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
Bleaches1
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

1.1 These test methods cover the sampling and chemical 2.1 ASTM Standards:2
analysis of chlorine-containing bleaches. The methods appear D1193 Specification for Reagent Water
in the following order:
3. Terminology
Sections
Sodium Hypochlorite (Soda Bleach) Solutions: 3.1 Definitions:
Sampling 5 3.1.1 available chlorine—the measure of the oxidizing pow-
Available Chlorine 6–9
Sodium Chlorate 10 – 14
der of the chlorine present as hypochlorite. It is expressed in
Total Chlorine 15 – 18 terms of chlorine with a gram-equivalent weight of 35.46.
Sodium Chloride 19 and 20
Total Alkalinity as Sodium Oxide (Na2O) 4. Reagents
21 – 24
Free Alkali as Sodium Hydroxide (NaOH)
Calcium Hypochlorite:
Sampling
iTeh Standards
30
25 – 28
4.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
Available Chlorine
Water (https://standards.iteh.ai)
Chloroisocyanuric Acids and Their Derived Salts:
31 – 34
35 – 40
all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
where such specifications are available.3 Other grades may be
Document Preview
Sampling 42
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
Moisture 51 – 54 sufficiently high purity to permit its use without lessening the
1.2 This standard does not purport to address all of the accuracy of the determination.
ASTM D2022-89(2016)
safety concerns, if any, associated with its use. It is the 4.2 Unless otherwise indicated, references to water shall be
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responsibility of the user of this standard to establish appro- understood to mean reagent water conforming to Specification
priate safety and health practices and determine the applica- D1193.
bility of regulatory limitations prior to use. Material Safety
Data Sheets are available for reagents and materials. Review
them for hazards prior to usage.
2
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
1
These test methods are under the jurisdiction of ASTM Committee D12 on the ASTM website.
3
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.

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1
 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 to 3 g of KI crystals in 50 mL of water in a
in dark-colored bottles) until analyzed, which shall be done 250-mL Erlenmeyer flask. Add 10 mL of 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 pipet beneath the surface of the solution until drained. Titrate at
and aliquots taken for determination of available chlorine, once with 0.1 N Na2S2O3solution until the iodine color is
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 mL of 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
reagent are recommended. 9. Calculation
5.3 Precision results will require sampling at a standard 9.1 Calculate the available chlorine as follows:
temperature such as 20°C. Results expressed in terms of weight Available chlorine as Cl, g/L 5 ~ AN 3 35.46! /V (2)
percent will require determination of the density or specific
gravity. This may be determined with a hydrometer or by Available chlorine as Cl, weight % 5 @ ~ AN 3 0.03546! /VS# 3 100
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 3 37.22! /V (3)
may be transferred to a volumetric flask and used for subse-
quent analysis. 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 = Na2S2O3 solution required for titration of the sample,
sium iodide and the released iodine is titrated with standard mL

7. Reagents
iTeh Standards
sodium thiosulfate solution to the usual starch end point. N = normality of the Na2S2O3solution,
V = original sample in aliquot used, mL, and

7.1 Acetic Acid, glacial. (https://standards.iteh.ai)

S = specific gravity of the sample.
SODIUM CHLORATE

7.3 Sodium Thiosulfate SolutionDocument

Standard, (0.1 N)— Preview
7.2 Potassium Iodide (KI), crystals, iodate-free.
10. Summary of Test Method
Dissolve 25 g of sodium thiosulfate (Na2S2O3 · 5H2O) crystals 10.1 Sodium chlorate is reduced with sodium bromide in 8
in freshly boiled and cooled water and dilute to 1 L. The N hydrochloric acid.4,5 After dilution and addition of potassium
solution is more stable if the glassware isASTM cleanedD2022-89(2016)
with iodide, the released iodine (equivalent to the hypochlorite plus
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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 (KIO3) 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 Na2S2O3 solution, carefully pipet a 50-
reaction vessel, A (a 1-qt fruit jar will serve), fitted with a 2-
mL aliquot of the KIO3 solution into a 250-mL Erlenmeyer
hole rubber stopper carrying a separatory funnel, B, conve-
flask and dilute to 100 mL with water. Add 1 g of KI crystals.
niently graduated or marked at the 10, 20, and 100-mL levels,
When it is dissolved, add 15 mL of 1.0 N hydrochloric acid and
and a delivery tube leading to a 50-mL test-tube gas trap, C,
titrate immediately with the Na2S2O3solution. When the solu-
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-
ity of the Na2S2O3solution as follows: 12.1 Hydrochloric Acid (sp gr 1.42)—Concentrated hydro-
chloric acid (HCl). For highest accuracy, it should be checked
Normality 5 ~ 50 3 0.1! /A (1) for the presence of oxidizing or reducing matter. When used for
where: an analysis of pure potassium chlorate (KClO3) by this method,
A = Na2S2O3 solution required for titration of the there should be no fading or return of the end point, and the
KIO solution, mL. assay error should not exceed 60.5 %.
3
7.4 Starch Indicator Solution (0.5 %)—Mix 0.5 g of soluble
4
starch with 5 mL of cold water and add to 95 mL of boiling Ditz, Hugo, “Determination of Chlorates in Electrolytic Bleaching Lyes and in
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- 5
White, J. F., “Determination of Available Chlorine in Solutions Containing
tion. Textone (NaClO2),” American Dye-stuff Reporter, Vol 31, 1942 pp. 484–7.

2
 D2022 − 89 (2016)
at once with 0.1 N Na2S2 O3solution. When the iodine color is
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 ~ NaClO3 ! , g/L 5 @ ~ B 2 A ! N 3 17.74# /V (4)

~ B 2 A ! N 3 0.01774
Sodium chlorate ~ NaClO3 ! , weight % 3 100
VS

where:
A = Na2S2O3 solution required for titration for available
chlorine (Section 8), mL
B = Na2S2O3 solution required for titration for sodium
chlorate (Section 13), mL
N = normality of the Na2S2O3solution,
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

Na2S2O3when necessary. iTeh Standards

solution of potassium iodide (KI). Decolorize with chloride by sodium metabisulfite in the presence of nitric acid.
The total chloride is then determined by a standard Volhard

(https://standards.iteh.ai)
12.4 Sodium Thiosulfate Solution Standard, (0.1 N)—See titration.
7.3.
16. Reagents
Document Preview
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 · 24 H O) in 50
2 4 3 4 2 4 2

13.1 Pipet an aliquot of the sample (same amount as used mL of water and add 45 mL of HNO3.
ASTM D2022-89(2016)
for available chlorine determination, Sections 6 – 9) into the 16.2 Nitric Acid, (sp gr 1.42)—Concentrated nitric acid
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reaction vessel. Assemble the apparatus and put 25 mL of KI (HNO3).
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 AgNO3 solution.
the sample. Close the stopcock and pour 100 mL of HCl into
the funnel. Open the stopcock and allow the acid to drain into 16.4 Silver Nitrate Solution Standard (0.05 N)—Prepare a
the sample. Draw in the last drops with suction, close the 0.05 N solution of silver nitrate (AgNO3) and standardize
stopcock, swirl the vessel to mix the acid, and let stand exactly against sodium chloride (NaCl) by Mohr’s Method (K2CrO4
5 min (use time clock). There will be a tendency for a vacuum indicator). 2.923 g of NaCl dissolved and diluted to exactly
to form and draw KI solution from the trap back into the 1000 mL yields a solution exactly 0.0500 N.
sample. This must be avoided by filling the funnel with water 16.5 Sodium Metabisulfite—(Na2S2O5), powder.
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-mL beaker add 50 mL of water and about 0.5
drain into the sample, swirling to dilute the acid. Add water g of Na2S2O5 powder. Then pipet into the mixture a sample
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 HNO3 to acidify the solution
funnel. Apply pressure at the mouthpiece to blow the contents and boil until all the SO2 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
Rinse the trap twice with water, each time blowing the contents titrate to complete decolorization with 0.05 N AgNO3 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-titrate the filtrate and washings with 0.05 N
stopper, and thoroughly mix the contents of the vessel. Titrate KCNS solution until a faint reddish color persists. For less

3
 D2022 − 89 (2016)
accurate work the filtration may be avoided by adding 1 mL of 22.2 Hydrogen Peroxide Solution (3 %)—Prepare a 3 %
nitrobenzene to coagulate the suspension before back-titrating solution of hydrogen peroxide (H2O2).
the excess AgNO3. 22.3 Methyl Red Mixed Indicator Solution—Dissolve 0.2 g
NOTE 1—This small amount of KCNS solution serves as an indicator to of methyl red in 100 mL of Formula 30 alcohol and 0.3 g
show when an excess of AgNO3 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
18. Calculation solutions thoroughly.
18.1 Calculate the total chlorine content as follows: 22.4 Sodium Hydroxide Solution (4 g/L)—Dissolve 4 g of
sodium hydroxide (NaOH) in water and dilute to 1 L.
Total Chlorine as Cl, g/L 5 @ ~ CN1 ! 2 ~ DN2 ! 3 35.46# /V (5)

Total chlorine as Cl, weight % 23. Procedure

23.1 Neutralize 30 mL of H2O2 solution (or three times the
@ ~ CN1 ! 2 ~ DN2 ! 3 0.03546# volume of sample used) in a 250-mL Erlenmeyer flask with
5 3 100
VS
NaOH solution, using methyl red mixed indicator solution.
where: Pipet 10 mL of the sample of liquid bleach (or more, so that the
C = AgNO3 solution required for titration of the sample, total volume of 0.1 N HCl required will be at least 10 mL into
mL, the neutralized H2 O2 solution, shake vigorously for 1 min, and
D = KCNS solution required for back-titration, total mL titrate with 0.1 N HCl, using methyl red mixed indicator
N1 = normality of the AgNO3 solution, solution.
N2 = normality of the KCNS solution,
V = original sample in aliquot used, mL, and 24. Calculation
S = specific gravity of the sample. 24.1 Calculate the total alkalinity as Na2O as follows:
SODIUM CHLORIDE
19. Summary of Test Method
iTeh Standards @~
~ !
Total alkalinity as Na2 O, g/L 5 KN3 3 31 /V

! #
Total alkalinity as Na2 O, weight % 5 KN3 3 0.031 /VS 3 100
(7)

19.1 Any chlorine present(https://standards.iteh.ai)

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,
and as chlorate. Document Preview
chlorine and the sum of the chlorine present as hypochlorite N
V
= normality of the HCl,
3
= mL of original sample used, and
S = specific gravity of the sample.
20. Calculation
20.1 Calculate the sodium chloride content ASTM D2022-89(2016)
as follows: FREE ALKALI AS SODIUM HYDROXIDE (NaOH)
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Sodium chloride ~ NaCl! , g/L 5 @ E 2 ~ F/2 ! 2 ~ G/3 ! # 3 1.649 (6)
25. Summary of Test Method
Sodium chloride ~ NaCl! , weight % 5 @ J 2 ~ K/2 ! 2 ~ L/3 ! # 3 1.649 25.1 A sample is added to a neutralized, mixed solution of
where: barium chloride and hydrogen peroxide, which precipitates any
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),
K = available chlorine, in weight percent (Section 9), and 26. Reagents
L = sodium chlorate, in weight percent (Section 14). 26.1 Barium Chloride Solution (100 g/L)—Dissolve 100 g
of barium chloride (BaCl2·2H2O) in water and dilute to 1 L.
TOTAL ALKALINITY AS SODIUM OXIDE (Na2O) Filter if turbid.
21. Summary of Test Method 26.2 Hydrochloric Acid, Standard (0.1 N)—See 22.1.
21.1 A sample is added to neutralized, dilute hydrogen 26.3 Hydrogen Peroxide Solution (3 %)—See 22.2.
peroxide solution which reduces the hypochlorite to chloride. 26.4 Phenolphthalein Indicator Solution (0.5 g/100 mL)—
The alkalinity is then titrated with standard hydrochloric acid Dissolve 0.5 g of phenolphthalein in 60 mL of 95 % ethyl
using methyl red mixed indicator. alcohol and dilute to 100 mL with water.
22. Reagents 26.5 Sodium Hydroxide Solution (4 g/L)—See 22.4.
22.1 Hydrochloric Acid, Standard (0.1 N)—Prepare a 0.1 N
solution of hydrochloric acid (HCl) and standardize against 27. Procedure
primary standard sodium carbonate and methyl red mixed 27.1 Place 50 mL of BaCl2 solution and 30 mL of H2O2
indicator. solution in a 250-mL Erlenmeyer flask (or 6-in. porcelain dish),