ASTM D5384-14(2019)
(Test Method)Standard Test Methods for Chlorine in Used Petroleum Products (Field Test Kit Method)
Standard Test Methods for Chlorine in Used Petroleum Products (Field Test Kit Method)
SIGNIFICANCE AND USE
4.1 Chlorinated compounds can lead to corrosion of equipment and poisoning of the catalyst. Chlorinated compounds also present a health hazard when incompletely combusted. Chlorine content of petroleum products is determined prior to their being recycled.
Note 1: Federal Regulations mandate that often the chlorine content of used oil must be determined before recycling. EPA regulation 40 CFR 261 bars the sale of used oil for fuel if it is contaminated with halogens measured as chlorine at levels exceeding 1000 mg/kg. Such oil is considered to be a hazardous waste unless it can be proven that the chlorine content is inorganic or that the halogenated organics are not hazardous constituents. The cost of disposing of a hazardous waste is many times higher than the cost of used oil disposal. Therefore it is critical for users, generators, haulers, reprocessors, and collectors to test the material they handle in order to comply with regulations, maintain safe operations, and avoid high disposal costs.
4.2 These test methods can be used to determine when a used petroleum product meets or exceeds requirements for total halogens measured as chloride. It is specifically designed for used oils, permitting on-site testing at remote locations by nontechnical personnel to avoid the delays of laboratory testing.
SCOPE
1.1 These test methods cover the determination of chlorine in used oils, fuels, and related materials, including: crankcase, hydraulic, diesel, lubricating and fuel oils, and kerosene, all containing
1.1.1 If the sample contains greater than 25 % water, the sodium metal reacts preferentially with the water rather than with the halogenated organics in the oil.
1.1.2 Bromide and iodide are also titrated and reported on a molar basis as chlorine. The method does not detect fluorine because AgF remains in the solution during the titration, while AgI, AgBr, and AgCl precipitate out and can therefore be detected.
1.1.3 Some of the chlorinated organic compounds that have been shown to be detectable by this method include trichloroethane, dichloroethane, trichlorobenzene, monochlorobenzene, chlorooctadecane, methylene chloride, perchloroethylene, Freon, and polychlorinated biphenyls. These nine compounds represent the major classes of chlorinated compounds that are found in used oils.
1.2 The entire analytical sequence, including sampling, sample pretreatment, chemical reactions, extraction, and quantification, is available in kit form using predispensed and encapsulated reagents. The overall objective is to provide a simple, easy to use procedure, permitting nontechnical personnel to perform a test in or outside of the laboratory environment in under 10 min. The test method also gives information to run the test without a kit.
1.2.1 Test Method A is preset to provide a greater than or less than result at 1000 mg/kg (ppm) total chlorine to meet regulatory requirements for used oils.
1.2.2 Test Method B provides results over a range from 200 mg/kg to 4000 mg/kg total chlorine.
1.3 For both test methods, positive bias will result from samples that contain greater than 3 % (mass/mass) total sulfur. While a false negative result will not occur, other analytical methods should be used on high sulfur oils.
1.4 Test Method B, Lower Limit of Quantitation—In the round-robin study to develop statistics for this test method, participants were asked to report results to the nearest 100 mg/kg. The lower limit of quantification could therefore only be determined to be in the range from 870 mg/kg5 to 1180 mg/kg5.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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 establish appropriate safety, health, and environmental practices and determine th...
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Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D5384 − 14 (Reapproved 2019)
Standard Test Methods for
Chlorine in Used Petroleum Products (Field Test Kit
Method)
This standard is issued under the fixed designation D5384; 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 While a false negative result will not occur, other analytical
methods should be used on high sulfur oils.
1.1 These test methods cover the determination of chlorine
in used oils, fuels, and related materials, including: crankcase, 1.4 Test Method B, Lower Limit of Quantitation—In the
hydraulic, diesel, lubricating and fuel oils, and kerosene, all round-robin study to develop statistics for this test method,
containing <25 % (mass/mass) water. participants were asked to report results to the nearest
1.1.1 If the sample contains greater than 25 % water, the 100 mg⁄kg. The lower limit of quantification could therefore
sodium metal reacts preferentially with the water rather than only be determined to be in the range from 870 mg⁄kg to
with the halogenated organics in the oil. 1180 mg⁄kg .
1.1.2 Bromide and iodide are also titrated and reported on a
1.5 The values stated in SI units are to be regarded as
molar basis as chlorine. The method does not detect fluorine
standard. No other units of measurement are included in this
becauseAgF remains in the solution during the titration, while
standard.
AgI, AgBr, and AgCl precipitate out and can therefore be
1.6 This standard does not purport to address all of the
detected.
safety concerns, if any, associated with its use. It is the
1.1.3 Some of the chlorinated organic compounds that have
responsibility of the user of this standard to establish appro-
been shown to be detectable by this method include
priate safety, health, and environmental practices and deter-
trichloroethane, dichloroethane, trichlorobenzene,
mine the applicability of regulatory limitations prior to use.
monochlorobenzene, chlorooctadecane, methylene chloride,
Specific safety statements are given in Sections 3, 6, and 7.
perchloroethylene, Freon, and polychlorinated biphenyls.
1.7 This international standard was developed in accor-
These nine compounds represent the major classes of chlori-
dance with internationally recognized principles on standard-
nated compounds that are found in used oils.
ization established in the Decision on Principles for the
1.2 The entire analytical sequence, including sampling,
Development of International Standards, Guides and Recom-
sample pretreatment, chemical reactions, extraction, and
mendations issued by the World Trade Organization Technical
quantification, is available in kit form using predispensed and
Barriers to Trade (TBT) Committee.
encapsulated reagents. The overall objective is to provide a
simple, easy to use procedure, permitting nontechnical person-
2. Referenced Documents
neltoperformatestinoroutsideofthelaboratoryenvironment
2.1 ASTM Standards:
in under 10 min. The test method also gives information to run
D4057 Practice for Manual Sampling of Petroleum and
the test without a kit.
Petroleum Products
1.2.1 Test Method A is preset to provide a greater than or
2.2 Federal Regulation:
less than result at 1000 mg⁄kg (ppm) total chlorine to meet
40 CFR 261 Identification and Listing of Hazardous Waste
regulatory requirements for used oils.
1.2.2 Test Method B provides results over a range from
3. Summary of Test Methods
200 mg⁄kg to 4000 mg⁄kg total chlorine.
3.1 The oil sample (approximately 0.3 g) is dispersed in a
1.3 For both test methods, positive bias will result from
hydrocarbon solvent and reacted with a mixture of metallic
samples that contain greater than 3 % (mass/mass) total sulfur.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
These test methods are under the jurisdiction of ASTM Committee D02 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility Standards volume information, refer to the standard’s Document Summary page on
of Subcommittee D02.03 on Elemental Analysis. the ASTM website.
Current edition approved May 1, 2019. Published June 2019. Originally AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
approved in 1995. Last previous edition approved in 2014 as D5384 – 14. DOI: 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
10.1520/D5384-14R19. www.access.gpo.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5384 − 14 (2019)
sodium catalyzed with naphthalene and diglyme at ambient 4.2 These test methods can be used to determine when a
temperature. This process converts organic halogens to their usedpetroleumproductmeetsorexceedsrequirementsfortotal
respective sodium halides. Halides in the treated mixture, halogens measured as chloride. It is specifically designed for
including those present prior to the reaction, are then extracted used oils, permitting on-site testing at remote locations by
into an aqueous buffer, which is then titrated with mercuric nontechnical personnel to avoid the delays of laboratory
nitrateusingdiphenylcarbazoneastheindicator.Theendpoint testing.
of the titration is the formation of the blue-violet mercury
5. Apparatus
diphenylcarbazone complex.
5.1 Both the fixed end point test (Test Method A) and the
3.1.1 PresetreagentquantitiesareusedforTestMethodAso
quantitative test (Test Method B) are available as completely
that the final result is clearly determined to be either above or
self-contained test kits containing all the reagents necessary to
below 1000 mg⁄kg total chlorine.
complete the test. Each kit includes a sampling syringe to
3.1.1.1 Analysis time is approximately ten minutes, and the
withdraw a fixed volume of sample for analysis; a first
necessary reagents are all contained in a small test kit. Each kit
polyethylene test tube into which the sample is introduced for
contains sufficient materials for ten analyses.
dilution and reaction with metallic sodium; a second polyeth-
3.1.2 A fixed concentration titrant of mercuric nitrate in
ylene tube containing a buffered aqueous extractant, the
waterisusedforTestMethodB.Atitrationisperformedonthe
mercuric nitrate titrant (Test Method A only), and diphenyl
extracted aqueous sample until the color changes from yellow
carbazone indicator; a polypropylene filter funnel; and a 1 mL
to blue. At this point, the titration is stopped and the chlorine
titration syringe filled with mercuric nitrate titrant (Test
concentration is determined based on the volume of titrant
Method B only).
added. (Warning—In case of accidental breakage onto skin or
5.2 If prepackaged kits are not used, the following materials
clothing,washwithlargeamountsofwater.Allthereagentsare
and reagents will be required.
poisonousandshouldnotbetakeninternally.)(Warning—The
5.2.1 Test Tubes, two test tubes capable of holding 30 mL,
gray ampules contain metallic sodium which is a flammable,
sealed with screw caps.
water-reactive solid. Reaction with water will generate flam-
5.2.2 Filtration Device, composed of a funnel containing a
mable hydrogen gas.) (Warning—In addition to other
plug of polypropylene felt (or equivalent) to retain residual
precautions, do not ship kits on passenger aircraft. Kits contain
hydrocarbons from 5 mL of aqueous solution.
metallic sodium and mercury salts. Used kits will pass the
5.2.3 For quantitative Test Method B only, a 1.0 mL poly-
USEPAToxic Characteristic Leaching Procedure (TCLP) test.
propylene tuberculin type syringe or equivalent. The syringe is
Check with your state environmental enforcement office to see
to be marked with divisions at every 0.025 mL.
if additional disposal regulations may apply.)(Warning—
When the sodium ampule in either kit is crushed, oils that
6. Reagents
contain more than 25 % (m/m) water will cause the sample to
6.1 Ifprepackagedkitsaretobeused,allnecessaryreagents
turn clear to light gray and will build noticeable pressure.
and instructions are contained within the kits.
Under these circumstances, the results can be biased exces-
sively low and should be disregarded.) (Warning—In addition
6.2 If not using prepackaged kits, the following must be
to other precautions, take care to ensure that fingers are not cut
prepared.
by glass in the kits. All reagents in prepackaged kits are
6.2.1 A solution of 10 % (m/m) naphthalene in bis-2-
contained in crushable glass ampules inside plastic test tubes.
methoxy-ethyl ether (diglyme). Dissolve 10 g of naphthalene
Each ampule should be crushed only once to reduce the risk of
into 90 g of bis-2-methoxy-ethyl ether.
glass pieces piercing the sides of the tube. Wear safety glasses
6.2.2 Adispersion of 40 % (m/m) ground sodium in mineral
and gloves throughout the testing procedure.)
oil.
6.2.3 A0.15 % (mass/volume) solution of s-diphenyl carba-
4. Significance and Use
zone in ethyl alcohol. Dissolve 0.15 g s-diphenyl carbazone
powder into 100 mL of ethyl alcohol.
4.1 Chlorinated compounds can lead to corrosion of equip-
6.2.4 For Test Method A, a 4.75 mmol⁄L solution of mer-
ment and poisoning of the catalyst. Chlorinated compounds
curic nitrate. Prepare a mercuric nitrate stock solution by first
also present a health hazard when incompletely combusted.
dissolving 5.14 g Hg(NO ) ·HO(Warning—EXTREMELY
3 2 2
Chlorine content of petroleum products is determined prior to
TOXIC) in 5 mLof 50 % (vol/vol) nitric acid.After solute has
their being recycled.
completely dissolved, make up to 150 mL with Type II water.
NOTE1—FederalRegulationsmandatethatoftenthechlorinecontentof
Stock solution = 0.100 mol⁄L. Prepare 4.75 mmol⁄L solution
used oil must be determined before recycling. EPAregul
...
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