Designation: E463 − 14a

Standard Test Method for

Determination of Silica in Fluorspar by Silico-Molybdate
Visible Spectrophotometry1
This standard is issued under the fixed designation E463; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope photometrically after extraction of the silico-molybdate com-

1.1 This test method covers the determination of silica in plex with normal butyl alcohol. Photometric measurement of
fluorspar in concentrations from 0.5 % to 10 %. the extract is made at 400 nm.
1.2 The values stated in SI units are to be regarded as 5. Significance and Use
standard. No other units of measurement are included in this
5.1 This test method is intended as a referee method for
standard.
compliance with compositional specifications for impurity
1.3 This standard does not purport to address all of the content. It is assumed that all who use this procedure will be
safety concerns, if any, associated with its use. It is the trained analysts capable of performing common laboratory
responsibility of the user of this standard to establish appro- practices skillfully and safely. It is expected that work will be
priate safety and health practices and determine the applica- performed in a properly equipped laboratory and that proper
bility of regulatory limitations prior to use. waste disposal procedures will be followed. Follow appropriate
2. Referenced Documents quality control practices such as those described in Guide
E882.
2.1 ASTM Standards:2
D1193 Specification for Reagent Water 6. Interferences
E50 Practices for Apparatus, Reagents, and Safety Consid-
erations for Chemical Analysis of Metals, Ores, and 6.1 The elements ordinarily present in commercial fluor-
Related Materials spars do not interfere in this test method.
E135 Terminology Relating to Analytical Chemistry for 7. Reagents and Materials
Metals, Ores, and Related Materials
E276 Test Method for Particle Size or Screen Analysis at No. 7.1 Purity of Reagents—Reagent grade chemicals shall be
4 (4.75-mm) Sieve and Finer for Metal-Bearing Ores and used in all tests. Unless otherwise indicated, it is intended that
Related Materials all reagents conform to the specifications of the Committee on
E882 Guide for Accountability and Quality Control in the Analytical Reagents of the American Chemical Society where
Chemical Analysis Laboratory such specifications are available.3 Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently
3. Terminology high purity to permit its use without lessening the accuracy of
3.1 Definitions—For definitions of terms used in this test the determination.
method, refer to Terminology E135. 7.2 Unless otherwise indicated, references to water shall be
4. Summary of Test Method understood to mean reagent water conforming to Type I or II of
Specification D1193. Type III or IV may be used if they effect
4.1 The sample is fused with anhydrous sodium borate and no measurable change in the blank or sample.
the melt is dissolved in dilute HCl. Silica is determined
7.3 Ammonium Molybdate Solution (100 g ⁄L)—Dissolve
1
This test method is under the jurisdiction of ASTM Committee E01 on 100 g of ammonium-heptamolybdate [(NH4)6Mo7O24·4H2O]
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct in 500 mL of water, dilute to 1 L, and mix.
responsibility of Subcommittee E01.02 on Ores, Concentrates, and Related Metal-
lurgical Materials. 7.4 Silica (SiO2)—Heat pure silicic acid in a platinum
Current edition approved Oct. 1, 2014. Published November 2014. Originally crucible to expel combined water by gradually increasing
approved in 1972. Last previous edition approved in 2014 as E463 – 14. DOI:
10.1520/E0463-14A.
2 3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Reagent Chemicals, American Chemical Society Specifications, American
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Standards volume information, refer to the standard’s Document Summary page on listed by the American Chemical Society, see the United States Pharmacopeia and
the ASTM website. National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.

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

1
 E463 − 14a
temperature to 1050 °C. Maintain at 1050 °C for at least 5 min. crucible to the beaker. Cover the beaker with a polyethylene
Cool to room temperature in a desiccator. sheet and secure it to the beaker with a rubber band.
7.5 Sodium Borate(Na2B4O7)—Anhydrous powder, low- NOTE 3—Hold the crucible while cooling to avoid contamination
silica content. problems. This prevents damage to the beaker.
NOTE 1—If low silica sodium borate is not available, prepare the 10.8 Place the beaker on a steam bath and swirl occasionally
reagent as follows: Transfer 247 g of boric acid to a large platinum dish. until the melt is completely dissolved (Note 4). Cool, remove
Expel water by gradually increasing the temperature to about 1000 °C. and rinse the platinum crucible and cover, and add the
When effervescence ceases, gradually introduce 106 g of sodium carbon-
ate into the molten mass. Maintain at a temperature of about 1000 °C until washings to the beaker. Transfer the solution to a 250-mL
a clear melt is obtained. volumetric flask. Rinse the beaker and add the rinsings to the
flask. Dilute to volume, mix, and examine the solution for any
8. Hazards insoluble material (Note 4). Transfer the solution to a dry
8.1 For precautions to be observed in this method, refer to polyethylene bottle.
Practices E50. NOTE 4—Complete dissolution of the melt requires about 2 h. In cases
of incomplete dissolution, a new sample must be taken.
9. Sample Preparation
10.9 Transfer 50-mL aliquots of the blank and sample
9.1 The analytical sample shall be pulverized, if necessary, solutions to 200-mL polyethylene or TFE-fluorocarbon bea-
to pass a 150-µm sieve (see Test Method E276). Dry at 105 °C kers.
to 110 °C for a minimum of 1 h.
10.10 Transfer (10.0, 20.0, 30.0, 40.0, and 50.0)-mL ali-
10. Procedure quots of the standard solutions to 200-mL polyethylene or
10.1 Transfer 7 g of Na2B4O7 to each of six 25-mL platinum TFE-fluorocarbon beakers. Dilute, if necessary, to a 50-mL
crucibles. Form a cavity in the center of the flux. volume with the remaining blank solution.
10.2 Into Crucibles 1 and 2, weigh 0.100 g to 1 g of the dry NOTE 5—Since commercially available Na2B4O7 frequently contains
sample. Choose sample weights to provide from 5 mg to 10 mg appreciable amounts of silica, each standard and sample solution must
contain the same amounts of this reagent. The dilution of the aliquots to
of SiO2. a 50-mL volume should, therefore, be carried out using a buret.
10.3 Into Crucibles 3 and 4, weigh 10.0 mg of SiO2 reagent. 10.11 Determine the pH of the blank, standard, and sample
10.4 Crucibles 5 and 6 serve as blanks. solutions using a pH meter. If the pH of the solutions lies
10.5 Mix the contents of the crucibles with a platinum or between 0.5 and 0.9 and within 0.1 units of each other, proceed
polyethylene rod. Transfer adhering particles to the crucible. to 10.12. If the pH lies outside these parameters, adjust the pH
with HCl (1 + 1).
10.6 Cover the crucible and heat gently until moisture is
expelled. Increase the temperature until complete fusion re- NOTE 6—Accurate pH adjustments are essential for maximum color
sults. development and color stability.

NOTE 2—A Meker burner or a muffle furnace maintained at 1000 °C

10.12 Add, while stirring, 10 mL of ammonium molybdate
may be used for this purpose. solution. Allow 10 min for color development, then dilute to
100 mL. Transfer the solution to a 250-mL separatory funnel
10.7 Transfer the platinum crucible and cover to a 400-mL
and add 25 mL of cool H2SO4 (1 + 1).
polyethylene or TFE-fluorocarbon beaker containing 150 mL
water and 25 mL HCl (1 + 1). Cool the crucible for about 3 s, 10.13 Add 75 mL of normal butyl alcohol and shake vigor-
then pour the melt dropwise into the beaker so that most of the ously for 1 min. Allow the phases to separate and discard the
flux settles on the crucible cover (Note 3). Transfer the cooled acid (lower) layer. Add 20 mL of H2SO4 (1 + 99) to the

TABLE 1 Precision Data

Relative
Average Standard Number
Standard
Concentration,A Deviation, of Participating
% Deviation,B
% % Laboratories

0.71 0.03 4.2 6

2.16 0.11 5.1 7
6.94 0.10 1.4 6
A
Each concentration represents a different grade of fluorspar.
B
Relative Standard Deviation (RSD), in this test method is calculated as follows:

RSD 5 s 100/X̄ d œ od 2
/sn 2 1d (2)

where:
X̄ = average concentration, %,
d = difference of the determination from the mean, and
n = number of determinations.

2
 E463 − 14a
separatory funnel, shake for 30 s, allow the phases to separate, 13. Calculation
and discard the acid layer. Repeat the washing twice more.
13.1 Subtract the average absorbance of the blank solutions
10.14 Transfer the butyl alcohol phase to a dry 100-mL from absorbances of the sample solutions. Convert the net
volumetric flask. Wash the separatory funnel twice with 1-mL absorbance of the sample solution to milligrams of SiO2 by
or 2-mL portions of butyl alcohol, and add the washings to the means of the calibration curve. Calculate the percentage of
volumetric flask. Add 1 mL of ethyl alcohol, dilute to volume SiO2 as follows:
with butyl alcohol, and mix.
Silica, % 5 A/ ~ B 3 10! (1)
11. Photometry
A = silica found in the aliquot used, mg, and
11.1 Concentration Range:
B = sample represented by the aliquot, g.
11.1.1 The recommended concentration range is from
0.2 mg to 2.0 mg of silica per 100 mL of solution, using a 1-cm
cell. 14. Precision and Bias

NOTE 7—Cells having other dimensions may be used, provided suitable 14.1 Precision—Table 1 indicates the precision of the test
adjustments can be made in the amounts of sample and reagent used. method between laboratories.
11.2 Adjust the photometer to the initial setting using water 14.2 Bias—No information on the accuracy of this test
as the reference solution. While maintaining this setting, take method is known. The accuracy of this test method may be
photometric readings of the blank, standard, and sample judged by comparison of accepted values for standard refer-
solutions using a light band centered at approximately 400 nm. ence materials with the mean determined through interlabora-
11.3 Stability of Color: tory testing.
11.3.1 After the addition of the ammonium molybdate, color
is fully developed within 10 min and is stable after extraction 15. Keywords
with butyl alcohol
15.1 fluorspar; photometric; silica; silico-molybdate magne-
12. Preparation of Calibration Curve sium
12.1 Subtract the average absorbance of the blank solution
from the average absorbance of each standard solution and plot
the net absorbances against milligrams of silica per 100 mL of
solution.

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