ASTM D5135-21

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of the standard as published by ASTM is to be considered the official document.
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Designation: D5135 − 16 D5135 − 21
Standard Test Method for
Analysis of Styrene by Capillary Gas Chromatography
This standard is issued under the fixed designation D5135; 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.
ε NOTE—Table 3 was editorially corrected in November 2016.
1. Scope*Scope
1.1 This test method covers the determination of the impurities typically found in styrene and uses those values to determine the
purity of styrene by difference by gas chromatography. Typical impurities in commercial styrene are found in Table 1.
1.2 This test method is applicable to impurity concentrations in the range of 0.001 to 1.00 % and for styrene purities of 99 % or
higher when using the internal standard procedure.up to 1 %.
1.2.1 The limit of detection is 0.0003 mass % and the limit of quantitation is 0.0010 mass %.
1.2.2 LOD and LOQ were calculated using data from ILS results for n-propylbenzene in Table 3.
1.3 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off
in accordance with the rounding-off method of Practice E29.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all the safety concerns, if any, associated with its use. It is the responsibility of
the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. For a specific hazard statement, see Section 9.
1.6 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.
2. Referenced Documents
2.1 ASTM Standards:
D3437 Practice for Sampling and Handling Liquid Cyclic Products
D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards
D4790 Terminology of Aromatic Hydrocarbons and Related Chemicals
D6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
This test method is under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons Aromatic, Industrial, Specialty and Related Chemicals and is the direct
responsibility of Subcommittee D16.07 on Styrene, Ethylbenzene and C9 and C10 Aromatic Hydrocarbons.
Current edition approved June 1, 2016Jan. 1, 2021. Published October 2016February 2021. Originally approved in 1990. Last previous edition approved in 20142016 as
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D5135 – 14.D5135 – 16 . DOI: 10.1520/D5135-16E01.10.1520/D5135-21.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
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D5135 − 21
TABLE 1 Impurities Known or Suggested to be Present in
Commercial Styrene
Ethylbenzene
o-xylene
m-xylene
p-xylene
Isopropylbenzene
n-propylbenzene
m-ethyltoluene
p-ethyltoluene
α-methylstyrene
m-vinyltoluene
p-vinyltoluene
Phenylacetylene
E355 Practice for Gas Chromatography Terms and Relationships
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
E1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
2.2 Other Document
OSHA Regulations, 29 CFR paragraphs 1910.1000 and 1910.1200
3. Terminology
3.1 See Terminology D4790 for definitions of terms used in this test method.
4. Summary of Test Method
4.1 In this test method, the chromatogram peak area for each impurity is compared to the peak area of the internal standard
(n-heptane or other suitable known) added to the sample. From the response factors of these impurities relative to that of the
internal standard and the amount of internal standard added, the concentration of the impurities are calculated. The styrene content
is obtained by subtracting the total amount of all impurities from 100.00.
5. Significance and Use
5.1 This test method is designed to obtain styrene purity on the basis of impurities normally present in styrene and may be used
for final product inspections and process control.
TABLE 2 Recommended Operating Conditions
Carrier gas helium
A
Carrier gas helium, nitrogen, or hydrogen
Carrier gas flow rate at 110°C, mL/min 1.2
Detector flame ionization
Detector temperature, °C 240
Injection port temperature, °C 230
Hydrogen flow rate, mL/min 30
Air flow rate, mL/min 275
Make up gas nitrogen
Make up gas flow rate, mL/min 23
Split flow, mL/min 150
Column 60 m × 0.32 mm ID × 0.5 μm
bonded polyethylene glycol-
fused silica capillary
Column temperature, °C 110
Chart speed, cm/min 1
Sample size, μL 0.6
A
Warning—Helium carrier gas was used to develop this standard. Use of
nitrogen or hydrogen carrier gas requires different conditions. The user must
conduct the necessary evaluation to determine that equivalent results are
obtained.
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D5135 − 21
5.2 This test method will detect the impurities shown in Table 1, non-aromatic hydrocarbons containing ten carbons or less, and
others where specific impurity standards are available. Absolute purity cannot be determined if unknown impurities are present.
6. Interferences
6.1 The internal standard chosen must be satisfactorily resolved from any impurity as well as the product peak. A peak will be
satisfactorily resolved from a neighboring peak if the distance from the valley to the baseline between the two peaks is not greater
than 50 % of the peak height of the smaller of the two peaks.
7. Apparatus
7.1 Gas Chromatograph—Any instrument having a flame ionization detector that can be operated at the conditions given in Table
2. The system shall have sufficient sensitivity to obtain a minimum peak height response for 0.001 weight % impurity of twice the
height of the background noise.
7.2 Column—A capillary column containing a stationary phase of cross-linked polyethylene glycol has been found to be
satisfactory. Any column can be used that is capable of resolving all significant impurities from styrene and from the internal
standard. The choice of column is based on resolution requirements. Any column may be used that is capable of resolving all
significant impurities from the major component. The column and conditions described in Table 2 have been used successfully and
shall be used as a referee in cases of dispute.
7.2.1 “Total non-aromatics” are defined as all components eluting before o-xylene, excluding benzene, toluene, ethylbenzene,
p-xylene, m-xylene, and cumene. The internal standard used for calibration is also excluded. Generally, non-aromatics are summed
and reported as a group. In certain cases, one or more individual non-aromatic components, such as 1,4-dioxane, may be reported
separately. In those cases, the grouping would not include the separately reported component(s), and the remaining non-aromatics
would be reported as “Nonaromatics other than (component(s)).”
7.2.2 “Total C9–plus aromatics” are defined as cumene, plus all components eluting after o-xylene. Generally, C9–plus aromatics
are summed and reported as a group. In certain cases, one or more individual C9–plus aromatic components, such as cumene or
p-diethylbenzene, may be reported separately. In those cases, the grouping would not include the separately reported component(s)
and the remaining C9–plus aromatics would be reported as “C9–plus aromatics other than (component(s)).” Very heavy
non-aromatics may also elute in this region, but they are not common in materials within the scope of Committee D16, and are
not considered in the definition.
7.3 Recorder—Electronic integration, with tangent capabilities is recommended.Chromatographic data systems are preferred but
electronic integration may be used if the user can demonstrate that the results are consistent with the precision statement.
7.4 100-mL Volumetric Flask.
7.5 Microsyringes, assorted volumes.
8. Reagents and Materials
8.1 Purity of Reagent—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available.
8.2 Carrier Gas, makeup and detector gases 99.999 % purity. Oxygen in carrier gas less than 1 ppm, less than 0.5 ppm is preferred.
Purify carrier, makeup and detector gases to remove oxygen, water, and hydrocarbons.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
D5135 − 21
8.3 Air, purify to remove hydrocarbons and water. Air should contain less than 0.1 ppm THC.
8.4 n-Heptane, 99.0 % minimum purity, or other internal standard, such as n-octane, previously analyzed to be free of compounds
coeluting with impurities in the sample.
8.5 Styrene, the highest purity available, but not less than 99.7 %.
8.6 Pure Compounds, for calibration, shall be those compounds that are typically present in commercial styrene. These should be
at least 99 % pure as they are to be used for determining response factors.
8.7 Equipment Setup Check Sample:
8.7.1 The purpose is to:
(a) Determine retention times for the components measured in GC standards;
(b) Verify there is adequate resolution to measure the components of interest in GC standards; and
(c) Dete
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