An American National Standard

Designation: D 5384 – 95 (Reapproved 2000)e1

Standard Test Methods for

Chlorine in Used Petroleum Products (Field Test Kit
Method)1
This standard is issued under the fixed designation D 5384; 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 (e) indicates an editorial change since the last revision or reapproval.

e1 NOTE—Warning notes were made part of the text in April 2000.

1. Scope bility of regulatory limitations prior to use. Specific safety

1.1 These test methods cover the determination of chlorine statements are given in Sections 3 and 6.
in used oils, fuels, and related materials, including: crankcase,
2. Referenced Documents
hydraulic, diesel, lubricating and fuel oils, and kerosene, all
containing <25 % (mass/mass) water. 2.1 ASTM Standards:
1.1.1 Bromide and iodide are also titrated and reported on a D 4057 Practice for Manual Sampling of Petroleum and
molar basis as chlorine. Petroleum Products2
1.2 The entire analytical sequence, including sampling, 3. Summary of Test Methods
sample pretreatment, chefru
mical reactions, extraction, and quantification, is available in 3.1 The oil sample (approximately 0.3 g) is dispersed in a
kit form using predispensed and encapsulated reagents. The hydrocarbon solvent and reacted with a mixture of metallic
overall objective is to provide a simple, easy to use procedure, sodium catalyzed with naphthalene and diglyme at ambient
permitting non-technical personnel to perform a test in or temperature. This process converts organic halogens to their
outside of the laboratory environment in under 10 min. The test respective sodium halides. Halides in the treated mixture,
method also gives information to run the test without a kit. including those present prior to the reaction, are then extracted
1.2.1 Method A is preset to provide a greater than or less into an aqueous buffer, which is then titrated with mercuric
than result at 1000 mg/kg (ppm) total chlorine to meet nitrate using diphenyl carbazone as the indicator. The end point
regulatory requirements for used oils. of the titration is the formation of the blue-violet mercury
1.2.2 Method B provides results over a range from 200 to diphenylcarbazone complex.
4000 mg/kg total chlorine. 3.1.1 Preset reagent quantities are used for Method A so that
1.3 For both methods, positive bias will result from samples the final result is clearly determined to be either above or below
that contain greater than 3 % (mass/mass) total sulfur. While a 1000 mg/kg total chlorine.
false negative result will not occur, other analytical methods 3.1.2 A fixed concentration titrant of mercuric nitrate in
should be used on high sulfur oils. water is used for Method B. A titration is performed on the
1.4 Method B Lower Limit of Quantitation—In the roun- extracted aqueous sample until the color changes from yellow
drobin study to develop statistics for this method, participants to blue. At this point, the titration is stopped and the chlorine
were asked to report results to the nearest 100 mg/kg. The concentration is determined based on the volume of titrant
lower limit of quantification could therefore only be deter- added. (Warning—In case of accidental breakage onto skin or
mined to be in the range from 870 to 1180 mg/kg5. clothing, wash with large amounts of water. All the reagents are
1.5 The values stated in SI units are to be regarded as the poisonous and should not be taken internally.) (Warning—The
standard. The values given in parentheses are for information gray ampules contain metallic sodium which is a flammable,
only. water-reactive solid. Reaction with water will generate flam-
1.6 This standard does not purport to address all of the mable hydrogen gas.) (Warning—In addition to other precau-
safety concerns, if any, associated with its use. It is the tions, do not ship kits on passenger aircraft. Kits contain
responsibility of the user of this standard to establish appro- metallic sodium and mercury salts. Used kits will pass the
priate safety and health practices and determine the applica- USEPA Toxic Characteristic Leaching Procedure (TCLP) test.
Check with your state environmental enforcement office to see
if additional disposal regulations may apply.) (Warning—
1
When the sodium ampule in either kit is crushed, oils that
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.
2
Current edition approved Aug. 15, 1995. Published October 1995. Annual Book of ASTM Standards, Vol 05.02.

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

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 D 5384 – 95 (2000)e1
contain more than 25 % (m/m) water will cause the sample to 6.2 If not using prepackaged kits, the following must be
turn clear to light gray and will build noticeable pressure. prepared.
Under these circumstances, the results can be biased exces- 6.2.1 A solution of 10 % (m/m) naphthalene in bis-2-
sively low and should be disregarded. (Warning—In addition methoxy-ethyl ether (diglyme). Dissolve 10 g of naphthalene
to other precautions, take care to ensure that fingers are not cut into 90 g of bis-2-methoxy-ethyl ether.
by glass in the kits. All reagents in pre-packaged kits are 6.2.2 A dispersion of 40 % (m/m) ground sodium in mineral
contained in crushable glass ampules inside plastic test tubes. oil.
Each ampule should be crushed only once to reduce the risk of 6.2.3 A 0.15 % (mass/volume) solution of s-diphenyl carba-
glass pieces piercing the sides of the tube. Wear safety glasses zone in ethyl alcohol. Dissolve 0.15 g s-diphenyl carbazone
and gloves throughout the testing procedure.) powder into 100 mL of ethyl alcohol.
6.2.4 For Method A, a 4.75-mmol/L solution of mercuric
4. Significance and Use nitrate. Prepare a mercuric nitrate stock solution by first
4.1 Chlorinated compounds can lead to corrosion of equip- dissolving 5.14 g Hg(NO 3 ) 2 ·H 2 O (WARNING-
ment and poisoning of the catalyst. Chlorinated compounds EXTREMELY TOXIC) in 5 mL of 50 % (vol/vol) nitric acid.
also present a health hazard when incompletely combusted. After solute has completely dissolved, make up to 150 mL with
Chlorine content of petroleum products is determined prior to Type II water. Stock solution = 0.100 mol/L. Prepare 4.75
their being recycled. mmol/L solution by putting 47.5 mL of stock solution into a
1-L volumetric flask and make up to 1 L with Type II water.
NOTE 1—Federal Regulations mandate that often the chlorine content
6.2.5 For Method B, a 13.7-mmol/L solution of mercuric
of used oil must be determined before recycling.
nitrate. Place 137 mL of stock solution (see 6.2.4) into a 1-L
4.2 These test methods can be used to determine when a volumetric flask and make up to 1 L with Type II water.
used petroleum product meets or exceeds requirements for total 6.2.6 An aqueous buffer solution containing 6 % (mass/
halogens measured as chloride. It is specifically designed for mass) sodium sulfate, 2.6 % (mass/mass) sodium phosphate
used oils, permitting on-site testing at remote locations by and 3.175 % (mass/mass) sulfuric acid (pH 1.5).
nontechnical personnel to avoid the delays of laboratory
testing. 7. Sampling
7.1 Take samples in accordance with the instructions in
5. Apparatus Practice D 4057.
5.1 Both the fixed end point test (Method A) and the 7.2 Free water, as a second phase, is to be removed.
quantitative test (Method B) are available as completely However, this second phase can be analyzed separately for
self-contained test kits containing all the reagents necessary to chloride content by using a method suitable for materials with
complete the test.3 Each kit includes a sampling syringe to high water content (Warning—The gray ampules contain
withdraw a fixed volume of sample for analysis; a first metallic sodium which is a flammable, water-reactive solid.
polyethylene test tube into which the sample is introduced for Reaction with water will generate flammable hydrogen gas.)
dilution and reaction with metallic sodium; a second polyeth- (Warning—When the sodium ampule in either kit is crushed,
ylene tube containing a buffered aqueous extractant, the oils that contain more than 25 % (m/m) water will cause the
mercuric nitrate titrant (Method A only), and diphenyl carba- sample to turn clear to light gray and will build noticeable
zone indicator; a polypropylene filter funnel; and a 1- mL pressure. Under these circumstances, the results can be biased
titration syringe filled with mercuric nitrate titrant (Method B excessively low and should be disregarded.).
only).
5.2 If prepackaged kits are not used, the following materials 8. Procedure (Methods A and B)
and reagents will be required. NOTE 2—Perform the test in a dry area with an ambient temperature
5.2.1 Test Tubes, two test tubes capable of holding 30 mL, greater than 15°C (60°F) and adequate light. In cold weather, a truck cab
sealed with screw caps. is sufficient.
5.2.2 Filtration Device, composed of a funnel containing a 8.1 Using a volumetric pipette, place 0.40 6 0.02 mL of
plug of polypropylene felt (or equivalent) to retain residual sample into one of the polyethylene tubes.
hydrocarbons from 5 mL of aqueous solution. 8.2 Using a volumetric pipette, add 1.5 mL of naphthalene/
5.2.3 For quantitative Method B only, a 1.0-mL polypropy- bis-2-methoxyethyl ether solution. Shake well.
lene tuberculin type syringe or equivalent. The syringe is to be 8.3 Add 200 mg of metallic sodium dispersion (80 mg Na)
marked with divisions at every 0.025 mL. and shake well for 1 min.
8.4 Add 7 mL of aqueous buffer solution to the mixture. Cap
6. Reagents and shake well. Vent the tube so that the resulting pressure is
6.1 If prepackaged kits are to be used, all necessary reagents released.
and instructions are contained within the kits. 8.5 Allow the aqueous and hydrocarbon phases to separate
for 2 min. Decant off the aqueous phase and pass 5 mL through
the polypropylene filter into a second polyethylene tube.
3
Clor-D-Tect 1000 (Method A) and Clor-D-Tect Q4000 (Method B), available
8.6 Method A (Qualitative at 1000 mg/kg)—Add 0.75 mL of
from Dexsil Corp., One Hamden Park Dr., Hamden, CT 06517, have been found 4.75 mmol/L mercuric nitrate solution to the 5 mL of aqueous
satisfactory for this purpose. filtrate. Shake well.

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 D 5384 – 95 (2000)e1
8.6.1 Add approximately 0.5 mL of diphenylcarbazone 11. Precision and Bias
indicator solution. Shake well. 11.1 For Method A, no formal statement is made about
8.6.2 Observe color. A violet solution means the original oil either the precision or bias of the test method because the result
sample contains less than 1000 mg/kg total chlorine. A yellow merely states whether there is conformance to the criteria for
or colorless solution means the oil sample contains greater than success specified in the procedure, that is, a blue or yellow
1000 mg/kg total chlorine. color in the final solution. In a collaborative study,4 ten
8.7 Method B (Quantitative to 4000 mg/kg)—Fill the 1 cc laboratories analyzed seven used oil samples and one unused
tuberculin syringe with 13.7 mmol/L of mercuric nitrate motor oil sample using prepackaged test kits. Each laboratory
solution to a volume of 1.0 mL by placing the tip of the syringe ran each sample in duplicate. Out of the eighty samples that
in the mercuric nitrate solution and withdrawing the plunger were run, one laboratory’s results disagreed with the rest of the
slowly until the syringe is full. If a burette is used instead of a laboratories’ results on one sample. All 79 other tests were in
syringe, fill the burette with the mercuric nitrate solution and agreement with their duplicates and with other laboratories’
dispense solution until the meniscus is at the zero point. results. These data indicate that all participants get results of
8.7.1 Add approximately 0.5 mL of diphenylcarbazone <1000 for all samples containing less than 870 mg/kg Cl, 9 out
solution to the 5 mL of aqueous filtrate and mix well. of 10 get >1000 on a sample at 1180 mg/kg, and all participants
8.7.2 Place the filled tuberculin syringe in the polyethylene get >1000 at and above 1272 mg/kg. These data indicate that
tube containing the aqueous filtrate and indicator reagent, and this test method makes correct predictions for samples contain-
slowly depress the syringe so that the mercuric nitrate titrant is ing <870 or >1272 mg/kg and probably correct predictions for
dispensed drop by drop. If the burette is used, add titrant drop samples between 870 and 1272 mg/kg Cl. See Table 1.
by drop. Gently shake the solution between each drop. Stop
titrating when a persistent violet color remains throughout the
TABLE 1 Repeatability and Reproducibility
solution.
Reproducibility
8.7.3 Examine the titrating syringe and determine where the mg/kg Cl (ppm) Repeatability 46.1X0.25
84.44X0.25
tip of the plunger is in relation to the scale marked on the 100 146 267
outside of the syringe barrel. Determine the amount of titrant 500 218 399
(to the nearest 0.025 mL) that has been used. 1000 259 474
1500 287 525
2000 308 565
9. Interpretation of Results 2500 326 597
3000 341 625
9.1 Calculations are not required when prepackaged kits are 4000 367 672
used.
9.2 For Method A, report results as either greater than or
less than 1000 mg/kg (ppm).
11.2 Precision and Bias Statement for Method B.
9.3 For Method B, calculate the concentration (mg/kg) of
11.2.1 Precision—The following criteria should be used for
total chlorine in the original oil sample by the following
judging the acceptability of results.
equation:
11.2.2 Repeatability—The difference between successive
~V 2 0.05!~c!~35.45!~F! test results obtained by the same operator with the same
Chlorine ~mg/kg! 5 m (1)
apparatus under constant operating conditions on identical test
where: material would, in the long run, and in the normal and correct
V = volume of mercuric nitrate titrant used, mL, operation of this test method, exceed the stated values only in
0.05 = volume of excess titrant required for color forma- one case in twenty.
tion, mL, Repeatability 5 46.1 X0.25 (2)
c = concentration of mercuric nitrate solution, meq/L,
for example, 27.4, where:
35.45 = average atomic weight of chlorine, X = method result, mg/kg.
F = dilution factor due to adding 7 mL of buffer 11.2.3 Reproducibility—The difference between two single
solution and extracting only 5 mL for analysis, for and independent results obtained by different operators work-
example, 1.4, and ing in different laboratories on identical test material would, in
m = mass of oil sample used, for example, 0.34 g for a the long run, and in the normal and correct operation of this test
volume of 0.4 mL motor oil, g. method, exceed the stated values only in one case in twenty.
Reproducibility 5 84.44 X0.25 (3)
10. Quality Control
10.1 Test each sample two times. For Method A, if the where:
results do not agree, a third test must be performed. Report the X = method result, mg/kg.
results of the two that agree. For Method B, the two results
should be within 20 % or 300 mg/kg (whichever is larger) of
each other. If they are not, perform a third test and report the 4
Data supporting this study is available from ASTM Headquarters. Request
results of the two tests that agree. RR:D02-1368.

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 D 5384 – 95 (2000)e1
11.2.4 In a collaborative study,4 using prepackaged kits, ten 12. Keywords
laboratories analyzed seven used oil samples and one unused
12.1 chlorine; field test; halogen; on-site testing; test kit;
motor oil sample.
used oil
11.2.5 Bias—No bias statement is made for this test method
because results obtained for total chlorine were determined
only by the test method itself.

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