Designation: D1394 − 76 (Reapproved 2014)

Standard Test Methods for

Chemical Analysis of White Titanium Pigments1
This standard is issued under the fixed designation D1394; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope all reagents shall conform to the specifications of the Commit-

1.1 These test methods cover procedures for the chemical tee on Analytical Reagents of the American Chemical Society,
analysis of white titanium dioxide pigments. where such specifications are available.3 Other grades may be
used, provided it is first ascertained that the reagent is of
1.2 The analytical procedures appear in the following order: sufficiently high purity to permit its use without lessening the
Sections accuracy of the determination.
Preparation of Sample 4
Qualitative Analysis 5 and 6 3.2 Unless otherwise indicated, references to water shall be
Moisture 7
Total Titanium:
understood to mean reagent water conforming to Type IV of
Jones Reductor Method 8 – 12 Specification D1193.
Aluminum Reduction Method 13 – 17
Aluminum Oxide 18 – 22
Silica 23 – 29
4. Preparation of Sample
1.3 The values stated in SI units are to be regarded as 4.1 The sample shall, in all cases, be thoroughly mixed and
standard. No other units of measurement are included in this comminuted before taking portions for analysis.
standard.
QUALITATIVE ANALYSIS
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 5. Reagents
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 5.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
bility of regulatory limitations prior to use. A specific hazard monium hydroxide (NH4OH).
statement is given in Section 19. 5.2 Ammonium Sulfate—((NH4)2SO4).
2. Referenced Documents 5.3 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
2.1 ASTM Standards:2 chloric acid (HCl).
D280 Test Methods for Hygroscopic Moisture (and Other 5.4 Hydrogen Peroxide (30 %)—Concentrated hydrogen
Matter Volatile Under the Test Conditions) in Pigments peroxide (H2O2).
D1193 Specification for Reagent Water
E50 Practices for Apparatus, Reagents, and Safety Consid- 5.5 Hydrogen Sulfide (H2S).
erations for Chemical Analysis of Metals, Ores, and 5.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
Related Materials (H2SO4).
3. Reagents 5.7 Sulfuric Acid (1+19)—Carefully mix 1 volume of
3.1 Purity of Reagent—Reagent grade chemicals shall be H2SO4(sp gr 1.84) with 19 volumes of water.
used in all tests. Unless otherwise indicated, it is intended that 5.8 Tartaric Acid.
1
These test methods are under the jurisdiction of ASTM Committee D01 on 5.9 Tin or Zinc Metal.
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.31 on Pigment Specifications.
Current edition approved Dec. 1, 2014. Published December 2014. Originally
3
approved in 1956. Last previous edition approved in 2009 as D1394 – 76 (2009). Reagent Chemicals, American Chemical Society Specifications, American
DOI: 10.1520/D1394-76R14. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.

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

1
 D1394 − 76 (2014)
6. Procedure
6.1 Place about 0.5 g of the sample in a 250-mL glass
beaker,4 and add 20 mL of H2SO4 (sp gr 1.84) and 7 to 8 g of
(NH4)2SO4. Mix well and boil for a few minutes. The sample
should go completely into solution; a residue denotes the
presence of silicon dioxide (SiO2) or siliceous matter. Cool the
solution, dilute with 100 mL of water, heat to boiling, let settle,
filter, wash with hot H2SO4 (1+19) until free of titanium, and
test the residue for lead, etc.
6.2 Test the filtrate for calcium, zinc, iron, chromium, etc.,
by the regular methods of qualitative analysis.5 For the iron
determination add to a portion of the filtrate 5 g of tartaric acid,
render slightly ammoniacal, pass in H2S in excess, and digest
on a steam bath. No precipitate after 30 min indicates the
absence of iron, nickel, cobalt, lead, copper, etc. A black
precipitate readily soluble in dilute HCl denotes iron. For
titanium, test a small portion of the original filtrate with H2O2
(a clear yellow-orange color should result) and another portion
with metallic tin or zinc (a pale blue to violet coloration should
result). Negative results should be shown for sulfide,
carbonate, or appreciable water-soluble matter.
MOISTURE

7. Procedure
7.1 Determine moisture and other volatile matter in accor-
dance with Test Method A of Test Methods D280.
TOTAL TITANIUM BY THE JONES REDUCTOR
FIG. 1 Jones Reduction
METHOD

8. Scope
10. Reagents
8.1 This method gives results similar to those obtained with
the Aluminum Reduction Method, Sections 13 – 17. 10.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
monium hydroxide (NH4OH).
9. Apparatus 10.2 Ammonium Sulfate ((NH4)2SO4).
9.1 Jones Reductor 6having a zinc column at least 450 mm 10.3 Carbon Steel or Iron—Pure iron or plain carbon steel.
in length, and 19 mm in diameter (Fig. 1 and Fig. 2). The
filtering pad must be tight enough to hold all the particles of 10.4 Ferric Sulfate Solution (1 mL = 0.02 g Fe)—Dissolve
amalgamated zinc resting on it, and may be made of asbestos 20 g of iron or carbon steel in a slight excess of HCl, oxidize
or, preferably, glass-wool supported by platinum gauze or a with approximately 12 mL of HNO3, add about 80 mL of
perforated porcelain plate. Use the least amount (0.1 to 1.0 %) H2SO4, and heat to dense white fumes. Cool, dilute with water
of mercury that will enable satisfactory control of hydrogen to 1 L, digest on a steam bath until sulfates are dissolved, and
evolution, since heavy amalgamation tends to reduce the rate filter if necessary. To oxidize any ferrous iron that may be
of reaction. Prepare the amalgam by washing 20-mesh zinc for present, add 0.1 N KMnO4 solution until a faint pink color
1 min in enough 1 N HCl to cover it, adding the proper amount persists for 5 min. Ferric ammonium sulfate (FeNH4(SO4)2 ·
of 0.25 M mercuric nitrate or chloride solution, and stirring 12H2O) may also be used to prepare this solution (See 15.4).
rapidly for 3 min. Decant the solution and wash the amalgam 10.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
with water and store under water to which a few drops of HCl chloric acid (HCl).
have been added. After using, keep the reductor filled with 10.6 Iron or Carbon Steel—Pure iron or plain carbon steel.
water when not in use, in order that basic salts will not be
formed and clog it. 10.7 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3).
4
10.8 Sodium Oxalate—National Institute of Standards and
Borosilicate glass has been found satisfactory for this purpose.
5
Treadwell, F. P., and Hall, William T., Qualitative Analysis, John Wiley & Sons, Technology standard reference material No. 40 of sodium
Inc., New York, NY, Vol. 1, Ninth English Ed., 1937. oxalate (Na2C2O4).
6
Directions for preparing a Jones Reductor may be found in Hillebrand, W. F.,
et al., Applied Inorganic Analysis, John Wiley & Sons, Inc., New York, NY, Second 10.9 Potassium Permanganate, Standard Reference Mate-
Ed., 1953, p. 108. rial (0.1 N, 1 mL = 0.008 g TiO2)—Dissolve 3.16 g of KMnO4

2
 D1394 − 76 (2014)
10.10 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H2SO4).
10.11 Sulfuric Acid (1+1)—Carefully mix 1 volume of
H2SO4 (sp gr 1.84) into 1 volume of water with rapid stirring.
10.12 Sulfuric Acid (1+19)—Carefully mix 1 volume of
H2SO4 into 19 volumes of water with rapid stirring.

11. Procedure
11.1 Determine the dry weight of a weighing bottle and cap
to 0.1 mg. Weight to 0.1 mg 300 to 350 mg of the sample to be
analyzed into the weighing bottle.
11.2 Dry the specimen in the opened weighing bottle for 2
h at 105 to 110°C. Cool in a desiccator, cap the bottle, and
weigh as rapidly as possible. Calculate the dry weight of the
specimen and use in the actual calculation.
11.3 Transfer the dried specimen to a dry 250 mL chemical-
and heat-resistant glass beaker,4 add 20 mL of H2SO4(sp gr
1.84) and 7 to 8 g of (NH4)2SO4. Mix well and heat on a hot
plate until dense white fumes are evolved, and then continue
the heating over a strong flame until solution is complete
(usually requires not over 5 min of boiling) or it is apparent that
the residue is composed of SiO2 or siliceous matter. Caution
should be observed in visually examining this hot solution.
Cool the solution, dilute with 100 mL of water, stir, heat
carefully to boiling while stirring, let settle, filter through
paper, and transfer the precipitate completely to the paper.
11.4 Wash the insoluble residue with cold H2SO4 (1+19)
until titanium is removed. Dilute the filtrate to 200 mL and add
about 5 mL of NH4OH to lower the acidity to approximately 10
FIG. 2 Jones Reductor, Assembled
to 15 % H2SO4 (by volume). Wash out the Jones reductor with
H2SO4 (1+19) and water, leaving sufficient water in the
in water and dilute to 1 L. Let stand 8 to 14 days, siphon off the reductor to fill to the upper level of the zinc. (These washings
clear solution (or filter through sintered glass, medium should require not more than one or two drops of 0.1 N KMnO4
porosity), and standardize against the National Bureau of solution to obtain a pink color.) Empty the receiver, and put in
Standards standard sample No. 40 of sodium oxalate it 25 mL of ferric sulfate solution. Reduce the prepared
(Na2C2O4) as follows: In a 400-mL beaker dissolve 250 to 300 titanium solution as follows:
mg Na2C2O4 in 250 mL of hot water (80 to 90°C) and add 15 11.4.1 Run 50 mL of H2SO4 (1+19) through the reductor at
mL of H2SO4(1+1). Titrate at once with the KMnO4 solution, such a uniform rate as to require 5 to 10 min for passage.
stirring the liquid vigorously and continuously. The KMnO4 11.4.2 Follow this with the titanium solution at such a
solution must not be added more rapidly than 10 to 15 mL/min, uniform rate as to require 10 min to pass through the reductor.
and the last 0.5 to 1 mL must be added dropwise with particular 11.4.3 Wash out with 100 mL of H2SO4 (1+19).
care to allow each drop to be fully decolorized before the next 11.4.4 Finally run through about 100 mL of water. Take care
is introduced. The solution shall not be below 60°C by the time that the reductor is always filled with solution or water to the
the end point has been reached. (More rapid cooling may be upper level of the zinc.
prevented by allowing the beaker to stand on a small hot plate
11.5 Gradually release the suction, wash thoroughly the
during the titration. The use of a small type thermometer as a
glass tube that was immersed in the ferric sulfate solution,
stirring rod is most convenient.) Keep the KMnO4 solution in
remove the receiver, and titrate immediately with 0.1 N
a glass-stoppered bottle painted black to keep out light or in a
KMnO4 solution. Run a blank determination, using the same
brown glass bottle stored in a dark place. Calculate the TiO2
reagents and washing the reductor as in the above determina-
equivalent in grams of TiO2 per millilitre of the KMnO4
tion.
solution as follows:
TiO2 equivalent 5 ~ W 3 1.192! /V 12. Calculation
where: 12.1 Calculate the percent of TiO2 as follows:
W = Na2C2O4 used, g, and ~V1 2 B! 3 T
V = KMnO4 solution required for the titration, mL. TiO2 , % 5
S
3 100

3
 D1394 − 76 (2014)
where: 15.7 Sodium Bicarbonate Solution—Make up a saturated
V1 = KMnO4 solution required for titration of specimen, mL solution at the time of analysis. About 10 g of sodium
B = KMnO4 solution required for titration of the blank, mL bicarbonate (NaHCO3) to 90 g of water is required.
T = TiO2 equivalent of the KMnO4 solution, g/mL, and 15.8 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
S = dried specimen, g.
(H2SO4).
12.2 The results calculated in accordance with 12.1 will
include iron, chromium, arsenic, and any other substance that 15.9 Titanium Dioxide (TiO2)—National Bureau of Stan-
is reduced by zinc and acid. However, appreciable quantities of dards standard sample No. 154 of titanium dioxide.
interfering materials are not likely to be encountered in normal,
white titanium pigments. 16. Procedure
16.1 Determine the dry weight of the weighing bottle and
TOTAL TITANIUM BY THE ALUMINUM cap. Weigh to the nearest 0.1 mg, 190 to 210 mg of the sample
REDUCTION METHOD to be analyzed into the weighing bottle.
13. Scope 16.2 Dry the specimen in the open weighing bottle for 2 h at
13.1 This method gives results similar to those obtained 105 to 110°C. Cool in a desiccator, cap the bottle, and weigh as
with the Jones Reductor Method (Sections 8 – 12). rapidly as possible. Calculate the dry weight of the specimen
and use in the actual calculation.
14. Apparatus 16.3 Transfer the dry specimen to a 500-mL dry, wide-
14.1 Delivery Tube, made of about 4-mm inside diameter mouth Erlenmeyer flask. Add 7 to 9 g of (NH4)2SO4 and 20 mL
glass tubing bent so that there is a horizontal run of about 6 in. of H2SO4. Mix well, heat on a hot plate until dense white
(152 mm) and a vertical drop of about 3 in. (76 mm) at one end, fumes are evolved, and continue the heating over a strong
and a vertical drop of about 6 in. at the other end. flame until solution is complete (usually requires not over 5
min of boiling) or it is apparent that the residue is composed of
14.2 Weighing Bottle, wide-mouth, with an external-fitting
SiO2 or siliceous matter. Cool and, with caution, add 120 mL
cap, and no larger than necessary for the required amount of
of water and 20 mL of HCl. Bring to a boil and remove from
sample.
heat.
15. Reagents 16.4 Insert the short end of the delivery tube into one hole
15.1 Aluminum Metal Foil, electrolytic grade. of a two-hole rubber stopper suitable for the Erlenmeyer flask.
Insert a glass rod with a slight hook or collar at the bottom end
15.2 Ammonium Sulfate—((NH4)2SO4). into the other hole of the stopper in such a way that the bottom
15.3 Ammonium Thiocyanate Indicator Solution—Dissolve end will be near the bottom of the flask when the stopper is
24.5 g of ammonium thiocyanate (NH4CNS) in 80 mL of hot inserted into the flask. Attach approximately 1 g of aluminum
water, filter, bring to room temperature, and dilute to 100 mL. foil to the bottom end of the rod by crumpling or coiling the
Keep in a well-stoppered, dark-colored bottle. foil around the rod. It may be possible to use a thermometer
15.4 Ferric Ammonium Sulfate Solution (1 mL = 0.005 g instead of a collared glass rod and, if one ranging from 0 to
TiO2)—Dissolve 30.16 g of fresh ferric ammonium sulfate 150°C is used, it can be used for determining temperature later.
(FeNH4(SO4)2 · 12H2O) in 800 mL of water containing 15 mL Insert the stopper, carrying the rod with the foil and the
of H2SO4 (sp gr 1.84). Add 5 mL of 3 % H2O2 and boil for at delivery tube, into the flask in such a way that the foil will be
least 15 min then cool to room temperature. Dilute to exactly near the bottom of the flask at the same time that the long end
1 L and mix well. Filter if cloudy. Standardize using 190 to 210 of the delivery tube will be near the bottom of a 250-mL beaker
mg of NBS standard reference material No. 154 of titanium containing about 150 mL of NaHCO3 solution.
dioxide and proceeding as directed in Section 16. Calculate the 16.5 As soon as dissolution of the aluminum is complete,
TiO2 equivalent of the solution in grams of TiO2 per millilitre heat the flask to gentle boiling for 3 to 5 min without removing
of solution, as follows: the delivery tube from the NaHCO3 solution. Cool to about
TiO 2 equivalent 5 ~ W 1 3 P ! / ~ V 2 3 100! 60°C, preferably by partial immersion of the flask in a vessel of
water. The NaHCO3 solution should siphon into the flask
where: during this cooling, giving an atmosphere of CO2 over the
W1 = National Bureau of Standards standard sample of TiO2 reduced titanium solution. Withdraw the stopper, but rinse the
used, g, glass rod attached to it with a little water, catching the rinse
P = percent TiO2 in National Bureau of Standards standard water in the flask before removing the stopper, rod, and
sample, and delivery tube completely.
V2 = ferric ammonium sulfate solution required for the
titration, mL. 16.6 Add 2 mL of NH4CNS indicator solution and titrate
immediately with ferric ammonium sulfate solution (15.4) to a
15.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- straw-colored end point. It is best to add the bulk of the ferric
chloric acid (HCl). ammonium sulfate solution at once, shake well, and finish the
15.6 Hydrogen Peroxide—3 %. titration drop by drop.

4
 D1394 − 76 (2014)
17. Calculations 19.13 Zinc Sulfate, Standard Solution(0.01 M)—Dissolve
2.90 g of zinc sulfate (ZnSO4 · 7H2O) in water and dilute to 1
17.1 Calculate the percent of TiO2 as follows:
L. Standardize as follows:
TiO2 , % 5 ~ V 3 3 T 1 3 100! /S 19.13.1 Dissolve with the aid of heat 0.50 g of high-purity
where: (99.8 %) aluminum wire, weighed to 0.1 mg, in 20 mL of
concentrated HCl. Transfer to a 1-L volumetric flask and dilute
V3 = ferric ammonium sulfate solution required for titration
to volume with water.
of specimen, mL,
T1 = TiO2 equivalent of the ferric ammonium sulfate 19.13.2 Place a 10-mL aliquot of this solution into a
solution, g/mL, and 500-mL Erlenmeyer flask containing approximately 90 mL of
S = dried specimen, g. water and 3 mL of HCl. Add 1 drop of methyl orange indicator
solution. Continue with step 20.4.
17.2 The results calculated in accordance with 17.1 will 19.13.3 Calculate the titre of the ZnSO4 solution as follows:
include chromium, arsenic, and any other substance which is
A 5 ~ 18.8955 3 W 1 ! /V 4
reduced by aluminum and subsequently oxidized by ferric ion.
However, appreciable quantities of interfering materials are not where:
likely to be encountered in normal, white titanium pigments. A = Al2O3 per millilitre of ZnSO4 solution, mL,
W1 = weight of aluminum wire dissolved in 19.13.2, g,
ALUMINUM OXIDE V4 = ZnSO4 solution consumed in the second titration, mL,
and
18. Scope
mol weight of Al2 O 3 3 10
18.1 This method covers the determination of aluminum 18.8955 5
2 3 mol weight of Al
oxide in titanium dioxide pigments.
20. Procedure
19. Reagents
20.1 Fuse about 1 g of pigment weighed to 0.1 mg with 10
NOTE 1—Precaution: All solutions should be stored in polyethylene
bottles.
g of NaHSO4 · H2O in a 250-mL Erlenmeyer flask until the
melt is clear. Use a 250-mL high-silica glass Erlenmeyer flask
19.1 Acetic Acid, glacial. to prevent cracking. Do not use more sodium bisulfate than
19.2 Ammonium Acetate Solution (Buffer Solution)— specified since excess concentrations of salt will interfere with
Dissolve 77 g of ammonium acetate in water, add 10 mL of the EDTA titration. Heat on a hot plate starting at low heat,
glacial acetic acid and dilute with water to 1 L. then gradually raise the heat until full heat is reached. When the
spattering has stopped and light fumes of SO3 appear, heat the
19.3 Ammonium Hydroxide (1+4)—Dilute 1 volume of flask in the full flame of a Meker burner, with the flask tilted so
concentrated ammonium hydroxide (sp gr 0.90) with 4 vol- that the fusion is concentrated at one end of the flask. Swirl
umes of water. constantly until the melt is clear. Avoid prolonged heating to
19.4 Ammonium Phosphate, Dibasic Solution—Dissolve prevent precipitation of titanium dioxide. Cool and add 25 mL
150 g of (NH4)2HPO4 in 700 mL of water. Adjust pH to 5.5 of H2SO4(1+1). Heat until the mass has dissolved, and a clear
with HCl (1+1). Dilute with water to 1 L. solution results. (If silica is present, a little insoluble silica may
remain.) Cool and add 120 mL of water.
19.5 EDTA Solution (0.02 M)—Dissolve 7.45 g of disodium
ethylenediamine tetraacetate dihydrate in water and dilute to 1 20.2 Measure out 200 mL of 6.25 M NaOH solution. Add 65
L. mL of this NaOH solution to the sample solution while stirring
constantly with a magnetic stirrer. Pour the remaining NaOH
19.6 Hydrochloric Acid (1+1)—Dilute 1 volume of concen- solution into a 500-mL volumetric flask. Slowly, and with
trated hydrochloric acid (sp gr 1.19) with 1 volume of water. constant stirring, add the sample solution to the NaOH solu-
19.7 Methyl Orange Indicator Solution—Dissolve 0.1 g of tion. Police with water, cool, and dilute to volume. (If the
methyl orange in 100 mL of water, in accordance with procedure is delayed at this point for more than 2 h, transfer the
Practices E50. contents of the volumetric flask to a polyethylene bottle.)
Either centrifuge for 5 min, or allow most of the precipitate to
19.8 Sodium Bisulfate Monohydrate—(NaHSO4 · H2O). settle out, then filter the supernatant liquid through a very fine
19.9 Sodium Fluoride (NaF). filter paper until a little more than 100 mL have been collected.

19.10 Sodium Hydroxide Solution (6.25 M)—Dissolve 500 g 20.3 Place a 100-mL aliquot of the above solution in a
of sodium hydroxide (NaOH) in water and dilute to 2 L. 500-mL Erlenmeyer flask, add 1 drop of methyl orange
indicator solution and acidify with HCl (1+1) until the color
19.11 Sulfuric Acid (1+1)—To 1 volume of water add changes to red; add approximately 3 mL in excess.
slowly with stirring 1 volume of concentrated H2SO4.
20.4 Add 25 mL of EDTA solution. (If the approximate
19.12 Xylenol Orange Indicator Solution—Dissolve 0.2 g of alumina level is known, use the following mathematical
xylenol orange tetrasodium salt in 100 mL of water. Renew formula for determining the amount of EDTA to add for best
solutions weekly. results: 4 × % Al2O3 + 5 = mL of 0.02 M EDTA.) Add,

5
 D1394 − 76 (2014)
dropwise, NH4OH (1+4) until the solution color is just com- determined by volatilizing the silica in the weighed filtration
pletely changed from red to orange-yellow. Add 10 mL of residue with hydrofluoric acid.
buffer solution and 10 mL of (NH4)2 · HPO4 solution, boil for
25. Apparatus
5 min, and cool quickly to room temperature in running water.
Add 3 drops of xylenol orange indicator solution. If the 25.1 Erlenmeyer Flask, 250-mL, high silica.
solution is purple, yellow-brown, or pink, bring the pH to 25.2 Filter Paper, very fine, ashless, acid washed.
5.3–5.7 with acetic acid. If the pH is correct, a pink color
indicates insufficient EDTA; repeat with a new aliquot, starting 25.3 Platinum Crucible and Cover.
with 20.3 and using 50 mL of EDTA solution in 20.4. 25.4 Oven, controlled at 120°C.
20.5 Titrate with ZnSO4 solution to a yellow-brown or pink 25.5 Muffle Furnace, controlled at 1000 6 25°C.
end point. This titration should be performed quickly near the
26. Reagents
end point by rapidly adding 0.2-mL increments until the first
color change occurs. This color will fade in 5 or 10 s, but is the 26.1 Hydrofluoric Acid (sp gr 1.15)—Concentrated hydro-
true end point. This step is critical, and failure to observe the fluoric acid (HF).
first color change will result in an incorrect value. The fading 26.2 Sodium Bisulfate—(NaHSO4· H2O).
end point does not occur in the second titration. This first
26.3 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
titration must be greater than 8 mL of ZnSO4 solution. For
(H2SO4).
most accurate work this first titration should require 10 to 15
mL of ZnSO4 solution. 26.4 Sulfuric Acid (1+1)—To 1 volume of water add slowly
with stirring 1 volume of concentrated H2SO4.
20.6 Add 2 g of NaF, boil for 2 to 5 min, and cool in running
water. Titrate the EDTA, released from its aluminum complex 26.5 Sulfuric Acid (1+9)—To 9 volumes of water add
by the fluoride, with ZnSO4 solution to the same end point as slowly with stirring 1 volume of concentrated H2SO4.
in 20.5. 27. Procedure
21. Calculation 27.1 Transfer 1 g of pigment weighed to 0.1 mg to a
21.1 Calculate the aluminum oxide content of the pigment 250-mL high silica Erlenmeyer flask containing 10 g of
sample as follows: NaHSO4 · H2O. If an SiO2 content in excess of 5 % is expected
a 0.5-g specimen of pigment may be used to facilitate complete
A 5 ~Z 3 T!/~2 3 S! (1) fusion with 10 g of NaHSO4 · H2O.
where: 27.2 Heat over a Meker burner, frequently swirling the flask
A = percent Al2O3, until decomposition and fusion is complete and clear (except
Z = ZnSO4 solution consumed in the second titration, mL, for SiO2). Be careful of overheating at start and of spattering
T = Al2O3 per millilitre of ZnSO4 solution, g, and of the fusion.
S = specimen used, g.
27.3 Allow to cool and to the cold melt, add 25 mL of
22. Precision H2SO4(1+1), and heat very carefully and very slowly until the
fusion is dissolved. Carefully evaporate to fumes of H2SO4.
22.1 Based on interlaboratory studies the following criteria
should be used for judging the acceptability of results at the 27.4 Cool and carefully add 150 mL of water. Pour very
95 % confidence level: small amounts of water down the sides of the flask with
22.1.1 Repeatability—Two results obtained by the same frequent swirling of the contents to avoid overheating and
operator on the same sample should be considered suspect if spattering. Let cool and filter through fine ashless filter paper,
they differ by more than 0.22 % relative. using a 60° gravity funnel.
22.1.2 Reproducibility—Two results, each the mean of du- 27.5 Wash out all silica from the flask onto the filter paper
plicates obtained by operators in different laboratories should with H2SO4(1+9). Police the flask carefully.
be considered suspect if they differ by more than 0.62 % 27.6 Place the filter paper in a platinum crucible and dry in
relative. a 120°C oven. Heat the partly covered crucible over a bunsen
SILICA burner. Avoid flaming the filter paper by heating first the cover
from above and then the crucible from below. When the filter
23. Scope paper is consumed, heat at 1000°C for 30 min in a muffle
furnace. Cool in a desiccator and weigh the crucible.
23.1 This method covers the determination of silica in
titanium dioxide (TiO2) pigments. 27.7 Add 2 drops of H2SO4 (1+1) and 5 mL of HF (sp gr
1.15). Carefully evaporate to dryness, first on a low heat hot
24. Summary of Method plate to remove the HF and then over a bunsen burner to
24.1 The fusion of TiO2 pigment with sodium bisulfate remove the H2SO4. Avoid spattering, especially after removal
leaves only the silica insoluble when the melt is dissolved in of the HF.
sulfuric acid. To assure no loss of the silica the sulfuric acid is 27.8 Ignite at 1000°C for 10 min. Cool in a desiccator and
taken to fuming to dehydrate the silica. The silica content is weigh the crucible again. The difference in weight is silica.

6
 D1394 − 76 (2014)
28. Calculation to be 3.44 %. Based on this, the following criteria should be
28.1 Calculate the silica content as follows: used for judging the precision of results at the 95 % confidence
level:
SiO2 , % 5 ~ W 2 /S 3 ! 3 100 29.1.1 Repeatability—Two results obtained by the same
where: operator should be considered suspect if they differ by more
W2 = SiO2 found, g, and than 5.1 % relative.
S3 = specimen used, g. 29.1.2 Reproducibility—Two results, each the mean of
duplicates, obtained by operators in different laboratories
29. Precision should be considered suspect if they differ by more than 9.7 %
29.1 On the basis of an interlaboratory test of this test relative.
method in which six laboratories tested, in duplicate, five
samples of titanium dioxide ranging in silica content from 1.5 30. Keywords
to 8.2 %, within-laboratory standard deviation was found to be 30.1 aluminum oxide; aluminum reduction; chemical analy-
1.79 % and between-laboratories standard deviation was found sis; Jones Reductor; titanium pigment

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