1、Designation: D3943 10 (Reapproved 2015)Standard Test Method forTotal Molybdenum in Fresh Alumina-Base Catalysts1This standard is issued under the fixed designation D3943; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of
2、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 This test method covers the determination of molybde-num in alumina-base catalysts and has been cooperativelytested at
3、 molybdenum concentrations from 8 to 18 weight %,expressed as MoO3. Any component of the catalyst other thanmolybdenum such as iron, tungsten, etc., which is capable ofbeing oxidized by either ferric or ceric ions after being passedthrough a zinc-amalgam reductor column (Jones reductor) willinterfer
4、e.1.2 The values stated 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 ap
5、pro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD7442 Practice for Sample Preparation of Fluid CatalyticCracking Catalysts and Zeolites for ElementalAnalysis
6、 byInductively Coupled Plasma Atomic Emission Spectros-copyE173 Practice for Conducting Interlaboratory Studies ofMethods for Chemical Analysis of Metals (Withdrawn1998)3E507 Test Method for Determination of Aluminum in IronOres by Flame Atomic Absorption Spectrometry3. Summary of Test Method3.1 The
7、 catalyst is digested in hot sulfuric acid to dissolvemolybdenum, destroy organic matter, and to expel nitrates ifpresent. The acid solution is diluted and passed through anamalgamated zinc column (Jones reductor) into a receivingflask containing an excess of ferric ammonium sulfate. Thecolumn quant
8、itatively reduces the molybdenum (Mo+6toMo+3) which in turn is reoxidized in the receiving flaskaccording to the reaction:Mo1313Fe13Mo1613Fe12(1)3.2 The ferrous ion produced (three per Mo+3oxidized) istitrated with standard ceric sulfate solution in the presence offerroin indicator. The indicator un
9、dergoes a color change (pinkto colorless or very faint blue-green) in the presence of excessceric ion. The amount of Fe+2titrated in the reaction:Fe121Ce14Fe131Ce13(2)is a direct measure of Mo+6concentration.4. Significance and Use4.1 This test method sets forth a procedure by whichcatalyst samples
10、can be compared either on an interlaboratoryor intralaboratory basis. It is anticipated that catalyst producersand users will find this method of value.5. Interferences5.1 Elements such as As, Sb, Cr, Fe, Ti, V, U, or W caninterfere in this analysis. If serious interference occurs, it willbe necessa
11、ry to isolate the molybdenum from the interferingspecies prior to measurement.5.2 Organics and nitrates can interfere or react with thezinc-amalgam if the sulfuric acid treatment is not properlycarried out as described in 9.1.6. Apparatus6.1 Beakers, 250-mL.1This test method is under the jurisdictio
12、n of ASTM Committee D32 onCatalysts and is the direct responsibility of Subcommittee D32.03 on ChemicalComposition.Current edition approved Dec. 1, 2015. Published December 2015. Originallyapproved in 1980. Last previous edition approved in 2010 as D394310. DOI:10.1520/D3943-10R15.2For referenced AS
13、TM 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.3The last approved version of this historical standard is referenced onwww.astm
14、.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States16.2 Jones Reductor Column, 30-cm long by 2 cm in outerdiameter, with a 100-mL reservoir.4Attach a piece of vinyltubing to the end of the delivery tube long enough to extend tothe bo
15、ttom of the filtering flask (see Test Method E507).6.3 Vacuum Filtering Flask, heavy-walled, 1000-mL.6.4 Buret, 50-mL, Class A (0.1-mL divisions).6.5 Stirring Motor, magnetic, and TFE-fluorocarbon-covered stirring bars, 7.11 by 14.2 mm.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall b
16、eused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.5Other grades may beused provided it is first ascertained that the rea
17、gent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D1193.7.3 Ceric Sulfate, 0.10 N standardized using sodium mol
18、yb-date following the procedure given in Annex A2.NOTE 1Refer to Section 8 on Hazards in Practice D7442 for hazardsassociated with handling of acids.7.4 Ferric Ammonium Sulfate SolutionFeNH4(SO4)212H2ODissolve 200 g of FeNH4(SO4)212 H2O in 1000 mLof water containing 20 mL of concentrated sulfuric ac
19、id. Addpotassium permanganate solution dropwise until a pink colorpersists for 1 min.7.5 Ferroin Indicator, 0.025 M solution of 1, 10-phenanthroline ferrous sulfate complex.7.6 Hydrochloric Acid (HCl), concentrated.7.7 Jones Reductor Amalgam.7.8 Mercuric Chloride (HgCl2) Solution, approximately2 %.
20、Dissolve 10 g of mercuric chloride (HgCl2) in water.Transfer to a 500mL volumetric flask, dilute to volume, andmix.7.9 Molybdenum Standard SolutionDissolve 1.0 g,weighed to the nearest 0.1 mg, of sodium molybdate dihydrate(Na2MoO42H2O) in water containing 10 mL of H2SO4,transfer to a 1-L volumetric
21、flask, dilute to volume, and mix(1 mL = 0.5948 mg MoO3).7.10 Phosphoric Acid (H3PO4), concentratedMix 130 mLof concentrated H2SO4with 250 mL of water. Add the acidslowly with constant stirring. Add 140 mL of concentratedH3PO4and 15 mL of a saturated solution of MnSO4(approxi-mately 60 g/100 mL). Dil
22、ute to 1000 mL with water.7.11 Potassium Permanganate (KMnO4), approximately0.1 M solution.7.12 Sulfuric Acid (H2SO4), concentrated, 1 + 1 and 1 + 19,dilutions with water, corresponding to 18 and 1.8 N solutions,respectively. Cautiously add the concentrated sulfuric acid tothe water, mix well, and a
23、llow to cool.7.13 Sulfuric Acid (H2SO4), dilute, 1 + 99, warm, dilutionswith water, corresponding to 0.18 N solution. Cautiously addthe concentrated sulfuric acid to the water and mix well.7.14 Zinc Metal, 20 mesh, low iron content.8. Sampling8.1 The selection of a representative analytical sample f
24、romthe bulk material is outside the scope of the present method. Itis presumed that parties using this test method for comparisonpurposes will have agreed on the selection of an analyticalsample which is appropriate to their needs.8.2 Pulverize the analytical sample to pass a 150-m (No.100) sieve. I
25、gnite the pulverized sample for 30 min at 550C ina muffle furnace. Allow to cool in a desiccator.9. Procedure9.1 Transfer a 0.75-g specimen, weighed to the nearest 1mg, into a 250-mL beaker. Add 20 mL of 1 + 1 H2SO4solutionand heat to fumes on a hot plate. Cool, rinse down with 10 mLof water and tak
26、e to fumes again. Cool, add 100 mL of waterand heat to dissolve. Cool to room temperature.9.2 Activate the Jones reductor by passive five 25-mLportions (1 min/25 mL of solution passed) of the 1 + 19H2SO4through the column, using slight vacuum. Do not allow theamalgam to become exposed to air. Test t
27、he column by passinga blank of 25 mL of 1 + 19 H2SO4through the reductor into areceiver containing 15 mL of ferric ammonium sulfate solu-tion. Add 2 to 3 drops of ferroin indicator and 10 mL ofconcentrated H3PO4and titrate with 0.1 N ceric sulfate solutionuntil the pink indicator color completely di
28、sappears and isreplaced by a colorless to faint blue green color which persistsfor at least 15 s. If more than 1 or 2 drops of ceric sulfatesolution are required, repeat the washing and testing until asuitable blank is obtained.9.3 Pass the sample through the reductor into a receivercontaining 25 mL
29、 of ferric ammonium sulfate solution and 10mL of the concentrated H3PO4, using slight vacuum. Keep thetip of the reductor (extended by a piece of vinyl tubing) belowthe surface of the solution in the receiver.9.4 Rinse the reductor with five 25-mL portions of 1 + 19H2SO4, adding the washings to the
30、receiver. Titrate the reducediron solution in the receiver immediately with 0.1 N cericsulfate solution using 2 to 3 drops of ferroin indicator. The faintblue-green color developed at the end point should persist for15 s.4The sole source of supply of the apparatus known to the committee at this time
31、is Part No. 8035-J10 from Thomas Scientific, 99 High Hill Rd. at 295, Swedesboro,NJ 08085. If you are aware of alternative suppliers, please provide this informationto ASTM International Headquarters. Your comments will receive careful consid-eration at a meeting of the responsible technical committ
32、ee,1which you may attend.5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the
33、 United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D3943 10 (2015)210. Calculation10.1 Calculate the percentage molybdenum as follows:MoO3% 5 D 2 E!A/10w (3)where:D = ceric sulfate solution required to titrate sample, mL,E = ceric sulfate solu
34、tion required to titrate blank, mL,A = mg MoO3/mL of ceric sulfate solution, andw = dried weight of specimen, g.10.2 Calculate the arithmetic mean of each set of observa-tions and report these values to two decimal places.11. Precision and Bias611.1 Eight laboratories participated in supplying data
35、underthe conditions outlined in Practice E173. Statistical datacalculated in accordance with this practice are recorded inResearch Report RR:D32-1020, along with standard deviationscalculated by an alternative procedure.11.2 No reference standards were available to determine thebias of the test meth
36、od.12. Keywords12.1 alumina-base catalysts (fresh); Jones Reduction; mo-lybdenumANNEXES(Mandatory Information)A1. ZINC AMALGAM FOR JONES REDUCTORA1.1 PreparationA1.1.1 Place 1000 g of 20mesh zinc (low iron content) ina stout, wide-mouthed glass bottle or jar.A1.1.2 Add 500 mL of a 2 % solution of me
37、rcuric chloride,prepared as described in 7.8, to the zinc.A1.1.3 Mix well with a stirring rod for 45 to 60 s. Ensure allzinc has been fully contacted.A1.1.4 Decant and discard the solution from the zincmixture.A1.1.5 Rinse the zinc amalgam at least 5 times withdeionized water.A1.2 ActivationA1.2.1 A
38、dd 500 mL of warm sulfuric acid (1:99), preparedas described in 7.13, to the rinsed amalgam.A1.2.2 Mix well with a stirring rod until all the zinc hasbeen contacted.A1.2.3 Decant and discard the acid solution from the zincmixture.A1.2.4 Rinse the activated zinc amalgam at least 2 to 3times with deio
39、nized water.A1.3 StorageA1.3.1 Prepare 1 L of deionized water to which 1 mL ofhydrochloric acid has been added.A1.3.2 Add sufficient water from A1.3.1 to the activatedzinc amalgam to ensure that all the zinc is covered.A1.3.3 Seal and store until needed.6Supporting data have been filed at ASTM Inter
40、national Headquarters and maybe obtained by requesting Research Report RR:D32-1020.D3943 10 (2015)3A2. STANDARDIZATION OF CERIC SULFATE SOLUTION USING SODIUM MOLYBDATEA2.1 StandardizationA2.1.1 Clean the Jones reductor thoroughly by passingrepeatedly through it dilute sulfuric acid (1 + 19) and wate
41、runtil a satisfactory blank is established.A2.1.2 Prepare a ferric ammonium sulfate solution, asdescribed in 7.3 and transfer 25 mL of this solution to thereceiving flask of the Jones reductor. Add 10 mL of concen-trated phosphoric acid to the receiving flask. Prepare thephosphoric acid-manganous su
42、lfate-sulfuric acid solution asdescribed in 7.4 and transfer 10 mL to the same receiving flaskof the Jones reductor.A2.1.3 Be sure that the tip of the reductor dips well beneaththe surface of the solution. Transfer 100 mL of the molybde-num standard solution (1 mL = 0.5948 mg MoO3) to a 250-mLbeaker
43、 and add 20 mL of (1 + 1)H2SO4.A2.1.4 With gentle suction, draw the molybdenum solutionthrough the reductor, while gently swirling the solution in thereceiving suction flask. Just before the surface of the liquidreaches the zinc, add 50 mL of cold H2SO4(1 + 19). Rinse thecolumn twice more by adding
44、50 mL of water each time. Addthe water just before the surface of the solution reaches thezinc. Close the stopcock while a portion of the last rinsingremains in the reductor funnel. Disconnect and rinse thereductor as a little water is allowed to run through the stem, andrinse the outside of the ste
45、m. Titrate the collected solution withthe ceric sulfate solution as described in 9.4. Correct for areagent blank that has been carried through the entire proce-dure using the same amount of reagents.A2.2 CalculationsA2.2.1 Calculate the molybdenum oxide equivalent of theceric sulfate solution as fol
46、lows:A 5 B/C 2 F! (A2.1)where:A = MoO3/mL of ceric sulfate solution,B = molybdenum used expressed as mg MoO3,C = ceric sulfate solution used in titration of themolybdenum, mL, andF = ceric sulfate solution needed to titrate the blank, mL.ASTM International takes no position respecting the validity o
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