1、Designation: D 49 83 (Reapproved 2002)Standard Test Methods ofChemical Analysis of Red Lead1This standard is issued under the fixed designation D 49; the number immediately following the designation indicates the year of originaladoption or, in the case of revision, the year of last revision. A numb
2、er in parentheses indicates the year of last reapproval. A superscriptepsilon (e) 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 This
3、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 and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2
4、.1 ASTM Standards:D 50 Test Methods for Chemical Analysis of Yellow, Or-ange, Red, and Brown Pigments Containing Iron andManganese2D 215 Practice for the Chemical Analysis of White LinseedOil Paints3D 280 Test Methods for Hygroscopic Moisture (and OtherMatter Volatile Under the Test Conditions) in P
5、igments2D 1193 Specification for Reagent Water4D 1208 Test Methods for Common Properties of CertainPigments2D 1301 Test Methods for Chemical Analysis of White LeadPigments2D 1959 Test Method for Iodine Value of Drying Oils andFatty Acids23. Treatment of Sample3.1 If the pigment is lumpy or not finel
6、y 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 ground. The sample in allcases shall be thoroughly mixed before taking portions foranalysis. All samples shall be preserved in stoppered b
7、ottles orcontainers.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 the specifications of the Committee on AnalyticalReagents of the American Chemical Society where suchspecifications are availab
8、le.5Other 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 determination.4.2 Unless otherwise indicated, references to water shall beunderstood to mean reagent water conforming to Type II ofSpec
9、ification D 1193.5. Moisture5.1 Determine moisture content with a 2-g specimen inaccordance with Method A of Test Methods D 280. Thespecimen is dried for2hat105C. The loss in weight isconsidered as moisture.6. Organic Color6.1 Boil2gofthesample with 25 mL of 95 % ethyl alcohol,let settle, decant the
10、 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. Boilanother 2-g portion of the sample with 25 mL of chloroform,let settle, and decant the supernatant liquid. If any one of theabove solution
11、s 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 colors resistant to the abovereagents, the test procedures described in the following books may beused, taking into account the nature of
12、 the pigment involved (1,2,3).67. Total Lead and Insoluble Matter7.1 Treat1gofthesample with 15 mL of HNO3(1 + 1) andsufficient H2O2to dissolve all PbO2on warming. If any1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and
13、 are the directresponsibility of Subcommittee D01.31 on Pigment Specifications.Current edition approved Dec. 20, 1983. Published January 1984. Originallypublished as D 49 17 T. Last previous edition D 49 82.2Annual Book of ASTM Standards, Vol 06.03.3Annual Book of ASTM Standards, Vol 06.01.4Annual B
14、ook of ASTM Standards, Vol 11.01.5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, 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.,
15、 and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.6The boldface numbers in parentheses refer to a list of references at the end ofthese test methods.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,
16、 PA 19428-2959, United States.insoluble 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 appreciable.7.2 To the original solution or filtrate from the insolublematter add 20 mL of H2S
17、O4(sp gr 1.84) and evaporate 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
18、 soluble barium compounds, 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 ma
19、gnesium, boil the HNO3H2O2solution (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, anddet
20、ermine the lead as sulfate. 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 BaSO4
21、addNH4OH in slight excess, 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 t
22、o boiling and pass H2S 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
23、 the zinc as Zn2P2O7. 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 D 50. In the filtrate from calcium determine magne-sium by precipitating
24、 with sodium phosphate 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
25、lead which reducePbO2to 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
26、 and contents on a steam 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:Disso
27、lve 30 g of the crystallized sodium acetate and 2.4 g of KIin 25 mL of 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 Soluti
28、on (0.1N)Dissolve 24.83 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 st
29、andardizing, as described in Section 5 ofTest Method D 1959.8.3 Starch SolutionStir 2 to3gofpotato 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 D 1959.NOT
30、E 3Lead PeroxideIf the pigment 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 a20
31、0-mL Erlenmeyer flask, add 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 o
32、f glacial acetic acid, and 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
33、light yellow, rub-up any undissolved 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 thevo
34、lume of Na2S2O3that had been added.10. Calculation10.1 Calculate the lead peroxide and true red lead contentsas follows:PbO2=I3 0.942Pb3O4= PbO23 2.866 = I 3 2.7where: I = iodine value of the Na2S2O3solution,0.942 5PbO2I25239.19253.81, and (1)2.86616 5Pb3O4PbO25685.57239.1911. Zinc11.1 If the volume
35、 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 titratewith standard K4Fe(CN)6solution in accordance with 16.1.11of Practice D 215
36、. Report as ZnO (includes cadmium). Iron,D492copper, or other interfering substances should first be removedas described in 25.2.3 of Practice D 215.12. Matter Soluble in Water12.1 Determine the amount of water soluble materialpresent in accordance with the procedure in Section 5 of TestMethods D 12
37、08 or determine in accordance with Test Meth-ods D 1301.13. 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 HNO3, boil, filter,wash with hot acid ammonium acetate solution, then dil
38、uteHCl 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 stannous chloride.15. Soluble Sulfates15.1 Sulfates Other Than Barium Sulfate
39、Treat 0.5 g of thesample with 5 mL of water,3gofNH4Cl, 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 min, let settle, dilute with hotwater, filter, and wash with hot water. Redis
40、solve 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. Filter and wash with hot water. Igniteand weigh as BaSO4. Calculate to SO3(inc
41、ludes 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 cover the bottom of the beaker (being heldon the bottom by means of a stirring ro
42、d). 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 15 mL of BaCl2solution (10 %), let stand on asteam bath for 1 h, filter, wash
43、 with hot water, ignite, and weighas BaSO4(any SrSO4present is not decomposed in thismethod).716. Iron Oxide16.1 Determine iron oxide in accordance with Section 12 ofTest Methods D 50, or in a large beaker, treat 20 g of thesample with 20 mL of water, 20 mL of HNO3(sp gr 1.42), and3 mL of formaldehy
44、de solution. Warm until all PbO2isdissolved, dilute with water, warm, filter off insoluble matter,and wash with hot water. Ignite filter and insoluble matter, andevaporate with H2SO4and HF. To filtrate from insoluble matteradd 14 mL of H2SO4(1 + 1), filter off PbSO4, and wash.Dissolve the residue fr
45、om HF and H2SO4in H2SO4and add tothe filtrate from PbSO4. Dilute to 500 mL and determine ironcolorimetrically in an aliquot, using the same amounts ofHNO3,H2SO4, and formaldehyde in the comparison solutionRef (7). Calculate to Fe2O3.17. Keywords17.1 chemicals analysis; lead dioxide; red lead; tetra
46、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; CommercialDyestuffs, Vol III.(4) Dinglers, Dinglers Polytechnisches Journal, DPJOA, V
47、ol 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, “Chemische-technisch Untersuchungs-Methoden,” Vol 2,p. 95, 6th Ed.ASTM Internati
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49、r own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the AST
