Designation: D7057 − 13

Standard Test Method for

Analysis of Isopropylbenzene (Cumene) by Gas
Chromatography (External Standard)1
This standard is issued under the fixed designation D7057; 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* D3437 Practice for Sampling and Handling Liquid Cyclic

1.1 This test method covers the determination of the purity Products
of isopropylbenzene (cumene) by gas chromatography. Cali- D4307 Practice for Preparation of Liquid Blends for Use as
bration of the gas chromatography system is done by the Analytical Standards
external standard calibration technique. D4790 Terminology of Aromatic Hydrocarbons and Related
Chemicals
1.2 This test method has been found applicable to the D6809 Guide for Quality Control and Quality Assurance
measurement of impurities such as nonaromatic hydrocarbons, Procedures for Aromatic Hydrocarbons and Related Ma-
benzene, toluene, ethylbenzene, phenol, cymenes, terials
t-butylbenzene, n-butylbenzene, n-propylbenzene, alpha- E29 Practice for Using Significant Digits in Test Data to
methylstyrene, sec-butylbenzene, and diisopropylbenzenes, Determine Conformance with Specifications
which are impurities that can be found in isopropylbenzene. E355 Practice for Gas Chromatography Terms and Relation-
The latter impurities can be analyzed over a range of 1 mg/kg ships
to 500 mg/kg by this method (see Table 1). The limit of E691 Practice for Conducting an Interlaboratory Study to
detection for these impurities is summarized in Table 1 as well. Determine the Precision of a Test Method
1.3 In determining the conformance of the test results using E1510 Practice for Installing Fused Silica Open Tubular
this method to applicable specifications, results shall be Capillary Columns in Gas Chromatographs
rounded off in accordance with the rounding-off method of 2.2 Other Document:
Practice E29. OSHA Regulations, 29 CFR paragraphs 1910.1000 and
1.4 The values stated in SI units are to be regarded as 1910.12003
standard. No other units of measurement are included in this
standard. 3. Terminology
1.5 This standard does not purport to address all of the 3.1 See Terminology D4790 for definition of terms used in
safety concerns, if any, associated with its use. It is the this test method.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 4. Summary of Test Method
bility of regulatory limitations prior to use. For specific hazard 4.1 Cumene (isopropylbenzene) is analyzed by a gas chro-
statements, see Section 8. matograph (GC) equipped with a flame ionization detector
(FID). A precisely repeatable volume of the sample to be
2. Referenced Documents
analyzed is injected onto the gas chromatograph. The peak
2.1 ASTM Standards:2 areas of the impurities are measured and converted to concen-
trations via an external standard methodology. Purity by GC
(the Cumene content) is calculated by subtracting the sum of
1
This test method is under the jurisdiction of ASTM Committee D16 on the impurities from 100.00, excluding Acetophenone (AP) and
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of 2-phenyl-2-propanol (DMPC or DMBA) which are artifacts of
Subcommittee D16.07 on Styrene, Ethylbenzene and C9 and C10 Aromatic
Hydrocarbons.
cumene hydroperoxide (CHP) thermal decomposition in the
Current edition approved June 1, 2013. Published June 2013. Originally inlet of the GC. Results are reported in weight percent.
approved in 2004. Last previous edition approved in 2009 as D7057 – 09. DOI:
10.1520/D7057-13.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Available from U.S. Government Printing Office Superintendent of Documents,
Standards volume information, refer to the standard’s Document Summary page on 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
the ASTM website. www.access.gpo.gov.

*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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 D7057 − 13
TABLE 1 Summary of Precision Data (mg/kg)
Range
Compound Repeatability Reproducibility
Studied
Benzene 1.004+0.006*Benzene 0.924+0.158*Benzene 1.0–295
Toluene 0.644+0.009*Toluene 1.505+0.069*Toluene 0.2–260
Ethylbenzene (EB) 1.249+0.022*EB 2.534+0.230*EB 5–370
n-Propylbenzene (NPB) -0.369+0.015*NPB -6.793+0.214*NPB 180–465
Phenol (PHE) 1.926+.0095*PHE 3.718+0.207*PHE 1–225
alpha-methylstyrene(AMS) 1.368+0.057*AMS 21.181+0.976*AMS 6–305
tert-Butylbenzene(TBB) 1.666+0.011*TBB 4.126+0.086*TBB 2–250
sec-Butylbenzene(SBB) 0.635+0.010*SBB 0.891+0.090*SBB 2–245
m-Cymene 0.618+0.011*m-Cymene 1.811+0.181*m-Cymene 5–240
o-Cymene 0.498+0.012*o-Cymene 1.951+0.156*o-Cymene 1–160
p-Cymene 0.485+0.019*p-Cymene 1.618+0.097*p-Cymene 2–270
n-Butylbenzene(NBB) 0.445+0.030*NBB 2.600+0.045*NBB 0.3–265
1,3-diisopropylbenzene(13DIPB) 0.727+0.010*13DIPB 1.570+0.720*13DIPB 1–210
1,4-diisopropylbenzene(14DIPB) 0.435+0.013*14DIPB 1.112+0.040*14DIPB 1–285
NonAromatics(NA) 0.441+0.242*NA 1.663+0.306*NA 5–95

TABLE 2 Recommended Operating Conditions

Detector flame ionization
5. Significance and Use Injection Port capillary splitter
5.1 This test method is suitable for setting specifications on Column A:
Tubing fused silica
the materials referenced in 1.2 and for use as an internal quality Stationary Phase crosslinked
control tool where isopropylbenzene is produced or is used in polydimethylsilicone (HP-1,
a manufacturing process. It may also be used in development DB-1 or equiv)
Film Thickness, µm 1.0
or research work involving isopropylbenzene. Length, m 60
Diameter, mm 0.32
5.2 This test method is useful in determining the purity of Temperatures:
isopropylbenzene with normal impurities present. If extremely Injector, °C 250
high boiling or unusual impurities are present in the Detector, °C 300
Oven, °C 85 hold for 13 min
isopropylbenzene, this test method would not necessarily Ramp 1 = 6°C/min to 125°C,
detect them and the purity calculation would be erroneous. hold for 2 min
Ramp 2 = 30°C/min to
5.3 Cumene hydroperoxide, if present, will yield thermal 250°C, hold for 7.5 min
decomposition products, primarily AP and DMPC as stated in Carrier Gas Helium
4.1, that will elute in the chromatogram thereby giving Flow Rate, mls/min 3
Split Ratio 60:1
incorrect results unless they are excluded as indicated in 4.1. It Sample Size, µL 1.0
is also possible to get erroneous results for trace alpha-
methylstyrene present in isopropylbenzene if the inlet has
become unduly contaminated with non-volatile foreign sub-
stances. 6.4 Injector—The specimen must be precisely and repeat-
5.4 The nonaromatic hydrocarbons commonly present from edly injected into the gas chromatograph. An automatic sample
the isopropylbenzene manufacturing process, particularly a injection device is highly recommended. Manual injection can
non-zeolitic one, will interfere with the determination of be employed if the precision stated in Table 1, Summary of
xylenes (if present). Precision Data, can be reliably and consistently satisfied.

6. Apparatus 7. Reagents and Materials

6.1 Gas Chromatograph—Any instrument having a flame 7.1 Purity of Reagents—Reagent grade chemicals shall be
ionization detector that can be operated at the conditions given used in all tests. Unless otherwise indicated, it is intended that
in Table 2. The system should have sufficient sensitivity to all reagents shall conform to the specifications of the Commit-
obtain a minimum peak height response for 1 mg/kg benzene tee on Analytical Reagents of the American Chemical Society,
of twice the height of the signal background noise. where such specifications are available.4 Other grades may be
used, provided it is first ascertained that the reagent is of
6.2 Columns—The choice of column is based on resolution
sufficiently high purity to permit its use without lessening the
requirements. Any column may be used that is capable of
accuracy of the determination.
resolving all significant impurities from isopropylbenzene. The
column described in Table 2 has been used successfully and
shall be used as a referee in cases of dispute. Unless the analyst 4
Reagent Chemicals, American Chemical Society Specifications, American
can be sure of peak identity, for example by gas Chemical Society, Washington, DC. For suggestions on the testing of reagents not
chromatography-mass spectrometry (GC-MS), the use of the listed by the American Chemical Society, see Analar Standards for Laboratory
column in Table 2 is strongly recommended. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
6.3 Recorder—Electronic integration is required. MD.

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 D7057 − 13

FIG. 1 Typical Chromatogram using Conditions in Table 2

7.2 Carrier Gas, Makeup, and Detector Gases—Helium, 10. Preparation of Apparatus
hydrogen, nitrogen, or other carrier, makeup and detector gases
10.1 Follow manufacturer’s instructions for mounting and
99.999 % minimum purity. Oxygen in carrier gas less than 1
ppm, less than 0.5 ppm is preferred. Purify carrier, makeup, conditioning the column into the chromatograph and adjusting
and detector gases to remove oxygen, water, and hydrocarbons. the instrument to the conditions described in Table 2 allowing
sufficient time for the equipment to reach equilibrium. See
7.3 Compressed Air—Purify air to remove water and hydro- Practice E355 for additional information on gas chromatogra-
carbons. Air for a FID should contain less than 0.1 ppm THC. phy practices and terminology.
7.4 Pure Compounds for Calibration—The purity of all
reagents should be 99.9 % or greater. If the purity is less than 11. Calibration
99 % the concentration and identification of impurities must be
known so that the composition of the standard can be adjusted 11.1 Prepare a synthetic mixture of high purity cumene
for the presence of the impurities. containing impurities at concentrations representative of those
expected in the samples to be analyzed in accordance with
8. Hazards Practice D4307. The weight of each hydrocarbon impurity
8.1 Consult current OSHA regulations, suppliers’ Material must be measured to the nearest 0.1 mg. Because the avail-
Safety Data Sheets, and local regulations for all materials listed ability of stock cumene with a purity higher than 99.97 % is
in this test method. problematic, the method of standard additions may be required
for impurities such as tert-butylbenzene and n-propylbenzene,
9. Sampling and Handling as well as for a number of the other impurities listed in 1.2 that
9.1 Sample the material in accordance with Practice D3437. are commonly present.

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 D7057 − 13
11.2 Inject the resulting solution from 11.1 into the gas 14.2 Report the purity of isopropylbenzene to the nearest
chromatograph, collect and process the data. A typical chro- 0.01 wt %.
matogram is illustrated in Fig. 1 based on the conditions listed
in Table 2. 15. Precision and Bias5
11.3 Determine the response factor for each impurity in the 15.1 The criteria in Table 1 should be used to judge the
calibration mixture as follows: acceptability at the 95 % probability level of the results
obtained by this test method. The criteria were derived from an
Rfi 5 Ci/Ai (1) Interlaboratory study of five samples analyzed in triplicate by
where: five laboratories. Practice E691 was followed for the design
Rfi = response factor for impurity i, and analysis of the data; the details are given in ASTM
Ci = concentration of impurity i in the calibration mixture, Research Report RR:D16-1033.
and 15.2 Repeatability—Results in the same laboratory should
Ai = peak area of impurity i. not be considered suspect unless they differ by more than the
11.4 Initially analyze the calibration solution a minimum of amounts calculated from the appropriate equations in Table 1.
three times and calculate an average Rfi. Subsequent calibra- Results differing by less than “r” have a 95 % probability of
tions may be a single analysis as long as the response factors being correct.
for all components of interest are within 65 % of the initial 15.3 Reproducibility—Results submitted by two laborato-
validation response factors. A “rolling” average as defined by ries should not be considered suspect unless they differ by
most modern chromatographic software may also be used. The more than the amounts calculated from the appropriate equa-
response factor for tert-butylbenzene is used for unknowns and tions in Table 1. Results differing by less than “R” have a 95 %
non-aromatics quantification. probability of being correct.
12. Procedure 15.4 Bias—Since there is no accepted reference material
suitable for determining the bias for the procedure in this test
12.1 Inject into the gas chromatograph an appropriate
method for measuring isopropylbenzene purity, bias has not
amount of sample sufficient to satisfy the sensitivity conditions
been determined.
as detailed in 6.1 and start the analysis.
12.2 Obtain a chromatogram and peak integration report. 16. Quality Guidelines
Fig. 1 illustrates a typical analysis of cumene using the column 16.1 Laboratories shall have a quality control system in
and conditions outlined in Table 2. place.
16.1.1 Confirm the performance of the test instrument or
13. Calculations
test method by analyzing a quality control sample following
13.1 Calculate the concentration of each impurity as fol- the guidelines of standard statistical quality control practices.
lows: 16.1.2 A quality control sample is a stable material isolated
Ci 5 ~ Ai! ~ Rfi! (2) from the production process and representative of the sample
being analyzed.
where: 16.1.3 When QA/QC protocols are already established in
Ci = concentration of component i in mg/kg, the testing facility, these protocols are acceptable when they
Ai = peak area of component i, and confirm the validity of test results.
Rfi = response factor for component i, 16.1.4 When there are no QA/QC protocols established in
13.2 Calculate the total concentration of all impurities in the testing facility, use the guidelines described in Guide
wt % (excluding AP and DMBA as per 5.3) as follows: D6809 or similar statistical quality control practices.
Ct 5 ( C /10000
i (3) 17. Keywords
where: 17.1 alpha-methylstyrene; analysis by gas chromatography;
Ct = total concentration of all impurities. benzene; butylbenzene; cumene; cymene; diisopropylbenzene;
ethylbenzene; isopropylbenzene; methyl cumene; nonaromatic
13.3 Calculate the purity of isopropylbenzene as follows:
hydrocarbons; propylbenzene; toluene
Cumene, weight percent 5 100.00 2 C t (4)
5
14. Report Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D16-1033. Contact ASTM Customer
14.1 Report the individual impurities to the nearest mg/kg. Service at service@astm.org.

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 D7057 − 13
SUMMARY OF CHANGES

Committee D16 has identified the location of selected changes to this standard since the last issue (D7057–09)
that may impact the use of this standard. (Approved June 1, 2013.)

(1) All sections updated to current D16 Editorial Guidelines.

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