ASTM D6277-07(2022)

Standard Test Method for Determination of Benzene in Spark-Ignition Engine Fuels Using Mid Infrared Spectroscopy

SIGNIFICANCE AND USE
5.1 Benzene is a compound that endangers health, and the concentration is limited by environmental protection agencies to produce a less toxic gasoline.  
5.2 This test method is fast, simple to run, and inexpensive.  
5.3 This test method is applicable for quality control in the production and distribution of spark-ignition engine fuels.
SCOPE
1.1 This test method covers the determination of the percentage of benzene in spark-ignition engine fuels. It is applicable to concentrations from 0.1 % to 5 % by volume.  
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.4 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.

General Information

• Status: Published
• Publication Date: 30-Apr-2022
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0F - Absorption Spectroscopic Methods

Relations

• Refers: ASTM D5842-23 - Standard Practice for Sampling and Handling of Fuels for Volatility Measurement
• Effective Date: 01-Oct-2023
• Refers: ASTM D5842-19 - Standard Practice for Sampling and Handling of Fuels for Volatility Measurement
• Effective Date: 01-Nov-2019
• Refers: ASTM E2056-04(2016) - Standard Practice for Qualifying Spectrometers and Spectrophotometers for Use in Multivariate Analyses, Calibrated Using Surrogate Mixtures
• Effective Date: 01-Apr-2016
• Refers: ASTM D4307-99(2015) - Standard Practice for Preparation of Liquid Blends for Use as Analytical Standards
• Effective Date: 01-Oct-2015
• Refers: ASTM D5769-10(2015) - Standard Test Method for Determination of Benzene, Toluene, and Total Aromatics in Finished Gasolines by Gas Chromatography/Mass Spectrometry
• Effective Date: 01-Jun-2015
• Refers: ASTM D5842-14 - Standard Practice for Sampling and Handling of Fuels for Volatility Measurement
• Effective Date: 15-Jan-2014
• Refers: ASTM D1298-12a - Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
• Effective Date: 15-May-2012
• Refers: ASTM D1298-12 - Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
• Effective Date: 01-Apr-2012
• Refers: ASTM D4057-06(2011) - Standard Practice for Manual Sampling of Petroleum and Petroleum Products
• Effective Date: 01-Jun-2011
• Refers: ASTM D5854-96(2010) - Standard Practice for Mixing and Handling of Liquid Samples of Petroleum and Petroleum Products
• Effective Date: 01-May-2010
• Refers: ASTM D4307-99(2010) - Standard Practice for Preparation of Liquid Blends for Use as Analytical Standards
• Effective Date: 01-May-2010
• Refers: ASTM D5769-10 - Standard Test Method for Determination of Benzene, Toluene, and Total Aromatics in Finished Gasolines by Gas Chromatography/Mass Spectrometry
• Effective Date: 01-May-2010
• Refers: ASTM E2056-04(2010) - Standard Practice for Qualifying Spectrometers and Spectrophotometers for Use in Multivariate Analyses, Calibrated Using Surrogate Mixtures
• Effective Date: 01-Mar-2010
• Refers: ASTM D5842-04(2009) - Standard Practice for Sampling and Handling of Fuels for Volatility Measurement
• Effective Date: 01-Jul-2009
• Refers: ASTM E168-06 - Standard Practices for General Techniques of Infrared Quantitative Analysis (Withdrawn 2015)
• Effective Date: 01-Mar-2006

Standards Content (Sample)

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.
Designation:D6277 −07 (Reapproved 2022)
Standard Test Method for
Determination of Benzene in Spark-Ignition Engine Fuels
Using Mid Infrared Spectroscopy
This standard is issued under the fixed designation D6277; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D5769Test Method for Determination of Benzene,Toluene,
and Total Aromatics in Finished Gasolines by Gas
1.1 This test method covers the determination of the per-
Chromatography/Mass Spectrometry
centage of benzene in spark-ignition engine fuels. It is appli-
D5842Practice for Sampling and Handling of Fuels for
cable to concentrations from 0.1% to 5% by volume.
Volatility Measurement
1.2 The values stated in SI units are to be regarded as
D5854Practice for Mixing and Handling of Liquid Samples
standard. No other units of measurement are included in this
of Petroleum and Petroleum Products
standard.
E168Practices for General Techniques of Infrared Quanti-
1.3 This standard does not purport to address all of the
tative Analysis
safety concerns, if any, associated with its use. It is the E1655 Practices for Infrared Multivariate Quantitative
responsibility of the user of this standard to establish appro-
Analysis
priate safety, health, and environmental practices and deter- E2056Practice for Qualifying Spectrometers and Spectro-
mine the applicability of regulatory limitations prior to use.
photometers for Use in Multivariate Analyses, Calibrated
1.4 This international standard was developed in accor- Using Surrogate Mixtures
dance with internationally recognized principles on standard-
3. Terminology
ization established in the Decision on Principles for the
3.1 Definitions:
Development of International Standards, Guides and Recom-
3.1.1 multivariate calibration, n—a process for creating a
mendations issued by the World Trade Organization Technical
calibrationmodelinwhichmultivariatemathematicsisapplied
Barriers to Trade (TBT) Committee.
to correlate the absorbances measured for a set of calibration
2. Referenced Documents
samples to reference component concentrations or property
values for the set of samples.
2.1 ASTM Standards:
3.1.1.1 Discussion—The resultant multivariate calibration
D1298Test Method for Density, Relative Density, or API
modelisappliedtotheanalysisofspectraofunknownsamples
Gravity of Crude Petroleum and Liquid Petroleum Prod-
to provide an estimate of the component concentration or
ucts by Hydrometer Method
property values for the unknown sample.
D4052Test Method for Density, Relative Density, and API
3.1.1.2 Discussion—Included in the multivariate calibration
Gravity of Liquids by Digital Density Meter
algorithms are Partial Least Squares, Multilinear Regression,
D4057Practice for Manual Sampling of Petroleum and
and Classical Least Squares Peak Fitting.
Petroleum Products
D4177Practice for Automatic Sampling of Petroleum and 3.1.2 oxygenate, n—an oxygen-containing organic com-
pound which may be used as a fuel or fuel supplement, for
Petroleum Products
D4307Practice for Preparation of Liquid Blends for Use as example, various alcohols and ethers.
Analytical Standards
4. Summary of Test Method
4.1 Asampleofspark-ignitionenginefuelisintroducedinto
This test method is under the jurisdiction of ASTM Committee D02 on
aliquidsamplecell.Abeamofinfraredlightisimagedthrough
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
the sample onto a detector, and the detector response is
Subcommittee D02.04.0F on Absorption Spectroscopic Methods.
determined.Wavelengthsofthespectrum,thatcorrelatehighly
Current edition approved May 1, 2022. Published May 2022. Originally
with benzene or interferences, are selected for analysis using
approved in 1998. Last previous edition approved in 2017 as D6277–07 (2017).
DOI: 10.1520/D6277-07R22.
selective bandpass filters or by mathematically selecting areas
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
of the whole spectrum. A multivariate mathematical analysis
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
converts the detector response for the selected areas of the
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. spectrum of an unknown to a concentration of benzene.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6277−07 (2022)
5. Significance and Use line, shall not exceed 0.3 % transmittance in the region from
–1 –1
700cm to 664 cm .
5.1 Benzene is a compound that endangers health, and the
concentration is limited by environmental protection agencies 7.2 Absorption Cell—The absorption cell can be either
to produce a less toxic gasoline. transmission or attenuated total reflectance.
7.2.1 Transmission Cells, shall have windows of potassium
5.2 This test method is fast, simple to run, and inexpensive.
bromide, zinc selenide, or other material having a significant
–1 –1
5.3 This test method is applicable for quality control in the
transmission from 712 cm to 660 cm . The cell path length
production and distribution of spark-ignition engine fuels.
of the transmission cell shall be 0.025mm 6 0.005mm. The
use of a wedged transmission cell with the same nominal path
6. Interferences
length is acceptable.
6.1 The primary spectral interferences are toluene and other
7.2.2 Attenuated Total Reflectance (ATR) Cells, shall have
monosubstituted aromatics. In addition, oxygenates can inter-
the following specifications:
fere with measurements made with filter apparatus. Proper
ATR element material ZnSe
choice of the apparatus, proper design of a calibration matrix,
beam condensing optics conical, non-focussing optics
integral to cell body
and proper utilization of multivariate calibration techniques
element configuration circular cross section with
can minimize these interferences.
coaxial conical ends
cone half angle 60°
7. Apparatus element length 1.55 in.
element diameter 0.125 in.
7.1 Mid-IR Spectrometric Analyzer (of one of the following
angle of incidence at
sample interface 53.8°
types):
maximum range of
7.1.1 Filter-based Mid-IR Test Apparatus—The type of
incidence angles ± 1.5°
apparatus suitable for use in this test method minimally
standard absorbance
−1
(1428 cm band of acetone) 0.38 AU ± 0.02 AU
employesanIRsource,aninfraredtransmissioncelloraliquid
material of construction 316 stainless steel
attenuated total internal reflection cell, wavelength discrimi-
seals Chemraz or Kalraz o-rings
nating filters, a chopper wheel, a detector, anA-D converter, a
8. Reagents and Materials (see Note 1)
microprocessor, and a method to introduce the sample. The
frequencies and bandwidths of the filters are specified in Table
8.1 Standards for Calibration, Qualification, and Quality
1.
Control Check Standards—Use of chemicals of at least 99%
7.1.2 Fourier Transform Mid-IR Spectrometer—Thetypeof
purity, where available, for quality control checks is required
apparatus suitable for use in this test method employs an IR
when preparing samples. (Warning—These materials are
source,aninfraredtransmissioncelloraliquidattenuatedtotal
flammable and may be harmful if ingested or inhaled.)
internalreflectioncell,ascanninginterferometer,adetector,an
8.1.1 tert-Amyl methyl ether, TAME [994-05-8].
A-D converter, a microprocessor, and a method to introduce
8.1.2 Benzene [1076-43-3].
thesample.Thefollowingperformancespecifications(through
8.1.3 tert-Butyl ethyl ether, ETBE [637-92-3].
the ATR cell) must be met:
8.1.4 tert-Butyl methyl ether, MTBE [1634-04-4].
–1 –1
scan range 4000 cm to 600 cm
8.1.5 1,3 Dimethylbenzene (m-xylene).
–1
resolution 4 cm
8.1.6 Ethanol [64-17-5].
–1
S/N at 674 cm >300:1 RMS
8.1.7 Ethylbenzene [100-41-4].
The signal to noise level will be established by taking a
8.1.8 3–Ethyltoluene [620-14-4].
singlebeamspectrumusingairornitrogenasthereferenceand
8.1.9 Heavy aromatic/reformate petroleum stream (high
declaring that spectrum as the background. The background
boiling cut: IPB of 150°C 6 5°C and EP of 245°C 6 8°C)
single beam spectrum obtained can be the average of multiple
certified to contain less than 0.025% benzene (an absorbance
FTIR scans, but the total collection time shall not exceed 60 s.
−1
oflessthan0.03at675cm usinga0.2mmcellandabaseline
If interference from water vapor or carbon dioxide is a
−1 −1
betweenapproximately680cm and670cm )[64741-68-0].
problem, the instrument shall be purged with dry air or
8.1.10 Hexane (an absorbance versus water of less than 0.1
nitrogen. A subsequent single beam spectrum shall be taken
at 250 nm usinga1cm cell) [110-54-3].
under the same conditions and ratioed to the background
8.1.11 2,2,4-Trimethylpentane (isooctane) [540-84-1].
spectrum. The RMS noise of the ratioed spectra, the 100%
8.1.12 Pentane (an absorbance versus water of less than 0.1
at 250 nm usinga1cm cell) [109-66-0].
8.1.13 Propylbenzene [103-65-1].
TABLE 1 Specification for Filters Used in Filter-based Mid-IR Test
8.1.14 Toluene [108-88-3].
Center Wavenumber Bandwidth (in wavelength units)
(± 0.15 % of wavenumber) (full width at half height) 8.1.15 1,3,5-Trimethylbenzene (mesitylene) [108-67-8].
-1
673 cm 1% of λ 8.1.16 m-Xylene [108-38-3].
c
-1
729 cm 1% of λ
c
-1
NOTE 1—Only some of the reagents are required in each calibration or
769 cm 1% of λ
c
-1
1205 cm 1% of λ qualification procedure.
c
-1
1054 cm 1% of λ
c
-1
1188 cm 1% of λ
c
9. Sampling and Sample Handling
-1
1117 cm 1% of λ
c
9.1 General Requirements:
D6277−07 (2022)
9.1.1 The sensitivity of the measurement of benzene to the differs from the known value by more than 0.12% by volume,
loss of benzene or other components through evaporation and then the measurement system is out-of-control and cannot be
the resulting changes in composition is such that the utmost used to estimate benzene concentrations until the cause of the
precaution and the most meticulous care in the drawing and out-of-control behavior is identified and corrected.
handling of samples is required.
11.3 If correction of out-of-control behavior requires repair
9.1.2 Fuel samples to be analyzed by the test method shall
to the instrument or recalibration of the instrument, the
be sampled using procedures outlined in Practices D4057,
qualificationofinstrumentperformancedescribedinA1.3shall
D4177,or D5842, where appropriate. Do not use the “Sam-
be performed before the system is used to measure benzene
pling by Water Displacement.” With some alcohol containing
content on samples.
samples, the alcohol will dissolve in the water phase.
9.1.3 Protect samples from excessive temperatures prior to
12. Procedure
testing. This can be accomplished by storage in an appropriate
12.1 Equilibrate the samples to between 15°C and 38°C
ice bath or refrigerator at 0°C to 5°C.
before analysis.
9.1.4 Donottestsamplesstoredinleakycontainers.Discard
and obtain a new sample if leaks are detected.
12.2 Clean the sample cell. If a separate baseline using the
emptycellisrequired,andifresidualfuelisinthesamplecell,
9.2 Sample Handling During Analysis:
remove the fuel by flushing the cell and inlet-outlet lines with
9.2.1 When analyzing samples by the mid infrared
enough pentane to ensure complete washing. Evaporate the
apparatus, the sample must be between a temperature of 15°C
residual pentane with either dry air or nitrogen.
to 38°C. Equilibrate all samples to the temperature of the
laboratory (15°C to 38°C) prior to analysis by this test
12.3 If needed, obtain a baseline spectrum in the manner
method.
established by the manufacturer of the equipment.
9.2.2 After analysis, if the sample is to be saved, reseal the
12.4 Priortotheanalysisofunknowntestsamples,establish
container and store the sample in an ice bath or a refrigerator
that the equipment is running properly by collecting the
at 0°C to 5°C.
spectrum of the quality control standard(s), by analyzing the
spectrum with the calibration model, and by comparing the
10. Calibration and Qualification of the Apparatus
estimatedbenzeneconcentrationtotheknownvaluefortheQC
10.1 Before use, the instrument must be calibrated accord-
standard(s).Introduceenoughstandardtothecelltoensurethat
ing to the procedure described in Annex A1. This calibration
the cell is washed a minimum of three times with the standard
can be performed by the instrument manufacturer prior to
solution.
deliveryoftheinstrumenttotheenduser.If,aftermaintenance,
12.5 Introduce the unknown fuel sample in the manner
the instrument calibration is repeated, the qualification proce-
established by the manufacturer. Introduce enough of the fuel
dure must also be repeated.
sample to the cell to ensure the cell is washed a minimum of
10.2 Before use, the instrument must be qualified according
three times with the fuel.
totheproceduredescribedinAnnexA1.Thequalificationneed
12.6 Obtain the spectral response of the fuel sample.
only be carried out when the instrument is initially put into
12.6.1 IfafilterbasedmidIRinstrumentisused,acquirethe
operation, recalibrated, or repaired.
absorbance for the fuel sample at the wavelengths correspond-
11. Quality Control Checks
ing to the specified filters.
11.1 Confirm the calibration of the instrument each day it is 12.6.2 IfanFTIRisused,acquirethedigitizedspectraldata
–1
for the fuel sample over the frequency region from 4000 cm
used by measuring the benzene concentration using the proce-
–1
dure outlined in Section 12 on at least one quality control to 600 cm .
sample of known benzene content. The preparation of known
12.7 Determine the benzene concentration (volume %) ac-
benzene concentration is described in 11.1.1 and 11.1.2.
cording to the appropriate calibration equation developed in
11.1.1 Standard(s) of known benzene concentration shall be
Annex A1.
made up by mass according to A1.1 and converted to volume
12.7.1 For filter based mid IR instruments, apply the cali-
% using the measured density as outlined in Section 13.At
bration equation determined in A1.2.4 to convert the absor-
least one standard shall be made up at 1.2% 6 0.2% by mass
bancesateachofthewavelengthstothebenzeneconcentration
benzene, that is, nominally 1.0% by volume. Additional
expressed in volume %.
standards may also be prepared and used for quality control
12.7.2 For FTIR instruments using a PLS calibration, deter-
checks.
mine t
...