1、Designation:E 39604 Designation: E396 12Standard Test Methods forChemical Analysis of Cadmium1This standard is issued under the fixed designation E396; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A nu
2、mber in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.NoteCorrections were made throughout and the year date changed on January 27, 2012.1. Scope1.1 These test methods cover the chemical analysis of cadm
3、ium having chemical compositions with the following limits:Element Concentration, max, %Antimony 0.001Arsenic 0.003Copper 0.015Lead 0.025Silver 0.010Thallium 0.003Tin 0.010Zinc 0.0351.2 The test methods appear in the following order:SectionsAntimony by the Rhodamine B Photometric Method0.0002 to 0.0
4、010%62-72Antimony by the Rhodamine B Photometric Method0.0002 to 0.0010%62-72Arsenic by the Molybdenum Blue Photometric Method0.001 to 0.005%40-50Arsenic by the Molybdenum Blue Photometric Method0.001 to 0.005%40-50Copper by the Neocuproine Photometric Method 0.002 to 0.030% 10-19Copper, Lead, Silve
5、r, and Zinc by the Atomic Absorption Method0.004 to 0.02% Cu, 0.01 to 0.05% Pb, 0.004 to 0.02 % Agand 0.01 to 0.05% Zn51-61Copper, Lead, Silver, and Zinc by the Atomic Absorption Method0.004 to 0.02% Cu, 0.01 to 0.05% Pb, 0.004 to 0.02 % Agand 0.01 to 0.05% Zn51-61Lead by the Dithizone Photometric M
6、ethod 0.001 to 0.05% 20-29Thallium by the Rhodamine B Photometric Method0.0003 to 0.005%30-39Thallium by the Rhodamine B Photometric Method0.0003 to 0.005%30-39Tin by the 8-Quinolinol Photometric Method 0.0025 to 0.0150% 73-821.3 This standard does not purport to address all of the safety problems,c
7、oncerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability ofregulatory limitations prior to use. Specific precautionary information is given in Section 6 and 25.8.2. Referenced D
8、ocuments2.1 ASTM Standards:2B440 Specification for CadmiumD1193 Specification for Reagent WaterE29 Practice for Using Significant Digits in Test Data to Determine Conformance with SpecificationsE50 Practices for Apparatus, Reagents, and Safety Precautions for Chemical Analysis of Metals Practices fo
9、r Apparatus,1These test methods are under the jurisdiction of ASTM Committee E-1E01 on Analytical Chemistry for Metals, Ores, and Related Materials and are the directresponsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys, and Related Metals.Current edition approved May 1, 2004
10、.Jan. 27, 2012. Published June 2004.February 2012. Originally approved in 1970. Last previous edition approved in 19982011 asE 39698.E396 05(2011). DOI: 10.1520/E0396-12.2For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at serviceastm.org. For Ann
11、ual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.1This 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 b
12、e 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 to be considered the official document.Copyright ASTM International, 100 Barr Harbor Driv
13、e, PO Box C700, West Conshohocken, PA 19428-2959, United States.Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related MaterialsE55 Practice for Sampling Wrought Nonferrous Metals and Alloys for Determination of Chemical CompositionE60 Practice for Photometric and Spe
14、ctrophotometric Methods for ChemicalAnalysis of Metals Practice forAnalysis of Metals,Ores, and Related Materials by SpectrophotometryE88 Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical CompositionE135 Terminology Relating to Analytical Chemistry for Met
15、als, Ores, and Related MaterialsE173 Practices for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals3E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method3. Terminology3.1 For definitions of terms used in this test meth
16、od, refer to Terminology E 135E135.4. Significance and Use4.1 These test methods for the chemical analysis of cadmium are primarily intended to test such material for compliance withcompositional specifications in Specification B 440B440. It is assumed that all who use these test methods will be tra
17、ined analystscapable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properlyequipped laboratory.5. Apparatus, Reagents, and Photometric Practice5.1 Apparatus and reagents required for each determination are listed in separate section
18、s preceding the procedure. Theapparatus, standard solutions, and reagents shall conform to the requirements prescribed in Practices E 50E50. Photometers shallconform to the requirements prescribed in Practice E 60E60.5.2 Photometric practice prescribed in these methods shall conform to Practice E 60
19、E60.6. Safety Hazards6.1 For precautions to be observed in the use of certain reagents in these test methods, refer to Practices E 50E50.7. Sampling7.1 Wrought products shall be sampled in accordance with Practice E 55E55. Cast products shall be sampled in accordance withPractice E 88E88. However, t
20、hese test methods do not supersede any sampling requirements specified in a specificASTM materialspecification.8. Rounding Calculated Values8.1 Calculated values shall be rounded to the desired number of places as directed in Practice E 29E29.9. Interlaboratory Studies9.1 These test methods have bee
21、n evaluated in accordance with Practices E 173E173, unless otherwise noted in the precisionsection.COPPER BY THE NEOCUPROINE PHOTOMETRIC METHOD10. Scope10.1 This test method covers the determination of copper in concentrations from 0.002 to 0.030 %.11. Summary of Test Method11.1 Copper is separated
22、as cuprous copper from other metals by extraction of the copper-neocuproine complex withchloroform. Photometric measurement is made at approximately 455 nm.12. Concentration Range12.1 The recommended concentration range is from 0.01 to 0.15 mg of copper for each 25 mL of solution, using a 1-cm cell.
23、NOTE 1This test method has been written for cells having a 1-cm light path. Cells having other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.13. Stability of Color13.1 The color develops within 5 min and the extracted complex is stable. H
24、owever, because of the volatile nature of the solvent,it is advisable to take photometric readings promptly.3Withdrawn. The last approved version of this historical standard is referenced at www.astm.org.E396 12214. Interferences14.1 The elements ordinarily present do not interfere if their concentr
25、ations are under the maximum limits shown in 1.1.15. Reagents15.1 Chloroform (CHCl3).15.2 Copper, Standard Solution (1 mL = 0.01 mg Cu)Dissolve 0.1000 g of copper (purity: 99.9 % min) in 10 mL ofHNO3(1 + 1). Add 25 mL of water, heat to boiling, and boil gently for 2 min to eliminate oxides of nitrog
26、en. Cool, transfer to a100-mL volumetric flask, dilute to volume, and mix. Transfer 5.00 mL to a 500-mL volumetric flask. Add 1 mL of HNO3(1 + 1),dilute to volume, and mix.15.3 Hydroxylamine Hydrochloride Solution (100 g/L)Dissolve 5.0 g of hydroxylamine hydrochloride (NH2OH HCl) in 50mL of water. P
27、repare fresh as needed.15.4 Metacresol Purple Indicator Solution (1 g/L)Dissolve 0.100 g of metacresol purple together with 1 pellet of sodiumhydroxide (NaOH) in about 10 mL of water by warming. Dilute to 100 mL, and mix.15.5 Neocuproine Solution (1 g/L)Dissolve 0.10 g of neocuproine (2,9-dimethyl-1
28、,10-phenanthroline hemihydrate) in 100mL of either methanol or 95 % ethanol.15.6 Sodium Citrate Solution (300 g/L)Dissolve 300 g of sodium citrate dihydrate in water, dilute to 1 L, and mix.15.7 Purity of WaterUnless otherwise indicated, reference to water shall be understood to mean reagent water a
29、s defined byType II of Specification D1193.16. Preparation of Calibration Curve16.1 Calibration Solution:16.1.1 Using pipets, transfer 2, 5, 10, 15, and 20 mL of copper solution (1 mL = 0.01 mg Cu) to five 150-mL beakers, and diluteto about 40 mL.16.1.2 Add 2 drops of metacresol purple indicator sol
30、ution, and then add HNO3(1 + 1) dropwise to the red color change of theindicator. Proceed as directed in 16.3.16.2 Reference SolutionAdd 40 mL of water to a 150- mL beaker. Proceed as directed in 16.1.2.16.3 Color Development:16.3.1 Add 10 mL of NH2OH HCl solution, and stir.Add 10 mL of sodium citra
31、te solution, and stir.Add NH4OH to the purplecolor of the indicator (pH about 8.5). Add 5.0 mL of neocuproine solution, stir, and allow to stand for 5 min.NOTE 2The precipitate that may form upon addition of sodium citrate solution will redissolve when the pH is raised to 8.5 with NH4OH.16.3.2 Trans
32、fer to a 125-mL separatory funnel marked at 80 mL, and dilute to the mark with water. Add 25.0 mL of CHCl3.Shake vigorously for 45 s, and allow the layers to separate. Draw off and discard about 1 mL of the CHCl3layer to rinse the stemof the separatory funnel.16.4 Photometry:16.4.1 Multiple-Cell Pho
33、tometerMeasure the cell correction using absorption cells with a 1-cm light path and a light bandcentered at approximately 455 nm (Note 3). Using the test cell, take the photometric readings of the calibration solutions.NOTE 3Avoid transfer of water to the absorption cell in the following manner. In
34、sert a loose plug of sterilized absorbent cotton into the stem of eachseparatory funnel. Just prior to filling the absorption cell with the solution in the separatory funnel, discard about 1 mL of the CHCl3layer through thecotton plug and immediately transfer a suitable portion of the CHCl3layer int
35、o the dry absorption cell.16.4.2 Single-Cell PhotometerTransfer a suitable portion of the reference solution to an absorption cell with a 1-cm light pathand adjust the photometer to the initial setting, using a light band centered at approximately 455 nm (Note 1). While maintainingthis adjustment, t
36、ake the photometric readings of the calibration solutions.16.5 Calibration CurvePlot the net photometric readings of the calibration solutions against milligrams of copper per 25 mLof solution.17. Procedure17.1 Test SolutionTransfer a 0.5-g sample, weighed to the nearest 1 mg, to a 150-mL beaker. Ad
37、d 5 mL of HNO3(1 + 1).When dissolution is complete, add 20 mL of water and boil gently to eliminate oxides of nitrogen. Cool, dilute to about 40 mL,and add 2 drops of metacresol purple indicator solution. Proceed as directed in 17.3.17.2 Reference SolutionCarry a reagent blank through the entire pro
38、cedure using the same amount of all reagents with thesample omitted, for use as the reference solution.17.3 Color DevelopmentProceed as directed in 16.3.17.4 PhotometryProceed as directed in 16.4.18. Calculation18.1 Convert the net photometric reading of the test solution to milligrams of copper by
39、means of the calibration curve.Calculate the percentage of copper as follows:E396 123Copper, % 5 A/B 3 10! (1)where:A = copper found in the 25 mL of final test solution, mg, andB = sample represented in 25 mL of final test solution, g.19. Precision and Bias19.1 PrecisionEight laboratories cooperated
40、 in testing this test method and obtained the data summarized in Table 1.19.2 AccuracyNo certified reference materials suitable for testing this test method were available when the interlaboratorytesting program was conducted. The user of this test method is encouraged to employ accepted reference m
41、aterials, if available,to determine the accuracy of this test method as applied in a specific laboratory.19.3E 173 E 173has been replaced by Practice E 1601E 1601. The reproducibility Index R19.3 E173 has been replaced by Practice E1601. The reproducibility Index R2corresponds to the Reproducibility
42、 Index R ofPractice E 1601E1601. Likewise the Repeatability Index R1corresponds to the Repeatability Index r of Practice E 1601E1601.LEAD BY THE DITHIZONE PHOTOMETRIC METHOD20. Scope20.1 This test method covers the determination of lead in concentrations from 0.001 to 0.05 %.21. Summary of Test Meth
43、od21.1 Lead dithizonate is extracted with chloroform from a buffered cyanide solution at a pH of 8.5. The excess dithizone in thechloroform is then removed by extraction with an ammoniacal sulfite solution. Photometric measurement is made at approximately515 nm.22. Concentration Range22.1 The recomm
44、ended concentration range is from 0.005 to 0.050 mg of lead for each 25 mL of solution, using a 1-cm cell(Note 1).23. Stability of Color23.1 The color is stable for at least2hifprotected from direct sunlight; however, because of the volatile nature of the solvent,it is advisable to take photometric
45、readings promptly.24. Interferences24.1 The elements ordinarily present in cadmium do not interfere if their concentrations are under the maximum limits shownin 1.1.25. Reagents25.1 Ascorbic Acid.25.2 Bromine Water (Saturated).25.3 Chloroform (CHCl3).25.4 Dithizone Solution (0.01 g/L of CHCl3)Dissol
46、ve 0.05 g of dithizone (diphenylthiocarbazone) in a freshly opened 700-gbottle of CHCl3. Mix several times over a period of several hours. Store in a cool, dark place. Just before use, dilute 50 mL ofthis solution to 500 mL with CHCl3in a dry borosilicate bottle or flask, and mix.25.5 Lead, Standard
47、 Solution (1 mL = 0.005 mg Pb)Dissolve 0.1000 g of lead (purity: 99.9 % min) in 20 mL of HNO3(1 + 1),and boil gently to eliminate oxides of nitrogen. Cool, transfer to a 200-mL volumetric flask, dilute to volume, and mix. Transfer5.00 mL to a 500-mL volumetric flask, dilute to volume, and mix. Prepa
48、re the final solution fresh as needed.25.6 Metacresol Purple Indicator Solution (1 g/L)Proceed as directed in 15.4.25.7 Potassium Cyanide Solution (200 g/L)Dissolve 200 g of potassium cyanide (KCN) (low in lead and sulfide) (WarningSee 25.8) in water, and dilute to 1 L. Bring to a boil and boil for
49、2 min. Cool, and store in a polyethylene bottle.25.8 Sodium Sulfite Wash SolutionDissolve1gofsodium sulfite (Na2SO3) in about 300 mLof water in a 1-Lvolumetric flask.Add 20 mL of the KCN solution and 475 mL of NH4OH (1 + 1) which has been prepared from a freshly opened bottle. Dilute toTABLE 1 Statistical InformationSpecimenCopper Found,%Repeatability(R1, E 173E 173)Reproducibility(R2, E 173E 173)1 0.0074 0.003 0.00132 0.0173 0.0018 0.0031E396 124volume, and mix. Store in a polyethylene bottle. (WarningThe preparation, stor
