ASTM D 2360-04a

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Designation: D 2360 – 04a

Standard Test Method for


Trace Impurities in Monocyclic Aromatic Hydrocarbons by
Gas Chromatography1
This standard is issued under the fixed designation D 2360; 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.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope* D 3437 Practice for Sampling and Handling Liquid Cyclic


1.1 This test method covers the determination of the total Products
nonaromatic hydrocarbons, and trace monocyclic aromatic D 3797 Test Method for Analysis of o-Xylene by Gas
hydrocarbons in the purity of toluene and mixed xylenes by gas Chromatography
chromatography. D 3798 Test Method for Analysis of p-Xylene by Gas
1.2 Nonaromatic aliphatic hydrocarbons containing 1 Chromatography
through 10 carbon atoms (methane through decanes) can be D 4492 Test Method for Analysis of Benzene by Gas
detected by this test method at concentrations ranging from Chromatography
0.001 % to 2.500 weight %. D 4790 Terminology of Aromatic Hydrocarbons and Re-
1.2.1 A small amount of benzene in mixed xylenes may not lated Chemicals
be distinguished from the nonaromatics and the concentrations D 5211 Specification for Xylenes for p-Xylene Feedstock
are determined as a composite. D 6809 Guide for Quality Control and Quality Assurance
1.3 Monocyclic aromatic hydrocarbon impurities containing Procedures for Aromatic Hydrocarbons and Related Ma-
6 through 9 carbon atoms (benzene through C9 aromatics) can terials
be detected by this test method at individual concentrations E 29 Practice for Using Significant Digits in Test Data to
ranging from 0.001 % to 1.000 weight %. Determine Conformance with Specifications
1.4 In determining the conformance of the test results using E 260 Practice for Packed Column Gas Chromatography
this method to applicable specifications, results shall be E 355 Practice for Gas Chromatography Terms and Rela-
rounded off in accordance with the rounding-off method of tionships
Practice E 29. E 691 Practice for Conducting an Interlaboratory Study to
1.5 This standard does not purport to address all of the Determine the Precision of a Test Method
safety concerns, if any, associated with its use. It is the E 1510 Practice for Installing Fused Silica Open Tubular
responsibility of the user of this standard to establish appro- Capillary Columns in Gas Chromatographs
priate safety and health practices and determine the applica- 2.2 Other Document:
bility of regulatory limitations prior to use. For specific hazard OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
statement, see Section 9. 1910.12003

2. Referenced Documents 3. Terminology


2.1 ASTM Standards: 2 3.1 Definitions:
D 841 Specification for Nitration Grade Toluene 3.1.1 For definition of terms used in this test method see
D 2306 Test Method for C8 Hydrocarbon Analysis by Gas Terminology D 4790.
Chromatography
4. Summary of Test Method
4.1 A known amount of an internal standard is added to the
1
This test method is under the jurisdiction of ASTM CommitteeD16 on
specimen that is then introduced into a gas chromatograph
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of (GC) equipped with a flame ionization detector (FID). The
Subcommittee D16.01 on Benzene, Toluene, Xylenes, Cyclohexane and Their peak area of each impurity and the internal standard is
Derivatives. measured and the amount of each impurity is calculated from
Current edition approved Aug. 1, 2004. Published August 2004. Originally
approved in 1966. Last previous edition approved in 2004 as D 2360 – 04e1.
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 Superintendent of Documents, U.S. Government Printing
the ASTM website. Office, Washington DC 20402.

*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.

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D 2360 – 04a
the ratio of the peak area of the internal standard versus the the event that the benzene concentration must be determined,
peak area of the impurity. Purity by GC is calculated by an alternate method must be selected to ensure an accurate
subtracting the sum of the impurities found from 100.00. assessment of the benzene concentration.
Results are reported either in weight percent or volume
percent. 7. Apparatus
7.1 Gas Chromatograph—Any instrument having a flame
5. Significance and Use ionization detector that can be operated at the conditions given
5.1 The determination of hydrocarbon impurities contained in Table 1. The system should have sufficient sensitivity to
in toluene and mixed xylenes used as chemical intermediates obtain a minimum peak height response for 10 mg/kg
and solvents is typically required. This test is suitable for n-butylbenzene of twice the height of the signal to background
setting specifications and for use as an internal quality control noise.
tool where aromatic monocyclic hydrocarbons are produced or 7.2 Columns—Both capillary and packed columns contain-
are used. This test method is applicable for determining the ing a stationary phase of cross-linked polyethylene glycol have
impurities from the aromatic hydrocarbon production process. been found satisfactory. The column must give satisfactory
Typical impurities are alkanes containing 1 to 10 carbon atoms, resolution of the internal standard from the solvent and the
benzene, toluene, ethylbenzene (EB), xylenes, and aromatic impurity peaks, and should be such that benzene is eluted
hydrocarbons containing nine carbon atoms. between n-nonane and n-decane. Table 1 contains a description
5.1.1 Refer to Test Methods D 3797, D 3798, and D 4492 of a column that has been found satisfactory.
for determining the purity of o-Xylene, p-Xylene, and benzene, 7.3 Recorder—Electronic integration is recommended.
respectively. 7.4 Microsyringe, 10 and 50, and 500-µL capacity.
5.1.2 Refer to Test Method D 2306 for determining the C8 7.5 Volumetric Flask, 50-mL capacity.
aromatic hydrocarbon distribution in mixed xylenes.
5.2 Purity is commonly reported by subtracting the deter- 8. Reagents
mined expected impurities from 100.00. However, a gas 8.1 Purity of Reagent—Reagent grade chemicals shall be
chromatographic analysis cannot determine absolute purity if used in all tests. Unless otherwise indicated, it is intended that
unknown or undetected components are contained within the all reagents shall conform to the specifications of the Commit-
material being examined. tee on Analytical Reagents of the American Chemical Society,
where such specifications are available.4
6. Interferences 8.2 Carrier Gas—Helium is recommended. However, hy-
6.1 The internal standard chosen must be satisfactorily drogen may be used. Carrier, makeup and detector gases
resolved from any impurity and the product peak. A peak will should have 99.999 % minimum purity. Oxygen in carrier gas
be satisfactorily resolved from a neighboring peak if the should be less than 1 ppm; less than 0.5 ppm is preferred.
distance from the valley to the baseline between the two peaks Purify carrier, makeup and detector gases to remove oxygen,
is not greater than 50 % of the peak height of the smaller of the water, and hydrocarbons.
two peaks. 8.3 Air—zero grade or better. Purify air to remove hydro-
6.2 In some cases for mixed xylenes, it may be difficult to carbons and water.
resolve benzene from the nonaromatic hydrocarbons and 8.4 High Purity p-Xylene, 99.999 weight % or greater
therefore the concentrations are determined as a composite. In purity.
8.4.1 Most p-xylene is available commercially at a purity
TABLE 1 Instrumental Parameters less than 99.9 % and can be purified by recrystallization. To
Detector Flame ionization prepare 1.9 L of high purity p-xylene, begin with approxi-
Column: mately 3.8 L of material and cool in an explosion-proof freezer
Tubing fused silica at −10 6 − 5°C until approximately 1⁄2 to 3⁄4 of the p-xylene
Stationary phase crosslinked polyethylene glycolA
Film thickness, µ 0.25 has frozen. This should require about 5 h. Remove the sample
Length, m 60 and decant the liquid portion. The solid portion is the purified
Diameter, mm 0.32 ID p-xylene. Allow the p-xylene to thaw and repeat the crystalli-
Temperatures:
Injector, °C 270 zation step on the remaining sample until the p-xylene is free
Detector, °C 300 of contamination as indicated by gas chromatography.
Oven: 8.5 Pure Compounds, for calibration, shall include
Initial, °C 60
Time 1, min 10 n-nonane, benzene, toluene, ethylbenzene (EB), o-xylene and
Final, °C 150 cumene. The purity of all reagents should be >99 weight %. If
Rate, °C/min 5 the purity is less than 99 %, the concentration and identification
Time 2, min 10
Carrier gas helium
Flow rate, mL/min 1.0
Split ratio 100:1 4
Reagent Chemicals, American Chemical Society Specifications, American
Sample size, µL 1.0 Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Analysis time, min 30 listed by the American Chemical Society, see Analar Standards for Laboratory
Linear velocity @ 145°C, cm/s 20 Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
A and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Polyethylene glycol such as Carbowax 20 M available from most chromato-
graphic suppliers, has been found suitable for this purpose. MD.

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D 2360 – 04a
of impurities must be known so that the composition of the 12.3 Into a 50-mL volumetric flask, add 50.0 µL of
standard can be adjusted for the presence of the impurities. n-butylbenzene (NBB) to 50.00 mLs of the calibration blend
8.5.1 Internal Standard—n-butylbenzene (NBB) is the rec- and mix well. Assuming a density of 0.857 for the calibration
ommended internal standard of choice, however, other com- blend and 0.856 for NBB, the resulting NBB concentration will
pounds may be found acceptable provided they meet the be 0.100 weight %, as determined from the equation in 12.2.
criteria as defined in Section 6. 12.3.1 All solutions and reference compounds must be
brought to the same temperature, preferably 25°C, prior to
9. Hazards adding the internal standard.
9.1 Consult current OSHA regulations, supplier’s Material 12.4 Inject the resulting solution from 12.3 into the chro-
Safety Data Sheets, and local regulations for all materials used matograph. A typical chromatogram is illustrated in Fig. 1.
in this test method. 12.5 Determine the response factor for each impurity rela-
tive to NBB by measuring the area under each peak and
10. Sampling calculate the relative response factor as follows:
10.1 Sample the material in accordance with Practice ~As!~Ci!
RRFi 5 (2)
D 3437. ~Cs!~Ai!

11. Preparation of Apparatus where:


RRFi = response factor for impurity i relative to the internal
11.1 Follow manufacturer’s instructions for mounting and standard,
conditioning the column into the chromatograph and adjusting Ai = peak area of impurity, i,
the instrument to the conditions described in Table 1 allowing As = peak area of the internal standard, NBB,
sufficient time for the equipment to reach equilibrium. See Cs = concentration of the internal standard, NBB,
Practices E 260 and E 355 and E 1510 for additional informa- weight percent, and
tion on gas chromatography practices and terminology. Ci = concentration of impurity i, as calculated in 12.2,
weight percent.
12. Calibration 12.6 Calculate the response factors to the nearest 0.001.
12.1 Prepare a synthetic mixture of high purity p-xylene
with representative impurities. The volume of each hydrocar- 13. Procedure
bon impurity must be measured to the nearest 0.1 µL and all 13.1 Bring the internal standard and the sample to be
liquid reference compounds must be brought to the same analyzed to identical temperatures, preferably 25°C. Make sure
temperature before mixing. Refer to Table 2 for an example of that the temperature of the sample is consistent with that of the
a calibration blend. The nonaromatic fraction is represented by calibration standard prepared in Section 12. Pipet 50.0 µL of
n-nonane, while o-xylene represents the xylene fraction. internal standard into a 50-mL volumetric flask containing
Cumene will represent the aromatic hydrocarbons containing 50.00 mLs of sample. Mix well.
nine carbon atoms or greater (C9 aromatics). 13.2 Depending upon the actual chromatograph’s operating
12.2 Using the exact volumes and densities in Table 2, conditions, inject an appropriate amount of sample into the
calculate the weight percent concentration for each impurity in instrument. Make sure that the injection amount is consistent
the calibration blend as follows: with those conditions used to meet the criteria in 7.1.
C i 5 ~~Di!~Vi!!/~~Vp!~Dp!!~100! (1)

where:
Di = density of impurity i from Table 2,
Vi = volume of impurity i, mLs,
Dp = density of p-xylene from Table 2,
Vp = volume of p-xylene, mLs, and
Ci = concentration of impurity i, weight percent.

TABLE 2 Preparation of Calibration Blend


Resulting Concentration
Recommended
Compound DensityA Volume Weight
Volume (µL)
Percent Percent
p-Xylene (see 8.4.1) 0.857 50.00 mL 99.72 99.72
Benzene 0.874 10.0 0.020 0.020
Toluene 0.862 10.0 0.020 0.020
Ethylbenzene 0.863 50.0 0.100 0.101
o-Xylene 0.876 50.0 0.100 0.099
Cumene 0.857 10.0 0.020 0.020
n-Nonane 0.714 10.0 0.020 0.017
A
Density at 25°C. Values obtained from Physical Constants of Hydrocarbons C1
to C10, ASTM Publication Data Series 4A, 1971. FIG. 1 Typical Analysis of Calibration Standard

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D 2360 – 04a
13.3 Measure the area of all peaks except the major com-
ponent(s). Measurements on the sample must be consistent
with those made on the calibration blend. The nonaromatic
fraction includes all peaks up to toluene (except for the peak
assigned as benzene). Sum together all the nonaromatic peaks
and report as a total area. The C9 aromatics fraction includes
cumene and all peaks emerging after o-xylene. Sum together
all the C9 aromatic peaks and report as a total area.
13.4 Fig. 2 illustrates the analysis of Specification D 841
toluene. Fig. 3 illustrates the analysis of Specification D 5211
mixed xylenes.

14. Calculations
14.1 Calculate the weight percent concentration of the total
nonaromatics and each impurity as follows:
~Ai!~RRFi!~Cs!
Ci 5 (3)
~ As !
14.2 Calculate the volume concentration of the total non- FIG. 3 Typical Analysis of Specification D 5211 for Xylenes
aromatics, total C9 aromatics and each trace aromatic as
follows: TABLE 3 Repeatability and Reproducibility
Intermediate
Vi 5 ~Ci!~Ds!/~Di! (4) Toluene
Precision
Reproducibility

where: Nonaromatics (0.023) 0.0067 0.0110


Ethylbenzene (0.017) 0.0041 0.0063
Vi = concentration of impurity i, volume percent, p-Xylene (0.010) 0.0038 0.0038
Di = density of impurity i from Table 2, and m-Xylene (0.012) 0.0031 0.0040
Ds = density of sample. o-Xylene (0.001) 0.0003 0.0003
14.3 Calculate the purity of the sample as follows: Toluene (99.94) 0.0160 0.0210
Intermediate
purity, weight percent 5 100.00 2 Ct (5) Mixed Xylenes Reproducibility
Precision

where: Nonaromatics (2.526) 0.150 0.816


Toluene (0.649) 0.052 0.153
Ct = total concentration of all impurities, weight percent. Cumene (0.010) 0.0007 0.0013
Xylenes (96.82) 0.180 0.819

15. Report
15.1 Report the following information:
15.1.2 Concentrations of impurities less than 0.001 %, re-
15.1.1 Individual impurities to the nearest 0.001 %. port as <0.001 %, and consider as 0.000 in summation of
impurities,
15.1.3 Total impurities to the nearest 0.01 %, and
15.1.4 Purity as “purity (by GC)” to the nearest 0.01 %.

16. Precision and Bias 5


16.1 Precision—The following criteria should be used to
judge the acceptability of the 95 % probability level of the
results obtained by this test method. The criteria was derived
from the round-robin between seven different laboratories. The
data from five laboratories was used in calculating the preci-
sion data for toluene. Two samples were analyzed. Each
sample was run twice in two days by two different operators.
Results of the interlaboratory study were calculated and
analyzed using Practice E 691.
16.1.1 The numbers in parentheses shown in the left hand
column of Table 3 are reported average concentrations of the
impurities.

5
Supporting data are available from ASTM International Headquarters. Request
FIG. 2 Typical Analysis of Specification D 841 on Toluene RR: D16-1020.

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D 2360 – 04a
16.2 Intermediate Precision, (formerly called 17. Quality Guidelines
Repeatability)—Duplicate results by the same operator should
17.1 Refer to Guide D 6809 for suggested QA/QC activities
not be considered suspect unless they differ by more than 6 the
that can be used as a part of this method. It is recommended
amount shown in Table 3. All values are in weight percent.
that the operator of this method select and perform relevant
16.3 Reproducibility—The results between two laboratories
should not be considered suspect unless they differ by more QA/QC activities like the ones in Guide D 6809 to help ensure
than 6 the amount shown in Table 3. All values are in weight the quality of data generated by this method.
percent.
16.4 Bias—Since there was no accepted reference material 18. Keywords
available at the time of interlaboratory testing, no statement on 18.1 impurities; purity; toluene; xylenes
bias can be made at this time. All values are in weight percent.

SUMMARY OF CHANGES

Committee D16 has identified the location of selected changes to this standard since the last issue
(D 2360 – 04e1) that may impact the use of this standard. (Approved August 1, 2004.)

(1) 1.4 was replaced.

Committee D16 has identified the location of selected changes to this standard since the last issue
(D 2360 – 03) that may impact the use of this standard. (Approved January 1, 2004.)

(1) 8.2 was modified to specify the purity of the carrier, (3) Section 17 was added to include recommendations for
makeup and detector gases and permit the use of hydrogen. QA/QC.
(2) 8.3 was added to specify the purity of air.

Committee D16 has identified the location of selected changes to this standard since the last issue
(D 2360 – 00) that may impact the use of this standard. (Approved June 10, 2003.)

(1) Corrected Equation 4. (3) Corrected Table 2 reference to p-Xylene from 7.3.1 to
(2) Added definition for Ds after Equation 4. 8.3.1.

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