ASTM D2022-89(2016)

Standard Test Methods of Sampling and Chemical Analysis of Chlorine-Containing Bleaches

ABSTRACT
These test methods detail the standard procedures for the sampling and chemical analysis of chlorine-containing bleaches including sodium hypochlorite (soda bleach) solutions, calcium hypochlorite, and chloroisocyanuric acids and their derived salts. Tests for sodium hypochlorite include the determination of available chlorine, sodium chlorate, total chorine, sodium chloride, total alkalinity as sodium oxide, and free alkali as sodium hydroxide. Tests for calcium hypochlorite include the determination of available chlorine, and water. And finally, tests for chloroisocyanuric acids and their derived salts include the determination of available chlorine by iodometric-thiosulfate and arsenite-iodometric methods, and moisture.
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 – 9  
Sodium Chlorate  
10 – 14  
Total Chlorine  
15 – 18  
Sodium Chloride  
19 and 20  
Total Alkalinity as Sodium Oxide (Na2O)  
21 – 24  
Free Alkali as Sodium Hydroxide (NaOH)  
25 – 28  
Calcium Hypochlorite:  
Sampling  
30  
Available Chlorine  
31 – 34  
Water  
35 – 40  
Chloroisocyanuric Acids and Their Derived Salts:  
Sampling  
42  
Available Chlorine (Iodometric—Thiosulfate Method)  
43 – 46  
Available Chlorine (Arsenite—Iodometric Method)  
47 – 50  
Moisture  
51 – 54  
1.2 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.

General Information

• Status: Published
• Publication Date: 30-Jun-2016
• ICS: 71.100.99 - Other products of the chemical industry
• Technical Committee: D12 - Soaps and Other Detergents
• Drafting Committee: D12.12 - Analysis and Specifications of Soaps, Synthetics, Detergents and their Components

Relations

• Replaces: ASTM D2022-89(2008) - Standard Test Methods of Sampling and Chemical Analysis of Chlorine-Containing Bleaches
• Effective Date: 01-Jul-2016
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006
• Refers: ASTM D1193-99e1 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1193-99 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Referred By: ASTM E1229-21 - Standard Specification for Calcium Hypochlorite
• Effective Date: 01-Jul-2016
• Referred By: ASTM D4610-98(2021) - Standard Guide for Determining the Presence of and Removing Microbial (Fungal or Algal) Growth on Paint and Related Coatings
• Effective Date: 01-Jul-2016

Overview

ASTM D2022-89(2016) is the internationally recognized standard outlining test methods for the sampling and chemical analysis of chlorine-containing bleaches. Published by ASTM International, this standard is designed to ensure consistency and accuracy when analyzing substances such as sodium hypochlorite (soda bleach) solutions, calcium hypochlorite, and chloroisocyanuric acids (and their derived salts). These methods address the determination of available chlorine, the presence of key chemical constituents, and essential quality characteristics-all vital for both industrial safety and regulatory compliance in the bleach and disinfectant industries.

Key Topics

• Sampling Procedures: Guidelines for collecting representative samples of liquid and solid chlorine-containing bleaches to ensure reliable analytical results.
• Chemical Analysis:
  • Sodium Hypochlorite Solutions: Determination of available chlorine, total chlorine, sodium chlorate, sodium chloride, total alkalinity as sodium oxide, and free alkali as sodium hydroxide.
  • Calcium Hypochlorite: Analysis for available chlorine and water content.
  • Chloroisocyanuric Acids and Derived Salts: Assessment of available chlorine by iodometric-thiosulfate and arsenite-iodometric methods, as well as moisture content.
• Safety Considerations: Outlines the necessity for users to establish appropriate safety and health practices, including reviewing Material Safety Data Sheets (MSDS) for reagents.
• Use of Reagent-Grade Chemicals: Ensures accuracy and precision by specifying that chemicals must meet standards such as those established by the American Chemical Society.

Applications

ASTM D2022-89(2016) is widely utilized across sectors where chlorine-based bleaching agents are manufactured, processed, or used. Key practical applications include:

• Quality Control: Routine monitoring of commercial bleach products in manufacturing settings to verify active ingredient content and identify impurities.
• Regulatory Compliance: Helping companies meet health, safety, and environmental regulations by providing validated analytical methods.
• Product Development: Supporting the research and formulation of new bleach products via precise chemical composition analysis.
• Process Verification: Confirming process consistency in the industrial production of sodium hypochlorite solutions, calcium hypochlorite tablets, and pool or disinfectant formulations containing chloroisocyanuric acids.

Related Standards

For those engaged in chlorine chemical analysis and bleach quality assurance, the following standards are frequently referenced alongside ASTM D2022-89(2016):

• ASTM D1193: Specification for Reagent Water-defining water purity levels critical for chemical testing.
• Reagent Chemical Specifications (American Chemical Society): Ensuring the use of high-purity chemicals for accurate results.
• Other ASTM Bleach and Disinfectant Standards: Additional protocols for physical and chemical testing of soaps, detergents, and cleaning products.

Practical Value

Implementing ASTM D2022-89(2016) helps organizations:

• Guarantee product uniformity through standardized testing.
• Maintain regulatory compliance with government and defense procurement requirements.
• Enhance customer confidence by supporting product labeling claims for available chlorine and purity.
• Prevent analytical errors by outlining proper sample handling, technical protocols, and reagent requirements.

Keywords

ASTM D2022, chemical analysis, chlorine-containing bleaches, sodium hypochlorite, calcium hypochlorite, chloroisocyanuric acids, available chlorine, iodometric titration, bleach testing, industrial bleach quality.

Standards Content (Sample)

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.
Designation: D2022 − 89 (Reapproved 2016)
Standard Test Methods of
Sampling and Chemical Analysis of Chlorine-Containing
Bleaches
This standard is issued under the fixed designation D2022; 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 These test methods cover the sampling and chemical
D1193 Specification for Reagent Water
analysis of chlorine-containing bleaches. The methods appear
in the following order:
3. Terminology
Sections
3.1 Definitions:
Sodium Hypochlorite (Soda Bleach) Solutions:
Sampling 5
3.1.1 availablechlorine—themeasureoftheoxidizingpow-
Available Chlorine 6–9
der of the chlorine present as hypochlorite. It is expressed in
Sodium Chlorate 10–14
terms of chlorine with a gram-equivalent weight of 35.46.
Total Chlorine 15–18
Sodium Chloride 19 and 20
4. Reagents
Total Alkalinity as Sodium Oxide (Na O) 21–24
Free Alkali as Sodium Hydroxide (NaOH) 25–28
4.1 Purity of Reagents—Reagent grade chemicals shall be
Calcium Hypochlorite:
used in all tests. Unless otherwise indicated, it is intended that
Sampling 30
Available Chlorine 31–34
all reagents shall conform to the specifications of the Commit-
Water 35–40
tee onAnalytical Reagents of theAmerican Chemical Society,
Chloroisocyanuric Acids and Their Derived Salts:
Sampling 42 where such specifications are available. Other grades may be
Available Chlorine (Iodometric—Thiosulfate Method) 43–46
used, provided it is first ascertained that the reagent is of
Available Chlorine (Arsenite—Iodometric Method) 47–50
sufficiently high purity to permit its use without lessening the
Moisture 51–54
accuracy of the determination.
1.2 This standard does not purport to address all of the
4.2 Unless otherwise indicated, references to water shall be
safety concerns, if any, associated with its use. It is the
understood to mean reagent water conforming to Specification
responsibility of the user of this standard to establish appro-
D1193.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Material Safety
Data Sheets are available for reagents and materials. Review
them for hazards prior to usage.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
These test methods are under the jurisdiction of ASTM Committee D12 on the ASTM website.
Soaps and Other Detergents and are the direct responsibility of Subcommittee Reagent Chemicals, American Chemical Society Specifications , American
D12.12 on Analysis and Specifications of Soaps, Synthetics, Detergents and their Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Components. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved July 1, 2016. Published August 2016. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
approved in 1962. Last previous edition approved in 2008 as D2022 – 89(2008). and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
DOI: 10.1520/D2022-89R16. MD.
SODIUM HYPOCHLORITE (SODA BLEACH) SOLUTIONS
5. Sampling
5.1 The stability of soda bleach is influenced to a consider- of metal contamination from equipment. Owing to the rela-
able degree by the purity of the alkali used in its preparation, tively unstable nature of bleach solutions, special attention
by the excess of alkali remaining, and by the kind and amount shall be given to the collection and preservation of the sample.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2022 − 89 (2016)
Exposure to heat and sunlight promotes decomposition, and 8. Procedure
shall be avoided. Samples shall be kept cool in a dark place (or
8.1 Dissolve 2 to3gofKI crystals in 50 mL of water in a
in dark-colored bottles) until analyzed, which shall be done
250-mLErlenmeyer flask.Add 10 mLof acetic acid, then pipet
without unnecessary delay.
the aliquot of sample into the solution, keeping the tip of the
5.2 Strong solutions of bleach shall be accurately diluted pipetbeneaththesurfaceofthesolutionuntildrained.Titrateat
and aliquots taken for determination of available chlorine,
once with 0.1 N Na S O solution until the iodine color is
2 2 3
chlorate, and total chlorine. The size of aliquots shall be such nearly gone, then add 1 mL of starch indicator solution and
that approximately 40 mLof the 0.1 N reagent is required. The
complete the titration to the disappearance of the blue color.
alkali determinations shall be made directly on the sample Record the titration as A (see Section 14).
received and sample sizes to require about 10 mL of 0.1 N
9. Calculation
reagent are recommended.
9.1 Calculate the available chlorine as follows:
5.3 Precision results will require sampling at a standard
temperaturesuchas20°C.Resultsexpressedintermsofweight
Available chlorine as Cl, g/L 5 AN 335.46 /V (2)
~ !
percent will require determination of the density or specific
Available chlorine as Cl, weight % 5 @~AN 30.03546!/VS# 3100
gravity. This may be determined with a hydrometer or by
weighing the sample, after pipetting the amount to be diluted
9.2 Calculate the sodium hypochlorite content as follows:
for analysis into a tared weighing bottle. The weighed sample
Sodium hypochlorite NaOCl , g/L 5 AN 337.22 /V (3)
~ ! ~ !
may be transferred to a volumetric flask and used for subse-
quent analysis.
Sodium hypochlorite ~NaOCl!, weight %
AVAILABLE CHLORINE
5@~AN 30.03722!/VS# 3100
6. Summary of Test Method
where:
6.1 The sample is added to an acidified solution of potas-
A =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 = normality of the Na S O solution,
2 2 3
V = original sample in aliquot used, mL, and
7. Reagents
S = 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
4,5
in freshly boiled and cooled water and dilute to 1 L. The
Nhydrochloricacid. Afterdilutionandadditionofpotassium
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
11.1 The apparatus (Fig. 1) consists of 1-L wide-mouth
N. To standardize the Na S O solution, carefully pipet a 50-
2 2 3
reaction vessel, A (a 1-qt fruit jar will serve), fitted with a 2-
mL aliquot of the KIO solution into a 250-mL Erlenmeyer
hole rubber stopper carrying a separatory funnel, B, conve-
flask and dilute to 100 mL with water. Add1gofKI crystals.
niently graduated or marked at the 10, 20, and 100-mL levels,
Whenitisdissolved,add15mLof1.0Nhydrochloricacidand
and a delivery tube leading to a 50-mL test-tube gas trap, C,
titrate immediately with the Na S O solution. When the solu-
2 2 3
which is fitted with rubber tubing and a glass mouthpiece, D.
tion becomes light yellow, add 1 mL of starch indicator
solution and complete the titration to the disappearance of the
12. Reagents
blue color. Standardize at least monthly. Calculate the normal-
12.1 Hydrochloric Acid (sp gr 1.42)—Concentrated hydro-
ity of the Na S O solution as follows:
2 2 3
chloric acid (HCl). For highest accuracy, it should be checked
Normality 5 50 30.1 /A (1)
~ !
forthepresenceofoxidizingorreducingmatter.Whenusedfor
ananalysisofpurepotassiumchlorate(KClO )bythismethod,
where: 3
there should be no fading or return of the end point, and the
A =Na S O solution required for titration of the
2 2 3
assay error should not exceed 60.5 %.
KIO solution, mL.
7.4 Starch Indicator Solution (0.5 %)—Mix 0.5 g of soluble
Ditz, Hugo, “Determination of Chlorates in Electrolytic Bleaching Lyes and in
starch with 5 mL of cold water and add to 95 mL of boiling
Lyes Obtained from Absorption Vessels During the Production of Potassium
water. Mix, cool, and store in a sterilized bottle. Replace
Chlorate,” Chemiker Zeitung, Vol 25, 1901 p. 727.
frequently or add 0.1 % salicylic acid to minimize deteriora-
White, J. F., “Determination of Available Chlorine in Solutions Containing
tion. Textone (NaClO ),” American Dye-stuff Reporter, Vol 31, 1942 pp. 484–7.
D2022 − 89 (2016)
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 2 A N 317.74 /V (4)
~ ! @~ ! #
~B 2 A!N 30.01774
Sodium chlorate NaClO , weight % 3100
~ !
VS
where:
A =Na S O solution required for titration for available
2 2 3
chlorine (Section 8), mL
B =Na S O solution required for titration for sodium
2 2 3
chlorate (Section 13), mL
N = normality of the Na S O solution,
2 2 3
FIG. 1 Apparatus for Determination of Sodium Chlorate in So-
V = original sample in aliquot used, mL, and
dium Hypochlorite (Soda Bleach) Solutions
S = specific gravity of the sample.
TOTAL CHLORINE
12.2 Sodium Bromide Solution (10 %)—Prepare a 10 %
solution of sodium bromide (NaBr).
15. Summary of Test Method
12.3 Potassium Iodide Solution (10 %)—Prepare a 10 %
15.1 All hypochlorite and chlorate present is reduced to
solution of potassium iodide (KI). Decolorize with
chloride by sodium metabisulfite in the presence of nitric acid.
Na S O when necessary.
The total chloride is then determined by a standard Volhard
2 2 3
titration.
12.4 Sodium Thiosulfate Solution Standard, (0.1 N)—See
7.3.
16. Reagents
12.5 Starch Indicator Solution (0.5 %)—See 7.4.
16.1 Iron Indicator Solution—Dissolve 6.25 g of ferric
13. Procedure ammonium sulfate (Fe (SO ) · (NH ) SO ·24H O) in 50
2 4 3 4 2 4 2
mL of water and add 45 mL of HNO .
13.1 Pipet an aliquot of the sample (same amount as used
16.2 Nitric Acid, (sp gr 1.42)—Concentrated nitric acid
for available chlorine determination, Sections6–9) into the
reaction vessel. Assemble the apparatus and put 25 mL of KI (HNO ).
solution in the gas trap. Close the funnel stopcock, pour 20 mL
16.3 Potassium Thiocyanate Solution Standard, (0.05 N)—
of NaBr solution into the funnel, open the stopcock, and with
Prepare a 0.05 N solution of potassium thiocyanate (KCNS)
gentle suction on the mouthpiece, draw the NaBr solution into
and standardize against 0.05 N AgNO solution.
the sample. Close the stopcock and pour 100 mL of HCl into
16.4 Silver Nitrate Solution Standard (0.05 N)—Prepare a
the funnel. Open the stopcock and allow the acid to drain into
0.05 N solution of silver nitrate (AgNO ) and standardize
the sample. Draw in the last drops with suction, close the
against sodium chloride (NaCl) by Mohr’s Method (K CrO
2 4
stopcock, swirl the vessel to mix the acid, and let stand exactly
indicator). 2.923 g of NaCl dissolved and diluted to exactly
5 min (use time clock). There will be a tendency for a vacuum
1000 mL yields a solution exactly 0.0500 N.
to form and draw KI solution from the trap back into the
sample. This must be avoided by filling the funnel with water 16.5 Sodium Metabisulfite—(Na S O ), powder.
2 2 5
and relieving the vacuum by opening the stopcock and adding
a small amount of water. 17. Procedure
13.2 After 5 min, open the stopcock and allow the water to 17.1 To a 250-mLbeaker add 50 mLof water and about 0.5
drain into the sample, swirling to dilute the acid. Add water gofNa S O powder. Then pipet into the mixture a sample
2 2 5
through the funnel sufficient to dilute the sample to about 700 aliquot of the same size as used for available chlorine and
mL. Close the stopcock, and add 10 mL of KI solution to the chlorate. Add about 10 drops of HNO to acidify the solution
funnel. Apply pressure at the mouthpiece to blow the contents and boil until all the SO has been expelled. Cool to room
of the trap back into the vessel, opening the stopcock to allow temperature and add 5 mL of iron indicator solution. From a
the necessary amount of gas to escape through the funnel. buret add 0.5 mL of 0.05 N KCNS solution (Note 1). Then
Rinsethetraptwicewithwater,eachtimeblowingthecontents titrate to complete decolorization with 0.05 NAgNO solution.
into the vessel as above. Finally, allow the contents of the Filter off the precipitate by suction and wash three times with
funnel to drain into the vessel, rinse down the funnel and water.Finally,back-titratethefiltrateandwashingswith0.05N
stopper, and thoroughly mix the contents of the vessel. Titrate KCNS solution until a faint reddish color persists. For less
D2022 − 89 (2016)
accurate work the filtration may be avoided by adding 1 mLof 22.2 Hydrogen Peroxide Solution (3 %)—Prepare a 3 %
nitrobenzene to coagulate the suspension before back-titrating solution of hydrogen peroxide (H O ).
2 2
the excess AgNO .
22.3 Methyl Red Mixed Indicator Solution—Dissolve 0.2 g
of methyl red in 100 mL of Formula 30 alcohol and 0.3 g
NOTE 1—This small amount of KCNS solution serves as an indicator to
show when an excess of AgNO solution has been added. The back
bromcresol green in 300 mL of Formula 30 alcohol. Grinding
titration is continued from the same buret and the total volume of KCNS
of the methyl red may be necessary to ensure complete
solution used is noted and used in the calculation.
solution. When reagents are completely dissolved, mix the two
solutions thoroughly.
18. Calculation
22.4 Sodium Hydroxide Solution (4 g/L)—Dissolve4gof
18.1 Calculate the total chlorine content as follows:
sodium hydroxide (NaOH) in water and dilute to 1 L.
Total Chlorine as Cl, g/L 5 CN 2 DN 335.46 /V (5)
@~ ! ~ ! #
1 2
23. Procedure
Total chlorine as Cl, weight %
23.1 Neutralize 30 mL of H O solution (or three times the
2 2
@~CN ! 2 ~DN ! 30.03546#
1 2
volume of sample used) in a 250-mL Erlenmeyer flask with
5 3100
VS
NaOH solution, using methyl red mixed indicator solution.
Pipet10mLofthesampleofliquidbleach(ormore,sothatthe
where:
total volume of 0.1 N HCl required will be at least 10 mL into
C = AgNO solution required for titration of the sample,
the neutralized H O solution, shake vigorously for 1 min, and
2 2
mL,
titrate with 0.1 N HCl, using methyl red mixed indicator
D = KCNS solution required for back-titration, total mL
solution.
N = normality of the AgNO solution,
1 3
N = normality of the KCNS solution,
24. Calculation
V = original sample in aliquot used, mL, and
S = specific gravity of the sample.
24.1 Calculate the total alkalinity as Na O as follows:
SODIUM CHLORIDE Total alkalinity as Na O, g/L 5 ~KN 331!/V (7)
2 3
19. Summary of Test Method Total alkalinity as Na O, weight % 5 @~KN 30.031!/VS# 3100
2 3
19.1 Any chlorine present as a sodium chloride is deter-
where:
mined by calculation as the difference between the total
K = mL of HCl required for titration of the sample,
chlorine and the sum of the chlorine present as hypochlorite
N = normality of the HCl,
and as chlorate.
V = mL of original sample used, and
S = specific gravity of the sample.
20. Calculation
FREE ALKALI AS SODIUM HYDROXIDE (NaOH)
20.1 Calculate the sodium chloride content as follows:
Sodium chloride ~NaCl!, g/L 5 @E 2 ~F/2! 2 ~G/3!# 31.649 (6)
25. Summary of Test Method
Sodium chloride NaCl , weight % 5 J 2 K/2 2 L/3 31.649
~ ! @ ~ ! ~ !# 25.1 A sample is added to a neutralized, mixed solution of
bariumchlorideandhydrogenperoxide,whichprecipitatesany
where:
carbonate and reduces the hypochlorite to chloride. The free
E = total chlorine, g/L (Section 18),
alkali is then titrated with standard hydrochloric acid using
F = available chlorine, g/L (Section 9),
phenolphthalein indicator.
G = sodium chlorate, g/L (Section 14),
J = total chlorine, in weight percent (Section 18),
26. Reagents
K = available chlorine, in weight percent (Section 9), and
L = sodium chlorate, in weight percent (Section 14).
26.1 Barium Chloride Solution (100 g/L)—Dissolve 100 g
of barium chloride (BaCl ·2H O) in water and dilute to 1 L.
2 2
TOTAL ALKALINITY AS SODIUM OXIDE (Na O)
Filter if turbid.
21. Summary of Test Metho
...