1、Designation: D 1411 04Standard Test Methods forWater-Soluble Chlorides Present as Admixtures in GradedAggregate Road Mixes1This standard is issued under the fixed designation D 1411; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision,
2、the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 These test methods are applicable to the determinationof water-soluble calcium, magnesium, and sodium ch
3、loridesused as admixtures in the preparation of graded aggregate roadmaterials.NOTE 1These test methods assume that the aggregate did not containsignificant amounts of the water-soluble chlorides in question before theadmixture was added. If significant amounts of these chlorides are knownor suspect
4、ed to be present, the aggregate shall be tested for theseconstituents according to these test methods and the proper correctionsmade.1.2 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 estab
5、lish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 653 Terminology Relating to Soil, Rock, and ContainedFluidsD 1193 Specification for Reagent Water3. Terminology3.1 Except as follows in 3
6、.2, all definitions are in accor-dance with Terminology D 653.3.2 Definitions of Terms Specific to This Standard:3.2.1 admixturea material other than water, aggregates,hydraulic cement, and fiber reinforcement used as an ingredi-ent and added immediately before or during the mixing of roadmaterials.
7、4. Significance and Use4.1 The percentage of calcium chloride, magnesium chlo-ride, and alkali chloride (calculated as sodium chloride) ingraded aggregate obtained from aggregate roads or aggregatebases under paved roads is of interest to highway departmentsusing calcium chloride or sodium chloride
8、stabilization. Thepercentages of calcium chloride or sodium chloride obtained inthese test methods are compared with the quantities added todetermine whether the road material and stabilizing agent wereproperly mixed, whether leaching of the stabilizing agentoccurred, etc.5. Purity of Reagents5.1 Pu
9、rity of ReagentsReagent grade chemicals shall beused 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.3Other grades may beuse
10、d, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.5.2 Unless otherwise indicated, reference to water shall beunderstood to mean distilled water or water of equal purityconforming to Specification D
11、1193.6. Preparation of Samples6.1 Submit samples from the field to the laboratory in sealedcontainers. For each individual sample, break up any largelumps in a mortar and quarter the sample. Accurately weighapproximately 300 g (dry weight) of a quartered sample andtransfer it to a 1-L bottle. Add 47
12、9 mL of water, 20 mL of ferricammonium sulfate (100 g/L) and 1 mL of ammonium hydrox-ide (sp gr 0.90). Agitate in a shaker overnight or for 12 to 15h. Filter through fluted filter paper, discarding the first 50 mL1These methods are under the jurisdiction of Committee D18 on Soil and Rockand are the
13、direct responsibility of Subcommittee D18.15 on Stabilization withAdmixtures.Current edition approved May 1, 2004. Published May 2004. Originallyapproved in 1956 . Last previous edition approved in 1999 as D 1411 99.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM
14、 Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3“Reagent Chemicals, American Chemical Society Specifications,” AmericanChemical Society, Washington, DC. For suggestions on the testing of reage
15、nts 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. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.1*A Summary of Changes section appears at the end of this s
16、tandard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.and retaining the remainder. Determine calcium, magnesium,and chloride in the clear filtrate.NOTE 2The addition of ferric ammonium sulfate and ammoniumhydroxide should give compl
17、ete coagulation of most of the dispersiblematerials and give clear filtrates.TOTAL CHLORIDES7. Summary of Test Method7.1 An excess of a standard silver nitrate solution is addedto the filtered sample, and the excess silver is back titrated witha standard ammonium thiocyanate solution to a red-orange
18、endpoint using Volhard indicator.8. Interferences8.1 In effect, this method is a “Total Halides” method as itcannot distinguish between chloride and other halides that maybe present.9. Reagents9.1 Ammonium Thiocyanate, Standard Solution (0.1 N)Dissolve 7.6 g of ammonium thiocyanate (NH4SCN) in water
19、and dilute to 1 L. Standardize against the 0.1 N AgNO3solution.9.2 Benzyl Alcohol, Chlorine-Free.9.3 Nitric Acid (sp gr 1.42)Concentrated HNO3.9.4 Silver Nitrate, Standard Solution (0.1 N)Dissolve17.0 g of silver nitrate (AgNO3) in water and dilute to 1 L.9.5 Volhard Indicator SolutionDissolve 10 g
20、of ferricammonium sulfate (FeNH4(SO4)212H2O) in 100 mL of waterand add 1 mL of HNO3.10. Procedure10.1 Acidify a suitable portion of the sample solution (seeSection 6) (10-mL aliquot) with 3 to 5 mL of concentratedHNO3, add a known volume of the 0.1 N AgNO3solution thatis in excess of the amount requ
21、ired to precipitate the chloride,and heat to boiling to coagulate silver chloride (AgCl). Cool toroom temperature, add 3 to 5 mL of benzyl alcohol, and shakevigorously. If help is needed to determine the point at which anexcess of AgNO3solution is achieved, add 5 mL of Volhardindicator and 1 mL of 0
22、.1 N ammonium thiocyanate prior to theaddition of 0.1 N AgNO3solution. The red orange color ofVolhard indicator will disappear when excess AgNO3solutionhas been added.10.2 Add Volhard indicator solution to the solution andtitrate the excess AgNO3with 0.1 N NH4SCN solution.11. Calculation11.1 Calcula
23、te the percentage of total chloride ion as fol-lows:chloride, %aN 2 a8N8! 3 0.0355bw3 100 (1)where:a = millilitres of AgNO3solution added,a8 = millilitres of NH4SCN solution required for thetitration,N = normality of the AgNO3solution,N8 = normality of NH4SCN solution,b = millilitres of solution in
24、aliquot taken, divided by500, andw = grams of sample used.CALCIUM CHLORIDE12. Summary of Test Method12.1 Calcium in an alkaline solution is titrated with standardEDTA solution using calcein modified as an indicator. Thecolor change is from green to blue.13. Interferences13.1 Strontium, and other cat
25、ions not complexed withcyanide at an alkaline pH will be titrated as calcium.14. Reagents14.1 Calcein Modified Indicator.414.2 Calcium Chloride, Standard SolutionPlace 15.00 gof primary standard calcium carbonate (CaCO3) in 300 mL ofwater and slowly add concentrated hydrochloric acid (HCl),while sti
26、rring continuously. When the calcium carbonate isdissolved, cool and transfer to a 1-L volumetric flask. Dilute tovolume with water and mix thoroughly. Pipet a 25-mL aliquotinto a 500-mL volumetric flask and dilute to volume with waterand mix thoroughly. One millilitre of the second dilution isequiv
27、alent to 0.000832 g of calcium chloride.14.3 EDTA Standard SolutionDissolve 3.792 g of diso-dium dihydrogen ethylenediaminetetraacetate dihydrate in wa-ter in a 1-L volumetric flask and dilute to volume with water.Standardize this solution by titrating 50.0 mL of the dilutecalcium chloride standard
28、solution.14.4 Hydroxylamine Hydrochloride, 10 % SolutionDissolve 10 g of hydroxylamine hydrochloride (NH2OHHCl)in 90 mL of water.14.5 Potassium Cyanide.14.6 Sodium Hydroxide, Standard Solution (2N)Dissolve 80 g of sodium hydroxide (NaOH) in 300 mL ofwater. Transfer to a 1-L volumetric flask and dilu
29、te to volumewith water.14.7 Sugar.15. Procedure15.1 Pipet a suitable aliquot of the solution of the sample(see Section 6) 10.0 mL of the solution, or approximately 6 gof the original sample) into a 500-mL Erlenmeyer flask anddilute to about 200 mL.15.2 Add 10 mL of the hydroxylamine hydrochloride so
30、lu-tion,1gofsugar, and swirl to dissolve. Add 40 mL of the 2 NNaOH solution and 0.1 g of potassium cyanide and about 0.2g of the indicator.15.3 Titrate with standard EDTA solution until the indicatorchanges from green to purple.16. Calculation16.1 Calculate the percentage of calcium chloride (CaCl2)
31、as follows:4A satisfactory indicator is available from G. Frederich Smith Chemical Co.,Columbus, OH.D1411042Let F 5 g CaCl2/mL EDTA (2)550.0 mL 3 0.000832 g CaCl2/mLmL of EDTA from standardizationCaCl2,%5 a 3 F 3 100!/bwwhere:a = millilitres of EDTA solution required for the sampletitration,b = mill
32、ilitres of solution in the aliquot taken, divided by500, andw = grams of sample used.MAGNESIUM CHLORIDE17. Summary of Test Method17.1 Calcium and magnesium, in a solution buffered to a pHof 10, are titrated with standard EDTA solution using erio-chrome black T as an indicator. The color change is fr
33、om redto blue. Magnesium chloride is calculated by subtracting theEDTA calcium equivalent volume determined in the analysisfor calcium chloride from the total EDTA volume used, toobtain the magnesium EDTA equivalent by difference.18. Interferences18.1 There are no known interferences.19. Reagents19.
34、1 Buffer Solution, Approximately pH 10Dissolve 65.5g of ammonium chloride in 300 mL of water. Add 570 mL ofammonium hydroxide (NH4OH) (sp gr 0.90) and dilute to 1 Lwith water.19.2 Eriochrome Black T Indicator SolutionDissolve 4.5g of hydroxylamine hydrochloride (NH2OHHCl) in 100 mL ofmethanol. Add 0
35、.5 g of Eriochrome Black T and mix.20. Procedure20.1 Pipet a suitable aliquot of the solution of the sample(see Section 6) (10.0 mL of the solution, or approximately 6 gof the original sample) into a 500-mL Erlenmeyer flask anddilute to approximately 200 mL.20.2 Add 10 mL of 10 % hydroxylamine hydro
36、chloride, 20mL of buffer, 0.1 g potassium cyanide, 5 drops of indicator, andtitrate with EDTA to a color change of red to blue.21. Calculation21.1 Calculate the percentage of magnesium chloride(MgCl2) as follows:Let F 5 g of MgCl2/mL EDTA (3)550.0 mL 3 0.000832 g CaCl2/mL 3 0.858mL of EDTA from stan
37、dardizationMgCl2,%5 a8 2 a! 3 F 3 100/bwwhere:a8 = millilitres of EDTA solution needed to titrate thealiquot for calcium and magnesium.a = millilitres of EDTA solution needed to titrate thealiquot for calcium,b = millilitres in the aliquot of the original sample solu-tion, divided by 500, andw = gra
38、ms of sample used.ALKALI CHLORIDE22. Procedure22.1 Alkali chlorides are calculated from the difference ofthe total chloride and calcium and magnesium determinations.23. Calculation23.1 Calculate the percentage of alkali chlorides as follows:Percent alkali chlorides as NaCl (4)5 a 3 1.648! 2 b 3 1.05
39、3! 2 c 3 1.227!where:a = percent total chlorides,b = percent calcium chloride, andc = percent magnesium chloride.PRECISION AND BIAS24. Precision and Bias24.1 PrecisionA limited interlaboratory round-robin testprogram has been conducted for the purpose of establishingprecision and bias values. Total
40、chlorides were determined byfour laboratories with four samples. Table 1 describes thestandard deviation (1s) and the 95 % confidence interval (d2s)for the total chloride contents tested. Two tests on similarspecimens from the same sample should not differ by morethan the amounts indicated in the d2
41、s columns.24.2 The bias for this round-robin test was on the order ofminus 35 %. That is, the average results in the four tentativetests were approximately 35 % lower than the actual valueswhich should have been obtained. A more extensive interlabo-ratory round-robin test series has been proposed to
42、 resolve thequestion of accuracy.525. Keywords25.1 admixture; chloride content; soil-stabilization5Details of the precision and bias analysis are on file with ASTM. Request RR:D181001.TABLE 1 Estimates of PrecisionSingle operator Multi-laboratoryMaterial 1s d2s 1s d2s2 % NaCl 0.0082 0.0232 0.0087 0.
43、02462.5 % CaCl20.0137 0.0387 0.0138 0.03903 % NaCl 0.0115 0.0325 0.0120 0.03393.5 % CaCl20.0128 0.0362 0.0172 0.0486D1411043SUMMARY OF CHANGESIn accordance with Committee D18 policy, this section identifies the location of changes made to this standardsin the last edition (1999) that may impact the
44、use of these test methods.(1) Sections 7, 12, and 17 were added to provide a summary ofthe test method, modeled after Test Method E449 and others.Renumbered subsequent sections.(2) Sections 8, 13, and 18 were added to review possibleinterferences associated with the test method, modeled afterTest Me
45、thod E449 and others. Renumbered subsequent sec-tions.(3) Section 9.4: deleted wording, “This is a primary standard”because strictly speaking, AgNO3is not a primary standard.(4) Section 10.1; added guidance for determining how muchAgNO3is needed to be in excess. Impossible to know howmuch is needed
46、to be in excess when working with unknownsamples unless this technique is used.(5) Updated Summary of Changes section.ASTM 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
47、 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 technical committee and must be reviewed every five years andif not revised, ei
48、ther 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 atten
49、d. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D1411044
