1、Designation: E 449 96 (Reapproved 2001)Standard Test Methods forAnalysis of Calcium Chloride1This standard is issued under the fixed designation E 449; 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 (e) 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-r
3、ide 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 Chloride
4、17 to 26Calcium Hydroxide 27 to 331.3 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 appro-priate safety and health practices and determine the applica-bility of regulatory limita
5、tions prior to use. Specific hazardstatements are given in Section 5.1.4 Review the current Material Safety Data Sheet (MSDS)for detailed information concerning toxicity, first aid proce-dures, handling, and safety precautions.2. Referenced Documents2.1 ASTM Standards:D 345 Test Method for Sampling
6、and Testing CalciumChloride for Roads and Structural Applications2D 1193 Specification for Reagent Water3E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial Chemicals4E 200 Practice for Preparation, Standardization, and Stor-age of Standard and Reagent
7、Solutions for ChemicalAnalysis4E 663 Practice for Flame Atomic Absorption Analysis53. Significance and Use3.1 Calcium chloride is available in 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
8、foods, in electrolytic cells, and in refrigera-tion brines. The test methods listed in 1.2 provide proceduresfor analyzing calcium chloride to determine if it is suitable forits intended use.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicate
9、d, these shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.6Other grades may be used, pro-vided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening
10、the accuracy ofthe determination.4.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean Type II or Type IIIreagent water conforming to Specification D 1193.5. Hazards5.1 While calcium chloride is a relatively harmless material,some of the reagents used in these
11、 methods present possiblesafety hazards. Potassium cyanide is extremely hazardous andmust be handled with great care. In addition to being poison-ous, solutions containing cyanide should never be mixed withacids to preclude the release of poisonous hydrogen cyanidegas. Concentrated hydrochloric acid
12、 and sodium hydroxidealso are hazardous chemicals which may produce serious burnson contact.6. Atomic Absorption Spectrophotometers6.1 Photometers and photometric practice used in thesemethods shall conform to Practice E 663.1These test methods are under the jurisdiction of ASTM Committee E15 onIndu
13、strial and Specialty Chemicalsand are the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved Dec. 10, 1996. Published June 1997. Originallypublished as E 449 72 T. Last previous edition E 449 90.2Annual Book of ASTM Standards, Vol 04.03.3Annual Book of ASTM Sta
14、ndards, Vol 11.01.4Annual Book of ASTM Standards, Vol 15.05.5Annual Book of ASTM Standards, Vol 03.06.6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Ana
15、lar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.7. Sampling7.1 Sampling of
16、 calcium chloride is not within the scope ofthese test methods. See the appropriate sections of Test MethodD 345.7.2 The sample to be analyzed shall be considered to be thatsample in a single bottle submitted to the analytical laboratory.7.3 The size of the sample shall be sufficient to perform alla
17、nalyses 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 solution is titrated with standardethylenediaminetetraacetate solution, usi
18、ng modified calcein IIas an indicator. The color change is from green to purple. a-hydroxynaphthol blue is also suitable as an indicator, in whichcase the color change is from red to blue.10. Interferences10.1 Strontium and other cations not complexed with cya-nide at pH of at least 10 will consume
19、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 (1mL = 0.00832 g CaCl2)Weigh 7.500 g of primary standardcalcium carbonate
20、(CaCO3). Transfer to a 600-mL beaker andadd 300 mL of water. Cover with a watch glass and slowly addto the beaker, while stirring, 15 mL of concentrated hydrochlo-ric acid (HCl) delivered from a pipet inserted between the lipof the beaker and the edge of the watch glass. When dissolutionof the CaCO3
21、is 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 (0.1M)Dissolve 37.22 g of disodium dihydrogen ethylenedi-aminetetraacetate dihydrate (EDTA) in water. Transfer to a 1-Lvolumetric
22、 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 asdirected in 13.2. Calculate the CaCl2equivalent of the EDTAsolution as follows:Calci
23、um 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) and 3 volumes ofwater.12.4 Hydroxylamine Hydrochloride Solution(10 %)Dissolv
24、e 10 g of hydroxylamine hydrochloride (NH2OHHCl)in 90 mL of water.12.5 a-Hydroxynaphthol Blue.712.6 Modified Calcein Indicator.812.7 Potassium Cyanide (KCN).12.8 Sodium Hydroxide Solution (80 g/L)Add slowly 80 gof sodium hydroxide (NaOH) in 300 mL of water stirringconstantly. Cool, transfer to a 1-L
25、 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-mL volumetric flask with water. Add 10 mL of HCl(1 + 3) and swirl to dissolve the sample. Cool to roomtemperature, make to volume with water, and m
26、ix. 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-mL volumetric flask with water. Add 10 mL of HCl(1 + 3) and mix. Cool to room temperature, make up to volumewith water, and mix. Pipet
27、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 20020 10030 7540 5050 4013.3 Pipet a 100-mL aliquot of the solution prep
28、ared in 13.1or 13.2 into a 500-mL Erlenmeyer 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. Add 0.1 g ofKCN, and swirl to dissolve and mix. Add about 0.2 g of ca
29、lceinindicator.13.4 Titrate with 0.1 M EDTA solution until the indicatorchanges from green to purple.NOTE 1If a-hydroxynaphthol 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:Calc
30、ium chloride, % 5 A 3 B!/C8# 3 100 2 D (2)where:A = millilitres of EDTA solution required for titration ofthe sample,B = calcium chloride equivalent of the EDTA solution,g/mL,C8 = mass of sample in the aliquot used, and7Available from Mallinckrodt Inc., Paris, KY.8Available from the G. Frederick Smi
31、th Co., Columbus, OH.E 4492D = 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 areacceptable for averaging (95 % confidence level).16. Precision and Bias1
32、6.1 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 on different days, has been estimated to be0.139 % absolute at 28 degre
33、es 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), obtained byanalysts in different laboratories, has been estimated to be0.22
34、9 % 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 interlaboratorystudy performed in 1970 on two samples of solid calcium chloride. Eightlaboratories partic
35、ipated in the study analyzing each sample in duplicateon each of two days. Practice E 180 was used in developing theseprecision statements.916.2 The bias of the test method has not been determined.MAGNESIUM CHLORIDE, POTASSIUMCHLORIDE, AND SODIUM CHLORIDE17. Scope17.1 This test method covers the det
36、ermination 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 an atomic absorption spectrometer. Theabsorption of a resonance line f
37、rom 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. Concentration Range19.1 The concentration range for each cation must beselected
38、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 chloride do notinterfere with these determinations.21. Apparatus21.1 At
39、omic 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 to 12.1.22.2 Hydrochloric Acid (1 + 3)Refer to 12.3.22.3 Magnesium Chl
40、oride, 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 flask. Dilute to volume withwater and mix. Pipet 10.0 mL of this solutio
41、n 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 Sodium Chloride, Standard Solution (1 mL = 0.100mg NaCl)Dissolve 1.000
42、 g of sodium chloride (NaCl) inwater and dilute to 1 L in a volumetric flask. Pipet 10.0 mL ofthis solution into a 100-mL volumetric flask. Dilute to volumewith water and mix.23. Procedure23.1 Pipet a 10.0-mL aliquot of the solution prepared in 13.1or 13.2 into a 100-mL volumetric flask. Dilute to v
43、olume 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 adding 5 mL ofCaCl2solution to a 100-mL volumetric flask and dilute
44、 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 maximum response.23.4.3 Optimize fuel, air, and burner adjustments whileas
45、pirating a calibration solution.23.4.4 When the instrument has operated long enough 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
46、the process with sample,standards, sample and again standards, adjusting the zerobetween 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 calibratio
47、n curve by plotting the correctedabsorbance values for the calibration solutions versus themicrograms of compound in 100 mL of solution.24.3 Read the micrograms of compound in the samplesolutions from the calibration curve. Calculate the percentage9Supporting data are available from ASTM Headquarter
48、s, as RR:E15-1015.E 4493compound as follows:Compound, % 5 A/B 3 104(3)where:A = micrograms of compound in 100 mL of sample solu-tion,B = grams of sample in 100 mL of sample solution,percent KCl as percent NaCl = percent KCl 3 0.7839, andpercent alkali chlorides as NaCl = percent NaCl + percentKCl as
49、 NaCl.25. Report25.1 Report the percentage of MgCl2to the nearest 0.01 %.Duplicate determinations that agree within 0.01 % absolute areacceptable for averaging (95 % confidence level). See Note 3.25.2 Report the percentage of KCl to the nearest 0.01 %.Duplicate determinations that agree within 0.12 % absolute areacceptable for averaging (95 % confidence level).25.3 Report the percentage of NaCl to the nearest 0.01 %.Duplicate determinations that agree within 0.05 % absolute areacceptable for averaging (95 % confidence level).25.4 Report the percentage of alkal
