Designation: D6229 − 06 (Reapproved 2010)
Standard Test Method for
Trace Benzene in Hydrocarbon Solvents by Capillary Gas
Chromatography1
This standard is issued under the fixed designation D6229; 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* 2.2 ASTM Adjuncts:
1.1 This test method covers the determination by capillary D2PP Determination of Precision and Bias Data3
gas chromatography of trace benzene in hydrocarbon solvents
at levels from 1.0 to 2400 vppm. 3. Summary of Test Method
NOTE 1—Lower levels of benzene may be determined by this test
3.1 A given volume of the sample is introduced into a gas
method. However the gas chromatography (GC) will have to be modified chromatograph equipped with two capillary columns con-
from those specified in this test method. The precision of the method may nected in series by switching valve. The specimen passes first
not apply to these lower benzene levels. through a short capillary column with a bounded nonpolar
1.2 For hazard information and guidance, see the supplier’s phase where the components are separated by boiling point.
Material Safety Data Sheet. After octane has eluted from the first column, the components
heavier than octane are back-flushed to vent. The octane and
1.3 The values stated in SI units are to be regarded as the
lighter components then pass through a second capillary
statement. The values in parenthesis are given for information
column with bounded polar phase where the aromatic and
only and are not necessarily the exact equivalent of the SI unit
nonaromatic components are separated. The eluted compo-
values.
nents are detected by a flame ionization detector, and the peak
1.4 For purposes of determining conformance of an ob- areas are integrated electronically. The concentration of ben-
served or a calculated value using this test method to relevant zene is calculated by a data processor using a response factor
specifications, test result(s) shall be rounded off “to the nearest determined by external standard technique.
unit” in the last right-hand digit used in expressing the
specification limit, in accordance with Practice E29. 4. Significance and Use
1.5 This standard does not purport to address all of the 4.1 This test method is similar to Test Method D4367 with
safety concerns, if any, associated with its use. It is the the exception that capillary columns are used and intended for
responsibility of the user of this standard to establish appro- trace level of benzene in hydrocarbon solvents. The need for
priate safety and health practices and determine the applica- trace benzene analysis in hydrocarbon solvents arose because
bility of regulatory limitations prior to use. of the increase of more stringent regulation of benzene level in
2. Referenced Documents these materials.
2.1 ASTM Standards:2 5. Apparatus
D4367 Test Method for Benzene in Hydrocarbon Solvents
by Gas Chromatography 5.1 Chromatograph—Any gas chromatographic instrument
E29 Practice for Using Significant Digits in Test Data to that has a backflush system operated by a switching valve
Determine Conformance with Specifications automatically, flame ionization detector, and can be operated at
E300 Practice for Sampling Industrial Chemicals the conditions given in Table 1.
5.2 Detector—The flame ionization detector shall have suf-
1
This test method is under the jurisdiction of ASTM Committee D01 on Paint
ficient sensitivity to detect 0.1 vppm of benzene at a peak
and Related Coatings, Materials, and Applications and is the direct responsibility of height of 3 times the noise level.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates
Current edition approved Dec. 1, 2010. Published December 2010. Originally
5.3 Columns—one 2–m (6.5–ft), 0.53 mm inside diameter
approved in 1998. Last previous edition approved in 2006 as D6229 – 06. DOI: fused silica capillary with 5-µm thick bounded methyl silicone
10.1520/D6229-06R10.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at
[email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available from ASTM International Headquarters. Order Adjunct No.
the ASTM website. ADJD6300.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
D6229 − 06 (2010)
TABLE 1 Instrument Conditions Found Satisfactory for 8. Preparation and Conditioning of Capillary Columns
Measuring Trace Concentrations of Benzene in Hydrocarbon
Solvents 8.1 Both columns prescribed by this procedure shall be
GC Parameter Values
obtained ready to use from reputable chromatographic suppli-
Detector Flame ionization detector (FID) ers.
Columns:
Length, m (A) 2; (B) 30 8.2 Columns shall be conditioned following column sup-
Inside diameter, mm (A) 0.53; (B) 0.53 plier recommended procedures before use.
Liquid phase, bonded (A) methyl silicone; (B) polyethylene glycol
Liquid phase thickness (A) 5 µm; (B) 0.5 µm 9. Preparation of Gas Chromatograph
Switching value temperature 150°C (302°F)
Temperature programme: 9.1 Connect columns A and B to the 6–port switching valve
Initial temperature 40°C (104°F) by referring to Fig. 1.
Initial time hold 8 min
Ramp rate 20°C (68°F)/min 9.1.1 Adjust the operating conditions to those listed in Table
Final temperature 200°C (392°F) 1, but do not turn on the detector. Check the system for leaks.
Final time hold 5 min
Sample size 1 µL 9.2 Adjust the column flow rate as follows:
Split ratio 1:10 9.2.1 Set the switching valve in the forward flow mode (Fig.
Column flow (He carrier gas) 5.0 mL/min
Backflush to vent activation time 3.0 min
2 (a)) and adjust the flow controller to give the required column
flow rate.
9.2.2 Set the switching valve in the backflush mode (Fig. 2
column and one 30–m (98.5–ft), 0.53-mm inside diameter (b)) and check that the column flow is as required.
fused silica capillary with 0.5-µm thick bounded polyethylene 9.2.3 Turn on the detector. Change the switching from the
glycol column. forward flow to the backflush mode several times and observe
the baseline. There shall be no baseline shift resulting from the
5.4 Switching Valve—A 6–port switching valve 175°C (347 pressure surge when the switching valves are changed. (A
°F) maximum temperature, housed in a separate, temperature- persistent drift indicates leaks somewhere in the system).
controlled oven, that can be activated automatically by the gas
chromatograph. 9.3 Determine the backflush activation time. The backflush
activation time varies for each column system and shall be
5.5 Sample Inlet System—The sample inlet system shall be determined experimentally as follows:
capable of split injection typically at a 1:10 split ratio. 9.3.1 Prepare a solution of 0.1 v % n–octane and 0.1 v %
NOTE 2—An auto injector was used in the generation of the repeatabil- n–nonane in benzene-free n–hexane. With the system in the
ity value of this test method, and is recommended. Manual injection with forward flow mode, introduce 1µL of the n–octane/n–nonane in
a syringe is acceptable; however, the observed precision may not apply. n–hexane mixture. Allow the chromatogram to run until the n
5.6 Data Acquisition System: –nonane has eluted from the second column and the chromato-
5.6.1 Recorder—A 0 to 1 mv range recorder or equivalent, graphic trace has returned to baseline. Measure the time in
with a full-scale response time of 2 s shall be used. minutes from the injection until the signal goes back to
5.6.2 Integrator—Means shall be provided for determining baseline after the n–octane peak. At this point all of the
the area of the benzene peak. This can be done by means of an n–octane but essentially none of the n–nonane shall have
electronic integrator or a computer based chromatography data eluted. One half of the measured time approximates the time to
system. The integrator/computer system shall have standard backflush (see 9.3.3).
chromatographic software for determining the retention times
NOTE 3—Some minor adjustment of the backflush activation time may
and areas of eluting peaks. be necessary for some samples.
5.7 Microsyringe—5 µL capacity. 9.3.2 Repeat the run, including the injection of the
5.8 Pipets—measuring 1 and 2 mL, graduated in 0.01 mL: n–octane/n–nonane in a n–hexane mixture, but switching the
5, 10, and 20 mL capacity. system to the backflush mode at the determined backflush
activation time. This should result in a chromatogram showing
5.9 Pipets—delivery 0.5, 1, 2, 5, 10, 25 mL capacity.
only n–hexane and n–octane, with little or no n–nonane
5.10 Flasks—volumetric, 25, 50, 100, and 500 mL capacity. evident.
9.3.3 If necessary, make additional runs, adjusting the
6. Reagents
backflush activation time until a chromatogram of all the
6.1 Purity of Reagents—All reagents shall be reagent grade n–octane (evidenced by a repeatable and constant area count)
chemicals with a minimum purity of 99 + mol %. and little or none of the n–nonane is obtained. The established
6.1.1 Benzene. backflush activation time for a particular type of sample shall
6.1.2 n-Hexane, benzene-free. be used in all subsequent calibration and analysis.
6.1.3 n-Octane, benzene-free.
6.1.4 n-Nonane, benzene-free. 10. Calibration and Standardization
10.1 5000 vppm Stock Solution—Prepare a 5000-vppm ben-
7. Sampling zene in n–hexane stock solution by accurately delivering 0.50
7.1 Take samples of solvents to be analyzed by this test mL of 99+ % purity benzene into a 100–mL volumetric flask
method using the procedures described in Practice E300. by means of a delivery pipet. Dilute to the mark with n–hexane.
2
D6229 − 06 (2010)
FIG. 1 Columns Connections to Switching Valve
FIG. 2 Flow Switching System
3
D6229 − 06 (2010)
This stock solution can be used to prepare various levels of 12. Calculation
benzene in n–hexane by accurately diluting the required
12.1 Using the software of the data system and the response
volume of this solution with n –hexane in a volumetric flask.
factor obtained in 10.3 calculate the benzene concentration (in
10.2 Calibration Standard Solution—Prepare a 10.0 vppm vppm) in the sample corresponding to the peak area determined
benzene in n –hexane calibration standard solution by accu- in 11.1. Manual calculation can be done by using the following
rately delivering 1.0 mL of the 5000 vppm stock solution into equation:
a 500–mL volumetric flask. Dilute to the mark with n–hexane.
Cx 5 Rf 3 Ax (2)
This calibration standard can be used in calibrate the procedure
by external standard technique. where:
10.3 Calibration—If the system has not been used for at Cx = the benzene concentration in the sample in vppm,
least 12 h, condition the system by running the GC method Rf = the response factor determined in 10.3, and
once without injecting any sample. After conditioning, intro- Ax = the area of the benzene peak in the sample.
duce 1 µL of the 10 vppm benzene in n–hexane calibration 12.2 If the results are desired on a weight basis, convert
standard by the recommended injection technique and allow vppm to wppm as follows:
the run to be completed. Determine the response factor for the Benzene, wppm 5 ~ C x /D ! 3 0.8844 (3)
benzene peak by means of the integrator/data system. The
response factor can also be calculated manually by using the where:
following equation: Cx = the benzene concentration in the sample in vppm,
R r 5 C b /A b (1) D = the relative density of the sample at 15.6/15.6°C
(60/60°F), and
where: 0.8844 = the relative density of benzene at 15.6/15.6°C
Rf = the response factor for benzene in vppm per unit area, (60/60°F).
Cb = the concentration of benzene in the calibration standard
in vppm, and 13. Report
Ab = the area of the benzene peak in the calibration standard.
13.1 Report the concentration of benzene in the sample to
10.4 Adjust the detector sensitivity in such a way that 3 the nearest 0.1 vppm. or 0.1 wppm.
times the noise level is equivalent to a benzene concentration
of at least 0.1 vppm. 14. Precision and Bias4
NOTE 4—The repeatability reported for this test method was determined 14.1 Precision—The following criteria should be used to
from data generated by a single point, external standard calibration with a
10 vppm benzene in n–hexane standard solution. If so desired, multipoint judge the acceptability (95 % confidence level) of the results
calibration can be done by preparing various levels of benzene in obtained by this test method. The criteria were derived from an
n–hexane and the data can be used to generate a calibration curve. interlaboratory study involving six samples having benzene
NOTE 5—Linearity of the benzene response has been confirmed from 1 levels from 1 to >500 vppm, run in duplicate in three
vppm to 2400 vppm. laboratories. The data were statistically evaluated by the D2PP
software3 used by D02 Committee.
11. Procedure
14.1.1 Repeatability—The repeatability of this test method
11.1 If the system has not been used for at least 12 h, is dependent on the benzene level, and is given by the equation:
condition the system by running the GC method once without
Repeatability ~ r ! 5 0.0076~ X113.30! 1.32 vppm (4)
injecting any sample. After conditioning, introduce 1 µL of the
0.1 v % n–octane and 0.1 v % n–nonane in n–hexane mixture where X is the benzene level.
(9.3.1) or any sample that requires analysis of trace level 14.1.2 Reproducibility—The reproducibility of this test
benzene. Identify the retention time for benzene in the method is dependent on the benzene level, and is given by the
chromatogram, and determine the area of the benzene peak equation:
using an electronic integrator/data system. A typical chromato-
Reproducibility ~ R ! 5 0.032~ X113.30! 1.32 vppm (5)
gram of a sample containing non-aromatics, benzene, and
toluene is shown in Fig. 3. where X is the benzene level.
14.2 Table 2 gives examples of calculated repeatability and
reproducibility for various levels of benzene, using Eq 4 and
Eq 5.
TABLE 2 Calculated Precision for Various Benzene Level
Benzene (vppm) Repeatability (r) Reproducibility (R) 14.3 Bias—Bias cannot be determined for this test method
5 0.4 1.5 because there is no available material having an accepted
10 0.5 2.1
20 0.8 3.3
reference value.
50 1.8 7.7
100 3.9 16.6
200 9.0 38.2
4
500 28.6 121.8 Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D01-1122.
4
D6229 − 06 (2010)
5
FIG. 3 Typical Chromatogram
D6229 − 06 (2010)
15. Keywords
15.1 benzene content; capillary GC; gas chromatography;
hydrocarbon solvents
SUMMARY OF CHANGES
Committee D01.35 has identified the location of selected changes to this standard since the last issue
(D6229 – 01) that may impact the use of this standard. (Approved April 1, 2006.)
(1) Added reference to Practice E29 in the scope section. (2) Added Practice E29 to list of Referenced Standards.
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