ASTM D2022-89(2008)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D2022 − 89(Reapproved 2008)
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 service@astm.org. 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, 2008. Published July 2008. Originally approved Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
in 1962. Last previous edition approved in 2003 as D2022 – 89(2003). DOI: and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
10.1520/D2022-89R08. 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 (2008)
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 (2008)
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 (2008)
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 (N
...