100% transmittance (T),

determine transmittance of each solution in a 1-cm cuvet at 535 nm (Note 6).
Plot % T versus micrograms of arsenic on semi-logarithmic graph paper.
B. Analysis (Note 7): Weigh accurately 5.00 ± 0.01 g of sample (Note 8) into a
100-ml beaker and dissolve or dilute with 10 ml of distilled water (Note 9).
Transfer the solution to be analyzed quantitatively to a generator flask and
reserve an empty flask for a reagent blank. To each flask add 5 ml of
concentrated hydrochloric acid, 2 ml of 15% potassium iodide solution , and
0.5 ml of 40% stannous chloride solution. Dilute to 40 ml with distilled water,
mix, and allow to stand in a 25 °C water bath for 15 mins.
Fill a scrubber tube with glass wool moistened with 10% lead acetate solution,
avoiding excess. Pipet 4.0 ml of silver diethyldithiocarbamate solution into
the absorber tube. When the 15-minute standing period has elapsed, remove
the generator flask from the bath, add 4 g of granular zinc (Note 5), and
ARSEN.01-4
immediately attach the scrubber tube and absorber tube. Immerse the
apparatus in the water bath at 25 °C for 30 mins.
Using the reagent blank as a reference solution at 100% transmittance (T)

determine transmittance of the solution in a 1-cm cuvet 535 nm (Note 6).
CALCULATION
Determine arsenic content of the sample solution by reference to the

standardization curve.
Micorgrams of Arsenic (From Graph)

Arsenic, ppm =
Sample Wt. (g)
NOTE AND PRECAUTIONS
1. This method is equivalent to the silver diethyldithiocarbamate procedure

adopted by the Association of Official Analytical Chemists (AOAC 25.006,
p. 428, 12th Ed., 1975). This is a primary procedure not usually used by
most laboratories.
2. A spectrophotometer providing narrow-band monochromatic light by

means of a prism or diffraction grating is recommended. However, other
photoelectric colorimeters or color comparators may be used for color
determination or color matching.
3. Reagents 2 through 12 must be arsenic free.
4. Small zinc granules adhering to the neck (24/40 Ts joint) of the generator
flask preclude a tight seal when attaching the scrubber tube and absorber.
Leaks cause low and erratic results. Avoid this problem by adding the zinc
granules through a small funnel, with a 0.5-inch I.D. by 2.5-inch long stem,
so that particles do not contact the neck.
In case of excessive foaming, repeat the entire series using less zinc;
however, the amount must be sufficient to provide adequate sweeping of
the solutions and assembly.
6. Sensitivity is increased by avoiding dilution of the trapping solutions.

While the 4-ml portions are too small to permit rinsing the cell between
samples, carry-over is insignificant if the cell is thoroughly clean and is
ARSEN.01-5
permitted to drain into a cloth or paper towel before introducing the next
solution.
7. Alternate wet ashing procedure recommended for starch samples. Weigh

accurately 5.00 ± 0.01 g of crude or refined sugar sample and transfer
quantitatively into an 800-ml Kjeldahl flask. (Following Note 8, transfer
quantitatively the 10 g of solution to a Kjeldahl flask with a minimum
amount of water.) in a hood, add cautiously 50 ml of concentrated nitric
acid (rinsing down any portion of the sample that might be in the neck of
the flask); then, add cautiously 10 ml of concentrated sulfuric acid while
swirling the flask gently.
Support the flask at an angle of about 60 degrees on an asbestos mat with a

2-inch hole, using a ringstand. Warm slightly with a gas flame and
discontinue heating if foaming or reaction becomes excessive. Repeat this
procedure until the reaction has quieted, then heat the flask cautiously and
rotate occasionally, if necessary, to prevent caking or charring of sample
upon glass exposed to flame. Maintain oxidizing conditions in the flask at
all times during digestion by cautiously adding small amounts of
concentrated nitric acid whenever mixture turns brown or darkens.
Continue digestion until organic matter is destroyed and copious fumes of
white sulfur trioxide (SO3) are evolved. (Final solution should be colorless
or, at most, light straw color.) Cool slightly, and cautiously add 75 ml of
water and 25 ml of saturated ammonium oxalate solution to assist in
expelling oxides of nitrogen from solution. Evaporate again to point where
SO3 fumes appear in neck of flask.
Cool, transfer quantitatively with distilled water to a 100-ml volumetric

flask, dilute to volume, and mix. Titrate a 25.0-ml aliquot with the 50%
sodium hydroxide solution to a bromophenol blue indicator end point.
Pipet a 25.0-ml aliquot of the digest into an arsine generator flask, add the
determined amount of 50% sodium hydroxide solution to neutralize the
excess sulfuric acid, then follow procedure for arsenic determination. Run
a complete blank determination, without sample, using all reagents and
steps in the procedure. Multiply the observed arsenic result by 4 to correct
for dilution.
8. Selection of representative 5-g samples of “70” or “80” sugars is difficult.

It is recommended that a large sample, e.g., 100 g, be diluted with an equal
weight of hot (near boiling temperature) distilled water. Sample and water
ARSEN.01-6
are shaken in a closed container until solution is complete. Shaking for 15

mins. usually is sufficient. After cooling to near room temperature, 10 g of
solution, equivalent to 5 g of original sample, is taken for analysis.
9. Dilute with only 5 ml of distilled water when analyzing 10 g of “70” or

“80” sugar solutions prepared as outlined in Note 8.
METHOD HISTORY
Combined the Arsenic methods for Corn Starch (Unmodified) (B-6), Corn Syrup
(E-4) and Corn Sugar (F-4) on 4-15-2010.
Corn Starch (Unmodified), Arsenic (B-6), Date of Acceptance 11-15-1958,

Revised 2-23-2001.
Corn Syrup, Arsenic (E-4), Date of Acceptance 4-5-1954, Revised 10-23-2001.
Corn Sugar, Arsenic (F-4), Date of Acceptance 11-15-1958, Revised 10-23-2001.

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ARSEN.

Arsenic is determined by the silver diethyldithiocarbamate method (Note 1).

1. Arsenic Apparatus: Consisting of three parts: generator flask, 125-mL

2. Spectrophotometer: An instrument having a continuously-variable

Analytical Methods of the Member Companies of the

3. Water Bath: Temperature-controlled at 25 ± 1°C.

1. Standard Arsenic Solution, 1 microgram arsenic per ml:

Stock Solution: Dissolve 0.132 g of National Bureau of Standards

Standard Solution: Pipet 10 ml of the stock solution into a 1-liter

2. Hydrochloric acid, Concentrated: Reagent grade (37% HC1, sp g 1.19).

3. Lead Acetate Trihydrate Solution, 10%: Dissolve 10 g of neutral lead

4. Potassium Iodide Solution, 15%: Dissolve 150 g or reagent grade

5. Silver Diethyldithiocarbamate Solution, 0.5%: Dissolve 1.0 g of silver

6. Stannous Chloride Dihydrate Solution, 40%: Dissolve 40 g of reagent

7. Zinc Metal: Granular, 20 mesh.

8. Ammonium Oxalate Monohydrate Solution, Saturated: Add 50 g of

9. Sodium Hydroxide Solution, 50%

10. Bromophenol Blue Indicator, 1%

11. Nitric Acid, Concentrated: Reagent grade (70% HNO3, sp g 1.42)

12. Sulfuric Acid, Concentrated: Reagent grade (96% H2SO4, sp g 1.84)

A. Standardization: Pipet 2.0, 5.0, and 10.0 milliliters of standard arsenic

Using the reagent blank as a reference solution at 100% transmittance (T),

Plot % T versus micrograms of arsenic on semi-logarithmic graph paper.

Using the reagent blank as a reference solution at 100% transmittance (T)

Determine arsenic content of the sample solution by reference to the

Micorgrams of Arsenic (From Graph)

NOTE AND PRECAUTIONS

1. This method is equivalent to the silver diethyldithiocarbamate procedure

2. A spectrophotometer providing narrow-band monochromatic light by

3. Reagents 2 through 12 must be arsenic free.

6. Sensitivity is increased by avoiding dilution of the trapping solutions.

7. Alternate wet ashing procedure recommended for starch samples. Weigh

Support the flask at an angle of about 60 degrees on an asbestos mat with a

Cool, transfer quantitatively with distilled water to a 100-ml volumetric

8. Selection of representative 5-g samples of “70” or “80” sugars is difficult.

are shaken in a closed container until solution is complete. Shaking for 15

9. Dilute with only 5 ml of distilled water when analyzing 10 g of “70” or

Corn Starch (Unmodified), Arsenic (B-6), Date of Acceptance 11-15-1958,

Corn Syrup, Arsenic (E-4), Date of Acceptance 4-5-1954, Revised 10-23-2001.

Corn Sugar, Arsenic (F-4), Date of Acceptance 11-15-1958, Revised 10-23-2001.

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