An American National Standard

Designation: D 2274 – 03a

Designation: 388/97

Standard Test Method for

Oxidation Stability of Distillate Fuel Oil (Accelerated
Method)1
This standard is issued under the fixed designation D 2274; 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 Department of Defense.

1. Scope D 4057 Practice for Manual Sampling of Petroleum and

1.1 This test method covers the measurement of the inherent Petroleum Products
stability of middle distillate petroleum fuels under specified D 4177 Practice for Automatic Sampling of Petroleum and
oxidizing conditions at 95°C. Petroleum Products
D 4625 Test Method for Distillate Fuel Storage Stability at
NOTE 1—Fuels used in establishing the precision measures for this test 43°C (110°F)
method were described as gas oil, diesel fuel, No. 2 heating oil, and DFM,
2.2 Military Specification:3
a Navy distillate fuel suitable for diesels, boilers, and gas turbines. (The
term DFM is no longer used when referring to fuel meeting MIL-F-16884 MIL-F-16884 Fuel, Navy Distillate
requirements; rather it is called F76 as it conforms to NATO F76
requirements.) While the test method may be used for fuels outside the 3. Terminology
range of these fuels, the precision measures may not apply. 3.1 Definitions of Terms Specific to This Standard:
1.2 This test method is not applicable to fuels containing 3.1.1 adherent insolubles (formerly adherent gum)—
residual oil or significant amounts of components derived from material which is produced in the course of stressing distillate
non-petroleum sources. fuel under the conditions of this test and which adheres to the
1.3 The values given in acceptable SI units are to be glassware after fuel has been flushed from the system.
regarded as the standard. The values in parentheses are for 3.1.2 filterable insolubles—material, which is produced in
information only. the course of stressing distillate fuel under the conditions of
1.4 This standard does not purport to address all of the this test, which is capable of being removed from the fuel by
safety concerns, if any, associated with its use. It is the filtration. This includes both material suspended in the fuel and
responsibility of the user of this standard to establish appro- material easily removed from the oxidation cell and oxygen
priate safety and health practices and determine the applica- delivery tube with hydrocarbon solvent.
bility of regulatory limitations prior to use. 3.1.3 inherent stability—the resistance to change when
exposed to air, but in the absence of other environmental
2. Referenced Documents factors such as water, or reactive metallic surfaces and dirt.
2.1 ASTM Standards:2 3.1.4 total insolubles—sum of the adherent and filterable
D 381 Test Method for Gum Content in Fuels by Jet insolubles.
Evaporation 3.1.5 zero time—the time the first of a batch of oxidation
D 943 Test Method for Oxidation Characteristics of Inhib- cells is placed in the heating bath.
ited Mineral Oils [Link] Discussion—This is the time taken as the start of the
D 1193 Specification for Reagent Water 16 h of residence in the heating bath.
4. Summary of Test Method
4.1 A 350-mL volume of filtered middle distillate fuel is
1
This test method is under the jurisdiction of Committee D02 on Petroleum aged at 95°C (203°F) for 16 h while oxygen is bubbled through
Products and Lubricants and is the direct responsibility of Subcommittee D02.14 on
Stability and Cleanliness of Liquid Fuels. the sample at a rate of 3 L/h. After aging, the sample is cooled
Current edition approved Nov. 1, 2003. Published December 2003. Originally to approximately room temperature before filtering to obtain
approved in 1964. Last previous edition approved in 2003 as D 2274–03.
2
For referenced ASTM standards, visit the ASTM website, [Link], or
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available from Standardization Documents Order Desk, Bldg. 4, 700 Robbins
the ASTM website. Ave., Philadelphia, PA 19111-5098. Attn: NPODS

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

1
 D 2274 – 03a

FIG. 1 Oxidation Cell

the filterable insolubles quantity. Adherent insolubles are then coils of copper and steel are used, it is important that any
removed from the oxidation cell and associated glassware with residues that could contain these metals be eliminated from the
trisolvent. The trisolvent is evaporated to obtain the quantity of apparatus by thorough cleaning prior to use. Similarly, to
adherent insolubles. The sum of the filterable and adherent preclude the presence of chromium ions, as well as to protect
insolubles, expressed as milligrams per 100 mL, is reported as laboratory personnel from potential harm, chromic acid shall
total insolubles. not be used for cleaning glassware in the practice of this
method.
5. Significance and Use 6.2 It has been found that commercial grades of acetone, if
5.1 This test method provides a basis for the estimation of used in the trisolvent, can have impurities which cause an
the storage stability of middle distillate fuels such as No. 2 fuel apparently greater level of adherent insolubles to be measured.
oil. It is, therefore, critical that only reagent (or higher) grade
5.2 The test method may not provide a prediction of the materials be used in preparing the trisolvent mixture.
quantity of insolubles that will form in field storage over any 6.3 Ultraviolet light exposure has been found to increase the
given period of time. The amount of insolubles formed in such amount of total insolubles. Therefore, the fuel being tested
field storage is subject to the specific conditions which are too shall be shielded from direct exposure to ultraviolet light
variable for this test method to predict accurately. (sunlight or fluorescent). Conduct all sampling, measuring,
5.3 Test Method D 2274 yields results more rapidly than filtration, and weighing away from direct sunlight and in as
Test Method D 4625, the 43°C bottle test. However, as a result dark an area as would be compatible with other laboratory
of the significantly elevated temperature and the pure oxygen operations. Storage before stress, the stress period and cool-
atmosphere, the nature and amount of insolubles may deviate down after stressing shall be in the dark.
to a greater extent than Test Method D 4625 from those formed
in field storage. 7. Apparatus
6. Interferences NOTE 2—It is suggested that all equipment be calibrated according to
6.1 Oxidation is a major chemical process causing adherent manufacturer’s instructions on a periodic basis to assure consistency of
results.
and filterable insolubles to form. Any substance such as copper
or chromium that catalyzes oxidation reactions will cause 7.1 Oxidation Cell, of borosilicate glass, as shown in Fig. 1,
greater quantities of insolubles to form. Since the apparatus shall consist of a test tube, condenser, and oxygen delivery
used in this test can also be used in Test Method D 943, where tube. This cell is identical to that used in Test Method D 943.

2
 D 2274 – 03a
tee on Analytical Reagents of the American Chemical Society,
where such specifications are available.6 Other grades may be
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, reference
to water shall be understood to mean reagent water as defined
by Type III of Specification D 1193.
8.3 2.2,4-trimethylpentanel (isooctane), 99.75 % purity pre-
filtered through a filter medium of the type specified in 7.7.
8.4 Oxygen, 99.5 % purity or better. When the oxygen is
delivered through a plant system of piping, a filter shall be
provided adjacent to the constant temperature bath to prevent
the introduction of line debris or moisture into the oxidation
cells; a pressure regulator adequate to maintain a constant flow
FIG. 2 Apparatus for Determining Filterable Insolubles of gas through the apparatus shall also be used. A tank of
oxygen of the specified purity can be used provided it is
equipped with a two-stage pressure regulator. (Warning—
7.2 Heating Bath, with a thermostatically controlled liquid
Oxygen vigorously accelerates combustion. Do not use equip-
medium, shall be capable of maintaining the bath temperature
ment having exposed surfaces containing oil or grease.)
at 95 6 0.2°C (203 6 0.4°F). It shall be fitted with a suitable
8.5 Trisolvent, a mixture of equal volumes of acetone,
stirring device to provide a uniform temperature throughout the
methanol, and toluene. See 8.1. (Warning—It is particularly
bath. It shall be large enough to hold the desired number of
important that technical, commercial, practical, or industrial
oxidation cells immersed to a depth of approximately 350 mm.
grades (however they are designated by the particular manu-
Further, the bath construction must permit shielding the fuel
facturer) are not to be used, as their use may lead to apparently
samples in the oxidation cells from light while they are
increased levels of adherent insolubles.) (Warning—Fire haz-
undergoing oxidation.4
ard, toxic.)
7.3 Flowmeters, shall have a capability of measuring 3 6
0.3 L/h of oxygen. One flowmeter shall be provided for each 9. Samples and Sampling
oxidation cell.
9.1 When obtaining samples for the laboratory, follow
7.4 Filter Drying Oven, shall be capable of safely evapo-
Practices D 4057 or D 4177, or other standard practice capable
rating the solvent at 80° 6 2°C (176° 6 4°F) for the drying of
of providing representative samples.
filter materials.
9.2 Analyze fuel samples as soon as possible after receipt.
7.5 Glassware Drying Oven, shall be capable of drying
When a fuel cannot be tested within one day, blanket it with an
glassware at 105° 6 5°C (221 6 9°F).
inert gas such as oxygen-free nitrogen, argon, or helium and
7.6 Filter Assembly, see Fig. 2, shall be capable of holding
store at a temperature no higher than 10°C (50°F) but not lower
the filters described in 7.7.
than the cloud point. (Warning—Plastic containers are not
7.7 Filter Media5, 47 mm diameter cellulose ester
acceptable for samples due to the potential for leaching of
surfactant-free membrane filters with a nominal pore size of
plasticizers. Samples should be taken preferably in metal cans
0.8 µm.
previously cleaned according to Practice D 4057. Borosilicate
7.7.1 Single filters are to be used for prefiltration.
glass containers can be used if they are wrapped or boxed to
7.7.2 A matched weight pair of filters or alternatively, a
exclude light. Do not use soft (soda) glass containers.)
preweighed control and sample, filters shall be used for
9.3 Test Samples—Reduction of the laboratory sample to
determination of filterable insolubles
test sample size (about 400 mL for each determination)
7.8 Evaporating Vessel, borosilicate glass beaker, 200-mL
depends upon the size of sample received by the laboratory. If
capacity, tall style.
the laboratory sample is stored in a tank, drum, or 19-L (5-gal)
7.9 Hot Plate, capable of heating a liquid in the evaporating
or larger can, use the pertinent procedures of Practice D 4057.
vessel (7.8) to 135°C (275°F).
Thoroughly mix smaller laboratory samples by shaking, roll-
8. Reagents and Materials ing, or other techniques before taking an aliquot portion by
pouring, pipetting, or other means. Clean any tube, thief, pipet,
8.1 Purity of Reagents—Reagent grade chemicals shall be beaker, or other substance that is to contact the laboratory
used in all tests. Unless otherwise indicated, it is intended that sample with trisolvent and rinse with a portion of the sample
all reagents shall conform to the specifications of the Commit-

6
Reagent Chemicals, American Chemical Society Specifications, American
4
This apparatus is available from suppliers of specialty petroleum testing Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
equipment. listed by the American Chemical Society, see Annual Standards for Laboratory
5
Supporting data have been filed at ASTM International Headquarters and may Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
be obtained by requesting Research Report RR: D02-1012. Filters may be qualified and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
using the procedure in this research report. MD.

3
 D 2274 – 03a
prior to use. Prior to mixing thoroughly and taking an aliquot, modified Test Method D 2274 procedure in which the time in the heating
allow samples that have been stored at temperatures much bath is extended to 40 h. Periods other than 16 h may also be used in
below 10°C (50°F) to warm to room temperature; thus allow- research or in other specifications. However, the precision values given in
Test Method D 2274 apply only to the 16 h period in the heating bath.
ing any separated wax to redissolve and to allow the viscosity
to decrease to a point where mixing is effective. 11.3 Cooling the Sample:
11.3.1 Sixteen 6 0.25 h from zero time, remove the samples
10. Preparation of Apparatus from the heating bath in the same sequence as they were placed
10.1 Preparation of Glassware Other Than Oxidation therein. Cover the opening of each cell with a piece of
Cells—Rinse all glassware thoroughly with trisolvent followed aluminum foil or plastic to prevent entrance of dirt, dust, or
by water, then wash with a mildly alkaline or neutral laboratory moisture. Record the time the first cell is removed.
detergent. Rinse three times with deionized or distilled water 11.3.2 Place in a dark, ventilated site at room temperature,
followed by acetone to remove water. which shall be above the cloud point of the fuel, until the fuel
10.2 Preparation of Oxidation Cells and Accessories— attains room temperature but for no longer than 4 h.
After completion of 10.1, fill oxidation cells with laboratory 11.4 Determining Filterable Insolubles:
detergent in water. Place the oxygen delivery tube in the 11.4.1 Assemble the filter apparatus as illustrated in Fig. 2
oxidation cell, place the condenser over the oxygen delivery using one set of matched pair filters. Apply suction or vacuum
tube and allow to soak at least two hours. Wash, drain, then as necessary to filter the sample in an adequate time (approxi-
rinse five times with tap water followed by three rinses with mately 80 kPa (12 psi)); pour the cooled sample through the
distilled or deionized water meeting Specification D 1193 Type filter. Pull all fuel through the filter before pouring isooctane
III requirements. Rinse with acetone; drain and allow the rinses into the filter assembly.
oxidation cell and oxygen delivery tube to dry. NOTE 4—If the filtration of the sample cannot be completed within 2 h
10.3 Preparation of Evaporating Beakers—Dry the 200-mL as a result of severe filter plugging, filter the remaining fuel through a
cleaned beakers (10.1) for 1 h in an oven at 105° 6 5°C (221 separate set of filters.
6 9°F). Place the beakers in a desiccator (without desiccant)
11.4.2 On completion of filtration, completely rinse the
and allow to cool for 1 h. Weigh beakers to the nearest 0.1 mg.
oxidation cell with three separate 50 6 5 mL volumes of
isooctane from a squeeze bottle or vessel capable of directing
11. Procedure
a fine stream of isooctane. Pass all rinsings through the filter
11.1 Preparing the Sample—Place one filter (described in assembly.
7.7) on the filter support and clamp the filter funnel to the 11.4.3 After filtration and rinsing of the oxidation apparatus
support as shown in Fig. 2. Apply suction (approximately 80 is complete, wash down the sides of the funnel with an
kPa (12 psi)). Pour 400 mL of the fuel through the filter (see additional 50 6 5 mL of isooctane directed as a fine stream.
7.7) into a clean (10.1) 500-mL glass suction flask. Repeat The stream of isooctane should be directed in a manner that,
preparation for each sample to be run. After filtration is where possible, would push particles to the middle of the filter
complete, discard the filter media. Never use the same filters pad.
for a second increment of fuel, because any material deposited 11.4.4 After filtration is complete, disconnect the top part of
on the filters by a previous increment of fuel can result in a the filter assembly and wash down the rim of the filter media
greater removal of solids from the next increment. and adjacent parts of the filter assembly with a further 50 6 5
11.2 Assembling the Oxidation Apparatus: mL of isooctane. Be certain the area of the filters previously
11.2.1 Place a clean oxygen delivery tube into a clean under the filtration funnel is adequately rinsed to eliminate any
oxidation cell (Section 10) and pour 350 6 5 mL of the filtered presence of residual distillate fuel. Discontinue the vacuum and
fuel into the cell. As soon thereafter as possible, but in no case disconnect the filter assembly. Discard the filtrate.
greater than 1 h after measuring the fuel, immerse the test cell 11.4.5 Dry the two filter media at 80°C (176°F) for 30 min,
in the 95°C (203°F) heating bath. During any interim period cool them for 30 min, and weigh the upper (sample) and lower
store the cell in the dark. The level of fuel in the oxidation cell (blank) filters separately to the nearest 0.1 mg.
shall be below the level of the liquid medium in the heating 11.5 Determining Adherent Insolubles:
bath. 11.5.1 After the final rinsing of the oxidation cell and the
11.2.2 Place a condenser over the oxygen delivery tube and oxygen delivery tube with isooctane, dissolve adherent in-
oxidation cell; connect the condenser to the cooling water. solubles from the surfaces of these pieces using three equal
Connect the oxygen delivery tube to the oxygen supply through rinses totalling 75 6 5 mL of trisolvent.
the flowmeter and adjust the oxygen flow to 3 6 0.3 L/h. Make 11.5.2 Examine the oxidation cell and the oxygen delivery
sure samples are protected from light. When the number of test tube for evidence of stain or color indicating incomplete
cells is less than the capacity of the heating bath, fill the empty removal. If such stain or color is noted, rinse with a fourth
positions with dummy oxidation cells containing 350 mL of a 25-mL volume of trisolvent.
stable petroleum liquid with physical properties similar to 11.5.3 Evaporate the trisolvent from the rinsings in either of
those of the fuel being tested. two ways.
11.2.3 Record the time the first oxidation cell is placed in [Link] Collect the rinsings in a tared 200-mL tall beaker.
the bath as zero time. Place the beaker and contents on a hot plate and evaporate the
NOTE 3—Military Specification MIL-F-16884 permits the use of a trisolvent at 135°C under a hood. When all the solvent has

4
 D 2274 – 03a
evaporated, place the tared beaker in a desiccator without TABLE 1 Calculated Precision Data for Several Levels of Total
desiccant to cool for 1 h. When dry and cool, weigh the beaker InsolublesA
to the nearest 0.1 mg. Total Insolubles, mg/
Repeatability Reproducibility
100 mL
[Link] Optionally, collect the rinsings in one or two
100-mL beakers of the type specified for Test Method D 381 0.1 0.30 0.60
0.5 0.45 0.89
and evaporate the trisolvent at 160°C by the Test Method 1.0 0.54 1.06
D 381 air-jet method. 1.5 0.60 1.17
2.0 0.64 1.26
11.5.4 Run an adherent insolubles blank by evaporating a 2.5 0.68 1.33
volume of trisolvent equal to that used in the test and correct 3.0 0.71 1.40
for the presence of impurities in the solvent. A
Same values apply if adherent insolubles are determined using optional drying
method.
12. Calculation
12.1 Calculate the filterable insolubles mass (A) in milli-
grams per 100 mL. Subtract the mass of the blank (bottom) 13.2 A report of filterable insolubles (A), and the adherent
filter W1, in milligrams, from that of the sample (top) filter W2, insolubles (B) is optional. Report units in milligrams per 100
in milligrams, (11.4) and divide by 3.5 to reduce the result to mL.
a 100-mL basis.
W 2 2 W1
14. Precision and Bias 7
A5 3.5 (1) 14.1 Precision—The precision (see Table 1) of this test
12.2 Calculate the adherent insolubles mass (B) in milli- method as determined by statistical examination of interlabo-
grams per 100 mL. Subtract the tare mass of the blank (W3) and ratory results is as follows:
sample (W4) beakers from their final masses (W5), (W6) 14.1.1 Repeatability—The difference between two test re-
respectively. Subtract the mass of the blank from the corrected sults, obtained by the same operator with the same apparatus
mass of the adherent insolubles (11.5) and divide by 3.5. under constant operating conditions on identical test material,
would in the long run, in the normal and correct operation of
~ W6 2 W 4 ! 2 ~ W 5 2 W 3 ! the test method, exceed the following values only in one case
B5 3.5 (2)
in twenty:
where: 4
0.54 ~=total insolubles, mg/100 mL! (4)
W 3 = tare mass of the blank beaker, mg,
W4 = tare mass of the sample beaker, mg, 14.1.2 Reproducibility—The difference between two single
W5 = final mass of the blank beaker, mg, and and independent results obtained by different operators work-
W6 = final mass of the sample beaker, mg. ing in different laboratories on identical test material would, in
12.3 Calculate the total insolubles mass (C) in milligrams the long run, in the normal and correct operation of the test
per 100 mL as the sum of the filterable insolubles (A) and the method, exceed the following values only in one case in
adherent insolubles (B). twenty:
4
C5A1B (3) 1.06 ~=total insolubles, mg/100 mL! (5)

where: 14.2 Bias—Since there is no accepted reference material

C = total insolubles, mg/100 mL, suitable for determining the bias for this test method no
A = filterable insolubles, mg/100 mL, and statement on bias is being made.
B = adherent insolubles, mg/100 mL.
15. Keywords
NOTE 5—Some specifications may require results in SI units of g/m3
rather than as mg/100 mL. In such cases, the values in mg/100 mL can be 15.1 diesel fuel; filterable insolubles; middle distillate fuel;
converted to SI units by multiplying by ten. oxidation stability

13. Report
13.1 Report total insolubles (C) in mg/100 mL, to the 7
Supporting data have been filed at ASTM International Headquarters and may
nearest 0.1 mg/100 mL be obtained by requesting Research Report RR: D02-1240.

5
 D 2274 – 03a

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