Designation: E 778 87 (Reapproved 2004)

Standard Test Methods for

Nitrogen in the Analysis Sample of Refuse-Derived Fuel1
This standard is issued under the fixed designation E 778; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope E 200 Practice for Preparation, Standardization, and Stor-

1.1 These test methods cover the determination of total age of Standard and Reagent Solutions for Chemical
Kjeldahl nitrogen in (prepared analysis) samples of (solid Analysis
forms) of refuse-derived fuel (RDF). The procedures measure E 790 Test Method for Residual Moisture in Refuse-
free ammonia or ammonia formed from the conversion of Derived Fuel Analysis Sample
organic nitrogenous compounds such as amino acids and E 791 Test Method for Calculating Refuse-Derived Fuel
proteins. However, the procedures may not convert the nitrog- Analysis Data from As-Determined to Different Bases
enous compounds of some wastes to ammonia. Examples of E 829 Practice for Preparing Refuse-Derived Fuel (RDF)
such compounds that may not be measured are nitro com- Laboratory Samples for Analysis
pounds, hydrozones, oxines, nitrates, semicarbazones, py- 3. Terminology
ridines, and some refractory tertiary amines.
1.2 Two alternatives are described for the final determina- 3.1 Definitions of Terms Specific to This Standard:
tion of the ammonia, the Kjeldahl-Gunning Test Method and 3.1.1 refuse-derived fuelsolid forms of refuse-derived
the Acid-Titration Test Method. fuels from which appropriate analytical samples may be
1.3 The analytical data from these test methods are to be prepared are defined as follows in ASTM STP 832:3
reported as part of the ultimate analysis where ultimate analysis RDF-1Wastes used as a fuel in as-discarded form with
is requested. only bulky wastes removed.
1.4 These test methods may be applicable to any waste RDF-2Wastes processed to coarse particle size with or
material from which a laboratory analysis sample can be without ferrous metal separation.
prepared. RDF-3Combustible waste fraction processed to particle
1.5 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-4Combustible 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-5Combustible 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 8.4.1 and Section 9. 4. Summary of Test Methods
2. Referenced Documents 4.1 The determination of nitrogen is made by either the
2.1 ASTM Standards: 2 Kjeldahl-Gunning Test Method (Section 11) or the Acid-
D 1193 Specification for Reagent Water Titration Test Method (Section 12). In both these methods the
E 180 Practice for Determining the Precision of ASTM nitrogen in the sample is converted into ammonium salts by
Methods for Analysis and Testing of Industrial Chemicals destructive digestion of the sample with a hot, catalyzed
mixture of concentrated sulfuric acid and potassium sulfate.
The salts are subsequently decomposed in a hot alkaline
1
These test methods are under the jurisdiction of ASTM Committee D34 on solution from which the ammonia is recovered by distillation,
Waste Management and are the direct responsibility of Subcommittee D34.06 on and finally determined by alkalimetric or acidimetric titration.
Recovery and Reuse.
Current edition approved Aug. 28, 1987. Published October 1987. Originally
published as E 778 81. Last previous edition E 778 81.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standards Document Summary page on Thesaurus on Resource Recovery Terminology, ASTM STP 832, ASTM, 1983,
the ASTM website. p. 72.

Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 E 778 87 (2004)
5. Significance and Use 7.3 Condenser, glass, water-cooled, having a minimum
5.1 The standard sample is available to producers and users jacket length of 500 mm.
of RDF as a method for determining the weight percent of 7.4 Kjeldahl Digestion Flask, of heat-resistant glass, having
nitrogen in the analysis sample. a capacity of 500 or 800 mL. Borosilicate glass has been found
5.2 Nitrogen is part of the ultimate analysis and can be used satisfactory for this purpose.
for calculation of combustion parameters. 7.5 Kjeldahl Connecting Bulb, cylindrical type, 45 mm in
diameter by 100 mm long, or larger, with curved inlet and
outlet tubes.
7.6 Receiving FlasksErlenmeyer flask having a capacity
of 250 or 300 mL.
7.7 Connecting TubeGlass tubing approximately 10 mm
in outside diameter by 200 mm in length.
7.8 Pure Gum Rubber Tubing.

8. Reagents
8.1 Purity of ReagentsReagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
where such specifications are available.5 Other grades may be
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of WaterUnless otherwise indicated, reference
A = electric heater to water shall be understood to mean reagent water, Type II,
B = Kjeldahl digestion flask conforming to Specification D 1193, prepared by the passage
C = Kjeldahl connecting bulb
D = condenser
through an ion-exchange column containing a strongly acid
E = connecting tube cation resin in the hydrogen form.
F = receiving flask 8.3 Potassium Sulfate (K2SO4), crystals.
FIG. 1 Kjeldahl Distillation Apparatus
NOTE 2Other satisfactory and permissible catalysts for the digestion,
together with the quantities of K2SO4 required in their use, are as follows:
6. Interferences and Limitations (1) Five grams of a mixture containing 32 parts by weight of K2SO4, 5
6.1 Because of the nature of RDF, nitrogenous compounds parts by weight of mercuric sulfate (HgSO4), and 1 part by weight of
may be present which will not readily be converted to ammonia selenium.
by this test method (1.1). Modifications to the digestion of the (2) Three-tenths gram of mercuric selenite (HgSeO3) with 7 to 10 g of
waste may enhance the conversion of these nitrogenous com- K2SO4.
pounds to the ammonium salts.4 (3) Three-tenths gram of cupric selenite dihydrate (CuSeO22H2O)
with 7 to 10 g of K2SO4. When this mixture is used, the addition of a
7. Apparatus sulfide to the alkali solution is not necessary.

7.1 Digestion UnitAn electrical heater of approximately 8.4 Mercury, metal (see Note 2).
500-W minimum rating or a gas burner of comparable capacity. 8.4.1 WarningAppropriate safety precautions should be
Either type of heater shall be provided with adequate means of used when handling and disposing of mercury and selenium
control to maintain digestion rates as described in 11.1 (Note compounds.
1). Commercially made, multiple-unit digestion racks provided 8.5 Sulfuric Acid (sp gr 1.84)Concentrated sulfuric acid
with fume exhaust ducts may be used. (H2SO4).
8.6 Potassium Permanganate (KMnO4), crystals.
NOTE 1If commercially made electrical heaters are used, auxiliary
voltage control equipment, such as an autotransformer, may be needed to 8.7 Zinc, mossy or granular.
maintain the specified rates of digestion and distillation. 8.8 Alkali SolutionDissolve 8.0 g of potassium sulfide
(K2S) and 500 g of sodium hydroxide (NaOH) in water and
7.2 Distillation Unit (Fig. 1)An electrical heater or gas
dilute to 1 L. The use of appropriate amounts of sodium sulfide
burner as described in 7.1. Either type shall be provided with
(Na2S) or potassium hydroxide (KOH) may be substituted for
adequate means of control to maintain rates as described in
the above, if desired (Note 2 (c)).
11.2. Commercially made, multiple-unit distillation racks pro-
vided with water-cooled glass or block tin condensers may be
used.
5
Reagent Chemicals, American Chemical Society Specifications, Am. Chemi-
cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
4
Kolthoff, I. M., and Stenger, V. A., Volumetric Analysis II, Intersciences the American Chemical Society, see Analar Standards for Laboratory U.K.
Publishers, Inc., New York, NY, pp. 173176. Chemicals, BDH Ltd., Poole, Dorset, and the United States Pharmacopoeia.

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 E 778 87 (2004)
8.9 Ethyl Alcohol (95 %)Ethyl alcohol conforming to 11. Procedure for Kjeldahl-Gunning Test Method
Formula No. 30 or 2A of the U.S. Bureau of Internal Revenue. 11.1 Digestion of Sample.
Methyl alcohol may be substituted. 11.1.1 After thoroughly mixing the RDF analysis sample to
8.10 SucroseNational Bureau of Standards primary stan- provide the best possible mix of heavy fines with milled fluff,
dard grade. weigh approximately 1 g to the nearest 1 mg of sample into a
8.11 Reagents Required for Kjeldahl-Gunning Test Method: weighing scoop.
8.11.1 Methyl Red Indicator Solution (0.4 to 1 g/L) 11.1.2 Carefully transfer the sample into a 500 or 800-mL
Dissolve 0.04 to 0.1 g of methyl red in 50 mL of 95 % ethyl Kjeldahl flask containing 7 to 10 g of K2SO4 and 0.6 to 0.8 g
alcohol or methyl alcohol and add 50 mL of water. Bromcresol of mercury (see Note 3).
green indicator solution of equal concentration may be used. 11.1.3 Add 30 mL of H2SO4(sp gr 1.84) to the mixture by
8.11.2 Sodium Hydroxide, Standard Solution (0.1 to 0.2 pouring it down the neck of the flask while rotating the flask to
N)Prepare and standardize a 0.1 to 0.2 N sodium hydroxide wash any sample adhering to the walls into the mixture. Swirl
(NaOH) solution against a primary standard, as described in the contents of the flask several times to ensure thorough
Practice E 200. mixing and wetting of the sample.
8.11.3 Sulfuric Acid, Standard Solution (0.2 N)Prepare 11.1.4 Incline the flask at an angle of 45 to 60 on the
and standardize a 0.2 N sulfuric acid (H2SO4) solution as digestion heater in a fume hood (Note 3). Heat the contents
described in Practice E 200. gradually. If frothing or foaming occurs, or both, lower the heat
8.12 Reagents Required Only for Acid-Titration Test and digest at a lower temperature until the frothing or foaming
Method: ceases.
8.12.1 Boric Acid Solution (50 g/L)Dissolve 5 g of boric NOTE 3When fume exhaust ducts or hoods are not available another
acid (H3BO3) in 100 mL of boiling water. Allow to cool to method must be used to exhaust fumes from the flask, such as aspiration.
room temperature before use.
11.1.5 Heat the contents to boiling, controlling the heat
8.12.2 Mixed Indicator SolutionPrepare a solution con-
input in such a manner that the H2SO4 vapors condense no
taining 0.125 % methyl red and 0.083 % methylene blue in
more than halfway up the neck of the flask (see Note 1).
95 % ethyl alcohol or in methyl alcohol. Prepare fresh solution
Continue the digestion until all sample particles are oxidized,
at bimonthly intervals.
as evidenced by a nearly colorless solution, or for at least 2 h
8.12.3 Sulfuric Acid, Standard Solution (0.1 to 0.2 N)
after the solution has reached a straw color. The total time of
Prepare and standardize a 0.1 to 0.2 N sulfuric acid (H2SO4)
digestion will require 3 to 6 h.
solution. Hydrochloric acid (HCl) of similar concentration, as
11.1.6 When the digestion is completed and the solution has
described in Practice E 200, may be substituted.
cooled, a few crystals of KMnO4 may be added to ensure
complete oxidation; further heating may be necesary to destroy
9. Precautions
the excess permanganate and decolorize the solution.
9.1 Due to the origins of RDF in municipal waste, common 11.2 Distillation of Digestate (see Fig. 1).
sense dictates that precautions should be observed when 11.2.1 Dilute the cooled digestion mixture to about 300 mL
conducting tests on the samples. Recommended hygienic with water and remove any heat of dilution by cooling the flask
practices include use of gloves when handling RDF; wearing under running water or by allowing it to stand until cool.
dust masks (NIOSH-approved type), especially while milling 11.2.2 Accurately pipet 20.0 mL of 0.2 N H2SO4 into a 250
RDF samples; conducting tests under a negative pressure hood or 300-mL Erlenmeyer flask. Add 6 drops of methyl red or
when possible; and washing hands before eating or smoking. bromcresol green indicator solution.
9.2 The hot acidic and basic solutions in this procedure pose 11.2.3 Attach the glass connecting tube to the discharge end
a significant potential hazard. Proper laboratory safety prac- of the condenser, using a short piece of rubber tubing as a seal.
tices and equipment should be employed throughout this 11.2.4 Incline the Erlenmeyer flask at a suitable angle and
procedure. insert this tube so that the end is immersed well below the
surface of the acid solution (see Fig. 1).
10. Sampling 11.2.5 Add 1 to 2 g of granular zinc to the digestion mixture
10.1 RDF products are frequently nonhomogeneous. For in the Kjeldahl flask (two or three small pieces, if mossy zinc
this reason significant care should be exercised to obtain a is used), and slowly add 100 mL of alkali solution so that it
representative laboratory sample from the RDF lot to be forms a distinct layer under the acid solution. This may be
characterized. accomplished by inclining the flask at an angle of 45 to 60 and
10.2 The sampling method for this procedure should be pouring the alkali solution slowly down the neck of the flask.
based on agreement between the involved parties. Failure to maintain discrete layers during the operation may
10.3 The laboratory sample must be air-dried and particle lead to a fairly fast exothermic reaction and loss of ammonia.
size reduced to pass a 0.5-mm screen as described in Practice 11.2.6 Quickly connect the flask to the distilling condenser
E 829. This procedure must be performed carefully to preserve through the Kjeldahl connecting bulb and swirl the contents to
the samples representative characteristics, other than particle promote thorough mixing.
size, while preparing the analysis sample to be used in the NOTE 4All connections must be air-tight so no loss of ammonia will
procedures. be experienced.

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 E 778 87 (2004)
11.2.7 Bring the contents of the Kjeldahl flask to a boil 13.2.3 Set up the distillation apparatus and distill as de-
carefully in order to avoid bumping or foaming, or both, and scribed in 11.2.3-11.2.9.
distill the ammonia over into the acid solution in the Erlenm- 13.2.4 Titrate the ammonia collected in the Erlenmeyer
eyer flask. flask containing the H3BO3 to the mixed indicator end point
11.2.8 Continue the distillation at a maximum rate of using 0.2 N H2SO4 as the titrant.
approximately 350 mL/h until 100 to 150 mL of distillate have 13.3 BlankRun a blank determination in the same manner
been collected. as described in 11.1 and 11.2, using approximately 1 g
11.2.9 Discontinue the boiling, and remove the glass con- (weighed to the nearest 1 mg) of sucrose as the sample material
necting tube from the condenser and Erlenmeyer flask. Rinse (Note 5 (2)).
the tube with water, collecting the washings in the Erlenmeyer
flask. 14. Calculation
11.2.10 Titrate the excess acid in the Erlenmeyer flask to a 14.1 Calculate the percent of nitrogen in the analysis sample
methyl red or bromcresol green end point, using 0.1 to 0.2 N as follows:
NaOH solution as the titrant.
~A 2 B! N 3 0.014
11.3 Blank DeterminationRun a blank determination in Nitrogen, % 5 3 100 (2)
C
the same manner as described in 11.1 and 11.2, using approxi-
mately 1 g of sucrose (weighed to the nearest 1 mg) as the where:
sample material. A = millilitres of H2SO4 required for titration of the
NOTE 5A blank determination must be made with every series of sample,
analyses performed. The blank determination serves two principal func- B = millilitres of H2SO4 required for titration of the
tions: blank,
(1) Since the principle of the method is ascertaining the amount of N = normality of H2SO4,
standardized acid being consumed in a reaction and a back-titration is C = grams of sample used, and
necessary, the blank is a check on the concentration of the standard 0.014 = milliequivalent weight of nitrogen.
solutions.
(2) The blank serves as a correction for nitrogen from sources other 15. Report
than the sample.
15.1 The results of the nitrogen analysis may be reported on
12. Calculation any number of bases, differing from each other in the manner
12.1 Calculate the percentage of nitrogen in the analysis by which moisture is treated.
sample as follows: 15.2 The numerical moisture value established by Test
Method E 790, shall be used for converting nitrogen data from
~B 2 A! N 3 0.014
Nitrogen, % 5 C 3 100 (1) the as-determined basis to the dry basis as in Test Method
E 791.
where:
A = millilitres of NaOH solution required for titra- 16. Precision and Bias 6
tion of the sample, 16.1 Precision:
B = millilitres of NaOH solution required for titra- 16.1.1 The standard deviations of individual determinations,
tion of the blank, in percent absolute, are as follows:
N = normality of the NaOH solution,
Typical Average
C = grams of sample used, and Value, % Within-Laboratory, % Between-Laboratories, %
0.014 = milliequivalent weight of nitrogen. 0.6 0.04 0.05

13. Procedure for Acid-Titration Test Method 16.1.2 These precision estimates are based on an interlabo-
ratory study conducted in accordance with Practice E 180.
13.1 Digestion of Sample.
16.2 BiasThe bias of this test method can not be deter-
13.1.1 Digest the sample as described in 11.1.
mined due to the lack of a recognized standard reference
13.2 Distillation of Digestate (see Fig. 1).
material.
13.2.1 Dilute the cooled digestion mixture to about 300 mL
with water and remove any heat of dilution by cooling the flask
under running water or by allowing it to stand until cool.
13.2.2 Add 20 mL of H3BO3 solution into a 250 or 300-mL 6
Supporting data are available on loan from ASTM Headquarters. Request
Erlenmeyer flask and add 6 drops of mixed indicator solution. RR:E38-1000.

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 E 778 87 (2004)

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