ASTM D6133-02(2008)

Standard Test Method for Acetone, <i>p</i>-Chlorobenzotrifluoride, Methyl Acetate or <i>t</i>-Butyl Acetate Content of Solventborne and Waterborne Paints, Coatings, Resins, and Raw Materials by Direct Injection Into a Gas Chromatograph

SIGNIFICANCE AND USE
With the need to calculate volatile organic content (VOC) of paints, and with acetone, p-chlorobenzotrifluoride, methyl acetate and t-butyl acetate considered as exempt volatile compounds, it is necessary to know the content of these analytes. This gas chromatographic test method provides a relatively simple and direct way to determine their content. However, because the detectors used in this test method are not selective, and because some coatings are very complex mixtures, compounds may be present in the sample that coelute with the analyte, giving a result that is erroneously high. Or a component may elute with the internal standard, giving a result that is erroneously low. It is therefore important to know the composition of the sample to ensure that there are no interferences, under the analysis conditions used. Test Method D 6438 employs mass-spectral detection of analytes and may be used as an alternative method.
SCOPE
1.1 This test method is for the determination of the total-concentration of acetone, p-chlorobenzotrifluoride, methyl acetate, or t-butyl acetate, or combination of any of the four, in solvent-reducible and water-reducible paints, coatings, resins, and raw materials. Because unknown compounds that co-elute with the analyte being measured or with the internal standard, will lead to erroneous results, this test method should only be used for materials of known composition so that the possibility of interferences can be eliminated. The established working range of this test method is from 1 % to 100 % for each analyte by weight.
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 and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-Jan-2008
• ICS: 87.040 - Paints and varnishes
• ICS: 87.060.01 - Paint ingredients in general
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.21 - Chemical Analysis of Paints and Paint Materials

Relations

• Replaces: ASTM D6133-02 - Standard Test Method for Acetone, <i>p</i>-Chlorobenzotrifluoride, Methyl Acetate or <i>t</i>-Butyl Acetate Content of Solventborne and Waterborne Paints, Coatings, Resins, and Raw Materials by Direct Injection Into a Gas Chromatograph
• Effective Date: 01-Feb-2008
• Referred By: ASTM D6438-05(2022) - Standard Test Method for Acetone, Methyl Acetate, and Parachlorobenzotrifluoride Content of Paints, and Coatings by Solid Phase Microextraction-Gas Chromatography
• Effective Date: 01-Feb-2008
• Referred By: ASTM D6886-18 - Standard Test Method for Determination of the Weight Percent Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography
• Effective Date: 01-Feb-2008
• Referred By: ASTM D7768-12(2018) - Standard Test Method for Speciated Organic Volatile Content of Waterborne Multi-Component Coatings by Gas Chromatography
• Effective Date: 01-Feb-2008
• Referred By: ASTM D7270-07(2021) - Standard Guide for Environmental and Performance Verification of Factory-Applied Liquid Coatings
• Effective Date: 01-Feb-2008
• Referred By: ASTM D3960-05(2018) - Standard Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings
• Effective Date: 01-Feb-2008

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D6133 −02(Reapproved2008)
Standard Test Method for
Acetone, p-Chlorobenzotrifluoride, Methyl Acetate or t-Butyl
Acetate Content of Solventborne and Waterborne Paints,
Coatings, Resins, and Raw Materials by Direct Injection Into
a Gas Chromatograph
This standard is issued under the fixed designation D6133; 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 D6438 Test Method for Acetone, Methyl Acetate, and
Parachlorobenzotrifluoride Content of Paints, and Coat-
1.1 This test method is for the determination of the total-
ings by Solid Phase Microextraction-Gas Chromatogra-
concentration of acetone, p-chlorobenzotrifluoride, methyl
phy
acetate, or t-butyl acetate, or combination of any of the four, in
E177 Practice for Use of the Terms Precision and Bias in
solvent-reducible and water-reducible paints, coatings, resins,
ASTM Test Methods
and raw materials. Because unknown compounds that co-elute
E691 Practice for Conducting an Interlaboratory Study to
with the analyte being measured or with the internal standard,
Determine the Precision of a Test Method
will lead to erroneous results, this test method should only be
used for materials of known composition so that the possibility
3. Summary of Test Method
of interferences can be eliminated. The established working
range of this test method is from 1 % to 100 % for each analyte
3.1 A suitable aliquot of whole paint is internally
by weight.
standardized, diluted with an appropriate solvent, and then
injected into a gas chromatographic column that separates the
1.2 The values stated in SI units are to be regarded as
chosen analytes from other volatile components. The analyte
standard. No other units of measurement are included in this
content is determined from area calculations of the materials
standard.
producing peaks on the chromatogram.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4. Significance and Use
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4.1 With the need to calculate volatile organic content
bility of regulatory limitations prior to use.
(VOC) of paints, and with acetone, p-chlorobenzotrifluoride,
methyl acetate and t-butyl acetate considered as exempt
2. Referenced Documents
volatile compounds, it is necessary to know the content of
2.1 ASTM Standards:
these analytes. This gas chromatographic test method provides
D3271 Practice for Direct Injection of Solvent-Reducible
a relatively simple and direct way to determine their content.
Paints Into a Gas Chromatograph for Solvent Analysis
However, because the detectors used in this test method are not
D3272 Practice for Vacuum Distillation of Solvents From
selective, and because some coatings are very complex
Solvent-Reducible Paints For Analysis (Withdrawn
mixtures,compoundsmaybepresentinthesamplethatcoelute
2008)
with the analyte, giving a result that is erroneously high. Or a
component may elute with the internal standard, giving a result
that is erroneously low. It is therefore important to know the
This test method is under the jurisdiction of ASTM Committee D01 on Paint
composition of the sample to ensure that there are no
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
interferences, under the analysis conditions used. Test Method
Current edition approved Feb. 1, 2008. Published February 2008. Originally
D6438employsmass-spectraldetectionofanalytesandmaybe
approved in 1997. Last previous edition approved in 2002 as D6133 – 02. DOI:
used as an alternative method.
10.1520/D6133-02R08.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. At the time of the revision of this test method, t-butyl acetate was not yet
The last approved version of this historical standard is referenced on approved as an exempt solvent, but was under review by the USEPA and was
www.astm.org. expected to be approved. Therefore, it has been included in this test method.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6133−02(2008)
5. Apparatus (a) Acetone—isopropanol, propylene oxide, acetonitrile, and
(b) Cyclohexanol—sec -amyl acetate.
5.1 Gas Chromatograph—Any instrument with temperature
programming capability may be used. It should be equipped
6.2 The following compound is known to co-elute or
with a flame ionization detector (see Table 1).
otherwise interfere with the analysis on an FFAP type column:
5.2 Column—Any column that provides baseline separation
(a) Cyclohexanol—butyl cellosolve.
of the analyte of interest (acetone, p-chlorobenzotrifluoride,
6.3 The analyst must verify that, under the analysis condi-
methylacetateor t-butylacetate),theinternalstandard,andany
tions being used, none of the components of the sample
volatile present in the samples may be used. It should be
interfere with the analyte being quantitated or with the internal
understood that column performance may be influenced by
standard being used.
manufacturing conditions, such as type of deactivation and
chemical bonding/crosslinking used. One or more of the
7. Reagents and Materials
followingcolumntypesmaybeused.Intermsofdurabilityand
over all efficiency, a bonded phase poly (5 % phenyl 95 % 7.1 Purity of Reagents—Use reagent grade chemicals in all
dimethylsiloxane) type of column should be considered first.
tests, unless otherwise specified. Other grades may be used,
(Any reference to specific product brands does not indicate an provided it is first ascertained that the reagent is sufficiently
endorsement for that particular brand of column).
high purity to permit its use without lessening the accuracy of
5.2.1 Capillary, 25 to 60 m, 0.25 mm-inside diameter, 0.25 the determination.
to 1.0-µm film thickness, fused silica bonded phase poly (5 %
7.2 Tetrahydrofuran (THF)—high performance liquid chro-
phenyl 95 % dimethylsiloxane (DB-5, HP-5, Rtx-5, Ultra-2,
matography (HPLC) grade, uninhibited.
BP-5, CP-Sil 8 CB, etc.)).
5.2.2 Capillary, 25 to 60 m, 0.25-mm inside diameter, 0.25 7.3 Cyclohexanol—98+ %.
to 1.0-µm film thickness, fused silica FFAP (polyethylene
7.4 Acetone—HPLC grade.
glycol nitrophthalic acid ester phase).
5.2.3 Capillary, 25 to 60 m, 0.25-mm inside diameter, 0.25 7.5 p-Chlorobenzotrifluoride —98+ %.
to 1.4-µm film thickness, fused silica bonded phase poly (6 %
7.6 Methyl Acetate—99+ %.
cyanopropyl/phenyl, 94 % dimethylsiloxane) (DB-624, SPB-
7.7 t-Butyl Acetate—99+ %.
624, Rtx-624, etc.).
5.3 Recorder—A recording potentiometer with a full-scale
7.8 Water—nanopure.
deflection of 1 to 10 mV, full-scale response time of2sor less
7.9 Chromatography Gases: Helium of 99.9995 % purity or
and sufficient sensitivity and stability to meet the requirements
higher.
of 5.1. The use of a reporting electronic integrator or computer
Hydrogen of 99.9995 % minimum purity (see Note 1).
based data system is preferred.
Air, “dry” quality, free of hydrocarbons.
6. Column Peak Interferences
NOTE 1—The preferred choice of carrier gas is hydrogen, but helium or
nitrogen may also be used. Chromatographic analysis time will increase
6.1 The following compounds are known to co-elute or
and there may be a possible reduction in resolution.
otherwise interfere with the analysis on a DB-5 type column:
7.10 Liquid Charging Devices—micro syringes of 10 or 25
µL capacity.
TABLE 1 Suggested Instrument Conditions
7.11 Analytical Balance—four places (0.0001 g).
Detector Flame Ionization Detection (FID)
Hydrogen Flow 30 mL/min
7.12 Sealable Vials—7-mL screw cap.
Air Flow 400 mL/min
Make-up (Helium) 30 mL/min
7.13 Medicine Droppers.
Carrier Gas (Hydrogen) 40 cm/s
Detector Temperature 250°C
7.14 Autosampler Vials.
A
Injection Port Temperature 200°C
B
Split Ratio 50:1
7.15 Pipete—5-mL glass or autopipete.
Initial Oven Temperature 40°C
Initial Temperature Hold Time 5 min
Program Rate 1 4°C/min 8. Hazards
Program Time 1 5 min
Final Temperature 1 60°C 8.1 Check the supplier’s Material Safety Data Sheet
Program Rate 2 20°C/min
(MSDS) on all chemicals before use.
Program Time 2 8 min
Final Temperature 2 220°C
Final Temperature Hold Time 2 min
9. Preparation of Apparatus
Total Run Time 20 min
Injection Volume 1.0 µL
9.1 Install the column in the chromatograph following the
A
The injection port temperature can be decreased to permit the analysis of manufacturer’s directions and establish the operating condi-
thermally unstable samples; however, each case must be individually investigated.
tions required to give the desired separation (see Table 1).
B
The split ratio may be adjusted according to the theoretical level of solvent
Allow sufficient t
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D6133–00 Designation: D 6133 – 02 (Reapproved 2008)
Standard Test Method for
Acetone, p-Chlorobenzotrifluoride, Methyl Acetate or t-Butyl
Acetate Content of Solvent-ReducibleSolventborne and
Water-ReducibleWaterborne Paints, Coatings, Resins, and
Raw Materials by Direct Injection Into a Gas
Chromatograph
This standard is issued under the fixed designation D 6133; 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.
1. Scope
1.1 This test method is for the determination of the total-concentration of acetone, p-chlorobenzotrifluoride, methyl acetate, or
t-butyl acetate, or combination of any of the four, in solvent-reducible and water-reducible paints, coatings, resins, and raw
materials. Because unknown compounds that co-elute with the anallyteanalyte being measured or with the internal standard, will
lead to erroneous results, this test method should only be used for materials of known composition so that the possibility of
interferences can be eliminated. The established working range of this test method is from 1 % to 100 % acetone for each analyte
by weight.
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 and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D 3271 Practice for Direct Injection of Solvent-Reducible Paints intoInto a Gas Chromatograph for Solvent Analysis
D 3272 Practice for Vacuum Distillation of Solvents fromFrom Solvent-Reducible Paints forFor Analysis
D 6438 Test Method for Acetone, Methyl Acetate, and Parachlorobenzotrifluoride Content of Paints, and Coatings by Solid
Phase Microextraction-Gas Chromatography
E180Practice for Determining the Precision ofASTM Methods forAnalysis and Testing of Industrial and Specialty Chemicals
177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E 691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Summary of Test Method
3.1 Asuitable aliquot of whole paint is internally standardized, diluted with an appropriate solvent, and then injected into a gas
chromatographic column that separates the chosen analytes from other volatile components. The analyte content is determined
from area calculations of the materials producing peaks on the chromatogram.
4. Significance and Use
4.1 With the need to calculate volatile organic content (VOC) of paints, and with acetone, p-chlorobenzotrifluoride, methyl
acetateand t-butylacetate consideredasexemptvolatillevolatilecompounds,itisnecessarytoknowthecontentoftheseanalytes.
This gas chromatographic test method provides a relatively simple and direct way to determine their content. However, because
the detectors used in this test method are not selective, and because some coatings are very complex mixtures, compounds may
This test method is under the jurisdiction of ASTM Committee D01 on Paint and Related Coatings, Materials, and Applications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
Current edition approved May 10, 2000.Feb. 1, 2008. Published September 2000.February 2008. Originally published as D6133–97.approved in 1997. Last previous
edition D6133–97.approved in 2002 as D 6133 – 02.
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
, Vol 06.01.volume information, refer to the standard’s Document Summary page on the ASTM website.
Annual Book of ASTM Standards, Vol 15.05.
At the time of the revision of this test method, t-butyl acetate was not yet approved as an exempt solvent, but was under review by the USEPA and was expected to be
approved. Therefore, it has been included in this test method.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 6133 – 02 (2008)
be present in the sample that coelute with the analyte, giving a result that is erroneously high. Or a component may elute with the
internal standard, giving a result that is erroneously low. It is therefore important to know the composition of the sample to ensure
thattherearenointerferences,undertheanalysisconditionsused.TestMethodD 6438employsmass-spectraldetectionofanalytes
and may be used as an alternative method.
5. Apparatus
5.1 Gas Chromatograph—Any instrument with temperature programming capability may be used. It should be equipped with
either a thermal conductivity, flame ionization or photoionization detector (see Table 1).
5.2 Column—Any column that provides baseline separation of the analyte of interest (acetone, p-chlorobenzotrifluoride, methyl
acetate or t-butyl acetate), the internal standard, and any volatile present in the samples may be used. It should be understood that
column performance may be influenced by manufacturing conditions, such as type of deactivation and chemical bonding/
crosslinking used. One or more of the following column types may be used. In terms of durability and over all efficiency, a bonded
phase poly (5 % phenyl 95 % dimethylsiloxane) type of column should be considered first. (Any reference to specific product
brands does not indicate an endorsement for that particular brand of column).
5.2.1 Capillary,25to60m,0.25mm-insidediameter,0.25to1.0-µmfilmthickness,fusedsilicabondedphasepoly(5 %phenyl
95 % dimethylsiloxane (DB-5, HP-5, Rtx-5, Ultra-2, BP-5, CP-Sil 8 CB, etc.)).
5.2.2 Capillary, 25 to 60 m, 0.25-mm inside diameter, 0.25 to 1.0-µm film thickness, fused silica FFAP (polyethylene glycol
nitrophthalic acid ester phase).
5.2.3 Capillary, 25 to 60 m, 0.25-mm inside diameter, 0.25 to 1.4-µm film thickness, fused silica bonded phase poly (6 %
cyanophenylpropylcyanopropyl/phenyl, 94 % dimethylsiloxane) (DB-624, SPB-624, Rtx-624, etc.).
5.3 Recorder—Arecording potentiometer with a full-scale deflection of 1 to 10 mV, full-scale response time of2sor less and
sufficient sensitivity and stability to meet the requirements of 5.1. The use of a reporting electronic integrator or computer based
data system is preferred.
6. Column Peak Interferences
6.1 The following compounds are known to co-elute or otherwise interfere with the analysis on a DB-5 type column:
(a) Acetone—isopropanol, propylene oxide, acetonitrile, and
(b) Cyclohexanol—sec -amyl acetate.
6.2 The following compound is known to co-elute or otherwise interfere with the analysis on an FFAP type column:
(a) Cyclohexanol—butyl cellosolve.
6.3 The analyst must verify that, under the analysis conditions being used, none of the components of the sample interfere with
the analyte being quantitated or with the internal standard being used.
7. Reagents and Materials
7.1 Purity of Reagents—Use reagent grade chemicals in all tests, unless otherwise specified. Other grades may be used,
provided it is first ascertained that the reagent is sufficiently high purity to permit its use without lessening the accuracy of the
determination.
7.2 Tetrahydrofuran (THF)—high performance liquid chromatography (HPLC) grade, uninhibited.
TABLE 1 Suggested Instrument Conditions
Detector Flame Ionization Detection (FID)
Hydrogen Flow 30 mL/min
Air Flow 400 mL/min
Make-up (Helium) 30 mL/min
Carrier Gas (Hydrogen) 40 cm/s
Detector Temperature 250°C
A
Injection Port Temperature 200°C
B
Split Ratio 50:1
Initial Oven Temperature 40°C
Initial Temperature Hold Time 5 min
Program Rate 1 4°C/min
Program Time 1 5 min
Final Temperature 1 60°C
Program Rate 2 20°C/min
Program Time 2 8 min
Final Temperature 2 220°C
Final Temperature Hold Time 2 min
Total Run Time 20 min
Injection Volume 1.0 µL
A
The injection port temperature can be decreased to permit the analysis of
thermally unstable samples; however, each case must be individually investigated.
B
The split ratio may be adjusted according to the theoretical level of solvent
composition.
D 6133 – 02 (2008)
7.3 Cyclohexanol— 98+ %.
7.4 Acetone—HPLC grade.
7.5 p-Chlorobenzotrifluoride —98+ %.
7.6 Methyl Acetate— 99+ %.
7.7 t-Butyl Acetate—99+ %.
7.8 Water—nanopure.
7.9 Chromatography Gases:
Helium of 99.9995 % purity or higher.
Hydrogen of 99.9995 % minimum purity (see Note 1).
Air, “dry” quality, free of hydrocarbons.
NOTE 1—The preferred choice of carrier gas is hydrogen, but helium or nitrogen may also be used. Chromatographic analysis time will increase and
there may be a possible reduction in resolution.
7.10 Liquid Charging Devices—micro syringes of 10 or 25 µL capacity.
7.11 Analytical Balance—four places (0.0001 g).
7.12 Sealable Vials— 7-mL screw cap.
7.13 Medicine Droppers.
7.14 Autosampler Vials.
7.15 Pipete—5-mL glass or autopipete.
8. Hazards
8.1 Check the supplier’s Material Safety Data Sheet (MSDS) on all chemicals before use.
9. Preparation of Apparatus
9.1 Install the column in the chromatograph following the manufacturer’s directions and establish the operating conditions
required to give the desired separation (see Table 1).Allow sufficient time for the instrument to reach equilibrium as indicated by
a stable base line.
10. Calibration
10.1 Using the information in Table 1 (as a guide), select the conditions of temperature and carrier gas flow that give the
necessary resolution of
...