Designation: D6748 − 02a (Reapproved 2012)

Standard Test Method for

Determination of Potential Instability of Middle Distillate
Fuels Caused by the Presence of Phenalenes and
Phenalenones (Rapid Method by Portable
Spectrophotometer)1,2
This standard is issued under the fixed designation D6748; 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.

1. Scope 2. Referenced Documents

1.1 This test method covers a procedure3 for the rapid 2.1 ASTM Standards:4
determination of phenalenes and phenalenones in middle D396 Specification for Fuel Oils
distillate fuels, including marine, automotive, heating, and gas D975 Specification for Diesel Fuel Oils
turbine fuel such as those specified in Specifications D396, D2069 Specification for Marine Fuels (Withdrawn 2003)5
D975, D2069, and D2880. Phenalenes and phenalenones affect D2880 Specification for Gas Turbine Fuel Oils
the potential instability of fuels, leading to fuel degradation D4057 Practice for Manual Sampling of Petroleum and
products during storage, which may cause performance prob- Petroleum Products
lems. D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.2 This test method is applicable to both dyed and undyed D4306 Practice for Aviation Fuel Sample Containers for
fuels at all points in the distribution chain from refinery to Tests Affected by Trace Contamination
end-user. It is not applicable to fuels containing residual oil. D4625 Test Method for Middle Distillate Fuel Storage
The portable apparatus allows the whole test to be conducted Stability at 43°C (110°F)
on site or in a laboratory and does not require the test sample D5854 Practice for Mixing and Handling of Liquid Samples
to be heated. of Petroleum and Petroleum Products
1.3 This test method is suitable for testing samples with a D6468 Test Method for High Temperature Stability of
relative absorbance of up to 5.00 absorbance units (AU). Middle Distillate Fuels
E131 Terminology Relating to Molecular Spectroscopy
NOTE 1—The precision of the test method has been established on E275 Practice for Describing and Measuring Performance of
relative absorbance up to 1.00 AU. For relative absorbance above 1.00 AU
Ultraviolet and Visible Spectrophotometers
the precision may not apply.
2.2 Other Standards:6
1.4 This standard does not purport to address all of the
Def Stan 05-50 Methods for Testing Fuels and Lubricants
safety concerns, if any, associated with its use. It is the
and Associated Products, Part 40 — Storage Stability of
responsibility of the user of this standard to establish appro-
Diesel Fuels
priate safety and health practices and determine the applica-
Def Stan 91–4 Fuel, Naval, Distillate NATO Code: F76 Joint
bility of regulatory limitations prior to use.
Service, Designation DIESO F76

3. Terminology
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee 3.1 Definitions:
D02.14 on Stability and Cleanliness of Liquid Fuels.
Current edition approved Nov. 1, 2012. Published November 2012. Originally
approved in 2002. Last previous edition approved in 2007 as D6748–02a (2007).
4
DOI: 10.1520/D6748-02AR12. For referenced ASTM standards, visit the ASTM website, [Link], or
2
This test method is being jointly developed with the Institute of Petroleum contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
where it is designated IP 463. Standards volume information, refer to the standard’s Document Summary page on
3
This process is covered by US Patent 5,378,632. Interested parties are invited the ASTM website.
5
to submit information regarding the identification of an alternative(s) to this The last approved version of this historical standard is referenced on
patented item to ASTM International Headquarters. Your comments will receive [Link].
6
careful consideration at a meeting of the responsible technical committee, which Available from United Kingdom Defence Standardization, Room 1138, Kenti-
you may attend. gern House, 65 Brown Street, Glasgow, G2 8EX. United Kingdom.

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

Copyright by ASTM Int'l (all rights reserved); 1

 D6748 − 02a (2012)
3.1.1 For definitions of terms relating to absorption spec- temperature. Chemical reactions may lead to a change in color
troscopy see Terminology E131. Terms of particular signifi- followed by the formation of soluble gums and insoluble
cance are the following: sediments. Insoluble sediments may overload filters, and plug
3.1.2 radiant energy, n—energy transmitted as electromag- nozzles and injectors.
netic waves. 5.2 This test method, which does not require the test sample
3.1.3 radiant power P, n—the rate at which energy is to be heated, uses a portable apparatus and allows tests to be
transported in a beam of radiant energy. carried out on site or in the laboratory to give a result within 35
3.2 Definitions of Terms Specific to This Standard: min.
3.2.1 absorbance, A, n—the logarithm to the base 10 of the 5.3 The potential beneficial effects of stability additives in
reciprocal of the transmittance, T. In symbols: fuels may not be recognized by this test method. Therefore, the
A 5 log10~ 1/T ! 5 2log10T (1) actual storage stability of middle distillate fuels with stability
additives may not be correctly indicated by these test results.
where:
5.4 The unstable reactive compounds (phenalenes and phe-
T = transmittance as defined in 3.2.5.
nalenones) detected by this test method may be present in fuels
3.2.2 absorbance units (AU), n—units of relative absor- containing catalytically cracked or straight run materials and
bance reported by the portable spectrophotometer. can affect the potential instability of the fuel.
3.2.3 pathlength of test portion b, n—the distance in mm, 5.5 If this test method is used by any party for a rapid
measured in the direction of propagation of the beam of radiant assessment of stability, it is the responsibility of parties
energy, between the surfaces of the portion on which the concerned to decide whether or not this procedure yields
radiant energy is incident and the surface of the test portion meaningful results.
from which it emerges.
5.6 Interpretation of results and correlation with other test
3.2.4 relative absorbance, n—the difference between the methods is given in Appendix X1.
absorbance (near infrared-visible band results) measured at the
two wavelengths, and reported in AU. 6. Apparatus7
3.2.5 transmittance, T, n—the ratio of the radiant power 6.1 Spectrophotometer, double beam, capable of measuring
transmitted by the test portion in the test cuvette to the radiant absorbance at one visible wavelength in the range 600-800 nm
power transmitted by the Reagent 1 control in the cuvette. and one near infrared wavelength in the range 800-850 nm with
Expressed in the following equation. a spectral bandwidth of 10 6 2 nm and an accuracy of 63 nm
T 5 P T /P R1 (2) (see Fig. 1). The display shall have a resolution of 0.01 of AU,
and a repeatability of measurement of 60.02 AU for ranges up
where: to 1.00 AU. See Practice E275.
PT = radiant power transmitted by the test portion, and
PR1 = the radiant power transmitted by the Reagent 1 NOTE 2—The two wavelengths used are proprietary and are not
adjustable.
control.
6.1.1 Zero Adjustment, a facility shall be incorporated to
4. Summary of Test Method allow the absorbance measured at the two individual wave-
4.1 A 5 mL volume of middle distillate fuel is mixed with an lengths to be set to zero when using Reagent 1 as a control.
equal volume of an immiscible reagent solution. A second 6.1.2 Absorbance Display, the relative absorbance, in AU,
reagent is then added, the new blend mixed and allowed to shall be the instantaneous difference between the absorbance
settle for 30 min. for two phases to separate. The top reagent measured at the two wavelengths. The peak wavelength
layer (darker) is then placed in the portable spectrophotometer represents the absorption due to the colored indolylphenalene
and the relative absorbance of near infrared and visible light, at salts which are formed, and the baseline wavelength is for
fixed single wavelengths, is measured instantaneously and normalizing the result.
automatically, and reported in AU. 6.2 Timer, capable of measuring 35 min to an accuracy of
4.2 When mixed with the oil sample containing phenalenes, 60.2 min.
the oxidizing Reagent 2 oxidizes the phenalenes to phenale- 6.3 Dispenser, for Reagent 1 made of polyethylene,
nones which are subsequently converted to colored indolylphe- polypropylene, or glass and capable of dispensing 5 mL of
nalene salts by the acidic Reagent 1. The spectrophotometer reagent with an accuracy of 60.5 mL.
measures the absorbance of light caused by the colored salts
6.4 Syringe 1, for test portion, 5 mL, polyethylene,
while eliminating the effect of the initial color of the fuel. The
polypropylene, or glass, with an accuracy of 60.25 mL.
absorbance of light is a measure of the concentration of the
colored salts that are formed.
7
The equipment, as listed in RR:D02-1522 was used to develop the precision
5. Significance and Use statement. The apparatus described in Section 6 and the reagents listed in Section 7
are both supplied by Stanhope-Seta, Chertsey, Surrey KT16 8AP, United Kingdom.
5.1 Storage stability depends on complex interactions. It To date, no other equipment has demonstrated through ASTM interlaboratory testing
varies with feedstock type and source, and the processing used. the ability to meet the precision of this test. This is not an endorsement or
The rate of degradation may not change uniformly with certification by ASTM International.

Copyright by ASTM Int'l (all rights reserved); 2

 D6748 − 02a (2012)

FIG. 1 Spectrophotometer

6.5 Syringe 2, for Reagent 2, preset at 35 µL, glass, with an 8.5 Allow the test sample to reach the local ambient
accuracy of 60.35 µL. temperature (10 to 30°C) before commencing the test.
6.6 Test Tube with Stopper, nominally 15 mL, polyethylene,
polypropylene, or glass. 9. Preparation and Calibration of Apparatus
6.7 Pipette, 5 mL, polyethylene, polypropylene, or glass. 9.1 For portable use ensure that the battery has been
charged.
6.8 Test Cuvette, 4.5 mL volume, optical methacrylate,
disposable, with two opposite ribbed sides. Dimensions shall 9.2 Zeroing the Spectrophotometer—Turn on the portable
be 45 mm high, 12.5 by 12.5 mm in width with a test portion spectrophotometer for at least 2 min. Fill a test cuvette with
pathlength 10 6 0.25 mm. Reagent 1, to within 5 mm of its top. Place the filled test
cuvette into the spectrophotometer drawer. Zero both wave-
7. Reagents and Materials lengths individually by separately pressing each select button
7.1 Reagent 1, proprietary, methanol solvent containing a and turning the corresponding zero button until 0.00 AU is
Lowry-Bronsted acid 7 (Warning—Acidic, flammable, toxic, displayed.
irritant). 9.2.1 Dispose of the cuvette and the aliquot of Reagent 1.
Do not reuse the cuvette.
7.2 Reagent 2, proprietary solution containing potassium
permanganate7 an oxidizing agent (Warning—Oxidizing NOTE 3—The spectrophotometer is correctly calibrated if the two
agent, toxic, irritant). wavelength readings are 0.00 6 0.01 AU.

7.3 Water, distilled or deionized, for flushing Syringe 2 used 9.3 Verification—A verification fluid is under development.
for Reagent 2.
10. Procedure
8. Sampling 10.1 Pour 5 mL of Reagent 1 into a test tube and add a 5 mL
8.1 Field Sampling—Take field samples in accordance with aliquot of the test sample using Syringe 1. Stopper the test tube
Practices D4057, D4177, or other comparable sampling prac- and vigorously shake the test tube for 10 6 2 s.
tices. Record the sampling date. Sample bulk fuel above its
10.2 Remove the stopper and add 35 µL of Reagent 2 using
cloud point and thoroughly mix prior to aliquot sampling. For
Syringe 2. Stopper the test tube and vigorously shake the test
shipping field samples, use only epoxy-lined steel cans that
tube for 10 6 2 s. Allow to settle for 30 to 35 min.
have been cleaned according to Practice D4306.
10.3 Switch on the spectrophotometer at least 2 min before
8.2 Store samples at normal room temperature (20 to 25°C)
the end of the 30 min period.
or colder.
10.4 At the end of the 30 min period, use a pipette to draw
8.3 Filter samples which contain free water or a water haze
the darker reagent layer (at the top) from the test tube and to
through a qualitative filter paper or a loose plug of cotton to
transfer that liquid to the test cuvette. Fill the cuvette to within
remove such water.
5 mm of its top. (Warning—Hold the cuvette using the two
8.4 Laboratory Subsampling—Sample fuel above its cloud ribbed sides to avoid affecting the optical path.)
point and thoroughly mix prior to aliquot sampling. At least 5
mL of sample is required for each test. Follow Practices D4057 10.5 Place the cuvette (with the ribbed side towards the
and D5854. Use clean amber or clean borosilicate glass drawer handle) in the spectrophotometer and close the drawer.
containers for laboratory handling. Shield fuel in clear bottles 10.6 Record the results from the digital display every 60 6
from sunlight to prevent photochemical reactions. Other labo- 5 s until two readings agree within 0.02 AU and report the
ratory containers may be used provided they are shown not to second of these reading as the measured relative absorbance.
affect the results of the test. Record a negative result as zero.

Copyright by ASTM Int'l (all rights reserved); 3

 D6748 − 02a (2012)
11. Report where:
11.1 Report the source, type, and identification of the x = average of results being compared.
material tested, plus the dates sampled and tested. 12.3 Reproducibility—The difference between two single
11.2 Refer to this test method and report any deviation, by and independent results obtained by different operators work-
agreement or otherwise, from the procedure specified. ing in different laboratories on identical test material would, in
11.3 Report the result of the test in absorbance units to the the long run, in the normal correct operation of the test method,
nearest 0.01 AU. exceed the following only in one case in twenty.
R 5 0.1799 ~ x10.2! AU (4)
12. Precision and Bias8
where:
12.1 The precision of this test method, as determined by
statistical analyses of interlaboratory results, is as follows: x = average of results being compared.
12.2 Repeatability—The difference between two test results 12.4 Bias—Since there is no accepted reference material
obtained by the same operator with the same apparatus under suitable for determining the bias of the procedures in Test
constant operating conditions, on identical test material would, Method D6748, bias cannot be determined.
in the long run, in the normal and correct operation of the test
method, exceed the following only in one case in twenty. 13. Keywords
r 5 0.0876 ~ x10.2! AU (3) 13.1 absorbance units; burner fuel; diesel fuel; infrared;
infrared spectrophotometer; marine fuel; middle distillate fuel;
8
Supporting data have been filed at ASTM International Headquarters and may potential instability; spectrometer; spectrophotometer; storage
be obtained by requesting Research Report RR:D02-1522. stability; turbine fuel; visible spectrophotometer

APPENDIX

(Nonmandatory Information)

X1. INTERPRETATION OF RESULTS AND CORRELATION WITH OTHER TEST METHODS

X1.1 Interpretation of Results: X1.2 Correlation with Other Test Methods—Further details
X1.1.1 The United Kingdom defense standard for NATO of these correlations are available in the research report which
F-76 diesel fuel, Def Stan 91-4, allows the requirement to test is being prepared.
the fuel by Def Stan 05-50 Part 40 (long test) (similar to Test X1.2.1 Results From a 1993 Test Program—See Fig. X1.1.
Method D4625) to be waived, if the result by this PI test, gives
a relative absorbance of less than 0.20 AU. This level of X1.2.2 Results From the 1999 Interlaboratory Test
absorbance has been deemed to be equivalent to 10 mg/L total Program—Fig. X1.2 compares the results determined by this
sediment. test method (PI test) with results originally measured by Test
X1.1.2 The significance of results from this test method can Method D4625 (three laboratories) during the Test Method
be further estimated by comparing results with other test D6468 interlaboratory test program.
methods.

NOTE 1—These test results are reproduced by permission of the Defence Evaluation and Research Agency, United Kingdom.
FIG. X1.1 Correlation Between Test Method D4625 and the Absorbance of 46 Fuels

Copyright by ASTM Int'l (all rights reserved); 4

 D6748 − 02a (2012)

FIG. X1.2 Correlation Between Results Obtained by the PI Test and Test Method D4625

ASTM International 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 International 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, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@[Link] (e-mail); or through the ASTM website
([Link]). Permission rights to photocopy the standard may also be secured from the ASTM website ([Link]/
COPYRIGHT/).

Copyright by ASTM Int'l (all rights reserved); 5