American Water Works Association

ANSI/AWWA B402-00
(Revision of ANSI/AWWA B402-95)

AWWA STANDARD
FOR
FERROUS SULFATE

Effective date: January 1, 2001.

First edition approved by AWWA Board of Directors June 2, 1968.
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

An American National Standard implies a consensus of those substantially concerned with its scope
and provisions. An American National Standard is intended as a guide to aid the manufacturer, the
consumer, and the general public. The existence of an American National Standard does not in any
respect preclude anyone, whether that person has approved the standard or not, from manufactur-
ing, marketing, purchasing, or using products, processes, or procedures not conforming to the
standard. American National Standards are subject to periodic review, and users are cautioned to
obtain the latest editions. Producers of goods made in conformity with an American National
Standard are encouraged to state on their own responsibility in advertising and promotional
materials or on tags or labels that the goods are produced in conformity with particular American
National Standards.

CAUTION NOTICE: The American National Standards Institute (ANSI) approval date on the front
cover of this standard indicates completion of the ANSI approval process. This American National
Standard may be revised or withdrawn at any time. ANSI procedures require that action be taken
to reaffirm, revise, or withdraw this standard no later than five years from the date of publication.
Purchasers of American National Standards may receive current information on all standards by
calling or writing the American National Standards Institute, 11 W. 42nd St., New York, NY 10036;
(212) 642-4900.

All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any
means, electronic or mechanical, including photocopy, recording, or any information or retrieval system,
except in the form of brief excerpts or quotations for review purposes, without the written permission of
the publisher.

Copyright © 2000 by American Water Works Association

Printed in USA

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 Committee Personnel
The AWWA Subcommittee on Ferrous Sulfate–Ferric Sulfate, which developed
this standard, had the following personnel at the time of approval:

Brannon H. Wilder, Chair

T.A. Barber Jr., Coca-Cola Company, Atlanta, Ga. (AWWA)

J.E. Brown, United Water Service, Houston, Texas (AWWA)
D.E. Gordon, QC Corporation, Baltimore, Md. (AWWA)
M.E. Kenney, Hobart, Ind. (AWWA)
C.L. Payne, Synergy Production Inc., Reisterstown, Md. (AWWA)
F.E. Rowe, Boliden Intertrade Inc., Atlanta, Ga. (AWWA)
Gene Shull, Fini Enterprises, Bacliff, Texas (AWWA)
B.H. Wilder, Atlanta, Ga. (AWWA)

The AWWA Standards Committee on Iron Salts, Aluminum Salts, and Related
Coagulant Aids, which reviewed and approved this standard, had the following
personnel at the time of approval:

Joe E. Brown, Chair

Gene Shull, Vice Chair

Consumer Members

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

T.A. Barber Jr., Coca-Cola Company, Atlanta, Ga. (AWWA)
J.E. Brown, United Water Service, Houston, Texas (AWWA)
J.P. Corless Jr., Washington Suburban Sanitary District—Water Operations,
Laurel, Md. (AWWA)
S.A. Dolan, United Water Delaware, Wilmington, Del. (AWWA)
E.D. Lowther Jr., American Water Works Service Company, Voorhees, N.J. (AWWA)
C.A. Owen, City of Tampa Water Department, Tampa, Fla. (AWWA)
R.S. Schultz, Bloomington Water Works, Hudson, Ill. (AWWA)
J.S. Trotter, City of Bloomington Utilities, Bloomington, Ind. (AWWA)
D.P. Wolz, City of Wyoming Clean Water Plant, Grandville, Mich. (AWWA)

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Copyright © 2000 American Water Works Association, All Rights Reserved

 General Interest Members

M.B. Alvarez, CH2M Hill, Orlando, Fla. (AWWA)

K.K. Au, American Water Works Service Company, Belleville, Ill. (AWWA)
D.T. Duke, East Liverpool, Ohio (AWWA)
J.D. Edwards, Burgess and Niple Ltd., Columbus, Ohio (AWWA)
J.J. Gemin, Earth Tech Inc., Kitchener, Ont. (AWWA)
R.D. Harriger, Eaglebrook Inc., Williamsburg, Va. (AWWA)
T.J. Lane,* Malcolm Pirnie Inc., Mahwah, N.J. (AWWA)
J.F. Myatt,† Earth Tech Inc., London, Ont. (AWWA)
P.J. Olson,* Standards Engineer Liaison, AWWA, Denver, Colo. (AWWA)
J.W. Patterson, J.W. Patterson Environmental Consultants,
Silverthorne, Colo. (AWWA)
L.W. VandeVenter, Metcalf & Eddy Inc., Wakefield, Mass. (NEWWA)
B.H. Wilder, Daytona Beach, Fla. (AWWA)

Producer Members

D.E. Gordon, QC Corporation Ltd., Baltimore, Md. (AWWA)

L.N. Hjersted, Kemiron Inc., Bartow, Fla. (AWWA)
C.B. Lind, General Chemical Corporation, Syracuse, N.Y. (AWWA)
J.J. Pavlicek, PVS Technologies, Detroit, Mich. (AWWA)
K.S. Salmen, Nalco Chemical Company, Naperville, Ill. (AWWA)
Gene Shull, Fini Enterprises, Bacliff, Texas (AWWA)
R.A. Smith, Rhodia Inc., Woodbury, Conn. (AWWA)

*Liaison, nonvoting
†Alternate

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Copyright © 2000 American Water Works Association, All Rights Reserved

 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 1.3 Application ............................................ 1

I Introduction ........................................ vii
2 References .......................................... 1
I.A Background......................................... vii
I.B History ............................................... viii 3 Definitions .......................................... 2
I.C Acceptance ......................................... viii
4 Requirements
II Special Issues ....................................... ix
4.1 Physical Requirements......................... 2
II.A Storage and Handling Precautions..... ix
4.2 Chemical Requirements ....................... 2
II.B Basis for Payment................................. x
4.3 Impurities.............................................. 3
III Use of This Standard............................ x
III.A Purchaser Options and Alternatives .. xi 5 Verification
III.B Modification to Standard..................... xi 5.1 Sampling ............................................... 4
IV Major Revisions.................................... xi 5.2 Test Procedures .................................... 4
V Comments ........................................... xii 5.3 Rejection................................................ 9

Standard 6 Delivery
1 General 6.1 Marking................................................. 9
1.1 Scope ...................................................... 1 6.2 Packaging and Shipping .................... 10
1.2 Purpose .................................................. 1 6.3 Affidavit of Compliance...................... 10

Copyright © 2000 American Water Works Association, All Rights Reserved

 This page intentionally blank.

Copyright © 2000 American Water Works Association, All Rights Reserved

 Foreword
This foreword is for information only and is not a part of AWWA B402.
I. Introduction.
I.A. Background. In 1903, the use of ferrous sulfate as a coagulant was
introduced in the United States in Quincy, Ill., by William B. Bull. Lime was used in
conjunction with ferrous sulfate because it aided in the oxidation and precipitation of
the iron as ferric hydroxide. The first large city to use this combination was St. Louis,
Mo., in 1904. “This was done in great haste in order that the visitors to the St. Louis
Exposition might not be repelled by the turbid water which St. Louisans put up with
since Kirkwood’s recommendation for sedimentation and slow sand filtration was
ruthlessly thrust aside in 1866. A permanent plant was soon built. Next among the
large cities to use sulfate of iron and lime were Cincinnati, 1907, and New Orleans,
1909.”*
The combination of ferrous sulfate and lime is an effective coagulant for the
clarification of turbid raw waters. Ferrous sulfate is also used as a base material for
the preparation of chlorinated copperas, another effective coagulant used for the
treatment of some waters. Chlorinated copperas is formed by reacting ferrous sulfate
(FeSO4•7H2O) with chlorine in the ratio of 7:1. Chlorine solution is added to a
solution of ferrous sulfate, usually in an enlarged pipe section that serves as a
retention tank and permits complete oxidation of the ferrous sulfate to the ferric
form.
Ferrous sulfate is produced as a coproduct in the manufacture of certain
metals and compounds, such as titanium dioxide. The principal sources providing
the greatest quantity of ferrous sulfate are the sulfate process for the
manufacture of titanium dioxide and the spent sulfuric acid solutions from the
pickling of steel, known as pickle liquor. For shipping, solutions made from these
two sources are reduced to moist and dried crystalline forms. For applications,
they are dissolved and applied to water through chlorine oxidizers or with lime.
Moist ferrous sulfate crystals are produced in a heptahydrate form (FeSO4•7H 2O)
containing up to 10 percent free moisture and 17 to 19 percent iron. This form of
ferrous sulfate is not free flowing and is generally used in large quantities for water
treatment. Dried ferrous sulfate, which is produced by dehydrating moist ferrous

*Baker, M.N., The Quest for Pure Water, AWWA, Denver (1948).

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Copyright © 2000 American Water Works Association, All Rights Reserved

sulfate crystals, can be obtained in two hydrate forms—heptahydrate (FeSO4•7H2O)
containing 19.5 to 20.5 percent iron and monohydrate (FeSO4•1H2O) containing 29
to 31 percent iron. The practice of shipping “pickle liquor” in liquid form began in
about 1965 and is still largely confined to areas within reasonable hauling distance
of heavy-steel producers. Today, liquid ferrous sulfate, produced by dissolving moist
or dried crystals, contains less free sulfuric acid than “pickle liquor.” Because of
transportation costs, it is generally sold within a 250-mi (402-km) radius of suppliers.
Liquid ferrous sulfate normally contains a minimum of 5.5 percent ferrous iron or 0.5
lb of ferrous iron per gal of liquid ferrous sulfate solution (60 kg/m3).
I.B. History. The first edition of this standard was prepared by the AWWA
Committee on Ferrous Sulfate and was approved by the AWWA Board of Directors on
June 2, 1968. The second edition of AWWA B402 was prepared by the AWWA
Standards Committee on Iron and Aluminum Salts and was approved by the AWWA
Board of Directors on Jan. 27, 1985. The third edition was prepared by the AWWA
Standards Committee on Iron Salts, Aluminum Salts, and Related Coagulant Aids
and was approved by the AWWA Board of Directors on Jan. 28, 1990. The fourth
edition of the standard was approved on Jan. 22, 1995. This edition was approved on
June 11, 2000.
I.C. Acceptance. In May 1985, the US 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.
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—

*Persons in Canada, Mexico, and non-North American countries should contact the
appropriate authority having jurisdiction.

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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 B402-00 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. 4.3.2 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.
II. Special Issues.
II.A. Storage and Handling Precautions. Moist ferrous sulfate heptahydrate
has a tendency to compact or cake in storage and has to be contained to prevent any
leakage of liquid ferrous sulfate, necessitating increased handling requirements. The
particle sizes and particle-size distributions of dried ferrous sulfate heptahydrate are
important if the material is to be stored for extended periods and then fed by
mechanical conveying equipment. The smaller the particles, the more readily the

†American National Standards Institute, 11 W. 42nd St., New York, NY 10036.

‡NSF International, 789 N. Dixboro Rd., Ann Arbor, MI 48105.

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Copyright © 2000 American Water Works Association, All Rights Reserved

compound will compact or cake in storage. Caking is an impediment to feeding with
conventional dry-conveying equipment. Heterogeneous particle size is also undesir-
able for feeding. In general, the cost of ferrous sulfate increases as particle coarseness
and uniformity increase. Particle size is of little importance if the compound is to be
dissolved and stored in an aqueous solution.
Ferrous sulfate monohydrate will not cake in storage if the material is
maintained in a dry storage area. Because of its concentrated state, monohydrate
normally takes longer to dissolve into a solution than does heptahydrate even though
both forms of ferrous sulfate are equally soluble.
For safety precautions, refer to material safety data sheets (MSDS) available
from the supplier or manufacturer.
II.B. Basis for Payment. The basis for payment when purchasing moist and
dried ferrous sulfate according to this standard is the net weight of the ferrous
sulfate supplied, excluding the weight of the container. One ton (907 kg) of dried
ferrous sulfate heptahydrate containing 19.5 percent soluble iron is equivalent to
0.67 tons (608 kg) of dried ferrous sulfate monohydrate containing 29 percent soluble
iron.
The basis for payment for liquid ferrous sulfate purchased according to this
standard is the quantity equal to the number of tons equivalent to dried ferrous
sulfate containing 19.5 percent soluble iron. This is calculated by determining the
total soluble-iron content of the liquid ferrous sulfate and dividing the weight (in
tons) of the liquid ferrous sulfate received by the ratio of 19.5 to the percentage of
total soluble iron in the liquid. For example, if 10 tons (9,070 kg) of liquid
ferrous sulfate are received with a total soluble-iron content of 7.5 percent, then
calculate 19.5/7.5 = 2.6 and 10/2.6 = 3.85. Therefore, 3.85 tons (3,493 kg) of
dried ferrous sulfate heptahydrate containing 19.5 percent total soluble iron is
equivalent to 10 tons (9,070 kg) of liquid ferrous sulfate containing 7.5 percent
total soluble iron.
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. The following items should be
covered in the purchaser’s specifications:

Copyright © 2000 American Water Works Association, All Rights Reserved

 1. Standard used—that is, AWWA B402, Standard for Ferrous Sulfate, of
latest revision.
2. Type of ferrous sulfate to be supplied (moist heptahydrate, dried heptahy-
drate, dried monohydrate, or liquid).
3. If liquid ferrous sulfate is required, the quantity equal to the number
of tons equivalent to dried ferrous sulfate containing 19.5 percent soluble iron
(Sec. II.B).
4. Particle size required for dried ferrous sulfate, if different from that
specified in Sec. 4.1.
5. If an analysis by a referee laboratory is required, the assignment of testing
costs (Sec. 5.3.1).
6. If dried ferrous sulfate is required, the quantity, container size, type, and
method of shipping (Sec. 6.2.1).
7. If liquid ferrous sulfate in tank cars is required, whether or not steam coils
for heating before unloading are required (Sec. 6.2.2).
8. Affidavit of compliance, certified analysis, or both, if required (Sec. 6.3).
9. 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.”
10. The specifications should state if an analysis by a certified laboratory for
the presence of barium, cadmium, chromium, mercury, nitrate, nitrite, selenium,
antimony, berillium, cyanide, nickel, thallium, and manganese is required.
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 changes made to the standard made in this
revision include the following:
1. Item number 10 has been added to Sec. III.A. Purchaser Options and
Alternatives.

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 V. Comments. If you have any comments or questions about this standard,
please call the AWWA Volunteer & 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.

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Copyright © 2000 American Water Works Association, All Rights Reserved

 American Water Works Association

ANSI/AWWA B402-00
(Revision of ANSI/AWWA B402-95)

AWWA STANDARD FOR

FERROUS SULFATE

SECTION 1: GENERAL
Sec. 1.1 Scope
This standard describes ferrous sulfate (FeSO4) in moist, dried, and solution
(liquid) forms for water supply service application.

Sec. 1.2 Purpose

The purpose of this standard is to provide purchasers, manufacturers, and
suppliers with the minimum requirements for ferrous sulfate, including physical,
chemical, packaging, shipping, and testing requirements.

Sec. 1.3 Application

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

SECTION 2: REFERENCES
This standard references the following documents. In their latest editions, they
form a part of this standard to the extent specified in this standard. In any case of
conflict, the requirements of this standard shall prevail.

Copyright © 2000 American Water Works Association, All Rights Reserved

2 AWWA B402-00

ASTM* E11, Standard Specification for Wire-Cloth Sieves for Testing Purposes.
Standard Methods for the Examination of Water and Wastewater. APHA,†
AWWA, and WEF.‡ Washington, D.C. (20th ed., 1998).

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§
Dried ferrous sulfate shall meet the following requirements for particle size: not
less than 90 percent shall pass a No. 10 US Standard Sieve with 9.21 openings per
linear inch, and 100 percent shall pass a No. 4 US Standard Sieve with 4.22 openings
per linear inch.
In many cases, these requirements can be reduced safely with a resultant
savings in purchase price. The allowable modification, however, can only be
determined by experience based on the purchaser’s storage conditions and feeding
equipment.

*American Society for Testing and Materials, 100 Barr Harbor Dr., West Conshohocken, PA
19428-2959.
†American Public Health Association, 1015 15th St. N.W., Washington, DC 20005.
‡Water Environment Federation, 601 Wythe St., Alexandria, VA 22314-1994.
§All sieve numbers referred to in this standard are US Standard Sieve Series numbers, as
specified in ASTM E11.

Copyright © 2000 American Water Works Association, All Rights Reserved

 FERROUS SULFATE 3

Sec. 4.2 Chemical Requirements

4.2.1 Moist ferrous sulfate. Moist ferrous sulfate shall contain not less than
17.5 percent, by weight, of total soluble iron in the heptahydrate form; not more than
2.0 percent, by weight, of free sulfuric acid, expressed as H2SO4; and not more than
3.0 percent, by weight, of insoluble matter.
4.2.2 Dried ferrous sulfate. Dried ferrous sulfate shall contain not less than
19.5 percent, by weight, of total soluble iron in the heptahydrate form; not less than
29 percent, by weight, of total soluble iron in the monohydrate form; not more than
2.0 percent, by weight, of free sulfuric acid, expressed as H2SO4; and not more than
3.0 percent, by weight, of insoluble matter. Dried ferrous sulfate heptahydrate may
contain up to 1 percent of either calcium carbonate or bentonite to inhibit caking;
however, the addition of either of these substances shall not reduce the available iron
to less than 19.5 percent in the dried ferrous sulfate heptahydrate form.
4.2.3 Liquid ferrous sulfate. Liquid ferrous sulfate shall contain a minimum
of 5.5 percent total soluble iron with 0.6 percent free sulfuric acid and not more than
0.9 percent insoluble matter. For material with a higher total soluble-iron content,
the free sulfuric acid and insoluble matter may be proportionally higher, if acceptable
to the purchaser.

Sec. 4.3 Impurities*

4.3.1 General. The ferrous sulfate supplied according to this standard shall
contain no substances in quantities capable of producing deleterious or injurious
effects on the health of those consuming a water that has been properly treated with
ferrous sulfate. Dried ferrous sulfate shall contain no detergent compound or
sequestering agent. In addition, the ferrous sulfate supplied shall not contain any
substances in quantities that will result in treated sludges that will be designated as
hazardous wastes by local, state, or federal authorities.
4.3.2 Product certifications. Ferrous sulfate 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

*See Sec. I.C. of the foreword.

Copyright © 2000 American Water Works Association, All Rights Reserved

4 AWWA B402-00

shall be accomplished by a certification organization accredited by the American

National Standards Institute.

SECTION 5: VERIFICATION
Sec. 5.1 Sampling
5.1.1 Sampling point. Samples shall be taken at the point of destination.
5.1.2 Moist or dried ferrous sulfate. If the ferrous sulfate is dried, a gross
sample of at least 10 lb (4.5 kg) shall be obtained by combining individual samples
obtained as follows:
5.1.2.1 For packaged material, the number of packages closest to 5 percent of
the total number shall be sampled, but no less than 5 nor more than 15 packages in
any one shipment shall be sampled. Sampling of packages may be done with a
sampling tube at least 3/4 in. (19.1 mm) in diameter. A minimum of five equal
portions shall be taken at different locations within a package.
5.1.2.2 For bulk material, a mechanical sampling device may be used.
5.1.2.3 The gross sample shall be mixed thoroughly and then divided to
provide three 1-lb (0.45-kg) material samples. These samples shall be stored in
airtight, moistureproof glass containers; each clearly identified with a label signed by
the sampler.
5.1.3 Liquid ferrous sulfate. If the ferrous sulfate is liquid, three 1-pt
(473-mL) samples shall be taken from each tank car or tank truck load. These
material samples shall be sealed in airtight glass containers; each clearly identified
with a label signed by the sampler.
5.1.4 Distribution of material samples. One of the three sealed material
samples is for immediate use by the purchaser for testing of the shipment according
to Sec. 5.2. The two remaining material samples shall be retained for future use
according to Sec. 5.3.1, if necessary.
5.1.5 Material sample retention. Material samples shall be retained for at
least 30 days after the date of receipt of the shipment before they are discarded.

Sec. 5.2 Test Procedures

5.2.1 Laboratory examination. Laboratory examination of the sample by the
purchaser shall be completed within five working days after receipt of the shipment.
5.2.2 Sample preparation.

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 FERROUS SULFATE 5

5.2.2.1 Moist or dried ferrous sulfate. Test samples of moist or dried ferrous
sulfate shall be obtained from one of the three material samples. The dried ferrous
sulfate sample shall be divided into two samples, one of 150–200 g for physical screen
size determination and a second of approximately 100 g for the chemical analyses.
The sample for physical screen size shall be used for the sieve analysis (Sec. 5.2.3).
The sample for chemical analyses shall be reduced by either mechanical grinding or
in a mortar by hand to such fineness that all of it passes through a No. 30 US
Standard Sieve. These operations shall be carried out rapidly to minimize the change
in moisture content of the sample. After thorough mixing, the sample for chemical
analyses shall be stored in an airtight glass container.
5.2.2.2 Liquid ferrous sulfate. Test samples of liquid ferrous sulfate shall be
obtained from the material sample and shaken thoroughly before each test portion is
withdrawn for analysis.
5.2.3 Sieve analysis for dried ferrous sulfate. Transfer the 150–200 g sample
(from Sec. 5.2.2.1) to an 8-in. diameter set of US Standard Sieves composed of a No. 4
sieve, a No. 10 sieve, and a pan. Sieve by lateral and vertical motions accompanied by
jarring action. Continue 5 min or until an additional 3 min of sieving time fails to
change the results of any sieve fraction by 0.5 percent of total sample weight.
5.2.4 Test procedure for insoluble matter.
5.2.4.1 Reagent. Deionized water containing 1 percent sulfuric acid by
weight.
5.2.4.2 Procedure.
1. Dissolve 3.5 g of the dried ferrous sulfate monohydrate sample, 5 g of the
moist or dried ferrous sulfate heptahydrate sample, or 13 g of the liquid ferrous
sulfate sample in 150 mL of deionized water containing 1 percent sulfuric acid.
Samples should be weighed to the nearest 0.1 g.
2. Filter through a Gooch crucible and wash the residue with several portions
of the acidified deionized water.
3. Transfer the filtrate to a 500-mL volumetric flask and fill to the 500-mL
mark with deionized water.
4. Dry the Gooch crucible to constant weight at 100o–150oC.
5.2.4.3 Calculation.

weight of insoluble residue

% insoluble material = -------------------------------------------------------------------------- × 100 (Eq 1)
weight of sample

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6 AWWA B402-00

5.2.5 Test procedure for total soluble iron.

5.2.5.1 Reagents.
5.2.5.1.1 The following reagents are used regardless of whether the zinc reduction
method or the stannous chloride reduction method is used:
1. 25 percent phosphoric acid.
2. 0.3 percent diphenylamine barium sulfonate.
3. Approximately 0.1N potassium dichromate. This is obtained by dissolving
4.903 g of the recrystallized dehydrated salt in 1 L of deionized water, allowing the
solution to stand a few hours, and then standardizing it against Sibley iron ore
provided by the National Institute of Standards and Technology.
5.2.5.1.2 The following reagents are used with the zinc reduction method:
1. Iron-free granulated zinc, 10–20 mesh.
2. Iron-free sulfuric acid, 1:3.
5.2.5.1.3 The following reagents are used with the stannous chloride reduction
method:
1. Saturated solution of mercuric chloride.
2. 5 g stannous chloride in dilute hydrochloric acid. The solution is obtained
by dissolving the stannous chloride in 10 mL of concentrated hydrochloric acid,
diluting to 50 mL with deionized water, and adding a few pieces of metallic tin. (This
solution keeps best when refrigerated.)
3. Concentrated hydrochloric acid.
5.2.5.2 Procedure. After thoroughly mixing the filtrate from the determina-
tion of the insoluble matter (Sec. 5.2.4), pipette a 100-mL portion of this solution into
a 250-mL Erlenmeyer flask. Prepare the solution for titration by using one of the
following methods:
1. Zinc reduction method: To the solution, add exactly 1 g of granulated zinc
and 20 mL of diluted sulfuric acid and close the mouth with a Bunsen valve. Heat
gently. The zinc should be dissolved in less than 25 min. After the zinc has been
dissolved, boil gently for 5 min and cool to room temperature with the Bunsen valve
in place. Rinse the Bunsen valve with deionized water; add 30 mL of phosphoric acid
and 7 to 10 drops of diphenylamine barium sulfonate indicator. The total volume of
the solution should be between 150 and 200 mL.
2. Stannous chloride reduction method: To the solution, add 10 mL of
hydrochloric acid and heat to boiling. Add the stannous chloride solution by drops
until the last trace of greenish-yellow color disappears. Then add one additional drop

Copyright © 2000 American Water Works Association, All Rights Reserved

 FERROUS SULFATE 7

in excess to ensure complete reduction. Cool to 20oC, add 60 mL of deionized water,

and then add, in one pouring, 20 mL of saturated mercuric chloride solution with
agitation to ensure instantaneous mixing. If a white, milky precipitate forms, add
30 mL of 25 percent phosphoric acid solution and 7 to 10 drops of diphenylamine
barium sulfonate indicator. The volume of the solution should be between 150 and
200 mL. If a dark precipitate forms, there is too much stannous chloride. If no
precipitate forms, there is too little stannous chloride. In either case, the entire
procedure must be repeated on a new sample.
3. Titration: Slowly titrate the prepared solution with standard potassium
dichromate solution, stirring constantly. Near the end point, the green color of the
solution deepens to a blue green or, in the presence of large amounts of iron, to
grayish blue. Beyond this point, the dichromate solution is added by drops until the
color changes to an intense violet blue. Subtract an indicator correction of 0.05 mL
from the volume of dichromate used.
5.2.5.3 Calculation.

% total soluble iron (Fe) =

(net mL K2 Cr 2 O 7 ) × ( NK 2 Cr 2 O 7 ) × 0.05585 × 5 × 100
-------------------------------------------------------------------------------------------------------------------------------------------------------------------
weight of sample, in grams (Sec. 5.2.4.2.) (Eq 2)

NOTES:
1. Copper in quantities greater than 1 mg lowers the results; trivalent arsenic
raises the results.
2. When potassium dichromate is used in titration, there is no fading. Back
the titration with the standard ferrous solution if possible. There is no interference
from either organic substances of zinc, aluminum, manganese, nickel, cobalt, or
chromium.
5.2.6 Test procedure for free acid.
5.2.6.1 Reagents.
1. Isopropyl alcohol, 99 percent.
2. Sodium hydroxide (carbonate free), 0.05N.
3. Phenolphthalein indicator.

Copyright © 2000 American Water Works Association, All Rights Reserved

8 AWWA B402-00

5.2.6.2 Procedure.
1. Place 8.45 g of the dried ferrous sulfate monohydrate sample, or 12.25 g of
the moist or dried ferrous sulfate heptahydrate sample, or 32.5 g of the liquid ferrous
sulfate sample in a 500-mL glass-stoppered Erlenmeyer flask.
2. Add 100 mL of isopropyl alcohol and shake with a rotary motion for 10 min.
3. Filter through a Gooch crucible, retaining as much of the ferrous sulfate in
the flask as possible.
4. Wash the residue in the flask with 25-mL portions of alcohol.
5. Wash the Gooch crucible with a final 25-mL portion.
6. Titrate the filtrate with sodium hydroxide using phenolphthalein as the
indicator.
7. Run a blank using the same procedure and the same amount of alcohol.
8. Subtract the reading obtained on the blank from that obtained on the
treated sample.
5.2.6.3 Calculation.

% free acid (as H 2 SO4 ) =

( mL NaOH – blank ) × ( N NaOH ) × 0.049 × 100
------------------------------------------------------------------------------------------------------------------------------------------
weight of sample, in grams (Sec. 5.2.6.2) (Eq 3)

5.2.6.4 Sodium hydroxide correction. The amount of NaOH used in the

determination includes the amount used in reacting with ferric sulfate that is taken
in solution by the alcohol. If the percentage of free acid, as calculated, does not exceed
the maximum set in the specifications, no correction needs to be made for the NaOH
used by the ferric sulfate. If the percentage of free acid, as calculated, exceeds the
amount specified, the quantity of NaOH used in the reaction with the ferric sulfate
must be subtracted from the actual quantity used in titrating the alcoholic solution.
This correction is determined as follows:
After the titration with the NaOH is completed, evaporate the alcohol on a
steam bath. Determine the amount of iron in the residue, either colorimetrically or
gravimetrically. Then calculate the quantity of NaOH used in the reaction with the
iron as ferric iron from Eq 4:

mL 0.05N NaOH =
weight of iron, in grams × ( 2.149g NaOH/gFe )
----------------------------------------------------------------------------------------------------------------------------------
0.002g NaOH/mL 0.05 N NaOH (Eq 4)

Copyright © 2000 American Water Works Association, All Rights Reserved

 FERROUS SULFATE 9

NOTE: Ferrous sulfate always contains some ferric sulfate. Ferrous sulfate is
insoluble in isopropyl alcohol, but ferric sulfate is slightly soluble and is the source of
the iron found in the alcoholic extract.

Sec. 5.3 Rejection

5.3.1 Notice of nonconformance. If the ferrous sulfate delivered does not meet
the requirements of this standard, a notice of nonconformance shall be provided by
the purchaser to the supplier within 10 working 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. Upon receipt of the request for a retest, the
purchaser shall forward to the supplier one of the sealed samples taken according to
Sec. 5.1.4. In the event that the 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 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 of material shall carry with it some means of
identification.
6.1.1.1 Each container of packaged material of moist or dried ferrous sulfate
shall have marked legibly on it the net weight of the contents, the name of the
manufacturer, the lot number, and a brand name, if any, and shall bear such other
markings as required by applicable regulations and laws.†
6.1.1.2 When shipped in bulk, the information required in Sec. 6.1.1.1 for
packaged material shall accompany the bill of lading.

*Governmental marking, packaging, and shipping references reflect US requirements. Users of

B402 from 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.

Copyright © 2000 American Water Works Association, All Rights Reserved

10 AWWA B402-00

6.1.2 Optional. The containers may also bear the statement: “Guaranteed by
(name of manufacturer) to meet AWWA B402, Standard for Ferrous Sulfate,”
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 ferrous sulfate shall conform to the current,
applicable federal, state, and local regulations. Each shipment shall comply with the
US Department of Transportation regulations for shipping and marking.
6.2.1 Moist or dried ferrous sulfate. Moist or dried ferrous sulfate shall be
shipped in bulk or in 50-lb or 100-lb (22.68-kg or 45.35-kg) moistureproof bags, as
specified by the purchaser. The supplier shall ensure that bulk trucks and cars are
suitably clean before loading.
6.2.1.1 The net weight of packages of the dried material shall not deviate from
the recorded weight by more than 2.5 percent. Objection to the weight of the material
received shall be based on a certified unit weight of not less than 10 percent of the
packages shipped and selected at random from the entire shipment.
6.2.2 Liquid ferrous sulfate. Liquid ferrous sulfate shall be shipped by tank
car or tank truck, as specified by the purchaser. In cold weather or in cold climates,
the purchaser may require in the purchase specifications that tank cars used for
liquid shipment shall be equipped with steam coils for heating the material before
unloading. No tank car or tank truck that has been used at any time for shipping
toxic materials of any kind shall be used for shipping liquid ferrous sulfate under this
standard. All truck shipments shall be accompanied by certified weight tickets. It is
the responsibility of the supplier to ensure that tank cars and tank trucks are
suitably clean before loading.

Sec. 6.3 Affidavit of Compliance

The purchaser may require the manufacturer or supplier to provide an affidavit
attesting that the ferrous sulfate supplied according to the purchaser’s specifications
complies with all applicable requirements of this standard. The purchaser may also
require that the manufacturer or supplier provide a certified analysis of the ferrous
sulfate. The purchaser may also elect to use in-house analytical equipment to ensure
compliance with this standard.

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