1、Designation: D49 83 (Reapproved 2014)Standard Test Methods ofChemical Analysis of Red Lead1This standard is issued under the fixed designation D49; the number immediately following the designation indicates the year of originaladoption or, in the case of revision, the year of last revision.Anumber i
2、n parentheses indicates the year of last reapproval.Asuperscriptepsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover procedures for the chemicalanalysis of red lead having the approximate formula Pb3O4(probably PbO22PbO).1.2 The values s
3、tated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not purport to 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
4、and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D50 Test Methods for ChemicalAnalysis ofYellow, Orange,Red, and Brown Pigments Containing Iron and Manga-neseD215 Practice for the Chemical Analysis of White Linsee
5、dOil Paints (Withdrawn 2005)3D280 Test Methods for Hygroscopic Moisture (and OtherMatter Volatile Under the Test Conditions) in PigmentsD1193 Specification for Reagent WaterD1208 Test Methods for Common Properties of CertainPigmentsD1301 Test Methods for Chemical Analysis of White LeadPigmentsD1959
6、Test Method for Iodine Value of Drying Oils andFatty Acids (Withdrawn 2006)33. Treatment of Sample3.1 If the pigment is lumpy or not finely ground, grind it toa fine powder and mix thoroughly. Large samples may bethoroughly mixed and a representative portion taken andpowdered if lumpy or not finely
7、ground. The sample in allcases shall be thoroughly mixed before taking portions foranalysis. All samples shall be preserved in stoppered bottles orcontainers.4. Purity of Reagents4.1 Reagent grade chemicals shall be used in all tests.Unless otherwise indicated, it is intended that all reagents shall
8、conform to the 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 oft
9、he determination.4.2 Unless otherwise indicated, references to water shall beunderstood to mean reagent water conforming to Type II ofSpecification D1193.5. Moisture5.1 Determine moisture content with a 2-g specimen inaccordance with Method A of Test Methods D280. Thespecimen is dried for2hat105C. T
10、he loss in weight isconsidered as moisture.6. Organic Color6.1 Boil2gofthesample with 25 mLof 95 % ethyl alcohol,let settle, decant the supernatant liquid; boil the residue with 25mL of distilled water and decant as before; boil the residuewith 25 mL of diluted NH4OH (1 + 4) and again decant. Boilan
11、other 2-g portion of the sample with 25 mL of chloroform,let settle, and decant the supernatant liquid. If any one of theabove solutions is colored, organic coloring matter is indicated.If the solutions remain colorless, organic colors are probablyabsent.NOTE 1If it is desired to test for organic co
12、lors resistant to the abovereagents, the test procedures described in the following books may be1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D01.31 on Pigment Specificat
13、ions.Current edition approved Dec. 1, 2014. Published December 2014. Originallyapproved in 1917. Last previous edition approved in 2008 as D49 83 (20081).DOI: 10.1520/D0049-83R0814.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.or
14、g. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washingt
15、on, 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.Copyright AST
16、M International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1used, taking into account the nature of the pigment involved (1,2,3).57. Total Lead and Insoluble Matter7.1 Treat1gofthesample with 15 mLof HNO3(1 + 1) andsufficient H2O2to dissolve all PbO2on warmin
17、g. If anyinsoluble matter is present, add 25 mL of water, boil, filter, andwash with hot water. The insoluble matter contains free SiO2and should be examined for BaSO4and silicates, if appre-ciable.7.2 To the original solution or filtrate from the insolublematter add 20 mL of H2SO4(sp gr 1.84) and e
18、vaporate to SO3fumes. Cool, add 150 mL of water, and 150 mL of 95 % ethylalcohol, let stand cold for 2 h, filter, on a Gooch crucible, washwith 95 % alcohol, dry at 105 to 110C, and weigh as PbSO4.Calculate to PbO.7.3 Red lead is rarely adulterated, but should the specimencontain soluble barium comp
19、ounds, the PbSO4obtained in 8.2will contain BaSO4. In this case, precipitate the lead as sulfidefrom a slightly acid (HCl) solution, dissolve the PbS in hotdiluted HNO3, and determine the lead as sulfate or chromate.7.4 If the specimen contains significant amounts of calciumor magnesium, boil the HN
20、O3H2O2solution (7.1) until allthe lead is converted into nitrate and then determine the lead asPbCrO4.7.5 If soluble barium, calcium, or magnesium are to bedetermined, precipitate the lead as sulfide from a slightly acidsolution (HCl), dissolve the PbS in hot diluted HNO3, anddetermine the lead as s
21、ulfate. Boil the filtrate from the PbS toexpel H2S, add a little bromine water to oxidize iron (ifpresent), boil to expel bromine, and precipitate the barium witha few millilitres of H2SO4(1 + 3). Filter and weigh as BaSO4.Calculate to BaO or BaCO3. To the filtrate from the BaSO4addNH4OH in slight e
22、xcess, filter off any precipitate ofFe(OH)3+ Al(OH)3, wash with hot water. Manganese, ifpresent, can be precipitated by adding bromine and NH4OHand warming. Filter, wash with hot water, ignite, and weigh asMn3O4. Unite all the filtrates, make slightly acid with aceticacid, heat to boiling and pass H
23、2S into the hot solution untilsaturated (20 to 30 min); add5gofNH4Cl and let stand 5 h,filter off any ZnS, wash with H2S water, dissolve the ZnS in hotdiluted HCl and determine the zinc by titration withK4Fe(CN)6. Or, boil off the H2S, filter out any separated sulfurand determine the zinc as Zn2P2O7
24、. Calcium may be deter-mined in the filtrate from the ZnS by expelling H2S and thenadding NH4OH and ammonium oxalate. Titrate the calciumoxide precipitate using the procedure described in 13.3 of TestMethods D50. In the filtrate from calcium determine magne-sium by precipitating with sodium phosphat
25、e solution, finallyweighing as Mg2P2O7.8. Lead Peroxide (PbO2) and True Red Lead (Pb3O4)NOTE 2Method of Diehl (4) modified by Topf (5)not applicablewhen substances are present, other than oxides of lead, that liberate iodineunder conditions given, or substances such as metallic lead which reducePbO2
26、to PbO without the liberation of iodine.8.1 Solutions Required: (a) Red Lead SolutionDissolve in1-L beaker 600 g of crystallized sodium acetate and 48 g of KIin about 500 mL of acetic acid (1 + 3) (made by mixing 150mL of glacial acetic acid with 450 mL of water). Warm thebeaker and contents on a st
27、eam bath, stirring occasionally, untila clear solution is obtained. Cool this solution to roomtemperature, dilute to exactly 1000 mL with the acetic acid(1 + 3) and mix thoroughly. If preferred, the red lead solutionmay be prepared separately for each titration, as follows:Dissolve 30 g of the cryst
28、allized sodium acetate and 2.4 g of KIin 25 mLof the acetic acid (1 + 3), warming gently and stirringuntil a clear solution is obtained. Cool this solution to roomtemperature, dilute to 50 mL with the acetic acid solution(1 + 3), and mix thoroughly.8.2 Sodium Thiosulfate Solution (0.1N)Dissolve 24.8
29、3 gof sodium thiosulfate (Na2S2O35H2O), freshly pulverized anddried between filter paper, and dilute with water to 1 litre at thetemperature at which the titrations are to be made. The solutionis best made with well-boiled water free from CO2, or let stand8 to 14 days before standardizing, as descri
30、bed in Section 5 ofTest Method D1959.8.3 Starch SolutionStir2to3gofpotato starch with 100mL of salicylic acid solution (1 %), and boil the mixture untilthe starch is practically dissolved, then dilute to 1 L (Note 3),or prepare as described in 7.8.2 of Test Method D1959.NOTE 3Lead PeroxideIf the pig
31、ment contains an appreciableamount of nitrite (nitrate has no effect on the method), leach outwater-soluble matter as below, dry the residue and determine PbO2asabove, calculating to basis of original specimen.9. Procedure9.1Weigh1gofthefinely ground sample, transfer to a200-mL Erlenmeyer flask, add
32、 20 mL of water; then add asquickly as possible 40 mL of the “red lead solution” at roomtemperature. If the sample is red lead that has been extractedfrom a paint or paste, in place of the water use 10 mL of amixture of 7 parts by volume of chloroform and 3 parts byvolume of glacial acetic acid, and
33、 then add without delay thered lead solution. Add 30 mL of water containing 5 or6gofsodium acetate and titrate at once with 0.1 N Na2S2O3solution,adding the latter rather slowly and keeping the liquid con-stantly in motion by whirling the flask. When the solution hasbecome light yellow, rub-up any u
34、ndissolved particles with therod until free iodine no longer forms, wash off rod, add theNa2S2O3solution until pale yellow, add starch solution, andtitrate until colorless. Add the 0.1 N iodine solution until bluecolor is just restored and subtract the amount used for thevolume of Na2S2O3that had be
35、en added.10. Calculation10.1 Calculate the lead peroxide and true red lead contentsas follows:PbO2= I 0.942Pb3O4= PbO2 2.866=I2.7where: I = iodine value of the Na2S2O3solution,5The boldface numbers in parentheses refer to a list of references at the end ofthese test methods.D49 83 (2014)20.942 5PbO2
36、I25239.19253.81, and (1)2.86616 5Pb3O4PbO25685.57239.1911. Zinc11.1 If the volume is appreciable, evaporate off the alcoholfrom the filtrate from total lead, make alkaline with NH4OH,then acid with HCl (sp gr 1.19), add 3 mL more of HCl, diluteto about 250 mL with water, heat nearly to boiling and t
37、itratewith standard K4Fe(CN)6solution in accordance with 16.1.11of Practice D215. Report as ZnO (includes cadmium). Iron,copper, or other interfering substances should first be removedas described in 25.2.3 of Practice D215.12. Matter Soluble in Water12.1 Determine the amount of water soluble materi
38、al pres-ent in accordance with the procedure in Section 5 of TestMethods D1208 or determine in accordance with Test MethodsD1301.13. Total Silica13.1 Digest5gofthesample in a covered casserole with 5mL of HCl and 15 mL of HNO3(1 + 1). Evaporate to drynessto dehydrate. Cool, treat with hot water and
39、HNO3, boil, filter,wash with hot acid ammonium acetate solution, then diluteHCl and finally hot water. Ignite and weigh as SiO2. Theresidue may be treated with H2SO4and HF in cases of doubt asto purity.14. Carbon Dioxide14.1 Determine carbon dioxide by the evolution method,using diluted HCl and stan
40、nous chloride.15. Soluble Sulfates15.1 Sulfates Other Than Barium SulfateTreat 0.5 g of thesample with 5 mL of water, 3 g of NH4Cl, and 5 mL of HClsaturated with bromine. Digest (covered) on steam bath about15 min. Add 25 mL of water, neutralize with dry Na2CO3, andadd about 2 g more. Boil 10 to 15
41、min, let settle, dilute with hotwater, filter, and wash with hot water. Redissolve in HCl,reprecipitate as above, and wash thoroughly with hot water.Acidify the united filtrates with HCl, adding a slight excess;boil and add a slight excess of BaCl2solution (10 %). Let standon a steam bath for 1 h. F
42、ilter and wash with hot water. Igniteand weigh as BaSO4. Calculate to SO3(includes SO3formedfrom SO2).15.2 Or, dissolve 0.5 g of the sample in 25 mL of water, 10mL of NH4OH (sp gr 0.90) and HCl in slight excess; dilute toabout 150 mL with water and add a piece of aluminum foilwhich should about cove
43、r the bottom of the beaker (being heldon the bottom by means of a stirring rod). Heat gently till alllead is precipitated, decant through a filter, pressing the leadsponge with a flattened rod, and washing with hot water. Addto the filtrate a little bromine water, boil until bromine isexpelled, add
44、15 mL of BaCl2solution (10 %), let stand on asteam bath for 1 h, filter, wash with hot water, ignite, and weighas BaSO4(any SrSO4present is not decomposed in thismethod).616. Iron Oxide16.1 Determine iron oxide in accordance with Section 12 ofTest Methods D50, or in a large beaker, treat 20 g of the
45、 samplewith 20 mL of water, 20 mL of HNO3(sp gr 1.42), and 3 mLof formaldehyde solution. Warm until all PbO2is dissolved,dilute with water, warm, filter off insoluble matter, and washwith hot water. Ignite filter and insoluble matter, and evaporatewith H2SO4and HF. To filtrate from insoluble matter
46、add 14mL of H2SO4(1 + 1), filter off PbSO4, and wash. Dissolve theresidue from HF and H2SO4in H2SO4and add to the filtratefrom PbSO4. Dilute to 500 mL and determine iron colorimetri-cally in an aliquot, using the same amounts of HNO3,H2SO4,and formaldehyde in the comparison solution Ref (7). Calcu-l
47、ate to Fe2O3.17. Keywords17.1 chemicals analysis; lead dioxide; red lead; tetra leadoxideREFERENCES(1) Zerr, and Mayer, Tests for Coal Tar Colors in Aniline Lakes.(2) Schultz, and Julius, A Systematic Survey of the Organic ColoringMatters.(3) Mulliken, Identification of Pure Organic Compounds; Comme
48、rcialDyestuffs, Vol III.(4) Dinglers, Dinglers Polytechnisches Journal, DPJOA, Vol 246, p. 196.(5) Zeitschrift fr Analytische Chemie, ZANCA, Vol 26, p. 296.(6) Skoog, D.A. and West, D. M., Fundamentals of Analytical Chemistry,Holt, Rinehart and Winston, Inc., New York, 1969, p. 192.(7) Lunge-Berl, “
49、Chemische-technisch Untersuchungs-Methoden,” Vol 2,p. 95, 6th Ed.6The solubility of BaSO4is increased by the presence of aluminum chloride (6).D49 83 (2014)3ASTM 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 rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technic
