1、Designation: E475 10E475 16Standard Test Method forAssay of Di-tert-Butyl Peroxide Using Gas Chromatography1This standard is issued under the fixed designation E475; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last
2、revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the assay of di-tert-butyl peroxide using gas chromatography. It is applicable to commercialdi-ter
3、t-butyl peroxide which may contain small amounts of isobutylene, tert-butanol, tert-butyl hydroperoxide, triisobutylenes, andwater as impurities.1.2 Review the current appropriate Material Safety Data Sheets (MSDS) for detailed information concerning toxicity, first aidprocedures, and safety precaut
4、ions.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 responsibilityof the user of this standard to establ
5、ish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. Specific hazards statements are given in Section 9.2. Referenced Documents2.1 ASTM Standards:2E203 Test Method for Water Using Volumetric Karl Fischer Titration3. Terminology3.1 Definit
6、ions:3.1.1 active oxygenthe oxidizing power present in organic peroxides expressed as oxygen (equivalent = 8.00).4. Summary of Test Method4.1 A sample is diluted in dodecane and injected into a gas chromatograph containing a wide-bore capillary column with anonpolar stationary phase. A temperature p
7、rogram is used to separate di-tert-butyl peroxide from impurities using helium as acarrier gas. The flame ionization detector response, proportional to component concentration, is recorded and the peak areas aremeasured. The concentration of di-tert-butyl peroxide is determined by area normalization
8、 after correcting for the area of thesolvent peak. The assay of di-tert-butyl peroxide is corrected for water, which is determined using a separate Karl Fischer titrationsince water is not detected using flame ionization detection. The area percent of di-tert-butyl peroxide is assumed to be equal to
9、mass percent.5. Significance and Use5.1 Di-tert-butyl peroxide is widely used as a catalyst and reaction initiator. Knowledge of the peroxide content is importantin such applications. This test method provides a procedure for determining the active peroxide content of commercial di-tert-butylperoxid
10、e.6. Interferences6.1 Interferences will be encountered if other components are present in the sample that have the same retention time asdi-tert-butyl peroxide.1 This test method is under the jurisdiction of ASTM Committee E15 on Industrial and Specialty Chemicals and is the direct responsibility o
11、f Subcommittee E15.02 onProduct Standards.Current edition approved March 1, 2010April 1, 2016. Published April 2010May 2016. Originally approved in 1973. Last previous edition approved in 20052010 asE475 00 (2005).E475 10. DOI: 10.1520/E0475-10.10.1520/E0475-16.2 For referencedASTM standards, visit
12、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.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard
13、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 that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is
14、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 Conshohocken, PA 19428-2959. United States17. Apparatus7.1 InstrumentationGas chromatograph, capable of column oven temperatu
15、re programming from 40 to 160C at a rate of10C/min and from 160 to 240C at a rate of 35C/min.7.2 Injection SystemGlass-lined sample injection port, maintained at 150C.7.3 Sample IntroductionMicroliter syringes or automatic syringe injectors, capable of delivering 0.5 L of a liquid sample,have been u
16、sed successfully.7.4 DetectionFlame ionization detector, maintained at 250C.7.5 Data Acquisition SystemElectronic data acquisition and area integration capabilities are recommended.7.6 Chromatographic Column30 m wide-bore capillary column (0.53 mm inside diameter) with a 5.0 m dimethylpolysi-loxane
17、stationary phase.8. Reagents and Materials8.1 Carrier Gas (Helium), chromatographic grade.8.2 Hydrogen, chromatographic grade.8.3 Compressed Air, oil-free.8.4 Dodecane, for use as a sample diluent, 99 % or greater chromatographic purity.9. Hazards9.1 Organic peroxides are strong oxidizing agents and
18、 present potential fire and explosion hazards. While di-tert-butyl peroxideis one of the more stable peroxides, contact with reducing agents and sources of heat, sparks, or open flames must be avoided.Organic peroxides in general are irritating to the skin, eyes, and mucous membranes. Avoid bodily c
19、ontact and handle only in awell-ventilated area.9.2 Consult current OSHA regulations and suppliers Safety Data Sheets (SDS) for all materials used in this method.10. Procedure10.1 Install the column in the chromatograph.The operating conditions required to give the desired separation are given in Ta
20、ble1. Set the helium flow to 10.0 mL/min and the oven temperature to 40C and allow sufficient time for the instrument to equilibrateas indicated by a stable baseline.10.2 Prepare test samples by transferring approximately 0.2 g of di-tert-butyl peroxide into a flask or vial and add approximately10 m
21、L of dodecane. Mix well.10.3 Inject 0.5 L of the sample solution into the chromatograph. A typical chromatogram is shown in Fig. 1 and Fig. 2.10.4 Determine the water content of the sample using a Karl Fischer titration in accordance with Test Method E203.NOTE 1Water can be determined in samples of
22、di-tert-butyl peroxide using Test Method E203 without pretreatment with SO2 if the sampletemperature is maintained below 20C during the titration. If the sample temperature cannot be maintained below 20C, the sample must be pretreatedby bubbling SO2 through the sample for several minutes prior to ti
23、trating.TABLE 1 Operating Conditions Required to Give the DesiredSeparationDetector flame ionization (FID)Temperatures, CTemperatures, CInjection port 150Detector 250Column temperature programInitial temperature, C 40Initial time, min 3Program rate, C/min 10Temperature 2, C 160Time 2, min 2Program r
24、ate, C/min 35Final temperature, C 240Final temperature, C 240Final time, min 2Carrier gas heliumFlow rate, mL/min 10.0Injection volume, L 0.5E475 16211. Calculation11.1 Measure the peak areas and calculate the total area by summing the individual areas for all peaks except for that of thesolvent pea
25、k, as follows:At 5A 11A21A311A n (1)where:At = total area (excluding the solvent peak), andA1.n = area of individual component peaks.11.2 Calculate the area percent of di-tert-butyl peroxide as follows:di2tert2butyl peroxide,area %5AD 1002W!At(2)FIG. 1 Typical ChromatogramFIG. 2 Typical Chromatogram
26、 (Expanded View)E475 163where:AD = area of the di-tert-butyl peroxide peak,At = sum total of all component peaks (except solvent), andW = mass percent of water in the sample, as determined in 10.4.The area percent of di-tert-butyl peroxide is assumed to be equal to the mass percent.11.3 If desired,
27、calculate the mass percent of active oxygen due to di-tert-butyl peroxide as follows:active oxygen,mass%5C 38.00073.11 (3)where:C = di-tert-butyl peroxide, mass %.12. Report12.1 Report the purity of the di-tert-butyl peroxide to the nearest 0.01 %.13. Precision and Bias13.1 Precision:13.1.1 Repeatab
28、ility (Single Analyst)The coefficient of variation for a single determination has been estimated to be 0.05 %relative at 18 degrees of freedom (df). The 95 % limit for the difference between two such runs is 0.13 % relative.13.1.2 Laboratory Precision (Within-Laboratory, Between-Days Variability, Fo
29、rmerly Called Repeatability)The coefficient ofvariation of results (each the average of duplicates) obtained by the same analyst on different days has been estimated to be 0.04 %relative at 9 df. The 95 % limit for the difference between two such averages is 0.10 % relative.13.1.3 Reproducibility (M
30、ultilaboratory)The coefficient of variation of results (each the average of duplicates) obtained byanalysts in different laboratories has been estimated to be 0.24 % relative at 8 df. The 95 % limit for the difference between twosuch averages is 0.67 % relative.NOTE 2The precision statements are bas
31、ed on an interlaboratory study3 performed in 1995 on one sample of di-tert-butyl-peroxide.13.2 BiasThe bias of this test method has not been determined due to the unavailability of suitable reference materials.14. Keywords14.1 active oxygen; di-tert-butyl peroxide; gas chromatography; peroxidesSUMMA
32、RY OF CHANGESSubcommittee E15.02 has identified the location of selected changes to this standard since the last issue(E475-00(2005)E475)-10) that may impact the use of this standard.(1) Updated units of measure to comply with the International SystemAdded reference to Safety Data Sheets (SDS) in 9.
33、2of Units(SI)(2) Added Summary of Changes section.ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent right
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36、u shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be
37、 obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:E15-1044. Contact ASTM CustomerService at serviceastm.org.E475 164
