ASTM E449-18

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it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: E449 − 08 (Reapproved 2013) E449 − 18
Standard Test Methods for
Analysis of Calcium Chloride
This standard is issued under the fixed designation E449; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope Scope*
1.1 These test methods cover the analysis of calcium chloride and solutions.
1.2 Procedures are given for the determination of calcium chloride, magnesium chloride, potassium chloride, sodium chloride,
and calcium hydroxide. The test methods appear in the following order:
Sections
Calcium Chloride 8 to 16
Calcium Chloride 8 to 17
Magnesium Chloride, Potassium Chloride, 17 to 26
and Sodium Chloride
Magnesium Chloride, Potassium Chloride, 18 to 28
and Sodium Chloride
Calcium Hydroxide 27 to 33
Calcium Hydroxide 29 to 36
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.4 Review the current Safety Data Sheet (SDS) for detailed information concerning toxicity, first aid procedures, handling, and
safety precautions.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 5.
1.5 Review the current Material Safety Data Sheet (MSDS) for detailed information concerning toxicity, first aid procedures,
handling, and safety precautions.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D345 Test Method for Sampling and Testing Calcium Chloride for Roads and Structural Applications
D1193 Specification for Reagent Water
D6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
E180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals
(Withdrawn 2009)
E200 Practice for Preparation, Standardization, and Storage of Standard and Reagent Solutions for Chemical Analysis
E663 Practice for Flame Atomic Absorption Analysis (Withdrawn 1997)
These test methods are under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons Aromatic, Industrial, Specialty and Related Chemicals and are the
direct responsibility of Subcommittee D16.16 on Industrial and Specialty Product Standards.
Current edition approved June 1, 2013Feb. 1, 2018. Published June 2013April 2018. Originally approved in 1972. Last previous edition approved in 20082013 as
E449 – 08.E449 – 08 (2013). DOI: 10.1520/E0449-08R13.10.1520/E0449-18.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E449 − 18
3. Significance and Use
3.1 Calcium chloride is available in various forms and purities. A major use is the de-icing and dust control of roads. It is also
used in the coal industry for dustproofing and freezeproofing, in foods, in electrolytic cells, and in refrigeration brines. The test
methods listed in 1.2 provide procedures for analyzing calcium chloride to determine if it is suitable for its intended use.
4. Reagents
4.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, these shall conform to
the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are
available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
4.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean Type II or Type III reagent
water conforming to Specification D1193.
5. Hazards
5.1 While calcium chloride is a relatively harmless material, some of the reagents used in these methods present possible safety
hazards. Potassium cyanide is extremely hazardous and must be handled with great care. In addition to being poisonous, solutions
containing cyanide should never be mixed with acids to preclude the release of poisonous hydrogen cyanide gas. Concentrated
hydrochloric acid and sodium hydroxide also are hazardous chemicals which may produce serious burns on contact.
6. Atomic Absorption Spectrophotometers
6.1 Photometers and photometric practice used in these methods shall conform to Practice E663.
7. Sampling
7.1 Sampling of calcium chloride is not within the scope of these test methods. See the appropriate sections of Test Method
D345.
7.2 The sample to be analyzed shall be considered to be that sample in a single bottle submitted to the analytical laboratory.
7.3 The size of the sample shall be sufficient to perform all analyses without the reuse of any portion of the sample.
CALCIUM CHLORIDE
8. Scope
8.1 This test method covers the determination of calcium chloride in the range from 0 to 100 %.
8. Scope
8.1 This test method covers the determination of calcium chloride in the range from 0 to 100 %.
9. Summary of Test Method
9.1 Calcium in an alkaline solution is titrated with standard ethylenediaminetetraacetate solution, using modified calcein II as
an indicator. The color change is from green to purple. α -hydroxynaphthol blue is also suitable as an indicator, in which case the
color change is from red to blue.
10. Interferences
10.1 Strontium and other cations not complexed with cyanide at pH of at least 10 will consume ethylenediaminetetraacetate
solution and will affect the accuracy of this test method.
11. Apparatus
11.1 Buret, 50-mL, Class A.
11.2 Weighing Bottle, glass-stoppered, 100-mL.
12. Reagents
12.1 Calcium Chloride, Standard Solution (1 mL = 0.00832 g CaCl )—Weigh 7.500 g of primary standard calcium carbonate
(CaCO ). Transfer to a 600-mL beaker and add 300 mL of water. Cover with a watch glass and slowly add to the beaker, while
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.
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stirring, 15 mL of concentrated hydrochloric acid (HCl) delivered from a pipet inserted between the lip of the beaker and the edge
of the watch glass. When dissolution of the CaCO is complete, boil gently to expel CO . Cool, and transfer to a 1-L volumetric
3 2
flask. Dilute to volume with water and mix.
12.2 Ethylenediaminetetraacetate, Standard Solution (0.1 mol/L (M))—Dissolve 37.22 g of disodium dihydrogen ethylenedi-
aminetetraacetate dihydrate (EDTA) in water. Transfer to a 1-L volumetric flask, dilute to volume with water, and mix. Standardize
as follows: Transfer a 50-mL aliquot of CaCl standard solution (1 mL = 0.00832 g CaCl ) to a 500-mL Erlenmeyer flask and dilute
2 2
to 200 mL with water. Proceed as directed in 13.2. Calculate the CaCl equivalent of the EDTA solution as follows:
Calcium chloride equivalent, g/mL 5 0.416/A (1)
where:
A = millilitres of EDTA solution required for the titration of the CaCl solution.
12.3 Hydrochloric Acid (1 + 3)—Mix 1 volume of concentrated hydrochloric acid (HCl, sp gr 1.19) and 3 volumes of water.
12.4 Hydroxylamine Hydrochloride Solution—(10 %)—Dissolve 10 g of hydroxylamine hydrochloride (NH OH·HCl) in 90 mL
of water.
12.5 α-Hydroxynaphthol Blue.
12.6 Modified Calcein Indicator.
12.7 Potassium Cyanide (KCN).
12.8 Sodium Hydroxide Solution (80 g/L)—Add slowly 80 g of sodium hydroxide (NaOH) in 300 mL of water stirring
constantly. Cool, transfer to a 1-L volumetric flask, dilute to volume with water, and mix.
12.9 Sugar, granulated.
13. Procedure
13.1 Solid Samples—Weigh 100.0 g of sample and wash into a 1000-mL volumetric flask with water. Add 10 mL of HCl (1 + 3)
and swirl to dissolve the sample. Cool to room temperature, make to volume with water, and mix. Pipet a 20-mL aliquot into a
500-mL volumetric flask, dilute to volume, and mix. Proceed as in 13.3.
13.2 Liquid Samples—Weigh 100.0 g of sample and wash into a 1000-mL volumetric flask with water. Add 10 mL of HCl
(1 + 3) and mix. Cool to room temperature, make up to volume with water, and mix. Pipet an aliquot containing about 2 g of CaCl
into a 500-mL volumetric flask, dilute to volume, and mix. Appropriate aliquot volumes are indicated in the table below. Interpolate
if necessary.
Expected CaCl Aliquot
Concentration, % Size, mL
10 200
20 100
30 75
40 50
50 40
13.3 Pipet a 100-mL aliquot of the solution prepared in 13.1 or 13.2 into a 500-mL Erlenmeyer flask and dilute to about 200
mL with water. Add in order 10 mL of hydroxylamine hydrochloride solution and 3 g of sugar. Swirl to dissolve. Add 40 mL of
NaOH solution (12.8) and swirl to mix. Add 0.1 g of KCN, and swirl to dissolve and mix. Add about 0.2 g of calcium indicator.
13.4 Titrate with 0.1 M EDTA solution until the indicator changes from green to purple.
NOTE 1—If α-hydroxynaphthol blue indicator is used, 0.4 g should be added and the solution titrated to a blue end point.
13.5 Analyze sample in duplicate.
14. Calculation
14.1 Calculate the calcium chloride concentration as follows:
Calcium chloride,%5 @~A 3B!/C'# 3100 2 D (2)
where:
A = millilitres of EDTA solution required for titration of the sample,
B = calcium chloride equivalent of the EDTA solution, g/mL,
C' = mass of sample in the aliquot used, and
D = percent calcium hydroxide expressed as calcium chloride (see 31.1.1).
D = percent calcium hydroxide expressed as calcium chloride (see 33.1.1).
14.2 Average the duplicate results. Duplicate determinations that agree within 0.3 % absolute are acceptable for averaging
(95 % confidence level).
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15. Report
15.1 Report the percentage of CaCl to the nearest 0.1 %. Duplicate determinations that agree within 0.3 % absolute are
acceptable for averaging (95 % confidence level).
16. Precision and Bias
16.1 The following criteria should be used An ILS was conducted which included eight laboratories analyzing two samples.
Each sample was analyzed in duplicate on two different days. Practice E180 was followed for judging the acceptability of results
(seethe design and analysis of the data; Note 2).the details are given is ASTM Research Report RR:E15-1015.
16.1.1 Intermediate Precision, formerly called Repeatability (Single Analyst)—The standard deviation of results (each the
average of duplicates), obtained by the same analyst on different days, has been estimated to be 0.139 % absolute at 28 degrees
of freedom. Two such values should be considered suspect (95 % confidence level) if they differ by more than 0.4 %.
16.1.2 Reproducibility (Multilaboratory)—The standard deviation of results (each the average of duplicates), obtained by
analysts in different laboratories, has been estimated to be 0.229 % absolute at 6 degrees of freedom. Two such values should be
considered suspect (95 % confidence level) if they differ by more then 0.8 % absolute.
NOTE 2—The precision statements are based on an interlaboratory study performed in 1970 on two samples of solid calcium chloride. Eight laboratories
participated in the study analyzing each sample in duplicate on each of two days. Practice E180 was used in developing these precision statements.
16.2 The bias of the test this method has not yet been determined.
17. Quality Guidelines
17.1 Laboratories shall have a quality control system in place.
17.1.1 Confirm the performance of the test instrument or test method by analyzing a quality control sample following the
guidelines of standard statistical quality control practices.
17.1.2 A quality control sample is a stable material isolated from the production process and representative of the sample being
analyzed.
17.1.3 When QA/QC protocols are already established in the testing facility, these protocols are acceptable when they confirm
the validity of test results.
17.1.4 When there are no QA/QC protocols established in the testing facility, use the guidelines described in Guide D6809 or
similar statistical quality control
...