1、Designation: E449 08 (Reapproved 2013)Standard Test Methods forAnalysis of Calcium Chloride1This standard is issued under the fixed designation E449; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A numb
2、er in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope1.1 These test methods cover the analysis of calcium chlo-ride
3、 and solutions.1.2 Procedures are given for the determination of calciumchloride, magnesium chloride, potassium chloride, sodiumchloride, and calcium hydroxide. The test methods appear inthe following order:SectionsCalcium Chloride 8 to 16Magnesium Chloride, Potassium Chloride,and Sodium Chloride17
4、to 26Calcium Hydroxide 27 to 331.3 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of thi
5、s standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardstatements are given in Section 5.1.5 Review the current Material Safety Data Sheet (MSDS)for detailed information concerning toxicity, first aidpr
6、ocedures, handling, and safety precautions.2. Referenced Documents2.1 ASTM Standards:2D345 Test Method for Sampling and Testing Calcium Chlo-ride for Roads and Structural ApplicationsD1193 Specification for Reagent WaterE180 Practice for Determining the Precision of ASTMMethods for Analysis and Test
7、ing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)3E200 Practice for Preparation, Standardization, and Storageof Standard and Reagent Solutions for Chemical AnalysisE663 Practice for FlameAtomicAbsorptionAnalysis (With-drawn 1997)33. Significance and Use3.1 Calcium chloride is available in
8、various forms andpurities. A major use is the de-icing and dust control of roads.It is also used in the coal industry for dustproofing andfreezeproofing, in foods, in electrolytic cells, and in refrigera-tion brines. The test methods listed in 1.2 provide proceduresfor analyzing calcium chloride to
9、determine if it is suitable forits intended use.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, these shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications a
10、re 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 ofthe determination.4.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean Type II or Type
11、IIIreagent water conforming to Specification D1193.5. Hazards5.1 While calcium chloride is a relatively harmless material,some of the reagents used in these methods present possiblesafety hazards. Potassium cyanide is extremely hazardous andmust be handled with great care. In addition to beingpoison
12、ous, solutions containing cyanide should never be mixed1These test methods are under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicalsand are the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved June 1, 2013. Published June 2013. Ori
13、ginallyapproved in 1972. Last previous edition approved in 2008 as E449 08. DOI:10.1520/E0449-08R13.2For referenced ASTM 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 Do
14、cument 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, Washington, DC. For suggestions on the testing of reagents notlisted by the American Che
15、mical 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.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 1942
16、8-2959. United States1with acids to preclude the release of poisonous hydrogencyanide gas. Concentrated hydrochloric acid and sodium hy-droxide also are hazardous chemicals which may produceserious burns on contact.6. Atomic Absorption Spectrophotometers6.1 Photometers and photometric practice used
17、in thesemethods shall conform to Practice E663.7. Sampling7.1 Sampling of calcium chloride is not within the scope ofthese test methods. See the appropriate sections of Test MethodD345.7.2 The sample to be analyzed shall be considered to be thatsample in a single bottle submitted to the analytical l
18、aboratory.7.3 The size of the sample shall be sufficient to perform allanalyses without the reuse of any portion of the sample.CALCIUM CHLORIDE8. Scope8.1 This test method covers the determination of calciumchloride in the range from 0 to 100 %.9. Summary of Test Method9.1 Calcium in an alkaline sol
19、ution is titrated with standardethylenediaminetetraacetate solution, using modified calcein IIas an indicator. The color change is from green to purple. -hydroxynaphthol blue is also suitable as an indicator, in whichcase the color change is from red to blue.10. Interferences10.1 Strontium and other
20、 cations not complexed with cya-nide at pH of at least 10 will consume ethylenediaminetetraac-etate solution and will affect the accuracy of this test method.11. Apparatus11.1 Buret, 50-mL, Class A.11.2 Weighing Bottle, glass-stoppered, 100-mL.12. Reagents12.1 Calcium Chloride, Standard Solution (1
21、mL = 0.00832g CaCl2)Weigh 7.500 g of primary standard calcium carbon-ate (CaCO3). Transfer to a 600-mL beaker and add 300 mL ofwater. Cover with a watch glass and slowly add to the beaker,while stirring, 15 mL of concentrated hydrochloric acid (HCl)delivered from a pipet inserted between the lip of
22、the beakerand the edge of the watch glass. When dissolution of theCaCO3is complete, boil gently to expel CO2. Cool, andtransfer to a 1-L volumetric flask. Dilute to volume with waterand mix.12.2 Ethylenediaminetetraacetate, Standard Solution (0.1mol/L (M)Dissolve 37.22 g of disodium dihydrogen ethyl
23、-enediaminetetraacetate dihydrate (EDTA) in water. Transfer toa 1-L volumetric flask, dilute to volume with water, and mix.Standardize as follows: Transfer a 50-mL aliquot of CaCl2standard solution (1 mL = 0.00832 g CaCl2) to a 500-mLErlenmeyer flask and dilute to 200 mL with water. Proceed asdirect
24、ed in 13.2. Calculate the CaCl2equivalent of the EDTAsolution as follows:Calcium chloride equivalent, g/mL 5 0.416/A (1)where:A = millilitres of EDTA solution required for the titration ofthe CaCl2solution.12.3 Hydrochloric Acid (1+3)Mix 1 volume of concen-trated hydrochloric acid (HCl, sp gr 1.19)
25、and 3 volumes ofwater.12.4 Hydroxylamine Hydrochloride Solution(10 %)Dissolve 10 g of hydroxylamine hydrochloride (NH2OHHCl)in 90 mL of water.12.5 -Hydroxynaphthol Blue.512.6 Modified Calcein Indicator.612.7 Potassium Cyanide (KCN).12.8 Sodium Hydroxide Solution (80 g/L)Add slowly 80 gof sodium hydr
26、oxide (NaOH) in 300 mL of water stirringconstantly. Cool, transfer to a 1-L volumetric flask, dilute tovolume with water, and mix.12.9 Sugar, granulated.13. Procedure13.1 Solid SamplesWeigh 100.0 g of sample and washinto a 1000-mLvolumetric flask with water.Add 10 mLof HCl(1 + 3) and swirl to dissol
27、ve the sample. Cool to roomtemperature, make to volume with water, and mix. Pipet a20-mL aliquot into a 500-mL volumetric flask, dilute tovolume, and mix. Proceed as in 13.3.13.2 Liquid SamplesWeigh 100.0 g of sample and washinto a 1000-mLvolumetric flask with water.Add 10 mLof HCl(1 + 3) and mix. C
28、ool to room temperature, make up to volumewith water, and mix. Pipet an aliquot containing about2gofCaCl2into a 500-mL volumetric flask, dilute to volume, andmix. Appropriate aliquot volumes are indicated in the tablebelow. Interpolate if necessary.Expected CaCl2Concentration, %AliquotSize, mL10 200
29、20 10030 7540 5050 4013.3 Pipet a 100-mL aliquot of the solution prepared in 13.1or 13.2 into a 500-mLErlenmeyer flask and dilute to about 200mL with water. Add in order 10 mL of hydroxylaminehydrochloride solution and3gofsugar. Swirl to dissolve.Add40 mL of NaOH solution (12.8) and swirl to mix. Ad
30、d 0.1 g ofKCN, and swirl to dissolve and mix. Add about 0.2 g ofcalcium indicator.13.4 Titrate with 0.1 M EDTA solution until the indicatorchanges from green to purple.5Available from Mallinckrodt Inc., Paris, KY.6Available from the G. Frederick Smith Co., Columbus, OH.E449 08 (2013)2NOTE 1If -hydro
31、xynaphthol blue indicator is used, 0.4 g should beadded and the solution titrated to a blue end point.14. Calculation14.1 Calculate the calcium chloride concentration as fol-lows:Calcium chloride, % 5 A 3 B!/C# 3100 2 D (2)where:A = millilitres of EDTA solution required for titration of thesample,B
32、= calcium chloride equivalent of the EDTA solution,g/mL,C = mass of sample in the aliquot used, andD = percent calcium hydroxide expressed as calcium chlo-ride (see 31.1.1).15. Report15.1 Report the percentage of CaCl2to the nearest 0.1 %.Duplicate determinations that agree within 0.3 % absolute are
33、acceptable for averaging (95 % confidence level).16. Precision and Bias16.1 The following criteria should be used for judging theacceptability of results (see Note 2).16.1.1 Repeatability (Single Analyst)The standard devia-tion of results (each the average of duplicates), obtained by thesame analyst
34、 on different days, has been estimated to be0.139 % absolute at 28 degrees of freedom. Two such valuesshould be considered suspect (95 % confidence level) if theydiffer by more than 0.4 %.16.1.2 Reproducibility (Multilaboratory)The standard de-viation of results (each the average of duplicates), obt
35、ained byanalysts in different laboratories, has been estimated to be0.229 % absolute at 6 degrees of freedom. Two such valuesshould be considered suspect (95 % confidence level) if theydiffer by more then 0.8 % absolute.NOTE 2The precision statements are based on an interlaboratory studyperformed in
36、 1970 on two samples of solid calcium chloride. Eightlaboratories participated in the study analyzing each sample in duplicateon each of two days. Practice E180 was used in developing these precisionstatements.716.2 The bias of the test method has not been determined.MAGNESIUM CHLORIDE, POTASSIUMCHL
37、ORIDE, AND SODIUM CHLORIDE17. Scope17.1 This test method covers the determination of magne-sium chloride, potassium chloride, and sodium chloride in theranges normally encountered in calcium chloride.18. Summary of Test Method18.1 A solution of the sample is aspirated into the air-acetylene flame of
38、 an atomic absorption spectrometer. Theabsorption of a resonance line from the spectrum of each cationis measured and compared with the response of the instrumentto calibration solutions of the same elements. Recommendedlines are: magnesium (2852 ), potassium (7664 ), andsodium (5889 ).19. Concentra
39、tion Range19.1 The concentration range for each cation must beselected to correspond with the optimum range of the instru-ment employed. Higher or lower concentration ranges may berequired for different instruments or different source lamps.20. Interferences20.1 Elements normally present in calcium
40、chloride do notinterfere with these determinations.21. Apparatus21.1 Atomic Absorption Spectrophotometer, capable of iso-lating the resonance line chosen for each cation sufficiently toavoid interference from other elements in the samples beinganalyzed.22. Reagents22.1 Calcium Chloride SolutionRefer
41、 to 12.1.22.2 Hydrochloric Acid (1+3)Refer to 12.3.22.3 Magnesium Chloride, Standard Solution (1mL = 0.050 mg MgCl2)Dissolve 0.128 g of 99.9 % magne-sium metal in 50 mL of HCl (1 + 3) in a covered 250-mLbeaker. Heat gently, if necessary, to complete solution. Cooland transfer to a 1-L volumetric fla
42、sk. Dilute to volume withwater and mix. Pipet 10.0 mL of this solution into a 100-mLvolumetric flask. Dilute to volume with water and mix.22.4 Potassium Chloride, Standard Solution (1 mL = 0.300mg KCl)Dissolve 0.300 g of potassium chloride (KCl) inwater and dilute to 1 L in a volumetric flask.22.5 S
43、odium Chloride, Standard Solution (1 mL = 0.100 mgNaCl)Dissolve 1.000 g of sodium chloride (NaCl) in waterand dilute to 1 L in a volumetric flask. Pipet 10.0 mL of thissolution into a 100-mL volumetric flask. Dilute to volume withwater and mix.23. Procedure23.1 Pipet a 10.0-mLaliquot of the solution
44、 prepared in 13.1or 13.2 into a 100-mL volumetric flask. Dilute to volume withwater and mix.23.2 To five 100-mL volumetric flasks add 2, 4, 6, 8, and 10mL of each standard solution respectively and 5 mL of CaCl2solution. Dilute to volume with water and mix.23.3 Prepare a zero calibration solution by
45、 adding 5 mL ofCaCl2solution to a 100-mL volumetric flask and dilute tovolume with water.23.4 Instrument Settings:23.4.1 Set the instrument parameters to values recom-mended by the manufacturer.23.4.2 Select the proper wavelength for the element to bedetermined and, if appropriate, adjust for maximu
46、m response.7Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: RR:E15-1015.E449 08 (2013)323.4.3 Optimize fuel, air, and burner adjustments whileaspirating a calibration solution.23.4.4 When the instrument has operated long enough
47、toattain stability adjust the readout to 100 % transmittance(percent T) or 0 absorbance (percent A) with water. Aspirateand record the readings of the standard samples with a briefwater aspiration after each. Repeat the process with sample,standards, sample and again standards, adjusting the zerobet
48、ween runs if necessary.24. Calculation24.1 Correct the average of the calibration solution readingsby subtracting the average zero calibration solution reading(expressed in absorbance units).24.2 Prepare a calibration curve by plotting the correctedabsorbance values for the calibration solutions ver
49、sus themicrograms of compound in 100 mL of solution.24.3 Read the micrograms of compound in the samplesolutions from the calibration curve. Calculate the percentagecompound as follows:Compound, % 5 A/B 3104(3)where:A = micrograms of compound in 100 mL of samplesolution,B = grams of sample in 100 mL of sample solution,percent KCl as percent NaCl = percent KCl 0.7839, andpercent alkali chlorides as NaCl = percent NaCl + percentKCl as NaCl.25. Report25.1 Report the percentage of MgCl2to the nearest 0.01 %.Duplicate determinations that agree within 0.
