Trace Non-Aromatic Hydrocarbons in High-Purity Aromatics

by GC
UOP Method 543-11
Scope
This method is primarily for determining total non-aromatic hydrocarbons below the 1 mass-% level
in individual or mixed aromatic hydrocarbon samples. For the purpose of this method, total non-
aromatics are defined as the composite of those components eluting before benzene. The applicability
is limited to samples containing compounds having a maximum of 11 carbon atoms. The method may
also be used to determine mass-ppm concentrations of benzene in specific sample types containing
predominantly C7 and higher boiling aromatics, or benzene and toluene in specific sample types
containing predominantly C8 and/or higher boiling aromatics. The lower limit of quantitation for any
single component is 1 mg/kg (mass-ppm).

References
ASTM D4052, “Density, Relative Density, and API Gravity of Liquids by Digital Density Meter,”
www.astm.org
ASTM D4307, “Preparation of Liquid Blends for Use as Analytical Standards,” www.astm.org
UOP Method 999, “Precision Statements in UOP Methods,” www.astm.org

Outline of Method
The sample is injected into a gas chromatograph (GC) that is equipped with a fused silica capillary
column internally coated with 1,2,3-tris(2-cyanoethoxy)propane (TCEP), and a flame ionization
detector (FID). The concentrations of individual or group impurities are determined by the external
standard method of quantitation, wherein peak areas of the sample components are compared to the
peak areas of a calibration blend analyzed under identical conditions and injection volumes.

Apparatus
References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.
Balance, readability 0.1 mg

IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO

DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).
© COPYRIGHT 1970, 1979, 1997, 2011 UOP LLC. All rights reserved.
Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West
Conshohocken, PA 19428-2959, USA. The UOP Methods may be obtained through the ASTM website, www.astm.org, or by
contacting Customer Service at service@astm.org, 610.832.9555 FAX, or 610.832.9585 PHONE.

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Chromatographic column, 60 m of 0.25-mm ID fused silica capillary, internally coated to a film

thickness of 0.4-µm with TCEP, Restek Cat. No. 10999
Freezer, explosion-proof, -23 to -5°C, Lab-Line Model 3552, VWR Scientific, Cat. No. 55700-158
Gas chromatograph, capable of temperature ramping, equipped with electronic pressure control, built
for capillary column chromatography utilizing a split injection system, having a glass injection port
insert, and equipped with a flame ionization detector that will give a minimum peak height response
of 10 times the background noise for 1 mg/kg of n-undecane when operated at the recommended
conditions, Agilent Technologies, Model 7890
Data system, electronic, for obtaining peak areas. This device must integrate areas at a sufficiently
fast rate so that narrow peaks typically resulting from the use of a capillary column can be
accurately measured. Agilent Technologies, ChemStation.
Regulator, air, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson
Tri-Gas, Model 3122-590
Regulator, hydrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-350
Regulator, nitrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-580
Sample injector, any syringe or injector capable of injecting a repeatable 1.0-µL volume of sample.
The use of an automatic injection device is required to achieve necessary repeatable injection
volumes. See Appendixes. Agilent Technologies, Model 7683.

Reagents and Materials

References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.
Air, zero-gas, total hydrocarbons less than 2 ppm as methane, local supply
Benzene, 99.9% purity, Sigma-Aldrich, Cat. No. 270709. CAUTION: Benzene is a known
carcinogen. All operations involving its use must be performed in a properly ventilated area, while
wearing appropriate personal protective equipment.
n-Dodecane, 99+% purity, Sigma-Aldrich, Cat. No. 297879
Hydrogen, zero-gas, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane, local
supply
Gas purifier, for hydrogen, to remove oxygen and moisture from carrier gas, VICI Mat/Sen, Cat.
No. P200-1
Nitrogen, zero-gas, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane, local
supply
Pipets, disposable, Pasteur, VWR, Cat. No. 14673-043
Pipet bulbs, VWR, Cat. No. 15001-362
Syringe, replacement, for recommended sample injector, 5-µL, Agilent Technologies, Cat. No.
5181-1273
Toluene, 99.5% purity, Sigma-Aldrich, Cat. No. 244511

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n-Undecane, 99+% purity, Sigma-Aldrich, Cat. No. U407
Vials, autosampler, for recommended sample injector, with caps, Agilent Technologies, Cat. No.
5182-0864
p-Xylene, 99+% purity, Sigma-Aldrich, Cat. No. 317195

Preparation of Apparatus
The analyst is expected to be familiar with general laboratory practices, the technique of gas
chromatography, and the equipment being used.
1. Install the gas purifier in the supply line between the carrier gas source and the carrier gas inlets on
the gas chromatograph.
• Column life is significantly reduced if the gas purifier is not used.

2. Install the fused silica column in the gas chromatograph according to the column and gas
chromatograph manufacturers’ instructions.
• CAUTION: Hydrogen gas leakage into the confined volume of the column oven can cause violent
explosion. It is, therefore, mandatory to check for leaks each time a connection is made and periodically
thereafter.

3. Establish the recommended operating conditions as given in Table 1.

• Different conditions may be used provided they produce the required sensitivity and chromatographic
separations equivalent to those shown in the Typical Chromatograms (Figures 1-2).

Table 1
Recommended Operating Conditions
Carrier gas hydrogen
Head pressure 138 kPa gauge (20 psig)
Linear velocity @ 120ºC 40 cm/sec
Equivalent flow @ 120ºC 1.6 mL/min
Split flow 50 mL/min
Injection port temperature 175ºC
Column temperature program
Initial temperature 120ºC (isothermal)
Detector flame ionization
Detector temperature 200ºC
Hydrogen flow ratea 38 mL/min
Air flow ratea 450 mL/min
Makeup gas nitrogen
Makeup gas flow ratea 45 mL/min
Sample size 1.0 µL, repeatable
a
Consult the manufacturer's instrument manual for suggested flow rates.

4. Program the column oven to 130°C and maintain this temperature until a stable baseline has been
obtained at the required sensitivity.
5. Cool the column oven to a stabilized 120°C.
6. Prepare a resolution test mixture containing approximately 1 mass-% each of n-undecane and n-
dodecane in benzene.

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• This qualitative mixture is analyzed to determine whether column separation is satisfactory. Since TCEP
is not a bonded stationary phase, deterioration is expected to occur relatively sooner than for bonded
phases. Therefore, column resolution should be checked on a weekly basis when samples are being
analyzed. The lifetime of the column can be extended by keeping the column at 50°C when not in use.

7. Analyze the resolution test mixture as described in Procedure.

8. Determine if the column has adequate resolution for this analysis by comparing the resolution test
mixture chromatogram with Figure 3.
• Replace the column if the valley between the n-dodecane peak and the benzene peak exceeds 20% of
the height of the n-dodecane peak.

Calibration
It is difficult to obtain light aromatic compounds for the preparation of a calibration blend that are free
of non-aromatic impurities. For this reason, the calibration blend is prepared in p-xylene, which can be
further purified by crystallization.
Purification Procedure for p-Xylene
To prepare approximately 100 mL of high purity p-xylene to be used in calibration blends, proceed as
follows:
1. Cool approximately 500 mL of commercial p-xylene in an explosion-proof freezer at -10 ± 5°C
until approximately one-half to three-quarters of the p-xylene crystallizes. This requires about 5
hours.
2. Remove the p-xylene from the freezer and decant and discard the liquid portion.
3. Allow the frozen p-xylene to thaw, and then repeat the above crystallization step on the remaining
p-xylene several times until no non-aromatics, benzene, or toluene are detected as indicated by the
gas chromatographic analysis (refer to Procedure).

Preparation of Calibration Blend

Quantitative results are based on the injection of repeatable volumes of both the calibration blend
and the sample. Absolute response factors, derived from the calibration blend, are used to relate the
peak areas of each known component to mg/kg.
1. Prepare a stock solution as described in ASTM Method D4307 to contain approximately 1
mass-% each of n-undecane, benzene and toluene in purified p-xylene. Thoroughly mix the
solution by shaking. Record all weights to the nearest 0.0001 g.
• This blend will be used as the stock solution in the preparation of the actual calibration blend. Label this
mixture as the stock solution.

2. Prepare the calibration blend to contain approximately 1 mass-% of the stock solution in p-
xylene. Thoroughly mix the calibration blend by shaking. Record all weights to the nearest
0.0001 g.
• If refrigerated, the stock solution and calibration blend should remain stable for several months.

3. Calculate the concentration of n-undecane, benzene and toluene in the calibration blend to the
nearest mg/kg using Equation 1. Using the above dilutions, the resulting calibration blend
should contain approximately 100 mg/kg of each added component.
10 6 A B
M= (1)
CD

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where:
A= mass of n-undecane, benzene or toluene in the stock solution, g
B= mass of stock solution in the calibration blend, g
C= total mass of the stock solution prepared, g
D= total mass of the calibration blend prepared, g
M= concentration of n-undecane, benzene, or toluene in the calibration blend, mg/kg
6
10 = factor to convert to mg/kg
4. Analyze the calibration blend in triplicate as described under Chromatographic Technique.
• The peak areas for each measured component from each of the triplicate runs should not deviate from
the average by more than 3% (relative) of the value. If greater deviations occur, make certain that there
are no problems with the equipment and then make additional runs until the required repeatability is
obtained on three consecutive runs.
• Confirm the stability of the chromatographic system by analyzing the calibration blend again at the end of
a series of analyses. If the results differ by more than 5% from the average of the triplicate runs, a
problem has developed with the chromatographic system, and the series of samples must be rerun after
the problem is resolved. Typical problems to look for include a leaky septum and a dirty or partially
plugged syringe.

5. Use the average peak areas to calculate the absolute response factor for n-undecane, benzene,
and toluene, to three significant figures, using Equation 2.
M
R= (2)
P
where:
R = absolute response factor for n-undecane, benzene or toluene
M = concentration of n-undecane, benzene or toluene in the calibration blend, from
Equation 1, mg/kg
P = average peak area for n-undecane, benzene or toluene in the calibration blend

Procedure
1. Fill an autosampler vial with an aliquot of the resolution test mixture, calibration blend, or
sample and place in the autosampler (or autoinjector) tray.
2. Inject a repeatable volume, nominally 1.0 µL, of the resolution test mixture into the gas
chromatograph and start the data system.
• The use of an autoinjector or autosampler automates the injection of the sample into the GC, starts the
data system, and the GC oven program simultaneously.

3. Identify the components in the resultant chromatogram and determine the areas of the impurity
peaks.
• Typical chromatograms are shown in Figures 1-2.
• Total non-aromatics are defined as all components eluting before benzene. Sum the peak areas for all
such components for use in Equation 3, Calculations.

4. Obtain the density, at 25°C, of the sample(s) using ASTM Method D4052, or if it is a pure
compound, from Table 2.

Calculations
Calculate the total non-aromatics, benzene or toluene concentrations using Equation 3. Use the n-
undecane absolute response factor for calculating the sum of the total non-aromatics. Report to the
nearest mg/kg, not to exceed 3 significant figures.

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ERG
Total non-aromatics, benzene, or toluene in the sample, mg/kg = (3)
F
where:
E = peak area of non-aromatics, benzene or toluene in the sample, units consistent
with P in Equation 2
F = density of the sample (from ASTM D4052, “Density, Relative Density, and API
Gravity of Liquids by Digital Density Meter,” or Table 2b), g/mL
G = density of p-xylene (from ASTM D4052 or Table 2 b), g/mL
R = absolute response factor for n-undecane, benzene or toluene, from Equation 2
b
If the sample is essentially a pure compound, e.g., benzene, Table 2 may be used. If the
sample is a mixture of aromatics, determine the density of the sample using ASTM
D4052, and for consistency, also determine the density of the p-xylene calibration blend
using ASTM D4052.

Table 2
Density @ 25°°C, g/mL
Benzene 0.874
Toluene 0.862
p-Xylene 0.857

Precision
Precision statements were determined using UOP Method 999, “Precision Statements in UOP
Methods,” from precision data obtained using an autosampler.

Repeatability and Site Precision

A nested design was carried out for determining impurities in three samples of benzene and one
sample of xylene by two analysts, with each analyst performing analyses on two separate days,
performing three analyses each day for a total of 48 analyses. Using a stepwise analysis of variance
procedure, the within-day estimated standard deviations (esd) were calculated at the concentration
means listed in Table 3. Two analyses performed in one laboratory by the same analyst on the same
day should not differ by more than the repeatability allowable differences shown in Table 3 with
95% confidence. Two analyses performed in one laboratory by different analysts on different days
should not differ by more than the site precision allowable differences shown in Table 3 with 95%
confidence.
Table 3
Repeatability and Site Precision, mg/kg
Repeatability Site Precision
Within- Allowable Within- Allowable
Component Mean Day esd Difference Lab esd Difference
Non-aromatics in benzene 1.6 0.03 0.1 0.06 0.4
Non-aromatics in benzene 11.1 0.06 0.2 0.28 1.7
Non-aromatics in xylene 19.6 0.13 0.4 0.36 2.2
Non-aromatics in benzene 47.2 0.16 0.5 1.31 8.0
Benzene in xylene 5.4 0.04 0.1 0.09 0.6
Toluene in xylene 2.8 0.03 0.1 0.03 0.1

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The data in Table 3 represent short-term estimates of the repeatability of the method. When the
test is run routinely, use of a control standard and a control chart is recommended to generate an
estimate of long-term repeatability.

Reproducibility
There is insufficient data to calculate the reproducibility of the test at this time.

Time for Analysis

The elapsed time and labor requirement for one analysis are the same, 0.5 hour. This does not
include the p-xylene purification procedure.

Suggested Suppliers
Agilent Technologies, 2850 Centerville Rd., Wilmington, DE 19808-1610, USA (302-633-8000)
www.agilent.com
Matheson Tri-Gas, 166 Keystone Dr., Montgomeryville, PA 18936, USA (215-641-2700)
www.mathesontrigas.com
Restek, 110 Benner Circle, Bellefonte, PA 16823 (814-353-1300) www.restek.com
Sigma-Aldrich, 1000 West Saint Paul Avenue, Milwaukee, WI 53233, USA (414-273-3850)
www.sigma-aldrich.com
VICI Mat/Sen, 7806 Bobbitt, Houston, TX 77055, USA (713-688-9345) www.vicimatsen.com
VWR International, 1310 Goshen Parkway, West Chester, PA 19380, YSA (610-431-1700)
www.vwr.com

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