ASTM D2022-89(1995)e1
(Test Method)Standard Test Methods of Sampling and Chemical Analysis of Chlorine-Containing Bleaches
Standard Test Methods of Sampling and Chemical Analysis of Chlorine-Containing Bleaches
SCOPE
1.1 These test methods cover the sampling and chemical analysis of chlorine-containing bleaches. The methods appear in the following order: Sections Sodium Hypochlorite (Soda Bleach) Solutions: Sampling 5 Available Chlorine 6 to 9 Sodium Chlorate 10 to 14 Total Chlorine 15 to 18 Sodium Chloride 19 and 20 Total Alkalinity as Sodium Oxide (Na O) 21 to 24 Free Alkali as Sodium Hydroxide (NaOH) 25 to 28 Calcium Hypochlorite: Sampling 30 Available Chlorine 31 to 34 Water 35 to 40 Chloroisocyanuric Acids and Their Derived Salts: Sampling 42 Available Chlorine (Iodometric-Thiosulfate Method) 43 to 46 Available Chlorine (Arsenite-Iodometric Method) 47 to 50 Moisture 51 to 54
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 and health practices and determine the applicability of regulatory limitations prior to use. Material Safety Data Sheets are available for reagents and materials. Review them for hazards prior to usage.
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Standards Content (Sample)
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e1
Designation: D 2022 – 89 (Reapproved 1995)
Standard Test Methods of
Sampling and Chemical Analysis of Chlorine-Containing
Bleaches
This standard is issued under the fixed designation D 2022; 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.
This standard has been approved for use by agencies of the Department of Defense.
e NOTE—Keywords were added editorially in February 1995.
1. Scope them for hazards prior to usage.
1.1 These test methods cover the sampling and chemical
2. Referenced Documents
analysis of chlorine-containing bleaches. The methods appear
2.1 ASTM Standards:
in the following order:
D 1193 Specification for Reagent Water
Sections
Sodium Hypochlorite (Soda Bleach) Solutions:
3. Terminology
Sampling 5
Available Chlorine 6-9
3.1 Definitions:
Sodium Chlorate 10-14
3.1.1 available chlorine—the measure of the oxidizing
Total Chlorine 15-18
Sodium Chloride 19 and 20
powder of the chlorine present as hypochlorite. It is expressed
Total Alkalinity as Sodium Oxide (Na O) 21-24
in terms of chlorine with a gram-equivalent weight of 35.46.
Free Alkali as Sodium Hydroxide (NaOH) 25-28
Calcium Hypochlorite:
4. Reagents
Sampling 30
Available Chlorine 31-34
4.1 Purity of Reagents—Reagent grade chemicals shall be
Water 35-40
used in all tests. Unless otherwise indicated, it is intended that
Chloroisocyanuric Acids and Their Derived Salts:
Sampling 42
all reagents shall conform to the specifications of the Commit-
Available Chlorine (Iodometric—Thiosulfate Method) 43-46
tee on Analytical Reagents of the American Chemical Society,
Available Chlorine (Arsenite—Iodometric Method) 47-50
where such specifications are available. Other grades may be
Moisture 51-54
used, provided it is first ascertained that the reagent is of
1.2 This standard does not purport to address all of the
sufficiently high purity to permit its use without lessening the
safety concerns, if any, associated with its use. It is the
accuracy of the determination.
responsibility of the user of this standard to establish appro-
4.2 Unless otherwise indicated, references to water shall be
priate safety and health practices and determine the applica-
understood to mean reagent water conforming to Specification
bility of regulatory limitations prior to use. Material Safety
D 1193.
Data Sheets are available for reagents and materials. Review
Annual Book of ASTM Standards, Vol 11.01.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
These test methods are under the jurisdiction of ASTM Committee D-12 on
listed by the American Chemical Society, see Analar Standards for Laboratory
Soaps and Other Detergents and are the direct responsibility of Subcommittee
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
D12.12on Analysis of Soaps and Synthetic Detergents.
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Current edition approved May 26, 1989. Published July 1989. Originally
published as D 2022 – 62 T. Last previous edition D 2022 – 87. MD.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 2022
SODIUM HYPOCHLORITE (SODA BLEACH) SOLUTIONS
5. Sampling
where:
A 5 Na S O solution required for titration of the
5.1 The stability of soda bleach is influenced to a consider- 2 2 3
KIO solution, mL.
able degree by the purity of the alkali used in its preparation,
7.4 Starch Indicator Solution (0.5 %)—Mix 0.5 g of soluble
by the excess of alkali remaining, and by the kind and amount
starch with 5 mL of cold water and add to 95 mL of boiling
of metal contamination from equipment. Owing to the rela-
water. Mix, cool, and store in a sterilized bottle. Replace
tively unstable nature of bleach solutions, special attention
frequently or add 0.1 % salicylic acid to minimize deteriora-
shall be given to the collection and preservation of the sample.
tion.
Exposure to heat and sunlight promotes decomposition, and
shall be avoided. Samples shall be kept cool in a dark place (or
8. Procedure
in dark-colored bottles) until analyzed, which shall be done
without unnecessary delay. 8.1 Dissolve 2 to3gofKI crystals in 50 mL of water in a
5.2 Strong solutions of bleach shall be accurately diluted 250-mL Erlenmeyer flask. Add 10 mL of acetic acid, then pipet
and aliquots taken for determination of available chlorine, the aliquot of sample into the solution, keeping the tip of the
chlorate, and total chlorine. The size of aliquots shall be such pipet beneath the surface of the solution until drained. Titrate at
that approximately 40 mL of the 0.1 N reagent is required. The once with 0.1 N Na S O solution until the iodine color is
2 2 3
alkali determinations shall be made directly on the sample nearly gone, then add 1 mL of starch indicator solution and
complete the titration to the disappearance of the blue color.
received and sample sizes to require about 10 mL of 0.1 N
reagent are recommended. Record the titration as A (see Section 14).
5.3 Precision results will require sampling at a standard
9. Calculation
temperature such as 20°C. Results expressed in terms of weight
percent will require determination of the density or specific
9.1 Calculate the available chlorine as follows:
gravity. This may be determined with a hydrometer or by
Available chlorine as Cl, g/L 5 ~AN 3 35.46!/V (2)
weighing the sample, after pipetting the amount to be diluted
Available chlorine as Cl, weight % 5 @~AN 3 0.03546!/VS# 3 100
for analysis into a tared weighing bottle. The weighed sample
9.2 Calculate the sodium hypochlorite content as follows:
may be transferred to a volumetric flask and used for subse-
quent analysis.
Sodium hypochlorite ~NaOCl!, g/L 5 ~AN 3 37.22!/V (3)
Sodium hypochlorite ~NaOCl!, weight %
AVAILABLE CHLORINE
5 @~AN 3 0.03722!/VS# 3 100
6. Summary of Test Method
where:
6.1 The sample is added to an acidified solution of potas-
A 5 Na S O solution required for titration of the sample,
2 2 3
sium iodide and the released iodine is titrated with standard
mL
sodium thiosulfate solution to the usual starch end point.
N 5 normality of the Na S O solution,
2 2 3
V 5 original sample in aliquot used, mL, and
7. Reagents
S 5 specific gravity of the sample.
7.1 Acetic Acid, glacial.
SODIUM CHLORATE
7.2 Potassium Iodide (KI), crystals, iodate-free.
7.3 Sodium Thiosulfate Solution Standard, (0.1 N)—
10. Summary of Test Method
Dissolve 25 g of sodium thiosulfate (Na S O ·5H O) crystals
2 2 3 2
10.1 Sodium chlorate is reduced with sodium bromide in 8
in freshly boiled and cooled water and dilute to 1 L. The
4,5
N hydrochloric acid. After dilution and addition of potassium
solution is more stable if the glassware is cleaned with
iodide, the released iodine (equivalent to the hypochlorite plus
sulfuric-chromic acid and thoroughly rinsed with water. Stan-
chlorate) is titrated with standard sodium thiosulfate solution
dardize against potassium iodate as follows: Weigh out accu-
and starch indicator.
rately 3.567 g of dry potassium iodate (KIO ) and transfer to a
1-L volumetric flask. Dissolve with water, make up to the
11. Apparatus
mark, and mix thoroughly. This solution will be exactly 0.1000
N. To standardize the Na S O solution, carefully pipet a 50- 11.1 The apparatus (Fig. 1) consists of 1-L wide-mouth
2 2 3
mL aliquot of the KIO solution into a 250-mL Erlenmeyer reaction vessel, A (a 1-qt fruit jar will serve), fitted with a 2-
flask and dilute to 100 mL with water. Add1gofKI crystals. hole rubber stopper carrying a separatory funnel, B, conve-
When it is dissolved, add 15 mL of 1.0 N hydrochloric acid and niently graduated or marked at the 10, 20, and 100-mL levels,
titrate immediately with the Na S O solution. When the solu-
2 2 3
tion becomes light yellow, add 1 mL of starch indicator
solution and complete the titration to the disappearance of the
Ditz, Hugo, “Determination of Chlorates in Electrolytic Bleaching Lyes and in
Lyes Obtained from Absorption Vessels During the Production of Potassium
blue color. Standardize at least monthly. Calculate the normal-
Chlorate,” Chemiker Zeitung, Vol 25, 1901 p. 727.
ity of the Na S O solution as follows:
2 2 3 5
White, J. F., “Determination of Available Chlorine in Solutions Containing
Normality 5 ~50 3 0.1!/A (1) Textone (NaClO ),” American Dye-stuff Reporter, Vol 31, 1942 pp. 484–7.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 2022
mL. Close the stopcock, and add 10 mL of KI solution to the
funnel. Apply pressure at the mouthpiece to blow the contents
of the trap back into the vessel, opening the stopcock to allow
the necessary amount of gas to escape through the funnel.
Rinse the trap twice with water, each time blowing the contents
into the vessel as above. Finally, allow the contents of the
funnel to drain into the vessel, rinse down the funnel and
stopper, and thoroughly mix the contents of the vessel. Titrate
at once with 0.1 N Na S O solution. When the iodine color is
2 2 3
nearly gone, add 5 mL of starch indicator solution and
complete the titration to the disappearance of the blue color.
Record the titration as B.
14. Calculation
14.1 Calculate the sodium chlorate content as follows:
Sodium chlorate ~NaClO !, g/L 5 @~B – A!N 3 17.74#/V (4)
~B – A!N 3 0.01774
Sodium chlorate ~NaClO !, weight % 3 100
FIG. 1 Apparatus for Determination of Sodium Chlorate in
VS
Sodium Hypochlorite (Soda Bleach) Solutions
where:
A 5 Na S O solution required for titration for available
2 2 3
and a delivery tube leading to a 50-mL test-tube gas trap, C,
chlorine (Section 8), mL
which is fitted with rubber tubing and a glass mouthpiece, D.
B 5 Na S O solution required for titration for sodium
2 2 3
chlorate (Section 13), mL
12. Reagents
N 5 normality of the Na S O solution,
2 2 3
12.1 Hydrochloric Acid (sp gr 1.42)—Concentrated hydro-
V 5 original sample in aliquot used, mL, and
chloric acid (HCl). For highest accuracy, it should be checked
S 5 specific gravity of the sample.
for the presence of oxidizing or reducing matter. When used for
TOTAL CHLORINE
an analysis of pure potassium chlorate (KClO ) by this method,
there should be no fading or return of the end point, and the
15. Summary of Test Method
assay error should not exceed 60.5 %.
15.1 All hypochlorite and chlorate present is reduced to
12.2 Sodium Bromide Solution (10 %)—Prepare a 10 %
solution of sodium bromide (NaBr). chloride by sodium metabisulfite in the presence of nitric acid.
The total chloride is then determined by a standard Volhard
12.3 Potassium Iodide Solution (10 %)—Prepare a 10 %
solution of potassium iodide (KI). Decolorize with titration.
Na S O when necessary.
2 2 3
16. Reagents
12.4 Sodium Thiosulfate Solution Standard, (0.1 N)—See
7.3.
16.1 Iron Indicator Solution—Dissolve 6.25 g of ferric
12.5 Starch Indicator Solution (0.5 %)—See 7.4. ammonium sulfate (Fe (SO ) · (NH ) SO ·24H O) in 50 mL
2 4 3 4 2 4 2
of water and add 45 mL of HNO .
13. Procedure
16.2 Nitric Acid, (sp gr 1.42)—Concentrated nitric acid
(HNO ).
13.1 Pipet an aliquot of the sample (same amount as used
16.3 Potassium Thiocyanate Solution Standard, (0.05 N)—
for available chlorine determination, Sections 6-9) into the
Prepare a 0.05 N solution of potassium thiocyanate (KCNS)
reaction vessel. Assemble the apparatus and put 25 mL of KI
and standardize against 0.05 N AgNO solution.
solution in the gas trap. Close the funnel stopcock, pour 20 mL
16.4 Silver Nitrate Solution Standard (0.05 N)—Prepare a
of NaBr solution into the funnel, open the stopcock, and with
0.05 N solution of silver nitrate (AgNO ) and standardize
gentle suction on the mouthpiece, draw the NaBr solution into
against sodium chloride (NaCl) by Mohr’s Method (K CrO
the sample. Close the stopcock and pour 100 mL of HCl into
2 4
indicator). 2.923 g of NaCl dissolved and diluted to exactly
the funnel. Open the stopcock and allow the acid to drain into
1000 mL yields a solution exactly 0.0500 N.
the sample. Draw in the last drops with suction, close the
stopcock, swirl the vessel to mix the acid, and let stand exactly 16.5 Sodium Metabisulfite—(Na S O ), powder.
2 2 5
5 min (use time clock). There will be a tendency for a vacuum
17. Procedure
to form and draw KI solution from the trap back into the
sample. This must be avoided by filling the funnel with water 17.1 To a 250-mL beaker add 50 mL of water and about 0.5
and relieving the vacuum by opening the stopcock and adding gofNa S O powder. Then pipet into the mixture a sample
2 2 5
a small amount of water. aliquot of the same size as used for available chlorine and
13.2 After 5 min, open the stopcock and allow the water to chlorate. Add about 10 drops of HNO to acidify the solution
drain into the sample, swirling to dilute the acid. Add water and boil until all the SO has been expelled. Cool to room
through the funnel sufficient to dilute the sample to about 700 temperature and add 5 mL of iron indicator solution. From a
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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D 2022
buret add 0.5 mL of 0.05 N KCNS solution (Note 1). Then solution of hydrochloric acid (HCl) and standardize against
titrate to complete decolorization with 0.05 N AgNO solution. primary standard sodium carbonate and methyl red mixed
Filter off the precipitate by suction and wash three times with indicator.
water. Finally, back-titrate the filtrate and washings with 0.05 N 22.2 Hydrogen Peroxide Solution (3 %)—Prepare a 3 %
KCNS solution until a faint reddish color persists. For less solution of hydrogen peroxide (H O ).
2 2
accurate work the filtration may be avoided by adding 1 mL of 22.3 Methyl Red Mixed Indicator Solution—Dissolve 0.2 g
nitrobenzene to coagulate the suspension before back-titrating of methyl red in 100 mL of Formula 30 alcohol and 0.3 g
the excess AgNO . bromcresol green in 300 mL of Formula 30 alcohol. Grinding
of the methyl red may be necessary to ensure complete
NOTE 1—This small amount of KCNS soluti
...
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