ASTM D4367-22

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: D4367 − 22
Standard Test Method for
Benzene in Hydrocarbon Solvents by Gas Chromatography
This standard is issued under the fixed designation D4367; 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 D6229 Test Method for Trace Benzene in Hydrocarbon
Solvents by Capillary Gas Chromatography
1.1 This test method covers the determination by gas
E29 Practice for Using Significant Digits in Test Data to
chromatography of benzene at levels from 0.01 to 1 volume %
Determine Conformance with Specifications
in hydrocarbon solvents.
E300 Practice for Sampling Industrial Chemicals
NOTE 1—For benzene levels lower than 0.01 volume %, use Test
Method D6229. 3. Summary of Test Method
1.2 The values stated in SI units are to be regarded as the 3.1 An internal standard, methyl ethyl ketone (MEK), is
standard. The values given in parentheses are for information added to the material and then introduced into a gas chromato-
only. graph equipped with two columns connected in series. The
specimen passes first through a column packed with the
1.3 For purposes of determining conformance of an ob-
nonpolar phase, methyl silicone, which separates the compo-
served or a calculated value using this test method to relevant
nents by boiling point. After octane has eluted, the flow
specifications, test result(s) shall be rounded off “to the nearest
through the nonpolar column is reversed, flushing out the
unit” in the last right-hand digit used in expressing the
components heavier than octane. The octane and lighter
specification limit, in accordance with the rounding-off method
components then pass through a column with the highly polar
of Practice E29.
phase, 1,2,3-tris(2-cyanoethoxy)propane, that separates the
1.4 For hazard information and guidance, see the supplier’s
aromatic and nonaromatic compounds. The eluted components
Material Safety Data Sheet. For specific hazard statements, see
are detected by a conventional detector and recorded on a strip
Section 7.
chart. The peak areas are measured and the concentration of
1.5 This standard does not purport to address all of the each component is calculated by reference to the internal
safety concerns, if any, associated with its use. It is the
standard.
responsibility of the user of this standard to establish appro-
4. Significance and Use
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use. 4.1 Benzene is classed as a toxic and carcinogenic material.
Aknowledge of the concentration of this compound may be an
1.6 This international standard was developed in accor-
dance with internationally recognized principles on standard- aid in evaluating the possible health hazards to persons
handling and using hydrocarbon solvents, but this test method
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom- is not intended to evaluate such hazards.
mendations issued by the World Trade Organization Technical
5. Apparatus
Barriers to Trade (TBT) Committee.
5.1 Chromatograph—Any gas chromatographic instrument
2. Referenced Documents that has a backflush system and flame ionization detector and
that can be operated at the conditions given in Table 1. The
2.1 ASTM Standards:
detector-recordercombinationmustproducea4-mmdeflection
for a 1-µL specimen containing 0.05 volume % MEK when
This test method is under the jurisdiction of ASTM Committee D01 on Paint
operated at maximum sensitivity.
and Related Coatings, Materials, andApplications and is the direct responsibility of
5.2 Columns, one 0.8-m (2.5-ft) length of 3.2-mm ( ⁄8-in.)
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
Current edition approved Jan. 1, 2022. Published January 2022. Originally
outside diameter stainless steel tubing and one 4.6-m (15-ft)
approved in 1984. Last previous edition approved in 2012 as D4367 – 02 (2012)
length of 3.2-mm ( ⁄8-in.) outsider diameter stainless steel
which was withdrawn January 2021 and reinstated in January 2022. DOI: 10.1520/
tubing.
D4367-22.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
5.3 Recorder, Strip Chart—Potentiometer with a full-scale
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
deflection of 1 mV, a full-scale response time of2sor less, and
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. a maximum noise level of 60.3 % of full scale.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4367 − 22
TABLE 1 Instrument Conditions Found Satisfactory for
6.3 Chloroform.
Measuring Low Concentrations of Benzene in
6.4 Diatomaceous Earth —Acid-washed, 60 to 80 mesh
Hydrocarbon Solvents (Note 2)
and 80 to 100 mesh.
Detector flame ionization
Columns two, stainless steel
6.5 Helium, 99.99 % pure.
Length, m (A) 0.8; (B) 4.6
Outside diameter, mm 3.2
6.6 Methanol.
Stationary phases (A) methyl silicone, 10 weight %
(B) TCEP, 25 weight % 6.7 Methylene Chloride.
Support (A) acid-washed calcined diatomite, 60 to
6.8 Methyl Ethyl Ketone (MEK), 99.9 mol %.
80-mesh
(B) acid-washed pink diatomaceous
6.9 Methyl Silicone.
earth, 80 to 100-mesh
Reference column any column or restriction may be used 4
6.10 1,2,3-Tris(2-Cyanoethoxy) Propane (TCEP).
Temperature, °C
Injection port 150
6.11 Calibration Standards.
Column, isothermal 100
+
6.11.1 Benzene, 99 mol %.
Detector block 150
+
6.11.2 Isooctane, 99 mol %.
Carrier gas helium
+
Flow rate, mL/min approximately 30
6.11.3 n-Nonane, 99 mol %.
Recorder range, mV 0 to 1
Chart speed, mm/min 10
Specimen size, µL 1.0 7. Hazards
Time to backflush, min approximately 2
7.1 Many hydrocarbon solvents are flammable and hazard-
Total cycle time, min approximately 30
ous; use special precautions when handling them. Of the
reagents used in this procedure, methanol, chloroform, meth-
ylenechloride,acetone,methylethylketone,benzene(see4.1),
5.4 Microsyringe, 5-µL capacity.
and n-nonane are hazardous.
5.5 Pipets, measuring 1 and 2 mL, graduated in 0.01 mL; 5,
7.2 Benzene is volatile and highly flammable. Exercise care
10, and 20-mL capacity.
to prevent accidental ignition. Benzene is also carcinogenic
and toxic; acute or chronic poisoning may result from inhala-
5.6 Flasks, volumetric, 25 and 100-mL capacity.
tion of benzene vapor, absorption of benzene through the skin,
5.7 Vibrator, electric.
or drinking benzene.
5.8 Vacuum Source.
8. Sampling
5.9 Evaporator, vacuum, rotary.
8.1 Take samples of solvents to be analyzed by this test
5.10 Flask, boiling, round-bottom, short-neck, with 24/40 T
method using the procedures described in Practice E300.
joint, 500-mL capacity. Suitable for use with the evaporator
(see 5.9).
9. Preparation of Columns
5.11 Lamp, infrared.
9.1 Column Packing Preparation—Prepare the two packing
5.12 Burets, automatic, with integral reservoir, 25-mL ca-
materials, one containing 10 % methyl silicone and the other
pacity.
25 % TCEP, as follows:
NOTE 2—Suppliers of stationary phases and supports can be found in
9.1.1 Weigh 45 g of the acid-washed calcined diatomite
Research Report RR:D01-1038, available from ASTM International
support60to80mesh,intoa500-mLflask(see5.10).Dissolve
Headquarters.
5 g of the methyl silicone in approximately 50 mL of
chloroform. (Warning—Chloroform is a toxic material and
6. Reagents and Materials
inhalation must be avoided.) Pour the methyl silicone–chloro-
6.1 Purity of Reagents—Reagent grade chemicals shall be
form solution into the flask containing the support. Attach the
used in all tests. Unless otherwise indicated, it is intended that
flask to the evaporator (see 5.9), connect the vacuum, and start
all reagents shall conform to the specifications of the Commit-
the motor. Turn on the infrared lamp and allow the packing to
tee onAnalytical Reagents of theAmerican Chemical Society,
mix thoroughly until dry.
where such specifications are available. Other grades may be
9.1.2 Weigh 75 g of acid-washed pink diatomaceous earth,
used, provided it is first ascertained that the reagent is of
80 to 100 mesh, into a 500-mL flask (see 5.10). Dissolve 25 g
sufficiently high purity to permit its use without lessening the
of TCEP in 200 mL of methanol and pour into the flask
accuracy of the determination.
containing the support. Attach the flask to the evaporator (see
6.2 Acetone. 5.9), connect the vacuum, and start the motor. Turn on the
infrared lamp and allow the packing to mix thoroughly until
dry, but do not heat the packing above 180 °C.
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
9.2 Column Preparation:
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. See Note 2.
D4367 − 22
9.2.1 Clean the stainless steel tubing as follows: Attach a at approximately 40 mL/min. Condition the columns in accor-
metal funnel to one end of the steel tubing. Hold or mount the dance with the following time-temperature schedule.
stainless steel tubing in an upright position and place a beaker
Temperature, °C Time, h
50 ⁄2
under the outlet end of the tubing. Pour about 50 mL of
100 ⁄2
methylenechlorideintothefunnelandallowittodrainthrough
150 1
thesteeltubingintothebeaker.Repeatthewashingwith50mL
170 3
of acetone. Remove the funnel and connect the steel tubing to
10.2 Connect the outlet of Column B to the detector port.
an air line, by means of vinyl tubing. Remove all solvent from
Adjust the operating conditions to those listed in Table 1, but
the steel tubing by blowing filtered, oil-free air through or
do not turn on the detector circuits. Check the system for leaks.
app
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