ASTM D1959-97

Standard Test Method for Iodine Value of Drying Oils and Fatty Acids (Withdrawn 2006)

SCOPE
1.1 This test method covers the Wijs procedure for determination of unsaturation (iodine value) in drying oils. It is applicable to all natural and synthetic drying oils and their fatty acids.  
1.2 When the iodine value is determined on oils or fatty acids having conjugated systems, the result is not a measure of total unsaturation, but rather is an empirical value that affords a comparison of total unsaturation.  
1.3 To obtain the total iodine value on conjugated samples, use Test Method D 1541.  
Note 1-This test method is essentially equivalent to Test Methods D 2075 and D 2078.
1.4 This standard may involve hazardous materials, operations, and equipment. This standard does not purport to address all of the safety problems 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.> For specific hazard statements, see Section 8.
WITHDRAWN RATIONALE
This test method covers the Wijs procedure for determination of unsaturation (iodine value) in drying oils. It is applicable to all natural and synthetic drying oils and their fatty acids.
Formerly under the jurisdiction of Committee D01 on Paint and Related Coatings, Materials and Applications, this test method was withdrawn in February 2006 in accordance with section 10.5.3.1 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.

General Information

• Status: Withdrawn
• Publication Date: 31-Dec-1996
• Withdrawal Date: 26-Feb-2006
• ICS: 87.060.20 - Binders
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications

Relations

• Referred By: ASTM D5768-02(2022) - Standard Test Method for Determination of Iodine Value of Tall Oil Fatty Acids
• Effective Date: 01-Jan-1997
• Referred By: ASTM D4252-89(2017) - Standard Test Methods for Chemical Analysis of Alcohol Ethoxylates and Alkylphenol Ethoxylates
• Effective Date: 01-Jan-1997
• Referred By: ASTM D49-83(2020) - Standard Test Methods of Chemical Analysis of Red Lead
• Effective Date: 01-Jan-1997

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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:D1959–97
Standard Test Method for
Iodine Value of Drying Oils and Fatty Acids
This standard is issued under the fixed designation D 1959; 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.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope 3.1.1 iodine value—a measure of the unsaturation of oils
and fatty acids and is expressed in terms of the number of
1.1 This test method covers the Wijs procedure for deter-
centigrams of iodine per gram of sample (weight percent of
mination of unsaturation (iodine value) in drying oils. It is
absorbed iodine).
applicabletoallnaturalandsyntheticdryingoilsandtheirfatty
3.1.1.1 Discussion—Total unsaturation of conjugated sys-
acids.
tems may be measured in accordance with Test Method
1.2 When the iodine value is determined on oils or fatty
D 1541.TheWijsiodinevaluemethodisnotreliablefortalloil
acids having conjugated systems, the result is not a measure of
fatty acids containing an appreciable quantity of rosin acids.
total unsaturation, but rather is an empirical value that affords
a comparison of total unsaturation.
4. Summary of Test Method
1.3 To obtain the total iodine value on conjugated samples,
4.1 The determination of the iodine value of oils containing
use Test Method D 1541.
isolated double bonds is based on the absorption of halogen
NOTE 1—This test method is essentially equivalent to Test Methods
under conditions selected to promote stoichiometrical results.
D 2075 and D 2078.
5. Significance and Use
1.4 This standard may involve hazardous materials, opera-
tions, and equipment. This standard does not purport to 5.1 This test method measures the unsaturation as iodine
address all of the safety problems associated with its use. It is
value by addition of an iodine/chlorine reagent. The amount of
the responsibility of the user of this standard to establish reagent absorbed is determined by back titrating the excess
appropriate safety and health practices and determine the
reagent and comparing it to a blank determination.
applicability of regulatory limitations prior to use. For specific 5.2 In samples containing conjugated double bonds, the
hazard statements, see Section 8.
iodine value obtained is empirical since the reagent does not
react stoichiometrically with conjugated unsaturation. Where
2. Referenced Documents
no conjugation is present, the iodine value obtained is a
2.1 ASTM Standards:
measure of the total unsaturation. By using proper specimen
D 1193 Specification for Reagent Water
weights, the empirical values obtained are useful for compara-
D 1541 Test Method for Total Iodine Value of Drying Oils
tive purposes.
and Their Derivatives
6. Apparatus
D 2075 Test Method for Iodine Value of Fatty Amines,
Amidoamines, and Diamines
6.1 Bottles—Glass-stoppered bottles or wide-mouth (Note
D 2078 Test Method for Iodine Value of Fatty Quarternary 2) Erlenmeyer flasks of 500-mL capacity.
Ammonium Chlorides
NOTE 2—Wide-mouth bottles or flasks are essential if stirring is done
D 5768 Test Method for Iodine Value of Tall Oil Fatty
by mechanical means.
Acids
6.2 Pipets, 20 and 25-mL capacity.
3. Terminology
7. Reagents
3.1 Definitions:
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests unless otherwise specified. Unless otherwise
This test method is under the jurisdiction of ASTM Committee D-1 on Paint indicated, it is intended that all reagents shall conform to the
and Related Coatings, Materials, andApplications and is the direct responsibility of
Specifications of the Committee onAnalytical Reagents of the
Subcommittee D 01.32 on Drying Oils.
American Chemical Society, where such specifications are
Current edition approved Aug. 10, 1997. Published October 1997. Originally
published as D 1959 – 61. Last previous edition D 1959 – 85.
Annual Book of ASTM Standards, Vol 11.01.
Annual Book of ASTM Standards, Vol 06.03.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D1959
available. Other grades may be used provided it is first
A 5 K Cr O used, g, and
2 2 7
ascertained that the reagent is of sufficiently high purity to
C 5 Na S O solutionrequiredfortitrationoftheK Cr O ,
2 2 3 2 2 7
permit its use without lessening the accuracy of the determi-
mL.
nation.
7.9 Starch Indicator Solution:
7.2 Purity of Water—Unless otherwise indicated, references
7.9.1 Use soluble starch that will pass the following test for
to water shall be understood to mean reagent water conforming
sensitivity: Make a paste with1gof starch and a small amount
to Type I of Specification D 1193.
of cold water. Add, while stirring, 200 mL of boiling water.
7.3 Acetic Acid (Glacial)(Caution—see 8.1)—Verify the
Dilute5mLofthissolutionwith100mLofwaterandadd0.05
absence of substances reducing permanganate as follows:
mL of 0.1 N iodine solution. The deep blue color produced
Dilute 2 mL of the acid with 10 mL of water and add 0.1 mL
must be discharged by 0.05 mL of 0.1 N Na S O solution.
2 2 3
of 0.1 N potassium permanganate (KMnO ) solution. The pink
4 7.9.2 Make a homogeneous paste of 10 g of soluble starch
color should not be entirely discharged at the end of 2 h.
in cold water.Add to this 1 Lof boiling water, stir rapidly, and
7.4 Solvent: isooctane or fresh cyclohexane to replace long
cool. Salicylic acid (1.25 g/L) may be added to preserve the
used carbon tetrachloride, now banned as too hazardous
indicator. If long storage is required, keep the solution in a
(Caution—See 8.2).
refrigerator at 4 to 10°C (40 to 50°F). Prepare fresh indicator
7.5 Carbon Tetrachloride (CCl)(Caution—See 8.2).
when the end point of the titration from blue to colorless fails
7.6 Chlorine (99.8% Cl)(Caution—see8.3)—Commercial
to be sharp.
gradesofchlorineavailableincylindersmaybeused,provided
7.10 Wijs Solution (Caution—see 8.4) (Note 3)—Dissolve
the gas is dried by passing through concentrated sulfuric acid
13.0 g of iodine in 1 L of acetic acid. Gentle heat may be
(H SO , sp gr 1.84) before passing it into the iodine solution
necessary to promote solution. Cool and remove a small
2 4
(see 7.10). Alternatively, the chlorine may be prepared by
quantity(100to200mL)andsetasideinacoolplaceforfuture
allowing concentrated hydrochloric acid (HCl, sp gr 1.19) to
use. Pass dry chlorine gas into the iodine solution until the
dropontopotassiumpermanganate(KMnO )orontoamixture
original titration is not quite doubled. A characteristic color
of KMnO and manganese dioxide (MnO ). Dry the gas thus
change takes place in the Wijs solution when the desired
4 2
generated by passing it through concentrated H SO .
amount of chlorine has been added; this may be used to assist
2 4
7.7 PotassiumIodideSolution(150g/L)—Dissolve150gof
in judging the end point. A convenient procedure is to add a
potassium iodide (KI) in water and dilute to 1 L.
small excess of chlorine and bring back to the desired titration
7.8 Sodium Thiosulfate, Standard Solution (0.1 N)—
by addition of some of the original iodine solution that was
Dissolve 24.8 g of sodium thiosulfate (Na S O ·5H O) in
taken out at the beginning. Determine the strength of the
2 2 3 2
water and dilute to 1 L. Standardize against potassium dichro-
original iodine solution and the finished Wijs solution by
mate (K Cr O ) as follows: Weigh to 0.1 mg, by difference
titration against 0.1 N Na S O solution, as directed in .
2 2 7
2 2 3
fromaweighingbottle,0.16to0.22gofK Cr O thathasbeen
2 2 7
NOTE 3—Iodine monochloride (Wijs solution) can be purchased com-
finelygroundandthendriedtoconstantweightat105to110°C
merciallyfromvariouslaboratorysupplyhouses.Thehalogenratioshould
prior to use. Place the K Cr O in a 500-mLflask or bottle a
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