ASTM E299-2017 red 1464 Standard Test Method for Trace Amounts of Peroxides In Organic Solvents《有机溶剂中的微量过氧化物的标准试验方法》.pdf

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1、Designation: E299 08E299 17Standard Test Method forTrace Amounts of Peroxides In Organic Solvents1This standard is issued under the fixed designation E299; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision.

2、A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the U.S. Department of Defense.1. Scope*1.1 This test method2,3 covers organic solvents co

3、ntaining active oxygen in the range from 5 to 80 g/g (ppm) or higher. Byusing a special reaction-absorption cell, the test method can be extended to cover the range from 0 to 5 ppm. The test method canbe used to determine numerous peroxide classes of varying reactivity such as hydroperoxides, diacyl

4、 peroxides, diaroyl peroxides,peresters, and ketone peroxides. The stable di-tert-alkyl peroxides do not react under the conditions of analysis.1.2 Solvents that can be analyzed successfully include saturated and aromatic hydrocarbons, alcohols, ethers, ketones, andesters. In addition, the test meth

5、od is applicable to olefinic solvents and to certain compounds that contain , and conjugatedunsaturation. Solid samples that are soluble in the acetic acid-chloroform solvent also can be analyzed.1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are fo

6、r information only.1.4 This standard does not purport to address the safety concerns, if any, associated with its use. It is the responsibility of theuser of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitationsprior to use.1.5 R

7、eview the current Material Safety Data Sheets (MSDS)(SDS) for detailed information concerning toxicity, first aidpractices, and safety precautions.2. Referenced Documents2.1 ASTM Standards:4D1193 Specification for Reagent WaterE180 Practice for Determining the Precision of ASTM Methods for Analysis

8、and Testing of Industrial and Specialty Chemicals(Withdrawn 2009)53. Summary of Test Method3.1 A sample is dissolved in a mixture of acetic acid and chloroform. The solution is deaerated and potassium iodide reagentsolution is added. The mixture is allowed to react in the dark for 1 h, thereby relea

9、sing an equivalent amount of iodine. Theabsorbance of the solution is measured at 470 nm and the amount of active oxygen present in the sample is determined by referenceto a calibration curve prepared from iodine.3.2 For samples containing 0 to 5 g/g (ppm) active oxygen, a special reaction-absorptio

10、n cell is employed. The sample isde-aerated and the reaction is carried out within the cell.Absorbance measurements are made at 410 nm to increase the sensitivity.4. Significance and Use4.1 Dilute solutions of peroxides in various organic solvents frequently are used as catalysts or reaction initiat

11、ors. Peroxides alsocan be formed through autoxidation in certain classes of compounds including ethers, acetals, dienes, and alkylaromatichydrocarbons and present a potential safety hazard. This test method provides a procedure for determining the peroxide or activeoxygen level.1 This test method is

12、 under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of SubcommitteeD16.15 on Industrial and Specialty General Standards.Current edition approved April 1, 2008Feb. 1, 2017. Published May 2008February 2017. Originally approved i

13、n 1966. Last previous edition approved in 20022008 asE299 97 (2002).E299 08. DOI: 10.1520/E0299-08.10.1520/E0299-17.2 Banerjee, D. K., and Budke, C. C., Analytical Chemistry, ANCHAM, Vol 36, 1964, pp. 792796.3 Banerjee, D. K., and Budke, C. C., Analytical Chemistry, ANCHAM, Vol 36, 1964, pp. 2367236

14、8.4 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.5 The last approved version of this historical standard is

15、referenced on www.astm.org.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. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends t

16、hat users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West

17、 Conshohocken, PA 19428-2959. United States15. Interferences5.1 Oxidizing or reducing substances present in the sample will interfere. Colored solutions can be analyzed if an absorbancecorrection is made.6. Apparatus6.1 SpectrophotometerBeckman Model DU or equivalent with matched 1-cm cells.6.2 Spec

18、ial Reaction-Absorption Cell (Fig. 1)When this cell is used, the regular Beckman cell carriage shall be replaced withthe attachment provided for measuring the absorbance in test tubes.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it

19、is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, wheresuch specifications are available.6 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its

20、use without lessening the accuracy of the determination.7.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean Type II or Type III reagentwater conforming to Specification D1193.7.3 Acetic Acid-Chloroform Solvent (2 + 1)Mix 2 volumes of acetic acid with 1 volu

21、me of chloroform.7.4 Acetic Acid-Chloroform Solvent (Containing Approximately 4 % Water)Add 40 mL of water to 1 L of solvent preparedas described in 7.3.7.5 Iodine.7.6 Nitrogen Cylinder.7.7 Potassium Iodide Solution (50 %)Dissolve 20 g of potassium iodide (KI) in 20 mL of de-aerated water. This reag

22、entshould be freshly prepared just prior to use.7.8 Water, De-aeratedPass nitrogen through distilled water for several minutes prior to use.8. Procedure8.1 High Range0 to 400 g of Active Oxygen:8.1.1 Preparation of Calibration Curve:8.1.1.1 Dissolve 0.1270 g of iodine in acetic acid-chloroform solve

23、nt (2 + 1) and dilute to 100 mL in a volumetric flask. Thissolution contains 1.27 mg of iodine/mL, which is equivalent to 80.0 g of active oxygen/mL.6 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents no

24、t listed bythe American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.FIG. 1 Absorption Cell for Low-Active OxygenE299 1728.1.1.2 Tran

25、sfer 0, 1, 2, 3, 4, and 5-mL aliquots of this solution to 25-mL volumetric flasks and dilute each to volume with theacetic acid-chloroform solvent. Mix thoroughly.8.1.1.3 Using a hypodermic needle or glass capillary, sparge the solution with nitrogen for 1 to 1.5 min, add 1 mL of freshlyprepared KI

26、solution, and continue the nitrogen flow for 1 min. Stopper and mix well.8.1.1.4 Measure the absorbance of each solution at 470 nm, using 1-cm cells and a water reference.8.1.1.5 Subtract the absorbance of the blank and plot the absorbance of each standard against micrograms of active oxygen per25 m

27、L.8.1.2 Analysis of Sample:8.1.2.1 Transfer a sample containing up to 400 g of active oxygen to a 25-mLvolumetric flask and dilute to volume with aceticacid-chloroform solvent (2 + 1) (Note 1). Mix thoroughly.NOTE 1A sample volume up to 15 mL may be used provided it is miscible with the amount of ac

28、etic acid-chloroform solvent required to dilute thesample to 25 mL.8.1.2.2 Sparge the solution with nitrogen for 1 to 1.5 min, add 1 mL of freshly prepared KI solution, and continue the nitrogenflow for an additional 1 min.8.1.2.3 Stopper, mix well, and allow the solution to stand in the dark for 1

29、h.NOTE 2Very reactive peroxides react within less than 10 min, while less reactive peroxides require up to 1 h for complete reaction.Ageneral reactiontime for 1 h is therefore specified.8.1.2.4 Measure the absorbance of the solution at 470 nm using 1-cm cells and a water reference.NOTE 3Depending on

30、 the amount and type of sample present, some precipitation of KI may occur. However, the KI crystals readily settle to thebottom in absorbance measurement.8.1.2.5 Subtract the absorbance of a blank carried through the entire procedure, and obtain the micrograms of active oxygenpresent in the sample

31、by reference to the calibration curve.8.2 Low Range0 to 40 g of Active Oxygen:8.2.1 Preparation of Calibration Curve:8.2.1.1 Dissolve 0.0634 g of iodine in acetic acid-chloroform solvent (2 + 1) and dilute to 100 mL. Transfer a 10-mL aliquotto another 100-mL volumetric flask and dilute to volume wit

32、h acetic acid-chloroform solvent. This solution contains 63.4 g ofiodine/mL which is equivalent to 4.0 g of active oxygen/mL.8.2.1.2 Transfer 0, 1, 3, 5, 8, and 10-mL aliquots to 25-mL volumetric flasks and dilute to volume with the aceticacid-chloroform solvent containing 4 % water. Mix well.8.2.1.

33、3 Transfer a portion of each standard to the special absorption cell (Fig. 1).Admit a flow of nitrogen through the side armand purge the solution for 3 min.8.2.1.4 Add 5 drops of freshly prepared de-aerated KI solution and replace the stopper loosely. Continue purging with nitrogenfor an additional

34、3 min.8.2.1.5 Tighten the stopper and close the stopcock on the inlet tube so that the solution is under a slightly positive nitrogenpressure.8.2.1.6 The absorption tubes shall be matched and provided with a glass ear for reproducible positioning before absorbancemeasurements are made. Insert the tu

35、be into the cell carriage and rotate until the glass ear contacts the side of the tube holder.Measure the absorbance of the solution at 410 nm against water contained in another matched absorption tube.8.2.1.7 Subtract the absorbance of the blank and plot absorbance against micrograms of active oxyg

36、en per 25 mL.8.2.2 Analysis of Sample:8.2.2.1 Transfer a 5.00-mLsample to a 25-mLvolumetric flask and dilute to volume with acetic acid-chloroform solvent (2 + 1)containing 4 % water. Mix well.8.2.2.2 Transfer a portion of the solution to the special absorption cell and develop the color as describe

37、d in 8.2.1.3, 8.2.1.4,and 8.2.1.5.8.2.2.3 Allow the sample to stand in the dark for 1 h.8.2.2.4 Measure the absorbance of the solution at 410 nm against water contained in the other matched absorption tube.8.2.2.5 Subtract the absorbance obtained for a blank carried through the entire procedure, and

38、 obtain the micrograms of activeoxygen present in the sample by reference to the calibration curve.9. Calculation9.1 Calculate the active oxygen content of the sample as follows:active oxygen,g/gppm!5 ABC (1)where:A = active oxygen found, g,E299 173B = sample used, mL, andC = density, g/mL.9.2 If a

39、specific peroxide is known to be present, convert the micrograms per gram (parts per million) of active oxygen toperoxide by using the appropriate conversion factor.Peroxide X,g/gppm!5active oxygen in sample,g/gppm!3F (2)where F = conversion factor for peroxide X.9.2.1 Conversion factors for some co

40、mmon peroxides are as follows:Cumene hydroperoxide 9.5125Benzoyl peroxide 15.1400t-butyl hydroperoxide 5.6328Lauroyle peroxide 24.915010. Report10.1 High RangeReport the concentration of the peroxide to the nearest 1 g/g (ppm).10.2 Low RangeReport the concentration of the peroxide to the nearest 0.1

41、 g/g (ppm).11. Precision and Bias711.1 PrecisionHigh RangeThe following criteria shall be used for judging the acceptability of results (Note 4):11.1.1 Repeatability (Single Analyst)The standard deviation for a single determination has been estimated to be 0.7 g/g(ppm) at 36 df. The 95 % limit for t

42、he difference between two such determinations is 2 g/g (ppm) .11.1.2 Laboratory Precision (Within-Laboratory, Between-Days Variability)The standard deviation of results, each theaverage of duplicates, obtained by the same analyst on different days, has been estimated to be 2.9 g/g (ppm) at 14 df. Th

43、e 95 %limit for the difference between two such averages is 8.1 g/g (ppm).11.1.3 Reproducibility (Multilaboratory)The standard deviation of results, each the average of duplicates, obtained byanalysts in different laboratories has been estimated to be 4.6 g/g (ppm) at 5 df. The 95 % limit for the di

44、fference between twosuch averages is 13 g/g (ppm).NOTE 4The above precision estimates are based on an interlaboratory study on three samples containing 30 to 90 g/g (ppm) of active oxygen. Oneanalyst in each of six laboratories performed duplicate determinations and repeated one day later, for a tot

45、al of 72 determinations. Practice E180 was usedin developing these precision estimates.11.2 BiasThe bias of this test method has not been determined due to the lack of suitable reference materials or methodology.11.3 PrecisionLow RangeThe following criteria shall be used for judging the acceptabilit

46、y of results (Note 5):11.3.1 Repeatability (Single Analyst)The standard deviation for a single determination has been estimated to be 0.07 g/g(ppm) at 24 df. The 95 % limit for the difference between two such determinations is 0.2 g/g (ppm).11.3.2 Laboratory Precision (Within-Laboratory, Between-Day

47、s Variability)The standard deviation of results, each theaverage of duplicates, obtained by the same analyst on different days, has been estimated to be 0.11 g/g (ppm) at 13 df. The 95 %limit for the difference between two such averages is 0.31 g/g (ppm).11.3.3 Reproducibility (Multilaboratory)The s

48、tandard deviation of results, each the average of duplicates, obtained byanalysts in different laboratories has been estimated to be 0.49 g/g (ppm) at 4 df. The 95 % limit for the difference between twosuch averages is 1.4 g/g (ppm).NOTE 5The above precision estimates are based on an interlaboratory

49、 study on three samples containing 3 to 10 g/g (ppm) of active oxygen. Oneanalyst in each of five laboratories performed duplicate determinations and repeated one day later, for a total of 60 determinations. Practice E180 wasused in developing these precision estimates.11.4 BiasThe bias of this test method has not been determined due to the lack of suitable reference materials or methodology.12. Keywords12.1 assay; organic; peroxides; spectrophotometric7 Supporting data have been filed at ASTM International Headq