ASTM D5384-95(2005)
(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
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.
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 Bromide and iodide are also titrated and reported on a molar basis as chlorine.
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 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 to 1180 mg/kg5.
1.5 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.6This 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 and health practices and determine the applicability of regulatory limitations prior to use. Specific safety statements are given in Sections 3, 6, and 7.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D5384–95 (Reapproved 2005)
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 bility of regulatory limitations prior to use. Specific safety
statements are given in Sections 3, 6, and 7.
1.1 These test methods cover the determination of chlorine
in used oils, fuels, and related materials, including: crankcase,
2. Referenced Documents
hydraulic, diesel, lubricating and fuel oils, and kerosene, all
2.1 ASTM Standards:
containing <25 % (mass/mass) water.
D4057 Practice for Manual Sampling of Petroleum and
1.1.1 Bromide and iodide are also titrated and reported on a
Petroleum Products
molar basis as chlorine.
1.2 The entire analytical sequence, including sampling,
3. Summary of Test Methods
sample pretreatment, chemical reactions, extraction, and quan-
3.1 The oil sample (approximately 0.3 g) is dispersed in a
tification, is available in kit form using predispensed and
hydrocarbon solvent and reacted with a mixture of metallic
encapsulated reagents. The overall objective is to provide a
sodium catalyzed with naphthalene and diglyme at ambient
simple, easy to use procedure, permitting nontechnical person-
temperature. This process converts organic halogens to their
neltoperformatestinoroutsideofthelaboratoryenvironment
respective sodium halides. Halides in the treated mixture,
in under 10 min. The test method also gives information to run
including those present prior to the reaction, are then extracted
the test without a kit.
into an aqueous buffer, which is then titrated with mercuric
1.2.1 Test Method A is preset to provide a greater than or
nitrateusingdiphenylcarbazoneastheindicator.Theendpoint
less than result at 1000 mg/kg (ppm) total chlorine to meet
of the titration is the formation of the blue-violet mercury
regulatory requirements for used oils.
diphenylcarbazone complex.
1.2.2 Test Method B provides results over a range from 200
3.1.1 PresetreagentquantitiesareusedforTestMethodAso
to 4000 mg/kg total chlorine.
that the final result is clearly determined to be either above or
1.3 For both test methods, positive bias will result from
below 1000 mg/kg total chlorine.
samples that contain greater than 3 % (mass/mass) total sulfur.
3.1.2 A fixed concentration titrant of mercuric nitrate in
While a false negative result will not occur, other analytical
waterisusedforTestMethodB.Atitrationisperformedonthe
methods should be used on high sulfur oils.
extracted aqueous sample until the color changes from yellow
1.4 Test Method B, Lower Limit of Quantitation—In the
to blue. At this point, the titration is stopped and the chlorine
round-robin study to develop statistics for this test method,
concentration is determined based on the volume of titrant
participants were asked to report results to the nearest 100
added. (Warning—In case of accidental breakage onto skin or
mg/kg. The lower limit of quantification could therefore only
5 clothing,washwithlargeamountsofwater.Allthereagentsare
be determined to be in the range from 870 to 1180 mg/kg .
poisonousandshouldnotbetakeninternally.)(Warning—The
1.5 The values stated in SI units are to be regarded as
gray ampules contain metallic sodium which is a flammable,
standard. The values given in parentheses are for information
water-reactive solid. Reaction with water will generate flam-
only.
mable hydrogen gas.) (Warning—In addition to other precau-
1.6 This standard does not purport to address all of the
tions, do not ship kits on passenger aircraft. Kits contain
safety concerns, if any, associated with its use. It is the
metallic sodium and mercury salts. Used kits will pass the
responsibility of the user of this standard to establish appro-
USEPAToxic Characteristic Leaching Procedure (TCLP) test.
priate safety and health practices and determine the applica-
Check with your state environmental enforcement office to see
if additional disposal regulations may apply.) (Warning—
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and are the direct responsibility of Subcommit-
tee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved May 1, 2005. Published May 2005. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
´1
approved in 1995. Last previous edition approved in 2000 as D5384–95(2000) . Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5384-95R05. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5384–95 (2005)
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-
6.2 If not using prepackaged kits, the following must be
sively low and should be disregarded.) (Warning—In addition
prepared.
to other precautions, take care to ensure that fingers are not cut
6.2.1 A solution of 10 % (m/m) naphthalene in bis-2-
by glass in the kits. All reagents in prepackaged kits are
methoxy-ethyl ether (diglyme). Dissolve 10 g of naphthalene
contained in crushable glass ampules inside plastic test tubes.
into 90 g of bis-2-methoxy-ethyl ether.
Each ampule should be crushed only once to reduce the risk of
6.2.2 Adispersion of 40 % (m/m) ground sodium in mineral
glass pieces piercing the sides of the tube. Wear safety glasses
oil.
and gloves throughout the testing procedure.)
6.2.3 A0.15 % (mass/volume) solution of s-diphenyl carba-
zone in ethyl alcohol. Dissolve 0.15 g s-diphenyl carbazone
4. Significance and Use
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.
NOTE 1—Federal Regulations mandate that often the chlorine content
Stock solution = 0.100 mol/L. Prepare 4.75 mmol/L solution
of used oil must be determined before recycling.
byputting47.5mLofstocksolutionintoa1-Lvolumetricflask
and make up to 1 L with Type II water.
4.2 These test methods can be used to determine when a
usedpetroleumproductmeetsorexceedsrequirementsfortotal 6.2.5 For Test Method B, a 13.7-mmol/L solution of mer-
halogens measured as chloride. It is specifically designed for curic nitrate. Place 137 mL of stock solution (see 6.2.4) into a
used oils, permitting on-site testing at remote locations by
1-L volumetric flask and make up to 1 L with Type II water.
nontechnical personnel to avoid the delays of laboratory
6.2.6 An aqueous buffer solution containing 6 % (mass/
testing.
mass) sodium sulfate, 2.6 % (mass/mass) sodium phosphate
and 3.175 % (mass/mass) sulfuric acid (pH 1.5).
5. Apparatus
7. Sampling
5.1 Both the fixed end point test (Test Method A) and the
quantitative test (Test Method B) are available as completely
7.1 Take samples in accordance with the instructions in
self-contained test kits containing all the reagents necessary to
Practice D4057.
complete the test. Each kit includes a sampling syringe to
7.2 Free water, as a second phase, is to be removed.
withdraw a fixed volume of sample for analysis; a first
However, this second phase can be analyzed separately for
polyethylene test tube into which the sample is introduced for
chloride content by using a test method suitable for materials
dilution and reaction with metallic sodium; a second polyeth-
with high water content. (Warning—The gray ampules con-
ylene tube containing a buffered aqueous extractant, the
tain metallic sodium which is a flammable, water-reactive
mercuric nitrate titrant (Test Method A only), and diphenyl
solid. Reaction with water will generate flammable hydrogen
carbazone indicator; a polypropylene filter funnel; and a 1- mL
gas.) (Warning—When the sodium ampule in either kit is
titration syringe filled with merc
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