Awwa B303-00

American Water Works Association
ANSI/AWWA B303-00
(Revision of ANSI/AWWA B303-95)
AWWA STANDARD
FOR
SODIUM CHLORITE
Effective date: January 1, 2001.

First edition approved by AWWA Board of Directors June 1, 1967.
This edition approved June 11, 2000.
Approved by American National Standards Institute October 6, 2000.
AMERICAN WATER WORKS ASSOCIATION

6666 West Quincy Avenue, Denver, Colorado 80235
Copyright © 2000 American Water Works Association, All Rights Reserved

AWWA Standard
This document is an American Water Works Association (AWWA) standard. It is not a specification.
AWWA standards describe minimum requirements and do not contain all of the engineering and
administrative information normally contained in specifications. The AWWA standards usually
contain options that must be evaluated by the user of the standard. Until each optional feature is
specified by the user, the product or service is not fully defined. AWWA publication of a standard
does not constitute endorsement of any product or product type, nor does AWWA test, certify, or
approve any product. The use of AWWA standards is entirely voluntary. AWWA standards are
intended to represent a consensus of the water supply industry that the product described will
provide satisfactory service. When AWWA revises or withdraws this standard, an official notice of
action will be placed on the first page of the classified advertising section of Journal AWWA. The
action becomes effective on the first day of the month following the month of Journal AWWA
publication of the official notice.
American National Standard

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and provisions. An American National Standard is intended as a guide to aid the manufacturer, the
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CAUTION NOTICE: The American National Standards Institute (ANSI) approval date on the front
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Copyright © 2000 by American Water Works Association

Printed in USA
ii

Committee Personnel
The AWWA Standards Committee on Disinfectants, which reviewed and
approved this standard, had the following personnel at the time of approval:
Robert D. Harriger, Chair

Gary F. Trojak, Vice-Chair
Consumer Members
B.S. Aptowicz, Philadelphia Water Department, Philadelphia, Pa. (AWWA)

J.T. Harvey, Little Rock Municipal Water Works, Little Rock, Ark. (AWWA)
A.A. Khan, Pepsico, Arlington, Texas (AWWA)
Stephen Poole, Aqualta Engineering, Edmonton, Alta. (AWWA)
D.L. Saenz, Los Angeles Water and Power, Sylmar, Calif. (AWWA)
A.T. Segars, Miami–Dade Water and Sewer Department, Hialeah, Fla. (AWWA)
General Interest Members
P.E. Cote, Earth Tech, Cumberland, Maine (AWWA)

J.H. Buckler,* Council Liaison, St. Louis County Water Company,
St. Louis, Mo. (AWWA)
D.J. Gates, Citrus Heights, Calif. (AWWA)
R.D. Harriger, Eaglebrook Inc., Williamsburg, Va. (AWWA)
S.J. Posavec,* Staff Liaison, AWWA, Denver, Colo. (AWWA)
K.B. Stark, NSF International, Ann Arbor, Mich. (AWWA)
Producer Members
David Hildebrand, Vulcan Chemicals, Wichita, Kan. (CI)

W.B. Huebner, Wallace & Tiernan Inc., Belleville, N.J. (AWWA)
P.A. Ross, Dow Chemical USA, Freeport, Texas (AWWA)
G.F. Trojak, The Chlorine Institute Inc., Washington, D.C. (CI)
*Liaison, nonvoting
iii

This page intentionally blank.

Contents
All AWWA standards follow the general format indicated subsequently. Some variations from this format may be
found in a particular standard.
SEC. PAGE SEC. PAGE
Foreword 4.3 Impurities.............................................. 3

I Introduction ........................................ vii
5 Verification
I.A Background......................................... vii
5.1 Sampling ............................................... 4
I.B History ............................................... viii
5.2 Test Procedures—General ................... 6
I.C Acceptance ......................................... viii
5.3 Test Procedure for Sodium Chlorite,
II Special Issues ....................................... ix
Idometric Method ............................ 6
II.A Handling, Storage, and Safety
5.4 Test Procedure for Sodium
Precautions.......................................... x
Hydroxide ......................................... 7
III Use of This Standard........................... xi
III.A Purchaser Options and
Carbonate ......................................... 8
Alternatives ...................................... xi
III.B Modification to Standard..................... xi
Chloride.............................................. 9
IV Major Revisions.................................... xi
5.7 Test Procedure for Sodium Sulfate ..... 9
V Comments ........................................... xii
5.8 Test Procedure for Arsenic ................ 10
Standard 5.9 Test Procedure for Sodium Nitrate... 10
1 General 5.10 Test Procedure for Sodium
1.1 Scope ...................................................... 1 Chlorate ........................................... 11
1.2 Purpose .................................................. 1 5.11 Rejection.............................................. 12
1.3 Application............................................. 1
6 Delivery
2 Reference............................................. 2 6.1 Marking............................................... 13

6.2 Packaging and Shipping .................... 13
3 Definitions........................................... 2
6.3 Affidavit of Compliance...................... 14
4 Requirements
Figure
4.1 Physical Requirements ......................... 2
1 Crystallization Temperature of Sodium
4.2 Chemical Requirements ....................... 2 Chlorite Solutions ............................. 4


Foreword
This foreword is for information only and is not a part of AWWA B303.
I. Introduction.
I.A. Background. Sodium chlorite is made by the partial reduction of
sodium chlorate to chlorine dioxide and the chlorine dioxide’s subsequent conversion
to sodium chlorite in an alkaline solution in the presence of hydrogen peroxide. An
excess of both peroxide and caustic is present to ensure complete reaction as follows:
2ClO 2 + H 2 O 2 + 2NaOH → 2NaClO2 + 2H2 O + O 2
Under unfavorable conditions, ClO2 is also known to disproportionate to chlorite

and chlorate as follows:
– – –
ClO2 + 2OH → ClO2 + ClO 3 + H 2 O
Any chlorine present would be in the hypochlorite form because of the strong
alkaline conditions. Any chlorate ion so formed is recycled through the process to
optimize recovery of sodium chlorite. Hypochlorite will react with hydrogen peroxide
to yield chloride as follows:
– –
OCl + H 2 O 2 → Cl + O2 + H2O
Because there is no source of ammonia or nitrogen in the process, chloramines

will not be present as an impurity.
Sodium chlorite is a dry flaked salt, which, because of its powerful oxidizing
nature, is shipped in steel drums bearing DOT Yellow (Class 5.1) oxidizer label. Dry
flaked material is formulated by mixing sodium chlorite solutions with stabilizing
salts in solution prior to either drying or filtering. The drying or filtering may be
coincidental with spraying under atomizing conditions to achieve particle uniformity
for flaking characteristics. As marketed in the solid form, sodium chlorite contains
approximately 80 percent by weight sodium chlorite; in the aqueous form, it contains
approximately 40 percent or less by weight sodium chlorite. Technical sodium chlorite
is a white flaked salt with a density of approximately 56 lb/ft3 (0.90 g/cc). Some

material may have a tint of orange, depending on the iron content. Sodium chlorite is
stable when sealed or in solution but can ignite in the presence of organic materials.
For this reason, the solution should not be allowed to dry out on floors but should be
hosed down with minimum splashing.
Sodium chlorite dissolves easily in water at ordinary temperatures to form a
pale-yellow solution. This solution is chemically stable under ordinary conditions of
temperature and pressure. Solutions above 25–30 percent weight per weight (w/w)
may crystallize at moderate ambient temperatures. Crystallization temperatures
may vary due to solutions originating either from dilution of slurried or dried
materials.
Sodium chlorite used for the on-site production of chlorine dioxide for use as a
disinfectant in the treatment of drinking water or for pesticidal use in processing
plant-flume water, sewage treatment, slime control in paper mills, and bacteria
control in oil wells requires US Environmental Protection Agency (USEPA)
registration. Sodium chlorite to be sold and used for drinking water treatment must
be registered under a label or labels indicating these uses.
I.B. History. The original AWWA Standard for Sodium Chlorite was prepared
by Committee 7440P. The standard was approved as tentative on Jan. 25, 1965, and
made a standard by the AWWA Board of Directors on June 1, 1967. The standard
was designated AWWA B303-67.
The AWWA Standards Committee on Chlorine, Chlorine Compounds, and
Related Alkalies prepared the 1988 edition approved by the AWWA Board of
Directors on June 19, 1988. The AWWA Standards Committee on Disinfectants
prepared the 1995 edition approved by the Board of Directors on June 17, 1995. This
edition was approved on June 11, 2000.
I.C. Acceptance. In May 1985, the U.S. Environmental Protection Agency
(USEPA) entered into a cooperative agreement with a consortium led by NSF
International (NSF) to develop voluntary third-party consensus standards and a
certification program for all direct and indirect drinking water additives. Other
members of the original consortium included the American Water Works Association
Research Foundation (AWWARF) and the Conference of State Health and Environ-
mental Managers (COSHEM). The American Water Works Association (AWWA) and
the Association of State Drinking Water Administrators (ASDWA) joined later.
ii

In the United States, authority to regulate products for use in, or in contact with,
drinking water rests with individual states.* Local agencies may choose to impose
requirements more stringent than those required by the state. To evaluate the health
effects of products and drinking water additives from such products, state and local
agencies may use various references, including two standards developed under the
direction of NSF, ANSI†/NSF‡ 60, Drinking Water Treatment Chemicals—Health
Effects, and ANSI/NSF 61, Drinking Water System Components—Health Effects.
Various certification organizations may be involved in certifying products in
accordance with ANSI/NSF 60. Individual states or local agencies have authority to
accept or accredit certification organizations within their jurisdiction. Accreditation
of certification organizations may vary from jurisdiction to jurisdiction.
Annex A, “Toxicology Review and Evaluation Procedures,” to ANSI/NSF 60 does
not stipulate a maximum allowable level (MAL) of a contaminant for substances not
regulated by a USEPA final maximum contaminant level (MCL). The MALs of an
unspecified list of “unregulated contaminants” are based on toxicity testing
guidelines (noncarcinogens) and risk characterization methodology (carcinogens). Use
of Annex A procedures may not always be identical, depending on the certifier.
AWWA B303-00 addresses additives requirements in Sec. 4.3 of the standard.
The transfer of contaminants from chemicals to processed water or the residual solids
is becoming a problem of greater concern. The language in Sec. 4.3.3 is a
recommendation only for direct additives used in the treatment of potable water to be
certified by an accredited certification organization in accordance with ANSI/NSF
Standard 60, Drinking Water Treatment Chemicals—Health Effects. However, users
of the standard may opt to make this certification a requirement for the product.
Users of this standard should also consult the appropriate state or local agency
having jurisdiction in order to
1. Determine additives requirements, including applicable standards.
2. Determine the status of certifications by all parties offering to certify
products for contact with, or treatment of, drinking water.
3. Determine current information on product certification.
*Persons in Canada, Mexico, and non-North American countries should contact the
appropriate authority having jurisdiction.
†American National Standards Institute, 11 W. 42nd St., New York, NY 10036.
‡NSF International, 789 N. Dixboro Rd., Ann Arbor, MI 48105.
iii

II. Special Issues.
II.A. Handling, Storage, and Safety Precautions. Aqueous sodium chlorite
solution is shipped in stainless-steel tank trucks according to US Department of
Transportation (DOT) regulations. The temperature in the tanks is maintained to
avoid crystallization. On receipt, the purchaser should dilute the solution appropri-
ately to prevent the crystallization of sodium chlorite. As received in loose-flake form
in metal containers, sodium chlorite will stand a considerable amount of rough
handling.
Sodium chlorite in contact with acid will react with rapid evolution of chlorine
dioxide gas. When heated above 347°F (175°C), dry sodium chlorite will decompose
rapidly, liberating oxygen, with the evolution of sufficient heat to make the
decomposition self-sustaining. If the decomposition of sodium chlorite is contained, as
in closed containers, the effect is explosive. Therefore, sodium chlorite should be
protected at all times from exposure to heat. In case of ignition, normal fire-fighting
equipment is relatively ineffective because sodium chlorite supplies its own oxygen.
The temperature of a sodium chlorite fire may exceed 3,992°F (2,200°C), and steam
explosions may result if water is sprayed directly on burning material. Mist settings
on nozzles should be used to cool burning material after the drums have been
isolated.
As a general rule, all flammables should be kept away from areas where
oxidizing agents, such as sodium chlorite, are stored. Sodium chlorite should be
stored only in an enclosed space specially prepared for this purpose. This storage
area should be kept cool and should be well ventilated and fireproof. Sodium chlorite
should be removed from the storage room only as needed for immediate use.
Nonreturnable shipping containers should be properly disposed of as soon as they are
empty. The shipping containers should never be used for any other purpose after they
are empty.
Sodium chlorite is a very active, strongly oxidizing chemical, which, in solid
form, reacts strongly with acids, sulfur, combustibles, and organic materials, such as
wood, rubber, fats, and oils. When sodium chlorite is to be removed from a drum, a
clean nonmetallic scoop or vessel uncontaminated with foreign matter should be
used. Dried or caked material should never be chipped or crushed, as ignition may
result. Complete instructions for the storage and safe handling of sodium chlorite
should be obtained from the manufacturer.
iv

Protective clothing should be worn when handling sodium chlorite. Plastic
gloves and eye protection should be worn as precautionary measures. Sodium chlorite
is poisonous if ingested. If any sodium chlorite comes into contact with clothing or
other combustible material (such as paper towels or cotton mops), spontaneous
ignition may occur upon drying. The clothing or combustible material should be
immediately soaked in water to remove all trace of the sodium chlorite, or
subsequently incinerated without delay. Refer to material safety data sheets (MSDS)
available from the chemical manufacturer or supplier for additional information.
III. Use of This Standard. AWWA has no responsibility for the suitability
or compatibility of the provisions of this standard to any intended application by any
user. Accordingly, each user of this standard is responsible for determining that the
standard’s provisions are suitable for and compatible with that user’s intended
application.
III.A. Purchaser Options and Alternatives. When purchasing sodium chlorite
under this standard, the purchaser’s specifications should include the following:
1. Standard used—that is, AWWA B303, Standard for Sodium Chlorite, of
latest revision.
2. An affidavit of compliance, if required (Sec. 6.3).
3. Quantity and form of sodium chlorite required (Sec. 4.1).
4. Sodium chlorite content required (Sec. 4.2).
5. Size and type of containers (Sec. 6.2).
6. Method of shipment desired.
7. Whether the recommended compliance with ANSI/NSF Standard 60,
Drinking Water Treatment Chemicals—Health Effects, is to be required. If this
certification is to be required, the purchaser’s specifications shall read, “This material
shall be certified as suitable for contact with or treatment of drinking water by an
accredited certification organization in accordance with ANSI/NSF Standard 60,
Drinking Water Treatment Chemicals—Health Effects.”
III.B. Modification to Standard. Any modification to the provisions, defini-
tions, or terminology in this standard must be provided in the purchaser’s
specifications.
IV. Major Revisions. Major revisions made to the standard in this edition
include the following:
1. The acceptance clause (Sec. I.C) and the Purchaser Options and
Alternatives (III.A) have been revised to approved wording.

2. A section on Product Certifications (4.3.3) has been added.
V. Comments. If you have any comments or questions about this standard,
please call the AWWA Volunteer and Technical Support Group, (303) 794-7711 ext.
6283, FAX (303) 795-7603, or write to the group at 6666 W. Quincy Ave., Denver, CO
80235.
vi

American Water Works Association
ANSI/AWWA B303-00
(Revision of ANSI/AWWA B303-95)
AWWA STANDARD FOR
SODIUM CHLORITE
SECTION 1: GENERAL
Sec. 1.1 Scope
This standard describes sodium chlorite, in either solid (granular, flake, or
powdered) or aqueous-solution form, for use in making chlorine dioxide for use in
water supply service. Sodium chlorite must be packaged, labeled, and registered
according to the Federal Insecticide, Fungicide, and Rodenticide Act as administered
by the US Environmental Protection Agency (USEPA).
Sec. 1.2 Purpose

The purpose of this standard is to provide purchasers, manufacturers, and
suppliers with the minimum requirements for sodium chlorite, including physical,
chemical, packaging, shipping, and testing requirements.
Sec. 1.3 Application

This standard can be referenced in specifications for purchasing and receiving
sodium chlorite and can be used as a guide for testing the physical and chemical
properties of sodium chlorite samples. The stipulations of this standard apply when
this document has been referenced and only to sodium chlorite used in water supply
service.

2 AWWA B303-00
SECTION 2: REFERENCE
This standard references the following document. In its latest edition, this
document forms a part of this standard to the extent specified in this standard. In
any case of conflict, the requirements of this standard shall prevail.
Standard Methods for the Examination of Water and Wastewater. APHA,*
AWWA, WEF.† Washington, D.C.
SECTION 3: DEFINITIONS
The following definitions shall apply in this standard:
1. Manufacturer: The party that manufactures, fabricates, or produces
materials or products.
2. Purchaser: The person, company, or organization that purchases any
materials or work to be performed.
3. Supplier: The party that supplies materials or services. A supplier may or
may not be the manufacturer.
SECTION 4: REQUIREMENTS
Sec. 4.1 Physical Requirements
4.1.1 Solid sodium chlorite. Solid sodium chlorite supplied according to this
standard shall be free flowing, contain no lumps, and be readily soluble in water. It
shall be stored in unopened original containers in a clean, cool, dry place.
4.1.2 Aqueous sodium chlorite solution. Aqueous sodium chlorite solution
may be clear and light-tan to straw-brown in color. The clarity shall permit the
reading of flow-measuring devices without difficulty.
Sec. 4.2 Chemical Requirements

4.2.1 Solid sodium chlorite. Solid sodium chlorite shall contain not less than
77.5 percent by weight NaClO2.
*American Public Health Association, 800 I Street N.W., Washington, DC 20001.

†Water Environment Federation, 601 Wythe St., Alexandria, VA 22314-1994.

SODIUM CHLORITE 3

shall contain not more than 50 percent by weight NaClO2. The purchaser may for
convenience of storage, low rate of consumption, or other reason, desire a
less-concentrated solution. (See Figure 1.)
Sec. 4.3 Impurities*

4.3.1 General. Sodium chlorite supplied according to this standard shall
contain no inorganic or organic substances in quantities capable of producing
deleterious or injurious effects on the health of those consuming water that has been
properly treated with the sodium chlorite. These quantities shall not be capable of
causing water so treated to exceed the USEPA safe drinking water standards.
4.3.2 Purity. Sodium chlorite based on 80 percent sodium chlorite content
shall contain not more than the following percentages of specific impurities by
weight:
4.3.2.1 Sodium chloride, 17.0 percent.
4.3.2.2 Sodium hydroxide, 3.0 percent.
4.3.2.3 Sodium carbonate, 2.0 percent.
4.3.2.4 Sodium sulfate, 3.0 percent.
4.3.2.5 Arsenic, 0.0003 percent.
4.3.2.6 Sodium nitrate, 0.1 percent.
4.3.2.7 Sodium chlorate, 4.0 percent.
4.3.3 Product certifications. Sodium chlorite is a direct additive used in the
treatment of potable water. This material should be certified as suitable for contact
with or treatment of drinking water by an accredited certification organization in
accordance with ANSI/NSF Standard 60, Drinking Water Treatment Chemicals—
Health Effects. Evaluation shall be accomplished in accordance with requirements
that are no less restrictive than those listed in ANSI/NSF Standard 60. Certification
shall be accomplished by a certification organization accredited by the American
National Standards Institute.
*See Sec. I.C of the foreword.

4 AWWA B303-00
Note: Prepared from 80% by weight Tech Grade Solid
Figure 1 Crystallization temperature of sodium chlorite solutions
SECTION 5: VERIFICATION
Sec. 5.1 Sampling
5.1.1 Sampling point. Samples shall be taken at the point of destination.
5.1.2 Solid sodium chlorite. Solid sodium chlorite samples from drums or
pails shall be taken with a clean sampling tube that is at least 2 cm in diameter.
5.1.2.1 Not less than 5 percent of the drums and pails shall be sampled. No
samples shall be taken from a container that has previously been opened.
5.1.2.2 The gross sample, weighing at least 2.0 kg, shall be thoroughly mixed
and divided to provide four 0.25-kg samples, which shall be sealed in airtight,
moistureproof, brown-glass containers. Each container shall be labeled to identify it,
and the label shall be signed and dated by the sampler. Distribution of portions shall
be as directed in Sec. 5.9.
5.1.3 Aqueous sodium chlorite solution. During the unloading of the tank or
tank car, five 0.5-L portions shall be taken at equally spaced intervals. The samples
shall be collected in a suitable glass container. As an alternative, two larger samples

SODIUM CHLORITE 5
may be taken, one at the beginning and one at the end of unloading. The total gross
sample should be at least 2.5 L.
5.1.3.1 The gross sample, totaling 2.5 L, shall be thoroughly mixed and three
0.2-L samples retained. These samples shall be sealed in airtight, moistureproof,
brown-glass containers and stored in a cool place. Each sample shall be labeled to
identify it, and the label shall be signed and dated by the sampler. Distribution of the
portions shall be as directed in Sec. 5.9.
5.1.4 Retention. Samples shall be retained 30 days after receipt of shipment
or longer if a complaint has been made to the supplier.
5.1.5 Solid samples. The 0.25-kg sample of solid sodium chlorite delivered to
the laboratory shall be mixed and reduced to approximately 100-g portions. One
portion shall be thoroughly mixed but not crushed by conventional methods, such as
mortar and pestle. The uniform mixture shall be stored in an airtight, moistureproof,
wide-mouth, brown-glass bottle and labeled appropriately with material description
and date of sample. The sample shall be kept in a cool, dry place and the container
kept closed, except when portions are being weighed from it, to avoid changes in
moisture content. Test solutions shall be prepared as follows:
1. Weigh approximately 40 g of sample to the nearest 0.1 mg in a weighing
bottle and transfer to a 1-L flask. Dissolve in distilled water, make up to volume, and
mix thoroughly. This solution is referred to as “test solution A.”
2. Pipette 50 mL of test solution A into a 500-mL volumetric flask, dilute to
volume, and mix thoroughly. This solution is referred to as “test solution B.”
5.1.6 Liquid samples. Using the 0.2-L sample of aqueous sodium chlorite
solution delivered to the laboratory, weigh 10 mL of the sample in a covered weighing
bottle. Transfer to a 500-mL volumetric flask and dilute to volume. This solution is
referred to as “test solution C.”
NOTE: The weight of 1 mL of 40 percent NaClO2 is approximately 1.36 g.
Aqueous sodium chlorite contains about half as much NaClO2 as the solid material.
The approximate amount of the NaClO2 present in the aqueous sodium chlorite can
be measured with an accurate hydrometer at a known temperature. Densities of
samples with equivalent sodium chlorite content may differ significantly, depending
on make-up salts or formulations present in the aqueous or dry material originally
used. A table showing the percentage of NaClO2 for various specific-gravity readings
may be obtained from the manufacturer.

6 AWWA B303-00
5.1.7 Chain of custody. A chain-of-custody form shall accompany all samples

and shall be properly completed by the individuals collecting samples.
Sec. 5.2 Test Procedures—General

The laboratory examination of the sample shall be completed within five
working days after receipt of the shipment.
Sec. 5.3 Test Procedure for Sodium Chlorite, Idometric Method

5.3.1 Principle. When sodium chlorite is added to a strongly acidic solution
containing potassium iodide, free iodine is formed via the following reaction:
– – + –
ClO2 4I + 4H → 2I 2 + Cl + 2H 2 O (Eq 1)
The iodine is subsequently reduced through titration with a standardized

sodium thiosulfate solution, using either a starch solution as a color indicator or
amperometric means to determine the titrimetric end point.
5.3.2 Reagents.
1. Crystalline potassium iodide (KI) or a 10 percent solution of KI.
2. 0.1N sodium thiosulfate solution. Dissolve 25 g Na 2S2O3•5H2O in 1 L
freshly boiled distilled water and standardize the solution against potassium biiodate
or potassium dichromate after at least two weeks in storage. Before placing in
storage, add a few millilitres CHCl3 (chloroform) to the solution to minimize bacterial
decomposition.
Standardize the 0.1N sodium thiosulfate by one of the following procedures:
a. Biiodate method. Dissolve 3.249 g anhydrous potassium biiodate
(KH[IO3]2) of primary standard quality in distilled water and dilute to 1,000 mL to
yield a 0.1000N solution. Store in a glass-stoppered bottle.
To 80 mL distilled water, add, with constant stirring, 1 mL concentrated
H 2SO 4, 10 mL 0.1000N KH(IO 3) 2 , and 1 g KI. Titrate immediately with 0.1N
Na 2S 2O 3 titrant until the yellow color of the liberated iodine is almost
discharged. Add 1 mL of the starch indicator solution and continue titrating
until the blue color disappears.
b. Dichromate method. Dissolve 4.904 g anhydrous potassium dichromate
(K2Cr2O7) of primary standard quality in distilled water and dilute to 1,000 mL to
yield a 0.1000N solution. Store in a glass-stoppered bottle.

SODIUM CHLORITE 7
Proceed as in the biiodate method, with the following exceptions:

Substitute 10 mL 0.1000N K 2Cr 2 O 7 for the KH(IO 3 ) 2 and let the reaction
mixture stand 6 min in the dark before titrating with the 0.1N Na 2S 2O 3 titrant.
1
normality Na2 S 2 O 3 = ------------------------------------------------------------------- (Eq 2)
mL Na 2 S 2 O 3 consumed
3. Approximately 0.5N hydrochloric acid (unstandardized).

4. Starch indicator solution. To 5 g starch (potato, arrowroot, or soluble),
add a little cold water and grind in a mortar to a thin paste. Pour paste into 1 L of
boiling distilled water, stir, and let settle overnight. Use the clear supernatant.
Preserve with 1.25 g salicylic acid, 4 g zinc chloride, or a combination of 4 g sodium
propionate and 2 g sodium azide/litre starch solution. Some commercial starch
substitutes are satisfactory, such as Thyodene or equal.
5.3.3 Procedure.
1. Pipette 25 mL of test solution B (Sec. 5.1.5(2)) or 10 mL of test solution C
(Sec. 5.1.6) into a 500-mL narrow-mouth Erlenmeyer flask containing 100–150 mL
distilled water.
2. Add 2 g of KI crystals, mix, and add 10 mL of 0.5N HCl.
3. Titrate the liberated iodine with standard 0.1N Na2S2O3 until most of the
iodine color is dispelled.
4. Add 2 mL of starch indicator and titrate until the blue color is discharged.
Record the number of millilitres of 0.1N sodium thiosulfate as “titration A.”
5.3.4 Calculation.
(titration) A × NNa 2 S 2 O 3 × 0.02261 × 100

percent NaClO2 = ----------------------------------------------------------------------------------------------------------------- (Eq 3)
weight of sample in test solution aliquot
NOTE: 0.02261 is the milliequivalent weight of sodium chlorite (NaClO2).
Sec. 5.4 Test Procedure for Sodium Hydroxide

5.4.1 Principle. The sodium hydroxide content is determined by titration with
standard sulfuric acid after treatment with barium chloride.
5.4.2 Reagents.
1. Barium chloride (BaCl2) crystals.
2. Phenolphthalein indicator, 1 percent solution.
3. Sulfuric acid, 0.1N standard solution.

8 AWWA B303-00
5.4.3 Procedure.
1. Pipette a 25-mL aliquot of test solution A (Sec. 5.1.5(1)) or test solution C
(Sec. 5.1.6) into a 250-mL Erlenmeyer flask.
2. Add approximately 0.5 g BaCl2 crystals and stopper the flask immediately
to prevent any atmospheric CO2 from entering the flask. Swirl to dissolve BaCl2.
Allow the flask to stand for 3–5 min before titrating to ensure complete precipitation
of the BaCO 3.
3. Titrate to a colorless end point with standard 0.1N H2SO4 using two drops
of phenolphthalein indicator. This titration is referred to as “titration C.”
5.4.4 Calculation.
( titration C ) × ( N H 2 SO 4 ) × 0.040 × 100

percent NaOH = --------------------------------------------------------------------------------------------------------------
weight of sample in aliquot (Eq 4)
NOTE: 0.040 is the milliequivalent weight of sodium hydroxide (NaOH).
Sec. 5.5 Test Procedure for Sodium Carbonate

5.5.1 Principle. The sodium carbonate content is determined by titration with
standard sulfuric acid of two samples, one of which has been treated with barium
chloride to precipitate the sodium carbonate (Sec. 5.4). The difference between these
two titrations is equivalent to the sodium carbonate present.
5.5.2 Reagents.
1. Sulfuric acid (H2SO4), 0.1N standard solution.
2. Phenolphthalein indicator, 1 percent solution.
5.5.3 Procedure.
(Sec. 5.1.6) into a 250-mL Erlenmeyer flask.
2. Titrate with 0.1N H2SO4 using phenolphthalein indicator to a colorless end
point. This titration is referred to as “titration D.” Save this sample for the sodium
chloride determination.
5.5.4 Calculation.
percent Na2 CO 3 =
(titration D – titration C) × N H 2 SO4 × 0.10599 × 100 (Eq 5)
-------------------------------------------------------------------------------------------------------------------------------------------------
weight of sample in aliquot
NOTE: 0.10599 is the milliequivalent weight of sodium carbonate (Na2CO 3).

SODIUM CHLORITE 9
Sec. 5.6 Test Procedure for Sodium Chloride

5.6.1 Principle. The sodium chloride content is determined by titration with
standard silver nitrate using the Mohr method.
5.6.2 Reagents.
1. Silver nitrate (AgNO 3), 0.1N standard solution.
2. Potassium chromate indicator, 30 percent solution.
5.6.3 Procedure. Titrate the solution reserved from the titration D determina-
tion (Sec. 5.5.3(2)) with 0.1N AgNO3 using six drops of K2CrO4 solution as indicator.
At the end point, the precipitate of AgCl will coagulate, and red Ag2CrO4 will form on
addition of excess AgNO3. Near the end point, add the AgNO3 drop by drop, stirring
well after each addition. Continue until the lemon-yellow color of the solution is
discharged and the first permanent reddish tint appears.
5.6.4 Calculation.
mL AgNO3 × N AgNO3 × 0.05845 × 100

percent NaCl = ----------------------------------------------------------------------------------------------------------
-
weight of sample in aliquot (Eq 6)
NOTE: 0.05845 is the milliequivalent weight of sodium chloride (NaCl).
Sec. 5.7 Test Procedure for Sodium Sulfate

5.7.1 Principle. The sodium sulfate content is determined turbidimetrically
by treatment with barium chloride with subsequent determination of the percent
transmittance of the turbid mixture at 420 nm.
5.7.2 Reagents.
1. Hydrochloric acid, concentrated.
2. Barium chloride (BaCl2) crystals.
5.7.3 Procedure.
(Sec. 5.1.6) into a 250-mL beaker. Add 5 mL of concentrated HCl and boil in the hood
until the solution is clear. Remove from heat and allow to cool.
2. After the sample is cool, dilute to 100 mL. Zero the colorimeter on the
sample using a 2-cm cell and the 420-nm filter. Add approximately 2.5 g of BaCl 2
crystals to the solution and mix well.
3. Transfer the turbid mixture to the 2-cm cell, read the percent transmit-
tance, and determine the weight of Na2SO4 from a standard curve.

10 AWWA B303-00
5.7.4 Calculation.
weight Na2 SO 4 curve × 100

percent Na2 SO4 = --------------------------------------------------------------------------
- (Eq 7)
weight of sample in aliquot
Sec. 5.8 Test Procedure for Arsenic

5.8.1 Principle. A sodium chlorite test sample is prepared and analyzed for
arsenic by atomic absorption spectrometry.
5.8.2 Reagents.
1. Nitric acid, concentrated HNO3.
5.8.3 Procedure.
1. For liquid samples, pour 25 mL of liquid sodium chlorite into a 150-mL
acid-washed beaker. For solid samples, dissolve 10 g of solid sodium chlorite in 100 mL
of deionized distilled water in a 150-mL acid-washed beaker.
2. Under a fume hood behind a splash shield, slowly acidify the sample with
concentrated HNO3 to a pH of less than 2. A purge or sparge setup is recommended
during acidification to volatilize any ClO2 released. Samples should be prepared
using a magnetic stirrer and slowly adding the acid.
3. Gently heat the solution to reduce the volume below 100 mL, making
certain that it does not boil.
4. Cool and quantitatively transfer to a 100-mL acid-washed volumetric flask
and make to volume with deionized distilled water.
5. Process a reagent blank by the same procedure.
6. Determine the presence of arsenic (As) (Sec. 5.8.4) according to Standard
Methods for the Examination of Water and Wastewater using the atomic absorption
technique. (Sec. 3113B).
5.8.4 Calculation.
mg As/L (test solution)

percent As = ------------------------------------------------------------------------------------------------------------
g sodium chlorite/L (test solution) × 104 (Eq 8)
Sec. 5.9 Test Procedure for Sodium Nitrate

Sodium nitrate shall be tested in accordance with Sec. 4110 Ion Chromatogra-
phy or 4500-NO-3 D. Nitrate Electrode Method in Standard Methods.

SODIUM CHLORITE 11
Sec. 5.10 Test Procedure for Sodium Chlorate

5.10.1 Principle. When sodium chlorate is added to a strongly acidic solution
(pH 0.1) containing potassium bromide, free bromine is formed. The solution is
neutralized with saturated dibasic sodium phosphate and reacted with potassium
iodide, with subsequent release of free iodine as described in Sec. 5.3.1. The iodine is
then reduced through titration with standardized sodium thiosulfate solution, either
by using a starch solution to indicate the end point or amperometric means to
determine the titrimetric end point.
5.10.2 Reagents. In addition to those reagents described in Sec. 5.3.2, the
following are required to complete the chlorate analysis.
1. 0.1N sodium thiosulfate (per Sec. 5.3.2).
2. Potassium iodide, ACS pure, free-flowing granular (per Sec. 5.3.2).
3. pH 7 buffer concentrate, commercial grade Fisher, 25 percent or equivalent.
4. Potassium bromide (KBr) solution, 5 percent freshly prepared. (Not to be
used if more than 1-week old.)
5. 12N hydrochloric acid, concentrated.
6. Saturated Na2HPO4.
5.10.3 Procedure.
1. Add 1 mL KBr solution and 10 mL 12N HCl (concentrated) to each of six
50-mL Erlenmeyer flasks equipped with tapered ground-glass stoppers.
2. Add 5 mL diluted material used for chlorite analysis (Sec. 5.1.6). Stopper
quickly, mix thoroughly, and place samples in a darkened area for 30 min.
3. To the other three flasks, add 5 mL distilled water used to prepare the
sample material used in step 2. Stopper, mix thoroughly, and place in dark for 30 min.
4. After 30 min, add approximately 0.5 g KI (crystals) to each flask, mix
thoroughly, and replace samples in dark until they are titrated in turn. KI should be
placed on glassine paper or plastic weigh-boats and added carefully to the flasks so
crystals do not adhere to insides of glass flasks.
5. Add 25 mL saturated Na2HPO4 solution to each of six 250-mL beakers (use
a 25- or 50-mL graduated cylinder to measure).
6. Consecutively with each sample, remove the reaction flask from the dark,
transfer contents into one of the beakers containing saturated Na2HPO4, and rinse
flask and stopper several times into the beaker to ensure iodine is completely
transferred. Repeat for all samples until contents of each reaction flask have been
transferred to the beakers containing phosphate buffer.

12 AWWA B303-00
7. Bring volume of each beaker to 175–200 mL with deionized water and

titrate consecutively with 0.1N sodium thiosulfate.
8. Determine average titrant volume for each series of samples and blanks.
ES in Eq 9 represents average volume for the titrant of samples. EB represents
average volume for the titrant of blanks.
9. A in Eq 9 represents the average titrant volume from triplicate samples of
the sodium chlorite feedstock titrated at pH 2, using same volumes of feedstock (Sec.
5.3.3).*
5.10.4 Calculation.
– [ ( ES mL – EB mL ) – A mL ] × 0.1N × 13 , 908
ClO3 = ---------------------------------------------------------------------------------------------------------------------- (Eq 9)
5 mL sample
1. Because sodium chlorate in diluted sodium chlorite feedstock is a

contaminant, the percent chlorate in undiluted feedstock is
– –3
– ClO3 mg/L ( DSF ) × 10 g/mg × 200 (DF)
ClO3 = -------------------------------------------------------------------------------------------------------------------- (Eq 10)
10 × specific gravity or density, (kg/L)
Where:
DFS = diluted feedstock
DF = dilution factor
Sec. 5.11 Rejection
5.11.1 Notice of nonconformance. If the sodium chlorite delivered to the
purchaser does not meet the requirements of this standard, the purchaser shall
provide a notice of nonconformance to the supplier within 10 days after receipt of the
shipment at the point of destination. The results of the purchaser’s tests shall prevail
unless the supplier notifies the purchaser within five working days after receipt of
the notice of nonconformance that a retest is desired. On receipt of the request for a
retest, the purchaser shall forward to the supplier one of the sealed samples taken
according to Sec. 5.1 of this standard. In the event that the test results obtained by
the supplier on retesting do not agree with the test results obtained by the purchaser,
the remaining sealed sample shall be forwarded, unopened, for analysis to a referee
*Chlorite ion determination must be done beforehand at pH 2. See Standard Methods Sec.
4500-ClO2 E.

SODIUM CHLORITE 13
laboratory agreed on by both parties. The results of the referee analysis shall be
accepted as final.
SECTION 6: DELIVERY*
Sec. 6.1 Marking
6.1.1 Required. Each shipment shall clearly identify the material. Each
package shall bear a yellow or white warning label as specified in US Department of
Transportation (DOT) regulations, and each package shall bear a legible marking
stating the net weight of the contents; the name of the manufacturer; the lot number;
and the brand name, if any. Because sodium chlorite is generally used by water
utilities to generate chlorine dioxide to control microbiological activity, it is a
pesticide as defined by current federal regulations. Each package must bear a label
reviewed and accepted by the USEPA. The label must list the following: brand name,
if any; manufacturer or distributor; the active ingredient and content; and net weight
of the contents. The label also must bear a USEPA registration number as well as the
USEPA establishment number indicating where the product was manufactured or
last repackaged.
6.1.2 Optional. Each package may also bear the statement: “This material
meets the requirements of AWWA B303, Standard for Sodium Chlorite,” provided
that the requirements of this document are met and the material is not of a different
quality in separate agreement between the supplier and purchaser.
Sec. 6.2 Packaging and Shipping

Packaging and shipping of sodium chlorite in any form shall conform to the
current regulations of the DOT† and other applicable federal, state, provincial, and
local requirements.
6.2.1 Solid sodium chlorite. Solid sodium chlorite may be shipped in 100-,
110-, or 220-lb (45.4-, 50-, or 100-kg) drums; 22- or 66-lb (10- or 30-kg) pails; and 1.1-
or 2.2-lb (0.5- or 1.0-kg) glass bottles. The drums and pails shall be made of steel with
*Governmental packaging and marking references reflect US requirements. Users of AWWA

B303 in Canada, Mexico, and non-North American countries should verify applicable local and
national regulatory requirements.
†Because of frequent changes in these regulations, their specific provisions should not be
included in the purchaser’s specifications.

14 AWWA B303-00
plastic liners, plastic-lined steel, or galvanized steel. Palleted drums shall be

packaged tight enough to hold the material without shifting. Sealing compound shall
not be used at the seams of the metal pails or drums.
6.2.1.1 Net weight. The net weight of the drums or pails shall be not less
than the recorded weight nor more than 10 percent greater. If exception is taken to
the weight of the material received, it shall be noted on the certified weight of not
less than 10 percent of the packages selected at random from the entire shipment.
may be shipped in tank trucks or railroad tank cars. The tanks shall be made of
stainless steel or any other suitable material that will not be attacked by the strongly
oxidizing solution. If smaller-than-tankload quantities are to be purchased, the
purchaser shall specify the size and type of container after consultation with the
manufacturer.
6.2.2.1 Weight certificates. The purchaser may require that bulk shipments
be accompanied by certified-weight certificates or the weights may be checked by the
purchaser at the point of delivery.
Sec. 6.3 Affidavit of Compliance

The purchaser may require an affidavit from the manufacturer or supplier that
the sodium chlorite supplied according to the purchaser’s order complies with all
applicable requirements of this standard.


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American Water Works Association

Effective date: January 1, 2001.

AMERICAN WATER WORKS ASSOCIATION

Copyright © 2000 American Water Works Association, All Rights Reserved

American National Standard

Copyright © 2000 by American Water Works Association

Copyright © 2000 American Water Works Association, All Rights Reserved

Robert D. Harriger, Chair

B.S. Aptowicz, Philadelphia Water Department, Philadelphia, Pa. (AWWA)

General Interest Members

P.E. Cote, Earth Tech, Cumberland, Maine (AWWA)

David Hildebrand, Vulcan Chemicals, Wichita, Kan. (CI)

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

SEC. PAGE SEC. PAGE

Foreword 4.3 Impurities.............................................. 3

1.1 Scope ...................................................... 1 Chlorate ........................................... 11

1.2 Purpose .................................................. 1 5.11 Rejection.............................................. 12

2 Reference............................................. 2 6.1 Marking............................................... 13

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

2ClO 2 + H 2 O 2 + 2NaOH → 2NaClO2 + 2H2 O + O 2

Under unfavorable conditions, ClO2 is also known to disproportionate to chlorite

Because there is no source of ammonia or nitrogen in the process, chloramines

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

AWWA STANDARD FOR

Sec. 1.2 Purpose

Sec. 1.3 Application

Copyright © 2000 American Water Works Association, All Rights Reserved

Sec. 4.2 Chemical Requirements

*American Public Health Association, 800 I Street N.W., Washington, DC 20001.

Copyright © 2000 American Water Works Association, All Rights Reserved

4.2.2 Aqueous sodium chlorite solution. Aqueous sodium chlorite solution

Sec. 4.3 Impurities*

*See Sec. I.C of the foreword.

Copyright © 2000 American Water Works Association, All Rights Reserved

Note: Prepared from 80% by weight Tech Grade Solid

Figure 1 Crystallization temperature of sodium chlorite solutions

Copyright © 2000 American Water Works Association, All Rights Reserved

Copyright © 2000 American Water Works Association, All Rights Reserved

5.1.7 Chain of custody. A chain-of-custody form shall accompany all samples

Sec. 5.2 Test Procedures—General

Sec. 5.3 Test Procedure for Sodium Chlorite, Idometric Method

The iodine is subsequently reduced through titration with a standardized

Copyright © 2000 American Water Works Association, All Rights Reserved

Proceed as in the biiodate method, with the following exceptions:

3. Approximately 0.5N hydrochloric acid (unstandardized).

(titration) A × NNa 2 S 2 O 3 × 0.02261 × 100

NOTE: 0.02261 is the milliequivalent weight of sodium chlorite (NaClO2).

Sec. 5.4 Test Procedure for Sodium Hydroxide

Copyright © 2000 American Water Works Association, All Rights Reserved

( titration C ) × ( N H 2 SO 4 ) × 0.040 × 100

NOTE: 0.040 is the milliequivalent weight of sodium hydroxide (NaOH).

Sec. 5.5 Test Procedure for Sodium Carbonate

NOTE: 0.10599 is the milliequivalent weight of sodium carbonate (Na2CO 3).

Copyright © 2000 American Water Works Association, All Rights Reserved

Sec. 5.6 Test Procedure for Sodium Chloride

mL AgNO3 × N AgNO3 × 0.05845 × 100