3500-Al Rev Edit 2011
3500-Al Rev Edit 2011
3500-Al Rev Edit 2011
3500-Al A. Introduction
1
ALUMINUM (3500-Al)/Eriochrome Cyanine R Method
Figure 3500-Al:1. Correction curves for estimation of aluminum in the presence of fluoride. Above the mg F⫺/L present, locate the point corresponding
to the apparent mg Al/L measured. From this point interpolate between the curves shown, if the point does not fall directly on one of the
curves, to read the true mg Al/L on the ordinate, which corresponds to 0.00 mg F⫺/L. For example, an apparent 0.20 mg Al/L in a sample
containing 1.00 mg F⫺/L would actually be 0.30 mg Al/L if no fluoride were present to interfere.
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ALUMINUM (3500-Al)/Eriochrome Cyanine R Method
2) Dissolve 8.791 g aluminum potassium sulfate (also imum transmittance between 525 and 535 nm. Adjust instrument
called potassium alum), AlK(SO4)2 䡠 12H2O, in water and to zero absorbance with the standard containing no aluminum.
dilute to 1000 mL. Correct this weight by dividing by the Plot concentration of Al (micrograms Al in 50 mL final
decimal fraction of assayed AlK(SO4)2 䡠 12H2O in the reagent volume) against absorbance.
used. b. Sample treatment in absence of fluoride and complex phos-
b. Standard aluminum solution: Dilute 10.00 mL stock alu- phates: Place 25.0 mL sample, or a portion diluted to 25 mL, in
minum solution to 1000 mL with water; 1.00 mL ⫽ 5.00 g Al. a porcelain dish or flask, add a few drops of methyl orange
Prepare daily. indicator, and titrate with 0.02N H2SO4 to a faint pink color.
c. Sulfuric acid, H2SO4, 0.02N and 6N. Record reading and discard sample. To two similar samples at
d. Ascorbic acid solution: Dissolve 0.1 g ascorbic acid in room temperature add the same amount of 0.02N H2SO4 used in
water and make up to 100 mL in a volumetric flask. Prepare fresh the titration and 1 mL in excess.
daily. To one sample add 1 mL EDTA solution. This will serve as a
e. Buffer reagent: Dissolve 136 g sodium acetate, blank by complexing any aluminum present and compensating
NaC2H3O2 䡠 3H2O, in water, add 40 mL 1N acetic acid, and for color and turbidity. To both samples add 1 mL ascorbic acid,
dilute to 1 L. 10 mL buffer reagent, and 5.00 mL working dye reagent as
f. Stock dye solution: Use any of the following products: prescribed in ¶ a2) above.
1) Solochrome cyanine R-200* or Eriochrome cyanine:† Dis- Set instrument to zero absorbance or 100% transmittance
solve 100 mg in water and dilute to 100 mL in a volumetric flask. using the EDTA blank. After 5 to 10 min contact time, read
This solution should have a pH of about 2.9. transmittance or absorbance and determine aluminum concen-
2) Eriochrome cyanine R:‡ Dissolve 300 mg dye in about 50 tration from the calibration curve previously prepared.
mL water. Adjust pH from about 9 to about 2.9 with 1 ⫹ 1 acetic c. Visual comparison: If photometric equipment is not avail-
acid (approximately 3 mL will be required). Dilute with water to able, prepare and treat standards and a sample, as described
100 mL. above, in 50-mL nessler tubes. Make up to mark with water and
3) Eriochrome cyanine R:§ Dissolve 150 mg in about 50 mL compare sample color with the standards after 5 to 10 min
water. Adjust pH from about 9 to about 2.9 with 1 ⫹ 1 acetic contact time. A sample treated with EDTA is not needed when
acid (approximately 2 mL will be required). Dilute with water to nessler tubes are used. If the sample contains turbidity or color,
100 mL. the use of nessler tubes may result in considerable error.
Stock solutions have excellent stability and can be kept for at d. Removal of phosphate interference: Add 1.7 mL 6N H2SO4
least a year. to 100 mL sample in a 200-mL erlenmeyer flask. Heat on a hot
g. Working dye solution: Dilute 10.0 mL of selected stock dye plate for at least 90 min, keeping solution temperature just below
solution to 100 mL in a volumetric flask with water. Working the boiling point. At the end of the heating period solution
solutions are stable for at least 6 months. volume should be about 25 mL. Add water if necessary to keep
h. Methyl orange indicator solution, or bromcresol green in- it at or above that volume.
dicator solution specified in the total alkalinity determination After cooling, neutralize to a pH of 4.3 to 4.5 with NaOH,
(Section 2320B.3d). using 1N NaOH at the start and 0.1N for the final fine adjust-
i. EDTA (sodium salt of ethylenediamine-tetraacetic acid di- ment. Monitor with a pH meter. Make up to 100 mL with water,
hydrate), 0.01M: Dissolve 3.7 g in water, and dilute to 1 L. mix, and use a 25-mL portion for the aluminum test.
j. Sodium hydroxide, NaOH, 1N and 0.1N. Run a blank in the same manner, using 100 mL distilled water
and 1.7 mL 6N H2SO4. Subtract blank reading from sample
4. Procedure reading or use it to set instrument to zero absorbance before
reading the sample.
a. Preparation of calibration curve: e. Correction for samples containing fluoride: Measure sam-
1) Prepare a series of aluminum standards from 0 to 7 g (0 ple fluoride concentration by the SPADNS or electrode method.
to 280 g/L based on a 25-mL sample) by accurately measuring Either:
the calculated volumes of standard aluminum solution into 1) Add the same amount of fluoride as in the sample to each
50-mL volumetric flasks or nessler tubes. Add water to a total aluminum standard, or
volume of approximately 25 mL. 2) Determine fluoride correction from the set of curves in
2) Add 1 mL 0.02N H2SO4 to each standard and mix. Add 1 Figure 3500-Al:1.
mL ascorbic acid solution and mix. Add 10 mL buffer solution
and mix. With a volumetric pipet, add 5.00 mL working dye
reagent and mix. Immediately make up to 50 mL with distilled 5. Calculation
water. Mix and let stand for 5 to 10 min. The color begins to fade
after 15 min. g Al (in 50 mL final volume)
3) Read transmittance or absorbance on a spectrophotometer, mg Al/L ⫽
mL sample
using a wavelength of 535 nm or a green filter providing max-
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ALUMINUM (3500-Al)/Eriochrome Cyanine R Method
R method in 27 laboratories. Relative standard deviation was tive standard deviation was 44.3% and relative error 1.3%. In 12
34.4% and relative error 1.7%. laboratories that applied no corrective measures, the relative
A second synthetic sample containing 50 g Al/L, 500 g standard deviation was 49.2% and the relative error 8.9%.
Ba/L, and 5 g Be/L in distilled water was analyzed in 35 A fifth synthetic sample containing 480 g Al/L and 750 g
laboratories. Relative standard deviation was 38.5% and relative F/L in distilled water was analyzed in 16 laboratories that relied
error 22.0%. on the curve to correct for the fluoride content. Relative standard
A third synthetic sample containing 500 g Al/L, 50 g Cd/L, deviation was 25.5% and relative error 2.3%. The 17 laboratories
110 g Cr/L, 1000 g Cu/L, 300 g Fe/L, 70 g Pb/L, 50 g that added fluoride to the aluminum standards showed a relative
Mn/L, 150 g Ag/L, and 650 g Zn/L in distilled water was standard deviation of 22.5% and a relative error of 7.1%.
analyzed in 26 laboratories. Relative standard deviation was
28.8% and relative error 6.2%. 7. Bibliography
A fourth synthetic sample containing 540 g Al/L and 2.5 mg SHULL, K.E. & G.R. GUTHAN. 1967. Rapid modified Eriochrome cyanine
polyphosphate/L in distilled water was analyzed in 16 laborato- R method for determination of aluminum in water. J. Amer. Water
ries that hydrolyzed the sample in the prescribed manner. Rela- Works Assoc. 59:1456.