Designation: E 1506 – 97 (Reapproved 2003)

Standard Test Methods for

Analysis of Acid-Grade Calcium Fluoride (Fluorspar)1
This standard is issued under the fixed designation E 1506; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope procedures for analyzing calcium fluoride to determine

1.1 These test methods cover the chemical analyses of whether it is suitable for this use.
acid-grade calcium fluoride (fluorspar). These test methods 4. Reagents
appear in the following sections:
Sections
4.1 Purity of Reagents—Reagent grade chemicals shall be
Volatiles as Moisture 6-13 used in all tests. Unless otherwise indicated, it is intended that
Silica 14-22 all reagents shall conform to the specifications of the Commit-
Assay as Calcium Fluoride (CaF2) 23-32
Soluble Chloride as NaC1 33-50
tee on Analytical Reagents of the American Chemical Society,
Calcium Carbonate 51-59 where such specifications are available.5 Other grades may be
Phosphorus 60-69 used, provided it is first ascertained that the reagent is of
Arsenic 70-78
Mixed Oxides (R2O3) 79-87
sufficiently high purity to permit its use without lessening the
Sulfide Sulfur 88-96 accuracy of the determination.
4.2 Purity of Water—Unless otherwise indicated, references
1.2 The values stated in SI units are to be regarded as the
to water shall be understood to mean Type II or Type III
standard. The values given in parentheses are for information
reagent water conforming to Specification D 1193.
only.
1.3 This standard does not purport to address all of the 5. Sampling
safety concerns, if any, associated with its use. It is the
5.1 Sampling of calcium fluoride is not within the scope of
responsibility of the user of this standard to establish appro-
these test methods. See the appropriate sections of Practice
priate safety and health practices and determine the applica-
E 300 for sampling procedures.
bility of regulatory limitations prior to use.
1.4 Review the current Material Safety Data Sheet (MSDS) VOLATILES AS MOISTURE
for each chemical used in this standard for detailed information
concerning toxicity, first-aid procedures, handling, and safety 6. Scope
precautions. 6.1 This test method covers the determination of volatiles as
percent moisture.
2. Referenced Documents
2.1 ASTM Standards: 7. Summary of Test Method
D 1193 Specification for Reagent Water2 7.1 The sample is dried in an air oven at 105 to 110°C, and
E 180 Practice for Determining the Precision of ASTM the weight loss is calculated as percent moisture.
Methods for Analysis and Testing of Industrial Chemicals3
E 300 Practice for Sampling Industrial Chemicals4 8. Apparatus
8.1 Top-Loading Balance, capable of weighing 1000 g to
3. Significance and Use the nearest 0.01 g.
3.1 Calcium fluoride is available in nature in various forms 8.2 Sample Pan, stainless steel or borosilicate glass, 152 by
and purities. A major use for it is in the manufacture of 152 by 51 mm (6 by 6 by 2 in.) deep.
hydrofluoric acid. The test methods listed in 1.1 provide 8.3 Cooling Rack, wood or metal, able to allow circulation
of air around the entire sample pan (for example, a “baker’s
rack”).
1
These test methods are under the jurisdiction of ASTM Committee E15 on
Industrial and Specialty Chemicalsand are the direct responsibility of Subcommittee
5
E15.02 on Product Standards. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Apr. 10, 2003. Published May 2003. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
approved in 1994. Last previous edition approved in 1997 as E 1506 – 97. listed by the American Chemical Society, see Analar Standards for Laboratory
2
Annual Book of ASTM Standards, Vol 11.01. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
3
Annual Book of ASTM Standards, Vol 15.05. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
4
Discontinued. See 2000 Annual Book of ASTM Standards, Vol 15.05. MD.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 E 1506 – 97 (2003)
TABLE 1 Volatiles as Moisture Checking Limits for Duplicates TABLE 2 Volatiles as Moisture
Volatiles Level, Standard Degrees of 95 % Limit, % Repeatability Reproducibility
% Deviation Freedom Absolute Volatiles 95 % 95 %
Standard Degrees of Standard Degrees of
6 0.0257 18 0.072 Level,% Limit, % Limit,%
Deviation Freedom Deviation Freedom
9 0.0822 18 0.230 Absolute Absolute
6 0.0238 9 0.067 0.0807 8 0.226
9 0.0666 9 0.186 0.0865 8 0.242

8.4 Forced Air Oven, capable of maintaining temperatures

of 105 to 110°C.
degrees of freedom. The 95 % limit for the difference between
9. Hazards two such averages is the value shown in Table 2.
13.1.3 Reproducibility (Multilaboratory)—The standard de-
9.1 See 1.3 and 1.4.
viation of results (each the average of duplicates) obtained by
10. Procedure analysts in different laboratories has been estimated to be the
value shown in Table 2 at the indicated degrees of freedom.
10.1 Tare a clean, dry sample pan to the nearest 0.01 g.
The 95 % limit for the difference between two such averages is
10.2 Add approximately 1000 g of representative sample to
the value shown in Table 2.
the pan and spread evenly. Wipe all external surfaces of the pan
free of sample. Weigh again to the nearest 0.01 g. NOTE 1—These precision estimates are based on an interlaboratory
10.3 Place the pan containing the sample in an air oven at study performed in 1992 in which samples of fluorspar from two lots, one
105 to 110°C for a minimum of 12 h. containing about 6 % volatiles as moisture and the other about 9 %
volatiles as moisture, were each analyzed in duplicate by one analyst on
10.4 Remove the pan from the oven and place on a cooling
each of two days in each of ten laboratories for a total of 120
rack for 1 h. determinations.6 Practice E 180 was used in developing these precision
10.5 Weigh the cooled pan to the nearest 0.01 g. estimates.
10.6 Return the pan to the cooling rack and cool for an
13.2 Bias—The bias of this test method has not been
additional 30 min. Then reweigh the pan to the nearest 0.01 g.
determined due to the unavailability of suitable reference
10.7 Repeat 11.6 until consecutive weights agree within
materials.
0.05 g.
10.8 Once a consistent weight has been obtained, dump the SILICA
sample on a flat, dry surface and spread it with a spatula. If the
fluorspar is dry, it will appear dusty, powdery, and flour-like in 14. Scope
consistency. If the fluorspar does not appear as such, repeat the 14.1 This test method covers the determination of percent
analysis using fresh sample. silica.
11. Calculation 15. Summary of Test Method
11.1 Calculate percent volatiles as moisture as follows: 15.1 The sample is treated with 10 % acetic acid to remove
~B 2 C! 3 100 carbonates and soluble salts, the residue is ignited in a 650°C
volatiles as moisture, weight % 5 (1) muffle furnace, treated with 48 % hydrofluoric acid (HF), and
~B 2 A!
then heated again at 650°C. The weight loss after the HF
where: treatment is calculated as percent silica.
A = weight of empty pan, g (10.1),
B = weight of pan plus sample before drying, g (10.2), and 16. Apparatus
C = weight of pan plus sample after drying to consistent 16.1 Analytical Balance, capable of weighing to the nearest
weight, g (10.7). 0.1 mg.
12. Report 16.2 Beaker, 150-mL glass, unscratched, and watchglass
cover.
12.1 Report the percent volatiles as moisture to the nearest 16.3 Graduated Cylinder, 25-mL glass.
0.01 %. 16.4 Graduated Cylinder, 10-mL polypropylene.
13. Precision and Bias 16.5 Platinum Crucible, 30-mL capacity with lid.
16.6 Platinum Wire, 4 cm by 2 mm.
13.1 Precision—The following criteria should be used for
16.7 Stirring Rod, borosilicate glass, unscratched.
judging the acceptability of results (see Note 1):
16.8 Muffle Furnace, capable of maintaining a temperature
13.1.1 Repeatability (Single Analyst)—The standard devia-
of 650 6 10°C or higher.
tion for a single determination has been estimated to be the
16.9 Desiccator, with desiccant.
value shown in Table 1 at the indicated degrees of freedom.
16.10 Steam Bath.
The 95 % limit for the difference between two such runs is the
16.11 Glass Filter Funnel.
value shown in Table 1.
16.12 Bunsen Burner, ringstand, ring, and heating mesh.
13.1.2 Laboratory Precision (Within-Laboratory, Between-
Days)—The standard deviation of results (each the average of
duplicates) obtained by the same analyst on different days has 6
Supporting data have been filed at ASTM International Headquarters and may
been estimated to be the value shown in Table 2 at the indicated be obtained by requesting Research Report RR: E15–1027.

2
 E 1506 – 97 (2003)
16.13 Disposable Pipets. 19.14 Gently heat the crucible over a Bunsen burner in a
16.14 Mortar and Pestle, 102-mm (4-in.) diameter, agate. hood until dry (see Note 2).
16.15 Tongs, platinum-tipped.
NOTE 2—The solution must be heated below boiling. Excess heat will
cause erratic results. If unable to control heating using a bunsen burner,
17. Reagents
heat the solution on a hot plate at 60°C or below. Evaporation of the 6 mL
17.1 Acetic Acid Solution (100 mL/L)—Dilute 10 mL of of HF used in this procedure should take approximately 2 h.
glacial acetic acid to 100 mL with water; mix well.
17.2 Hydrofluoric Acid (HF), 48 %. 19.15 Cool the crucible, then repeat 19.13 and 19.14.
17.3 Ashless Cellulose Filter Aid, Whatman accelerator 19.16 Cover the crucible with a platinum lid; then carefully
powder,7 or equivalent. place it into a muffle furnace maintained at 650 6 10°C.
17.4 Filter Paper, 9-cm diameter, low-ash, acid-washed, 19.17 Heat the crucible for 5 min; then place it into a
medium-porosity, able to retain 8-µm particles. desiccator to cool.
17.5 Filter Paper, 9-cm diameter, low-ash, acid-washed, 19.18 Weigh the crucible, cover, and residue to 0.0001 g.
fine-porosity, able to retain 2.5-µm particles.
17.6 Ethanol, pure or denatured. 20. Calculation
17.7 Filter Pulp Slurry (40 g/L)—Slurry 10 g of cellulose
filter aid with 250 mL of water. 20.1 Calculate percent silica as follows:
~B 2 C! 3 100
18. Hazards silica, weight % 5 A (2)

18.1 See 1.3 and 1.4. where:

A = weight of sample, g (19.2),
19. Procedure B = weight of crucible, cover, and residue before HF
19.1 Transfer 8 to 10 g of sample (previously dried to treatment, g (19.12), and
constant weight at 105 to 110°C) into a mortar. Grind with a C = weight of crucible, cover, and residue after HF treat-
pestle until the particle size is 100 to 500 mesh. ment, g (19.18).
19.2 Weigh 1.0 g of the ground sample to the nearest 0.0001
g, and transfer it to a 150-mL beaker. 21. Report
19.3 Wet the sample with 1 mL of ethanol, then add 15 mL
21.1 Report the percent silica to the nearest 0.01 %.
of 10 % acetic acid to the beaker.
19.4 Add a glass stirring rod to the beaker, cover with a
watchglass, and place on a steam bath. 22. Precision and Bias
19.5 Heat for 30 6 1 min, stirring every 5 min. 22.1 Precision—The following criteria should be used for
19.6 Remove from the steam bath, add 5 mL of filter pulp judging the acceptability of results (see Note 3):
slurry to the beaker, cover, and allow to sit for approximately 22.1.1 Repeatability (Single Analyst)—The standard devia-
12 h. tion for a single determination has been estimated to be
19.7 Gravity filter the solution through medium-porosity 0.0319 % absolute at 50 df. The 95 % limit for the difference
filter paper. between two such runs is 0.09 % absolute.
19.8 Rinse the beaker several times with minimal portions
22.1.2 Laboratory Precision (Within-Laboratory, Between-
of hot water (total wash water approximately 35 mL), filtering
Days)—The standard deviation of results (each the average of
each wash through the same filter paper. Save the filtrate for the
duplicates) obtained by the same analyst on different days has
determination of Mixed Oxides (Section 79).
been estimated to be 0.0362 % absolute at 25 df. The 95 %
19.9 Wipe the beaker clean with one fourth of a fine-
limit for the difference between two such averages is 0.10 %
porosity filter paper, and transfer the wipe paper and the filter
absolute.
paper with the residue into a 30-mL platinum crucible.
19.10 Place a platinum wire across the top of the platinum 22.1.3 Reproducibility (Multilaboratory)—The standard de-
crucible. Rest the crucible lid on the wire and place the crucible viation of results (each the average of duplicates) obtained by
into a cool muffle furnace. analysts in different laboratories has been estimated to be
19.11 Heat the furnace slowly (1-h cycle) to 650 6 10°C. 0.0529 % absolute at 11 df. The 95 % limit for the difference
Once the temperature has reached 650°C, check the crucible between two such averages is 0.15 % absolute.
every 10 min until the paper is entirely burned off. NOTE 3—These precision estimates are based on an interlaboratory
19.12 Cool the crucible to room temperature in a desiccator, study performed in 1992 in which samples of fluorspar from two lots, one
then weigh the crucible, cover, and residue to 0.0001 g. containing about 0.5 % silica and the other about 1 % silica, were each
19.13 Using a 10-mL polypropylene graduate cylinder, analyzed in duplicate on each of two days by one analyst in each of 14
carefully pour 3 mL of 48 % HF into the crucible. laboratories for a total of 112 determinations.6 Practice E 180 was used in
developing these precision estimates.

22.2 Bias—The bias of this test method has not been

7
Available from Whatman LabSales, P.O. Box 1359, Hillsboro, OR, 97123- determined due to the unavailability of suitable reference
9981. materials.

3
 E 1506 – 97 (2003)
ASSAY AS CALCIUM FLUORIDE (CaF2) cool. Add additional ammonium oxalate if necessary to keep
crystals present at the bottom of the bottle at all times.
23. Scope 27.7 Ammonium Oxalate Solution (1 g/L)—Add 0.1 g of
23.1 This test method covers the determination of assay as ammonium oxalate to 100 mL of water and mix well.
percent calcium fluoride (CaF2). 27.8 Filter Paper, 9-cm diameter, low-ash, acid-washed,
medium-porosity, able to retain 8-µm particles.
24. Summary of Test Method 27.9 Filter Pulp Slurry (40 g/L)—Slurry 10 g of cellulose
24.1 The residue remaining after the determination of silica filter aid with 250 mL of water.
(see 19.18) is treated with H2SO4, dried, then dissolved in HCl. 27.10 pH Paper—Litmus.
Ammonium oxalate is added to the HCl solution to precipitate
calcium oxalate, then the precipitate is dried and weighed. 28. Hazards
Percent CaF2 is calculated from the weight of the calcium 28.1 See 1.3 and 1.4.
oxalate collected.
29. Procedure
25. Interferences
29.1 Add 5 mL of concentrated sulfuric acid to the residue
25.1 Iron causes a positive interference. If iron is suspected
remaining in the crucible from 19.18.
to be present, its effect can be minimized by adding 1 mL of
concentrated HNO3 to the solution described in 29.8 before 29.2 Partially cover the crucible and gently heat over a
boiling. bunsen burner in a hood until all H2SO4 is driven off (see Note
25.2 Strontium precipitates, as the oxalate, along with 4).
calcium oxalate to produce erroneously high results. NOTE 4—Do not heat directly with the flame.
25.3 A small amount of CaF2 is lost in the acetic acid
treatment used in 19.3, resulting in an erroneously low result. 29.3 Repeat 29.1 and 29.2 using 3 mL of concentrated
To correct for this loss, the term 0.15 is included in the sulfuric acid.
calculation in 30.1. 29.4 Cool the crucible and transfer the crucible, cover, and
residue into a 400-mL beaker.
26. Apparatus 29.5 Add 10 mL of concentrated hydrochloric acid, 5 g of
ammonium chloride, and 200 mL of hot water to the beaker;
26.1 Analytical Balance, capable of weighing to the nearest
mix well.
0.1 mg.
26.2 Beakers, borosilicate glass, 800-mL, 400-mL, and 29.6 Warm the solution to between 70 and 80°C on a hot
watchglass covers. plate in a hood; keep at this temperature for 2 h.
26.3 Graduated Cylinders, borosilicate glass, 10-mL, 25- 29.7 Remove the crucible and lid from the solution using
mL. platinum or nickel-tipped tongs. Rinse each with warm water,
26.4 Platinum Crucible, 30-mL capacity with lid. collecting the washings in the beaker. Scrape any remaining
26.5 Platinum Wire, 4 cm by 2 mm. residue from the crucible into the solution with a rubber
26.6 Stirring Rod, borosilicate glass. policeman.
26.7 Muffle Furnace, capable of maintaining a temperature 29.8 Cover with a watchglass, then boil the solution for 10
of 1200 6 10°C or higher. min to dissolve any solid matter (see Note 5 and 25.1).
26.8 Desiccator, with desiccant. NOTE 5—If insolubles are still present after the 10-min boil, filter the
26.9 Funnel, borosilicate glass. solution through medium-porosity filter paper, then return the residue and
26.10 Bunsen Burner. paper to the crucible. Place platinum wire across the top of the crucible,
26.11 Ringstand, equipped with ring and heating gauze. rest the lid on the wire, and place the crucible into a cool muffle furnace.
26.12 Tongs, platinum- or nickel-tipped. Heat the furnace slowly to 650°C (610°C, 1-h cycle). At 650°C, check the
crucible every 10 min until the paper burns off. Repeat 29.1 to 29.8 using
1 mL of concentrated sulfuric acid. Combine the filtrates in one beaker,
27. Reagents
then continue with 29.9.
27.1 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H2SO4). 29.9 Allow the solution to cool, then add ammonium
27.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- hydroxide dropwise while mixing, until the solution tests basic
chloric acid (HCl). (blue) to Litmus paper.
27.3 Hydrochloric Acid Solution (1 + 1)—Wearing goggles, 29.10 Mix well, cover, and then boil for 1 min.
carefully add 250 mL of concentrated HCl (sp gr 1.19) to 250 29.11 Allow the solution to cool slightly. If necessary, add
mL of water. Mix well. ammonium hydroxide dropwise while mixing until the solution
27.4 Ammonium Chloride (NH4Cl). tests basic (blue) to Litmus paper.
27.5 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- 29.12 Gravity filter this solution through medium-porosity
monium hydroxide (NH4OH). filter paper, into an 800-mL beaker.
27.6 Ammonium Oxalate Solution (Saturated)—Add 30 g of 29.13 Wash the filter paper and residue several times with
ammonium oxalate to a 1-L polyethylene bottle. Add 1000 mL hot water, collecting the filtrates in the 800-mL beaker (see
of hot water to the bottle and mix well. Allow the solution to 29.12).

4
 E 1506 – 97 (2003)
29.14 Wash the filter paper and residue with 20 mL of hot 31. Report
1 + 1 HCl solution, then four 20-mL portions of hot distilled 31.1 Report the percent calcium fluoride to the nearest
water, collecting the filtrates in the 400-mL beaker. 0.01 %.
29.15 Adjust the pH of the solution in the 400-mL beaker
with ammonium hydroxide until it tests basic (blue) to Litmus 32. Precision and Bias
paper.
32.1 Precision—The following criteria should be used for
29.16 Boil this solution for 1 min, then allow to cool slightly
judging the acceptability of results (see Note 6):
just below boiling.
32.1.1 Repeatability (Single Analyst)—The standard devia-
29.17 Filter through the original filter paper. Wash with hot tion for a single determination has been estimated to be
water and collect the filtrate in the 800-mL beaker. Save the 0.1778 % absolute at 30 df. The 95 % limit for the difference
filter cake for the determination of Mixed Oxides (Section 79). between two such runs is 0.50 % absolute.
Bring the filtrate to a boil. Add 100 mL of saturated ammonium 32.1.2 Laboratory Precision (Within-Laboratory, Between-
oxalate solution, then add 5 mL of filter pulp slurry and stir to Days)—The standard deviation of results (each the average of
mix. duplicates) obtained by the same analyst on different days has
29.18 Boil the solution for 30 s, then allow it to cool until been estimated to be 0.1169 % absolute at 15 df. The 95 %
precipitate settles. The sample can sit overnight before filter- limit for the difference between two such averages is 0.33 %
ing, if necessary or convenient. absolute.
29.19 Gravity filter the solution through medium-porosity 32.1.3 Reproducibility (Multilaboratory)—The standard de-
filter paper. viation of results (each the average of duplicates) obtained by
29.20 Rinse the beaker with 10 to 15 mL of cold 0.1 % analysts in different laboratories has been estimated to be
ammonium oxalate solution. Transfer the washings into the 0.3559 % absolute at 6 df. The 95 % limit for the difference
filter, using them to wash the precipitate. between two such averages is 1.00 % absolute.
29.21 Repeat 29.20 two more times.
NOTE 6—These precision estimates are based on an interlaboratory
29.22 Wash the residue with three 10 to 15-mL portions of study performed in 1992 on two samples (one a commercial sample, the
0.1 % ammonium oxalate solution. other a reference material) each containing approximately 98 % calcium
29.23 Wash the residue with three 10 to 15-mL portions of fluoride. One analyst in each of eight laboratories performed duplicate
cold water. determination of a sample of NIST Standard Reference Material 79a on
29.24 Weigh a 30-mL platinum crucible and cover to 0.0001 each of two separate days for a total of 32 determinations. The same
protocol was used on a sample of commercial material except that seven
g (Weight B). laboratories participated for a total of 28 determinations.6 Practice E 180
29.25 Transfer the filter paper and residue into the platinum was used in developing precision estimates.
crucible.
32.2 Bias—An average of 97.71 % calcium fluoride was
29.26 Place a platinum wire across the top of the platinum
obtained on NIST Standard Reference Material 79a which has
crucible, rest the lid on the wire, and place the crucible into a
a certified value of 97.39 %. This certified value, with a
cool muffle furnace.
standard deviation of 0.06 % absolute for a single determina-
29.27 Heat the furnace slowly to 1200°C. Check to see if all
tion, was obtained using the U.S. Customs Laboratory Method
paper is burned off.
(volumetric permanganate) as given in the certificate.
29.28 Keep crucible at 1200°C for 20 min.
29.29 Remove crucible and place in a desiccator containing SOLUBLE CHLORIDE AS NaCl
fresh desiccant; allow to cool to room temperature.
29.30 Immediately weigh the crucible, cover, and residue to 33. Volumetric Procedure, Scope
0.0001 g (Weight C).
33.1 This test method covers the volumetric determination
of trace quantities of soluble chloride as percent NaCl.
30. Calculation
30.1 Calculate assay as percent CaF2 as follows: 34. Summary of Test Method
~C 2 B! 3 1.3923 3 100 34.1 Soluble chloride is extracted from fluorspar with hot
assay as CaF2, weight % 5 A 1 0.15 (3)
water; the extract is filtered, then titrated to a colorimetric end
where: point with standardized silver nitrate solution.
A = weight of fluorspar sample, g, (see 19.2),
B = weight of crucible and cover, g, (see 29.24), 35. Apparatus
C = weight of crucible, cover, and residue, g (see 35.1 Analytical Balance, capable of weighing to the nearest
29.30), 0.1 mg.
1.3923 = conversion factor for CaO (molecular weight 35.2 Pipets, 1-mL, 10-mL glass.
(MW) = 56.08) to CaF2(MW = 78.08), and 35.3 Graduated Cylinder, 100-mL glass.
0.15 = correction for amount of calcium fluoride lost in 35.4 Beakers, 150-mL, 250-mL.
the acetic acid treatment, considered to be 0.0015 35.5 Burets, 10-mL, 25-mL glass.
g CaF 2/g sample.
35.6 Volumetric Flask, 1-L glass.

5
 E 1506 – 97 (2003)
36. Reagents where:
36.1 Potassium Chromate Indicator Solution (50 g/L)— A = 0.0141 N AgNO3 used for sample, mL,
Dissolve 50 g K 2CrO4 in 500 mL of water. Add silver nitrate B = 0.0141 N AgNO3 used for blank, mL,
solution (see 36.3) until a definite red precipitate is formed. C = Cl/mL of titrant, µg,
Allow to stand 12 h, filter through fine-porosity filter paper and D = weight of sample, g (see 38.1), and
dilute the filtrate to 1 L with water. 1.6485 = conversion Cl (MW = 35.45) to NaCl
36.2 Sodium Chloride Standard Solution (0.0141 N)— (MW = 58.45); and 58.56/35.45 = 1.6485.
Dissolve 0.8241 g of NaCl (previously dried to constant weight
at 105 to 110°C) in water and dilute to 1 L; mix well. 40. Report
36.3 Silver Nitrate Standard Titrant (0.0141 N)—Dissolve 40.1 Report the soluble chloride as NaCl to the nearest
2.395 g of AgNO3(previously dried to constant weight at 105 0.01 %.
to 110°C) in water and dilute to 1 L; mix well.
36.3.1 Pipet 10.0 mL of 0.0141 N NaCl (see 36.2) into a 41. Precision and Bias
150-mL beaker, add 40 mL of water and 1 mL of K2CrO4
indicator solution. Using a 25-mL buret, titrate this solution 41.1 Precision—The following criteria should be used for
with the 0.0141 N AgNO3 to a faint brown end point (see Note judging the acceptability of results (see Note 8):
7). Similarly determine a blank using all of the above reagents, 41.1.1 Repeatability (Single Analyst)—The standard devia-
but no NaCl. The titer of the AgNO 3 in µg Cl/mL, A, is as tion for a single determination has been estimated to be
follows: 0.00068% absolute with 32 df. The 95 % limit for the differ-
~500 3 10! ence between two such determinations is 0.002 % absolute.
A5 B (4) 41.1.2 Laboratory Precision (Within-Laboratory, Between-
Days)—The standard deviation of results (each the average of
where: duplicates), obtained by the same analyst on different days, has
500 = Cl in 0.0141 N NaCl, µg/mL, and been estimated to be 0.00035 % absolute with 16 df. The 95 %
B = AgNO3 required for titration of the solution, net mL.
limit for the difference between two such averages is 0.001 %
absolute.
Store standardized solution in a brown glass bottle.
36.4 Filter Paper, 12.5-cm diameter, fine-porosity. 41.1.3 Reproducibility (Multilaboratory)—The standard de-
36.5 Denatured Alcohol. viation of results (each the average of duplicates), obtained by
analysts in different laboratories, has been estimated to be
37. Hazards 0.0012 % absolute with 7 df. The 95 % limit for the difference
37.1 See 1.3 and 1.4. between two such averages is 0.004 % absolute.
41.2 Bias—The bias of this test method has not been
38. Procedure determined due to the unavailability of suitable reference
38.1 Weigh 25 g of sample (previously dried to constant materials.
weight at 105 to 110°C) to the nearest 1 g into a 150-mL
NOTE 8—These precision estimates are based on an interlaboratory
beaker; wet the sample with 10 mL of denatured alcohol.
study performed in 1993 on two samples of acid-grade fluorspar contain-
38.2 Add 100 mL of hot distilled water to the beaker. Using ing approximately 0.001 and 0.002 % sodium chloride. One analyst in
a magnetic stirrer, stir the mixture for 1 h; allow the mixture to each of eight laboratories performed duplicate determinations on each of
cool and the fluorspar to settle. two days for a total of 64 determinations.6 Practice E 180 was used in
38.3 After a minimum of 2-h settling time, gravity-filter the developing the precision data.
solution through a 12.5-cm diameter fine-porosity filter paper,
collecting the filtrate in a 250-mL beaker. 42. Ion Chromatography Procedure, Scope
38.4 Pipet 1 mL of potassium chromate indicator solution 42.1 This test method covers the ion-chromatography deter-
into the beaker. mination of trace quantities of soluble chloride as µg/g (ppm)
38.5 Using a 10-mL buret, titrate with 0.0141 N AgNO3 NaCl.
dropwise to a faint brown end point; mL = A (see Note 7).
NOTE 7—To aid in the determination of the end point, place a 250-mL 43. Summary of Test Methods
beaker with the same volume of water and indicator next to the sample, as
a comparator. The first brownish color that appears in the sample is the end 43.1 Soluble chloride is extracted from fluorspar with hot
point. water, the extract made to volume, filtered, and then the
chloride concentration is determined by ion chromatography.
38.6 Similarly, determine a blank using all of the above
reagents, but no sample; mL = B.
44. Apparatus
39. Calculation 44.1 Balance, capable of weighing to the nearest 0.1 g.
39.1 Calculate percent soluble chloride as NaCl as follows: 44.2 Volumetric Flask, 250-mL.
~A 2 B! 3 C 3 1.6485 44.3 Filter Medium, chloride-free, 0.45-µm pore size, or
Soluble chloride as NaCl, weight % 5 (5)
D 3 10 4 less. (Gelman IC Acrodiscs fitted to a syringe work well.)

6
 E 1506 – 97 (2003)
44.4 Ion Chromatographic System, able to produce baseline 49. Report
separation of fluoride, chloride, nitrate, phosphate, and sul- 49.1 Report soluble chloride as NaCl to the nearest 0.1 µg/g
fate.8 (ppm).
45. Reagents 50. Precision and Bias
45.1 Chloride Standard9—Dilute the standard with deion- 50.1 Precision—Use the following criteria for judging the
ized water to a chloride concentration within the linear range of acceptability of results (see Note 10):
the detector and near the chloride level in the sample extract. 50.1.1 Repeatability (Single Analyst)—The standard de-
45.2 Deionized Water, chloride-free. viation for a single determination has been estimated to be 1.26
µg/g with 18 df. The 95 % limit for the difference between two
46. Hazards such determinations is 3.53 µg/g.
46.1 See 1.3 and 1.4. 50.1.2 Laboratory Precision (Within-Laboratory,
Between-Days)—The standard deviation of results (each the
47. Procedure average of duplicates), obtained by the same analyst on
47.1 Weigh 25 g of sample (previously dried to constant different days, has been estimated to be 1.08 µg/g with 9 df.
weight at 105 to 110°C) to the nearest 0.1 g into a 250-mL The 95 % limit for the difference between two such averages is
volumetric flask. Add 200 mL of hot (near boiling) deionized 3.02 µg/g.
water to the flask. Using a magnetic stirrer, stir the sample for 50.1.3 Reproducibility (Multilaboratory)—The standard
1 h. deviation of results (each the average of duplicates), obtained
47.2 Cool the sample to room temperature under running by analysts in different laboratories, has been estimated to be
water, make to volume with deionized water, then mix well. 2.26 µg/g with 8 df. The 95 % limit for the difference between
47.3 Allow most of the fluorspar to settle (15 to 20 min), two such averages is 6.32 µg/g.
then filter a portion of the solution through a chloride-free, 50.1.4 Bias—The bias of this test method has not been
fine-porosity (0.45 µm, or less) filtered medium. determined due to the unavailability of suitable reference
47.4 Chromatograph a portion of the filtrate, then compare materials.
the area of the resultant chloride peak to that of a chloride NOTE 10—These precision estimates are based on an interlaboratory
standard similarly chromatographed. study performed in 1995 on one sample of acid-grade fluorspar containing
approximately 15 µg/g of sodium chloride. One analyst in each of ten
NOTE 9—If the chloride level of the filtrate is such that the resultant laboratories performed duplicate determinations on each of two days for
peak is outside the linear range of the detector, dilute the extract a total of 40 determinations.6 Practice E 180 was used in developing the
appropriately with deionized water and rechromatographed. precision data.
48. Calculation CALCIUM CARBONATE
48.1 Calculate the soluble chloride concentration as µg/g
(ppm) NaCl as follow: 51. Scope
A 3 B 3 1.6485 3 9.60 3 C 51.1 This test method covers the determination of calcium
Soluble chloride as NaCl, µg/g ~ppm! 5 D carbonate in the range from 0 to 2 %.
(6)
52. Summary of Test Method
where: 52.1 Calcium carbonate is extracted from fluorspar with
A = area of sample peak, dilute acetic acid; the extract is made alkaline with potassium
B = µg/g chloride in the standard,
hydroxide, and then calcium is titrated with disodium ethyl-
1.6485 = conversion Cl (MW 35.45) to NaCl (MW 58.45)
enediaminetetraacetate (EDTA) solution using hydroxynaph-
= 58.45/35.45 = 1.6485,
9.60 = 250/25 3 0.96, thol blue as an indicator and calculated as calcium carbonate.
250/25 = dilution factor, 53. Apparatus
0.96 = adjustment to dilution factor required since 25 g
of sample displaces approximately 10 mL water, 53.1 Analytical Balance, capable of weighing to the nearest
C = any additional dilution factor needed to keep the 0.1 mg.
Cl peak within the linear range of the detector, 53.2 Beakers, 600, 400, 250, and 150-mL glass, un-
and scratched, and watchglass covers.
D = area of standard peak. 53.3 Graduated Cylinders, 100, 25, and 10-mL.
53.4 Stirring Rod, borosilicate glass, unscratched.
53.5 Steam Bath.
53.6 Glass Filter Funnel.
8
A system known to produce adequate separation includes a DIONEX Model 53.7 Mortar and Pestle, 102-mm (4-in.) diameter, agate.
20101 Ion Chromatograph equipped with a CDM-2 detector set at 10 µS; a 53.8 Buret, Class A, 50-mL, 0.1-mL division, polytetrafluo-
DIONEX AS4A anion column, AG4A guard column and ASRS suppresser column;
roethylene stopcock.
an eluant consisting of 1.7 mM NaHCO3 in 1.8 mM Na2CO 3; isocratic elution at 2.0
mL/min; a 50-µL sample injection. 53.9 Volumetric Flask, 1-L.
9
Use DIONEX Five Anion Standard Part No. 037157, or similar. 53.10 Hot Plate, stirrer.

7
 E 1506 – 97 (2003)
53.11 Pipet, 50-mL. 54.12.4 Standardize the EDTA solution in triplicate using
the steps described in 54.12.2 and 54.12.3, and average the
54. Reagents three results to the nearest 0.000001 g/mL.
54.1 Acetic Acid Solution (100 mL/L)—See 17.1. 55. Hazards
54.2 Ashless Cellulose Filter Aid—Whatman accelerator
powder,7 or equivalent. 55.1 See 1.3 and 1.4.
54.3 Filter Paper, 9-cm—See 17.4. 56. Procedure
54.4 Ethanol—Pure or denatured.
56.1 Transfer 8 to 10 g of sample (previously dried to
54.5 Filter Pulp Slurry (40 g/L)—See 17.7. constant weight at 105 to 110°C) into a mortar. Grind with a
54.6 Litmus Paper. pestle until the particle size is 100 to 500 mesh.
54.7 Hydroxynaphthol Blue Indicator—Fisher Scientific 56.2 Weigh 1.0 g of the ground sample to the nearest 0.0001
H346-100,10 calcium indicator, or equivalent. g, and transfer it to a 150-mL beaker.
54.8 Potassium Hydroxide (30 % weight/volume)— 56.3 Wet the sample with 1 mL of ethanol, then add 15 mL
Dissolve 300 g of potassium hydroxide (KOH) in water and of acetic acid (100 mL/L) to the beaker.
dilute to 1 L; mix well. Store in a plastic bottle. 56.4 Add a glass stirring rod to the beaker, cover with a
54.9 Triethanolamine Solution (1 + 1)—Mix 50 mL of tri- watchglass, and place on a steam bath.
ethanolamine (NC6H15O3) with 50 mL of water; mix well. 56.5 Heat for 30 6 1 min, stirring every 5 min.
54.10 Calcium Carbonate (CaCO3)—High purity, mini- 56.6 Remove from the steam bath, add 5 mL of filter pulp
mum 99.95 %. slurry to the beaker, cover, and allow to sit for approximately
54.11 Hydrochloric Acid (1 + 10)—Mix 1 volume of con- 12 h.
centrated hydrochloric acid (HCl) with 10 volumes of water. 56.7 Gravity-filter the solution through medium porosity
54.12 Disodium Ethylenediaminetetraacetate (EDTA) Stan- filter paper.
dard Solution (0.025 M)—Dissolve 9.3062 g of disodium 56.8 Rinse the beaker several times with minimal portions
ethylenediaminetetraacetate dihydrate (C 10 H 14 N 2 of hot water (total wash water approximately 35 mL), filtering
Na2O8·2H2O)10 in water. Transfer the solution to a 1-L each wash through the same filter paper.
volumetric flask; dilute to volume with water; and mix well. 56.9 Add 5 mL of triethanolamine solution to the filtrate in
Standardize as follows. a 250-mL beaker.
54.12.1 Dry 3 g of CaCO3 in a 110°C oven for 1 h. Remove 56.10 Dropwise, add 30 % KOH to the solution until it tests
from oven and allow to cool in a desiccator. Weigh 2.4970 g of neutral with litmus paper.
the dried CaCO3 into a 600-mL beaker, cautiously add 75 mL 56.11 Add 10 mL additional 30 % KOH; mix well.
of 1 + 10 HCl to the beaker, cover, and warm gently to dissolve 56.12 Add 0.5 g of hydroxynaphthol blue indicator to the
the CaCO3. Cool the solution and transfer into a 1-L volumetric solution; mix well.
flask, dilute to volume with water, and mix well (solution 56.13 Titrate the solution with standardized 0.025 M EDTA
concentration: 1 mL = 1.0000 mg of Ca). solution to a blue end point. Record C, the millilitres of EDTA
54.12.2 Pipet 50 mL of the solution prepared in 54.12.1 into required for the titration.
a 400-mL beaker, add 5 mL of 1 + 1 triethanolamine to the
beaker, and dilute to 200 mL with water. Dropwise, add 30 % 57. Calculation
KOH until the solution tests neutral with litmus paper. Add an @~C 3 F! 2 0.0010# 3 1.7848 3 100
additional 10 mL of 30 % KOH to the solution and mix well. % CaCO3 5 B (8)
54.12.3 Add 0.5 g hydroxynaphthol blue indicator and
titrate immediately with 0.025 M EDTA solution to a blue end where:
point. Record A, the millilitres of EDTA required for the C = mL of 0.025 M EDTA solution used in titration
titration. (56.13),
B = sample weight (56.2),
calcium oxide equivalent of EDTA in g CaO/mL EDTA F = factor representing g CaO/mL EDTA (54.12.4),
0.0010 = correction for calcium fluoride dissolved in the
5 50.0/A3 1.3992 3 0.001
5F (7)
acetic acid treatment, estimated to be 0.0010 g/g
of sample, and
where: 1.7848 = conversion factor for CaO (MW = 56.08) to
50.0 = mL of CaCO3 solution used in titration, CaCO 3 (MW = 100.09) (that is, 100.09/
A = mL of EDTA solution used for titration, 56.08 = 1.7848).
1.3992 = conversion factor for calcium to calcium oxide,
MW CaO = 56.08/MW Ca = 40.08, and 58. Report
0.001 = conversion of mg to g. 58.1 Report the percent calcium carbonate to the nearest
0.01 %.
59. Precision and Bias
10
Correct American Chemical Society name is (ethylenedinitrilo) tetraacetic 59.1 Precision—The following criteria should be used for
acid disodium salt dihydrate. judging the acceptability of results (see Note 11):

8
 E 1506 – 97 (2003)
59.1.1 Repeatability (Single Analyst)—The standard devia- 63.2 Hydrazine Sulfate Solution (1.5 g/L)—Prepare fresh
tion for a single determination has been estimated to be daily. Dissolve 1.5 g of hydrazine sulfate ((NH2)2·H2SO4) in
0.0148 % absolute at 38 df. The 95 % limit for the difference water, dilute to 1 L, and mix.
between two such determinations is 0.04 % absolute. 63.3 Ammonium Molybdate—Hydrazine Sulfate Solution—
59.1.2 Laboratory Precision (Within-Laboratory, Between- Dilute 250 mL of Ammonium Molybdate Solution (20 g/L) to
Days)—The standard deviation of results (each the average of 600 mL, add 100 mL of Hydrazine Sulfate Solution (1.5 g/L),
duplicates), obtained by the same analyst on different days, has dilute to 1 L and mix well.
been estimated to be 0.0156 % absolute at 19 df. The 95 % 63.4 Phosphorus Stock Solution (1 mL = 1.0 mg P)—
limit for the difference between two such averages is 0.04 % Transfer 2.292 g of anhydrous disodium hydrogen phosphate
absolute. (Na2HPO4), previously dried to a constant weight at 105°C, to
59.1.3 Reproducibility (Multilaboratory)—The standard de- a 500-mL volumetric flask; dissolve in about 100 mL of water,
viation of results (each the average of duplicates), obtained by dilute to volume, and mix.
analysts in different laboratories, has been estimated to be 63.5 Phosphorus Standard A (1 mL = 0.1 mg P)—Pipet 50
0.0910 % absolute at 8 df. The 95 % limit for the difference mL of Phosphorus Stock Solution into a 500-mL volumetric
between two such averages is 0.25 % absolute. flask, add 50 mL of HClO4(1 + 5), dilute to volume, and mix.
59.2 Bias—The bias of this test method has not been 63.6 Phosphorus Standard B (1 mL = 0.01 mg P)—Pipet 10
determined due to the unavailability of suitable reference mL of Phosphorus Stock Solution into a 1-L volumetric flask,
materials. add 100 mL of HClO4(1 + 5), dilute to volume, and mix.
NOTE 11—These precision estimates are based on an interlaboratory
63.7 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
study performed in 1994 on two samples of acid-grade fluorspar contain- chloric acid (HCl).
ing approximately 0.55 and 0.79 % calcium carbonate. One analyst in 63.8 Hydrochloric Acid (1 + 1)—Add 100 mL of concen-
each of ten laboratories performed duplicate determinations on each of trated HCl to 200 mL of water and mix well.
two days for a total of 80 determinations.6 Practice E 180 was used in 63.9 Hydrochloric Acid (1 + 100)—Add 1 mL of concen-
developing the precision data. trated HCl to 100 mL of water and mix well.
PHOSPHORUS 63.10 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3).
60. Scope 63.11 Perchloric Acid (sp gr 1.54)—Concentrated perchlo-
ric acid (HClO4).
60.1 This test method covers the determination of total
63.12 Perchloric Acid (1 + 5)—Add 100 mL of concen-
phosphorus.
trated perchloric acid to 500 mL of water and mix well.
61. Summary of Test Method 63.13 Ferric Chloride Solution (20 g/L)—Add 20 g of ferric
chloride to a 1-L volumetric flask, add 10 mL of concentrated
61.1 The sample is dissolved in nitric acid, fumed with
HCl, dilute to mark with water, and mix well.
perchloric acid, then reacted with ammonium molybdate to
63.14 Ammonium Hydroxide (sp gr 0.90)—Concentrated
form heteropoly phosphomolybdate. The phosphomolybdate is
ammonium hydroxide (NH4OH).
reduced with hydrazine sulfate to form the molybdenum blue
63.15 Ammonium Chloride Solution (20 g/L)—Add 20 g of
complex, which is measured at 650 nm or 825 nm, depending
ammonium chloride to a 1-L volumetric flask, add water, dilute
on the concentration of analyte. Hydrobromic acid is added to
to mark, and mix well.
eliminate interference by arsenic.
63.16 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric
62. Apparatus acid (H2SO4).
63.17 Sulfuric Acid (3 + 37)—Add 30 mL of concentrated
62.1 Spectrometer, capable of measurements at 650 nm and sulfuric acid to 370 mL of water and mix well.
825 nm. 63.18 Sodium Sulfite.
62.2 Analytical Balance, capable of weighing to the nearest 63.19 Sodium Sulfite Solution (100 g/L)—Dissolve 100 g of
0.1 mg. sodium sulfite in water, dilute to 1 L and mix.
62.3 Beakers, 400-mL.
63.20 Hydrobromic Acid (sp gr 1.490)—Concentrated hy-
62.4 Graduated cylinders, 10-mL, 25-mL, 50-mL, 100-mL.
drobromic acid (HBr).
62.5 Bunsen burner, hot plate, hot water bath.
63.21 Hydrobromic Acid (1 + 4)—Add 100 mL of concen-
62.6 Funnel, No. 40 Whatman filter paper, 11-cm.
trated HBr to 400 mL of water and mix well.
62.7 Volumetric flasks, 100-mL, 500-mL, 1000-mL, boro-
silicate glass, volumetric.
64. Hazards
62.8 Pipets, 1-mL, 10-mL, 20-mL, 50-mL.
62.9 Erlenmeyer flask, 250-mL. 64.1 See 1.3 and 1.4.

63. Reagents 65. Preparation of Calibration Curve

63.1 Ammonium Molybdate Solution (20 g/L)—Add 300 65.1 0.05–0.30 mg P/100 mL Calibration Range:
mL of H2SO4 to 500 mL of water and cool. Add 20 g of 65.1.1 Pipet 5-, 10-, 15-, 20-, 25-, and 30-mL portions of
ammonium heptamolybdate ((NH4)6Mo7O27·4H2O), dilute to 1 Phosphorus Standard A (1 mL = 0.1 mg P) into separate
L, and mix. 100-mL volumetric flasks.

9
 E 1506 – 97 (2003)
65.1.2 Add 20 mL of concentrated perchloric acid to each 66.8 Add 10 mL of HClO4 to the flask, heat on a hot plate
flask, dilute to volume, and mix well. until fumes appear, then heat one minute more.
65.1.3 Pipet 10 mL of each solution into separate 100-mL 66.9 Cool the flask, then add 20 mL of HBr (1 + 4). Heat on
volumetric flasks. a hot plate until strong white fumes appear, then for one minute
65.1.4 Add 15 mL of sodium sulfite (100 g/L) to each flask, more.
swirl and gently boil the solutions for approximately 30 66.10 Cool the flask, wash the contents into a 100-mL
seconds on a hot plate in a hood. volumetric flask with water, make to volume and mix well.
65.1.5 Add 50 mL of ammonium molybdate-hydrazine Pipet 20 mL of this solution into a second 100-mL volumetric
sulfate solution to each flask and heat the flasks in a boiling- flask.
water bath for approximately 20 minutes. 66.11 Add 15 mL of sodium sulfite solution and gently boil
65.1.6 Quickly cool the solutions in an ice bath, dilute each the solution for approximately 30 seconds on a hot plate in a
to 100 mL with water, and mix well. hood.
65.1.7 Prepare a reagent blank as follows: Transfer 12 mL 66.12 Add 50 mL of ammonium molybdate-hydrazine sul-
of HClO4(1 + 5) to a 100-mL flask, then continue from 65.1.4. fate solution and heat the flask in a boiling water bath for
65.1.8 Using water as a reference, record the absorbance of approximately 20 minutes.
each standard solution and the reagent blank at 650 nm. 66.13 Cool the solution, dilute to 100 mL with water, and
65.1.9 Prepare a calibration curve by plotting the absor- mix well.
bances of the standards (corrected for reagent blank) versus mg 66.14 Read the absorbance of the solution at 650 nm or 825
of P/100 mL of solutions. nm as appropriate; Absorbance = A.
65.2 0.005–0.03 mg P/100 mL Calibration Range: 66.15 Similarly determine the absorbance of a blank solu-
65.2.1 Pipet 5-, 10-, 15-, 20-, 25-, and 30-mL portions of tion containing all reagents, but no sample; Absorbance = B.
Phosphorus Standard B (1 mL = 0.01 mg P) into separate
100-mL volumetric flasks. 67. Calculation
65.2.2 Develop the color of these standards following 67.1 Using the calibration curves or a straight-line formula,
65.1.2-65.1.6. determine the concentration of P in mg/100 mL equivalent to
65.2.3 Prepare a reagent blank as follows: Transfer 12 mL the blank-corrected absorbance (A − B); concentration = C.
of HClO4(1 + 5) to a 100-mL flask, then continue from 65.1.4. C 3 100 3 100 3 5 50 3 C
65.2.4 Using water as a reference, record the absorbance of P ~%! 5 W 3 1000 5 W (9)
each standard solution and the reagent blank at 825 nm.
65.2.5 Prepare a calibration curve by plotting the absor- where:
bances of the standards (corrected for reagent blank) versus mg C = mg P/100 mL, equivalent to the blank-corrected
of P/100 mL of solution. sample absorbance,
W = sample weight in g,
100 = original sample volume in mL,
66. Procedure
100 = conversion factor to percent,
66.1 Weigh 1.0000 g of dried fluorspar to 0.0001 g and 5 = dilution factor (100 mL/20 mL), and
transfer to a 400-mL beaker. Weight = W. 1000 = conversion factor, milligrams to g.
66.2 Add 10 mL of HNO3, 10 mL of HClO4, cover the
beaker with a watch glass, and heat the mixture on a hot plate. 68. Report
When the sample is nearly totally dissolved, remove from the 68.1 Report results to the nearest 0.001 %.
hot plate, cool, then carefully wash down the watch glass and 68.2 Minimum reportable quantity is 0.001 %.
the sides of the beaker with water. Carefully evaporate the
sample to near dryness on a hot plate. 69. Precision and Bias
66.3 Remove from heat, cool, add 10 mL of concentrated
HNO3 and 100 mL of water and heat the solution on a hot plate 69.1 Studies are planned to determine the precision of this
to dissolve the salts. test method.
69.2 The bias of this test method cannot be determined
66.4 Remove the beaker from the hot plate and cool. Add 5
unless a suitable reference material becomes available.
mL of ferric chloride solution to the beaker, then add ammo-
nium hydroxide until iron precipitates.
ARSENIC
66.5 Boil the solution for 3 minutes on a hot plate then
gravity filter through No. 40 Whatman filter paper. Discard the
70. Scope
filtrate.
66.6 Add 20 mL of HCl (1 + 1) to dissolve residual matter 70.1 This test method covers the determination of total
then transfer the residue to the filter, collecting the filtrate in a arsenic.
250-mL Erlenmeyer flask.
66.7 Wash the beaker with 20-mL portions of hot water, 71. Summary of Test Method
transferring each wash to the filter cake. Continue the washings 71.1 The sample is oxidized with bromine and nitric acid
until there is no yellow color left on the filter paper (3–5 then arsenic is determined using Graphite-Furnace Atomic
washings); collect all washings in the Erlenmeyer flask. Absorption Spectroscopy.

10
 E 1506 – 97 (2003)
72. Apparatus 75. Procedure
72.1 Atomic Absorption Spectrometer, equipped with a 75.1 Weigh 0.100 g of dried fluorspar to 0.0001 g and
graphite furnace, Zeeman background correction, and an ar- transfer to a 250-mL Phillips beaker.
senic electrodeless discharge lamp.11 75.2 Add 10 mL of Br2/CCl4(2 + 3), swirl to mix, cover the
72.2 Analytical Balance, capable of weighing to the nearest beaker with a watch glass, and allow to sit in a fume hood for
0.1 mg. 15 min.
72.3 Volumetric flasks, 100-mL, 500-mL, borosilicate glass, 75.3 Add 10 mL of HNO3 to the sample, swirl to mix, cover,
volumetric. and allow the sample to sit in a fume hood for 15 min.
72.4 Pipets, 1-mL, 2-mL, 10-mL. 75.4 Heat on a hot plate at low-medium heat until brown
72.5 Phillips beaker, 250-mL with watch glass cover. bromine fumes are no longer visible, then continue digestion
until the sample volume is approximately 5–8 mL.
73. Reagents 75.5 Rinse down the sides of the beaker and the watch glass
73.1 Nitric Acid (sp gr 1.42)—Concentrated nitric acid with approximately 50 mL of water.
(HNO3). 75.6 Cover the sample and heat to just boiling on a hot plate.
73.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- Cool.
chloric acid (HCl). 75.7 Using water, quantitatively transfer the sample to a
73.3 Palladium Sponge. 100-mL volumetric flask, make to volume, and mix well.
73.4 Palladium Solution (5 g/100 mL)—Weigh 5.0 g of Pd 75.8 Determine the sample’s absorbance using Graphite-
metal into a 250-mL beaker. Add 25 mL concentrated HCl and Furnace Atomic Absorption Spectroscopy using the following
25 mL concentrated HNO3. Heat until completely dissolved. conditions:
Cool, then dilute to 100 mL with water. Mix well.
NOTE 12—The following conditions are specific for the Perkin-Elmer
73.5 Magnesium Nitrate—Alfa Puratronic or equivalent. equipment described in 72.1. If other equipment is used for the analysis,
73.6 Magnesium Nitrate Solution (1 g/100 mL)—Dissolve conditions will have to be changed appropriately.
1.0 g of Mg(NO3)2 in water, then make to 100 mL. Mix well. Wavelength: 193.7 nm
73.7 Bromine/Carbon Tetrachloride (2 + 3)—Mix 500 mL Slit width: 0.7 nm
of Br2 and 750 mL of CCl4. Integration time: 5 s
73.8 Palladium/Magnesium Nitrate Matrix Modifier— Lamp: Electrodeless discharge, set at 330 ma
Measurement mode: Absorbance of peak area
Dilute 6.0 mL of 5 g/100 mL Pd Solution and 10.0 mL of 1 Gas: Argon
g/100 mL Mg(NO3)2 solution to 100 mL with water and mix Zeeman background correction: On
well. Furnace settings:
73.9 Arsenic Stock Solution (1000 mg/L)—Fisher Cat. No. Step Temperature,° C Ramp Hold Time, s Read
SA449, or equivalent. 1 150 1 60
73.10 Arsenic Stock Solution (100 mg/L)—Pipet 10.0 mL of 2 400 10 30
1000 mg/L Stock Solution into a 100-mL volumetric flask. Add 3 2400 0 5 X
4 2600 ... 5
2 mL of concentrated HNO3 and 10 mL of concentrated HCl
and dilute to volume with water. Mix well. 75.9 Similarly determine the absorbances of a reagent blank
73.11 Arsenic Stock Solution (10 mg/L)—Pipet 10.0 mL of and appropriate standards.
100 mg/L Stock Solution into a 100-mL volumetric flask. Add
2 mL of concentrated HNO3 and dilute to volume with water. 76. Calculation
Mix well. A1 3 C 3 100 A1 3 C 3 1000
73.12 Arsenic Standard Solution (1.0 mg/L)—Pipet 10.0 µg/g ~ppm wt/wt! As 5 A2 3 0.1 5 A2
mL of 10 mg/L Stock Solution into a 100-mL volumetric flask. (10)
Add 2 mL of concentrated HNO3 and dilute to volume with
where:
water. Mix well.
A1 = blank-corrected sample absorbance,
73.13 Arsenic Standard Solution (0.10 mg/L)—Pipet 10.0 C = concentration of standard in µg/g,
mL of 1 mg/L Standard Solution into a 100-mL volumetric 100 = sample volume in mL, and
flask. Add 2 mL of concentrated HNO3 and dilute to volume 0.1 = sample weight in g.
with water. Mix well.
73.14 Arsenic Standard Solution (0.01 mg/L)—Pipet 10.0 77. Report
mL of 0.10 mg/L Standard Solution into a 100-mL volumetric
77.1 Report results to the nearest 1 µg/g (ppm).
flask. Add 2 mL of concentrated HNO3 and dilute to volume
77.2 Minimum reportable quantity is 1 µg/g (ppm).
with water. Mix well.
74. Hazards 78. Precision and Bias
74.1 See 1.3 and 1.4. 78.1 Laboratory Precision (Within-Laboratory, Between-
Days)—The standard deviation of results, each the average of
duplicates, obtained by the same analyst on different days, has
11
A system known to produce adequate results includes: a Perkin-Elmer Model been estimated to be 2 µg/g with 41 df. The 95 % limit for the
PE 5000 Spectrometer and a Perkin-Elmer Model 6100 HGA Graphite Furance. difference between two such averages is 6 µg/g.

11
 E 1506 – 97 (2003)
NOTE 13—This precision estimate is based on the analysis of a single 84.7 Combine the above filter paper and filter cake with the
sample in one laboratory over the period from May 1995 to October 1996. filter paper and filter cake from the ammonium hydroxide
78.2 The bias of this test method cannot be determined precipitate from the determination of percent calcium fluoride
unless a suitable reference material becomes available. (see 29.17) in the crucible, then place the crucible in a muffle
furnace and carefully ignite at 800°C.
MIXED OXIDES (R2O3) 84.8 After all the paper has burned off, heat the crucible for
5 min more.
79. Scope
84.9 Place the crucible in a desiccator to cool, then weigh to
79.1 This test method covers the determination of percent 0.0001 g; weight = B.
mixed oxides (R2O3).
85. Calculation
80. Summary of Test Method
~B 2 C!
80.1 The acetic acid extract from the determination of % mixed oxides ~R2O3! 5 A 3 100 (11)
percent silica (see 19.8) is oxidized with hydrochloric and
nitric acids, then treated with ammonium hydroxide to precipi- where:
tate metal hydroxides. This precipitate is combined with the B = weight of crucible plus ash, see 84.8,
ammonium hydroxide precipitate from the determination of C = weight of crucible, see 84.6,
percent calcium fluoride (see 29.17), the combined precipitates A = weight of sample, see 18.2, and
are calcined at 800°C, then the residue is weighed and 100 = conversion to percent.
calculated as percent mixed oxides (R2O3).
86. Report
81. Apparatus 86.1 Report results to the nearest 0.01 %.
81.1 Analytical Balance, capable of weighing to the nearest 86.2 Minimum reportable quantity is 0.01 %.
0.1 mg.
81.2 Desiccator desiccant (silica gel is suitable). 87. Precision and Bias
81.3 Muffle furnace, capable of maintaining a temperature 87.1 Studies are planned to determine the precision of this
of at least 800°C. test method.
81.4 Platinum crucible, 30-mL. 87.2 The bias of this test method cannot be determined
81.5 Graduated cylinders, 10-mL, 50-mL. unless a suitable reference material becomes available.

82. Reagents SULFIDE SULFUR

82.1 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3). 88. Scope
82.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- 88.1 This test method covers the determination of sulfide
chloric acid (HCl). sulfur in the range from 0.001 to 0.2 %.
82.3 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
monium hydroxide (NH4OH). 89. Summary of Test Method
82.4 Filter Paper, 9-cm, low ash, acid-washed, medium- 89.1 Fluorspar is mixed with HCl, boric acid, and amalgam-
porosity, able to retain 8-µm particles. ated zinc. Hydrogen sulfide is then distilled from the mixture.
The evolved hydrogen sulfide is carried off by a stream of
83. Hazards oxygen-free nitrogen or argon, and collected in zinc acetate
83.1 See 1.3 and 1.4. solution. Hydrochloric acid and iodine are added to the zinc
acetate solution, and the excess iodine is back titrated with
84. Procedure sodium thiosulfate.
84.1 Transfer the filtrate from the determination of percent
silica (see 19.8) to a 250-mL beaker, and add 5 mL of HCl and 90. Apparatus
1 mL of HNO3 to the beaker. 90.1 Analytical Balance, capable of weighing to the nearest
84.2 Boil the solution for 2–3 min, remove the beaker from 1 mg.
the heat, and allow to cool. 90.2 Sulfide Evolution Apparatus, consisting of a nitrogen
84.3 Add 3–5 drops of 0.5 % phenolphthalein indicator or argon gas cylinder with appropriate regulator, flow meter,
solution to the sample. While stirring, add ammonium hydrox- gas washing bottles (250 mL), one with alkaline pyrogallol and
ide to the solution until it turns pink, then boil the solution for one with zinc acetate solution (30 g/L), separatory funnel,
one minute more. 500-mL three-neck flask, condenser, gas washing bottle (125
84.4 Allow the solution to cool, then gravity filter it through mL), and connecting glass tubing (see Fig. 1).
medium-porosity filter paper.
NOTE 14—Hydrofluoric acid produced by the reaction between fluor-
84.5 Wash the filter cake with about 50 mL of hot water. spar and hydrochloric acid gradually corrodes the 500-mL flask. After
84.6 Heat a 30-mL platinum crucible at 800°C for 20 min. each run, tap the bottom of the flask gently on the table top to make certain
Cool to room temperature in a desiccator, then weigh to the that it is still safe to use. Also, rinse down the inside of the condenser after
nearest 0.0001 g; weight = C. each run to remove any globules of mercury that may be deposited there.

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 E 1506 – 97 (2003)

FIG. 1 Sulfide Distillation Apparatus

90.3 Graduated Cylinder, 100-mL, glass. fate solution into a 200-mL volumetric flask, dilute to the mark
90.4 Pipet, 10-mL. with water, and mix well.
90.5 Heating Mantel, for 500-mL round-bottom flask. 91.12 Alkaline Pyrogallol—Add 50 mL of 10 % aqueous
90.6 Micro-Burette, readable to 0.01 mL. Pyrogallol to 200 mL of 50 % weight/vol aqueous KOH. Mix
well. Store in a tightly-capped container until used.
91. Reagents
91.1 Zinc, 20 Mesh—Clean by treating for a few minutes 92. Hazards
with 1:19 HCl; decant off the HCl just prior to amalgamation. 92.1 See 1.3 and 1.4.
91.2 Amalgamated Zinc—Dissolve 2 g of mercuric chloride
in 50 mL of water, and add a few drops of HCl to acidify the 93. Procedure
solution. Heat to 50–60°C to dissolve any salt. Add 50 g of
clean zinc to the heated solution. Allow the mixture to stand for 93.1 Assemble the apparatus shown in Fig. 1, making
3 to 5 min, stirring occasionally. Pour off the supernatant certain that all Teflont stoppers and connections are tight.
liquid, and wash the zinc at least 5 times by decantation to NOTE 15—The apparatus operates under a slight positive pressure, and
remove excess mercuric chloride. Do Not allow the amalgam- therefore, all connections must be tight. Even a small leak may result in
ated zinc to dry. Store under water, and weigh wet. a serious loss of hydrogen sulfide.
91.3 Hydrochloric Acid (1 + 2)—Dilute 1 vol of concen- 93.2 Place 50 mL of zinc acetate solution into the gas
trated HCl with 2 vol of water. washing bottle.
91.4 Hydrochloric Acid (1 + 19)—Dilute 10 vol of concen-
93.3 Weigh 3 g of dried sample to the nearest 0.001 g, and
trated HCl with 190 vol of water.
transfer it to the 500-mL three-neck flask; record the sample
91.5 Digestion Acid—Mix 400 mL of concentrated HCl
weight as A.
with 1000 mL of water. Add 1 g of chromic chloride or 0.33 g
of chrome metal to the solution, and mix well until the chrome 93.4 Add 2.5 g of amalgamated zinc and 2 g of boric acid to
dissolves. the flask.
91.6 Boric Acid. 93.5 Connect the flask to the gas train, and with the pinch
91.7 Starch Solution, 1 %. clamp open, adjust the nitrogen flow to about 100 mL/min, and
91.8 Nitrogen or Argon, oxygen-free. purge the apparatus for 10 min.
91.9 Iodine, 0.005 N—Prepare fresh. Pipet 10 mL of stan- 93.6 Add 85 mL of digestion acid to the separatory funnel.
dard 0.1 N iodine to 200 mL with water, and mix well. 93.7 Open the separatory funnel stop cock. Using a pipet
91.10 Zinc Acetate Solution (30 g/L)—Dissolve 30 g of zinc bulb, force about 80 mL of the acid into the 500-mL flask,
acetate and 6 mL of glacial acetic acid in water and dilute to making certain that no air enters the flask. Close the stop cock.
1000 mL. 93.8 Boil the contents of the flask for 30 min, adjusting the
91.11 Sodium Thiosulfate, Standard Solution (0.01 N)— temperature so that froth about half-fills the flask, but does not
Prepare fresh. Pipet 20 mL of standard 0.1 N sodium thiosul- rise high enough to enter the neck of the flask.

13
 E 1506 – 97 (2003)
93.9 Carefully disconnect the delivery tube from the con- B = sodium thiosulfate used for the sample, mL,
denser, at the ball and socket joint, and seal the outlet tube on C = sodium thiosulfate used for the blank, mL,
the gas washing bottle with tubing and a clamp. A = sample weight, g,
93.10 Remove cap from gas washing bottle. Quickly add 0.016 = milliequivalent weight of sulfur, and
10.0 mL of 0.005 N iodine solution and 10 mL of HCl (1+2) N = normality of sodium thiosulfate.
solution to the zinc acetate collection solution in the gas
washing bottle. Replace cap. Keeping the outlet tube sealed, 95. Report
allow the mixture to stand for about 15 min. 95.1 Report the concentration of sulfide sulfur to the nearest
93.11 Remove cap, open pinch clamp, and rinse the gas inlet 0.0001 %.
tube carefully, collecting the washings in the bottle. Take care 95.2 Minimum reportable quantity is 0.0001 %.
that all the zinc sulfide adhering to the inlet tube has been
dissolved completely. 96. Precision and Bias
93.12 Using 0.005 N sodium thiosulfate, back-titrate the 96.1 Laboratory Precision (Within-Laboratory, Between-
excess iodine, adding 1 mL of starch solution just before the Days)—The standard deviation of results, each the average of
end-point is reached. Continue titrating to the clear end-point. duplicates, obtained by the same analyst on different days, has
Record B, the millilitres of 0.005 N sodium thiosulfate needed been estimated to be 0.0003 % with 17 df. The 95 % limit for
for the titration. the difference between two such averages is 0.0008 %.
93.13 Similarly, determine a blank, using all of the same
reagents, but no sample. Record C, the millilitres of 0.005 N NOTE 16—This precision estimate is based on the analysis of a single
sodium thiosulfate needed for the blank. sample in one laboratory over the period from April to October 1996.
96.2 Bias—The bias of this test method cannot be deter-
94. Calculation mined unless a suitable reference material becomes available.
94.1 Calculate:
~C – B! 3 N 3 0.016 3 100 97. Keywords
% sulfide sulfur 5 (12)
A 97.1 arsenic; calcium carbonate; calcium fluoride; fluorspar;
mixed oxides (R2O3); moisture; phosphorus; silica; soluble
where: chloride; sulfide sulfur; volatiles

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