ASTM D5974-15

Standard Test Methods for Fatty and Rosin Acids in Tall Oil Fractionation Products by Capillary Gas Chromatography

SIGNIFICANCE AND USE
3.1 Tall oil fractionated products derived from tall oil are important commercial materials, primarily composed of fatty acids and rosin acids, but also containing some neutral material (see Terminology D804). For many applications, it is necessary to know the level of the individual fatty acids and rosin acids present in these products. Gas chromatography has proven to be a useful tool for such determinations (see Test Methods D509), and capillary chromatography, described in these test methods, is considered to be the most effective gas chromatographic technique currently available. In particular situations, other techniques may be more suitable than gas chromatography. For example, the presence of fatty acid esters in the sample would result in transesterification during the derivatization step that may affect the results.  
3.2 Due to hydrogen bonding, unmodified tall oil fatty acids and rosin acids cannot be volatilized at atmospheric pressure without undergoing decomposition. So, it is necessary to convert the free acids to the more volatile and more stable methyl esters, prior to chromatographic separation.  
3.3 These test methods describe four ways to prepare methyl esters. The classic method is through the use of diazomethane, but diazomethane is a hazardous and toxic material, and so is no longer the preferred agent. The use of diazomethane is detailed in Appendix X1.  
3.3.1 TMAH causes isomerization of a sample’s di- and polyunsaturated fatty acids, when it is used in even a slight excess. This leads to inaccurate results for the individual fatty acid components. TMAH should be used for materials containing only rosin acids, or when the identification or quantitation of individual fatty acid components is not important.  
3.3.2 TMPAH is the recommended methylating agent when the identification or quantitation of individual di- and polyunsaturated fatty acids is required. TMPAH produces results that are very similar to those of diazomethane, but with...
SCOPE
1.1 These test methods cover the determination of the amounts of the individual fatty acids and rosin acids in fractionated tall oil products, using capillary gas chromatographic separation of the volatile methyl esters of these acids.  
1.2 Four methods for forming the methyl esters, and two methods for determining the amounts of the individual fatty acids and rosin acids are described.  
1.2.1 The classic method for the formation of methyl esters is through the use of diazomethane, but diazomethane is a hazardous and toxic material, and so is no longer the preferred reagent. The use of diazomethane is detailed in the Appendix. Methyl esters may be formed through the use of tetramethylammonium hydroxide (TMAH), trimethylphenylammonium hydroxide (TMPAH), or N,N-dimethylformamide dimethyl acetal (DMF-DMA).  
1.2.2 The two methods for determining the amount of the individual fatty acids and rosin acids are the “internal standard” method, which yields absolute values, and the “area percent” method, which yields relative values.  
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: 30-Jun-2015
• ICS: 67.080.10 - Fruits and derived products
• ICS: 67.200.10 - Animal and vegetable fats and oils
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.34 - Pine Chemicals and Hydrocarbon Resins

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: D5974 − 15
Standard Test Methods for
Fatty and Rosin Acids in Tall Oil Fractionation Products by
1
Capillary Gas Chromatography
This standard is issued under the fixed designation D5974; 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 E691Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.1 These test methods cover the determination of the
amounts of the individual fatty acids and rosin acids in
3. Significance and Use
fractionated tall oil products, using capillary gas chromato-
graphic separation of the volatile methyl esters of these acids.
3.1 Tall oil fractionated products derived from tall oil are
important commercial materials, primarily composed of fatty
1.2 Four methods for forming the methyl esters, and two
acidsandrosinacids,butalsocontainingsomeneutralmaterial
methods for determining the amounts of the individual fatty
(seeTerminologyD804).Formanyapplications,itisnecessary
acids and rosin acids are described.
to know the level of the individual fatty acids and rosin acids
1.2.1 The classic method for the formation of methyl esters
present in these products. Gas chromatography has proven to
is through the use of diazomethane, but diazomethane is a
be a useful tool for such determinations (see Test Methods
hazardous and toxic material, and so is no longer the preferred
D509), and capillary chromatography, described in these test
reagent. The use of diazomethane is detailed in theAppendix.
methods, is considered to be the most effective gas chromato-
Methyl esters may be formed through the use of tetramethyl-
graphic technique currently available. In particular situations,
ammonium hydroxide (TMAH), trimethylphenylammonium
other techniques may be more suitable than gas chromatogra-
hydroxide (TMPAH), or N,N-dimethylformamide dimethyl
phy. For example, the presence of fatty acid esters in the
acetal (DMF-DMA).
sample would result in transesterification during the derivati-
1.2.2 The two methods for determining the amount of the
zation step that may affect the results.
individualfattyacidsandrosinacidsarethe“internalstandard”
method, which yields absolute values, and the “area percent”
3.2 Duetohydrogenbonding,unmodifiedtalloilfattyacids
method, which yields relative values.
and rosin acids cannot be volatilized at atmospheric pressure
1.3 This standard does not purport to address all of the
without undergoing decomposition. So, it is necessary to
safety concerns, if any, associated with its use. It is the
convert the free acids to the more volatile and more stable
responsibility of the user of this standard to establish appro-
methyl esters, prior to chromatographic separation.
priate safety and health practices and determine the applica-
3.3 These test methods describe four ways to prepare
bility of regulatory limitations prior to use.
methyl esters. The classic method is through the use of
diazomethane, but diazomethane is a hazardous and toxic
2. Referenced Documents
material, and so is no longer the preferred agent. The use of
2
2.1 ASTM Standards:
diazomethane is detailed in Appendix X1.
D509Test Methods of Sampling and Grading Rosin
3.3.1 TMAH causes isomerization of a sample’s di- and
D804Terminology Relating to Pine Chemicals, Including
polyunsaturated fatty acids, when it is used in even a slight
Tall Oil and Related Products
excess. This leads to inaccurate results for the individual fatty
acidcomponents.TMAHshouldbeusedformaterialscontain-
ing only rosin acids, or when the identification or quantitation
1
These test methods are under the jurisdiction of ASTM Committee D01 on
of individual fatty acid components is not important.
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.34 on Pine Chemicals and Hydrocarbon
3.3.2 TMPAH is the recommended methylating agent when
Resins.
the identification or quantitation of individual di- and polyun-
Current edition approved July 1, 2015. Published August 2015. Originally
saturated fatty acids is required. TMPAH produces results that
approved in 1996. Last previous edition approved in 2010 as D5974–00(2010).
DOI: 10.1520/D5974-15.
are very similar to those of diazomethane, but without the
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
hazards that are associated with diazomethane.Aconsiderable
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
excess of TMPAH may cause isomerization of conjugated
Standards volume information, refer to the standard’s Document Summary page on
th
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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: D5974 − 00 (Reapproved 2010) D5974 − 15
Standard Test Methods for
Fatty and Rosin Acids in Tall Oil Fractionation Products by
1
Capillary Gas Chromatography
This standard is issued under the fixed designation D5974; 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
1.1 These test methods cover the determination of the amounts of the individual fatty acids and rosin acids in fractionated tall
oil products, using capillary gas chromatographic separation of the volatile methyl esters of these acids.
1.2 Four methods for forming the methyl esters, and two methods for determining the amounts of the individual fatty acids and
rosin acids are described.
1.2.1 The classic method for the formation of methyl esters is through the use of diazomethane, but diazomethane is a hazardous
and toxic material, and so is no longer the preferred reagent. The use of diazomethane is detailed in the Appendix. Methyl esters
may be formed through the use of tetramethylammonium hydroxide (TMAH), trimethylphenylammonium hydroxide (TMPAH),
or N,N-dimethylformamide dimethyl acetal (DMF-DMA).
1.2.2 The two methods for determining the amount of the individual fatty acids and rosin acids are the “internal standard”
method, which yields absolute values, and the “area percent” method, which yields relative values.
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
2.1 ASTM Standards:
D509 Test Methods of Sampling and Grading Rosin
D804 Terminology Relating to Pine Chemicals, Including Tall Oil and Related Products
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Significance and Use
3.1 Tall oil fractionated products derived from tall oil are important commercial materials, primarily composed of fatty acids
and rosin acids, but also containing some neutral material (see Terminology D804). For many applications, it is necessary to know
the level of the individual fatty acids and rosin acids present in these products. Gas chromatography has proven to be a useful tool
for such determinations (see Test Methods D509), and capillary chromatography, described in these test methods, is considered to
be the most effective gas chromatographic technique currently available. In particular situations, other techniques may be more
suitable than gas chromatography. For example, the presence of fatty acid esters in the sample would result in transesterification
during the derivatization step that may affect the results.
3.2 Due to hydrogen bonding, unmodified tall oil fatty acids and rosin acids cannot be volatilized at atmospheric pressure
without undergoing decomposition. So, it is necessary to convert the free acids to the more volatile and more stable methyl esters,
prior to chromatographic separation.
3.3 These test methods describe four ways to prepare methyl esters. The classic method is through the use of diazomethane, but
diazomethane is a hazardous and toxic material, and so is no longer the preferred agent. The use of diazomethane is detailed in
Appendix X1the Appendix.
1
These test methods are under the jurisdiction of ASTM Committee D01 on Paint and Related Coatings, Materials, and Applications and are the direct responsibility of
Subcommittee D01.34 on Pine Chemicals and Hydrocarbon Resins.
Current edition approved June 1, 2010July 1, 2015. Published June 2010August 2015. Originally approved in 1996. Last previous edition approved in 20052010 as
D5974 – 00 (2005).(2010). DOI: 10.1520/D5974-00R10.10.1520/D5974-15.
2
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’sstandard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D5974 − 15
3.3.1 TMAH causes isomerization of a sample’ssample’s di- and polyunsaturated fatty acids,
...