Designation: E 815 – 99

Standard Test Method for

Determination of Calcium Fluoride in Fluorspar by
Complexometric Titration1
This standard is issued under the fixed designation E 815; 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 and manufacture of hydrofluoric acid.

1.1 This test method covers the determination of calcium 4.2 This test method is intended to be used for compliance
fluoride in acid-grade fluorspar and other types of fluorspar that with compositional specifications for calcium fluoride content.
can be rendered soluble by the procedure described in the test It is assumed that all who use these procedures will be trained
method. analysts capable of performing common laboratory procedures
1.2 This standard does not purport to address all of the skillfully and safely. It is expected that work will be performed
safety concerns, if any, associated with its use. It is the in a properly equipped laboratory and that proper waste
responsibility of the user of this standard to establish appro- disposal procedures will be followed. Appropriate quality
priate safety and health practices and determine the applica- control practices must be followed such as those described in
bility of regulatory limitations prior to use. Guide E 882.

2. Referenced Documents 5. Interferences

2.1 ASTM Standards: 5.1 None of the elements normally found in fluorspar
D 1193 Specification for Reagent Water2 interfere with this test method.
E 50 Practices for Apparatus, Reagents, and Safety Precau- 6. Apparatus
tions for Chemical Analysis of Metals3
E 276 Test Methods for Particle Size or Screen Analysis at 6.1 Fluoride Ion-Selective Electrode. 5
No. 4 (4.75-mm) Sieve and Finer for Metal-Bearing Ores 6.2 Magnetic Stirrer and TFE-Fluorocarbon-Coated Spin
and Related Materials3 Bar.
E 882 Guide for Accountability and Quality Control in the 6.3 pH Meter with High Impedance—Suitable for ion-
Chemical Analysis Laboratory4 selective electrode.
6.4 Polyethylene Beakers, 100-mL.
3. Summary of Test Method 6.5 Single Junction Ag/AgCl Reference Electrode. 6
3.1 The sample is decomposed by digesting with nitric and 7. Reagents and Materials
perchloric acids and the fluorine is expelled by fuming. The
residue is dissolved in dilute hydrochloric acid, the solution 7.1 Purity of Reagents—Reagent grade chemicals shall be
made alkaline, and the calcium titrated with standard EDTA used in all tests. Unless otherwise indicated, it is intended that
solution. Calcium present as carbonate is determined in a all reagents conform to the specifications of the Committee on
separate sample with EDTA solution, after extracting the Analytical Reagents of the American Chemical Society where
former with dilute acetic acid. A correction for calcium such specifications are available.7 Other grades may be used,
fluoride, solubilized by dilute acetic acid digestion, is applied, provided it is first ascertained that the reagent is of sufficient
by determining the fluoride in the acetic acid extract by fluoride high purity to permit its use without lessening the accuracy of
ion-selective electrode. The CaF 2 content is then calculated. the determination.
7.2 Purity of Water—Unless otherwise indicated, references
4. Significance and Use to water shall be understood to mean reagent water as defined
4.1 Fluorspar is used as a flux in steelmaking, glass industry, by Type I of Specification D 1193.
7.3 Acetic Acid Solution (1 + 10)—Mix 1 volume of glacial
1
This test method is under the jurisdiction of ASTM Committee E-1 on
5
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct Orion model 94-91 has been found suitable for this purpose.
6
responsibility of Subcommittee E01.02 on Ores, Concentrates, and Related Metal- Orion model 90-01-00 has been found suitable for this purpose.
7
lurgical Materials. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Nov. 10, 1999. Published January 2000. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as E 815 – 81. Last previous edition E 815 – 94. 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 03.05. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
4
Annual Book of ASTM Standards, Vol 03.06. MD.

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

1
 E 815
acetic acid (CH3COOH) with 10 volumes of water. standardization with CaCO3 can be omitted. The “standard” CaF 2 sample
7.4 Calcium Carbonate, high purity (minimum 99.95 % should then be carried through all steps of the procedure.
CaCO3). 9.2 Calibration—Transfer 10 mL of acetic acid (1 + 10)
7.5 Ethylenediaminetetraacetic Acid Disodium Salt (7.3) into a series of seven 100-mL polyethylene beakers and
(EDTA)-—Na2C10H1 4O8N2·2H2O Solution (0.025 mol/L)— add 20 mL of potassium acetate buffer (7.9) (Note 2). Add
Dissolve 9.3062 g of EDTA in water, transfer to a 1-L standard fluoride solution (7.12) and water according to the
volumetric flask, dilute to volume, and mix. following:
7.6 Hydrochloric Acid (2 + 98)—Mix 2 volumes of concen- Test Standard F− mL Solution mg Water, mL
trated hydrochloric acid (HCl) with 98 volumes of water. 1 0 0 5
2 0.5 0.05 4.5
7.7 Hydrochloric Acid (1 + 10)—Mix 1 volume of concen- 3 1.0 0.10 4.0
trated hydrochloric acid (HCl) with 10 volumes of water. 4 2.0 0.20 3.0
7.8 Hydroxynaphthol Blue Indicator— Grind 0.2 g of the 5 3.0 0.30 2.0
6 4.0 0.40 1.0
salt with 50 g sodium chloride (NaCl). 7 5.0 0.50 0
7.9 Potassium Acetate Buffer—Dilute 283 mL of glacial
acetic acid (CH3COOH) to 1200 mL with water. While cooling Stir the solution, immerse the electrodes (6.1 and 6.5) and
and stirring, add 50 % (W/V) potassium hydroxide solution wait for 3 to 5 min for potential to reach equilibrium. Record
(KOH) to adjust the pH to 5.0 (approximately 350 mL of KOH the potential in millivolts. Plot millivolts (linear scale) versus
solution are required). F− concentration in milligrams (log scale) on a semilog paper.
7.10 Potassium Hydroxide Solution (22.5 %) (W/V)— NOTE 2—Potential measurements in calibration standards and sample
Dissolve 225 g of potassium hydroxide (KOH) in water and should be carried out concurrently.
dilute to 1 L with water. Store in a plastic bottle.
7.11 Potassium Hydroxide Solution (50 %) (W/V)— 10. Procedure
Dissolve 500 g of potassium hydroxide (KOH) in water and 10.1 Determination of Total Calcium:
dilute to 1 L. Store in a plastic bottle. 10.1.1 Transfer approximately 0.50 g of the sample to a
7.12 Sodium Fluoride Solution—Dissolve 0.2210 g sodium small weighing bottle, previously dried at about 105°C. Dry
fluoride (NaF) in water in a polyethylene beaker and dilute to the bottle and contents for 1 h at 105 to 110°C. Cap the bottle
1 L in a volumetric flask. Store in a stoppered polyethylene and cool to room temperature in a desiccator. Momentarily
bottle. This solution has a concentration of 1 mL 5 0.10 mg F− release the cap to equalize the pressure and weigh the capped
and is stable for 6 months. bottle to the nearest 0.1 mg. Repeat the drying and weighing
7.13 Triethanolamine Solution (1 + 1)—Mix 50 mL of tri- until there is no further weight loss. Transfer the sample to a
ethanolamine (NC6H15O3) with 50 mL of water. 400-mL beaker and reweigh the capped bottle to the nearest 0.1
mg. The difference between the two weights is the weight of
8. Sampling, Test Specimens, and Test Units the sample taken for analysis.
8.1 Pulverize the test units so that 95 % passes a No. 100 10.1.2 Decomposition of Sample—Add 5 mL of HNO3,
mesh sieve (150-µm) in accordance with Test Methods E 276. cover with a watch glass, and digest on a hot plate. Cool
9. Calibration and Standardization somewhat, add 5 mL of HClO4, and evaporate first to fumes of
HClO 4. When decomposition appears to be complete, tilt the
9.1 Standardization—Weigh and transfer 2.4970 g of cover and evaporate carefully to complete dryness. Allow to
CaCO3(dried at 110°C for 1 h and cooled in a desiccator) to a cool, add 5 mL of HCl, dilute to approximately 50 mL with
600-mL beaker. While covered, cautiously add 75 mL of HCl water, and heat until all the soluble salts have dissolved. This
(7.7) and warm. Cool, transfer to a 1-L volumetric flask, dilute is the main solution.
to volume with water, and mix. This solution has a concentra-
tion of 1 mL 5 1.0000 mg of calcium. NOTE 3—If an insoluble residue remains, filter through a fine-textured
paper, and wash the paper thoroughly with hot HCl (7.6), ignite the paper
9.1.1 Titration—
and residue in a platinum crucible, and treat the insoluble residue again
9.1.1.1 Transfer a 50.00-mL aliquot of this solution to a with HNO3 and HClO4 as in sample decomposition, and combine this
400-mL beaker, add 5 mL of triethanolamine (7.13), dilute to solution with the main filtrate. If the volume exceeds 90 mL, evaporate it
200 mL, make just alkaline with potassium hydroxide solution to about 80 mL and cool.
(7.10), using a strip of litmus paper, and then add an additional 10.1.3 Transfer the solution to a 100-mL volumetric flask,
15 mL of potassium hydroxide solution (7.10). dilute to volume, and mix.
9.1.1.2 Add 0.2 g of hydroxynaphthol blue indicator and 10.1.4 Transfer an appropriate aliquot (20.00 mL in the
titrate immediately with 0.025 M EDTA solution ( 7.5). At the range from 80 to 100 % CaF2 and 25.00 mL in the range from
equivalence point, the color changes from pink to blue. 40 to 80 % CaF2) to a 400-mL beaker. Add 5 mL of trietha-
Determine the calcium equivalent of the EDTA solution as nolamine (7.13). Make the solution just alkaline with potas-
follows: sium hydroxide solution (7.10) and add 15 mL of additional
1 mL of EDTA solution 5 ~50.0/V! 5 C mg of calcium (1) KOH solution (7.10). Titrate with EDTA solution as described
in Section 8.
where: 10.2 Determination of Soluble Calcium:
V 5 millilitres of EDTA used.
10.2.1 Transfer 1.00 g of sample to a 250-mL beaker. Add
NOTE 1—If a sample with a known CaF2 content is available, the 20 mL of acetic acid (1 + 10) (7.3) and digest at just below

2
 E 815
TABLE 1 Precision Data where:
Average
Relative Number of V 5 volume of titrant, mL,
Fluorspar Grade
Concentration, %
Standard Participating
C 5 calcium equivalent of EDTA solution, mg/mL,
Deviation,A % Laboratories
a 5 millilitres of aliquot,
Spanish acid 97.63 0.195 14 b 5 grams of sample used, and
African acid 96.78 0.257 14
Mexican ceramic 91.84 0.173 14 T 5 total calcium present,% .
Mexican metallurgical 87.72 0.263 14 11.2 Calculate soluble calcium as follows:
A
Calculate the relative standard deviation, RSD, in this test method as follows:
~2!~V!~C! 2 ~5.2737!~F2!
RSD 5 ~100/ X̄! =(d 2/~n 2 1! Soluble calcium, % S 5 10 (3)

where:
X̄ 5 average concentration, %, where:
d 5 difference of the determination from the mean, and V 5 volume of titrant, mL,
n 5 number of determinations. C 5 calcium equivalent of EDTA solution, mg/mL,
F 5 fluoride ion concentration, mg.
11.3 Calculate calcium fluoride as follows:
Calcium fluoride, % 5 ~T 2 S! 3 1.948 (4)
boiling point for 60 min. Cool, filter through a fine-textured
filter paper, and wash five times with acetic acid (1 + 10) (7.3), where:
collecting the filtrate and washings into a 50-mL volumetric T 5 total calcium percent found in 11.1, and
flask. Dilute the contents to mark with water. S 5 soluble calcium percent found in 11.2.
10.2.2 Pipet a 25-mL aliquot into a 400-mL beaker and 12. Precision and Bias 8
evaporate to dryness. Redissolve the residue in 1 to 2 mL of 12.1 Precision—Table 1 indicates the precision of the test
hydrochloric acid and dilute to 200 mL with water. Add 5 mL method between laboratories.
of triethanolamine (7.13) and proceed as in total calcium 12.2 Bias—No information on the bias of this test method is
determination. Record the titration. Calculate milligrams of known. Accepted reference materials may have not been
calcium (X) in the 50-mL volume by multiplying the titration included in the materials used in the interlaboratory study.
(in millilitres) by 2C (proceed as in 9.1). Users of this test method are encouraged to employ accepted
10.2.3 Transfer a 10-mL aliquot into a 100-mL polyethylene reference materials, if available, and to judge the bias of this
beaker, add 20 mL of potassium acetate buffer (7.9) and 5 mL test method from the difference between the accepted value for
of water (Note 2), and mix (pH should be 5.0). Measure the the calcium fluoride content and the mean value from inter-
potential in millivolts using reference and fluoride ion-selective laboratory testing of the reference material.
electrodes as described in 9.2. Obtain the milligrams of F− by
referring to the graph in 9.2. 13. Keywords
13.1 calcium content; calcium fluoride content; fluorspar;
11. Calculation soluble calcium content
11.1 Calculate total calcium as follows: 8
Supporting data giving the results of cooperative testing are available from
Total calcium, % T 5 ~10!~V!~C!/~a!~b! (2) ASTM Headquarters. Request RR: E16-1003.

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