SD-129 ARTICLE 24 — LIQUID PENETRANT STANDARDS SD-129

STANDARD TEST METHOD FOR SULFUR

IN PETROLEUM PRODUCTS
(GENERAL BOMB METHOD)1
SD-129

(Identical with ASTM D 129-95)

(This specification is available in SI Units only.)

1. Scope 2. Referenced Documents

1.1 This test method covers the determination of 2.1 ASTM Standards:
sulfur in petroleum products, including lubricating oils D 1193 Specification for Reagent Water2
containing additives, additive concentrates, and lubricat- D 1552 Test Method for Sulfur in Petroleum Products
ing greases that cannot be burned completely in a wick (High-Temperature Method)3
lamp. The test method is applicable to any petroleum E 144 Practice for Safe Use of Oxygen Combustion
product sufficiently low in volatility that it can be Bombs4
weighed accurately in an open sample boat and con-
taining at least 0.1% sulfur.
NOTE 1 — This test method is not applicable to samples containing
elements that give residues, other than barium sulfate, which are
insoluble in dilute hydrochloric acid and would interfere in the
precipitation step. These interfering elements include iron, aluminum,
calcium, silicon, and lead which are sometimes present in greases, 3. Summary of Test Method
lube oil additives, or additive oils. Other acid insoluble materials
that interfere are silica, molybdenum disulfide, asbestos, mica, etc. 3.1 The sample is oxidized by combustion in a bomb
The test method is not applicable to used oils containing wear metals, containing oxygen under pressure. The sulfur, as sulfate
and lead or silicates from contamination. Samples that are excluded in the bomb washings, is determined gravimetrically
can be analyzed by Test Method D 1552.
as barium sulfate.
1.2 This standard does not purport to address all
of the safety concerns, if any, associated with its use. 3.2 Warning — Strict adherence to all of the
It is the responsibility of the user of this standard to provisions prescribed hereafter ensures against explo-
establish appropriate safety and health practices and sive rupture of the bomb, or a blow-out, provided the
determine the applicability of regulatory limitations bomb is of proper design and construction and in good
prior to use. See 3.2 for specific precautionary directions mechanical condition. It is desirable, however, that the
incorporated in the test method. bomb be enclosed in a shield of steel plate at least
13 mm thick, or equivalent protection be provided
1 This test method is under the jurisdiction of ASTM Committee against unforseeable contingencies.
D-2 on Petroleum Products and Lubricants and is the direct responsi-
bility of Subcommittee D02.03 on Elemental Analysis.
Current edition approved Aug. 15, 1995. Published October 1995.
Originally published as D 129-22. Last previous edition D 129-91. 2 Annual Book of ASTM Standards, Vol 11.01.
This test method was adopted as a joint ASTM-IP standard in 1964. 3 Annual
In the IP, this test method is under the jurisdiction of the Book of ASTM Standards, Vol 05.01.
Standardization Committee. 4 Annual Book of ASTM Standards, Vol 14.02.

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SD-129 1998 SECTION V SD-129

4. Apparatus and Materials 5.2 Purity of Water — Unless otherwise indicated,

references to water shall mean water as defined by
4.1 Bomb,5,6having a capacity of not less than 300
Type II or III of Specification D 1193.
mL, so constructed that it will not leak during the test
and that quantitative recovery of the liquids from the 5.3 Barium Chloride Solution (85 g/litre) — Dissolve
bomb may be achieved readily. The inner surface of 100 g of barium chloride dihydrate (BaCl2 · 2H2O) in
the bomb may be made of stainless steel or any other distilled water and dilute to 1 litre.
material that will not be affected by the combustion
5.4 Bromine Water (saturated).
process or products. Materials used in the bomb assem-
bly, such as the head gasket and lead-wire insulation, 5.5 Hydrochloric Acid (sp gr 1.19) — Concentrated
shall be resistant to heat and chemical action, and shall hydrochloric acid (HCl).
not undergo any reaction that will affect the sulfur
5.6 Oxygen, free of combustible material and sulfur
content of the liquid in the bomb.
compounds, available at a pressure of 41 kgf/cm2
4.2 Sample Cup, platinum, 24 mm in outside diameter (40 atm).
at the bottom, 27 mm in outside diameter at the top, 5.7 Sodium Carbonate Solution (50 g/litre) — Dis-
12 mm in height outside, and weighing 10 to 11 g. solve 135 g of sodium carbonate decahydrate (Na2CO3
· 10H2O) or its equivalent weight in distilled water
4.3 Firing Wire, platinum, No. 26 B & S gage, 0.41
and dilute to 1 litre.
mm (16 thou), 27 SWG, or equivalent.
5.8 White Oil, USP, or Liquid Paraffin, BP, or
NOTE 2: Caution — The switch in the ignition circuit shall be of equivalent.
a type which remains open, except when held in closed position by
the operator.

4.4 Ignition Circuit, capable of supplying sufficient 6. Procedure

current to ignite the cotton wicking or nylon thread 6.1 Preparation of Bomb and Sample — Cut a piece
without melting the wire. The current shall be drawn of firing wire 100 mm in length. Coil the middle
from a step-down transformer or from a suitable battery. section (about 20 mm) and attach the free ends to the
4.5 Cotton Wicking or Nylon Sewing Thread, white. terminals. Arrange the coil so that it will be above
and to one side of the sample cup. Insert between two
loops of the coil a wisp of cotton or nylon thread of
such length that one end will extend into the sample
cup. Place about 5 mL of Na2CO3 solution in the bomb
5. Reagents and Materials
(Note 3) and rotate the bomb in such a manner that
5.1 Purity of Reagents — Reagent grade chemicals the interior surface is moistened by the solution. Intro-
shall be used in all tests. Unless otherwise indicated, duce into the sample cup the quantities of sample and
it is intended that all reagents shall conform to the white oil (Notes 5 and 6) specified in the following
specifications of the Committee on Analytical Reagents table, weighing the sample to the nearest 0.2 mg (when
of the American Chemical Society, where such specifi- white oil is used, stir the mixture with a short length
cations are available.7 Other grades may be used, of quartz rod and allow the rod to remain in the sample
provided it is first ascertained that the reagent is of cup during the combustion).
sufficiently high purity to permit its use without less-
NOTE 3 — After repeated use of the bomb for sulfur determinations,
ening the accuracy of the determination. a film may be noticed on the inner surface. This dullness can be
removed by periodic polishing of the bomb. A satisfactory method
for doing this is to rotate the bomb in a lathe at about 300 rpm
5 Criteria for judging the acceptability of new and used oxygen and polish the inside surface with emery polishing papers Grit No.
combustion bombs are described in Practice E 144. 2⁄ , or equivalent paper,8 coated with a light machine oil to prevent
0
6 A bomb conforming to the test specifications in IP Standard IP 12 cutting, and then with a paste of grit-free chromic oxide9 and water.
is suitable. This procedure will remove all but very deep pits and put a high
7 Reagent
polish on the surface. Before the bomb is used it shall be washed
Chemicals, American Chemical Society Specifications,
American Chemical Society, Washington, DC. For suggestions on
the testing of reagents not listed by the American Chemical Society, 8 Emery
see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Polishing Paper Grit No. 2⁄0 can be purchased from Norton
Dorset, U.K., and the United States Pharmacopeia and National Co., Troy, N.Y.
Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rock- 9 Chromic oxide may be purchased from J. T. Baker & Co., Phil-

ville, MD. lipsburg, N.J.

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SD-129 ARTICLE 24 — LIQUID PENETRANT STANDARDS SD-129

with soap and water to remove oil or paste left from the polishing thoroughly clean the bomb before again putting it in
operation.
use (Note 3).
NOTE 4: Caution — Do not use more than 1.0 g total of sample
and white oil or other low sulfur combustible material or more than NOTE 8: Caution — Do not go near the bomb until at least 20 s
0.8 g if the IP 12 bomb is used. after firing.

Weight of Weight of 6.4 Collection of Sulfur Solution — Rinse the interior

Sulfur Content, % Sample, g White Oil, g of the bomb, the oil cup, and the inner surface of the
5 or under 0.6 to 0.8 0.0 bomb cover with a fine jet of water, and collect the
Over 5 0.3 to 0.4 0.3 to 0.4 washings in a 600-mL beaker having a mark to indicate
NOTE 5 — Use of sample weights containing over 20 mg of 75 mL. Remove any precipitate in the bomb by means
chlorine may cause corrosion of the bomb. To avoid this, it is of a rubber policeman. Wash the base of the terminals
recommended that for samples containing over 2% chlorine, the until the washings are neutral to the indicator methyl
sample weight be based on the chlorine content as given in the
following table: red. Add 10 mL of saturated bromine water to the
washings in the beaker. (The volume of the washings
Weight of Weight of is normally in excess of 300 mL.) Place the sample
Chlorine Content, % Sample, g White Oil, g cup in a 50-mL beaker. Add 5 mL of saturated bromine
2 to 5 0.4 0.4 water, 2 mL of HCl, and enough water just to cover
Over 5 to 10 0.2 0.6 the cup. Heat the contents of the beaker to just below
Over 10 to 20 0.1 0.7
Over 20 to 50 0.05 0.7
its boiling point for 3 or 4 min and add to the beaker
containing the bomb washings. Wash the sample cup
NOTE 6 — If the sample is not readily miscible with white oil, and the 50-mL beaker thoroughly with water. Remove
some other low sulfur combustible diluent may be substituted. any precipitate in the cup by means of a rubber
However, the combined weight of sample and nonvolatile diluent
shall not exceed 1.0 g or more than 0.8 g if the IP 12 bomb is used. policeman. Add the washings from the cup and the
50-mL beaker, and the precipitate, if any, to the bomb
6.2 Addition of Oxygen — Place the sample cup in washings in the 600-mL beaker. Do not filter any of
position and arrange the cotton wisp or nylon thread the washings, since filtering would remove any sulfur
so that the end dips into the sample. Assemble the present as insoluble material.
bomb and tighten the cover securely. (Caution — See
Note 7.) Admit oxygen slowly (to avoid blowing the 6.5 Determination of Sulfur — Evaporate the com-
oil from the cup) until a pressure is reached as indicated bined washings to 200 mL on a hot plate or other
in the following table: source of heat. Adjust the heat to maintain slow boiling
of the solution and add 10 mL of the BaCl2 solution,
Capacity of Minimum Gage Maximum Gage either in a fine stream or dropwise. Stir the solution
Bomb, ml Pressure,A kgf/cm2 (atm) Pressure,A kgf/cm2 (atm)
during the addition and for 2 min thereafter. Cover
300 to 350 39 (38) 41 (40)
the beaker with a fluted watch glass and continue
350 to 400 36 (35) 38 (37)
400 to 450 31 (30) 33 (32) boiling slowly until the solution has evaporated to a
450 to 500 28 (27) 30 (29) volume approximately 75 mL as indicated by a mark
on the beaker. Remove the beaker from the hot plate
A
(or other source of heat) and allow it to cool for 1
The minimum pressures are specified to provide sufficient oxygen
for complete combustion and the maximum pressures represent a hr before filtering. Filter the supernatant liquid through
safety requirement. an ashless, quantitative filter paper (Note 9). Wash the
precipitate with water, first by decantation and then on
NOTE 7: Caution — Do not add oxygen or ignite the sample if
the bomb has been jarred, dropped, or tilted.
the filter, until free from chloride. Transfer the paper
and precipitate to a weighed crucible and dry (Note
6.3 Combustion — Immerse the bomb in a cold 10) at a low heat until the moisture has evaporated.
distilled-water bath. Connect the terminals to the open Char the paper completely without igniting it, and
electrical circuit. Close the circuit to ignite the sample. finally ignite at a bright red heat until the residue is
(Caution — See Note 8.) Remove the bomb from the white in color. After ignition is complete, allow the
bath after immersion for at least 10 min. Release the crucible to cool at room temperature, and weigh.
pressure at a slow, uniform rate such that the operation
requires not less than 1 min. Open the bomb and NOTE 9 — A weighed porcelain filter crucible (Selas type) of 5
to 9-mm porosity may be used in place of the filter paper. In this
examine the contents. If traces of unburned oil or case the precipitate is washed free of chloride and then dried to
sooty deposits are found, discard the determination and constant weight at 500 6 25°C.

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SD-129 1998 SECTION V SD-129

NOTE 10 — A satisfactory means of drying, charring, and igniting same apparatus under constant operating conditions on
the paper and precipitate is to place the crucible containing the wet
filter paper in a cold electric muffle furnace and to turn on the identical test material, would in the long run, in the
current. Drying, charring, and ignition usually will occur at the normal and correct operation of the test method, exceed
desired rate. the following values only in one case in twenty.
6.6 Blank — Make a blank determination whenever 9.1.2 Reproducibility — The difference between
new reagents, white oil, or other low-sulfur combustible two single and independent results obtained by different
material are used. When running a blank on white oil, operators working in different laboratories on identical
use 0.3 to 0.4 g and follow the normal procedure. test material would, in the long run, in the normal and
correct operation of the test method, exceed the follow-
ing values only in one case in twenty:
7. Calculation Sulfur,
7.1 Calculate the sulfur content of the sample as Weight % Repeatability Reproducibility
follows: 0.1 to 0.5 0.04 0.05
0.5 to 1.0 0.06 0.09
1.0 to 1.5 0.08 0.15
Sulfur, weight percent p (P − B)13.73/W 1.5 to 2.0 0.12 0.25
2.0 to 5.0 0.18 0.27
where:
NOTE 11 — The precision shown in the above table does not apply
Pp grams of BaSO4 obtained from sample, to samples containing over 2% chlorine because an added restriction
Bp grams of BaSO4 obtained from blank, and on the amount of sample which can be ignited is imposed.
Wp grams of sample used.
NOTE 12 — This test method has been cooperatively tested only
in the range of 0.1 to 5.0% sulfur.

NOTE 13 — The following information on the precision of this

8. Report method has been developed by the Institute of Petroleum (London):
(a) Results of duplicate tests should not differ by more than the
8.1 Report the results of the test to the nearest following amounts:
0.01%.
Repeatability Reproducibility
0.016 x + 0.06 0.037 x + 0.13

9. Precision and Bias10 where x is the mean of duplicate test results.

(b) These precision values were obtained in 1960 by statistical
9.1 The precision of this test is not known to have examination of interlaboratory test results.12 No limits have been
been obtained in accordance with currently accepted established for additive concentrates.
guidelines (for example in Committee D-2 Research
9.2 Bias — Results obtained in one laboratory by
Report, “Manual on Determining Precision Data for
Test Method D 129 on NIST Standard Reference Mate-
ASTM Methods on Petroleum Products and Lubri-
rial Nos. 1620A, 1621C, and 1662B were found to be
cants”).11 0.05 mass % higher than the accepted reference values.
9.1.1 Repeatability — The difference between two
test results, obtained by the same operator with the
10. Keywords
10 Supportingdata is available from ASTM Headquarters. Request 10.1 bomb; sulfur
RR:D02-1278.
11 Annual Book of ASTM Standards, Vol 05.03. 12 IP Standards for Petroleum and Its Products, Part 1, Appendix E.

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