NOTICE: This standard has either been superseded and replaced by a new version or discontinued.

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Designation: D 3228 – 96 An American National Standard

Standard Test Method for

Total Nitrogen In Lubricating Oils and Fuel Oils By Modified
Kjeldahl Method1
This standard is issued under the fixed designation D 3228; 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 sulfate. After digestion, sodium sulfide is added to precipitate

1.1 This test method is applicable for the determination of the mercury, and the mixture is made alkaline with caustic.
nitrogen in lubricating oils when present in the concentration Nitrogen, now in the form of ammonia, is distilled into a boric
from 0.03 to 0.10 mass %, and for the determination of acid solution. The ammonia is titrated with standard sulfuric
nitrogen in fuel oils when present in the concentration from acid using methyl purple as an indicator.
0.015 to 2.0 mass %. This test method is also applicable to the 4. Significance and Use
analysis of additive concentrates and additive packages.
4.1 The concentration of nitrogen is a measure of the
NOTE 1—This test method may not be applicable to certain materials presence of nitrogen-containing additives. Knowledge of its
containing N–O or N–N linkage. However, the samples used in the
concentration can be used to predict performance.
cooperative program to establish the precision of the test method were
compounded with currently available ashless additives containing nitro- 5. Apparatus
gen. Complete recovery of the nitrogen present in these additives was
obtained.
iTeh Standards
1.2 The values given in acceptable SI units are to be
5.1 Buret, 50-mL, graduated in 0.1-mL subdivisions, one for
each titrant. Other size burettes may also be used.
5.2 Flask, Erlenmeyer, 300-mL. Other sizes are also accept-
regarded as the standard.
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1.3 This standard does not purport to address all of the
able.
5.3 Heater, electrical or gas.
safety concerns, if any, associated with its use. It is the
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responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
5.4 Kjeldahl Distillation Apparatus.
NOTE 2—Commercially available semi-automatic Kjeldahl apparatus
bility of regulatory limitations prior to use. For specific are acceptable. In such cases manufacturer prescribed sizes of burettes and
precautionary statements, see Note 2, Note 3, Note 5, and ASTM
Note D3228-96
flasks may be used.
6. 5.5 Kjeldahl Flask, at least 500-mL volume.
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2. Referenced Documents 6. Reagents
2.1 ASTM Standards: 6.1 Purity of Reagents—Reagent grade chemicals shall be
D 1193 Specification for Reagent Water2 used in all tests. Unless otherwise indicated, it is intended that
D 4057 Practice for Manual Sampling of Petroleum and all reagents shall conform to the specifications of the Commit-
Petroleum Products3 tee on Analytical Reagents of the American Chemical Society,
E 200 Practice for Preparation, Standardization, and Stor- where such specifications are available.5 Other grades may be
age of Standard and Reagent Solutions for Chemical used, provided it is first ascertained that the reagent is of
Analysis4 sufficiently high purity to permit its use without lessening the
accuracy of the determination.
3. Summary of Test Method 6.2 Purity of Water—Unless otherwise indicated, references
3.1 The sample is digested in a mixture of concentrated to water shall be understood to mean reagent water as defined
sulfuric acid, potassium sulfate, mercuric oxide, and copper by Types II and III of Specification D 1193.
6.3 Boric Acid Solution (40 g/L)—Dissolve 40 g of boric
1
This test method is under the jurisdiction of ASTM Committee D-2 on
5
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee Reagent Chemicals, American Chemical Society Specifications, American
D02.03 on Elemental Analysis. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Apr. 10, 1996. Published June 1996. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 3228 – 73. Last previous edition D 3228 – 95. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 05.02. MD. Other commercial catalyst reagent mixtures that provide equivalent results,
4
Annual Book of ASTM Standards, Vol 15.05. such as copper and titanium compounds, are also acceptable.

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1
 D 3228
acid (H3BO3) in 1 L of boiling water. 8.3 Warm the contents of the Kjeldahl flask on the digestion
6.4 Catalyst Reagent6—For each test carefully weigh and rack and repeat the swirling. Apply low heat until the frothing
mix 9.9 g of potassium sulfate (K 2SO4), 0.41 g of mercuric has stopped. Samples that do not froth or char shall be
oxide (HgO), and 0.08 g of copper sulfate (CuSO4). subjected to a 20-min low-heating period. Careful periodic
6.5 Methyl Purple Indicator Solution7—Aqueous solution swirling of the solution in the Kjeldahl flask shall also be made.
containing approximately 0.1 % active constituent (not methyl Gradually apply intermediate heat to raise the temperature of
violet). Other appropriate indicator solutions may also be used. the solution to boiling.
6.6 Sodium Hydroxide Solution (1000 g/L)—Dissolve 1000 8.4 Maintain a minimum volume of 15 mL of liquid in the
g of sodium hydroxide (NaOH) in 1 L of water. (Warning— Kjeldahl flask during the digestion period. Add volumes of 5 to
See Note 2.) 15 mL of H2SO4(rel dens 1.84) when the volume does not
conform to this condition. Use the H2SO4 to wash down the
NOTE 3—Warning: Causes burns. Poison.
neck of the Kjeldahl flask after the contents have been allowed
6.7 Sodium Sulfide Solution (40 g/L)—Dissolve 40 g of to cool sufficiently so that sulfur trioxide (SO3) fumes have
sodium sulfide (Na2S) in warm water 194°F (90°C); cool and subsided. The volume of H2SO4(rel dens 1.84) added will
dilute to 1 L. depend upon the carbonaceous material in the Kjeldahl flask.
6.8 Sucrose (NIST)—Primary standard grade. After all of the carbonaceous material has been digested and
6.9 Sulfuric Acid (rel dens 1.84)—Concentrated sulfuric the solution has cleared, continue the digestion for two more
acid (H2SO4). (Warning—See Note 3.) hours at rapid rate of boiling. The total volume of liquid
NOTE 4—Warning: Causes severe burns. Strong oxidizer. remaining in the Kjeldahl flask after digestion approximates
the volume in the Kjeldahl flask for the blank.
6.10 Sulfuric Acid, Standard (0.05 M)—Slowly add 3 mL
of concentrated sulfuric acid (H2SO4, rel dens 1.84) to 500 mL NOTE 6—For some samples, a two hour digestion period may be
of water in a suitable size beaker. Mix the acid and water; allow unnecessary, if the solution has completely cleared.
it to cool and transfer to a 1-L volumetric flask. Dilute to the 8.5 Turn off the heat, but allow the Kjeldahl flask to remain
mark with water; mix well. Standardize sulfuric acid to the in the fume duct or hood until the evolution of SO3 fumes has
iTeh Standards
nearest 0.0005 mol/L against 0.1 mol/L NaOH solution using
phenolphthalein indicator. Standardize the NaOH solution
subsided. Remove the Kjeldahl flask from the rack and cool to
approximately room temperature.

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against primary standard grade potassium hydrogen phthalate 8.6 Place a 300-mL receiving flask containing 25 mL of
(HOOCC6H4COOK). Use the procedure outlined in Sections H3BO3 solution and 5 drops of methyl purple indicator solution
14 to 19 of Practice E 200. under the condenser with the delivery tube tip extending to the
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NOTE 5—Commercially available pre-standardized H2SO4 and NaOH
solutions may be used.
bottom of the receiving flask.
8.7 Measure approximately 275 mL of water and add a
portion of this water to the Kjeldahl flask and swirl the contents
6.11 Sulfuric Acid (0.005 M)—Prepare by ten-fold dilution
until the salt cake has dissolved (Note 4). Add the remainder of
ASTM D3228-96
of the standard 0.05 M sulfuric acid prepared and standardized
the water and cool the contents of the Kjeldahl flask to room
in 6.10. https://standards.iteh.ai/catalog/standards/sist/498fd4c0-cc79-4cc0-aa93-9a39e7070822/astm-d3228-96
temperature.
7. Sampling NOTE 7—It can be necessary to warm the contents in the Kjeldahl flask
7.1 Take the sample in accordance with the instructions in to facilitate solution of the salt cake.
Practice D 4057. 8.8 Add 25 mL of Na2S solution to the cooled contents of
7.2 Ensure that the sample is thoroughly representative of the Kjeldahl flask, to precipitate the mercury, and swirl to mix.
the material to be tested and that the portion of the sample used
for test is thoroughly representative of the whole sample. NOTE 8—Precaution: In addition to other precautions, when the Na2S
solution is added to the cooled digestion flask, considerable hydrogen
8. Procedure sulfide is evolved. Therefore, conduct 8.8 and 8.9 in a hood with a suitable
draft.
8.1 Transfer 1.0 to 1.5 g of sample, weighed to the nearest NOTE 9—Precaution—In addition to other precautions, care must be
0.1 mg, into a Kjeldahl flask. Avoid contact of the sample with exercised in the disposal of the mercuric sulfide. Laboratories processing
the neck of the Kjeldahl flask. Add the catalyst reagent mixture large volumes of Kjeldahl nitrogen determinations should consider the use
to the Kjeldahl flask. Add two or three beads to prevent of a recovery trap for mercury.
bumping. 8.9 Place the Kjeldahl flask in a slurry of ice and water. Cool
8.2 Wash down the neck of the Kjeldahl flask with 20 mL of the contents in the Kjeldahl flask to approximately 40°F
H2SO4(rel dens 1.84). Swirl the contents of the Kjeldahl flask (4.5°C). Slowly add 75 mL of NaOH solution (1000 g/L) down
to facilitate the mixing of the sample, catalyst reagent, and the inclined neck of the Kjeldahl flask, without agitation, to
H2SO4. form two layers.
8.9.1 Carefully remove the Kjeldahl flask from the ice bath
6
Commercially prepared catalyst reagent mixture, brand name Kel-Pak #1 may so that mixing of the layers does not occur. Carefully place the
be used and is available from Matheson Scientific, 1850 Greenleaf Ave., Elk Grove Kjeldahl flask on the Kjeldahl distillation rack.
Village, IL 60007.
7
Fleisher Methyl Purple Indicator, U.S. Patent No. 241669, may be obtained
8.9.2 Immediately connect the Kjeldahl flask to the distilla-
from Harry Fleisher Chemical Co., Benjamin Franklin Station, Washington, DC tion apparatus and mix the contents of the Kjeldahl flask
20004, or from any chemical supply company handling Fleisher Methyl Purple. thoroughly by swirling. The digestion flask must be connected