1、Designation: D4252 89 (Reapproved 2017)Standard Test Methods forChemical Analysis of Alcohol Ethoxylates and AlkylphenolEthoxylates1This standard is issued under the fixed designation D4252; the number immediately following the designation indicates the year oforiginal adoption or, in the case of re
2、vision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the various test methods usedto evaluate those properties pertinent to th
3、e characterization ofalcohol ethoxylates and alkylphenol ethoxylates with respect tosuitability for desired uses.1.2 The procedures for sampling and analysis appear in thefollowing order:SectionsSamplingLiquids 6Solids 7Methods of Chemical AnalysisWater or moisture 8Refractive index 9 and 10pH 11Aci
4、dity or basicity 12 and 13Hydroxyl number 1420Cloud point 21Iodine number 22Ash 23Iron 24Ethylene oxide content 25Polyethylene glycols 26321.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to
5、 address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Material SafetyData Sheets are available for reagen
6、ts and materials. Reviewthem for hazards prior to usage. Specific hazard statementsappear in Section 5 and Note 1 and Note 3.2. Referenced Documents2.1 ASTM Standards:2D459 Terminology Relating to Soaps and Other DetergentsD482 Test Method for Ash from Petroleum ProductsD1068 Test Methods for Iron i
7、n WaterD1172 Guide for pH of Aqueous Solutions of Soaps andDetergentsD1193 Specification for Reagent WaterD1209 Test Method for Color of Clear Liquids (Platinum-Cobalt Scale)D1218 Test Method for Refractive Index and RefractiveDispersion of Hydrocarbon LiquidsD1613 Test Method for Acidity in Volatil
8、e Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related ProductsD1959 Test Method for Iodine Value of Drying Oils andFatty Acids (Withdrawn 2006)3D2024 Test Method for Cloud Point of Nonionic SurfactantsD2959 Test Method for Ethylene Oxide Content of Poly-ethoxylated Nonioni
9、c SurfactantsE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)3E200 Practice for Preparation, Standardization, and Storageof Standard and Reagent Solutions for Chemical AnalysisE203 Test Method for Water Using
10、Volumetric Karl FischerTitrationE394 Test Method for Iron in Trace Quantities Using the1,10-Phenanthroline Method3. Significance and Use3.1 Alcohol ethoxylates and alkylphenol ethoxylates areimportant surfactants in household and industrial cleaners.1These test methods are under the jurisdiction of
11、ASTM Committee D12 onSoaps and Other Detergents and are the direct responsibility of SubcommitteeD12.12 on Analysis and Specifications of Soaps, Synthetics, Detergents and theirComponents.Current edition approved Jan. 1, 2017. Published February 2017. Originallyapproved in 1983. Last previous editio
12、n approved in 2009 as D4252 89(2009).DOI: 10.1520/D4252-89R17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website
13、.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on
14、standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1They may be used as either nonionic surfactants or sulfated andused as anionic surfa
15、ctants. Careful control of the ethoxylatecharacteristics is desired as variations may result in eitherdesirable or undesirable end-use properties.4. Purity of Reagents4.1 Reagent-grade chemicals shall be used in all tests.Unless otherwise indicated, it is intended that all reagents shallconform to t
16、he specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.4Other grades may be used, pro-vided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determi
17、nation.4.2 Unless otherwise indicated, references to water shall beunderstood to mean Type III reagent water conforming toSpecification D1193.5. Safety Precautions5.1 All reagents and chemicals should be handled with care.Before using any chemical, read and follow all safety precau-tions and instruc
18、tions on the manufacturer label. Clean up anyspill immediately. For information on cleaning up spills refer tothe Laboratory Disposal Manual, Manufacturing ChemistsAssociation, Washington, DC.SAMPLING6. Liquids6.1 Thoroughly mix the sample before sampling. If a solidlayer or crystals have formed on
19、the bottom of the bottle, meltin an oven or water bath at 55C and mix well before sampling.7. Solids7.1 Melt in an oven or water bath at 55C and mix wellbefore sampling. If it is necessary to heat at temperatures above60C, replace the gas cap with an inert gas, such as oxygen-freenitrogen, helium, o
20、r argon before heating.WATER OR MOISTURE8. Procedure8.1 Determine water or moisture in accordance with TestMethod E203.REFRACTIVE INDEX9. Procedure9.1 Measure the refractive index at 50C in accordance withTest Method D1218.10. Precision10.1 The following criteria should be used for judging theaccept
21、ability of results:5,610.1.1 Repeatability (Single Analyst)The standard devia-tion of results (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be0.00021 units absolute at 36 df. Two such averages should beconsidered suspect (95 % confidence level
22、) if they differ bymore than 0.00059 units absolute.10.1.2 Reproducibility (Multilaboratory)The standard de-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been estimated to be0.00059 units absolute at 7 df. Two such averages should beconsidere
23、d suspect (95 % confidence level) if they differ bymore than 0.0020 units absolute.10.1.3 Checking Limits for DuplicatesReport the refrac-tive index of the sample to the nearest 0.0001. Duplicate runsthat agree within 0.00025 units are acceptable for averaging(95 % confidence level).pH11. Procedure1
24、1.1 Determine the pH in accordance with Test MethodD1172, except prepare the solution by transferring 1 6 0.001g of the sample to a 100 mL volumetric flask and diluting inaccordance with Test Method D1172. Measure the pH 10 minafter diluting the sample solution to volume.ACIDITY OR BASICITY12. Proce
25、dure12.1 Determine acidity or basicity in accordance with TestMethod D1613 using a 3+1 solution of isopropyl alcohol andwater as the solvent and a 10-g sample.13. Precision13.1 The following criteria should be used for judging theacceptability of results:6,713.1.1 Repeatability (Single Analyst)The s
26、tandard devia-tion of results (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be 0.017meq/100 g at 27 df. Two such averages should be consideredsuspect (95 % confidence level) if they differ by more than0.049 meq/100 g.13.1.2 Reproducibility (Mu
27、ltilaboratory)The standard de-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been established to be0.12 meq/100 g at 5 df. Two such averages should be4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washi
28、ngton, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.5The preci
29、sion estimates are based on an interlaboratory study on ALFONIC1412-60, MAKON-10, NEODOL 25-9, PLURONIC 25R1, and TERGITOL15-S-3 by nine laboratories.6Statistical analysis was performed in accordance with Practice E180 fordeveloping precision estimates. Data supporting the precision statements are o
30、n fileat ASTM International Headquarters. Request RR: RR:D12-1004.7The precision estimates are based on an interlaboratory study on ALFONIC1412-60, MAKON-10, NEODOL 25-9, PLURONIC 25R1 and TERGITOL15-S-3 by six laboratories.D4252 89 (2017)2considered suspect (95 % confidence level) if they differ by
31、more than 0.44 meq/100 g.13.1.3 Checking Limits for DuplicatesReport the acidityor basicity of the sample to the nearest 0.05 meq/100 g.Duplicate runs that agree within 0.051 meq/100 g are accept-able for averaging (95 % confidence level).HYDROXYL NUMBER14. Terminology14.1 Definitions:14.1.1 hydroxy
32、l numberthe number of milligrams of po-tassium hydroxide equivalent to the hydroxyl content of1gofsample.15. Summary of Test Method15.1 The hydroxyl groups are esterified by reaction withphthalic anhydride in a pyridine medium at the temperature ofreflux of the mixture. After cooling, the excess of
33、phthalicanhydride is hydrolyzed with water and the phthalic acidformed is titrated to the phenolphthalein end point withstandard sodium hydroxide solution. The hydroxyl content iscalculated from the difference in titration of the blank and ofthe sample solution.16. Apparatus16.1 Reflux Assembly, con
34、sisting of a reflux condenser and a250-mL Erlenmeyer flask, 24/40 standard taper joint withTFE-fluorocarbon sleeves.16.2 Buret, 50 mL, graduated in 0.1-mL intervals. Class Aor equivalent.16.3 Pipet, 25-mL capacity, Class A or equivalent.16.4 Insulating Pad, 312 by 312 by 1 in., preferably notasbesto
35、s.17. Reagents17.1 Pyridine, A. R.To be acceptable, each lot should passthe following quality test: Place7gofphthalic anhydride and50 mL of pyridine (Warningsee Note 1) in a glass-stopperedflask, shake vigorously until dissolved. Heat at 50 or 60C for30 min, allow to stand at room temperature in the
36、 dark for 24h and then measure the Pt-Co color (Test Method D1209). Thepyridine is acceptable if the color does not exceed 200.NOTE 1Warning: Avoid breathing pyridine vapors, as they are toxic.Dispose of pyridine wastes in a well ventilated hood.17.2 Sodium Hydroxide, (1 N), carbonate free. Purchase
37、 orprepare, standardize, and store according to Practice E200.17.3 Phthalic Anhydride ReagentDissolve 98 6 1gofphthalic anhydride in 700 mL of pyridine (Note 1), shake toeffect solution. Store in a brown bottle. Preferably, the solutionshould stand overnight before using. Prepare a fresh reagenteach
38、 week or more frequently if the Pt-Co color (Test MethodD1209) exceeds a value of 200.17.4 Sodium Hydroxide (0.1 N)Purchase or prepare,standardize, and store according to Practice E200.17.5 Hydrochloric Acid (0.1 N)Purchase or prepare bydiluting 8.3 mL of concentrated hydrochloric acid to 1 L withdi
39、stilled water. Standardize and store according to PracticeE200.17.6 Phenolphthalein Indicator SolutionDissolve1gofphenolphthalein in 100 mL of pyridine.17.7 Isopropyl Alcohol, A. R.18. Procedure18.1 Weigh into a clean and dry 250-mL Erlenmeyer flaskwith ground glass joint to the nearest 0.1 mg an am
40、ount ofsample calculated by means of the following equation but donot use more than 10 g of sample:Amount of Sample, g 5MF 3100(1)where:M = molecular weight of sample andF = number of hydroxyl groups per molecule.18.2 Pipet accurately 25 mL of phthalic anhydride reagentinto the flask and swirl to ef
41、fect solution. Add two boilingchips, attach a dry reflux condenser with a ground glass jointfitted with a TFE-fluorocarbon sleeve to the flask, and refluxfor1honanelectric hotplate.18.3 Turn off the hotplate and insert an insulated padbetween the flask and the hot plate. Allow to cool for 20 min.Was
42、h down the condenser, first with 25 mL of pyridine andthen with 25 mL of water.18.4 Remove the flask from the condenser.Add 4 or 5 dropsof phenolphthalein indicator to the flask and titrate withstandard 1 N sodium hydroxide solution to a faint pink endpoint (Note 2).18.5 Make a blank determination f
43、ollowing 18.2 18.4.NOTE 2It is essential that the sample titration requires at least threefourths of the blank titration. The difference between the two titrationsshould be of the order of 10 mL. If this is not the case the sample sizeshould be adjusted accordingly and the analysis rerun.18.6 Determ
44、ine the free acidity or free alkalinity as de-scribed in Section 12 or as follows: To 25 mL of a 3 + 1isopropyl alcohol/water mixture in a 250-mL Erlenmeyer flaskadd 2 to 3 drops of phenolphthalein indicator solution andtitrate with standard 0.1 N sodium hydroxide solution to a faintpink. Accurately
45、 weigh 10 to 20 g of sample and add to thecontents of the flask.18.7 If the solution is colorless titrate with standard 0.1 Nsodium hydroxide solution to a faint pink. If the solution ispink titrate with standard 0.1 N hydrochloric acid to justcolorless.19. Calculations19.1 Calculate the hydroxyl nu
46、mber from the followingequations:19.1.1 For samples containing free acidity:Hydroxyl Number, mg KOH/g 5FB 2 S!NW1C 3 N1W1G356.1(2)D4252 89 (2017)319.1.2 For samples containing free alkalinity:Hydroxyl Number, mg KOH/g 5FB 2 S!NW2C 3 N1W1G356.1(3)where:B = volume of 1 N sodium hydroxide solution requ
47、ired forblank titration (18.5), mL,S = volume of 1 N sodium hydroxide solution required forsample titration (18.4), mL,N = normality of 1 N sodium hydroxide solution,W = weight of sample taken (18.1), g,C = volume of 0.1 N sodium hydroxide/hydrochloric acidrequired for acidity/alkalinity titration (
48、18.7), mL,N1= normality of 0.1 N sodium hydroxide/hydrochloricacid used for acidity/alkalinity titration (18.7), andW1= weight of sample used for acidity/alkalinity titration(18.6), g.19.2 Calculate the apparent molecular weight from thefollowing equation:Apparent Molecular Weight 556,100H3 F (4)whe
49、re:H = hydroxyl number (mg KOH/g sample).F = number of hydroxyl groups per molecule.20. Precision20.1 The following criteria should be used for judging theacceptability of the results:6,820.1.1 Repeatability (Single Analyst)The standard devia-tion of results (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be 1.10 %relative at 30 df. Two such averages should be consideredsuspect (95 % confidence level) if they differ by more than3.18 % relative.20.1.2 Reproducibility (Multilaboratory)The s
