Designation: D 1615 60 (Reapproved 1995)e1

AMERICAN SOCIETY FOR TESTING AND MATERIALS 100 Barr Harbor Dr., West Conshohocken, PA 19428 Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Glycerol, Ethylene Glycol, and Pentaerythritol in Alkyd Resins1

This standard is issued under the xed designation D 1615; 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.

e1 NOTEKeywords were added editorially and editorial changes made throughout in May 1995.

1. Scope 1.1 These test methods cover the determination of glycerol, ethylene glycol, and pentaerythritol in alkyd resins and resin solutions. Other polyhydric alcohols that can be oxidized by periodic acid to formaldehyde or formic acid, or both, will interfere with the determination of glycerol and ethylene glycol (see Test Methods D 2456 or D 2998). Urea, melamine, or phenolic resins interfere and render this procedure inapplicable. 1.2 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 563 Test Method for Phthalic Anhydride Content of Alkyd Resins and Resin Solutions2 D 1193 Specication for Reagent Water3 D 1398 Test Method for Fatty Acid Content of Alkyd Resins and Alkyd Resin Solutions2 D 2456 Test Method for Identication of Polyhydric Alcohols in Alkyd Resins2 D 2998 Test Method for Polyhydric Alcohols in Alkyd Resins2 3. Purity of Reagents 3.1 Reagent grade chemicals shall be used in all tests.
1 These test methods are under the jurisdiction of ASTM Committee D-1 on Paint and Related Coatings, Materials, and Applications and are the direct responsibility of Subcommittee D01.33 on Polymers and Resins. Current edition approved Sept. 19, 1960. Originally issued 1958. Replaces D 1615 58 T. 2 Annual Book of ASTM Standards, Vol 06.03. 3 Annual Book of ASTM Standards, Vol 11.01.

Unless otherwise indicated, it is intended that all reagents shall conform to the specications of the Committee on Analytical Reagents of the American Chemical Society, where such specications are available.4 Other grades may be used, provided it is rst ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. 3.2 Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to Specication D 1193.3
NOTE 1The reagents and samples used in these methods may, under some conditions, be hazardous. Refer to the manufacturers Material Safety Data Sheets for specic handling and safety precautions. Safe laboratory handling procedures and all applicable OSHA regulations are to be followed.

GLYCEROL AND ETHYLENE GLYCOL 4. Summary of Test Method 4.1 The primary hydroxyl groups of ethylene glycol and glycerol are oxidized to formaldehyde by periodic acid; the secondary hydroxyl group of glycerol is oxidized to formic acid. By acidimetric and iodometric titration, the proportions of formic acid and formaldehyde can be determined respectively, and calculated to glycerol and ethylene glycol by algebraic equations. The equations for the oxidation of the polyhydric alcohols are as follows:

4 Reagent Chemicals, American Chemical Society Specications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.

D 1615
C3H8O3 + 2H5I06 glycerol periodic acid + HCOOH + 2HIO3 formic iodic acid acid C2H6O2 + H5I06 ethylene periodic glycol acid 2HCHO + HIO3 formaliodic dehyde acid

2HCHO formaldehyde

+ 5H2O water

+ 3H2O water

source of heat. Keep the beaker covered with a watch glass6 during boiling. 7.2.2 Cool to room temperature, and lter through a rapid paper into a 100-mL volumetric ask. (Take the sample for pentaerythritol determination from this same volumetric ask.) Fill to the mark and agitate. 7.2.3 Pipet 20 mL (15 aliquot) (Note 2) into a 1-L Erlenmeyer, glass-stoppered ask. Add 2 drops of methyl purple indicator solution and neutralize with NaOH. Pipet into the 1-L ask also 50 mL of HIO4 solution, stopper, and swirl to mix thoroughly.
NOTE 2The aliquot should be so chosen, if possible, that 15 to 20 % of the periodic acid is consumed during the oxidation. Considerable excess of periodic acid is required to complete the oxidation, and in case more than 20 % is consumed the results should be disregarded and a smaller aliquot taken. On the other hand, too small an aliquot is not advisable, for in such a situation the difference between titration and blank is small and any titration errors are magnied.

With pentaerythritol, there is no reaction. 5. Apparatus 5.1 Burets, 50 and 100-mL capacity. 5.2 Pipets, 20 and 50-mL capacity. 5.3 Beakers, two of 400-mL capacity. 5.4 Erlenmeyer Flasks, four of 1000-mL capacity, glassstoppered. 5.5 Volumetric Flasks, two of 100-mL capacity. 5.6 Graduated Cylinder, 10-mL capacity. 5.7 Filter Paper, fast, qualitative grade. 5.8 Watch Glass. 6. Reagents 6.1 Methyl Purple Indicator Solution. 5 6.2 Periodic Acid (11 g/L)Dissolve 11 g of periodic acid (HIO4) in water and dilute to 1 L. Prepare fresh daily and store in a brown bottle. 6.3 Potassium Iodide Solution (200 g/L)Dissolve 200 g of potassium iodide (KI) in water and dilute to 1 L. 6.4 Sodium Hydroxide, Standard Solution (0.1 N)Prepare and standardize a 0.1 N aqueous sodium hydroxide (NaOH) solution. 6.5 Sodium Thiosulfate, Standard Solution (0.2 N) Prepare and standardize a 0.2 N aqueous sodium thiosulfate (Na2S2O3) solution. 6.6 Starch Indicator SolutionDissolve 5 g of soluble starch in water and dilute to 1 L. Preserve the solution with 1 g of salicyclic acid. 6.7 Sulfuric Acid (1+5)Carefully mix 1 volume of concentrated sulfuric acid (H2SO4, sp gr 1.84) with 5 volumes of water. 7. Procedure 7.1 Determine the phthalic anhydride in accordance with Test Method D 563. Following this, extract the fatty acids in accordance with 5.6 through 7 of Test Method D 1398, except do not discard the aqueous phase. 7.2 Test the remaining water solution containing the polyalcohols for glycerol and ethylene glycol in the following manner: 7.2.1 Transfer the solution to a 400-mL beaker and evaporate to about 60-mL volume, using an electric hot plate as
5 Methyl purple indicator manufactured by the Fleisher Chemical Co., Benjamin Franklin Station, Washington 4, D.C., U.S. Patent No. 2,416,619, has been found satisfactory for this purpose.

7.3 Simultaneously prepare two blanks containing 20 mL of water. Allow to stand 50 to 70 min at room temperature. 7.4 To the aliquot of the sample (7.2.3) and the blank, add 100 mL of water and 3 drops of methyl purple indicator and titrate with 0.1 N NaOH solution to neutrality. Use the 50-mL buret and record the volume to the nearest 0.01 mL. 7.5 To the solution that has just been titrated, add 150 mL of water, 30 mL of KI solution, and 25 mL of H2SO4 (1+5). Titrate with 0.2 N Na2S2O3 solution to faint iodine color, add 10 mL of starch indicator and titrate to the disappearance of the blue color.
NOTE 3If the end point is not stable, as indicated by return of the blue color in the stoppered ask in 5 min, add water and titrate to a stable end point. Use the 100-mL buret and record the volume to the nearest estimated 0.05 mL.

8. Calculations 8.1 Calculate the percentage of glycerol, G, as follows:

G 5 @~A 2 B!N 3 0.09206!/WF# 3 100

5 millilitres of NaOH solution required for titration of the sample, B 5 millilitres of NaOH solution required for titration of the blank, N 5 normality of the NaOH solution, 0.09206 5 grams of glycerol equivalent to 1 mL of 1 N NaOH solution (acidimetric), W 5 grams of sample used, and F 5 aliquot fraction 5 15. 8.2 Calculate the percentage of glycerol and ethylene glycol, T, as a percentage of glycerol as follows:
~T 5 @~B8 2 A8!N 3 0.023015!/WF# 3 100

where: A

where: A8

5 millilitres of Na2S2O3 solution required for titration of the sample,

The Speedyvap watch glass has been found satisfactory for this purpose.

D 1615
5 millilitres of Na2S2O3 solution required for titration of the blank, 0.023015 5 grams of glycerol equivalent to 1 mL of 1 N Na2S2O3 solution (iodometric), N 5 normality of the Na2S2O3 solution, W 5 grams of sample used, and F 5 aliquot fraction 5 15. 8.3 If E is the percentage of ethylene glycol, then B8
E 5 1.348~T 2 G!

zaldehyde,7 add 100 mL of technical grade anhydrous methanol (CH3OH). 12.2 Hydrochloric Acid (sp gr 1.19)Concentrated hydrochloric acid (HCl). 12.3 Methanol-Water Wash Solution (1 + 1)Mix equal volumes of technical anhydrous CH3OH and water. (Because of heat of solution, prepare this solution in advance.) One fourth of the wash solution is to be stored in a refrigerator and used cold; the remainder is kept at room temperature. 13. Procedure 13.1 Transfer an aliquot of the 100-mL of sample solution (7.2.2) containing 0.15 to 0.55 g of pentaerythritol to a 100-mL beaker. Evaporate on a steam bath to a volume of approximately 5 mL. To the hot solution (incipient boiling) add 15 mL of benzaldehyde-methanol reagent and 12 mL of HCl. Swirl and allow to stand at room temperature 15 min, swirling occasionally during this time to prevent the precipitate from adhering to the bottom of the beaker. Place the beaker in an ice bath, maintaining the temperature at 0 to 2C for 1 h or more. 13.2 Remove the reaction mixture from the ice bath and immediately lter with suction through a weighed fritted-glass crucible of medium porosity. Rinse the beaker with 25 mL of the cold (0 to 2C) methanol wash solution and add to the crucible. Continue to transfer and wash the precipitate with 100 mL of methanol-water wash solution at 20 to 25C as follows: 13.2.1 Disconnect the vacuum line, pour a 10-mL portion of the wash solution from the beaker to the crucible, and stir the precipitate to form a homogeneous slurry, using a short at-end glass rod. Connect the vacuum line and draw the wash solution through the crucible. Repeat this washing operation six times. With the last 30 mL of methanol-water wash solution, rinse the interior walls of the crucible and rinse and remove the short stirring rod. 13.3 Aspirate thoroughly and dry the precipitate at 105C for 2 h. Cool in a desiccator and weigh. 14. Calculations 14.1 Calculate the percentage of monopentaerythritol, P, of the resin from the precipitate obtained in accordance with 14.3 follows:
P 5 @~W2 1 0.0269! 3 43.6#/W1F

When E 5 O, the sample is free of ethylene glycol.

NOTE 4In practice, samples containing no ethylene glycol have given calculated E values of up to 1 %. Therefore, samples with E values of 1 % or less should be considered as containing no ethylene glycol, and samples with higher E values may be corrected by 1 % at the discretion of the analyst.

9. Precision and Bias 9.1 RepeatabilityThe average difference between duplicate runs performed by the same analyst in the same laboratory should approximate the following values:
Percentage of glycerol Percentage of glycol 0.1 0.4

Not more than once in twenty times would the difference be expected to exceed:
Percentage of glycerol Percentage of glycol 0.3 1.0

9.2 Reproducibility: 9.2.1 The average difference between results obtained by different analysts in different laboratories, when reported as the average of duplicate determinations, should approximate:
Percentage of glycerol Percentage of glycol 0.2 0.5

9.2.2 Not more than once in twenty times should the difference be expected to exceed:
Percentage of glycerol Percentage of glycol 0.6 1.2

PENTAERYTHRITOL 10. Summary of Test Method 10.1 Monopentaerythritol reacts with benzaldehyde to form a dibenzal which is crystalline and can be handled gravimetrically. 11. Apparatus 11.1 Beakers, 100-mL capacity. 11.2 Delivery Pipets (for aliquots), 10 to 50-mL capacity. 11.3 Steam Bath. 11.4 Ice Bath. 11.5 Crucible, medium porosity, fritted glass. 11.6 Suction Flask. 11.7 Water Aspirator. 11.8 Desiccator. 11.9 Drying Oven, capable of maintaining a temperature of 105C. 11.10 Glass Rod, at-end. 12. Reagents and Materials 12.1 Benzaldehyde-Methanol ReagentTo 20 mL of ben3

where: W1 5 grams of sample, W2 5 grams of precipitate, and F 5 aliquot fraction. 14.2 To convert the percentage of monopentaerythritol, P, to the percentage of commercial technical monopentaerythritol, use the following arbitrary formula which is based on the assumption that the commercial grade contains 85 % monopentaerythritol:
Commercial monopentaerythritol, % 5 P/0.85

15. Precision and Bias 15.1 Repeatability The average difference in percentage
7

Merck, N. F. grade benzaldehyde has been found satisfactory for this purpose.

D 1615
of monopentaerythritol found, between duplicate runs performed by the same analyst in the same laboratory, should approximate 0.25. Not more than once in twenty times would the difference be expected to exceed 0.6. 15.2 ReproducibilityThe average difference in percentage of monopentaerythritol found, between results obtained by different analysts in different laboratories, when reported as the average of duplicate determinations should approximate 0.5. Not more than once in twenty times would the difference be expected to exceed 1.4. 16. Keywords 16.1 alkyd resins; ethylene glycol; glycerol; pentaerythritol

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every ve years and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428.