ASTM E776-87(1996)
(Test Method)Standard Test Method for Forms of Chlorine in Refuse-Derived Fuel
Standard Test Method for Forms of Chlorine in Refuse-Derived Fuel
SCOPE
1.1 This test method covers the determination of the forms of chlorine in refuse-derived fuel-three (RDF): total chlorine, water-soluble chloride, and water-insoluble chlorine.
1.2 This test method may be applicable to any waste material from which a laboratory analysis sample can be prepared.
1.3 This standard may involve hazardous materials, operations, and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific precautionary statements see Section 6 and 11.2.1.
General Information
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Standards Content (Sample)
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Designation: E 776 – 87 (Reapproved 1996)
Standard Test Method for
Forms of Chlorine in Refuse-Derived Fuel
This standard is issued under the fixed designation E 776; 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 (ϵ) indicates an editorial change since the last revision or reapproval.
1. Scope 3.1.1 refuse-derived fuels—solid forms of refuse-derived
fuels from which appropriate analytical samples may be
1.1 This test method covers the determination of the forms
prepared are defined as follows in ASTM STP 832:
of chlorine in refuse-derived fuel-three (RDF): total chlorine,
RDF-1—Wastes used as a fuel in as-discarded form with
water-soluble chloride, and water-insoluble chlorine.
only bulky wastes removed.
1.2 This test method may be applicable to any waste
RDF-2—Wastes processed to coarse particle size with or
material from which a laboratory analysis sample can be
without ferrous metal separation.
prepared.
RDF-3—Combustible waste fraction processed to particle
1.3 This standard does not purport to address all of the
sizes, 95 % passing 2-in. square screening.
safety concerns, if any, associated with its use. It is the
RDF-4—Combustible waste fraction processed into powder
responsibility of the user of this standard to establish appro-
form, 95 % passing 10-mesh screening.
priate safety and health practices and determine the applica-
RDF-5—Combustible waste fraction densified (compressed)
bility of regulatory limitations prior to use. For specific
into the form of pellets, slugs, cubettes, or briquettes.
precautionary statements see Section 6 and 11.2.1.
3.1.2 total chlorine—all chlorine as determined in the
2. Referenced Documents
refuse-derived fuel.
3.1.3 water-insoluble chlorine—water-insoluble chlorides
2.1 ASTM Standards:
and chlorine in the refuse-derived fuel.
D 1193 Specification for Reagent Water
3.1.4 water-soluble chloride—those chlorides which are
E 144 Practice for Safe Use of Oxygen Combustion
water-solubilized by water extraction as determined in the
Bombs
refuse-derived fuel.
E 180 Practice for Determining the Precision of ASTM
Methods forAnalysis and Testing of Industrial Chemicals
4. Summary of Test Method
E 287 Specification for Burets
4.1 The forms of chloride and chlorine are determined. The
E711 Test Method for Gross Calorific Value of Refuse-
5 various procedures in the method convert the forms of chlorine
Derived Fuel by the Bomb Calorimeter
into a water-soluble chloride form that can be quantitated by
E 829 Practice for Preparing Refuse-Derived Fuel (RDF)
5 titration.
Laboratory Samples for Analysis
4.1.1 Total Chlorine—The sample is combusted in an oxy-
3. Terminology gen atmosphere. The chlorine is converted to chloride and
absorbed in an alkaline solution.
3.1 Definitions of Terms Specific to This Standard:
4.1.2 Water-Soluble Chlorides—A portion of the analysis
sample is successively extracted with hot chloride-free water.
4.1.3 Water-Insoluble Chlorine—Water-insoluble chlorine
is calculated from the results of the total chlorine and the
water-soluble chloride determination where:
water2insoluble chlorine 5 total chlorine 2 water2soluble chlorides
(1)
This test method is under the jurisdiction of ASTM Committee D34 on Waste
Management and is the direct responsibility of Subcommittee D34.06 on Recovery
and Reuse.
Current edition approved Aug. 28, 1987. Published October 1987. Originally
published as E 776 – 81. Last previous edition E 776 – 81.
Annual Book of ASTM Standards, Vol 11.01.
Annual Book of ASTM Standards, Vol 14.02.
4 6
Annual Book of ASTM Standards, Vol 15.05. Thesaurus on Resource Recovery Terminology, ASTM STP 832, ASTM, 1983,
Annual Book of ASTM Standards, Vol 11.04. p. 72.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 776 – 87 (1996)
FIG. 1 Graph From a Potentiometric Titration of Chloride
4.2 The chlorides contained in the alkaline solution (4.1.1) reduced beforehand by treatment with ferrous sulfate or a
and the extraction solution (4.1.2) are determined by potentio- similar reducing agent.
metric (see Section 13) or modified Volhard titration (see 7.2.2 Salts of mercury and palladium interfere by reacting
Section 14). with thiocyanate. They may be removed by precipitation with
hydrogen sulfide before the addition of silver nitrate. The
5. Significance and Use
excess of sulfide is easily removed by gently boiling the acid
solution for a few minutes. Sulfite can be eliminated in the
5.1 The standard is available to producers and users of RDF
same way.
fordeterminingthecontentandformsofchlorinepresentinthe
7.2.3 Cyanide is also precipitated by silver nitrate. It is
fuel.
usually determined separately by the Liebig-Deniges method
and a correction is applied to the results of the Volhard
6. Precautions
titration.
6.1 Due to the origins of RDF in municipal waste, common
7.2.4 The Volhard method, as with the potentiometric
sense dictates that some precautions should be observed when
method, directly applied to a mixture of halides can determine
conducting tests on the samples. Recommended hygienic
only total halide content excluding fluoride. Preliminary treat-
practices include use of gloves when handling RDF; wearing
ment is necessary for the determination of chloride alone in a
dust masks (NIOSH-approved type), especially while milling
mixture.
RDF samples; conducting tests under negative pressure hood
when possible; and washing hands before eating or smoking.
8. Apparatus
8.1 Balance, having a sensitivity of 0.1 mg.
7. Interferences
8.2 Apparatus for Bomb Combustion of the Sample.
7.1 Potentiometric Titration Method A:
8.2.1 Oxygen Bomb, similar to that used in the determina-
7.1.1 Iodide and bromide are also titrated as chloride.
tion of the calorific value of refuse-derived fuels as described
Ferricyanide causes high results and must be removed. Chro-
in Test Method E 711E711.
mate and dichromate interfere and should be reduced to the
8.2.2 Capsule, for holding the sample, approximately 25
chromic state or be removed. Ferric iron interferes if present in
mm in diameter at the top, approximately 12 mm deep, and
an amount substantially higher than the amount of chloride.
conforming to Test Method E 711E711.
Chromic ions, ferrous ions, and phosphates do not interfere.
8.2.3 Firing Wire, as specified in Test Method E 711E711.
7.1.2 Grossly contaminated sample solutions usually re-
8.2.4 Firing Circuit, as specified in Test Method
quire pretreatment. Where contamination is minor, some con-
E711E711.
taminants can be destroyed simply by the addition of nitric
acid.
Scott’s Standard Method of Chemical Analysis, edited by M. H. Furman, D.
7.2 Volhard Titration Method B:
Van Nostrand Co., Inc., New York, NY.
7.2.1 Compounds that have a strong oxidizing action inter-
Koltoff, I. M., and Stenger, V. A., Volumetric Analysis II, Interscience
fere by reacting with thiocyanate. These compounds should be Publishers, Inc., New York, NY.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 776 – 87 (1996)
8.2.5 Metal Vessel, cylindrical, such that the bomb will be distilled or boiled water, dilute to 1 L, and standardize against
fully immersed when approximately 2 L of water are added. 0.025 N AgNO solution as directed in 14.1.2.
8.3 Magnetic Stirrer and Stirring Bars.
10. Sampling
8.4 Apparatus for Potentiometric Titration:
8.4.1 Potentiometric Titration Assembly, using a silver in-
10.1 RDF products are frequently nonhomogeneous. For
dicator electrode and a calomel reference electrode containing this reason significant care should be exercised to obtain a
a saturated sodium nitrate solution as a bridge.
representative laboratory sample from the RDF lot to be
characterized.
NOTE 1—All glassware and graduated apparatus should be Class A or
10.2 The sampling method for this procedure should be
equivalent as described in Specification E 287E 287.
based on agreement between the involved parties.
9. Reagents
10.3 The laboratory sample must be air-dried and the
particle size reduced to pass a 0.5-mm screen as described in
9.1 Purity of Reagents—Reagent grade chemicals shall be
Practice E 829E 829. This procedure must be performed care-
used in all tests. Unless otherwise indicated, it is intended that
fully to preserve the sample’s representative characteristics
all reagents shall conform to the specifications of the Commit-
(otherthanparticlesize)whilepreparingtheanalysissampleto
tee on Analytical Reagents of the American Chemical Society
be used in the procedures.
where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
PREPARATION OF CHLORINE SOLUTIONS FOR
sufficiently high purity to permit its use without lessening the
ANALYSIS
accuracy of the determination.
9.2 Purity of Water—Unless otherwise indicated, reference
11. Total Chlorine (Oxygen Bomb Method)
to water shall be understood to mean at least Type III reagent
11.1 Preparation of Sample and Bomb (see Note 3):
water conforming to Specification D 1193D 1193.
11.1.1 Sample Weight—Weigh to the nearest 0.1 mg about 1
9.3 Potassium Hydroxide Solution (0.2 N)—Dissolve 13.2
g of thoroughly mixed air-dried analysis RDF sample into the
g of potassium hydroxide (KOH) in water and dilute to 1 L
bombcapsule.Apelletmaybemadefromtheair-driedanalysis
with water.
RDF sample, accurately weighed, and placed into the bomb
9.4 Oxygen—The oxygen used for combustion shall be free
capsule. Place the capsule containing the sample into the
of combustible matter. Oxygen manufactured from liquid air,
capsule holder.
guaranteed to be greater than 99.5 % pure, will meet this
requirement.
NOTE 2—There is a tendency for chlorine to adhere to the bomb walls,
especially if the bomb is pitted or has been used previously to determine
9.5 Sodium Chloride (NaCl)—Primarystandardquality(pu-
high levels of chlorine. Unless the bomb is thoroughly cleaned before use,
rity of 100 6 0.02 %).
the blanks may have values in excess of reality.
9.6 Sodium Chloride, Primary Standard Solution (0.025
N)—Crush 10 to 20 g of primary standard sodium chloride 11.1.2 Firing Wire—Connect a length of firing wire to the
(NaCl) to 100-mesh fineness and dry in a glass container at
ignition terminals in such a manner that the loop of firing wire
120°C for 2 h. Stopper and keep desiccated. Dissolve 5.844 g is in contact with the sample.
6 0.1 mg of dried primary standard NaCl in water and dilute
11.1.3 Bomb Preparation—Add 20 to 25 mL of 0.02 N
to 1 L. Dilute 25.00 mL of this solution to 100.0 mL. potassium hydroxide solution to the bomb and wet the entire
9.7 Methanol.
internal surface of the bomb with this solution (see Note 3).
9.8 NitricAcid (1 + 1)—Mixequalvolumesofconcentrated Assemble the bomb.
nitric acid (HNO , sp, gr, 1.42) and water.
NOTE 3—Sodium hydroxide solution at appropriate concentration may
9.9 Silver Nitrate, Standard Solution (0.025 N)—Dissolve
be used.
4.247 g of silver nitrate (AgNO ) in water and dilute to 1 L.
11.2 Addition of Oxygen—Admit oxygen to the bomb
Store in an amber glass bottle. Standardize against 0.025 N
slowly to avoid blowing the sample from the capsule until a
sodium chloride solution as directed in 13.1.1 and 14.1.1.
pressure of 25 atm is reached.
9.10 Potassium Chromate – Potassium Dichromate
11.2.1 Caution—The following precautions are recom-
Indicator—(K CrO–K Cr O )—Dissolve 4.2gofK CrO
2 4 2 2 7 2 4
mended for safe calorimeter operation. Additional precautions
and 0.7 g of K Cr O in 100 mL of water.
2 2 7
are given in Practice E 144E 144.
9.11 Nitrobenzene.
11.2.1.1 The weight of RDF sample and the pressure of the
9.12 Ferric Ammonium Sulfate Indicator Solution—Add
oxygen admitted to the bomb must not exceed the bomb
sufficient concentrated HNO (sp gr 1.42) to a cold saturated
manufacturer’s recommendations.
solution of ferric ammonium sulfate [FeNH (SO ) ·12H O] to
4 4 2 2
11.2.1.2 Bombpartsshouldbeinspectedcarefullyaftereach
remove the brown color.
use. Threads on the main closure should be checked frequently
9.13 Potassium Thiocyanate, Standard Solution (0.025
for wear. Cracked or significantly worn parts should be
N)—Dissolve3gof potassium thiocyanate (KCNS) in freshly
replaced. The bomb should be returned to the manufacturer
occasionally for inspection and possibly proof firing.
Reagent Chemicals,American Chemical Society Specifications,Am. Chemical
11.2.1.3 The oxygen supply cylinder should be equipped
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
with an approved type of safety device, such as a reducing
American Chemical Society, see “Analar Standards for Laboratory U.K. Chemi-
cals,” BDH Ltd., Poole, Dorset, and the “United States Pharmacopeia.” valve, in addition to the needle valve and pressure gage used in
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 776 – 87 (1996)
potentiometric method (Section 13) should be used. If theVolhard method
regulating the oxygen feed to the bomb. Valves, gages, and
is to be used (Section 14), the color and turbidity must first be removed by
gaskets must meet industry safety codes. Suitable reducing
aluminum hydroxide [A1(OH) ] coagulation or by some other suitable
valves and adaptors for 300 to 500 psi (2070 to 3450 kPa)
method of turbidity or color removal without interfering with the chloride
discharge pressures are obtainable from commercial sources of
content of the solution.
compressedgasequipment.Thepressuregageshallbechecked
periodically for accuracy. ALTERNATIVE PROCEDURES
11.2.1.4 During ignition of a sample, the operator must not
13. Potentiometric Titration (Method A)
permit any portion of his body to extend over the calorimeter.
11.3 Preparation of the Chlorine Solution—Immerse the
13.1 Standardization of Reagents—Prepare a standard solu-
bomb in a cold-water bath, connect it to the firing circuit, and
tion of silver nitrate by adding 10.0 mL of standard 0.025 N
close the circuit to ignite the sample.Allow the bomb to stand
NaCl solution to a 250-mL beaker. Add 40 to 50 mL o
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