Designation: D 612 – 88 (Reapproved 1999) An American National Standard

AMERICAN SOCIETY FOR TESTING AND MATERIALS

100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Method for

Carbonizable Substances in Paraffin Wax1
This standard is issued under the fixed designation D 612; 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.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope fitted with a well-ground glass stopper, the stopper and the
1.1 This test method covers determination of carbonizable tube bearing identical and indestructible numbers. The tube
substances in paraffin wax. The test method is applicable to shall be 140 6 2 mm in length and between 14.5 and 15.0
paraffin wax for pharmaceutical use, as defined by the U.S. mm in outside diameter, and shall be calibrated at the 5 6 0.2-
National Formulary, with a melting point as determined in mL and
accordance with Test Method D 87, between 117 and 149°F 10 6 0.2-mL liquid levels. The capacity of the tube with
(47 and 65°C). stopper inserted shall be between 13.6 and 15.6 mL. A
1.2 The values stated in inch-pound units are to be regarded rolled edge may be provided for suspending the tube on the
as the standard. cover of the water bath.
1.3 This standard does not purport to address all of the 5.2 Water Bath, suitable for immersing the test tube
safety concerns, if any, associated with its use. It is the above the 10-mL line and equipped to maintain a temperature
responsibility of the user of this standard to establish appro- of 158 6 1.0°F (70 6 0.5°C). The bath shall be provided with
priate safety and health practices and determine the applica- a cover of any suitable material, with holes approximately
bility of regulatory limitations prior to use. Specific precau- 16 mm in diameter through which the test tubes may be
tionary statements are given in Notes 1-5 and Annex A1. suspended.
5.3 Color Comparator, of a suitable type for observing the
2. Referenced Documents color of the acid layer in comparison with the reference
2.1 ASTM Standards: standard color solution. The size and shape of the comparator
D 87 Test Method for Melting Point of Petroleum Wax are optional, but the size and shape of the apertures shall
(Cooling Curve)2 conform to the dimensions prescribed in Fig. 1.
D 1193 Specification for Reagent Water3
6. Reagents
3. Summary of Test Method 6.1 Purity of Reagents—Reagent grade chemicals shall be
3.1 Five millilitres of melted wax are treated with 5 mL of used in all tests. Unless otherwise indicated, it is intended that
concentrated, nitrogen-free sulfuric acid at 158°F (70°C). The all reagents shall conform to the specifications of the Commit-
color of the acid layer is compared with that of a colorimetric tee on Analytical Reagents of the American Chemical Society,
reference standard. If the color is not darker than the standard, where such specifications are available.5 Other grades may be
the wax is reported as passing the test. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
4. Significance and Use accuracy of the determination.
4.1 This test method is a means for ascertaining whether 6.2 Purity of Water—Unless otherwise indicated,
pharmaceutical paraffin wax conforms to the standards for references to water shall be understood to mean distilled
quality prescribed by the U.S. National Formulary. water, such as reagent water corresponding to Specification D
1193, Type III, or water of equal purity.
5. Apparatus 6.3 Cobaltous Chloride Solution (0.5 N)—Dissolve about
5.1 Test Tube, as shown in Fig. 1, of heat-resistant glass4 65 g of cobaltous chloride (CoCl2·6H2O) in enough diluted
hydrochloric acid (HCl, 1 + 39) (Warning—See Note 1.) to
make 1000 mL of solution. Transfer exactly 5 mL of this
1
This test method is under the jurisdiction of ASTM Committee D-2 on solution to a flask; add 15 mL of sodium hydroxide (NaOH,
Petroleum Products and Lubricants and is the direct responsibility of
Subcommittee D02.10 on Petroleum Wax. 1 + 5) (Warning—See Note 2.), and 5 mL of hydrogen
Current edition approved Oct. 31, 1988. Published December 1988. Originally
published as D 612 – 41. Last previous edition D 612 – 45 (1983)e1.
5
2
Annual Book of ASTM Standards, Vol 05.01. Reagent Chemicals, American Chemical Society Specifications, American
3
Annual Book of ASTM Standards, Vol 11.01. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
4
Borosilicate glass has been found satisfactory for this purpose. listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U. K., and the United States Pharmacopeia
and National Formulary, U. S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.

1
 D 612

FIG. 1 Color Comparator for Carbonizable Substances in Liquid Petrolatum

peroxide. Boil for 10 min, cool, and add 2 g of potassium (Warning—See Note 1.) (1 + 39) to make 1000 mL of
iodide (KI) and 20 mL of sulfuric acid (H 2SO4, 1 + 4)
solution. Transfer exactly 10 mL of the solution to a flask, add
(Warning—See Note 3.). When the precipitate has dissolved,
5 mL of HCl (sp gr 1.19), 25 mL of water, and about 3 g of
titrate the liberated iodine with 0.1 N sodium thiosulfate
KI. Stopper and allow the mixture to stand for 5 min. Dilute
(Na2S2O3) solution using starch solution as an indicator. Each
the mixture with 50 mL of water, and titrate the liberated
millilitre of 0.1 N Na2S2O3 solution consumed is equivalent to iodine with 0.1 N Na2S2O3 solution, using starch solution as
0.023799 g of CoCl2·6H2O. Adjust the final volume of CoCl2 an indicator. Each millilitre of 0.1 N Na2S2O3 solution is
solution by the addition of diluted HCl (1 + 39) so that 1 mL equiva- lent to 0.02703 g of FeCl3·6H2O. Adjust the final
contains 59.5 mg of CoCl2·6H2O. volume of the FeCl3 solution by the addition of diluted HCl (1
NOTE 1—Warning: Hydrochloric acid (concentrated) causes burns, + 39) so that 1 mL contains 45.0 mg of FeCl3·6H2O.
vapor extremely irritating. See A1.2. 6.7 Sulfuric Acid (94.7 6 0.2 %)—The sulfuric acid
NOTE 2—Warning: Sodium hydroxide, corrosive, can cause severe (H2SO4) (Warning—See Note 3.) shall be nitrogen-free when
burns or blindness. Evolution of heat produces a violent reaction or
eruption upon too rapid a mixture with water. See A1.4.
analyzed in accordance with the following procedure: Dilute a
NOTE 3—Warning: Sulfuric acid (concentrated) causes burns, vapor small amount of the acid with an equal volume of water and
irritating, strong oxidizer. See A1.3. superimpose 10 mL of the cooled liquid upon diphenylamine
solution (1 g of diphenylamine in 100 mL of concentrated
6.4 Colorimetric Reference Standard Solution—Prepare a
H2SO4). A blue color should not appear at the zone of contact
reference standard pale amber solution for color comparison
within 1 h. This test detects as little as 0.0002 % NO3.
by mixing together 1.5 parts of CoCl 2 solution, 3.0 parts of
FeCl3 solution, and 0.5 parts of CuSO4 solution. Measure 5 7. Procedure
mL of this mixture into a test tube as specified in 3.1. This
pale amber reference standard shall then be overlaid with 5 7.1 Clean a test tube with cleaning solution 6 (Warning—
mL of white mineral oil. See Note 5.), rinse with tap water followed by distilled water,
6.5 Cupric Sulfate Solution (0.5 N)—Dissolve about 65 g and dry in an oven at 105° C for 1 h.
of cupric sulfate (CuSO4·5H2O) in enough diluted HCl NOTE 5—Warning: Nochromix6 is corrosive. See A1.1.
(1 + 39) (Warning—See Note 1.) to make 1000 mL of 7.2 Melt a representative portion of the sample on a
solution. Transfer exactly 10 mL of this solution to a flask, steam bath or hot water bath. Fill the test tube to the 5-mL
add 50 mL of water, 4 mL of acetic acid (Warning—See Note mark with H2SO4 (94.7 6 0.2 %). Then add the melted wax,
4.), and3g of KI. Allow the mixture to stand for 5 min, then at a temperature not more than 10°F (5.5°C) above its
titrate the liberated iodine with 0.1 N Na2S2O3 solution, using melting point, to the 10-mL mark, insert the stopper loosely,
starch solution as an indicator. Each millilitre of 0.1 N and place the test tube in position in the water bath at 158 6
Na2S2O3 solution is equivalent to 0.02497 g of CuSO4·5H2O. 1.0°F (706 0.5°C).
Adjust the final volume of CuSO4 solution by the addition of 7.3 After the test tube has been in the water bath for 5 min,
diluted HCl (1 + 39) so that 1 mL contains 62.4 mg of loosen the stopper sufficiently to release any pressure and
CuSO4·5H2O. reinsert, remove the test tube from the bath quickly, hold with
NOTE 4—Warning: Acetic acid (glacial) is corrosive, combustible,
vapor irritating. See A1.5.
6
A solution of sulfuric acid and Nochromix a trademark of Godax Laboratories,
6.6 Ferric Chloride Solution (0.5N)—Dissolve about 55 g 480 Canal St., New York, NY 10013, has been found suitable for this purpose.
of ferric chloride (FeCl3·6H2O) in enough diluted HCl
2
 D 612
a finger over the stopper, and give three vigorous, vertical
shakes over an amplitude of about 5 in. (127 mm), shaking the whenthe acid layer is not darker than the reference standard
test tube quickly and at a rate corresponding to 5 shakes/s. colorimetric solution or, if completely emulsified, when the
Repeat every minute. Do not keep the test tube out of the bath emulsion is not darker than a similar emulsion produced by
longer than 3 s for each shaking period. vigorously shaking the reference standard colorimetric
solution with white mineral oil in equal proportions.
NOTE 6—A shaking machine may be used provided that the results
obtained agree with those obtained by the prescribed manual agitation. 8.2 If the acid layer is darker than the reference standard
colorimetric solution, or if the emulsified paraffin wax and
7.4 At the end of 10 min from the time the test tube was
first placed in the bath, remove the test tube, immediately acid are darker than a similar emulsion of the reference
place it in the color comparator, and compare the acid layer standard colorimetric solution and white mineral oil in equal
with 5 mL of the standard colorimetric solution and 5 mL of propor- tions, the paraffin wax shall be reported as not passing
white mineral oil in a test tube that has been shaken vigorously the test.
for 10 s and allowed to stand just long enough for the contents
to separate into two layers. 9. Precision and Bias
7.5 In some cases the acid remains trapped with the wax as 9.1 No statement is made about either the precision or the
an emulsion, and no lower layer is obtained to compare with bias of this test method for measuring carbonizable substances
the standard colorimetric solution. When this occurs, compare in white refined waxes since the result only states whether
the emulsion with the standard colorimetric solution and white there is conformance to the criteria for success specified in the
mineral oil shaken vigorously to give a similar emulsion, and procedure.
without waiting for the two liquids to separate.
8. Interpretation of Results 10. Keywords
8.1 Paraffin wax shall be reported as passing the test 10.1 carbonizable substances; petroleum wax; wax

ANNEX

(Mandatory Information)

A1. PRECAUTIONARY STATEMENTS

A1.1 Glass Cleaning Solution (Nochromix6 )

Keep in tightly closed container in approved acid storage
Warning—Corrosive, potent, clear liquid. Solution is a cabinet.
mixture of sulfuric acid (concentrated) and Nochromix, 6 a Keep cool.
white crystalline, inorganic oxidizer. Loosen closure carefully when opening.
Handle carefully with special highly acid resistant gloves
Use with adequate ventilation.
only.
Do not close container airtight. Do not allow water to get into container because of violent
reaction.
A1.2 Hydrochloric Acid (Concentrated) Warning— Keep container closed when not in use.
Poison. Corrosive. May be fatal if swallowed. Use protective clothing and goggles when handling.
Liquid and vapor cause severe burns. Harmful if inhaled. Wash thoroughly after handling.
Do not get in eyes, on skin, or on clothing.
Do not breathe vapor, spray, or mist. A1.4 Sodium Hydroxide
Dilute by addition of acid to water.
Before using, secure information on procedures and protec-
Keep in tightly closed container in approved acid storage
tive measures for safe handling.
cabinet.
Keep cool. Do not get in eyes, on skin, or on clothing.
Loosen closure carefully when opening. Avoid breathing dusts or mists.
Use with adequate ventilation. Do not take internally.
Keep container closed when not in use. When handling, use chemical safety goggles or face shield,
Use protective clothing and goggles when handling. protective gloves, boots, and clothing.
Wash thoroughly after handling. When mixing with water, add slowly to surface of solution
A1.3 Sulfuric Acid (Concentrated) to avoid violent spattering. In the preparation of solutions do
not use hot water, limit temperature rise, with agitation, to
Do not get in eyes, on skin or on clothing. 10°C/min or limit solution temperature to a maximum of
Do not breathe vapor, spray, or mist. 90°C. No single addition should cause a concentration
Dilute by addition of acid to water. increase greater than 5 %.

3
 D 612
A1.5 Acetic Acid (Glacial)
Keep cool.
Do not get in eyes, on skin, or on clothing.
Do not breathe vapor, spray or mist. Loosen closure carefully when opening.
Dilute by addition of acid to water. Use with adequate ventilation.
Keep away from heat and open flame. Keep container closed when not in use.
Keep in tightly closed container in approved acid storage Use protective clothing and goggles when handling.
cabinet.
Wash thoroughly after handling.

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in
connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity
of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years
and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional
standards and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428.