ASTM D 2360-04a
ASTM D 2360-04a
ASTM D 2360-04a
1
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!
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.
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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
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 %.
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.)
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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