ASTM D3703-07(2012)
(Test Method)Standard Test Method for Hydroperoxide Number of Aviation Turbine Fuels, Gasoline and Diesel Fuels
Standard Test Method for Hydroperoxide Number of Aviation Turbine Fuels, Gasoline and Diesel Fuels
SIGNIFICANCE AND USE
5.1 The magnitude of the hydroperoxide number is an indication of the quantity of oxidizing constituents present. Deterioration of the fuels results in the formation of hydroperoxides and other oxygen-carrying compounds. The hydroperoxide number measures those compounds that will oxidize potassium iodide.
5.2 The determination of the hydroperoxide number of aviation turbine fuels, gasoline and diesel is significant because of the adverse effect of hydroperoxide upon certain elastomers in the fuel systems.
5.3 The determination of hydroperoxide number of gasoline is significant because hydroperoxides have been demonstrated to decrease both Research and Motor Octane Numbers. In addition, hydroperoxides have adverse effects on certain fuel system components.
5.4 The determination of hydroperoxide number of diesel fuel is significant because hydroperoxides have been demonstrated to increase the Cetane Number. In addition, hydroperoxides have adverse effects on certain fuel system components.
SCOPE
1.1 This test method covers the determination of the hydroperoxide content expressed as hydroperoxide number of aviation turbine, gasoline and diesel fuels.
1.2 The range of hydroperoxide number included in the precision statement is 0 to 50 mg/kg active oxygen as hydroperoxide.
1.3 The interlaboratory study to establish the precision of this test method consisted of spark-ignition engine fuels (regular, premium and California Cleaner-Burning gasoline), aviation gasoline, jet fuel, ultra low sulfur diesel, and biodiesel. However, biodiesel was not included in the precision calculation because of the large differences in results within labs and between labs.
1.4 This test method detects hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide. It does not detect sterically-hindered hydroperoxides such as dicumyl and di-t-butyl hydroperoxides
1.5 Di-alkyl hydroperoxides added commercially to diesel fuels are not detected by this test method.
1.6 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific warning statements, see 7.3, 7.6, 9.2, and Annex A1.
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Standards Content (Sample)
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Designation: D3703 − 07(Reapproved 2012)
Standard Test Method for
Hydroperoxide Number of Aviation Turbine Fuels, Gasoline
and Diesel Fuels
This standard is issued under the fixed designation D3703; 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of the hy-
D1193 Specification for Reagent Water
droperoxide content expressed as hydroperoxide number of
D4057 Practice for Manual Sampling of Petroleum and
aviation turbine, gasoline and diesel fuels.
Petroleum Products
1.2 The range of hydroperoxide number included in the
D6447 Test Method for Hydroperoxide Number of Aviation
precision statement is 0 to 50 mg/kg active oxygen as hydrop-
Turbine Fuels by Voltammetric Analysis
eroxide.
2.2 Other Standards:
CRC Report No. 559 Determination of the Hydroperoxide
1.3 The interlaboratory study to establish the precision of
Potential of Jet Fuels
this test method consisted of spark-ignition engine fuels
4500-C1 B. Iodometric Method I—Standard Methods for
(regular, premium and California Cleaner-Burning gasoline),
the Examination of Water and Wastewater
aviationgasoline,jetfuel,ultralowsulfurdiesel,andbiodiesel.
However, biodiesel was not included in the precision calcula-
3. Terminology
tion because of the large differences in results within labs and
3.1 Definitions of Terms Specific to This Standard:
between labs.
3.1.1 hydroperoxide, n—organic peroxide having the gener-
1.4 This test method detects hydroperoxides such as t-butyl alized formula ROOH.
hydroperoxide and cumene hydroperoxide. It does not detect 3.1.1.1 Discussion—This test method detects hydroperox-
sterically-hindered hydroperoxides such as dicumyl and di-t- idessuchast-butylhydroperoxide[(CH ) COOH]andcumene
3 3
butyl hydroperoxides hydroperoxide [C H C(CH ) OOH]. It does not detect
6 5 3 2
sterically-hindered hydroperoxides such as dicumyl and di-t-
1.5 Di-alkyl hydroperoxides added commercially to diesel
butyl hydroperoxides.
fuels are not detected by this test method.
3.1.2 hydroperoxide number, n—an indication of the quan-
1.6 The values stated in SI units are to be regarded as the
tity of oxidizing constituents present in certain liquid fuels as
standard. The values given in parentheses are for information
determined by this test method.
only.
3.1.2.1 Discussion—The higher the quantity of oxidizing
constituents in the fuels, the higher the hydroperoxide number.
1.7 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4. Summary of Test Method
responsibility of the user of this standard to consult and
4.1 A quantity of sample dissolved in 2,2,4-
establish appropriate safety and health practices and deter-
trimethylpentane is contacted with aqueous potassium iodide
mine the applicability of regulatory limitations prior to use.
solution. The hydroperoxides present are reduced by the
For specific warning statements, see 7.3, 7.6, 9.2, and Annex
A1.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
This test method is under the jurisdiction of ASTM Committee D02 on the ASTM website.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Available from the Coordinating Research Council, Inc., 219 Perimeter Center
D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material. Parkway, Atlanta, GA 30346.
CurrenteditionapprovedJune1,2012.PublishedJuly2012.Originallyapproved Published by the American Health Assoc., the American Water Works Assoc.
´1
in 1978. Last previous edition approved in 2007 as D3703–07 . DOI: 10.1520/ and Water Environment Federation. Available from American Public Health
D3703-07R12. Publication Sales, P. O. Box 753, Waldorf, MD 20604–0753.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3703 − 07 (2012)
potassium iodide.An equivalent amount of iodine is liberated, where such specifications are available. Other grades may be
which is titrated with an aqueous sodium thiosulfate solution. used, provided it is first ascertained that the reagent is of
The results are calculated as milligrams of hydroperoxide per sufficiently high purity to permit its use without lessening the
kilogram of sample expressed as hydroperoxide number. (See accuracy of the determination.
Note 1.) 7.1.1 Commercially available solutions already prepared
may be used in place of laboratory preparations, if they meet
NOTE 1—The original standard D3703 was published in 1978 as
the method requirements.
Standard Test Method for Peroxide Number of Aviation Turbine Fuels.
This test method originally used carbon tetrachloride (CCl ), which was
7.2 Purity of Water—Unless otherwise indicated, references
determined to be carcinogenetic. CCl was later replaced with 1,1,2-
to water shall be understood to mean reagent water that meets
trichloro-1,2,2 trifluoroethane. 1,1,2-trichloro-1,2,2-trifluoroethane is an
the requirement of Type I, II, or III of Specification D1193.
ozone depleting substance. The use of an ozone depleting substance
precludes its use by many operators.
7.3 Acetic Acid Solution—Mix 4 mLof concentrated hydro-
chloric acid (HCl, sp gr 1.19) with 996 mL of glacial acetic
5. Significance and Use
acid (CH COOH). (Warning—Poison. Corrosive. Combus-
tible. Can be fatal if swallowed. Causes severe burns. Harmful
5.1 The magnitude of the hydroperoxide number is an
if inhaled. See A1.2).
indication of the quantity of oxidizing constituents present.
Deterioration of the fuels results in the formation of hydrop-
7.4 Nitrogen Gas, 99.9995% Minimum purity
eroxides and other oxygen-carrying compounds. The hydrop-
7.5 Carbon Dioxide, 99.9995% Minimum purity
eroxide number measures those compounds that will oxidize
7.6 2,2,4-trimethylpentane (iso-octane), (Warning—
potassium iodide.
Flammable, dangerous fire risk. Toxic by injection and inha-
5.2 The determination of the hydroperoxide number of
lation. See A1.1.)
aviationturbinefuels,gasolineanddieselissignificantbecause
7.7 Potassium Dichromate Solution, Standard (0.1 N), ACS
of the adverse effect of hydroperoxide upon certain elastomers
reagent grade. Dissolve 2.452 g of the dried potassium dichro-
in the fuel systems.
mate (K Cr O ) in water and dilute to 500 mL in a volumetric
2 2 7
5.3 The determination of hydroperoxide number of gasoline
flask. This solution is 0.1 N. As an alterative, the lab may use
is significant because hydroperoxides have been demonstrated
commercially prepared solution.
to decrease both Research and Motor Octane Numbers. In
7.8 Potassium Dichromate Solution, Standard (0.01 N),
addition, hydroperoxides have adverse effects on certain fuel
(Warning—Avoid contact with eyes and skin and avoid
system components.
breathing of dust)—Dilute 100 mL of 0.1 N K Cr O solution
2 2 7
5.4 The determination of hydroperoxide number of diesel
with water to 1000 mL in a volumetric flask.)
fuel is significant because hydroperoxides have been demon-
7.9 Potassium Iodide Solution, Dissolve 120 g of potassium
strated to increase the Cetane Number. In addition, hydroper-
iodide (KI) in 100 mL of water. Larger quantities of solution
oxides have adverse effects on certain fuel system components.
may be prepared, provided the concentration of KI in water is
equivalent. Protect the solution from sunlight by storing in
6. Apparatus
brown bottles and blanketed with nitrogen or carbon dioxide.
6.1 Iodine Number Flask, 250 mL, glass-stoppered.
Discharge any color from this solution by placing 1 mL of KI
solution, 50 mL of water, and 5 mL of starch solution in a
6.2 Burettes, 10-mL, 25-mL, Class A with polytetrafluoro-
300-mL flask and blanketing with nitrogen or carbon dioxide.
ethylene (PTFE) stop cock.
If a blue color develops, add 0.005 N Na S O solution from a
2 2 3
6.3 Volumetric Flasks, 100-mL and 1000-mL, 2000 mL
microburet until color just disappears.Add a sufficient quantity
Class A with PTFE stoppers.
of Na S O solution, thus determined, to the main KI solution
2 2 3
6.4 Mixing Cylinders, 100 mL and 500-mL, glass-
to convert all free iodine to iodide. When properly prepared, 1
stoppered.
mL of KI solution should not turn blue when starch solution is
added, but with starch plus one drop of 0.01 N K Cr O
2 2 7
6.5 Microburet, 10-mL, Class A.
solution plus two drops of HCl, the blue color should develop.
6.6 Analytical Balance, capable of weighing to the nearest
Store this solution under nitrogen or carbon dioxide.
milligram.
7.10 Sodium Thiosulfate Solution, Standard (0.1 N), Dis-
6.7 Brown Bottles, 100-mL, 300-mL, 1000-mL with screw
solve 12.5 g of sodium thiosulfate (Na S O ·5H O) plus 0.1 g
2 2 3 2
caps with inert inserts.
of sodium carbonate (Na CO ) in 500 mL of water (the
2 3
Na CO is added to stabilize the Na S O solution). Let this
2 3 2 2 3
6.
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