Designation: E 449 – 96

AMERICAN SOCIETY FOR TESTING AND MATERIALS

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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Analysis of Calcium Chloride1
This standard is issued under the fixed designation E 449; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope It is also used in the coal industry for dustproofing and

1.1 These test methods cover the analysis of calcium chlo- freezeproofing, in foods, in electrolytic cells, and in refrigera-
ride and solutions. tion brines. The test methods listed in 1.2 provide procedures
1.2 Procedures are given for the determination of calcium for analyzing calcium chloride to determine if it is suitable for
chloride, magnesium chloride, potassium chloride, sodium its intended use.
chloride, and calcium hydroxide. The test methods appear in 4. Reagents
the following order:
4.1 Purity of Reagents—Reagent grade chemicals shall be
Sections
Calcium Chloride 8 to 16 used in all tests. Unless otherwise indicated, these shall
Magnesium Chloride, Potassium Chloride, 17 to 26 conform to the specifications of the Committee on Analytical
and Sodium Chloride Reagents of the American Chemical Society, where such
Calcium Hydroxide 27 to 33
specifications are available.6 Other grades may be used, pro-
1.3 This standard does not purport to address all of the vided it is first ascertained that the reagent is of sufficiently
safety concerns, if any,associated with its use. It is the high purity to permit its use without lessening the accuracy of
responsibility of the user of this standard to establish appro- the determination.
priate safety and health practices and determine the applica- 4.2 Purity of Water—Unless otherwise indicated, references
bility of regulatory limitations prior to useSpecific hazard to water shall be understood to mean Type II or Type III
statements are given in Section 5. reagent water conforming to Specification D 1193.
1.4 Review the current Material Safety Data Sheet (MSDS)
for detailed information concerning toxicity, first aid proce- 5. Hazards
dures, handling, and safety precautions. 5.1 While calcium chloride is a relatively harmless material,
some of the reagents used in these methods present possible
2. Referenced Documents safety hazards. Potassium cyanide is extremely hazardous and
2.1 ASTM Standards: must be handled with great care. In addition to being poison-
D 345 Test Method for Sampling and Testing Calcium ous, solutions containing cyanide should never be mixed with
Chloride for Roads and Structural Applications2 acids to preclude the release of poisonous hydrogen cyanide
D 1193 Specification for Reagent Water3 gas. Concentrated hydrochloric acid and sodium hydroxide
E 180 Practice for Determining the Precision of ASTM also are hazardous chemicals which may produce serious burns
Methods for Analysis and Testing of Industrial Chemicals4 on contact.
E 200 Practice for Preparation, Standardization, and Stor-
age of Standard and Reagent Solutions for Chemical 6. Atomic Absorption Spectrophotometers
Analysis4 6.1 Photometers and photometric practice used in these
E 663 Practice for Flame Atomic Absorption Analysis5 methods shall conform to Practice E 663.

3. Significance and Use 7. Sampling

3.1 Calcium chloride is available in various forms and 7.1 Sampling of calcium chloride is not within the scope of
purities. A major use is the de-icing and dust control of roads. these test methods. See the appropriate sections of Test Method
D 345.
7.2 The sample to be analyzed shall be considered to be that
1
These test methods are under the jurisdiction of ASTM Committee E-15 on sample in a single bottle submitted to the analytical laboratory.
Industrial Chemicals and are the direct responsibility of Subcommittee E15.52 on
Alkalies.
6
Current edition approved Dec. 10, 1996. Published June 1997. Originally Reagent Chemicals, American Chemical Society Specifications, American
published as E 449 – 72 T. Last previous edition E 449 – 90. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
Annual Book of ASTM Standards, Vol 04.03. listed by the American Chemical Society, see Analar Standards for Laboratory
3
Annual Book of ASTM Standards, Vol 11.01. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
4
Annual Book of ASTM Standards, Vol 15.05. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
5
Annual Book of ASTM Standards, Vol 03.06. MD.

1
 E 449
7.3 The size of the sample shall be sufficient to perform all 12.5 a-Hydroxynaphthol Blue. 7
analyses without the reuse of any portion of the sample. 12.6 Modified Calcein Indicator. 8
12.7 Potassium Cyanide (KCN).
CALCIUM CHLORIDE 12.8 Sodium Hydroxide Solution (80 g/L)—Add slowly 80 g
of sodium hydroxide (NaOH) in 300 mL of water stirring
8. Scope constantly. Cool, transfer to a 1-L volumetric flask, dilute to
volume with water, and mix.
8.1 This test method covers the determination of calcium
12.9 Sugar, granulated.
chloride in the range from 0 to 100 %.
13. Procedure
9. Summary of Test Method 13.1 Solid Samples—Weigh 100.0 g of sample and wash
9.1 Calcium in an alkaline solution is titrated with standard into a 1000-mL volumetric flask with water. Add 10 mL of HCl
ethylenediaminetetraacetate solution, using modified calcein II (1 + 3) and swirl to dissolve the sample. Cool to room
as an indicator. The color change is from green to purple. a temperature, make to volume with water, and mix. Pipet a
-hydroxynaphthol blue is also suitable as an indicator, in which 20-mL aliquot into a 500-mL volumetric flask, dilute to
case the color change is from red to blue. volume, and mix. Proceed as in 13.3.
13.2 Liquid Samples—Weigh 100.0 g of sample and wash
10. Interferences 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
10.1 Strontium and other cations not complexed with cya- with water, and mix. Pipet an aliquot containing about 2 g of
nide at pH of at least 10 will consume ethylenediaminetetraac- CaCl2 into a 500-mL volumetric flask, dilute to volume, and
etate solution and will affect the accuracy of this test method. mix. Appropriate aliquot volumes are indicated in the table
below. Interpolate if necessary.
11. Apparatus Expected CaCl2 Aliquot
Concentration, % Size, mL
11.1 Buret, 50-mL, Class A. 10 200
11.2 Weighing Bottle, glass-stoppered, 100-mL. 20 100
30 75
40 50
12. Reagents 50 40

12.1 Calcium Chloride, Standard Solution (1 13.3 Pipet a 100-mL aliquot of the solution prepared in 13.1
mL 5 0.00832 g CaCl2)—Weigh 7.500 g of primary standard or 13.2 into a 500-mL Erlenmeyer flask and dilute to about 200
calcium carbonate (CaCO3). Transfer to a 600-mL beaker and mL with water. Add in order 10 mL of hydroxylamine
add 300 mL of water. Cover with a watch glass and slowly add hydrochloride solution and 3 g of sugar. Swirl to dissolve. Add
to the beaker, while stirring, 15 mL of concentrated hydrochlo- 40 mL of NaOH solution (12.8) and swirl to mix. Add 0.1 g of
ric acid (HCl) delivered from a pipet inserted between the lip KCN, and swirl to dissolve and mix. Add about 0.2 g of calcein
of the beaker and the edge of the watch glass. When dissolution indicator.
of the CaCO3 is complete, boil gently to expel CO2. Cool, and 13.4 Titrate with 0.1 M EDTA solution until the indicator
transfer to a 1-L volumetric flask. Dilute to volume with water changes from green to purple.
and mix.
NOTE 1—If a-hydroxynaphthol blue indicator is used, 0.4 g should be
12.2 Ethylenediaminetetraacetate, Standard Solution (0.1 added and the solution titrated to a blue end point.
M)—Dissolve 37.22 g of disodium dihydrogen ethylenedi-
aminetetraacetate dihydrate (EDTA) in water. Transfer to a 1-L 14. Calculation
volumetric flask, dilute to volume with water, and mix. 14.1 Calculate the calcium chloride concentration as
Standardize as follows: Transfer a 50-mL aliquot of CaCl2 follows:
standard solution (1 mL 5 0.00832 g CaCl2) to a 500-mL Calcium chloride, % 5 @~A 3 B!/C8# 3 100 2 D (2)
Erlenmeyer flask and dilute to 200 mL with water. Proceed as
directed in 13.2. Calculate the CaCl2 equivalent of the EDTA where:
solution as follows: A 5 millilitres of EDTA solution required for titration of
Calcium chloride equivalent, g/mL 5 0.416/A (1) the sample,
B 5 calcium chloride equivalent of the EDTA solution,
where: g/mL,
A 5 millilitres of EDTA solution required for the titration of C8 5 mass of sample in the aliquot used, and
the CaCl2 solution. D 5 percent calcium hydroxide expressed as calcium
12.3 Hydrochloric Acid (1 + 3)—Mix 1 volume of chloride (see 31.1.1).
concentrated hydrochloric acid (HCl, sp gr 1.19) and 3 15. Report
volumes of water. 15.1 Report the percentage of CaCl2 to the nearest 0.1 %.
12.4 Hydroxylamine Hydrochloride Solution—(10 %)—
Dissolve 10 g of hydroxylamine hydrochloride (NH2OH·HCl) 7
Available from Mallinckrodt Inc., Paris, KY.
in 90 mL of water. 8
Available from the G. Frederick Smith Co., Columbus, OH.

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 E 449
Duplicate determinations that agree within 0.3 % absolute are 22. Reagents
acceptable for averaging (95 % confidence level). 22.1 Calcium Chloride Solution—Refer to 12.1.
16. Precision and Bias 22.2 Hydrochloric Acid (1 + 3)—Refer to 12.3.
16.1 The following criteria should be used for judging the 22.3 Magnesium Chloride, Standard Solution (1
acceptability of results (see Note 2). mL 5 0.050 mg MgCl2)—Dissolve 0.128 g of 99.9 %
16.1.1 Repeatability (Single Analyst)—The standard magnesium metal in 50 mL of HCl (1 + 3) in a covered 250-mL
deviation of results (each the average of duplicates), obtained beaker. Heat gently, if necessary, to complete solution. Cool
by the same analyst on different days, has been estimated to be and transfer to a 1-L volumetric flask. Dilute to volume with
0.139 % absolute at 28 degrees of freedom. Two such values water and mix. Pipet 10.0 mL of this solution into a 100-mL
should be considered suspect (95 % confidence level) if they volumetric flask. Dilute to volume with water and mix.
differ by more than 0.4 %. 22.4 Potassium Chloride, Standard Solution (1
16.1.2 Reproducibility (Multilaboratory)—The standard mL 5 0.300 mg KCl)—Dissolve 0.300 g of potassium chloride
deviation of results (each the average of duplicates), obtained (KCl) in water and dilute to 1 L in a volumetric flask.
by analysts in different laboratories, has been estimated to be 22.5 Sodium Chloride, Standard Solution (1 mL 5 0.100
0.229 % absolute at 6 degrees of freedom. Two such values mg NaCl)—Dissolve 1.000 g of sodium chloride (NaCl) in
should be considered suspect (95 % confidence level) if they water and dilute to 1 L in a volumetric flask. Pipet 10.0 mL of
differ by more then 0.8 % absolute. this solution into a 100-mL volumetric flask. Dilute to volume
with water and mix.
NOTE 2—The precision statements are based on an interlaboratory
study performed in 1970 on two samples of solid calcium chloride. Eight 23. Procedure
laboratories participated in the study analyzing each sample in duplicate
on each of two days. Practice E 180 was used in developing these 23.1 Pipet a 10.0-mL aliquot of the solution prepared in 13.1
precision statements.9 or 13.2 into a 100-mL volumetric flask. Dilute to volume with
16.2 The bias of the test method has not been determined. water and mix.
23.2 To five 100-mL volumetric flasks add 2, 4, 6, 8, and 10
MAGNESIUM CHLORIDE, POTASSIUM mL of each standard solution respectively and 5 mL of CaCl2
CHLORIDE, AND SODIUM CHLORIDE solution. Dilute to volume with water and mix.
17. Scope 23.3 Prepare a zero calibration solution by adding 5 mL of
CaCl2 solution to a 100-mL volumetric flask and dilute to
17.1 This test method covers the determination of volume with water.
magnesium chloride, potassium chloride, and sodium chloride
23.4 Instrument Settings:
in the ranges normally encountered in calcium chloride.
23.4.1 Set the instrument parameters to values
18. Summary of Test Method recommended by the manufacturer.
18.1 A solution of the sample is aspirated into the air- 23.4.2 Select the proper wavelength for the element to be
acetylene flame of an atomic absorption spectrometer. The determined and, if appropriate, adjust for maximum response.
absorption of a resonance line from the spectrum of each cation 23.4.3 Optimize fuel, air, and burner adjustments while
is measured and compared with the response of the instrument aspirating a calibration solution.
to calibration solutions of the same elements. Recommended 23.4.4 When the instrument has operated long enough to
lines are: magnesium (2852 Å), potassium (7664 Å), and attain stability adjust the readout to 100 % transmittance
sodium (5889 Å). (percent T) or 0 absorbance (percent A) with water. Aspirate
and record the readings of the standard samples with a brief
19. Concentration Range water aspiration after each. Repeat the process with sample,
19.1 The concentration range for each cation must be standards, sample and again standards, adjusting the zero
selected to correspond with the optimum range of the between runs if necessary.
instrument employed. Higher or lower concentration ranges
may be required for different instruments or different source 24. Calculation
lamps. 24.1 Correct the average of the calibration solution readings
20. Interferences by subtracting the average zero calibration solution reading
(expressed in absorbance units).
20.1 Elements normally present in calcium chloride do not
interfere with these determinations. 24.2 Prepare a calibration curve by plotting the corrected
absorbance values for the calibration solutions versus the
21. Apparatus micrograms of compound in 100 mL of solution.
21.1 Atomic Absorption Spectrophotometer, capable of 24.3 Read the micrograms of compound in the sample
isolating the resonance line chosen for each cation sufficiently solutions from the calibration curve. Calculate the percentage
to avoid interference from other elements in the samples being compound as follows:
analyzed. Compound, % 5 A/~B 3 10 4 (3)

9 where:
Supporting data are available from ASTM Headquarters, as RR:E15-1015.

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 E 449

A 5 micrograms of compound in 100 mL of sample hydroxide in the range from 0.01 to 1.0 %.
solution,
28. Summary of Test Method
B 5 grams of sample in 100 mL of sample solution,
percent KCl as percent NaCl 5 percent KCl 3 0.7839, and 28.1 The sample is dissolved in water and titrated with
percent alkali chlorides as NaCl 5 percent NaCl + percent standard hydrochloric acid to the phenolphthalein end point.
KCl as NaCl. 29. Reagents
25. Report 29.1 Hydrochloric Acid, Standard (0.1 N)—Prepare and
25.1 Report the percentage of MgCl2 to the nearest 0.01 %. standardize in accordance with Practice E 200.
Duplicate determinations that agree within 0.01 % absolute are 29.2 Phenolphthalein Indicator Solution (10 g/L)—Prepare
acceptable for averaging (95 % confidence level). See Note 3. in accordance with Practice E 200.
25.2 Report the percentage of KCl to the nearest 0.01 %.
Duplicate determinations that agree within 0.12 % absolute are 30. Procedure
acceptable for averaging (95 % confidence level). 30.1 Weigh to 60.1 g about 10 g of solid sample or an
25.3 Report the percentage of NaCl to the nearest 0.01 %. equivalent weight of solution. Dissolve solid samples in 25 mL
Duplicate determinations that agree within 0.05 % absolute are of water. If necessary dilute liquid samples to 25 to 30 mL.
acceptable for averaging (95 % confidence level). Cool if necessary; add 1 drop of phenolphthalein indicator
25.4 Report the percentage of alkali chlorides to the nearest solution and titrate with 0.1 N HCl solution until the red color
0.01 %. Duplicate determinations that agree within 0.12 % nearly dissappears.
absolute are acceptable for averaging (95 % confidence level).
31. Calculation
26. Precision and Bias 31.1 Calculate the percent Ca(OH)2, P, as follows:
26.1 The following criteria should be used for judging the P 5 @~M 3 H 3 0.03705!/G# 3 100 (4)
acceptability of results: (See Note 2 and Note 3.)
26.1.1 Repeatability (Single Analyst)—Estimates of the where:
standard deviation of results, in percent absolute, (each result M 5 millilitres of HCl required for titration of the sample,
the average of duplicates), obtained by the same analyst on H 5 normality of the HCl, and
different days are shown in Table 1 with the applicable degrees G 5 grams of sample.
of freedom. Two such values should be considered suspect 31.1.1 Convert P to percent CaCl2, C8, as follows:
(95 % confidence level) if they differ by more than the C8 5 P 3 1.4978 (5)
indicated percent absolute.
26.1.2 Reproducibility (Multilaboratory)—Estimates of the where:
standard deviation of results, in percent absolute, (each result P 5 percent calcium hydroxide.
the average of duplicates), obtained by analysts in different 32. Report
laboratories are shown in Table 1 with applicable degrees of
32.1 Report the percentage of Ca(OH)2 to the nearest
freedom. Two such values should be considered suspect (95 %
0.01 %. Duplicate determinations that agree within 0.01 %
confidence level) if they differ by more than the indicated
absolute are acceptable for averaging (95 % confidence level).
percent absolute.
NOTE 3—Precision data for magnesium chloride are calculated from 33. Precision and Bias
results on one sample only. The other, containing 0.0025 % MgCl2, was 33.1 The following criteria should be used for judging the
tested but this was too low for calculating a reliable precision estimate. acceptability of results.
However the data indicate that precision at this level appears to be no
33.1.1 Repeatability (Single Analyst)—The standard
poorer than that at the 0.115 % level.
deviation of results (each the average of duplicates), obtained
26.2 The bias of this test method has not yet been by the same analyst on different days, has been estimated to be
determined. 0.005 % absolute at 15 degrees of freedom. Two such values
CALCIUM HYDROXIDE should be considered suspect (95 % confidence level) if they
differ by more than 0.02 % absolute.
27. Scope 33.1.2 Reproducibility (Multilaboratory)—The standard
27.1 This test method covers the determination of calcium deviation of results (each the average of duplicates), obtained
TABLE 1 Repeatability and Reproducibility Values (Atomic Absorption Method)
Average Weight Percent Checking Repeatibility Reproducibility
Limits
95 % 95 %
Determination for
Standard Degrees Range Standard Degrees Range
Sample 1 Sample 2 Duplicates
Deviation of Freedom Percent Deviation of Freedom Percent
Absolute Absolute
MgCl2 0.12 ... 0.01 0.0029 6 0.010 0.0095 5 0.0346
KCl 1.44 2.71 0.12 0.0546 14 0.165 0.0982 6 0.340
NaCl 0.68 1.39 0.05 0.0331 15 0.100 0.079 7 0.264
Alkali Cl as NaCl 1.91 3.62 0.12 0.0534 16 0.160 0.279 7 0.931

4
 E 449
by analysts in different laboratories, has been estimated to be differ by more than 0.036 % absolute.
0.011 % absolute at 7 degrees of freedom. Two such values 33.2 The bias of this method has not yet been determined.
should be considered suspect (95 % confidence level) if they

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if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
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