Standard Test Method for Unsaponifiable Matter in Pine Chemicals, Including Rosin, Tall Oil, and Related Products

SIGNIFICANCE AND USE
3.1 This test method is designed to broaden the scope of the previous edition of the test method by the inclusion of tall oil and tall oil derived from products as test materials. Test Methods D803 currently includes a method for the determination of unsaponifiable matter.  
3.2 The amount of unsaponifiable matter in tall oil and other related products is important in characterizing such products as it indicates the level of nonacidic material, both free and combined, present in the test material. The unsaponifiable in naval stores products is primarily composed of higher molecular weight alcohols, sterols, and hydrocarbons.
SCOPE
1.1 This test method covers the determination of the percentage of material in pine chemicals products as defined in Terminology D804 including rosin, tall oil, and related products, other than insoluble dirt or similar visible foreign matter that does not yield a water-soluble soap when the sample is saponified with potassium hydroxide.  
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.
Note 1: It has been reported that this method may not be applicable to gum rosin, especially any gum rosin containing volatile terpenes. Volatile terpenes are by definition unsaponifiable matter, and can be lost under the drying conditions described in 8.4. The method is applicable to tall oil rosin and wood rosin as these rosins do not contain volatile terpenes.  
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.

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Publication Date
30-Nov-2022
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ASTM D1065-18(2022) - Standard Test Method for Unsaponifiable Matter in Pine Chemicals, Including Rosin, Tall Oil, and Related Products
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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: D1065 −18 (Reapproved 2022)
Standard Test Method for
Unsaponifiable Matter in Pine Chemicals, Including Rosin,
Tall Oil, and Related Products
This standard is issued under the fixed designation D1065; 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 D803 Test Methods for Testing Tall Oil
D804 Terminology Relating to Pine Chemicals, Including
1.1 This test method covers the determination of the per-
Tall Oil and Related Products
centage of material in pine chemicals products as defined in
E177 Practice for Use of the Terms Precision and Bias in
Terminology D804 including rosin, tall oil, and related
ASTM Test Methods
products, other than insoluble dirt or similar visible foreign
E691 Practice for Conducting an Interlaboratory Study to
matter that does not yield a water-soluble soap when the
Determine the Precision of a Test Method
sample is saponified with potassium hydroxide.
1.2 The values stated in SI units are to be regarded as
3. Significance and Use
standard. No other units of measurement are included in this
3.1 This test method is designed to broaden the scope of the
standard.
previous edition of the test method by the inclusion of tall oil
1.3 This standard does not purport to address all of the
and tall oil derived from products as test materials. Test
safety concerns, if any, associated with its use. It is the
Methods D803 currently includes a method for the determina-
responsibility of the user of this standard to establish appro-
tion of unsaponifiable matter.
priate safety, health, and environmental practices and deter-
3.2 Theamountofunsaponifiablematterintalloilandother
mine the applicability of regulatory limitations prior to use.
related products is important in characterizing such products as
NOTE 1—It has been reported that this method may not be applicable to
it indicates the level of nonacidic material, both free and
gum rosin, especially any gum rosin containing volatile terpenes. Volatile
combined, present in the test material. The unsaponifiable in
terpenes are by definition unsaponifiable matter, and can be lost under the
naval stores products is primarily composed of higher molecu-
drying conditions described in 8.4. The method is applicable to tall oil
rosin and wood rosin as these rosins do not contain volatile terpenes.
lar weight alcohols, sterols, and hydrocarbons.
1.4 This international standard was developed in accor-
4. Apparatus
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
4.1 Erlenmeyer or Other Flat-Bottom Flask, of 125 mL to
Development of International Standards, Guides and Recom-
250 mL capacity, with standard-taper 24/40 joint.
mendations issued by the World Trade Organization Technical
4.2 Erlenmeyer Flask, of 250 mL to 300 mL capacity, with
Barriers to Trade (TBT) Committee.
wide mouth.
2. Referenced Documents
4.3 Separatory Funnels, of 300 mL to 500 mL capacity,
2.1 ASTM Standards: with glass or polytetrafluoroethylene (PFTE) stoppers.
D509 Test Methods of Sampling and Grading Rosin
4.4 Graduated Cylinder, one of 10 mL to 25 mL and one of
50 mL to 100 mL capacity.
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, andApplications and is the direct responsibility of 4.5 Beaker, of up to 250 mL capacity.
Subcommittee D01.34 on Pine Chemicals and Hydrocarbon Resins.
Current edition approved Dec. 1, 2022. Published December 2022. Originally
5. Reagents
approved in 1949. Last previous edition approved in 2018 as D1065 – 18. DOI:
10.1520/D1065-18R22.
5.1 Purity of Reagents—Reagent grade chemicals shall be
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
used in all tests. Unless otherwise indicated, it is intended that
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
all reagents shall conform to the specifications of the Commit-
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. tee onAnalytical Reagents of theAmerican Chemical Society,
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D1065 − 18 (2022)
where such specifications are available. Other grades may be 7.5 Potassium Hydroxide, Ethanolic (Saponification) Solu-
used, provided it is first ascertained that the reagent is of tion (132 g KOH/L)—Dissolve 132 g of KOH (preferably
sufficiently high purity to permit use without lessening the pellets) in 150 mL of water and dilute to 1 L with ethanol
accuracy of the determination. (95 %) denatured by Formula No. 3A or No. 30 of the U.S.
Bureau of Internal Revenue.
5.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean distilled, or deionized 7.6 Thymol Blue Indicator Solution—Dissolve 0.1 g of
water. thymol blue in 100 mL methanol (99.5 %).
8. Procedure
6. Preparation of Sample
8.1 Weigh 5.0 g 6 0.1 g (to 0.01 g) of the sample into the
6.1 Procurement and handling of samples will vary depend-
125-mL(250-mL) Erlenmeyer or other flat-bottom flask, using
ing upon the physical state of the material. In all instances, the
the 10-mL or 25-mL graduated cylinder add 15 mL of the
sampling should conform to accepted sampling techniques
ethanolic KOH solution (132 g KOH/L), attach to the
which ensure the sample is representative of the material being
condenser, and heat to reflux and maintain for 1.5 h. Remove
sampled.
the flask, add 30 mLwater, transfer to a separatory funnel, and
6.2 Uniform liquid material should be mixed well and an
rinse the flask with an additional 20 mL of water that is added
aliquot removed for analysis.Titer in fatty acid samples should
to the separatory funnel. Rinse the flask with 40 mL of ethyl
be resolubilized by gentle heating and agitation. Rosin crystal-
ether, adding the ether rinse to the separatory funnel. Stopper
lization in liquid samples, such as distilled tall oil (DTO),
and shake the separatory funnel, then allow to stand until the
should be resolubilized by heating to 160 °C with periodic
ether layer separates from the water/soap layer. Drain the
agitation. Homogeneous representative samples are impera-
aqueous soap layer (lower layer) into a second separatory
tive.
funnel, allowing a few drops of the aqueous layer to remain
above the stopcock to prevent loss of ether extract by creepage
6.3 Solids that melt at relatively low temperature (that is,
through the stopcock joint.
tall oil pitch) should be warmed to liquification to facilitate
mixing and pouring. Homogeneous representative samples are
8.2 To the aqueous soap layer in the second funnel, add
imperative.
30 mL ether and extract as before. Drain the aqueous soap
layer into the original saponification flask. Add the ether layer
6.4 Solids that melt at relatively high temperatures (that is,
fromthesecondseparatoryfunneltothefirstseparatoryfunnel,
rosin) should be fractured and chipped if possible, (see Test
thereby combining the extracts. Pour the aqueous soap layer
Methods D509). The sample taken for analysis shall consist of
from the original saponification flask into the second separa-
small pieces of rosin chipped from a freshly exposed part of a
tory funnel, add 30 mL ether and extract for
...

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