PL3B4-156UU /
EPA-600/2-84-057
February 1984
DESIGN AND DEVELOPMENT OF A HAZARDOUS WASTE
REACTIVITY TESTING PROTOCOL
By '
C. D. Wolbach, R0 R. Whitney, and I). B. Spannagel
Energy & Environmental Division
Acurex Corporation
Mountain View, California 94039
Contract No. 68-02-3176-38
Project Officer
Naomi Barkley
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
U.S. Environmc-ntM P;-oiC'.;:Jon Agency
Region V, Lib;v.,,y /•'
230 Soutn D^;r;-vn S\-^l .X
Chicago, illincis 60604
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
U.S DEPARTMEN! OF COMMERCf
SPRINGFIELD, VA 22161
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1. REPORT NO. 2.
EPA-600/2-84-057
4. TITLE AND SUBTITLE
DESIGN AND DEVELOPMENT OF A HAZARDOUS WASTE
REACTIVITY TESTING PROTOCOL
7. AUTHOR(S)
C. Dean Wolbach, Richard R. Whitney and
Ursula Spannagel
9. PiM^OWMING ORGANIZATION NAME AND ADDRESS
Acurex Corporation
Energy and Environmental Division
Mountain View, CA 94042
12. SPQNSpRiNG AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory--Cin. , OH
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268 -
3. RECIPIENT'S ACCESSION NO.
TO * ii.flfLaz_ :
5. REPORT DATE
February 1984
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIEAT'ION REPORT Sio.
10. PROGRAM ELEMENT NO.
TEJY1A
11. CONTHAC'T'/GRANT NO.
68-02-3176 (Task 38)
13. TYPE OF REPORT AND PERIOD COVERED
Final Report - 6/82 - 8/83 .... ..
14. SPONSORING AGENCY CODE
EPA/600/14
IS. SUPPLEMENTARY NOTiS
Project Officer: Naomi P. Barkley 513/684-7875
18. ABSTRACT
A test protocol to determine the gross chemical composition of waste
materials has been developed for use at uncontrolled hazardous waste sites.
Included is a field test kit, flow diagrams, a descriptive manual and a mixing
device to observe the effects of mixing two hazardous wastes. Prior knowledge
of the chemical composition of the waste materials is not required for this
protocol.
Unidentified wastes were classified by reactivity groups using this test
scheme in the laboratory and in the field. Small amounts of wastes that indicated
compatibility were placed in the mixing device to verify that mixing would not
generate immediate catastrophic results.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b.lOENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (Tlia Report 1
UNCLASSIFIED
"b&mifffi"*1"""
c. COSATi Field/Group
',. i1 - '
21. NO. OF PAGES
3S4
22. PRIC£
SPA Fotm 2220-1 (R«». 4-77) FWKVIOUI COITION is OSSOLETI
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DISCLAIMER
The Information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under Contract
No. 68-02-3176-38 to the Acurex Corporation. It has been subject to the
Agency's peer and administrative review., and it has been approved for
publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement, or recommendation for use.
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FOREWORD
The U.S. Environmental Protection Agency was created because of
increasing public and government concern about the dangers of pollution to;
the health and welfare of the American people. Noxious air, foul water, and
spoiled land are tragic testimonies to the deterioration of our natural ! ,
environment. The complexity of that environment and the interplay of its '< \
components require a concentrated and integrated attack on the problem. I
Research and development is that necessary first step in problem
solution, and it involves defining the problem, measuring its impact, and j
searching for solutions. The Municipal Environmental Research Laboratory !
develops new and improved technology and systems to prevent, treat, and '
manage wastewater and solid and hazardous waste pollutant discharges from '
municipal and community sources, to preserve and treat public drinking water l-
supplies, and to minimize the adverse economic, social, health, and aesthetic
effects of pollution. This publication is one of the products of that
research and is a most vital communications link between the researcher and
the user community.
Waste materials must often be recontainerized during cleanup of
uncontrolled or abandoned hazardous waste dump sites under the activities
funded by regulations to the Resource Conservation and Recovery Act
(Superfund). The potential for catastrophic reactions when unknown materials
are mixed is high. To lessen the degree of risk we have prepared a hazardous
waste reactivity test protocol by which unknown materials may be classified
into various reactivity categories. This report documents the preliminary
development of the protocol and the test kit used to conduct the protocol in
the field.
Francis T. Mayo
Director
Municipal Environmental Research
Laboratory
m
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ABSTRACT
A project was conducted to develop a test scheme (protocol) to determine
the gross chemical composition of waste materials in the field. Such a test
scheme is needed during remedial actions at hazardous waste disposal sites,
where it is necessary to predict the potential consequences of mixing wastes
from separate sources. Earlier procedures have assumed a prior knowledge of
the chemical composition of the wastes. Information obtained from these
tests is used to classify wastes into reactivity groups and thus predict
compatibility.
The test scheme developed here includes a field test kit, a series of
flow diagrams, and a manual for using the flow diagrams and test procedures,
Because small-scale mixing is needed as a safeguard before large-scale mixing
takes place (even when the chemical composition of two wastes indicates
compatibility), a simple device is included for observing the effects of
mixing two hazardous materials.
The protocol was challenged with more than 60 compounds in the
laboratory and 28 waste samples in the field. Of 755 laboratory
observations, 15 were false positives and 2 were false negatives (including
replicate tests). All but one of the field samples were classified into the
correct reactivity group based on the bulk chemical composition listed in the
suppliers' manifest. The one incorrectly identified sample was found to be
incorrectly labeled by the supplier and was correctly classified according to
its actual composition.
This report was submitted in fulfillment of Contract No. 68-02-31/6-38
by the Acurex Corporation under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period July 1982 to May 1983, and
work was completed as of March 1983.
IV
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CONTENTS
Foreword ii1
Abstract . iv
Figures . vii
Tables viii
Acknowledgments . . ..... x
1. Introduction 1
2. Conclusions and Recommendations ....... 3
3. Discussion 5
3.1 Organization of Test Procedures. .......... 9
3.2 Reference Compounds ... ........ 10
3.3 Description of Procedure Sets 12
3.3.1 PS 1 — pH and redox tests 12
3.3.2 PS 2 -- solution-reactivity and special
functionality tests ....... 14
3.3.3 PS 3 — flame test 14
3.3.4 PS 4 -- sodium fusion and ferrox test .... 19
3.3.5 PS 5 -- organic functionality tests 21
3.3.5.1 PS 5A -- tests for hydrocarbon
classification 26
3.3.5.2 PS 5B -- tests for organic functional
groups containing oxygen 26
3.3.5.3 PS 5C -- tests for organic functional
groups containing nitrogen ..... 27
3.3.5.4 PS 5D -- tests for organic functional
groups containing sulfur 28
3.3.6 PS 6 -- inorganic functionality tests .... 28
3.4 Results of Tests Used to Verify Procedure Sets ... 30
3.4.1 PS 1 — pH and redox tests 30
3.4.2 PS 2 -- solution-reactivity and special
functionality tests ....... 30
3.4.2.1 Solution reactivity tests ...... 30
3.4.2.2 Special functionality tests 39
3.4.3 PS 3 — flame tests 39
3.4.4 PS 4 -- sodium fusion and ferrox test .... 39
3.4.5 PS 5 -- organic functionality tests 51
3.4.5.1 PS 5A -- tests for hydrocarbon
classification . bl
3.4.5.2 PS 5B -- tests for organic functional
groups containing oxygen ...... bl
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3.4.5.3 PS 5C -- tests for organic functional
groups containing nitrogen ...... 55
3,4.5.4 PS 5D — tests for organic functional
groups containing sulfur ...... 57
3.4.6 PS 6 -» Inorganic functionality tests . . . . 57
3.4.7 Summary of functionality test results . . . . 57
3.5 Results of Blind Analyses Using the Test
Schemes . . . . 59
3.5.1 Results of blind analyses of the reference
compounds ................. 59
3.5.2 Results of blind analyses of other pure
compounds ................. 65
3.6 Device for the Determination of Compatibility of
Unknown Materials ................ 65
3.7 Field Evaluation of the Test Kit .......... 70
3.8 Assembly of Field Test Kit ............. 78
3.9 Safety ....................... 82
References ............................ 86
Appendix -- Field Test Kit Instruction Manual .......... 87
VI
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FIGURES
Number Page
1 Sequence of procedure sets . ......... 11
2 Procedure set 1 -- pH and redox tests . 15
3 Procedure set 2 -- solution-reactivity and special
functionality tests ...... 16
4 Procedure set 3 — flame test . . 17
5 Procedure set 4 — sodium fusion and ferrox tests .... 20
6a Procedure set 5A -- organic functionality tests for
hydrocarbon classification ........ 22
6b Procedure set 5B -- organic functionality tests for
groups containing oxygen 23
6c Procedure set 5C -- organic functionality tests for
functional groups containing nitrogen ......... 24
6d Procedure set 5D -- organic functionality tests for
functional groups containing sulfur 25
7 Procedure set 6 -- inorganic functionality tests .... 29
8 Device for determining the effects of mixing of unknown
materials 67
9 Cooler 1 -- equipment organization 79
10 Cooler 2 — equipment organization HO
11 Cooler 3 — equipment organization . 81
VI 1
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TABLES
Number
1 Summary of Specific Test Procedures
10 Results of Hydrocarbon Classification Tests for a Series
of Hydrocarbons ...................
11 Summary of Functionality Test Results for Oxygen-
Containing Organic Compounds .........
12 Summary of Functionality Test Results for Nitrogen- and
Sulfur-Containing Organic Compounds .........
16 Blind Test Results for Oxygen Functional Groups
VI 1 1
2 Reference Compounds for Hazardous Waste Compatibility
Testing ..... ... ..... ........... 13
3 Response of Reference Compounds to pH and Redox Tests . . 31
4 Response of Reference Compounds to Solution-Reactivity
Tests ..... ...... .............. 35
5 General Summary of Solution-Reactivity Test Results . . . 40
6 Response of Reference Compounds to Special
Functionality Tests .................. 41
7 Response of Reference Compounds to the Flame Tests. ... 45
8 General Summary of Flame Test Results .......... 47
9 Response of Organic Test Compounds to Sodium Fusion and
Ferrox Tests ..................... 48
13 Summary of Test Results for Inorganic Compounds and
Elemental Metals .................... 58
14 General Summary of Functionality Test Results ...... 60
15 Results of Duplicate Blind Analyses of the Reference
Compounds Using the Test Schemes ........... 61
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Number Page
17 Blind Test Results for Nitrogen and Sulfur Functional
Groups 64
18 Results of Blind Analysis of Selected Pure Compounds and
Binary Mixtures 66
19 Results of Mixing Experiments 69
20 Results of Analysis for Evolved Gases in Mixing
Experiments .... ............ 70
21 Description of Samples Tested and Summary of Results
of the Field Evaluation ................ 72
22 Detailed Results of Field Testing of Hazardous Waste
Samples ......... .... 74
23 Hazards of Test Kit Reagents 84
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ACKNOWLEDGMENTS
The authors wish to acknowledge the special support given this project
by Mr. Richard Cannes of the Incineration Research Branch, Industrial
Environmental Research Laboratory, Office of Research and Development,
U.S. Environmental Protection Agency. Mr. Carnes acted as a technical
advisor, donated his reference library, obtained waste samples, and opened
the U.S. Environmental Protection Agency Combustion Research Facility in
Jefferson, Arkansas, for field testing. In addition, his continued moral
support and encouragement were fundamental both in initiating this project
and in bringing it to a successful conclusion.
A special acknowledgment is also due to the Project Officer, Ms. Naomi
Barkley. Her insight into the necessity of transforming this work from a
technical exercise into a useful tool, and her continued enthusiasm in
helping us overcome often convoluted problems of chemical logic were also
crucial to the success of this project.
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SECTION 1
INTRODUCTION
During remedial action at an abandoned waste disposal site, it is
frequently necessary to determine whether waste materials from separate
sources can be safely mixed for bulk recontainerization, shipment, and
ultimate proper disposal. At operating Resource Conservation and Recovery
Act (RCRA) facilities, waste composition may need to be verified against
shipper manifests. The history of hazardous waste management contains
numerous accounts of disasters resulting from the mixing of incompatible
wastes. Proper management of hazardous waste therefore requires test
procedures to identify potential reactivity hazards and avoid the
consequences of mixing such hazardous wastes.
A document has been developed that classifies wastes by chemical class
or general reactive properties or both and lays out a sequence of activities
to determine the compatibility of two wastes (Reference 1). The key elements
of this document are a compatibility chart and a flow diagram for its use.
But, the authors presuppose a knowledge of the waste composition. This
information is often available from generators of hazardous wastes, but
during remedial action at an abandoned hazardous waste disposal site, it is
seldom available. The need to test mix two wastes on a small scale is
emphasized even if the compatibility chart indicates compatibility.
The purpose of the present study is to establish a series of qualitative
test procedures that will enable field workers to classify hazardous waste
materials according to their gross chemical composition when little or no
prior knowledge is available regarding their components. Information about
chemical composition is then used to predict which waste materials can be
mixed safely before actually performing mixing tests. Note that only
qualitative results are obtained, and thus for low-level contaminants, overly
conservative conclusions could be drawn.
Because of the environment in which these classification test procedures
will be used, limitations on the schemes, test procedures, and equipment have
been addressed during the course of this study. These limitations are:
• The procedures must be safe and easy to perform by nonchemists
® The procedures must give definitive, objective results
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• The equipment must be standard, readily available, portable, and use
a minimal number of utility hookups, since the tests may be applied
in remote field locations
• The procedures must be performed as rapidly as possible, since
numerous waste samples may require testing
• The test procedures must be able to be performed with slightly
restricted manual dexterity, since they may be performed in areas
where protective clothing is required
Standard organic and inorganic qualitative test procedures have been
identified from the literature* These test procedures have been organized
into a scheme for classification of waste materials according to their
chemical composition. These procedures have been evaluated by applying them
to a set of 58 reference compounds chosen to represent materials likely to be
found at hazardous waste disposal sites.
A field test kit has been assembled that contains all necessary
equipment and materials for conducting the test procedures. A device for
determining the effects of mixing hazardous wastes has also been assembled
and is included in the field test kit. The mixing device enables
investigators to observe gas and heat evolved when small quantities of waste
materials are mixed. The test kit includes a complete manual for its use
(Appendix A).
The test kit has been used in a week-long field evaluation at the EPA
Combustion Research Facility located in Jefferson, Arkansas. During the-
field evaluation, the test procedures were applied to 25 actual waste
samples. The protocol has been shown to be applicable to mixtures of
materials.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
A series of qualitative test procedures has been incorporated into test
schemes for categorizing hazardous waste materials. Test results are used to
classify waste materials according to their gross chemical composition. All
reagents and equipment required for the tests have been incorporated into a
field test kit, which includes a manual for its use.
The test schemes have been verified using representative pure compounds
and mixtures of compounds. Actual results have been compared with the
results that were expected because of chemical structures of the reference
compounds. Each test scheme was shown to provide reliable results for the
reference compounds. The schemes were applied to the reference compounds in
blind tests by two different analysts to verify the procedure sequences.
During initial verification, more than 750 individual observations were made,
with 15 false positive and 2 false negative observations recorded.
The test kit was used in a field evaluation at the EPA Combustion
Research Facility in Jefferson, Arkansas. During the field evaluation,
25 hazardous waste materials with a total of 29 phases were examined using
the test procedures. The test results provided accurate descriptions of all
of the phases based on haulers' records for the waste materials. An average
of less than 90 min was required for the testing of a single waste material.
The tests were performed under simulated field conditions.
The field evaluation of the test kit demonstrates three important
positive aspects of the test kit:
® The test procedures were shown to be applicable to field conditions
© The test procedures provided accurate descriptions of actual
hazardous wastes
« The complete categorization of an unknown waste required an average
of less than 90 min
In general, the kit and protocol meet all the criteria listed in
Section 1. The tests are simple and can be conducted by nonchemists with
some training. However, some laboratory experience is highly desirable. The
results of the procedures are definitive in almost every case. For those not
definitive, an hour or two of training is adequate for the technician to be
able to correctly interpret the results. All equipment except specially
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constructed shipping boxes and the glass reactor vessel for the mixing device
is standard. The time requirements, although not as short as could be
desired, are brief when compared to normal laboratory analysis.
Significant weaknesses were the lack of identification of trace
materials in complex matrices and the identification of water-based organics.
The field use of the kit may also be limited by weather conditions. The kit
probably cannot be used in conditions where the temperature is less than 5°C
(40°F) or greater than 33°C (90°F), when wind is greater than 15 mph, or
during precipitation (i.e., rain, snow, etc.).
Based on the results of the laboratory development and particularly on
the results of the field evaluation, the test kit has considerable potential
for applications in hazardous waste management. This approach presents an
attractive alternative to laboratory analysis for the qualitative gross
categorization of waste materials.
Though the primary purpose of the development effort was to determine
compatibility characteristics, the test results can potentially be used to:
• Predict best disposal technology
® Identify generic wastes
• Predict degree of hazard
Additional testing of real waste materials should be undertaken to
demonstrate further the applicability of the test kit to actual hazardous
waste materials.
The field testing of additional waste materials from a wide range of chemical
classes should identify any remaining limitations of the test procedures or
the test kit and provide a statistical basis for their general acceptance.
Additional development effort is needed to identify specific tests for
three reactivity groups for which test procedures have not been found --
epoxides, isocyanates, and nitrides. In addition, general tests are needed
for polymerizable materials and organics dissolved in water, and a mor*5
definitive means for identifying explosives is required.
Finally, the test procedures should be challenged from the viewpoint of
detection limits. All procedures are currently expected to give positive
results at the 20-percent level, and they may give positive results at the
5-percent level. These detection limits must be verified and documented,
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SECTION 3
DISCUSSION
A series of test procedures (References 2, 3, 4, and 5) has been
assembled to classify hazardous wastes based on their gross chemical
composition. These test procedures are based on established qualitative
chemical tests. Specific functional group tests have been identified for all
but 5 of the 41 reactivity groups (RGN's) listed in Reference 1. A complete
listing of tests by reactivity group is presented in Table 1. Details of the
test procedures are lengthy and are therefore described fully in the field
test kit manual (Appendix A).
Basically five types of tests are involved in the classification
sequence:
• Physical observation
• Treated paper tests
• Ignition tests
* Solubility-reactivity tests
• Functionality tests
The latter two are spot-plate or small-test-tube tests.
Physical examination of the waste material reveals the phase (liquid,
sludge, solid) and may give clues about the material present (elemental
metals, for example). Separate test paper is used to conduct tests for pH,
and for oxidative and reductive potential. Ignition (flame) tests are
performed using a small crystal or droplet of material first on a nichrome
wire then on a spatula or in a small crucible. Combustible materials arc
classified as organics, and explosives are identified. Solubility-reactivity
tests are performed by treating small amounts of the waste material with a
few drops each of various acids and solvents. Functionality tests for
sulfide and cyanide are performed concurrently. Additional functionality
tests are used to make a final assignment of waste materials into reactivity
groups based on the functional group present. These tests are based on
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TABLE 1. SUMMARY OF SPECIFIC TEST PROCEDURES
RGN
Reactivity group name
Name of test
Reference
1 Acids, minerals nonoxidizing
2 Acids, mineral, oxidizing
3 Acids organic
4 Alcohols and glycols
5 Aldehydes
6 Amides
7 Amines, aliphatic and
aromatic
8 Azocompounds, diazo
compounds, and hydrazines
9 Carbamates
10 Caustics
11 Cyanides
12 Dlthiocarbamates
13 Esters
14 Ethers
15 Fluorides, inorganic
16 Hydrocarbons, aromatic
17 Halogenated organics
18 Isocyanates
PH
pH, oxidation
pH, flame
Vanadate
Dinitrophenylhydrazine,
Schiff's test
Oxamide test
p-Ni trobenzenedi azoni um-
tetrafluoroborate
Dimethyl ami nobenzaldehyde <
glutaconic aldehyde
Diphenylcarbohydrazide
pH
Ferrous sulfate, ferric
chloride
Cupric chloride, acetic
acid
Hydroxamate
Iodine test
Zirconium al 1 z
Friedel-Crafts and
ferrox test
Sodium fusion
No test identified
Paper test
Paper tests
Paper test
49 p. 176
2, pp» 264-65
4, pp. 264-65
4S p. ?40
4, p. 666
4, p. 269
4, p. 390
Paper test
2, pp. 172, 174
4, pp. 304-05
4, p. 214
2, p. 267
4, p. '1?U
?., pp. ?•{;*-:* 4
2, pp. ?:n-:i?
2, pp. 17^. ]?/-I?0
(j.oni.
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TABLE 1. (continued)
Reactivity group name
Name of test
Reft» rone e
19 Ketones
20 Mercaptans and other organic
sulfides
21 Metals, alkali and alkaline
earth, elemental and alloys
22 Metals, other elemental in
the form of powders, vapors,
or sponges
23 Metals, other elemental, and
alloys as sheets, rods,
moldings, drops, etc.
24 Metals and metal compounds,
toxic
25 Nitrides
26 Nitriles
27 Nitro compounds
28 Hydrocarbon, aliphatic,
unsaturated
29 Hydrocarbon, aliphatic,
saturated
30 Peroxides and
hydroperoxides, organic
31 Phenols and creosols
32 Organophosphates,
phosphothioates, and
phosphodithioates
Dim' trophenyl hydra/ine,
Schiff's test
Lead acetate
Water, hydrochloric acid,
phosphornolybdic acid
Phosphomolybdic acid
Phosphomolybdic acid
Zinc sulfide, ammonium
sulfide
No test identified
Oxamide test
Tetrabase fusion
Baeyer test, ferrox test
Ferrox test
Ferric chloride test
Sodium fusion
?. pp. ?M-d!>
2, p. 274
3, p. 362
3, p. 362
3, p. 362
5, ppa 134-35
4, pp. 264-65
4, p. 295
2, p. 162
2, pp. 231-32
2, pp. 231-32
Potassium iodide-starch 4, p. 615
2, p. 22H
2, p. in tt
(continued)
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TABLE 1. (concluded)
RGN
Reactivity group name
Name of test
33 Sulfides, inorganic
34 Epoxides
101 Combustible and flammable
materials, miscellaneous
102 Explosives
103 Polymerizable compounds
104 Oxidizing agents, strong
105 Reducing agents, strong
106 Water and mixtures
containing water
Lead acetate
No test identified
Flame test
Flame test
No test identified
Iodide-starch
Methylene blue
Copper sulfate
107 Water-reactive substances Water spot test
Other Test Procedures
Organic All RGN's
Organic All RGN's with
heteroatoms (N, 09 Ps
S, X)
Al
All RGN's
Ferrox test
Sodium fusion
Flame test
Reference
Paper test
2, pp. 160-61
2, pp. 160-61
Paper test
Paper test
2, p. 161
Spot test
2, pp, 231-32
2, p. 172 ff
2, pp. 160-1
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established qualitative organic and inorganic procedures and are referenced
1n Table 1.
WARNING
The detection limits of these tests in some cases may not be
sufficient to identify trace quantities of materials (e.g.,
cyanide at several parts per million) that could be hazardous
to personnel if subjected to acid treatment.
3.1 ORGANIZATION OF TEST PROCEDURES
The procedures have been organized into a visual examination phase and
six procedure sets (PS), as outlined below:
« PS 1 -- pH and redox test to identify acids, caustics, oxidizing and
reducing agents
® PS 2 --. Solution-reactivity and special functionality tests to
determine reactivity and/or solubility in a series of acids
and solvents and identify the presence of water, sulfide,
and cyanide
® PS 3 — Flame tests to identify combustible (organic) and extremely
heat-sensitive (explosive) materials (additional
"indicators" of composition may also be obtained)
© PS 4 — Ferrox and sodium fusion tests to provide elemental analysis
for organic waste materials
© PS 5 -- Functional group tests for specific identification of
organic functional groups (RGN's)
• PS 6 -- Functional group tests for specific identification of
inorganic RGN's
The procedure sets have been organized into a master scheme for
examination of unknown waste materials. The organizational sequence of
procedure sets into a general scheme is described in the following
paragraphs.
Test procedures are organized into a scheme for the classification of
unknown hazardous wastes into reactivity groups (References 2, 3, 4, and 5).
Preliminary procedures classify the material as acid, base, oxidizing,
reducing, or water reactive, and primarily organic or inorganic. The results
of preliminary tests are used to give direction to subsequent testing
procedures which are used for further classification, ultimately into
reactivity groups. The scheme is organized in a manner such that materials
with high reactivity or unusual hazards are identified early in the testing
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sequence, In some cases, information gained in the early stages of testing
can be used to classify the material and eliminate the need for further
testing, provide cautions to be applied in subsequent testing activities, or
indicate the need for direction by qualified supervisory personnel.
The sequence in which test procedures are carried out is shown
schematically in Figure 1. The testing sequence begins with a visual
examination of the waste material to classify it as a solid, sludge, slurry,
or liquid* This examination may give a strong indication of its identity
(i«,ees metal )0
The testing for all four classes is initiated with PS 1 (pH and redox
tests). This procedure is followed because the most extreme hazards of
liquids -- strong acidity and/or strongly oxidizing properties -- can be
detected by tests in PS 1 and the most extreme hazards anticipated from
solids is their explosiveness which can be detected by the flame test (PS 3),
Acidity and oxidative potential is a secondary hazard for solids and
explosive solids are not expected to cause a problem in the PS 1 test
sequence. If the material is strongly acidic, strongly oxidizing, or
caustic, it is classified into the proper reactivity group; RGN 1, 3, 2} or
10, respectively. Further testing can be eliminated since these reactivity
classes are incompatible with most other classes of wastes.
Slurries are separated by filtration into solid and liquid portionss if
possible, after the pH and redox tests have been conducted and testing is
continued separately for each of the phases. Likewise, two-phase liquids are
separated and tests are conducted on the separate phases.
The next test set is PS 2 (for both liquids and solids) to determine the
solubility and reactivity properties of the waste material with acids and
organic sol vents. The flame test (PS 3) is carried out to determine
flammability and explosiveness,, Results from PS 2 and PS 3 help identify
whether the waste material is primarily organic or inorganic, and whether it
has the potential to form extremely hazardous compounds when mixed with water
or acids (hydrogen cyanide, hydrogen sulfide).
For organic materials, functionality tests (PS 4 and PS 5) are performed
to assign specific. RGN's to the waste material. Inorganic materials are
classified into specific RGN's using PS 6.
3.2 REFERENCE COMPOUNDS
A series of 58 compounds was selected from those listed in Appendix 1 of
Reference 1. These compounds, which represent, materials likely to be found
in hazardous waste sites, were selected using the following criteria:
® Compounds had to be commercially available
» At least one compound was selected for each reactivity group
10
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O
O
1
„
START
STOP
CONTINUE
J PROCEDURE
) RESULT
CLASSIFY
INTO RGN
— I _.^
/~\
I START j
. V.
V I SUAL
EXAMINATION
V
.— — — ' — - — _ _ * — -^
PROCEDURE
SET 6
PROCEDURE SET 4
PROCEDURE
SET 6
PROCEDURE SET 5
O
START
STOP
CONTINUE
PROCEDURE
O
RESULT
Figure 1. Sequence of procedure sets.
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© Polyfunctional materials were selected when possible, so that
reactivity groups would be well represented by the reference
compounds, and so that potential interferences could be introduced
to simulate mixtures likely to be found in real waste samples
A list of the reference compounds chosen for this study and the assigned
reactivity groups for each compound is presented in Table 2. All reactivity
groups are represented except RGN 25 (nitrides). These materials are not
commercially available and are extremely dangerous to synthesize, so they
were omitted from the investigation.
3.3 DESCRIPTION OF PROCEDURE SETS
Procedures employed for the examination of hazardous waste materials are
broken into six procedure sets which were briefly outlined in Section 3.1.
Results obtained early in the testing sequence are used to give direction to
subsequent testing procedures. The organization of procedure sets into an
overall testing sequence is described in Section 3.1. Detailed descriptions
of the six procedure sets are presented in the following paragraphs. The
test procedures were verified using the reference compounds (Section 3.2).
The first step in testing is determination of pH and redox potential,
3,3.1 PA-l.-"-._PM.-a-nd..Kedox Jes_ts
Oxidation, reduction, and pH tests are performed on the waste material
using appropriate test papers. Some of the most reactive waste materials (as
judged by incompatibilities according to the compatibility chart) are
determined by these simple tests, so these are performed early in the testing
sequence.
Determination of pH is made by means of pH indicator strips (Merck).
Mineral acids (RGN 1) are arbitrarily designated as those materials having a
pH of less than 1,5, and materials are classified as organic acids (RGN 3) if
the pH is 1.5 to 4.5. Definitive distinction between these two classes ii
made by means of one flame test (PS 3), but for purposes of determining
compatibility characteristics the delineation of these two classes by the
simple pH test will suffice,, Materials are classified as caustic (RGN 10} if
have a pH of 10.5 or greater.
Oxidizing agents (RGN 104) are determined with (commercially available)
starch-iodide paper, and reducing agents (RGN 105) are detected using
(laboratory prepared) methylene blue paper. Oxidizing acids (RGN 2) are
those materials with a pH less than 2 to 3 with a positive oxidation test.
For the purposes of predicting compatibility characteristics,
classification of a waste material as a strong acid (RGN 1 or 2) or as a
strong oxidizing agent (RGN 104) adequately defines the waste material such
that no further testing is necessary. This is because acids and oxidizing
agents are listed as incompatible by the compatibility chart with most ether
classes of waste materials,, Similarly, if the material has the combined
12
-------
TABLE 2. REFERENCE COMPOUNDS FOR HAZARDOUS WASTE COMPATIBILITY TESTING
*
AldU*rb
Ot*c«ton« ttcolMtl
tthj) scryllt*
MuwoOoflc acid
Meitfluorophoiphortc acid
P«ia$i>ua cyanide
Hyflroflugrlc acid
Hyd f Bay act l opnenon*
La»ulfiropK«njr1 Itocyinatc
Bfc^cnyn!
Ch'^"U inhydrld*
Dlpicrjl *»»««
B*rija
SOOIJM
eang* ic4<0«
B«i-.u» o»ta«
Ac»t<«'tT
8
U
J
J
V 1
•
i i < i*1 o
(••ui)
I
a
i
t
X
•
(
,
3 3 1 3 ?
«
1
H
X
»
'
X
3311
1
I
I
I
(
S
1
I
*
E
I
I
? 1 S ? J
. I
i
J
.)
* 1
"
,
(j 4
13
-------
properties of caustic (RGN 10) and reducing agent (RGN 105), further testing
1s probably unnecessary for the purpose of compatibility prediction. It is
recommended, however, that PS 3 be conducted on those materials falling into
RGN's 1, 2, 104 s or 10 and 105 so that explosive hazards do not go
undetected.
A flow diagram for PS 1 is shown in Figure 2.
3*3.2 PS___2_— Solution-Reactivity and Special Functionality Tests
Early in the testing sequence, the reactivity of waste material with
water, mineral acids and bases, and common organic solvents is determined by
direct treatment of the waste material with a series of reagents. The waste
material is treated with water, nitric acid, hydrochloric acid, sulfunc
acid, methanol , acetone, hexane, and toluene. The results of these drop
tests give clues as to the identity of the waste material and also flag
important potentials for reactions with materials likely to be found in
hazardous waste disposal sites. If the material is found to be water
reactive, (RGN 107) it is so labeled and further testing is suspended.
(According to the compatibility chart, water-reactive materials should not be
mixed with any other type of waste.)
A flow diagram for PS 2 is shown in Figure 3. Materials are first
classified according to their reactivity or solubility in water. Materials
are then tested for sulfide (RGN 33) and cyanide (RGN 11). If the material
is found to contain sulfide or cyanide, further testing is suspended due to
the hazard of handling these materials. Liquids are tested for the presence
of water (RGN 106). Aqueous solutions are considered to be primarily
inorganic (for the purposes of compatibility) and nonaqueous liquids are
assumed to be organic.
Drop tests (the testing of the material with a few drops of selected
solvents) are performed and materials may be tentatively classified as
organic or inorganic, based upon their solubility characteristics.
Generally, materials which are soluble in organic solvents are classified as
organic. Confirmation of the organic/inorganic classification is made by
means of the flame test (PS 3), discussed in the following section.
Classification of a material as organic or inorganic is made by means of
the flame test. Materials of unusual flammability (e.guj explosives —
RGN 102) are also identified in this manner. The test consists of placing a
small portion of waste material on a ni chrome wire in a propane flame. If no
visible observation can be made with the nichrome wire test, then a slightly
larger portion in a crucible spoon is subjected to the flame. The flow
scheme for PS 3 is shown in Figure 4,
-------
COHOUCT f»
MO REDOX TESTS
_J
Q BEDUUHG J
Figure 2, Procedure set 1 — pH and redox tests.
-------
Figure 1, Procedure set 2 -- solution/reactivity and special functionality
tests,
-------
o
\ i
SI»R!
SIOP
BtSUlI
D
O
HMO BOH
INDICATOR
commit WHY
Oco
ir Ptsin is AS
LHBU41UL
DS 0«U)
pnonnm.y
cixit/Mir, mnv
CAtrnn, iirnnmtN
OIYGtN
Figure 4. Procedure set 3 — flame test.
-------
Results (observations) upon ignition can provide additional insight
regarding the composition of waste materials. In general, observations upon
Ignition can be characterized by one of the following descriptions:
• Burns violently, sparks, sputters, or explodes
® Burns .
-- Produces very bright (colored) flame
-- Burns with a blue flame leaving no smoke or sooty residue
-- Burns with yellow flame and produces black smoke and/or sooty
residue
-- Burns leaving light-colored residue
• Imparts a color to the flame but does not burn
• Melts or fuses, but does not burn
* Evaporates (sublimes) but does not burn
Materials that react violently upon ignition (sputter, spark, explode,
or burn with violence) are characterized as explosive (RGN 102).
Waste materials that burn are generally classified as organic except
those that give exceptionally bright or colored flames (active free metals —
RGN's 21, 22, 23, and 24). Materials that burn with a yellow flame
and produce smoke and/or leave a sooty residue are classifed as organic.
This behavior is indicative of organic materials with heteroatoms other than
oxygen or aromatic materials. Materials that burn with a nonluminous (blue)
flame and produce no smoke or residue are classified as organic. This
behavior is characteristic of aliphatic hydrocarbons or materials that
contain oxygen as the only heteroatom.
Materials that render a flame colored but do not burn are classified as
inorganic. (This behavior is highly characteristic of inorganic salts.) The
color of the flame can be indicative of the cations present. In addition,
solid materials that fuse but do not burn or evaporate are classified as
inorganic,
Solids that produce no apparent response upon ignition are classified as
inorganic. Liquids that evaporate but leave no residue are either water
solutions of volatile materials (RGN 106) or perhaps chlorinated organic
sol vents. The results of PS 2 are consulted to distinguish these two
possibilities.
Flame tests are conducted primarily to classify materials as organic or
inorganic. In addition, more specific indicators are also given regarding
the composition of organic waste materials. While the observations to be
made in the flame test are somewhat subjective, it is anticipated that most
observers can be trained in less than 1 hr to identify explosives and
18
-------
distinguish between organic and inorganic waste materials in a vast majority
of real-world situations.
3.3.4 PS 4 — Sodium Fusion and Ferrox Tests
The classification of material as primarily organic or inorganic is made
in PS 2 or 3. PS 4 is .conducted if it is determined that the material is
organic, and provides elemental analysis information. The flow diagram for
PS 4 is shown in Figure 5.
This procedure set consists primarily of two tests: sodium fusion with
specific tests for nitrogen (N), sulfur (S), phosphorus (P), and halogen (X);
and the ferrox test to identify oxygen (0).
The waste material is first subjected to fusion with sodium metal. The
waste material is thus decomposed, and heteroatoms form sodium sulfide
(sulfur), sodium cyanide (nitrogen), sodium phosphate (phosphorus) and/or
sodium halide (halogen). Separate tests are performed on the fusion extract
for sulfide, cyanide, and phosphate. In the presence of sulfur, the
thiocyanate test is also performed for nitrogen. In the presence of
nitrogen, sulfur, or phosphorus, oxygen is assumed to be present. Organic
sulfides, thiazoles, and hydrazides are an exception to this assumption.
Appropriate functionality tests are performed if nitrogen (PS 5C) or sulfur
(PS 5D) are determined to be present in the sodium fusion procedure. If
nitrogen, sulfur, or phosphorus are present, tests for functional groups
containing oxygen (PS 5B) are also performed. Organic waste materials
containing halogen are classified as halogenated organics (RGN 17).
If nitrogen, sulfur, and/or phosphorus are not detected by the sodium
fusion procedure, the ferrox test for organic oxygen compounds is performed.
This procedure is applied in the presence or absence of halogen. Appropriate
functionality tests for organic oxygen compounds (PS 58) are performed if the
ferrox test is positive. If the ferrox test is negative, the waste material
is classified as a hydrocarbon (RGN 16, 28, or 29) or as a halogenated
organic (RGN 17). The latter four reactivity groups are mutually exclusive,
so RGN's 16, 28, and 29 are not considered in the presence of halogen. In
the absence of halogen, optional tests are performed (PS 5A see
section 3.3.5.1) to classify the hydrocarbon waste. If the identification of
the potential presence of PCB's is desirable then the Friedel-Crafts test
should be performed when halogens are present.
Two reactivity groups are determined directly in PS 4, namely
organophosphates, phosphothioates, and phosphodithioates (RGN 32) and
halogenated organics (RGN 17). Organic waste materials containing phosphorus
are classified into RGN 32, since by definition this reactivity group
contains most organic waste materials that contain phosphorus. (It is likely
that any other organic phosphorus materials would have compatibility
characteristics similar to those materials defined by RGN 32.) Halogenated
organics are classified into RGN 17 by definition if the fusion procedure
indicates the presence of halogen.
19
-------
ro
O
j 1
npouuwt
DCIA'.SIH
lino RGK
OOWMNW mti !<
WVM.T IS « INi
Figure 5a Procadure set 4 — sodium fusion and ferrox tests,
-------
In summary, PS 4 provides for the elemental analysis of materials
determined to be primarily organic in PS 2 or 3. Results of PS 4 are used to
determine the sequence of tests to be performed in PS 5.
3.3.5 PS 5 — Organic Funct ion_a_1Mty_Jesjts_
PS 5 consists of functional group tests for classification of organic
waste materials. This procedure set consists of four major parts:
® PS 5A — Hydrocarbon classification tests (optional)
• PS 5B — Tests for organic functional groups containing oxygen
• PS 5C — Tests for organic functional groups containing nitrogen
• PS 5D — Tests for organic functional groups containing sulfur
(optional)
PS 5 includes specific tests for classification of waste materials into 20
RGN's and is outlined in Figures 6a through 6d. The functional groups
determined in PS 5 are:
© PS 5A -- Hydrocarbons
-- R6N 16: Hydrocarbons, aromatic
-- R6N 28: Hydrocarbons, aliphatic, unsaturated
-- RGN 29: Hydrocarbons, aliphatic, saturated
• PS 5B — Oxygen functional groups
-- RGN 3: Organic acids
-- RGN 4: Alcohols and glycols
-- RGN 5: Aldehydes
« RGN 13: Esters
-- RGN 14: Ethers
-- RGN 19: Ketones
-- RGN 31: Phenols and cresols
-- RGN 34: Epoxides
-- RGN 30: Peroxides
• PS 5C — Nitrogen functional groups
-- RGN 6: Amides
-- RGN 7: Amines
-- RGN 8: Azo compounds, diazo compounds, and hydrazines
— RGN 9: Carbamates
-- RGN 18: Isocyanates
— RGN 26: Nitriles
— RGN 27: Organic nitro compounds
21
-------
(
c
_ _ OPTIONAL PROCEDURES
"~\ START
) STOP
-X CONTINUE
PROCEDURE
~~7) RESULT
wW"*"*^
n /K^TFY
INTO RGN
V
^— -*-^
I FERROX )
Figure 6a. Procedure set 5A — organic functionality tests
hydrocarbon classification*
22
-------
OFTIONM
o
CD
O
D
o
START
STOP
CONTINUE
PROCIOUIU
RI5UIT
CUSMFV
INTO RGH
COtlTlllUC ONLY II
RESULT IS « INDICATED
pH '5
(FRW PS I) ) I (FROM PS T)
^ POSITI»C J ( POSITIVf J ^POSITIVE )
VNMOAIE
TEST
oiftnnoniENvi
HVDRA7INE
TEST
TEST
TEST
rrRKic
CHI 01 IDE
TES1
Figure 6b. Procedure set 5B — organic functionality tests for functional
groups containing oxygen.
23
-------
fNJ
OPTIONAL
I j STOP
V_X CONTINUE
PROCEDURE
CLASSIFY
WTO RGN
CONTINUE ONLY IF
RESULT IS AS INDICATED
^POSITIVE J
^""—r—^
POSITIVE
POSITIVE
RSN
RGN 18
(OPTIONS,)
DIPHEHYLCARBO-
HYDRAZ1DE
TEST
?
!
DIMETHYLAMIME
BEHZALDEHYDE
TEST
aurAcoNic
ALDEHYDE
TEST
OX AM IDE
TEST
P-NITROBENZENE-
OIAZONIUM
TETRA-
FLUOROBORATE
1 '
_L J_
TETRABASE
TEST
RGK
6 OR 26
6c. Procedure set 5C — organic
groups containing nitrogen.
functionality tests for functional
-------
_ OPTIONAL PROCEDURES
o
START
STOP
CONTINUE
PROCEDURE
O
DCSUIT
O
CLASSIFY
INTO RGN
CONTINUE ONI? If
RESULT IS AS INDICATED
N
COPPER
CHLORIDE
LEAD
ACETATE
Figure 6d. Procedure set 5D -- organic functionality tests for
functional groups containing sjiTfur.
25
-------
• PS 5D -- Sulfur functional groups
-- RGN 12: Dithiocarbamates
-- RGN 20: Mercaptans and other organic sul fides
Each of the procedure subsets 58 to 5D is performed only if the
respective element is determined to be present in PS 4. If the element was
found to be absent in PS 4, it can be concluded that all reactivity groups
determined in that subset are absent. If sulfur, nitrogen, or phosphorus are
present,, oxygen is also assumed to be present, and PS 5B is conducted in
addition to the appropriate procedure subset. If oxygen, nitrogen, halogen,
sulfur, and phosphorus are all found to be absent, it is concluded that the
material is hydrocarbon and PS 5A is conducted. If any of the elements
listed above are present, the three hydrocarbon RGN's are assumed to be
absent. The Friedel -Crafts test may be conducted even if heteroatoms are
present to identify the aroniatie structure. Each of the individual procedure
subsets are explained in the following paragraphs.
3.3.5.1 PS jA_--_Tests__f_o_r Hydrocarbon Cl assi f i cati on (Opti onal )
Three classes of hydrocarbons (RGN's 16, 28, and 29) are distinguished
by the Friedel-Crafts test and the Baeyer test. The flow diagram for PS 5A
is shown in Figure 6d. These three RGN's are mutually exclusive (by
definition); therefore, if one test result is positive, the other test
logically need not be run. However, it should be noted that some compounds
(e.g., styrene) have both aromatic (RGN 16) and unsaturated aliphatic
(RGN 28) functionality. It is suggested that either both tests be performed
or the Friedel-Crafts test (RGN 16) be performed first in this sequence.
RGN 16 is the more serious category from a toxicity criteria. If both the
Friedel-Crafts test and the Baeyer test are negative, the material is
classified as RGN 29.
Since the hydrocarbon RGN's are similar in their compatibility
characteristics and are all relatively unreactive, this procedure subset is
labeled optional .
It should be noted that while it is likely that hydrocarbons may go
undetected In mixtures containing other more reactive organics, the
compatibility characteristics of any waste material will be dominated by the
characteristics of the more reactive material.
3 • ^ « 5 . 2 j^AB_.r^.TgltA.J^^QrMQl£-^AcJiQnal Groups Containing Oxygen
Tests for functional groups containing oxygen involve tests for nine
specific reactivity groups. These tests are performed on all organic wastes
except those materials shown not to contain sul fur , nitrogen, or phosphorus
by the fusion procedure and those that give a negative ferrox testo The flow
diagram for procedure subset 5B is shown in Figure 6b. If the ferrox test is
negative, all the RGN's in PS 5B are assumed to be absent.
26
-------
Three of the reactivity groups are identified by means of results
obtained in PS 1 and PS 2. Organic acids (RGN 3) are identified by means of
their pH (pH 1.5 to 4.5). Organic peroxides (RGN 30) respond as oxidizing
agents and should be identified as RGN 104 in PS 1. The result is confirmed
as peroxide by the EM Quant® peroxide test strip in this procedure set. Note
that this confirmation would take place only if optional testing of materials
classified as RGN 104 were conducted. No specific test was found for
identification of epoxides (RGN 34), but this reactivity group is tentatively
identified by its vigorous, sometimes'violent reaction with mineral acids,
particularly nitric acid.
The remaining six RGN's identified in PS 5B are less reactive than RGN's
3, 30, or 34. If one of these three reactive RGN's are identified, it is
advisable to omit further tests for other RGN's. Furthermore, compatibility
characteristics of the less reactive RGN's are similar, so tests for the
remaining six RGN's are labeled optional.
Dinitrophenylhydrazine is used to identify carbonyl compounds (aldehydes
and ketones, RGN's 5 and 19), and the Schiff's test is used to distinguish
between the two. Separate tests are conducted to identify alcohols (RGN 4),
esters (RGN 13), ethers (RGN 14), and phenols (RGN 31).
3.3.5.3 PS5C -- Tests for Organic Functional Groups Containing Nitrogen
Functional group tests for organic compounds containing nitrogen are
contained in PS 5C. These tests are performed only if nitrogen is detected
by the sodium fusion procedure (PS 4). The flow diagram for classification
of the seven, reactivity groups containing nitrogen is shown in Figure 6c. If
nitrogen is absent, as determined by the sodium fusion procedure (PS 4), all
the RGN's in PS 5C are thus determined to be absent.
Three reactivity groups are considerably more reactive than others:
carbamates (RGN 9), isocyanates (RGN 18), and azo compounds, diazo compounds,
and hydrazines (RGN 8). The diphenylcarbohydrazide test is conducted to
identify RGN 9. Azo compounds are identified by the dimethylamino-
benzaldehyde test and hydrazines are identified by the glutaconic aldehyde
test. If either of these tests are positive, the material is classified as
RGN 8. No suitable test procedure has been identified for isocyanates
(RGN 18).
If a material is classified as RGN 8, 9, or 18, the need for further
testing in PS 5C is eliminated. Tests for RGN's 6, 7, 26, and 27 are
included, but are labeled optional, because compatibility characteristics of
these materials are similar and the reactivity hazard of these materials is
not as great. Amides and nitriles are not distinguished by the test
procedure, but these materials are very similar in their reactivity
properties.
27
-------
3,3.5,4 PS 5D — Tests for Organic, Funct^ona] JB^
JOptionaJ)
Tests for two reactivity groups that contain sulfur are included in
PS 5D. Since the reactivity characteristics of these RGN's are similar, the
procedure subset is labeled optional. If sulfur is shown to be absent in the
sodium fusion procedure (PS 4), both RGN's 12 and 20 are therefore determined
to be absent. The flow diagram for procedure subset 5D is shown in
Figure 6d.
3.3.6 PS_6_~- Inorganic Functionality Tests
If it is determined from PS 2 or 3 that a material is inorganic, three
test procedures are conducted to identify inorganic materials not identified
in previous procedure sets (PS 1 and 2). Inorganic materials detected in
PS 1 and PS 2 are the following:
® RGN 1: Acids, mineral, nonoxidizing
• RGN 2: Acids, mineral, oxidizing
® RGN 10: Caustics
• RGN 11: Cyanides
® RGN 33: Sulfides, inorganic
• RGN 104: Oxidizing agents, strong
• RGN 105: Reducing agents, strong
• RGN 106: Water and mixtures containing water
Tests for remaining inorganic RGN's (15, 21, 22, 23, 24) comprise PS 69
outlined in Figure 7.
Elemental metals or alloys can often be identified visually, but are
identified by the phosphomolybdic acid test. Alkali and alkaline earth
metals (RGN 21) react with water to give solutions that are basic (PS 2),
Visual inspection can be used to identify the form of other elemental metals
(RGN's 22 or 23),
It should be noted that all elemental metals except mercury (which is
readily identified visually) are solids, so the phosphomolybdic acid test is
not conducted if the waste material under investigation is a liquid.
Solid materials are dissolved (using concentrated nitric acid if
necessary). This solution or liquid waste material is treated with zinc
sulfide to determine the presence of heavy metals* which are assumed to be
toxic (RGN 24). Inorganic fluorides (RGN 15) are identified by means of the
zirconium alizarinate test.
28
-------
SHEET5, RODS,
DROPS, MOULDINGS
o
STSRT
STOP
CONTIHUE
PROCEDURE
O
RESULT
CLASSIFY
INTO RGN
Figure 7. Procedure set 6 — Inorganic functionality tests.
-------
It should be noted that a test is not included for nitrides (RGN 25) ,
but these materials are explosive and are thus, identified in PS 3. (Nitrides
are not available commercially and were therefore not included as part of
this study).
3.4 RESULTS OF TESTS USED TO VERIFY PROCEDURE SETS
3 • 4 • ! PS I — pH and _Redox_ Te s_ts
The 58 reference compounds (see Table 2) were tested for
oxidation/reduction potential and for pH using test papers. Oxidizing agents
were identified by means of starch-iodide test paper (Fisher). Reducing
agents were identified in a similar manner with methylene blue or
294-dichloroindophenol test paper. The pH of reference compounds was
determined using colorpHast® indicator (Merck).
The results of testing the reference compounds using the three test
paper procedures above are described in Table 3. No anomalous results were
obtained.
Merck pH test strips and Fisher iodide-starch paper were chosen for use
in the test kit because they are commercially available, reliable9 and easy
to usee Methyl ene blue test strips were easy to use, reliable, and easy to
prepare.
3 • ^ > 2 Pj^ 2 — Jplutijjn Re Tests
3,4,2.1
The reference compounds were treated with water, a series of mineral
acids and bases , and four organic solvents to assess solubility and/or
reactivity characteristics. These characteristics can give clues regarding
the general chemical characteristics of the waste material. In addition,
these tests quickly predict the compatibility of the water material with
other waste materials likely to be found at a hazardous waste disposal site*
While the materials can be categorized according to solubility and
reactivity by this set of spot tests, the utility of the information derived
is limited. The information is of general utility in handling the waste
materials, Those materials found to be soluble in hexane and/ or toluene can
be classified as organic. Likewise, materials found to be soluble in acetone
and/or methanol but not in water can be considered organic. Host
water- reactive materials can be identified by means of this drop test,
The results of solution-reactivity tests conducted on the reference
compounds are presented in Table 4. None of the observations represent a
deviation from those expected. The results of these tests are correlated by
grouping the test materials according to general chemical class (i,e,,
elemental metal, hydrocarbon,, organic oxygen compound) and noting the
response of all the reference compounds of that particular general class, A
30
-------
TABLE 3. RESPONSE OF REFERENCE COMPOUNDS TO pH AND REDOX TESTS
Response3
Compound
Chromic oxide
Cadmium
Sodium
Arsenic pentasulfide
Chromium
Copper
Lead
Nickel
Barium
Barium iodide
Barium oxide
Calcium hypochlorite
Selenium di ethyl dithiocarbamate
Hydrofluorosilicic acid
Peracetic acid
RGN(s)
2,24,104
23S24
25,105,107
24,33
23,24
23,24
23,24
22,24
21,24,107
24
10,24,107
10,104
12,24
1,15
3,30,104
pH Oxidizing
0 +
NR NR
14
6 NR
NR NR
NR NR
NR NR
NR NR
14
5 +
14 NR
9 +
7 NR
0 +
2 +
Reducing
_b
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
aNR = no response
+ = positive test result
- = negative test result
(continued)
bThe test paper was decolorized (bleached) by the strong oxidizing
agent. Results are clear when test material is diluted with water.
31
-------
TABLE 3, (continued)
Compound
Fluoboric acid
Hexafl uorophosphoric acid
Potassium cyanide
Hydrofluoric acid
Trinitrobenzoic acid
Picric acid
Dipicrylamine
Dimethyl ami noazobenzene
Arninopropionitrile
Aminothiazole
Benzoyl peroxide
Malonic nitrile (cyanoacetic
acid)
Toluene diisocyanate
Hydroxylamine hydrochloride
RGN(s)
1,15
1,15
11
1,15
3,27,102
27,31,102
27,31,102
738
7,26
7
30,102
3S26
18,107
105
pH
0
0
12
0
0
2
6
NR
11
7
NR
2
NR
NR
Response3
Oxidizing Reducing
+ NR
"f NR
NR NR
NR NR
NR MR
NR MR
NR NR
NR MR
NR NR
NR NR
+ NR
NR NR
NR NR
NR +
no response
positive test response
negative test response
(cent inue
test paper was decolorized (bleached) by the strong oxidizing
agent. Results are clear when test material is diluted with water.
-------
TABLE 3. (continued)
Response3
Compound
Malathion
Parathion
Ethyl zimate
Vinyl acetate
Bromoxynil
Chlorophenyl isocyanate
Styrene
Ethyl ene glycol monomethyl ether
Polypropylene
Propylene oxide
Methyl methacrylate
Ethyl acrylate
Mercaptobenzothi azol e
Lannate
Hydroxyacetophenone
aNR = no response
+ = positive test response
RGN(s)
13,32
27,32
12,24
13,103
13,17,26
17,18,107
16,28,103
4,14
29,101
34,103
13,103
13,103
20
9
19,31
PH
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Oxidizing
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Reducing
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
(continued)
^*wwi VI ¥ w %r v» vP w 1 W.JWVSIC.JVd
- = negative test response
bThe test paper was decolorized (bleached) by the strong oxidizing
agent. Results are clear when test material is diluted with water.
33
-------
TABLE 3. (concluded)
Compound
Mercaptoethanol
n-Butyl acrylate
Acrolein
Di acetone alcohol
Aldicarb
Zineb
Dlphenamide
Hexene
Decane
TEPA
Acetamide
Naphthalene
Polysulfide polymer
RGN(s)
4,20
13,103
5,103
4,19
9
12S24
6
28
28
7S32
6
16
2QS1491Q5
pH
NR
NR
NR
NR
NR
NR
3
NR
NR
7
5
NR
NR
Response5
Oxidizing Reducing
NR +
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR +
aNR = no response
+ 3 positive test response
- = negative test response
test paper was decolorized (bleached) by the strong oxidizing
agent. Results are clear when test material is diluted with water,
34
-------
TABLE 4. RESPONSE OF REFERENCE COMPOUNDS TO SOLUTION-REACTIVITY TESTS
Compound
Chromic oxide
Cadmium
Sodium/oil
dispersion
Arsenic pentasulfide
Chromium
Copper
Lead
f
Nickel
%
Ba ri um
Barium Iodide
Barium oxide
Calcium hypochlorite
RGN(s) Water
2,24.104 Dissolves
readily,
turns orange
23,24 NR
21,105,107 Slow gas
evolution
24,33 Dissolves
slowly
23,24 NR
Z3.24 NR
23,24 NR
22,24 NR
21,24,107 Fast
gas evolution
24 Dissolves
10,24,107 Dissolves
very slowly
10,104 Dissolves,
fumes
Hydrochloric
acid
Dissolves,
turns
brown
Dissolves
with gas
evolution
Slow gas
evolution
Dissolves
slowly
Gas
evolution
Slow gas
evolution
Slow gas
evolution
i
Slow gas
evolution
Fast gas
evolution
Dissolves
Gas
evolution
Fast gas
evolution
Nitric acid
ni ssol ves
slightly
Violent
reaction.
brown fumes
Slow gas
evolution
Dissolves
slowly
NR
Fast gas
evolution.
brown fumes
Slow
gas evolution
Gas evolution.
brown fumes
Fast gas
evolution,
brown fumes
Fumes,
black residue
Gas evolution
Fast gas
evolution
Response
Sodium
Sulfurlc acid hydroxide Methanol Acetone Hexane Toluene
Dissolves Dissolves Violent Violent NRa NR
slightly readily reaction, reaction,
turns black turns black
Slow NR NR NR NR NR
reaction (gas
evolution)
Slow gas Gas Gas Gas NR NR
evolution evolution evolution evolution
Dissolves Dissolves NR NR NR NR
slowly slowly
Slow gas NR NR NR NR NR
evolution
NR NR NR NR NR NR
NR NR NR NR NR NR
,
Very slow Gas Gas Gas NR NR
gas evolution evolution evolution evolution
Fumes, Dissolves Dissolves Dissolves NR NR
black residue
Dissolves Dissolves NR NR NR NR
very slowly
Fast gas NR NR MR NR NR
evolution
Turns brown NR Dissolves Dissolves NR NR
= no observable response
(continued)
-------
TABLE 4. (continued)
Response
Compound »6H{s) Meter
Selenium diethyl- 12,24 FfRa
dithiocsrbamate
Hydrofluorosllicic 1.15 Dissolves
add
Peracetlc acid 3,30,10« Dissolves
Fluobor-ic acid 1,15 Dissolves
Hexafluorophosphoric 1,15 Dissolves
add
Potassium cyanide 11 Dissolves
Hydrofluoric acid 1,15 Dissolves
us Trinitrobenzoic acid 3,37,102 Dissolves
Picric acid 27,31,102 Dissolves
dpi cry! ami rse 27,31,102 Dissolves
slowly
Dimethyl aralpoazo- 7,8 KR
benzene
teiinopropioRitrile 7,26 Dissolves
farinothiazclp 7 KR
Benzoyl peroxide 30,102 WR
Hydrochloric
acid
NR
Dissolves
Dissolves
Dissolves
Dissolves
Fumes
Dissolves
Dissolves
slowly
Dissolves
9
Dissolves
slowly
Dissolves,
turns red
White f lines
Dissolves,
turns brown
NR
Nitric acid
Brown fumes
Dissolves
Dissolves
Dissolves
Dissolves
Fupes
Dissolves
Dissolves
Dissolves
Dissolves
slowly
Dissolves,
turns red
then black
White fumes
Dissolves,
turns brown
NR
Sulfuric acid
Gas
evolution
D1 ssol ves
Fumes
Fares
Fisses
Fumes
Fanes
Dissolves
Dissolves
Dissolves
slowly
NR
White fumes,
viscous
residue
Dissolves.
turns brown
Fumes, turns
black
Sodium
hydroxide
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves,
turns red
Turns
orange
Turns dark
red
Dissolves
Dissolves
MR
NR
Methanol
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
Acetone
NR
Dissolves
NR
Dissolves
Dissolves
NR
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
ni ssol ves
Dissolves
si only
Hexane
HR
NR
NR
NR
NR
m
NR
NR
Dissolves
NR
Dissolves
Dissolves
Nft
NR
Toluene
Dissolves
NR
"»
NR
NR
m
NR
Dissolves
very
slowly
Dissolves
NR
Dissolves
Dissolves
NR
Dissolves
slowly
no observable response
(continued)
-------
TABLE 4. (continued)
Response
Compound
Malonlc nitrile
(cyanoacetic acid)
Toluene dilsocyanate
Hydroxylamine
hydrochlorlde
Malathion
Parathlon
CO
Ethyl zimate
Vinyl acetate
Brom^xyni!
Chloro^henyl
isocyanate
Styrene
Ethylene glycol
monomethyl ether
Propypropylene
Propylene oxide
RGN(s)
3,26
18,107
105
13,32
27,32
12,24
13.103
13,17,26
17.18,107
16,28,103
4,14
29,101
34,103
Hydrochloric
Water acid
Dissolves Dissolves
NR NR
Dissolves Dissolves
slowly slowly
MR Dissolves
NR Dissolves,
turns gray
KR Dissolves
turns gray
Dissolves Dissolves
White emulsion Turn^ brown
HR NR
NS Dissolves
Dissolves Dissolves
»Ra NR
Gas evolution Dissolve;.,
gas evolu-
tion
Nitric add
Dissolves
Gas evolution,
turns brown
Dissolves
Gas evolution,
turns brown
Turns brown
Gas evolution,
brown fumes
Dissolves
Turns brown
Turns brown
Dissolves
Dissolves
NR
Violent
spattering
Sulfuric acid
Dissolves
Gas evolu-
tion, white
residue
Foaming
Gas evolu-
tion, turns
yellow
Dissolves,
turns yellow
Gas evolution
Turns brown
Turns brown
Turns brown
Turns brown
Dissolves
turns yel low
NR
Violent
spattering,
turns black
Sodium
hydroxide
Dissolves
NR
Dissolves
NK
Turns
yellow
NR
Dissolves
Turns
brown
NR
NR
Dissolves
NR
Dissolves
Ntethano!
Dissolves
HR
Dissolves
Dissolves
Di ssol ves
Dissolves
Dissol ves
NR
Dissolves
Dissolves
Dissolves
NR
Dissolves
Acetone
Dissolves
Dissolves
Dissolves
slowly
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
Dissolves
Hexane
NR
Dissolves
m
Dissolves
Dissolves
m
Dissolves
Dissolves
Dissolves
slowly
Dissolves
Dissolves
NR
Dissolves
Toluene
NR
Dissolves
NR
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
Dissolves
aNR = no observable response
(continued)
-------
TABLE. 4, (concluded)
Response
Co^n-
Methyl methacrylate
Ethyl acrylate
MercapiobefUQthiMoie
Lannate
Hydroxyacetophenone
Me^captoethanol
n-Butyl acrylate
CO
0° Acrolein
Di acetone alcohol
AldlMfb
Z I nsb
Dipbetenae
He xc •" e
Decene
TEPA
Acetcraide
Naphthalene
"o'ysulfid* polymer
RGN(s)
13,303
13,103
2G
9
19,31
4,20
13,103
5.103
",19
9
12,24
6
28
28
7,33
6
16
(4,20,10-;
Mater
NR
US
MR
WR
NR
Dissolves
NR
Dissolves
m
NR'
NS
NR
WR
Di ssol yes
Dissolves
hR
MR
Hydrochloric
acid
Dissolves
Dissolves
Dissolves
Dissolves
NR
Dissolves
NR
Dissolves
Turns orange
Dissolves
Dissolves
Dissolves
Dissolves
m
DissoJves
NR
NR
W
Nitric acid
Dissolves
Dissolves
Gas evolution,
brown fumes
Dissolves
Dissolves
Dissolves,
turns pink
NR
Dissolves
Turns orange
Dissolves
Dissolves
Dissolves
Di ssol ves
NR
Dissolves
slowly
HR
NR
Brown fumes
Sulfuric acid
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Faams
Dissolves
Turns black
Turns brown
Dissolves
Dissolves
Dissolves
Di sso! ves
Dissolves
Gas evolution,
turns blac!(
Dissolves
m
Dissolves
Sodium
hydroxide
NR
NR
Dissolves
Dissolves
slowly
Dissolves
NR
NR
Fuines, white
residue
Dissolves
NR
NR
NR
NR
NR
Dissolves
Dissolves
NR
NR
Methanol
Dissolves
Dissolves
NR
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
HK
MB
Acetone
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Hsxane
Dissolves
Dissolves
NR
Dissolves
NR
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
NR
NR
Toluene
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
Dissolves
NR
Dissolves
ill sso! ves
oeservjb'e
-------
generalized summary of the solution reactivity tests is presented in
Table 5.
3.4.2.2 Special Functionality Tests
Concurrent with the solution reactivity tests, the reference compounds
were tested for the presence of sulfide and cyanide, and liquids were tested
for the presence of water. Sulfide is detected using lead acetate test
paper, cyanide is determined by a spot test (Table 1), and the presence of
water is determined in liquids by anhydrous copper sulfate. These tests are
conducted early in the testing sequence to identify these hazards before
extensive testing is initiated. Since they involve spot tests, they are
conveniently performed concurrently with the solution reactivity tests.
The results of the special functionality tests are presented in Table 6,
Sulfide-containing test materials render anhydrous copper sulfate black (by
formation of copper sulfide). Aminoproprionitrile produces a violet color,
the origin of which is unknown. These were the only anomalous results
oberserved in the special functionality tests.
3.4.3 PS 3 - Flame Tests
The behavior of each of the reference compounds upon ignition was
observed by performing the flame test. In most cases, an adequate
observation was made using a wire loop. In those cases where observation was
not possible using a wire loop, a porcelain spatula was used. The responses
of each of the test materials to the flame test are presented in Table 7.
Five categories of behavior are presented in Table 7: fusion (melting) of
the test material, burning, color of the flame produced, smoke produced
during ignition, and any residue remaining after ignition.
A generalized summary of the behavior of the reference compounds upon
ignition is presented in Table 8. Most of the test materials respond as
predicted, that is, organic materials burn and inorganic materials do not
burn. Notable exceptions are elemental metals which burn with
characteristically colored flames and oxidizing and reducing agents which
generally exhibit vigorous to violent behavior upon ignition. Therefore care
must be taken when classifying combustible materials as organic. In
particular, one must be sure to consult the results of PS 1 and PS 2, because
the behavior of oxidizing and reducing agents in the flame test can be
misleading. Solubility information from PS 2 is used in conjunction with the
flame test results to classify these materials as organic or inorganic.
Three of the four compounds falling into the explosive category (RGN 102)
showed distinctive behavior in the flame test. However, trinitrobenzoic acid
did not show an exceptional response.
3.4.4 JS__4 — Sodium Fusion and Ferrox Test
A determination of the presence of heteroatoms in the reference
compounds was made using tests in PS 4. Nitrogen, sulfur, chloride, and
phosphorus were detected by fusion of the material with metallic sodium and
39
-------
TABLE 5* GENERAL SUMMARY OF SOLUTION-REACTIVITY TEST RESULTS
Response
Compound Water
Hydrocarbons NRa
Esters, ethers, NR
acids, aldehydes,
and ketones
Nitro compounds and Dissolves
pitretes
Amines MR or
Dissolves
Isocyanates, KS
rntriles
Marcaptans NR
Phosphorus NR
compounds
Epoxides Dissolves,
gas
Reactive olefins US.
(polymenzable)
Inorganic acids Dissolve?
Metallic el ementi KR except
N« and Ba
evolution)
Ox urging ag;nts Dissolves
Salts «nd •„<,'. des Dissolves
or MR
Hydrochloric
acid
NR
Dissolves
Dissolves
Dissolves
m
HS> or
dissolves
NR or
dissolves
Dissolves,
gas
Dissolves
Dissolves
Slow gas
evolution
Dissol yes,
Ca(OCl)v,
rumes
Dissolves,
fumes, or NS
Nitric acid
NR
Dissolves
(color
change)
Dissol vts
Dissolves
(discolored)
Vigorous
reaction,
brown fumes
Brown fumes
Brown fumes
Violent
spattering
Dissolves or
m
Dissolves
Gas, brown
fksies (some
metals
violent
reaction)
Dissolves,
Ca(OCi)2,
fumes
Dissolves,
fuc*i, o," NR
Sulfurlc acid
m
Dissolves
(turns
brown)
Dissolves
MR or
darkens •
MR or
darkens
NR or
darkens
Darkens
Viorous
reaction
Dissolves
or darkens
Dissolves,
fumes
Slow reaction
(gas evolu-
tion)
Dissolves,
Ca{QCl)z,
fusses
Dissolves,
'.ccas, or KR
Sodium
hydroxide
NR
Dissolves
or NR
Dissolves,
red color
m
NR
Dissolves
or NR
Dissolves
or NR
Dissolves
or MR
NR'
Dissolves
KR except
Ha and Ba
(gas evolu-
tion)
Dissol Vis
Dissolves
or NP,
Polar
solvents
setfwnol ,
acetone
Dissolves,
acetone
Dissolves
or NR
Dissolves
or NR
Dissolves
or NR
Dissolves
or MR
Dissolves
or NR
Dissolves
or NR
Dissolves
or NR
Dissolves
or NR
Dissolves
or NR
NR except
Ha and Ba
(gas evolu-
tion)
CrD3,
sioient
Ca(OCl)2,
SR
HP
Non polar
solvents
hexane, toluene
Dissolves
(except poly-
propylene)
Dissolves or
NR
Dissolves or
NR i
Dissolves or
NR
Dissolves or
NR
Dissolves or
NR
Dissolves or
NR
Dissolves or
NR
Dissolves or
NR
NR
NR
MR
HP,
",A - rfc i^e
response
-------
TABLE 6. RESPONSE OF REFERENCE COMPOUNDS TO THE SPECIAL FUNCTIONALITY TESTS
Compound
Chromic oxide
Cadmium
Sodium
Arsenic pentasulfide
Chromium
Copper
Lead
Nickel
Barium
Barium iodide
Barium oxide
Calcium hypochlonte
Selenium d i ethyl -
dithiocarbamate
Hyd rof 1 uoros i 1 i c i c
acid
Peracetic acid
RGN(s)
2,24,104
23,24
25,105,107
24,33
23,24
23,24
23,24
23,24
21,24,107
24
10,24,107
10,104
12,24
1,15
3,30,104
Response3
CM- S= H20b
NA
NA
NA
+ NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
+
+
a-f = positive test response
- - negative test response
(continued)
bTest only conducted with liquid test materials. Solids are
listed as NA, not applicable,
cBlack copper sulfide is produced with waste materials containing
sulfides
41
-------
TABLE 6. (continued)
Compound
Fluoboric acid
Hexaf 1 uorophosphoric
acid
Potassium cyanide
Hydrofluoric acid
Trinitrobenzoic acid
Picric acid
Dipicrylaim'ne
Dimethyl ami nozaobenzene
Ami nopropionit rile
Aminothiazole
Benzoyl peroxide
Malonic nit rile
(cyanoacetic acid)
Toluene diisocyanato
Hydroxylamine
hydrochloride
RGN(s)
1,15
1,15
11
1,15
3,27,102
27,31,102
27,31,102
7,8
7,26
7
30,102
3,26
18,107
105
Response3
CM- S= H20b
+
4-
+ - NA
„.„-).
NA
NA
NA
NA
Turns
v i ol et
NA
NA
NA
_
NA
- positive test response
= negative test response
icontinued)
only conducted with liquid test materials. Solids are
listed as NA9 not applicable.
cBlack copper sulfide is produced with waste materials containing
sulfides
42
-------
TABLE 6. (continued)
Compound
Malathion
Parathion
Ethyl zimate
Vinyl acetate
Bromoxynil
Chlorophenyl isocyanate
Styrene
Ethyl ene glycol monomethyl
ether
Polypropylene
Propylene oxide
Methyl methacrylate
Ethyl acrylate
Mercaptobenzothi azol e
Lannate
Hydroxyacetophenone
Response3
RGN(s) CM- S= H20b
13,32
27,32
12,24 - - NA
13,103
13,17,26
17,18,107 - - NA
16,28,103
4,14
29,101 NA
34,103 -
13,103
13,103
20 NA
9 NA
19,31 NA
a+ = positive test response (continued)
- = negative test response
bTest only conducted with liquid test materials. Solids are
listed as NA, not applicable.
C81ack copper sulfide is produced with waste materials containing
sulfides
43
-------
TABLE 6. (concluded)
Compound
Mercaptoethanol
n~Butyl acryl ate
Acrolein
Diacetone alcohol
Aldicarb
Zineb
Diphenamide
Hexene
Decene
TEPA
Acetamide
Naphthalene
Polysulfide polymer
RGN(s)
4,20
13,103
5,103
4,19
9
12,24
6
28
28
7,32
6
16
14,20,105
Response3
CM- S= H20b
+ Turns
blackb
-
,.
NA
NA
NA
_
_
NA
HA
NA
+ Turns
blackc
a+ - positive test response
- = negative test response
^Test only conducted with liquid test materials. Solids
listed as NA, not applicable,
C81ack copper sulfide is produced with waste materials containing
sulfides
44
-------
TABLE 7. RESPONSE OF REFERENCE COMPOUNDS TO THE FLAME TESTS
>• Response
Compound
Chronic oxide
Cadmium
Sodium
Arsenic pentasulfsde
Chromium
Copper
Lead
Nickel
Barium
Barium iodide
Barium oxide
Calcium hypochlorite
Selenium diethyl dithiocarbaraate
Hydrofluoroailic acid
Peracetie acid
Fluoboric acid
Hexafl uorophosphoric acid
Potassium cyanide
Hydrofluoric add
Trinitrobenzoic acid
Picric acid
DipicrylMine
Aninopropionitrile
Amlnothiazole
Beruoy) peroxide
Malonic nitrile (cyanoacetic
acid)
RGN(s)
2,24,104
23,24
24.105,107
24,33
23,24
23,24
23.24
22.24
21,24,107
24
10,24.107
10,104
12,24
1,15
3,30
1,15
1.15
11
1,15
3,27,102
27,31,102
7,27,102
7,26
7
30,102
3,26
Kelt
No
No
No
No
No
No
No
No
No
-Yes
Yes
Yes
No
(Liquid)
No
(Liquid)
(Liquid)
Yes
(Liquid)
Yes
Yes
Yes
Yes
Yes
No
Yes
Burn
Yes, sparkles
Yes
Yes
Yes
Bright sparkles
NO
Yes
No
Yes
No
No
No
Yes
No
Yes
No
Yes
No
No
Yes
Sparkles
Yes, sparkles
Yes
Yes
Violent
Yes
Flame
Bright (white)
Yellow-red
Yellow
Blue
White
Green
Light blue
None observed
Orange
Orange
Orange
Orange
Yellow
Yellow (Ha)
None
Bright green
Yellow
Pink
Yellow (Na)
Yellow
Yellow
Yellow
Blue-red
Blue
Yeliow
Yellow
Smoke
.„
Yellow
NC
Gray
No
No
NO
No
No
No
No
No
White
No
White
No
No
No
No
Black
Black
Black
White
No
No
White
Residue
Green
Gray
Gray
Gray
Gray
Black
Gray
Gray
Gray
No
Colorless
Colorless
No
No
No
No
No
No
No
Black, sooty
Black, sooty
Black, sooty
No
No
No
No
(continued)
45
-------
TABLE 7. (concluded)
'" Response
Compound
Toluene dUsocyanate
Hydroxylamine hvdrochlorlde
MalatMon
Parathion
Ethyl zimate
Vinyl acetate
Broraoxynf]
Chlorophenyl Isocyanate
Stryene
Ethylsng glyeol monomethy) ether
Polypropylene
Propylene oxide
Methyl rnethacrylate
Ethyl acrylate
Mercaptobenzothiazole
Lannste
Hydrax^aeetaphenone
Hercapthoethanol
n-Butyl acrylate
Acrolein
Diacetons alcohol
Aldlcarb
2!neb
Diphc-nainlde
Hexene
Oeeene
TEPA
Acetamlde
Naphthalene
RGN(s)
18.107
105
13,32
27.32
12.24
13,103
17.26,31
17,18,107
16,28,103
4,14
29.101
34,104
13,103
13,103
20
9
19.31
4,20
13,103
5,103
4,19
9
12,24
6
28
28
7.32
a
18
Melt
(Liquid)
Yes
(Liquid)
(Liquid)
Yes
(Liquid)
(Liquid)
(Liquid)
(Liquid)
^Liquid)
Yes
(Liquid)
(Liquid)
(Liquid)
Yes
Yes
Yes
(Liquid)
(Liquid)
(Liquid)
(Liquid)
Yes
No
Yes
(Liquid)
(Liquid)
Yes
Yes
Yes
Burn
Yes , foams
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
No
Yes
Flame
Yellow
--
Yellow
Yellow
Yellow
Blue
Yellow
Yellow
Yellow
Blue
Yel 1 ow
Yel 1 ow
Yellow
Yellow
Yellow
Yellow
Yellow
Blue
Blue
Hhite, yellow
Blue
Bright yellow
None obser¥ed
Yellow
Yellow
Yel 1 ow
Yellow
--
Yellow
Smoke
White
--
Black
Black
White
No
Black
Black
Black
No
No
NO
No
NO
White
White
Black
White
No
No
No
No
White
White
No
No
Black
White
Black
Sestdue
Sobty
White
Black
Black
Gray
No
Black
Black
Black
No
Black
No
No
No
Gray
Sray
Black, sooty
Gray
No
No
Ho
No
White
Gray
Ho
No
Sooty
Gray
Black, sooty
46
-------
TABLE 8. GENERAL SUMMARY OF FLAME TEST RESULTS
General compound class
Flame test
Metals and metal salts
Acids -- inorganic
Aliphatic hydrocarbons and
oxygen compounds
Aromatic hydrocarbons
Qrganosulfur, phosphorus,
and nitrogen compounds
Explosives (picrates)
Colored flames; cadmium, chromium, lead,
barium, and sodium burn brightly, others do
not burn; CrOs burns very brightly
Generally do not burn, fluoboric acid bright
green; most give yellow (sodium) flame
Benzoyl peroxide burns violently, others have
blue flames -- no smoke — no residue;
alkenes give yellow flames
Yellow flames, black smoke
Burns with white-yellow smoke
Burns violently (sparkles)
analysis of the resulting extract for cyanide (nitrogen), sulfide (sulfur),
halide (halogen), and phosphate (phosphorus). If any of these heteroatoms
were detected by the fusion procedure, oxygen was also assumed to be present.
If nitrogen, sulfur, and phosphorus were determined to be absent by the
fusion procedure, oxygen was detected in the waste material by means of the
ferrox test. All of the organic test materials were tested for the presence
of nitrogen, sulfur, halogen, and phosphorus with the sodium fusion procedure
and for the presence of oxygen with the ferrox test. The results of these
tests are presented in Table 9.
Two of the test materials, aminothiazole and mercaptobenzathiazole, gave
negative cyanide tests. The fusion extracts from these reference compounds
were subsequently tested for thiocyanate, which gave positive results for
both extracts. Therefore, in the test scheme for materials containing
sulfur, nitrogen is detected by both the cyanide and the thiocyanate tests
(i.e., in those cases when sulfur is present and the cyanide test is
negative, a test for thiocyanate is also performed). No other anomalous
results were obtained for the sodium fusion tests.
All of the organic reference compounds were subjected to the ferrox
test. Variable results were obtained for compounds containing nitrogen and
sulfur, so this test cannot be used alone to detect oxygen. For example,
organic nitro compounds give a negative response and aminothiazole gives'a
47
-------
TABLE 9. RESPONSE OF ORGANIC REFERENCE COMPOUNDS TO SODIUM FUSION AND FERROX
TESTS
Compound
Trinitrobenzoic acid
Picric acid
Dipicrylamine
Dimethyl ami noazobenzene
Aminopropionitrile
Aminothiazole
Benzoyl peroxide
Malonic nitrile
Toluene diisocyanate
Malathion
Parathion
Ethyl zimate
Vinyl acetate
Bromoxynil
RGN(s)
3,27,102
27,31,102
7,27,102
7,8
7,26
7
30,102
3,26
18,107
13,32
27,32
12,24
13,103
13,17,26
Fusion
results9
Heteroatoms Ferrox
present N S P X results'5
N, 0 + - - -
N, 0 + - _ -
N, 0 + - - -
N + - - -
N + - - - -r
N, S c + - - +
0 - - - - +
N, 0 + - - - +
N9 0 + - - -
S, P . + + _ +
N, S, P + + + - +
N, S + + - - +
n - +
N, 0, Br + - - + i-
a+ = positive test response
- = negative test response
^Stabilized with catechol derivative
cNitrogen detected as thiocyanate
(continued:
48
-------
TABLE 9. (continued)
Compound
Chlorophenyl isocyanate
Styrene
Ethyl ene glycol monomethyl ether
Polypropylene
Propylene oxide
Methyl methacrylate
Ethyl acrylate
Mercaptobenzothiazole
Lannate
Hydroxyacetophenone
Mercaptoethanol
n~Butyl acrylate
Acrolein
Diacetone alcohol
Diphenamide
RGN(s)
17,18,107
16,28,103
4,14
29,101
34,103
13,103
13,103
20
9
19,31
4S20
13,103
5,103
4,19
6
Fusion
results3
Heteroatoms Ferrox
present N S P X results'3
N, 0, Cl + - - +
None - +
0 - - - - +
None - - - -
0 - - - - +
0 - - . - +
0 - - - - +
S, N c - - - +
N, Os S + + - - +
0 - - - - +
0, S - + - - +
0 - - - - +
0 - - - - +
0 - - - - +
N, 0 + - - - +
a+ - positive test response (continued)
- = negative test response
^Stabilized with catechol derivative
cNitrogen detected as thiocyanate
49
-------
TABLE 9. (concluded)
Compound
Hexene
Decane
TEPA
Acetamide
Naphthalene
Polysulfide polymer
RGN(s)
28
28
7,32
6
16
14,20,105
Fusion
results3
Heteroatoms Ferrox
present N S P X results'3
None - - - ~
None - - - -
N, P5 0 + - + - +
N, 0 + - - - +
None - - - -
S _ + r . i
a+ = positive test response
- = negative test response
^Stabilized with catechol derivative
GNitrogen detected as thiocyanate
50
-------
positive response. However, for compounds containing oxygen as the only
heteroatom (ethers, esters, etc.), the ferrox test gave consistently positive
results. For hydrocarbons and for several chlorinated hydrocarbons tested
(methylene chloride, chloroform), the responses were negative. Styrene,
however, gave a positive result which was attributed to the catechol
stabilizer added.
The ferrox test can therefore be used to distinguish between
hydrocarbons or halogenated hydrocarbons and organic comounds containing
oxygen. The test is inconclusive when applied to organic materials
containing nitrogen or sulfur.
3•4•5 PS 5 — Organic Functionality Tests
3.4.5.1 Pj_5A_^_Jests[for'Hydrocarbon Classificajnon
Two tests were investigated for classification of hydrocarbons as
aromatic, saturated, or unsaturated. The Friedel-Crafts test for aromatics
is performed first in the sequence, followed by the Baeyer test for
unsaturation.
Since only a limited number of hydrocarbons are present among the
reference compounds selected for this study, some additional hydrocarbons
were selected for verification of these test procedures. The results of
these tests are presented in Table 10. Results correspond to those expected,
and no anomalous results were observed. In all cases the test results were
clear and easily interpreted.
3.4.5.2 PS SB — Tests for Organic Functional Groups Containing Oxygen
Eight functional group tests were performed on all of the organic
reference compounds. These eight tests were as follows:
® pH test for organic acids (RGN 3) (conducted as part of PS i)
© Vanadium oxinate test for alcohols (RGN 4)
« Dinitrophenylhydrazine (DNPH) test for carbonyl compounds (RGN's 5
or 19)
• Schiff's test for aldehydes (RGN 5)
© Hydroxamate test for esters (RGN 13)
• Iodine test for esters (RGN 14)
® Starch-iodide test for organic peroxides (RGN 30)
® Ferric chloride test for phenols (RGN 31)
51
-------
TABLE 10. RESULTS OF HYDROCARBON CLASSIFICATION TESTS FOR A SERIES OF
HYDROCARBONS
Results3
Compound Friedel-Crafts test Baeyer test
Bt.-s; *;3B as-as- .33* x 3t"3S-3S3aml»^it3i^-aia« a a ;n-.3-s:3i3-3S-3JS:*ia-*aB-a a*.-a -a 3 .a =s s s -= -= » a =a at M -SB sr -s -3 -K
Stryene + +
Polypropylene
Hexene - +
Decene - *
Hexane
Decane
Naphthalene +
Benzene +
Hexadecane
Xylene (mixed isomers) +
Octadiene - +
Toluene +
- positive test response
= negative test response
52
-------
The results of the functional group tests for organic oxygen compounds
are presented in Table 11. Ten false positive and one false negative test
result were obtained in this series of tests (out of a total of 296
individual observations). Some specific comments regarding the test results
are worthy of note.
With the exception of the iodine test for ethers all tests show good
correlation with the expected test results. The high number of false
positives (6 out of 37) in the iodine test for ethers is not surprising,
since all compounds which can reduce iodine to iodide decolorize the reagent
also. Among the compounds tested, dithiocarbamatess mercaptans, malathion,
acrolein, and aminoproprionitrile gave false positive results. Therefore,
positive test results should be disregarded when mercaptans, thiocarbamates,
or aldehydes are found to be present.
Aside from the iodine test for ethers, the ferric chloride test for
phenols is the only test which gave misleading results, one false positive
and one false negative. First, a wide range of colors can be obtained
depending on the phenolic compound involved, which increases the potential of
misinterpretation. Aminoproprionitrile and mercaptoethanol reacted positive,
whereas picric acid (trinitrophenol) did not. For the purpose of reactivity
group identification false test results may be of limited significance when
the test interferences are caused by substituents belonging to a reactivity
group which has a higher incompatibility rating.
Although the vanadate test for alcohols led to the expected results it
was difficult to observe a positive result. Many nonalcoholic compounds gave
a yellow-orange or light brown-purple color which could be distinguished from
the pink-orange characteristic color of the alcohol-vanadate complexes by
using a positive control, The vanadate test for alcohols was preferred over
the xanthate test because many of the nonalcohol compounds gave a similar
color response to the xanthate test, as did alcohols. In addition, the
procedure is lengthy and five different reagents are required.
No problems were encountered in distinguishing between positive and
negative test responses in the dinitrodiphenylhydrazine tests for aldehydes
and ketones. An alternate test for ketones and aldehydes, which uses
azobenzenephenylhydrazide as a reagent was also tested with all compounds,
but positive results — a blue to pink chloroform layer -- were less distinct
than results in the dinitrophenylhydrazine test which forms brightly colored
precipitates with aldehydes and ketones. The Schiff's test for aldehydes
gave equally satisfactory results. The p-nitrobenzene-diazonium
tetrafluoroborate test for phenols and amines gives easily detectable results
in the form of yellow, orange, or brown precipitates, but othro- and
para-substituted aromatic amines and phenols do not react with the reagent
(i.e., p-hydroxyacetophenone gave a negative test).
53
-------
TABLE 11. SUMMARY OF FUNCTIONALITY TEST RESULTS FOR OXYGEN-CONTAINING
ORGANIC COMPOUNDS
Compound name
Selenium
dlethyldithlocarbamate
Peracetic acid
Trinitrobenzoic acid
Picric acid
Dipicrylamlne
Dimethyl amlnoazobenzene
ArainopropfonttrDs
Arainothiazole
Benzoyl par-oxide
Halonic nltMle
(cyanoacstic acid)
Toluent dtisoeyanate
Nslathion
ParatMon
Ethy! jtmate
Vinyl acetate
Bromosyni!
Chlorophenyl iiocyanatst
Styrene
Ithylene glyeol
monowethyl ether
Polypropylene
Propylena oxid®
Methyl raethacrylate
Ethyl acrylate
Mercaptobenzothlazolc
lannate
Hydroxyacetophenone
Hercaptoethanol
H-butyl acrylate
Acroleln
Di acetone alcohol
Polysulfids polymer
Hexene
Detene
TEPA
Acetamide
Naphthalene
Diphsnanslde
Test results*
RGN 30
RGN 4 RGN 5 potassium- RGN 31
RGN 3 vanadium RGN 5/19 Schlff's RGN 13 RGN 14 iodide ferric
RGM(s) pH oxinate DNPH test hydroxamate Iodine starch chloride
12,24 .... - + . _
3,30,104 * +
3.27,102 4 ... ....
27,31,102 b - - - c
7,27.102 .... ....
7.8 .... +.
7,26 .... b
7 .... b
30.102 .... b
3,26 4 ... ....
18,107 .... ...
13.32 .... 4 b - -
27.32 - ....
12.24 .... b
13.103 .... 4 ...
13.17.26 .... 4 ...
17.18.107 .... ....
16,28.103 .... , . „
4.14 4 - 4 ...
29,101 .... .
34.103 .... ....
13.103 .... 4 . _ „
13.103 .... 4 ...
20 .... sj
9 .... .
19,31 4 4
4,20 - 4 - . b
13.103 .... 4 ...
5,103 ..44 - b - -
4,19 - 4 4 - ....
14,20,105 b 4
28 .... ....
28 .... .....
7,32 ..... ....
6 .... ....
16 .... .....
6 .... .
'4 » ps-stUwe tast response
- » negative test response
^Falst positive
-------
3.4.5.3 PS 5C -- Tests for Organic Functional Groups Containing Nitrogen
Six functional group tests were conducted for organic functional groups
containing nitrogen. These tests were performed only for those reference
compounds containing nitrogen, sulfur, or phosphorus, since these compounds
most realistically represent those materials upon which these test procedures
will be applied according to the test schemes. The test procedures conducted
are as follows:
© Oxamide test for amides and nitriles (RGN's 6 and 26)
• p-Nitrobenzene-diazonium tetrafluoroborate (NBDTF) test for amines
(RGN 7)
® Dimethyl aminobenzaldehyde (DMAB) test for azo compounds (RGN 8)
• Glutaconic aldehyde test for hydrazines (RGN 8)
• Diphenylcarbohydrazide (DPCH) test for carbamates (RGN 9)
® Tetrabase fusion test for organic nitro compounds (RGN 27)
The results of the functionality tests for organic nitrogen compounds
(as well as organic sulfur compounds) are compiled in Table 12. A total of
166 observations were made; four false positive results were recorded. In
addition, in a number of cases, color development was observed before the
completion of the test procedure, necessitating the inclusion of controls
into the test procedures. In two cases, the intense color of the reference
compounds interfered with the test results themselves.
The oxamide test for amides and nitriles gave consistent results, but
involves two heating steps. The test requires caution to avoid charring of
the test material during heating. This procedure does not distinguish
between amides and nitriles, but these two classes of compounds have very
similar compatibility characteristics so it was not considered critical to
distinguish between these two classes.
Tests for azo compounds and hydrazines were found to be very sensitive
and easy to perform and no particular difficulties were encountered.
Likewise the tetrabase fusion test for nitro compounds was found to be easy
to perform and provided reasonably clear results. The diphenylcarbohydrazide
test for carbamates was found to give false positive results, especially with
the isocyanates (i.e., isocyanates are undoubtedly converted to carbamates
during the course of the test procedure).
The dinitrochlorobenzene test for amines gave acceptable results with
the reference compounds but is expected to provide marginal results for real
waste materials. The test depends upon development of a brown ring which was
found to be difficult to observe even for the pure reference compounds. For
real waste materials, which are expected to be gross mixtures in many cases,
the color of the test may be obscured by the waste material itself. A second
55
-------
TABLE 12. SUMMARY OF FUNCTIONALITY TEST RESULTS FOR NITROGEN- AND
SULFUR-CONTAINING ORGANIC COMPOUNDS
Compound
Selenium
diethyldithiocarbamate
Trinitrobenzoic acid
Picric acid
Dipicrylaraine
Dimethyl ami noazobenzene
Aminopropionitri 1e
Ami nothi azol e
Malonic nitrile
(cyanoacetic acid)
Toluene diisocyanate
Malathion
Parathion
Ethyl ziraate
Broraoxynll
Chlorophenyl isocyanate
Hercaptobenzoth i azol e
Lannate
Mercaptoethanol
Polysulfide polymer
TEPA
Acetaraide
Diphenamide
Phenyl hydrazine
Test results3
Nitrogen-containing RGN's
RGN 8
RGN 6 or 26 RGN 7 RGN 8 glutaconic RGN 9 RGN 27
RGN(s) oxamide DNCB DMAB aldehyde DPCH tetrabase
12,24 .... d -
3,27,102 - b c c - +
27,31,102 - - c c - +
78?7>102 + +
7 b + c c - b
7,26 + + .
7,8 + .
3,26 + .
18,107 - d -
13,32 .... .
27,32 - ... +
12,24 - -
13,17,26 - -
17,18,107 - d -
20 d -
9 + +
4,20 - -
14,20,105
7,32 .... .
6 + -
6 + -
8 + -
Sulfur-containing
RGN's
RGN 12 RGN 20
cupric lead
chloride acetate
+
— B
-
_
-
_ ^
-
_
-
-
., _
+
-
- —
+
+
+
_
_
- »
a+ = positive test response
- = negative test response
^Compo'iixi Interferes because it is intensely colored
cSse a color change i^fthuut one of the test steps; interference can be identified with a control
-------
test for amines, the NBDTFB gave more definitive results but also gives
positive results with phenols. Results for both tests are presented in
Table 12, and reagents for both are included in the test kit. Amines can be
distinguished from phenols by means of the ferric chloride test for phenols.
3,4,5,4 PS 5D — Tests for Organic Functional Groups Containing Sulfur
Two tests were conducted for organic functional groups containing
sulfur. These two tests were applied to the organic reference compounds
containing sulfur and/or nitrogen. The test procedures are:
• The cupric chloride test for dithiocarbamates (RGN 12)
• Lead acetate test for organic sulfides
The test results are summarized in Table 12. No anomalous results were
obtained, and test responses were easily observed and interpreted.
3.4.6 PSJ5__~- Inorganic Functionality Tests
Several metal-detecting reagents were tested for their suitability for
the purpose of reactivity group determination. Although the reactions with
dimethyl benzylidenerhodanine, diphenylcarbazone, and quinalizarine were easy
to observe* the reactions are not general enough for the purpose of
classification of heavy metals, alkali, and alkaline earth metals in one
group each.
Zinc sulfide and ammonium sulfide were used to detect heavy metals. The
test is simple and observations are easy with no interferences if test
conditions are observed: acidic with zinc sulfide and almost neutral (a pH
of about 5) for ammonium sulfide.
Elemental metals were easily identified with phosphomolybdic acid. No
interferences were encountered. Alkali and alkaline earth metals were
detected by their reactivity with water. Those alkali or alkaline earth
metals that are not water reactive (e.g., magnesium) are classified as other
metals by this scheme. Inorganic fluorides were determined with a mixture of
zirconium nitrate and sodium alizarinate. The decolorization of the reagent
by fluoride was easily observed in a spotplate. The observations were
equally good by spotting the test solution of zirconium-alizarin impregnated
filter paper, but some additional time is required to prepare the paper which
can only be stored for a limited time without fading. The test results are
summarized in Table 13.
3.4.7 Summary of Functionality Test Results
Specific comments regarding the test procedures and results are
contained in Sections 3.4.1 through 3.4.6. In particular, information
concerning functionality tests is discussed in Sections 3.4.5 through 3.4.6.
In all, over 750 individual functionality test observations were made (PS 4,
5, and 6). Sixteen false positive results and six false negative results
57
-------
TABLE 13
SI.
METALS
TEST RESULTS FOR INORGANIC COMPOUNDS AND ELEMENTAL
00
Cosapoynd
carbofsate
Ferrous sulfate
Silver sulfate
Cuprous chloride
Cupric chloride
Nickel nitrate
Har curie eMonde
Csbalt chloride
Zirtc acetate
Lead acetate
Sariuni nitrate
Antimony potassiua tartrate
Stannous chiorlde
fengcifiese sulfate
Haijneslura nitrate
Potassius p]«t1n1c acid
Aluminum nitrate
Chroaium trioside
Cadmium
Arsenic pcnlasulfiiie
Copper
Lead
Kicks!
San usi
Barium iodide
Barium oxide
Calciun; hypoed! oride
Selenium dlethyldithiocarbaMte
H>'drof]uori>si]ic acid
Fluoboric acid
Hsxaflucrophosptiorlc acid
Sodium f'uorlae
Zinc
Tin
Aluminum
Potassium cyanide
iGN Ib
22,23,24
RGK 24
Zirconium
alizarinate
Hiosphoseolybdic Dimethyl benzyl-
acid Quinalizarine idenerhodanine
Zinc
suiflde
tenon i urn Diphenyl-
sulfide carbazotse
24
{105)
24
24.{105}
24
24
24
24
24
24
24
24/105
24
24
24
24
24,102,104
22,24
21.10
24.33
22,24
22
22,24
22.24
21
24
10,24
10,104
12,24
1,15
2,35
1.15
15
23
23
22
U
= positJvs ".e«t response
- m?.ji>!i>«> test
-------
were recorded. A summary of the reliability of the test procedures employed
as applied to the reference compounds is shown in Table 14. In light of the
multiple functionality of many of the reference compounds, the frequency of
false positive and false negative observations is considered to be
acceptable.
3.5 RESULTS OF BLIND ANALYSES USING THE TEST SCHEMES
3.5.1 Results of Blind Analyses of the Reference Compounds
The test schemes were evaluated by subjecting the reference compounds to
the schemes. The reference compounds were submitted as unknowns after
concealing their identities and assigning numbers to them. Testing was
carried out following the sequence indicated in the schemes and assigning
RGN's based on the individual test results.
The experimentally determined RGN's for each compound are summarized in
Table 15 for the purpose of comparison with their known RGN's. Several of
thtse compounds exhibited properties during testing which were inconsistent
with their assigned RGN's (Appendix 1 of Reference 1). After evaluation of
the chemical structure of these compounds, it was discovered that some of the
RGN's were incorrectly assigned, and these were corrected. The RGN changes
are indicated in Table 15.
Two blind test runs (A and B) were conducted by two different
technicians to determine the reproducibility of the results. The second set
of blind analyses was carried out by a technician who was not involved in the
development of the test procedures and had no specific training in chemical
analysis. He was given the test kit instruction manual and also a draft of
this report. He was instructed in how to use the test equipment and given
minimal instructions on the critical points of each test, e.g.,
interpretation of the flame test in terms of flammability, explosiveness,
combustibility, and residue. Also some initial assistance was given in
interpretation of the precipitate formation or color development for certain
tests. Aside from this initial assistance, he carried all reference
compounds through the test scheme and assigned RGN's without further
assistance. The test results for the technician new to the program are
presented in column B of Tables 15, 16, and 17.
Potassium cyanide and dimethyl aminazobenzene were not submitted to the
blind tests to prevent unnecessary exposure as recommended by the Acurex
safety officer. Several other compounds were also eliminated because
sufficient quantities for testing were not available, as indicated in
Table 15. Of the remaining reference compounds (test run A), seven were
assigned incorrect RGN's or no RGN could be determined. For three of these
compounds the results are explained by their chemical behavior during
testing. Chromium was not detected as elemental metal because of its extreme
insolubility under the test conditions. Barium iodide, barium oxide, and
barium cannot be detected as barium sulfide, and toluene diisocyanate showed
positive amine and ester test results, while the isocyanate group was not
detected because no qualitative test method was available. Other
59
-------
TABLE 14. GENERAL SUMMARY OF FUNCTIONALITY TEST RESULTS
Test name
Parameter
Positive False Falsa
Tests results positive negative
conducted expected results results
Sodium fusion
Cyanlde/thlocyanate
Sulflde
Phosphate
Hallde
Ferrox test
PH
Vanadium oxinate
Dinitrophenylhydrazine
Schlff's test
Hydroxamate
Iodine test
Ferric chloride
Potassium Iodide-starch
Oxamlde
0initrochlorobenzene
Dimethyl ami nobenzaldehyde
Glutaconic aldehyde
01pheny1carbohydraz1de
Tetrabase fusion
Copper chloride
lead acetate
Baeyer's test
Frlectel -Crafts test
Zirconium allzarlnate
Phosphomolybdic acid
Sol fide
Organic nitrogen compounds
Organic sulfur compounds
Organic phosphorus compounds
Organic halogen compounds
Organic oxygen compounds
Adds (organic)
Alcohols
Aldehydes and ketones
Aldehydes
Esters
Ethers
Phenols
Peroxides
Amides and/or nitriles
Amines
Azo compounds
Hydrazines
Carbamates
Nitro compounds
OUhlocarbamates
Hercaptans and other
organic sulfides
Unsaturated hydrocarbons
Aromatic hydrocarbons
Inorganic fluorides
Elemental metals
Heavy metal compounds
40
40
40
40
40
40
40
40
40
40
40
40
40
22
22
22
23
22
22
22
22
13
3
10
16
16
18
8
2
2
10
3
3
3
i
6
3
2
2
5
4
1
1
1
4
2
3
4
3
c
10
16
0
0
0
0
1
2
0
0
0
, 1
6
1
0
0
1
0
0
3
0
0
0
0
0
0
0
0
0
0
0
0
i
0
0
0
0
0
0
i
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Total
755
122
15
60
-------
TABLE 15. RESULTS OF DUPLICATE BLIND ANALYSES OF THE REFERENCE COMPOUNDS
USING THE TEST SCHEMES
Compound
Chromium oxide
Cadmi urn
Sodium
Arsenic pentasulfide
Chromium
Copper
Lead
Nickel
Barium
Barium Iodide
Barium oxide
Calcium hypochlorlte
Selenium di ethyl -
dithiocarbamate
Hydrofluorosilicic acid
Peracetic acid
Fluoboric add
Hexafluorophosphoric acid
Hydrofluoric acid
Trinltrobenzoic acid
Picric acid
Oipicrylamine
Aminoproprionitrile
Aminobeniothiazole
Benzoyl peroxide
Cyanoacetic acid
Toluene diisocyanate
Hydroxylamine-HCl
SGN(s)
2* 24.104*
22 '24*
10f. 21. 102, 105, 107
24*. 33
23,24
23,24
23.24
22,24
10.21,243,107
24*
10.24«.107a
10f,104
12,24
1,15
3,30b,104f
2f ,5
2^15
1.15
3', 27,102
3,27b,31b,102
7,27,102
7,26
7
30,102
3,26
18^.107*
IDS'
RGN(s)
(experimental)
Run A
24,102
22,24,102
10.102,107
33
ND
23,24
23,24
22.24
10,21,102,107
KD
10
10,104
12
1,15
3,104
2,15
2.15
1.15
3
3,102
102
6/26, 7, 14C
7
13C.30.102
3.6/26
7C,13C
NO'
RGN(s)
(experimental )
Run B Consents
104,2 Reacts like explosive, color interference
22,24 Reacts me explosive
Reacts like explosive
MO Some add reset ion, insoluble under test
conditions
23,24
23.24
22,24
10,21,24,102,107 Reacts like explosive
104
t°
10,22
10,104
12,19 •
1,15
3 Eliminated froa scheme after PS 1
2.15
2.15
1,15
3,6/26c Eliminated froai scheme after PS 1
3,27,31 Eliminated frcw scheme after PS 3
3C,31C102
6/26,7
7,6/26c
30,104,102
3
9 May hydrolyze during test
ND: No RGN determined
Not done, insufficient sample
6/26: Same test for either RGN
aNot detectable by test used
bNot tested for this RGN due to elimination from scheme
cIncorrect RGN
dNo test available for this RGN
eRGH not detected
fCorrected RGN
(continued)
-------
TABLE 15. (concluded)
Coaipound
Malathlon
Paratblon
Ethyl zioiate
Vinyl acetate
Bromoxynl]
p-Chloroptenyl isocyariite
Styrene
Ethyl ene glycol-
uioriomethy! ether
Polypropylene
Propyiefieoxide
Methyl methacry'ate
Ethyl acrylate
Mercdptobenzothiazole
Lannate
Hydrojtyacetophenone
Kercaptoethanol
b-8utylacrylate
Acrolein
Oiacetone alcohol
Aldicarb
Pol /sul fide
Hexene
Oecene
Teps
Acetaralde
Naphtnalene
Diphenanside
n-Uecane
.G.t,)
13f,32
27e»" ,32
12,24
13,103e
13e.f, 17,26*
17,18d,107a
IS, 28, 103d
4,14*
W.1014
340,103^,107
13,103d
13,103d
20
9
19,31
*e,20,105f
13,103d
5,103d
48,19
9
14£.^20,101as105e
28
Z8
7f,32
6
16
6
29
RGN(s)
{experimental )
i'.un A
3,13,32
4C,32
12,146
13
17
17
16,26
4
29
4.107
4C,13
13
7C,20
9
19,31
20,105
NO
5
19
HD
»f 3,20
28
28
32
6/26
16
NO
29
{experimental)
Hun B Cowmen ts
32 pH 3
«?J,32,£/26C
12,14
13
13, 17, 26. 107*
9C,17,6/26C
16,28
4.14
—
107 Hydro) yzes to alcohol
13 ,-
13
20
9 •
19
20
13
5
4,19
17C.32C
20.14
28
23
—
S/26
16
6/26
29
fffi: Mo RSf! determined
-- ifet done, insufficient sample
e/26: SaBis test for either RGN
sNst detectable by test used
&fte>. tested for this RGH due to eiimination from scheme
r Incorrect RGN
''No test av?nai>l2 ,"'.f this 3GN
8RGrt "ot '.'atectad
-------
TABLE 16. BLIND TEST RESULTS FOR OXYGEN FUNCTIONAL GROUPS3
Compound
Selenium dlethyl-
dHhloearbaiMte
Trlnltrobenzolc add
Picric add
Oipicryisraine
Am1nopropr1onKr1le
Amtnobenzothlazole
Benzoyl peroxide
Cyanoacetlc «c1d
Toluene dllsocyanate
MalatMon
Parathlon
Ethyl zlmate
Vinyl acetate
Bromoxynll
CMorophenyl Isocyanate
Ethyl ene glycol
nonoRiethyl ether
PropwU-ne ox id*
Methyl methacrylati
Ethyl acrylate
Kercaptobenzothlazole
Lannate
Hydroxyaeetophenone
Nercaptoeth«nol
n-Butyl acrylate
Acroleln
Dlacetone alcohol
Aldlearb
Polysulflde
Taps
Acetaralde
Oiphenasntde
False positives ++
False negatives --
Total number of tests
> RGH 5
RGN 4 or 19
vanadate DNPH
RGN(s) A B A B
12.24 - - «•
3.27.102 b - b -
3.27,31,102 b b -
7,27,102 b - b -
7,26 «• - -
7 - .
30. 102, (13) b - b
3,26 - - -
18,107 - - -
13.32 c - c
27.32 - c - c
12,24 - - -
13,103 - - -
13,17,25 - - -
17,18,107 - - -
4,14 + -f - -
29.101 + b - b
34.103,107 ++ - - -
13.103 - - - -
20 - - -
9 ....
19,31 -- -- * +
4,20.105 -- -- - -
13,103 - - - -
5,103 - - + +
4,19 — + + «•
9 - c - c
20,14.101.105 - - - -
7.32 - c - c
6 - -
6 .
11 01
32 00
28 25 28 25
RGN 5, RGN 31
Schlffs RGN 13 RGH 14 ferric
test hydroxamate Iodine chloride
AB AB A B AB
„_ __ « _ . _
b - b - b - b -
b- b- b- b +
b - b b b -
. . -. -. .-
__ ._ _. _^
b t b - b - b
. . .
++ _ - -
-c +c -c c
c — c - c - c
- - - +4- f* -
(• + - .
-- --.(. -. ._
-- -- -- _-
-- -- — + .-
b - b - b - b
+ + . .
+ + - .
.- -- .- _ .
-- ._ .. ,
+ - -- .. +
-.- -. .. ..
t - .
t+ -- .. ..
-- -- -- ..
c - c - c - c
-- -- — + _-
c - c c c
-- -- -. __
-- -- -- - -
00 10 11 00
00 30 20 01
28 25 28 25 28 25 28 25
a+ • positive test response
- » negative test response
''Functional tests not done, compound eliminated earlier in testing sequence
Clnsuff1c1ent test material remaining for testing
63
-------
TABLE Yi, TEST RESULTS FOR NITROGEM AND SULFUR FUNCTIONAL GROUPS*
Compound
Selenium diethyi-
dithio c»rbamate
Trlnltrobenzolc *cid
Picric acid
Dipicrylamiiie
Aninopropricnitrlle
AwinQbeniathlazole
Cyanoacetfe acid
Toluene (iilsocyanatt
Malathlon
Parathlon
•Ethyl zlmate
BroiBoxynll
Chlorophenyl Isocyinate
ttercaptobenzothlazole
Lannate
en Hercaptoethanol
•*» Aldicarb
PoIysyHide
Tepa
Acetamide
Dipnenamide
Total
Faise positives ++
False negatives --
RGM 9
0PC.H
RGN(s) & B
12B24 - -
3,27.102 b
3,27,31,102 b
7,27,102 b
7 , 26 -
?
3,25
13^32 - c
27.32
12.24
13S17,26
17,18,107 - ++
20
9 * *
4,20,105
9 — c
20,14,101,105
7,32 - c
6
S
16 16
0 2
1 0
RGH 8
OHA8
A B
«
b -
t»
b
.
.
.
-
c
.
.
_
-
.
-
c
c
.
-
16 16
0 0
0 0
RGN 8 RGSJ 6
gliitatogjc or 26
acid cxdsiidv
A B A B
- - - -
b b ++
b - b -
b - b -
- + +
- +*
. +
. .
c c
- *•*•
- . .
_ +
- ++
- -
- -
c c
c - c
- 4- +
- -0-
16 16 16 16
00 04
00 21
RGN
3/31
RSS 7 ferric
S80TFB chloride
AS A
•
b b
b b
b — b
+ +
+ +
.
»+ -
c
.
.> .a
-
-
*+
.
- C
C
.
-
16 16 16
20 0
1 1 0
8
_
.
-
.
-
.
.
.
C
.
-
-
.
.
.
c
c
.
-
16
0
0
RGN 27 RGN
12
tetra- cupric
base chloride
A B A
+
b - d
b + d
b „ d
d
. .
d
d
c
-- ;.
- +
d
d
. .
.
c
—
c d
-
- -
16 16 11
00 0
1 1 0
B
•*•
d
d
d
d
-
d
d
_
.
+
d
d
-
.
c
+
d
..
-
10
0
0
. RGN 20
lead
acetate
A
„
d
d
d
d
.
d
&
.
.
•i
d
d
•i
-
•f
.
+
C
.
-
11
0
0
B
„
d
d
d
d
-
d
d
.
.
-
d
d
+
-
+•
c
+
d
_
•
10
0
0
- positive test response
- nsyatiiie test response
ns! group test not done, confound eJiiEinated earlier In testing sequence
^insufficient test material remaining for testing
^Testing rot require-1 {according to results of PS 4j
-------
difficulties were the detection of water reactivity (RGN 107) which was
defined as reaction with visible gas evolution or spattering. This resulted
in nondetection of RGN 107 for three compounds: barium oxide, toluene
isocyanate, and chlorophenyl isocyanate. In addition, polymerizable
compounds were not detectable. Several materials (chromium trioxide,
cadmium, and barium) reacted violently during the flame test, although they
are not considered explosives. The functional group results for the blind
analyses are presented in Tables 16 and 17.
The comparison of results from both test replicates show good
correlation of most RGN's. The individual functionality tests also showed
good agreement, with 18 disagreeing individual test results out of the
261 individual determinations.
3.5.2 Results of Blind Analyses of Other Pure^^ton^unds
Two sets of unknown laboratory chemicals were tested by following the
te$',t scheme. Six unknowns were mixtures of two compounds (HWC-X, 1-6);
twelve unknowns were single compounds (HWC-X, 11-22). The RGN's determined
from testing as compared to their actual RGN's are presented in Table 18.
Out of the 12 single unknown compounds tested all RGN's were correctly
assigned for 9 compounds and for the remaining 3 the most significant RGN's
were assigned. Four RGN's were incorrectly assigned (false positive) and
one RGN was not detected. For the six unknown mixtures, the RGN's were only
partially identified because several of the tests which would identify
functional groups of the second component of the mixture were not conducted
according to the test scheme in the following instances: (1) in the presence
of certain functional groups, (2) at a specific pH (less than 3,) or (3)
where the mixture exhibited explosive behavior during the flame test.
Nevertheless, the most significant RGN's were assigned for all of the
six mixtures.
3.6 DEVICE FOR THE DETERMINATION OF THE COMPATIBILITY OF UNKNOWN MATERIALS
Two important criteria for evaluating the compatibility of two or more
substances when mixed together are heat generation and gas evolution. Both
can create hazards in the form of pressure increases and formation of toxic
gases. These effects are measured with a simple mixing device which ,is easy
to assemble and use under field conditions. A diagram of the device is shown
in Figure 8.
The device consists of a 120-mL glass reaction vessel equipped with a
rubber stopper with holes for a hand-operated glass stirring rod with a
Teflon paddle, a thermocouple (K-type stainless steel, Omega), a burette for
adding liquids, and Teflon tubing which is connected to a 50-mL impinger.
The temperature is measured with a battery-operated digital thermometer
(Omega Model 727C). The reaction vessel and the irnpinger bottle are held in
a wooden block; the cavity for the reaction vessel is deep enough to provide
protection in the event of glass breakage but still permits visual
observation of the reaction. The reaction vessel is held by a clamp and
metal stand. Violent reactions during mixing can be detected by adding small
65
-------
TABLE 18. RESULTS OF BLIND ANALYSES OF SELECTED PURE COMPOUNDS
AND BINARY MIXTURES
Hazardous
waste
combination
Two Componen
1
2
3
4
5
6
Compound
ts
Picric acid, ethylene glycol
monomethyl ether
MercaptobenzotM azol e ,
diacetone alcohol
Styrene, hyd roxyacetophenone
Bromoxynil, vinyl acetate
Mercaptoethanol , hexane
Chlorophenyl , isecyanate
RGN(s)
(known)
4*5,149,31,273,
102
20, 4b, 19, 105
163,103,4,19,
31,28d
17, 26*3, 13, 103^
4,20,283
17.18d.107b
RGN(s)
(experimental )
1 102
20,19,7,105
4,19,31.32C,16,
28
9,17,13
4, 20
17,19C96/26C
l_lnglg_Cginggunds_
11
12
13
14
15
16
17
18
19
20
21
22
Iodine
Sodium borohydride
Sodium dlathyldithiocarbamate
Stannous sulfata
Benzole acid
Bromobenzene
Phenylhydrazine
0-MJtroanll ina
Pyrogallol
Tin (granules)
Biphertyl
Hydrofluoric «cid
104,2
105
12
245105,1
3
17
8
7,2/b
3,31,105
22924
16
1,15,106
104,2
105.14C.102.17C
12
1,24,105
3,19^
17
14C.8
7
3,31,105
22,24
16
1,15,106
aftot tasted for this RGH due to elimination from test scheme
bRGN not detected
cI(Korrect RGM
dfto test available for this RGN
66
-------
Addition
buret
Thermocouple'
z
Stirring rod
ns
Water.
Teflon
tube
1
,— Digital
^/thermometer
-Support block
120-mL-
reaction
vessel
Midget-'
impinger
(ground
glass seal)
Figure 8. Device for determining the effects of mixing of unknown materials,
67
-------
amounts of the test materials to a test tube before carrying out the reaction
in the mixing device. If the mixture creates heat or forms gases or fumes in
test tube quantities no mixing with larger quantities is necessary. To avoid
any accidents,, the experiment should be carried out behind a safety shield.
Pressure changes are detected by observing bubbles in the impinger. The
pressure changes which can be detected with the device used in the present
experiment are sufficiently small to aid in determining noncompatibility for
instantaneous reactions. Very small pressure increases or pressure buildup
over long periods of time are not detected with this device.
The reactivity tests are carried out by placing 3 to 5g of the solid or
3 to 5 ml of the liquid test material in the reaction vessel, then closing
the stoppers and adjusting the thermocouple so it reaches the test material,
The impinger is filled with 10 ml of water and connected to the reaction
vessel. The temperature of the test material is recorded before the second
(liquid) test material is added from a buret, the stopcock is closed, and
both materials are mixed by turning the stirring rod. The reaction is
observed for foaming, color changes, fumes, and temperature changes. Gas
evolution is observed as bubbles appearing in the impinger solution. The
gases can be identified by analysis of the impinger solution for tulfide,
cyanide, carbonate, halogen, and acidity (pH), A series of compounds was
selected for testing based on RGN's predicted to be incompatible from the
hazardous waste compatibility chart. The test results are summarized in
Table 19.
For the most part, those reactions that would be predicted (from basic
chemical principles) to generate heat or gas were observed to do so in the
test mixing device. In several cases, the compatibility chart predicts
reactions that may not actually occur spontaneously. For example, the
compatibility chart predicts heat evolved when mineral acids (RGN 2) and
chlorinated organics (R6N 17) are mixed. No observable effect was noted when
sulfuric acid was mixed with freon, however,. This apparent anomaly is not
considered to be a shortcoming of the mixing device.
Additional tests were conducted to collect and analyze gases formed
during mixing. The gases were collected in a solution of 5 rnL of 0.1N barium
nitrate and 5 ml of 0.1N sodium hydroxide, and were analyzed for sulfide,
cyanide, halogen,, carbonate, and pH changes. The results are summarized in
Table 20. The starting temperature (in the reaction vessel) and pH are
listed as Tj and pHj, respectively. The final temperature and pH (in the
impinger) are T£ and
Similar but more elaborate mixing devices have been used for determining
the reactivity of waste materials with water (Reference 6 and 7). These
reactors are pressure sealed and pressure changes are measured with pressure
gauges. Toxic gases formed during the reaction with water such as HCNS !^SS
SOg, CQS COgs NOX are identified by connecting a gas detector manifold
constructed from a series of Draeger tubes to the reaction vessel.
68
-------
Compound !
TABLE 19. RESULTS OF MIXING EXPERIMENTS
Predicted Gas
Compound II reaction3 a'F (°C) evolution^
Comments
Barium oxide
Barium (metal)
Propylene oxide
Trlchlorotrlfluoro-
ethane
Barium iodide
Ammonium chloride
Sodium nitrite
Acetamlde
Chlorophenyl
isoeyanate
Chlorophenyl
isocyanate
Pfithalic acid
Propylene oxide
Glycerol
o-N1troan1Hne
Acroleim
Octadlene
Octadiena
Benzole acid
Benzole acid
Picric acid
Phthallc acid
Beruoyl peroxide
Octadiene
Propylene oxide
Propylene oxide
aReactivity Code
H
F
G
GT
GF
£
P
S
U
Water
Water
Water
Sulfuric acid (3M)
Hydrochloric acid (3M)
Sodium hydroxide (3H)
Nitric acid (cone.)
Nitric acid (cone.)
Hydrochloric acid (2M)
Sodium hydroxide (5M)
Sodium hydroxide (2.5M)
Sodium hydroxide (5M)
Sulfuric acid (1M)
Sodium hydroxide (J.5M)
Sodium hydroxide (2.5M)
Sulfuric acid (2H)
Hydrochloric acid (2M)
Zinc + water
Chromium + water
Zinc + water
Nickel
Methanamine
Nickel
Diphenylamine
Sodium diethyl
dithiocarbamate
Consequences
Heat generation
Fire
Innocuous and nonflammable gas
Toxic gas generation
Flammable gas generation
Explosion
Violent polymerization
H
GF8H
H.GT
S
H
H.GT
H.GT
H,G
H.F.G
H
H,P
H
H
M.P
H
H
GF
GF
GF
GF
H.GT
H,E
H,P
U
generation
49
82 +
3 H-
0
-1 - Dissolves '
-12
-10 +
-12
-1
17 *
13
0
5
1
48 + Violent
polymerization
1
3
0
2
1 - Dark green
color formed
1
4
2
-5 t
2 +
Solubllizatlon of toxic substances
May be hazardous but unknown
= positive test reponse
» negative test response
69
-------
TABLE 20. RESULTS OF THE ANALYSIS FOR EVOLVED GASES IN MIXING EXPERIMENTS
Compound
Reagent
(°C)
(°C) Gas pHi
Analysis
0.4g
20
KCN
mL
in
H20
5
mL
2N
H2S04
17
19
Yes
14
13
CM' not
detected
2g Al powder 5 mL
2.5N NaOH
17
98
Yes 14
lg Ca(OCl)2
0.4g Na2$ in
20 mL H20
094g CaCOs in
20 mL H20
6 mL 17
2N HC1
5 mL 16
2N H2S04
5 mL 16
2N H2S04
25 Yes 14 — Cl~ as
AgCl
19 Yes 14 14 S% as
PbS
18 Yes 14 13 C02" as
BaCOs
3.7 FIELD EVALUATION OF THE TEST KIT
A field evaluation of the test kit was conducted on March 8 through
11, 1983 at the EPA Combustion Research Facility in Jefferson, Arkansas.
Twenty-five hazardous waste samples were collected from two sites prior to the
field evaluation by Mr. Richard Carnes, EPA Technical Advisor for the project.
Four of the samples had two distinct layers. For these samples, the layers
were sampled and analyzed separately, bringing the total number of samples
analyzed to 29. The gross identity of the waste materials was known to the
technical advisor but not to the field crew until after the testing was
completed.
The tests were performed outside (day 1) on a temporary plywood working
surface and in a trailer with a counter (days 2 and 3) because of inclement
weather. The wind was gust ing from 20 to 30 mphs and the temperature was in
the mid-30's (°F). It is believed that these conditions simulated field
conditions closely,
Only two significant difficulties were encountered in performing thy
tests under field conditions. The first was that several of the samples
contained two phases and the kit was not equipped with -a separatory funnel or
equivalent device. Based on this.experiences several small separatory
funnels were added to the test kit equipment list. A second problem
encountered was performing the tests under adverse weather conditions; a
particular problem was wind. Under windy conditions reagent bottles and
sample vials tipped over and the flame was difficult to maintain and cor.tro!.
Overall, the tests proved relatively easy to perform under, field conditions,
70
-------
A list of the samples including the composition and a summary of results
is presented in Table 21. The detailed results of tests performed on the
samples as well as the RGN's predicted from knowledge of the samples, are
presented in Table 22. The results of PS 1 are given as N/N, A(4)/N,
B(12)/R, etc. The first letter refers to the acidity or basicity. When the
material is acidic or basic, the pH is given in parentheses. The second
letter indicates the redox response of the material. R stands for reducing
and 0 stands for oxidizing. The second column (PS 2) lists the response to
the solubility/reactivity tests. The flame test results (PS 3) are given in
the next column. Columns headed PS 4 through PS 6 present the results of the
functionality tests. The first (PS 4) column gives the results of the sodium
fusion and ferrox test for elements (N, X, S, P, 0). An 0 in parentheses
means oxygen is assumed to be present. The word "none" means that no
heteroatoms were found, while — indicates that the tests were not
performed.
The last three columns list, respectively, the RGN's expected from the
waste description, the RGN's found by the protocol, and additional special
comments. A ?? in the predicted RGN's column indicates that insufficient
information was available to identify potential RGN's.
Twenty-eight of the twenty-nine samples were categorized correctly
(according to the impartial judgment of the project technical advisor onsite)
in the field evaluation. Sample 6E was described as "waste solvents with
amines" but was characterized as RGN's 10 (caustic), 24 (metal compounds),
and 106 (water). Upon contacting the source of this sample it was found that
indeed we had accidentally been given the water layer of a two-layer system.
Amines dissolved in the water would account for the caustic (RGN 10)
description and could act as a chelating agent to carry heavy metals into the
water. Another sample, 3D, was described as ethanol wash (two layers). The
upper layer was identified as aromatic hydrocarbon (RGN 16), but only water
(RGN 106) was detected in the lower layer. Two oil samples containing PCB's
(samples 16E and 17E) were identified only as aromatic hydrocarbons. The PCB
levels in these samples were not known, but are assumed to be low (trace
level) in which case the chloride was present at too low a level to be
detected.
Sample 8DU was identified as organic but examination was not carried
beyond the flame test. The flame test results indicated to a technician that
the material might be an explosive. Further testing would have been at the
discretion of a qualified supervisor. In fact, the material was the organic
layer from the still bottom of a solvent recovery refinery. The lower
(water) layer was found to contain metals. Thus, the flame behavior of 8DU
was probably due to burning metallic materials in the sample.
Sample 3E, a waste naphtha, was found to have sulfur present but no
sulfur compounds were identified. Sulfur is common in naphtha, either as
elemental sulfur or as organic sulfides. Organic sulfur groups other than
mercaptans, triocarbamates, and disulfides are not detected by the methods
used in the test scheme. The failure to identify sulfur-containing organic
species may also indicate a difference in sensitivity between the test for
71
-------
TABLE 21. DESCRIPTION OF SAMPLES TESTED AND SUMMARY OF
RESULTS OF THE FIELD EVALUATION
"•.J
ro
Sample*
ID
2D
30U
3DL
4DU
4SL
50
8D
?D
SOU
8DL
IE
21
Jt
4£
5E
Saiiple
Identification
Dirty PCE
TCE Still botttwis, oil,
hydrocarbons
Ethanol wash and oils
Ethanol wash and oils
Toluene in thinrser wash
Toluene in thinner wash
MEK, xylene, and solvents
Acetone and M£K
MEK from paint
manufacturing
St^l! bottoms from solvent
recovery refinery
Still bottoms from solvent
recovery refinery
Organochlonne waste streaais
tostewater from storage tank
waste naphtha
Carbon tetracnloride
NIB* with waste solvents
Saaple
description
Yellow-brown liquid
Darlc brown enulsion very snail upper layer
Brown liquid (upper layer of two layers)
Pale brown liquid (lower layer of two layers)
?ale yellow liquid (upper layer of two layers)
Pale brown liquid (lower layer of two layers)
Very light ten eculsion
Light purple enulsion
Green-brown eaulsion
Dark brown slurry (upper layer of two layers)
Pale yellow liquid {lower layer of two layers)
Very dark (opaque) viscous liquid
Tan liquid (very SIM!) Mount of dark brown
liquid on top)
Light brown clear liquid.
Dark brown clear liquid
Light pink clear liquid
R
Predicted
17
17
16,28
4,106
16
106
16,19
19
IS
b
b
17
106
16,28, or 29
17
19
SK(S)
Found
4,17
16,17
16
106
16,19
t
106
4,16,19 *
19
16,19
102
24,106
17
10,24,106
4,16,31
3,15,17
4,19,31
aSo'jrc,Ps of hazardous waste sasiples are baing kept anonymous at the request of the
project technical advisor
(continued)
°SC« OiSCUSSlC'S
C,N;I? vsil defined by j^ste description
^AHo ^Q^od io contain organics
-Water noi ?: :-d3ctea b^ Mite description
-------
TABLE 21. (concluded)
OJ
Sample8
6£b
7E
8E
9E
JOE
HE
12E
13EU
13EL
14E
15E
16E
17E
Sample
identification
Waste solvents with amines
Thiocarbohydrazlde with ^S
Spent caustic
Ethylene dichloride still
bottoms
Waste solvents, waste ink
Haste varnish
Water base insecticide
Oil base insecticide
Oil base insecticide
Tnbromocumene
PCS oil , high level
PCB oil, low level
Siiicone oil (with PCB's)
RGS(s)
Saiapl e
description
Light brown clear liquid
Red-orange clear liquid
Clear colorless viscous liquid with small
amount of black participate
Very dark blue liquid
Dark gray viscous liquid
Light brown clear viscous liquid
Hi Iky white opaque viscous suspension
Yellow clear liquid (upper layer of two layers)
Cloudy light yellow liquid (lower layer of two
1 ayers )
Opaque red-brown viscous suspension
Light yellow-green clear liquid
Light orange clear liquid
Very light yellow-green clear liquid
Predicted
7
33.105.106
10,106
17
b
16
106C
d
-------
TABLE 22. DETAILED RESULTS OF FIELD TESTING OF HAZARDOUS HASTE SAMPLES
Samjjle
ID
20
3DU
3DL
4DU
4DL
5D
60
7D
PS 1«
N/N
«/M
S/N
N/N
N/N
N/N
N/N
N/N
N/N
PS 2
Soluble organic; in-
soluble M, adds;
S, CH, WjjO negative
Solutsls organic; In-
soluble HjO, acids;
S, CN, HjO negative
Soluble organic; in-
soluble HgQ, icids;
S, CM, H2" negative
Soluble J'/O, acids;
Insoluble organic;
S, CN negative; HjO
posit iva
Soluble organic,
H20, acids; S, CN,
H20 negative
Soluble HoQ, acjds;
Insoluble organic ;
S, C$ negative, hjO
positive
Soluble Ac, HeOH;
Insoluble hexarse,
toluene,
H?0, adds;
('soluble H2S04)
S, C«, H20 negative
Soluble organic;
insoluble Mj>0, acids;
Ss £^e H^O
-------
TABLE 22. (continued)
en
Results of testing
Sample PS 1*
SOU N/N
80L A(4)/N
IE N/N
2E B(11)/N
3E N/N
4E A(4)/N
5E N/N
6E B(12)/N
PS 2
Soluble toluene,
hexane; insoluble
Ac. HZ0, acids;
S, CN, H20
negative
Soluble HpO, acids;
Insoluble organic;
S, CN negative; H20
positive
Soluble Ac, toluene;
insoluble H20, acids;
S, CN, H20 negative
Soluble H20, acids, Ac,
HeOH; insoluble
toluene, hexane;
S, CN negative; H20
positive
Soluble toluene
hexane; insoluble
H^O. acid, Ac, MeOH;
S, CN. H20 negative
Soluble organic;
insoluble acids, H20;
S, CN, H20 negative
Soluble organic,
acids; insoluble H20;
S, CN, H20 negative
Soluble K20, acids; Ac,
MeOH; insoluble
toluene, hexane;
S, CN negative; H2Q
positive
Expressed as acidity/redox (i.e., B/R-base,
b -- not done
CM = metal
F - fluoride
RGK(s) RGN(s) Additional
PS 3 PS 4 PS 5 PS 6C expected found conatents
Crackles, — b .- .. ?? 102
burns,
organic
Evaporates, -- -- M positive ?? 24,106
residue, F negative
inorganic
Evaporates, X, N (0) No N RGN's 17 17 Probably also
then burns found contains t'
hydrocarbons
Boils, — — M positive1 106 10,24, t
gray residue, F negative 106
Inorganic
Burns S(0) 4.31
-------
TABLE 22. "(continued)
0%
Results of testing
Sample
7E
8E
9£
IDE
HE
12E
13EU
13EL
HE
PS 1* PS Z5
B{>10}/R Solubilities not done;
S, K?Q positive; CM
negative
B(1Z)/N Insoluble organic;
reacts violently with
acfds, H20 pressnt;
S, CN negative
H/N Soluble organic;
insoluble Hj>0, acids;
S, CN, H20 negative
H/N Soluble organic,
HgO, acids
N/N Soluble organic;
Insoluble adds;
S, CN, H20 negative
B(10)/N Soluble H?0, acid, Ac,
MeOH; insoluble
toluene, hexane;
S, CN negative;
H20 positive
N/N Soluble Hgfi, acid, Ac,
MeOH; insoluble
toluene, hexane;
S, CM negative;
HjO positive
N/N Soluble h20, acid, Ac,
MeOH; inso!un!e
toluene, hesane;
S, CN negative;
H^Q positive
N/N Soluble organic;
insoluble H70, adds;
S, CN, HZ0 -legativs
RGN(s) RGN(s) Additional
PS 3 PS 4 PS 5 PS 6C expected found conments
33,105,106 10,33,
105,106
Bolls, - - — M negative 10,106 10,106 Unusual material, reactive
gra>, F negative
inorganic
Burns, smoke, X only 17 only -- 17 17
residue,
organic
Burns H{0) 13,5 — ?? 6,13,19 Looks like black paint,*'
positive difficult to observe, dark
, sample
Sums, tone 16 only -- 16 18
organic
Burns, -- 19 only M negative 106 19,106 Water soluble organic
slightly F negative
Burns, None 16 only — 16,106 IS, 106
organic
Boils, does — -- M negative 16,106 106
not burn F negative
Burns X only 16,1? — IS, 17 16,17
aE;ipr«sad as iir sdity/redox {I.e., S/R-baie, reducing; N/N neutral, nonoxldiiing and nonreducing; A acid)
b -~ not cone
(continued)
-------
TABLE 22. (concluded)
Sample PS la PS ^
Results of testing
PS 3 PS 4 PS 5
RGN(s)
PS 6 expected
RGN(s)
found
Additional
comments
15E
16E
17E
N/N
N/N
N/N
Soluble organic; Burns
insoluble H,0,
acids; S, CN, H20
negative
Soluble toluene, Burns
hexane; insoluble
H/>, acids, Ac,
MeOH; S, CN, H?0
negative
Soluble toluene, Burns
hexane, Ac;
insoluble H20,
acid, MeOH; S, CN,
HjO negative
X only 16, 17
None
None
16 only
16 only
16, 17
16, 17
16, 17
Expressed as acidity/redox (i.e., B/R-base, reducing; N/N neutral, nonoxidizing and nonreducing; A acid)
^ -- not done
CM = metal
F = fluoride
16, 17
16
16
refer to predicted RGN
-------
sulfur and the specific functionality tests. The same conclusion can be
reached from the results of sample 10E. A positive nitrogen response was
obtained but no nitrogen compounds were detected in this waste sample.
A carbon tetrachloride waste sample (4E) was found to contain aromatics
and organic acids as well as being in R6N 17 (chlorinated organics).
Two minor shortcomings of the test schemes were pointed out by the field
evaluation. The test schemes are organized such that aqueous liquids are not
tested for organics. The sodium fusion procedure, as well as a number of
specific organic functionality tests are not amenable to aqueous solutions,
For compatibility purposes, the classification of aqueous organics as aqueous
mixtures would probably suffice. For purposes of predicting optimum
destruction technology, the inability to detect organics in water may be 3
serious limitation.
During the field test, approximately 40 man-hours were spent in actual
sample analysis. Since 29 phases were analyzed, an average analysis time of
approximately 1.3 hr/sample was realized. This average analysis time Is
expected to be quite acceptable in real-world field applications.
3.8 ASSEMBLY OF FIELD TEST KIT
The field test kit contains all equipment, reagents, and safety devices
necessary for carrying out all tests as specified in the test manual.
The field test kit was designed to meet the following requirements:
small volume and few containers for ease of transportation, easy access to
all test materials and equipment, and prevention of leaking of reagents and
breakage of equipment during transport., Smaller items such as spatulas,
spoons, burner accessories, spotplates, beakers, etc. are put into larger
containers which were labeled to facilitate identification of contents. The
specific equipment and reagents used in the test kit and their distribution
in the coolers are shown in Figures 9, 10, and 11. For transportation
purposes all test equipment was placed into three 13-in. by 22-in. by 15-in.
Coleman coolers. Other containers of similar dimensions and durability can
be used also. For safe transportation and to organize the reagents according
to procedure sets, all reagents required for the tests within a procedure set,
were placed together in a specially designed redwood box. Wood was used
because of its ruggedness, its resistance to most solvents and acidss and
because a support with holes matching the different diameters of the reagent
bottles could be manufactured with simple tools at relatively low cost. The
kit includes four reagent cases, one each for PS 1, PS 2, PS 6; PS 4, PS 5A.,
PS 5B; and PS 5C, PS 5D. A similar boxs with a foam insert was constructed
to hold the mixing device (see Figure 11). The reagent boxes were packed in
cooler 1 together with some small equipment and supplies; larger equipment
including safety shield, test tubes, mixing device, beakers, and -funnels were
packed in cooler 2; and safety equipment (coveralls, rubber and latex gloves,,
respirator, goggles), paper towels, and propane tanks were put in cooler 3,
Water- and alcohol-based reagents were placed in 3~oz« polyethylene reagent
dropping bottles; and noncorrosive solids and test papers were placed in
78
-------
\
\
v
\
\
\
\
\
\
\
1
\
\
\
A
C
D
B
E
G
vv \\\\\\\\\\\\\
F
H
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\\A\\\\\\\\\\\\\\\ \T \ \ \ \ \y
A Spatulas, ceramic spoons, wire loops, glass rods, test tube
holders, pipet bulbs
B Lighter, flame tips, stand for propane torch, forceps, wire
screens, scissors, pliers, screwdriver
C Test tube rack and 4-in. test tubes
D Test tube rack and 3-in. test tubes
E Reagents for PS 1, PS 2, PS 6
F Reagents for PS 4, PS 5A
6 Reagents for PS 5B
H Reagents for PS 5C, PS 50
Figure 9. Cooler 1 — equipment organization,
79
-------
A Pasteur pipets
B Spotplates
C Separatory funnels"
0 Beakers
E Safety shield
Figure lOa. Cooler 2 -- equipment organization top tray.
«
\ST" —
\
\
\
\ ^A
\
\
\
K VB J
\
\i
\
\ D
^ V
Vl333:^I23S33333X333^XXAAAA^
_J
\ c /
—-1
1
1
__-*y
sssAAiA-n:js
\
\
\
N
\
\
K
\
\
\
;\
\
\
N
!\
K
^
^
?
A Pipets, Spotplates, funnels, beakers
B Filter papers watchglasses, parafilm, extra sample vials
C Pencils,, pens, markers, labels, tape
D Clamp, stand, ring support, ken-wipes, paper towels, pipet
figure lOb. Cooler 2 ~~ equipment organization,
80
-------
\
\
\
\
\
Jv
\
\
\
\
\
\
\
\
\
\
\
\
\
^
A
L__
X
_
B
"4^°
A
c
E
F
J
I
H
G
\
\
\
N
\
\
\
\
\
\
\
\
\
\
\
\
\
\\v\\ \\\\\\ \ \\ \\\\\ \\\\\\\\\\\\\\\ \\\y
A Latex gloves
B Mixing device
C Wash solvents (acetone, methanol)
D Acid gloves
E Respirators, goggles
F Safety suits
G Rack with sample vials
H Test tubes, 4 in.
I Test tubes, 3 in.
J Sodium hydroxide and barium nitrate solutions
K Propane tanks (2) |
L Glycerol
Behind cutaway
Figure 11. Cooler 3 -- equipment organization,
81
-------
30~mL polyethylene screw cap bottles. Corrosive liquids, and reagents
dissolved in hexane, toluene , acetone, and chloroform as well as the neat
solvents are placed in 30-mL Teflon dropping bottles- For shipment all
dropping caps were replaced with regular screw caps,
The test kit arrived in perfect condition without any reagent spills at
the field test site after shipment by air cargo.
3.9 SAFETY
Safe handling of reagents and hazardous waste samples is of paramount
importance to field testing operations. It is assumed that analysts will be
trained in the safe handling of hazardous waste materials. Some key safety
principles are discussed in the following paragraphs. The first, section
deals with generalities regarding safe operation of the field test. kit. The
second section describes safe handling of hazardous waste samples and the
third describes safe handling of equipment and reagents contained within the
test kit. Finally, a short section on safe transportation of the test kit Is
included.
Safety Precautions
The safe performance of the field test procedures depends primarily upon
the use of very small amounts of materials, such that undesirable effects of
reactions resulting from the test procedures are kept to a minimum* For this
reason, the tests should be conducted with the smallest quantities of test
materials feasible, and only small samples of the waste materials (i.e., SOg
or less) should be kept at the testing site. Since several of the test
procedures
that tests
include the use of
be performed in an
a flame and reactive reagents, it is essential
area well removed from bulk storage areas,
Personal protective clothing and devices are provided
These include: safety glasses and goggles, latex exam gloves ar
/vac coveralls, and half-face respirators,, Gloves and
with the test k
,nd heavy
gloves, Tyvac
protection are mandatory, and the use of other personal protective device;: is
very strongly encouraged any time samples or- reagents are being handled or
tests are being conducted. In addition, a portable safety shield is provide:
as an added margin or' safety for conducting tests and should be employed,
particularly for the sodium fusion procedure and other procedures that-
involve heating of waste materials.
Hazardous waste samples may contain virtually any stable
element or compound known and
context it is assumed that no
cherries!
most are complex mixtures. For the present
prior knowledge of the waste material is
available.
of hazards:
Waste materials may present any or several of the following types
82
-------
« Toxic
• Explosive
• Extremely corrosive
® Violently reactive when mixed with certain other substances (e.g.,
water-reactive materials)
• Materials which emit toxic or explosive fumes
® Biologically hazardous materials (e.g., biological warfare agents}
• Radiologically hazardous materials
• "Exotic" chemical toxins (e.g., chemical warfare agents)
The present testing sequence does not address the problems of
biologically hazardous materials,, radioactive materials, or exotic chemical
toxins. Normally, prior knowledge of the presence of these materials will be
available and further special precautions will have to be taken.
Extreme caution is mandatory when sampling drums for field testing.
Although the methodology described herein does not describe drum sampling,
the safe collection of samples for testing is nonetheless worthy of mention
here. Drums are opened in an open area removed as much as possible from bulk
storage areas. Personnel collecting the samples are outfitted with full
protective clothing, including heavy gloves. Samples are collected using
dip-tubes or other suitable means and transferred to medium-size containers.
For testing, small aliquots of the samples are transferred to small
containers and care is taken to wipe the exterior of the sample container
free of any contamination from the sample.
_Sa_fe Conduct of Field Tests
Tests are conducted in an open, well-ventilated area removed from bulk
storage areas for drums. Protective clothing and devices are used, as
discussed in the previous sections. Small amounts of test materials and
reagents are employed to minimize the effects of potentially catastrophic
reactions.
Reagents employed in the test kit are hazardous in themselves. The
specific hazards presented by the reagents in the kit are as listed in
Table 23,
In addition to the hazards specified above, most of the dissolved
reagents are toxic and most of the reagents should be treated as potential
carcinogens.
Wastes from the test procedures should be treated as hazardous (they are
probably more hazardous than the waste materials themselves) and allowance
83
-------
TABLE 23. HAZARDS OF TEST KIT REAGENTS
Reagent(s)
Acetone, methanol ,
toluene, hexane
Hydrochloric,
sulfuric acid
Nitric acid
Sodium hydroxide
Propane
Di ethyl ether
Procedure set(s)
where employed
PS 2, 4
PS 2
PS 2S 45 6
PS 2
PS 3
PS 49 5
Flammable
Corrosive
Corrosive
Caustic
Compressed
Extremely
Hazard
presented
liquid
liquid
liquid oxidizer
gass flammable
flammable, volatile
Sodium metal PS 4
Phenylhydrazine PS 5
Iodine/carbon disulfide PS 5
Stannous chloride PS 5
Ethane! PS 5
Potassium hydroxide/ PS 5
methanol
Hydroxylamine PS 5
hydrochloride
Potassium permanganate/ PS 5
acetone
Aluminum chloride PS 5
Phosphomolybdic acid PS 6
Zinc sulfide, ammonium PS 6
sulfide
1iquid
Water-reactive flammable solid
strong reducing agent
Strong reducing agent, corrosive
Extremely flammable, oxidizing,,
volatile liquid
Strong reducing agent
Caustic, flammable liquid
Strung reducing agent
Strong oxidizer, flammable
Water-reactive solid
Strong oxidizing agent,,
corrosive liquid
Emits toxic gas (HgS)
-------
should be made for proper disposal. These waste materials can he placed in
polyethylene containers placed in a drum and surrounded by vermiculite or
other absorptive material.
Safe Transportation of the Test Kit
The test kit is designed to withstand the rigors of shipping. Hazardous
materials are contained in unbreakable containers. Materials which adversely
affect polyethylene are stored in Teflon bottles. The containers are fitted
with solid caps for shipping; these are replaced with dropper caps at the
testing site. Glass vessels are protected from breakage.
The specific hazards presented by many of the reagents are presented in
the preceeding section. Many of these materials may not be shipped in the
same container. For example, acids may not be shipped in the same container
with flammable liquids. For this reason, acids and other corrosives are
shipped in one cooler and all flammable liquids shipped in a second cooler.
Metallic sodium and nitric acid must both be shipped separately; carbon
disulfide cannot be shipped by air.
The above regulations apply to commercial (air cargo) shipping. It is
recommended that, for reasons of convenience in transportation, the field
test kit be transported by private vehicle when possible.
85
-------
REFERENCES
*1. Hatayama, H. K., J. J. Chen, E. R, de Vera, R. D. Stephens, and D. L.
Strom, "A Method of Determining the Compatibility of Hazardous Wastes/'
EPA/600/2-80-076,, U.S. Environmental Protection Agency, Cincinnati, Ohio,
1980, NTIS PB No. 80-221005.
2. Cheronis, N. D., and J. B. Entrikin, "Semimicro Qualitative Organic
Analysis," Interscience Publishers, Inc»s New York, New Yorks 3960.
3. Feigl, F.s "Spot Tests in Inorganic Analysis," Elsevier Publishing
Company, New York, New York, 1972.
4. Fe1gl9 F., "Spot Tests in Organic Analysis," Elsevier Publishing
Company, New York, New York, 1966.
5e Rand, H. C.s A. E. Greenberg, and M. J. Taras, "Standard Methods for the
Examination of Water and Wastewater," 14th ed., American Public Health
Association,, Washington, D.C., 1978.
6, Simmons, B. P., I. Tan, T. H, Li, R. D. Stephens, and D. L. Strom, "A
Method for Determining the Reactivity of Hazardous Wastes," U.S.
Environmental Protection Agency, Cincinnati, Ohio, 1982 (Preliminary),
7, Flynn, J. P. and H. E. Rossow, "Classification of Chemical Reactivity
Hazards/' Dow Chemical Co., Midland, Michigan, December 1970 for
National Academy of Science and U.S. Coast Guard, USCGD 29-74, NTIS
AD-733 049.
"^This EPA report is no longer available from EPA or NTIS. An updated
version of this report entitled "A Proposed Guide for Estimating the
Incompatibility of Selected Hazardous Wastes Based on binary Chemical
Reactions" is scheduled to be published in 1984 by the American Society
for Testing and Materials (ASTM) D34 Committee on Waste Disposal.
86
-------
APPENDIX
FIELD TEST KIT INSTRUCTION MANUAL
TABLE OF CONTENTS
A.I Introduction and Safety ............ . . 90
A.1.1 Scope . 90
A. 1.2 Safety 91
A.1.2.1 General safety precautions 93
A.1.2.2 Handling of hazardous waste samples ..... 93
A.1.2.3 Safe conduct of field tests . 94
A.2 Procedure Sequences ....'.. ........ 94
A.2.1 Sequence of procedure sets 94
A.2.2 Procedure set descriptions 98
A.2.2.1 PS 1 — pH and redox tests . . 98
A.2.2.2 PS 2 -- solution-reactivity and
special functionality tests 98
A.2.2.3 PS 3 — flame test . 108
A.2.2.4 PS 4 -- sodium fusion and ferrox tests . . . 109
A.2.2.5 PS 5 -- organic functionality tests 110
A.2.2.6 PS 6 — inorganic functionality tests .... 113
A.3 Hazardous Waste Classification Field Data Sheet . . 113
A. 4 Test Procedures 113
A.4.1 PS 1 — pH and redox tests 113
A.4.1.1 pH tests for acids and caustics ....... 113
A.4.1.2 Redox tests 116
A.4.2 PS 2 -- solution-reactivity and special
functionality tests ....... 116
A.4.2.1 Solution-reactivity tests 116
A.4.2.2 Cyanide test H6
A.4.2.3 Sulfide test 117
A.4.2.4 Copper-sulfate test for water 117
A.4.3 PS 3 — flame tests 117
A.4.4 PS 4 — sodium fusion and ferrox tests 118
A.4.4.1 Sodium fusion procedure 118
A.4.4.2 Ferrox test for organic compounds
containing oxygen ..... 120
A.4.5 PS 5 — organic functionality tests 121
A.4.5.1 PS 5A — hydrocarbon classification tests . . 121
A.4.5.2 PS 5B -- tests for functional groups
containing oxygen .... 122
87
-------
A.4.5.3 PS 5C —• tests for functional groups
containing nitrogen .............. 126
A.4.5.4 PS 5D —• tests for functional groups
containing sulfur .............. 129
A.4.6 PS 6 — inorganic functionality tests ........ 130
A.4.6.1 Zirconium alizarinate test for fluorides . . 130
A.4.6.2 Tests for metals and metal compounds . . . . 131
A.5 Device for Test Mixing Hazardous Waste Materials 132
A.5.1 Description 132
A.5.2 Cautions 132
A.5.3 Procedure ............. .^ ........ 13?
A.5.4 Additional indicator tests for carbonate and
thiocyanate ..................... 134
A.5.4.1 Barium nitrate test for evolution of carbon
dioxide ................... 134
A.5.4.2 Ferric chloride test for thiocyanate . . . . 134
A.5.5 Equipment maintenance and reagent refill ....... 135
A.5.5.1 Equipment cleaning ............. 135
A.5.5.2 Reagent refill ............... 135
Attachment A -- Reagents For Hazardous Waste
,/ Field Test Kit ............... 137
Attachment B< -- Equipment For Hazardous Waste
Field Test Kit ............... 139
Attachment C -- Kit Organization .............. 141
FIGURES
]Number
A-l Sequence of procedure sets ............... 97
A-2 Procedure set 1 -- pH and redox tests .......... 99
A-3 Procedure set 2 -- solution-reactivity and special
functionality tests ................... 10!)
A-4 Procedure set 3 -- flame tests ............. 101
A-5 Procedure set 4 -- sodium fusion and ferrox tests .... 102
A-6a Procedure set 5A -- organic functionality tests for
hydrocarbon classification . . . „ -^,-. ..„..„...,
A~6b Procedure set 58 — organic functionality tests for
functional groups containing oxygen ............ 104
A-Sc Procedure set 5C -- organic functionality tests for
functional groups containing nitrogen .......... 105
A-6d Procedure set 5D — organic functionality tests for
functional groups containing sulfur ........... 106
-------
Number
A-7 Procedure set 6 —- inorganic functionality tests .... 107
A-8 Hazardous waste classification field test results .... 114
A-9 Test mixing device ... ......... 133
TABLES
Number Page
A-l Reactivity Group Definitions ........ 92
A-2 Reagents and Hazards ........ 95
A-3 Procedure Sets ........ ..... 96
A-4 RGN's Determined in PS 5 ................ Ill
A-5 References for Additional Tests of Impinger Solutions . . 134
89
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A.I INTRODUCTION AND SAFETY
This manual describes the use of the Hazardous Waste Classification
Field Test Kit developed for the U.S. Environmental Protection Agency (EPA)
by Acurex Corporation. The development of the test kit and verification of
the test procedures is described in EPA Report , "Hazardous Waste
Compatibility Testing for Applicability to Remedial Action at Uncontrolled
Hazardous Waste Sites."
A.1.1 jvcj)p_e
The tests described herein are intended to provide qualitative
information regarding the bulk chemical composition of hazardous waste
materials. The test procedures are used to classify waste materials into
reactivity groups (RGN's) defined in EPA Report 600/2-80-076, "A Method for
Determining the Compatibility of Hazardous Wastes." The information thus
obtained is intended to be used to determine compatibility characteristics of
hazardous wastes, in conjunction with the compatibility chart in
EPA-600/2-80-076. But it may be used for other purposes such as hauler
manifest verification or prediction of best disposal technology. These test
procedures do _not address the potential of radioactive or biological hazards,,
It should also be stressed that these procedures provide only qualitative
information without regards to concentration. Therefore, a specific hazard
(i.e., sulfide) will be identified even at a level such that it poses a
minimal hazard. To this extent, the test results may lead to misleadlngly
conservative conclusions, Conversely, these procedures will probably not
identify materials at low concentrations (Ca <5 percent) that may cause
long-term hazards. The lower limits of response for the various tests have
not been determined.
Preliminary procedures are provided to give information regarding
general reactivity characteristics of waste materials such as
acidity/basicity, oxidative/reductive potential, reactivity/solubility
characteristics, and combustibility. Additional procedures are provided as
specific, class tests for complete categorization of waste materials according
to chemical functionality. Any or all of these procedures can be employed,
depending upon the discretion of a qualified supervisor and the completeness
of information required.
The kit and manual are designed for use by technicians with minimal
knowledge of the meaning of the results. The analyst is expected to havt5 had
some limited laboratory experience and at least 1 week of hands-on training.,
The test procedures have been designed to limit judgment decisions to a
minimum,
A simple device to detect heat and gas evolution upon mixing of twc
waste materials is included in the test kit. It is strongly recommended that,
this device be used to test the compatibility of the wastes e'>'en If thr-
compatibility chart, indicates the wastes to be compatible,.
-------
On the other hand, completion of the testing sequence prior to mixing is
strongly recommended for the following reasons:
• To identify hazards that may be dangerous upon mixing even in small
quantities
® To identify long-term adverse effects of mixing not observed in the
mixing device but predicted by the compatibility chart
« To utilize, the classification information obtained in testing for
purposes other than compatibility prediction (e.g., identification
of specific wastes pr waste stream categories)
The test procedures described herein are organized into six series of
tests, each included to provide specific information about the waste
material. In several cases, results obtained at a specific stage in the
testing sequence can sufficiently define the chemical characteristics of the
waste material such that the need for further testing is eliminated. These
cases are pointed out in the discussion of the procedure sequences. Each of
the six procedure sets is summarized with a flow diagram, which provides an
overview of procedures involved in that particular procedure set.
Section A.2 of this manual includes a presentation and discussion of the
procedure sets, and generalized instructions on the use of the test sequence.
Section A.3 includes a test data sheet and instructions for its use.
Section A.4 contains specific instructions for conducting each of the test
procedures, including instructions for preparation of reagents. A
description of testing to determine the effects of mixing wastes is presented
in Section A,5. Lists of equipment and supplies are included as
attachments.
Specific test procedures are provided for classification of waste
materials into the RGN's listed in Table A-l. In many cases specific
classification may not be required (i.e., distinction between aliphatic and
aromatic hydrocarbons). In those cases where, in the opinion of the authors,
tests are not absolutely required for purposes of defining compatibility
characteristics, the procedures are labeled optional (and are indicated by
broken lines on the flow diagrams). Likewise, when, in the opinion of the
authors, further testing may present a hazard (i.e., sulfides, cyanides), a
"stop" is indicated in the flow diagrams.
A.1.2 Safety
Safe handling of reagents and hazardous waste samples is of paramount
importance to field testing operations. It is assumed that analysts will be
trained in the safe handling of hazardous waste materials. Some key safety
principles are discussed in the following paragraphs. The first subsection
deals with generalities regarding safe operation of the field test kit. The
second subsection describes safe handling of hazardous waste samples and the
third describes safe handling of equipment and reagents contained within the
test kit.
91
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Table A-l. REACTIVITY GROUP DEFINITIONS
Reactivity
group no.
Reactivity group name
1 Acids, mineral, nonoxidizing
2 Acids, mineral, oxidizing
3 Acids, organic
4 Alcohols and glycols
5 Aldehydes
6 Amides
7 Amines, aliphatic and aromatic
8 Azo compounds, diazo compounds, and hydrazines
9 Carbamates
10 Caustics
11 Cyanides
12 Dithiocarbomates
13 Esters
14 Ethers
15 Fluorides, inorganic
16 Hydrocarbons, aromatic
17 Halogenated organics
18 Isocyanates
19 Ketones
20 Mercaptans and other organic sulfides
21 Metals, alkali and alkaline earth, elemental
22 Metals, other elemental and
vapors, or sponges
23 Metals, other elemental and
drops, etc,
24 Metals and rretal compounds,
25 Nitrides
26 Nitriles
27 Nitro compounds
28 Hydrocarbons, aliphatic, unsaturated
29 Hydrocarbons, aliphatic, saturated
30 Peroxides and hydroperoxides, organic
31 Phenols and cresols
32 Organophosphates, phcsphothioates, phospbodithiostes
33 Sulfides, inorganic
34 Epoxides
101 Combustible and flammable materials, miscellaneous
102 Explosives
103 Polymerizable compounds
104 Oxidizing agents,, strong
105 Reducing agents, strong
106 Hater and mixtures containing water
107 Water reactive substances
and alloys
alloys in the form of powders,
alloys as sheets, rods, moldings,
toxic
92
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A.1.2.1 General Safety Precautions--
The safe performance of the field test procedures depends primarily upon
the use of very small amounts of materials, such that undesirable effects of
reactions resulting from the test procedures are kept to a minimum. For this
reason, the tests should be conducted with the smallest quantities of test
materials feasible, and only small samples of the waste materials (i.e., 50g
or less) should be kept at the testing site. Since several of the test
procedures include the use of a flame and reactive reagents, it is essential
that tests be performed in an area well removed from bulk storage areas.
Personal protective clothing and devices are to be provided with the
test kit. These include: safety glasses and goggles, latex exam gloves and
heavy viton gloves, Tyvac coveralls, and half-face respirators. Gloves and
eye protection are mandatory and the use of other personal protective devices
is very strongly encouraged any time samples or reagents are being handled or
tests are being conducted. In addition, a portable safety shield is provided
as an added margin of safety for conducting tests and should be employed
particularly for the sodium fusion procedure and other procedures where
heating of waste materials is involved.
Emergency procedures and facilities at the site must be identified
before testing is initiated. As a minimum, the phone numbers of the nearest
fire and medical facilities should be posted, along with directions to the
nearest emergency facilities.
A.1.2.2 Handling of Hazardous Waste Samples--
Hazardous waste samples may contain virtually any stable chemical
element or compound known and most are complex mixtures. For the present
context it is assumed that no prior knowledge of the waste material is
available. Waste materials may present any or several of the following types
of hazards:
« Toxic
• Explosive
• Extremely corrosive
« Violently reactive when mixed with certain other substances (i.e.,
water-reactive materials)
» Materials which emit toxic or explosive fumes
© Biologically hazardous materials (i.e., biological warfare agents)
« Radiologically hazardous materials
• "Exotic" chemical toxins (i.e., chemical warfare agents)
The present testing sequence does not address the problems of
biologically hazardous materials, radioactive materials, or exotic chemical
93
-------
toxins. Normally, prior knowledge of the presence of these materials will
available and further special precautions will have to be taken.
be
Extreme caution is mandatory when sampling drums for field testing,
Although the methodology described herein does not describe drum sampling,
some aspects of the safe collection of samples for testing is nonetheless
worthy of mention. Drums should be opened in an open area removed as much as
possible from bulk storage areas. Personnel collecting the samples should be
outfitted with full protective clothing, including heavy gloves. Samples
should be collected using dip tubes or other suitable means and transferred
to medium-size containers. For testing, small aliquots of the samples should
be transferred to small containers (approximately 5 ml) and care should be
taken to wipe the exterior of the sample container free of any contaminarkn
from the sample.
A.1.2.3 Safe Conduct of Field Tests--
Tests should be conducted in an open, well-ventilated area removed frw;
bulk storage areas for drums. Protective clothing and devices should be
employed, as discussed in the previous sections. Small amounts of test
materials and reagents are employed to minimize the effects of potentially
catastrophic reactions.
Reagents employed in the test kit are hazardous in themselves,. The
specific hazards presented by the reagents in the kit are presented In
Table A-2.
In addition to the hazards specified in Table A~2, most of the dissolved
reagents are toxic and most of the reagents should be treated as potential
carcinogens,
Wastes from the test procedures should be treated as hazardous (they are
probably more hazardous than the waste materials themselves) and allowance
should be made for proper disposal. These waste material? can be placed in
polyethylene containers placed in a drum and surrounded by vermiculate cr
other absorptive material. These waste materials will fall into the
regulatory category of laboratory wastes.
A.,2 PROCEDURE SEQUENCES
The procedures employed for chemical categorization of hazardous wastes
are organized into six procedure sets (PS), briefly summarized in Table A-3,
The first step in the classification of an unknown hazardous waste
material is the physical (visual) examination of the v«ste material. The
physical state of the material (solid, liquid, etc,) may provide considerable
insight as to its identity (1,e,, metal castings). Depending upo.-i the
physical state of the neateria! f the procedure sets arn performed in the
sequence indicated in Figure A-l.
94
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TABLE A-2. REAGENTS AND HAZARDS
Reagent(s)
Acetone, methanol ,
toluene, hexane
Hydrochloric,
sulfuric acid
Nitric acid
Sodium hydroxide
Propane
Di ethyl ether
Procedure set(s)
where employed
PS 2, 4
PS 2
PS 2, 4, 6
PS 2
PS 3
PS 4, 5
Flammable
Corrosive
Corrosive
Caustic
Compressed
Extremely
Hazard
presented
liquid
liquid
liquid; oxidizer
gas; flammable
flammable, volatile
Sodium metal PS 4
Phenylhydrazine PS 5
Iodine/carbon disulfide PS 5
Stannous chloride PS 5
Ethanol PS 5
Potassium hydroxide/ PS 5
methanol
Hydroxylamine PS 5
hydrochloride
Potassium permanganate/ PS 5
acetone
Aluminum chloride PS 5
Phosphomolybdic acid PS 6
Zinc sulfide, ammonium PS 6
sulfide
1iquid
Water-reactive, flammable solid;
strong reducing agent
Strong reducing agent
Extremely flammable, oxidizing,
volatile liquid
Strong reducing agent
Caustic, flammable liquid
Strong reducing agent
Strong oxidizer, flammable
Water-reactive solid
Strong oxidizing agent,
corrosive liquid
Emits toxic gas
95
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Table A-3. PROCEDURE SETS
PS
Title
Information obtained
1 pH and Redox Tests
Solution-Reactivity and
Special Functionality Tests
Flame Test
Sodium Fusion and
Ferrox Tests
5 Organic Functionality Tests
6 Inorganic Functionality Tests
Acidity, basicity, oxidizing and
reducing potential
Identification of sulfides and
cyanides, reactivity and solubility
in acids and solvents, reactivity
with water., presence of water
Combustibility, classification as
organic or inorganic, Identification
of explosives
Identification of oxygen, nitrogen,
phosphorus, sulfur, and halogen in
organic waste materials
Presence of specific organic
functional groups
Presence of elemental metals, heavy
metal compounds, and inorganic
fluorides
96
-------
U3
-g
O START
STOP
CONTINUE
PROCEDURE
C~^ RESULT
CLASSIFY
INTO RGN
I ST&5U |
VIS
EKAM1
i
UAL
fiATlON
f LIQUID "\
f SLURRY, SLUDGE J
1
f
PROCEDURE SET £
PROCEDURE SET 4
!
1
PROCEDURE SET 6
PROCEDURE SET 5
APPARENTLY METAL
OPTIONAL
PROCEDURE
SET 2
PROCEDURE
SET G
START
SIOP
COIITI HUE
PROCEDURE
WSULT
Figure A-l« Sequence of procedure sets,
-------
Procedure set 1 (PS 1) provides considerable information in a very short
period of time and thus is performed first. PS 1 may be performed
concurrently with PS 2, for convenience if desired. Next, the combustibility
of the material is observed by performing the flame test (PS 3) which should
be conducted, even if not indicated from PS 2S to detect potentially
explosive materials. The results of PS 2 and PS 3 are used to determine
whether the material is primarily organic in nature (combustible) or
primarily inorganic. Generally, flammable materials or materials that are
solvent-soluble are classified as organic and materials that fuse or
evaporate are classified as inorganic. Appropriate functionality tests are
applied to fully characterize the material, depending upon its classification
as organic or inorganic. For the purposes of the tests employed herein,
slurries and sludges are treated in the same manner as liquids.
It is recommended, where possible, that slurries be filtered and the
solid and liquid portions be analyzed separately. Otherwise, unless
specified, separate portions of untreated waste materials are used for each
of the tests. When two or more liquid phases exist, it is advisable to test
each phase as a different sample.
A.2.2 Procedure _Set_Desc_rj_ptions
Flow diagrams for procedure sets 1 through 6 are shown in Figures A-2
through A-7, and are explained in detail in Sections A.2.2.1 through A,2.2.6.
Specific instructions for conducting the test procedures are given in
Section A.4.
A.2.2.1 PS 1 — pH and Redox Tests--
Oxidation, reduction, and pH tests are performed on a waste material by
means of test papers. These tests identify some of the most reactive
materials and therefore are performed early in the testing sequence,
Acids (RGN's 1, 2S 3} or bases (caustics — RGN 30} are identified by
means of the pH test. Mineral acids are identified by a pH of 1,5 cr l>ss,
Organic acids are so designated by pH of 2 to 5. Bases (caustics) have a pH
of 10.5 to 14. Oxidizing agents (RGN 104) and reducing agents (RGN 106) are
determined by similar paper tests.
Classification of a waste material into RGN's 1, 2, or 104 adequately
defines the waste material such that further testing 's unnecessary. Also,
if the material is caust/ic (RGN 10) jsnd a reducing agent (RGN 105) further
testing is unnecessary, as indicated in Figure A-2. Performance of the flame
test to identify explosives is recommended, however> as Indicated ir,
Figure A-2. The procedures used for these tests are described in
Section A.4.1.
A.2.2.2 PS 2 ~ Solution-Reactivity and Special Functionality Tests--
The waste material is treated with water, a base, and with various acid?
and solvents to determine its reactivity and solubility characteristics. The
flow diagram for PS 2 is shown in Figure A-2, The first step is treatment
with water. Materials which are water reactive (RGN 107) (as indicated by
98
-------
£ MBlClllliS
Figure A-2. Procedure set 1 — pH and redox tests.
-------
o
o
O m
V_X o»lli
cu
maxum
MSUL1
F~j CUSSiFt WIO HUt
3rocsdure set 2 — solution/reactivity and special functionality
-------
Figure A-4. Procedure set 3 — flame tests.
-------
ws
4--i
in
X"
o
t,
it-
ID
C
VJ
T!
Q
t'S
T3
SiJ
*.J
Q
t,
102
\
-------
— OPTIONAL PROCEDURES
o
o
START
STOP
CONTINUE
PROCEDURE
RESULT
CLASSIFY
INTO RGN
NEGATIVE
FERROX
A1C13,
X"""" ^V
f BAEYER \
( KMn04 POSITIVE J
^-«^__.__---^
— ~] — — - — — 1 — — — I
RGN
16
RGN
28
RGN
29
Figure A-6a.
Procedure set 5A — organic functionality tests for
hydrocarbon classification.
103
-------
— __ OfTIOWM. PSOCEWJ8IS
o
CZ3
o
D
•o
5t»8!
SW
COSTIWJI
PROCEDWI
RJSUIT
CiASSlPV
I SVC RSI!
corninvE MI? if
RESUU 18 AS HlOiCAIEB
VWfltVMS
TtSt
1
TEST
OTMWWATE
?E5t
ioasi*
TtST
Procedure set 58 — organic functionality tests for funct-one]
groups containing oxygen.
-------
O
en
_____ OPTIONAL PROCEDURES
O
o
START
STOP
CONTINUE
PROCEDURE
RESULT
CLASSIFY
INTO RGN
CONTINUE ONLY IF
RESULT IS AS INDICATED
DIPHENYLCARBO-
HYDRAZIDE
TEST
DIHETHYLAMINE
BENZALDEHYOE
TEST
( POSITIVE J
POSITIVE
(OPTIOKAL)
~~T~" ~~
fiLUTACQNIC
ALDEHYDE
TEST
OXAM1DE
TEST
P-NITROBENZENE-
DIAZONIUM
TETRA-
FLUQRGBORATE
TETRABASE
TEST
POSITIVE
Figure A-6c. Procedure set 5C — organic functionality tests for functional
groups containing nitrogen.
-------
_.___ OPTIONAL PROCEDURES
START
STOP
CONTINUE
PROCEDURE
KESULT
CLASSIFY
IHTO KEH
CONTINUE ONLY IF
aesuu is AS INDICATED
o
Figure A~6d. Procedure Sfet 5D -- organic functionality tests f<
functional groups containing suffur,
106
-------
o
SOLID
WASTE |
HATERIAl I
SHEETS, RODS,
DROPS, MOULDINGS
o
START
STOP
CONTINUE
PROCEDURE
RESULT
CLASSIFY
INTO RON
Figure A-7. Procedure set 6 -- inorganic functionality tests,
-------
fuming, bubbling, or spattering) are flagged and testing is suspended.
Separate portions of the waste materials are then tested for sulfide (RGN 33)
and cyanide (RGN 11); likewise, if these RGN's are present, further testing
is suspended. Liquid waste materials are tested for the presence of water
(RGN 106) with anhydrous copper sulfate. Acid, base, and solvent test? are
performed (see Section A.4.2) except on materials containing sulfide or
cyanide. Generally, materials that are soluble in organic solvents are
classified as organic, and the testing is continued with PS 4. Sulfide and
cyanide containing wastes are considered inorganic.
CAUTION
Sulfide and cyanide wastes must not be treated with acid.
Materials that are soluble in water and acids but not in solvents,, or are
insoluble in water., acid, and solvents may be organic or inorganic, and
testing is continued with PS 3.
A.2.2.3 PS 3 - Flame Test-
Observation of the behavior of a material upon ignition can provide a
great deal of insight regarding its composition. Results (observations) upon
ignition are characterized by one of the following descriptions:
® Burns violently
« Burns (with or without smoke)
• Produces a colored flame, but does not burn
• Fuses (melts) but does not burn
• Evaporates or sublimes but does not burn
Figure A-4 shows the classification observations. While these observation-;
are somewhat subjective, it is anticipated that most observers can make a
distinction between organics, inorganics, and free metals using the fume
test. RGN 107 (explosive) is determined directly by means of the flame-
test.
In summary, materials that burn are classified as organic. Materials
that melt, evaporate, or only color a flame are classified as inorganic,
In addition, several observations are made that csr« give furthes cluv,
regarding the composition of the material. A material that, burns with d !-;oft
blue flame (no smoke) is most likely an organic material containing only
carbon, hydrogen, and oxygen. Materials that burn with a yellow fla^e and
produce a sooty flame are probably aromatic or contain nitrogen, sulfur, or
phosphorus.
108
-------
The test procedures are explained in Section A.4.J.
It is always advisable to begin testiiui wild a sm.-ill
safely identify materials that are unusually tlamm.ihl
explosive.
If explosive materials are encountered, it is highly advisable to suspend
further testing at this point.
It should be noted that this procedure generally does not identify the
potential of water-based organics. If, after conducting PS 6, no RGN's are
identified except RGN 106 (water and mixtures containing water), it is
suggested that the waste be considered as water-containing organics. Some
nrganic functionality tests can be performed; however the sodium fusion
procedure should not be performed with materials containing water as the
major constituent.
A. 2. 2. 4 PS 4 — Sodium Fusion and Ferrox Tests--
If it is determined, by results of PS 2 and/or PS 3 that a waste
material is organic, the sodium fusion test is performed to determine the
presence of halogen (chlorine, bromine, or iodine) (X), sulfur (S), nitrogen
(N), and/or phosphorus (P). The ferrox test is performed, in the absence of
sulfur, nitrogen, or phosphorus, to determine the presence of oxygen (0).
The flow diagram for PS 4 is shown in Figure A-5.
Note
The sodium fusion procedure is not recommended for explosive
materials.
If the waste material is found to contain nitrogen, sulfur, or
phosphorus, testing is continued with PS 5 C, D, or E as appropriate. If any
of these elements is present, oxygen is also assumed to be present, and PS 58
is conducted. PS 5B is also conducted if the result of the ferrox test is
positive. If the ferrox and halogen test results are negative, optional
testing is continued to classify hydrocarbons (PS 5A). If, on the other
hand, the ferrox test is negative and halogen is present, the testing
sequence is complete. If the halogen test is positive, the analyst may wish
to conduct PS 5A to differentiate between halogenated aromatics (e.g.,
PCB s), halogenated alkanes (e.g., chloroform), and halogenated alkenes
(e.g., trlchloroethylene) .
In summary, PS 4 is used to determine the elements present in an organic
waste material. The results are used as a guide for which functionality
tests are to be performed in PS 5. The test procedures are outlined in
Section A. 4. 4.
109
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A.2,2.5 PS 5 -- Organic Functionality Tests--
Elemental analysis information obtained in PS 4 is used as a starting
point for PS 59 This set of procedures includes specific tests for 21 RGN's
and is outlined in Figures A-6a through A-6d. PS 5 contains four major
subsets: tests for hydrocarbon classification and tests for functionalities
containing sulfur, nitrogen, and/or oxygen only.
The 21 reactivity groups determined in PS 5, arranged according to
procedure subset, are listed in Table A-4.
Each of the procedure subsets 58 through 5D? is performed only if the
respective element was determined to be present in PS 4. If the element was
found to be absent in PS 4, it can be concluded that al! reactivity groups
determined in that subset are absent. If sulfur, nitrogen, or phosphorus ar
present, oxygen is also assumed to be present, and PS 5B is conducted in
addition to the appropriate subset. If"oxygen, nitrogen, halogen, sulfur,
and phosphorus are all found to be absent, it is concluded that the material
is hydrocarbon and PS 5A is conducted. If any of these listed elements are
present, the three hydrocarbon RGN's are considered to be absent. Each of
the individual procedure subsets are explained in the following paragraphs.
A.2.2.5.1 PS 5A --hydrgca£b_qn_c]_ajs si f itaypj]_tes_ts__(ppti_o_na_l )--Threc-
classes of hydro^aTb^nTTRG^s 16, 28, and~29T~are dfstfngufsYed by" the
Friedel-Crafts test and the Baeyer test. The flow diagram for PS 5A is shown
in Figure A-6a. These three RGN's are mutually exclusive (by definition),,
therefore, if one test result is positive, the other need not be run. It is
suggested that the Friedel-Crafts test be performed first in this sequence.
If both the Friedel-Crafts test and the Baeyer test are negative, the
material is classified as RGN 29.
Since the hydrocarbon RGN's are similar in their compatibility
characteristics and are all relatively unreactive, this procedure subset is
labeled "optional," The test procedures for these tests are outlined in
Section A.4.5.1.
It is frequently desirable to detect aromatics, even in the presence of
functional groups. It is therefore recommended that the Friedel-CfrtKs te.il:
be performed, particularly if organic halogens are present,
A.2.2.5*2 PS 5B -- tests for organic functional oroups contai
____________ _
i_Tests for functional groups containing oxygon involve
specific RGN's. These tests are performed on all organic wastes eKCfyi rnas
materials shown not to contain sulfur,, nitrogen, or phosphorus '\y the f;js;or<
procedure and those that give a negative ferrox test,, I he flow tiiayr^i lor
procedure subset 5B is shown in Figure A-6b and the test procedures are
presented in Sections A.4.5,2,1 through A,^.5.2.7„
Three of the RGN's are identified by means of results obtained in PS
and PS 2. Organic acids (RGN 3} are identified by means of tneir pH s.pH
5). Organic peroxides (RGN 30) respond as oxidizing agents and shcuhi un-
identified in PS 2. The result is confirmed by a special piper test
110
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TABLE A-4. RGN'S DETERMINED IN PS 5
PS 5A — Hydrocarbons
RGN 16 — Aromatic hydrocarbons
RGN 28 -- Unsaturated aliphatic hydrocarbons
RGN 29 -- Saturated aliphatic hydrocarbons
PS 58 — Oxygen functional groups
RGN 3 -- Organic acids
RGN 4 -- Alcohols and glycols
RGN 5 — Aldehydes
RGN 13 — Esters
RGN 14 — Ethers
RGN 19 — Ketones
RGN 31 — Phenols and cresols
RGN 34 -- Epoxides
RGN 30 — Peroxides
PS 5C -- Nitrogen functional groups
RGN 6 — Amides
RGN 7 -- Amines
RGN 8 -~ Azo compounds, diazo compounds, and hydrazines
RGN 9 — Carbamates
RGN 18 — Isocyanates
RGN 26 — Nitriles
RGN 27 -- Organic nitro compounds
PS 5D -- Sulfur functional groups
RGN 12 — Dithiocarbamates
RGN 20 -- Mercaptans and other organic sulfides
111
-------
(Section A. 4. 5. 1.1). No specific test is included for epoxides (RGN 34), but
this RGN is tentatively identified by its vigorous, sometimes violent
reaction with mineral acids, particularly nitric acid.
The remaining six RGN!s identified in PS 5B are less reactive than
RGN's 39 30, or 34. If one of these reactive RGN's are identified, it is
advisable to omit further tests for other RGN!s« Furthermore, compatibility
characteristics of the less reactive RGN's are similar, so tests for the
remaining six RGN's are labeled optional.
Di nitrophenyl hydrazi ne is used to identify carbonyl compounds (aldehydes
and ketones, RGN's 5 and 19), and the Schiff's test is used to distinguish
between the two. Separate tests are conducted to identify alcohols (RGN 4),
esters (RGN 13), ethers (RGN 14), and phenols (RGN 3).
A.2.2.5.3 _PS__5C_j~_ tots for organic functional groups a)n^a^
nitrogen — Functional group tests for organic compounds containing nitrogen
are contained in PS 5C. These tests are performed only if nitrogen is
detected by the sodium fusion procedure (PS 4), The flow diagram for
classification of the seven RGN's containing nitrogen is shown in
Figure A-6c. The test procedures are described in Sections A. 4. 5. 3.1 through
A. 4, 5. 3. 5.
Three RGN's are considerably more reactive than others: carbamates
(RGN 9), isocyanates (RGN 18), and azo compounds, diazo compounds, and
hydrazi nes (RGN 8). The diphenylcarbohydrazide test is conducted to identify
RGN 9, Azo compounds are identified by the dimethyl ami nobenzaldehyde test
and hydrazi nes are identified by the glutaconic aldehyde test. If either or
these tests are positive., the material is classified as RGN 8, No suitable
test procedure is included for isocyanates (RGN 18).
If a material is classified as RGN 8S 9, or 18, it is suggested that
further testing in PS 5C be eliminated. Tests for RGN's 6, 7, 26, and 27 are
included, but are labeled optional, because compatibility characteristics of
these materials are similar and the reactivity hazard of these materials 'is
not as great. Amides arid nitriles are not distinguished by the test
procedure, but these materials are very similar in their reactivity
properties,
A ,2.2, 5. 4 .PS_§Q_ir tjes_t£ for . ™,
!M_!!yi~-Tests for two RGlPs" that con t a fn "sulfur a?e~7ncTuded iF PS'To Vincc-
the reactivity characteristics of these RGN's are similar, the procedure
subset is labeled optional. If sulfur is shown to be absent in the sochun
fusion procedure (PS 4), both RGN's 12 and 20 are absent.
The flow diagram for procedure subset 50 is shown In Figure A-6d, sn-n
the test procedures for RGN's 12 and 2U are outlined in Sections A^-. 5.4.1.
through A. 4. 5. 4. 2.
112
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A. 2. 2. 6 PS 6 — Inorganic Functionality Tests--
If a waste material is classified as inorganic in PS 1-3S three test
procedures are conducted to identify inorganic materials not already
identified (PS 1 and 2). The flow diagram for PS 6 is shown in Figure A- 7
and specific test procedures are described in Sections A. 4.6.1 to A. 4. 6.2.
Elemental metals or alloys can often be identified visually; their
presence is confirmed by the phosphomolybdic acid test. Alkali and alkaline
earth metals (RGN 21) react with water to give solutions that are basic (PS
2). Visual inspection can be used to identify the form of elemental metals
(RGN's 22 or 23). It should be noted that all elemental metals except
mercury (which is readily identified visually) are solids, so the
phosphomolybdic acid test is not conducted if the waste material under
investigation is a liquid,
Toxic metal compounds (RGN 24) are identified by a simple zinc sulfide
test, and inorganic fluorides (RGN 15) are identified by the zirconium
alizarinate test. No specific test procedure is included for nitrides
(RGN 25) but these materials are explosive and are thus detected in PS 3.
A. 3 HAZARDOUS WASTE CLASSIFICATION FIELD DATA SHEET
A data sheet used in recording the results of hazardous waste
classification tests is shown in Figure A-8. As procedure sets are completed
the appropriate sections are filled in. Conclusions regarding the
classification of materials into reactivity groups are recorded at the bottom
of the data sheet. RGN's identified during the course of the testing
sequence are circled. Numbers are crossed out for those RGN's found to be
absent* At the end of the test sequence, the circled reactivity groups are
used to define the gross chemical composition and thus determine
compatibility characteristics of the waste material,
Note
It is important to consult Sections A. 2 and A. 4 of the test manual
for the proper interpretation of test results.
A. 4 TEST PROCEDURES
A.4.1
A. 4. 1.1 pH Tests for Acids and Caustics (RGN's 1, 2, 3, 10)--
Pjrocedure:
The pH is determined by spotting the liquid material or the solid
suspended or dissolved in water on the pH paper and comparing the color with
the corresponding color and pH from the color table. The test paper is
moistened with water before applying the test material.
Substances that do not dissolve in water or interfere with the color
reactions of the pH paper cannot be tested for pH with this procedure.
113
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Sample: Analyst:
Date:
Preliminary" Observations:
PROCEDURE SET !
PH _________ (RQN 1, 2, 3, 10)
Oxidation _ _ _ (RGN 104) Reduction ________ (RGN 105)
PROCEDURj SET 2.
H?0 React _ {RGN 107) H?0 Present (R6N 100)
S {W31) CN (RGN 11~~ ~~
Solubility-Reactivity Tests
Burns Violently (RGN 102)
Observations:
Hi 1
Fysloss: fi S SCN
p _____ ~™
Ferrox
figure A-8. Hazardous waste ol&ssification ^ek test results (ps^e I of
-------
Sample:
Date:
PROCEDURE SET
PS 5A Hydrocarbons
A1C13 (RON 16) KMn04 (RGN 28) (RGN 29)
PS SB Oxygen RGN's
pH (RGN 3)
(RGN 34)
DNPH {RGN 5
Hydroxamate
Ferric Chloride
Oxidation
Vanadate
or 19) Schiff's
(RGN 13) Iodine
(RGN 31)
(RGN 30)
(RGN 4, 31)
(RGN 5)
(RGN 14)
PS 5C Nitrogen RGN's
ONPCH (RGN 9) (RGN 18)
OMAB Glut. Aid (RGN 8)
Oxamlde (6 or 2&) DBTFB (RGN 7)
Tetrabase ___ (RGN 27)
PS 5D Sulfur RGN's
Copper Chloride (RGN 12)
Lead Acetate _____ (RGN 20)
PROCEDURE SET 6
Phosphomolybdic Acid (RGN 21, 22, or 23)
ZnS (RGN 24~]
Zirconium ATTzIrinate (RGN 15)
REACTIVITY CLASS(ES) (circle)
15 9 13 17 21 25 29 33 102 106
2 6 10 14 18 22 26 30 34 103 107
3 7 11 15 19 23 27 31 35 104
4 8 12 16 20 24 28 32 36 105
Comments:
Figure A-8. Hazardous waste compatibility field test results (page 2 of 2)
115
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A. 4. 1.2 Redox Tests (RGN's 104 and 105)-
To test for reducing agents filter paper strips impregnated with
methyl ene-blue and/or with 2,6-dichloroindophenol are spotted with the liquid
or dissolved test material. Strong reducing agents decolorize both methyl ene
blue and 2,6-dichloroindophenol. Weak reducing agents decolorize
2,6-dichloroindophenol only, which turns pale pink and then colorless.
Oxidizing agents are tested by spotting the liquid or dissolved test
material on potassium-iodide starch paper which turns purple when an
oxidizing agent is present.
1. Methyl ene blue: 0.2g of methyl ene blue are dissolved in 100 ml of
water,,
2. 2s6-dichloroindophenol : 0«,2g of 2,6-dichloroindophenol are
dissolved in 100 ml of ethanol .
3. Kl/starch paper: Potassium-iodide starch paper (VWR Scientific)
4. Filter paper strips: Whatman filter paper disks were impregnated
with the indicator solutions, dried, cut into strips and stored in
closed glass vials. The papers can be used for at least 3 months.
A • 4 « 2 PS_2_ -_-_ _Sp 1 u t i on - R e a c t i v 1 _ty_ a n d_ _S_p e cj_a j_ Furictjjo naJJ ty_Jes_t s_
A. 4.24 Solution-Reactivity Tests--
The reactivity of the compounds is tested with water, concentrated
nitric acid, concentrated sulfuric acid, 3M sodium hydroxide, hexane,
toluene, acetone, and methanol . The test material is placed on a ceramic
spotplate -- 2 drops or a small spatula tip per cavity for each reagent.
Then I to 3 drops of the reagents are added and the reactions are recorded
The reaction characteristics recorded are: solubility/rcisci&ility,
coloration., gas evolution, fuming, charring, precipitation,, vno.ence of
reaction. In cases where the mselbi'sity or formation of a precipitate is
difficult to observe, the reaction mixture is drawn into a Pasteur pioel 4"
better observation,
A. 4. 2. 2 Cyanide Test —
Cyanide is determined by treating 2 to 3 drops of the hquid ^-iste
solution in water with 1 drop of chloramine T solution followed by ' drop or
pyridine-barbituric acid solution. If the solution turns <; dcrjt wl :>;-
carmine after 10 to 30 sec, it is a positive response,
-------
Reagents:
1. Chloramine T solution: Ig of chloramine T is dissolved in 100 ml of
distilled water.
2. Pyndine-barbituric acid: 1.5g of barbituric acid (Aldrich Chemical
Company) is mixed with 5 ml of water and 7.5 ml of pyridine. The
mixture is treated with 1.5 ml of hydrochloric acid (concentrated),
and diluted to 25 ml.
A.4.2.3 Sulfide Test —
Prqoedure:
The presence of sulfide is determined by placing a strip of lead-acetate
paper moistened with 1 drop of water over the spotplate cavity containing
2 to 3 drops of the waste solution and 1 to 3 drops of 3M hydrochloric acid.
Black PbS forms on the paper after 0.5 to 1 min if sulfide is present.
_Rea£ent_s:
1. 3M HCL: 25 ml of concentrated hydrochloric acid is diluted to
100 ml with distilled water.
2. Lead-acetate paper: (VWR Scientific)
A.4.2.4 Copper Sulfate Test for Water--
Liquid waste materials are tested for the presence of water with
anhydrous copper sulfate. A small spatula tip of anhydrous copper sulfate is
treated with a few drops of waste material in the depression of a porcelain
spotplate. The copper sulfate turns dark blue in the presence of water.
1. Copper sulfate: anhydrous copper sulfate (CuS04) is used.
A •4 •3 PS_3_nJ:lam§_!§sti
PTOcedure:
Depending on the type and intensity of the reaction, the flame test is
carried out with a wire loop, a spatula, or with a ceramic spoon.
Mire Loop. The wire loop is dipped in concentrated hydrochloric acid
and heated until the flame regains its original color. After dipping the
wire in distilled water, a few crystals or drops of the compound are scooped
up and kept just above the flame for a few seconds. Then it is lowered into
the hot part of the flame and the reactions such as color of flame, smoke,
sparking, and residue are observed and recorded.
Spatula. To observe residues from inorganic salts, or when the
observations with the wire loop are inconclusive, it becomes necessary to use
117
-------
more material. The spatula tip is cleaned in the same manner as the wire
loop and a spatula-tip full of material is heated.
Cjjirami c _Spqon . A good way to test for residues, especially from
solutions of inorganics or liquids, is to heat the material on a ceramic
spoon,
_Note:
1. It is important to start out with a small amount on the wire loop in
case of a violent reaction of the test material with the flame,
A • 4 • 4 £Sjl_i: iJ^1jJ!H_f^J.i0J[LaJ] d Ferrox Test
A. 4,4.1 Sodium Fusion Procedure--
procedure:
A spatula tip of the solid test material or a few drops of the liquid
test material is placed in a 4-in. Pyrex test tube. A pellet of sodium is
added and the mixture is carefully heated to a red glow. In some cases a
light flash can be observed when the sodium reacts with the test material,
When the mixture is still red-hot, more test material is added and the
mixture is again heated to a red glow. After cooling, methanol is added
dropwise to destroy the excess sodium. After all bubbling has ceased about
2 ml of distilled water is added and the mixture is filtered. The filt;ete
is then tested for cyanide, sulfide, halide, and phosphate according to
procedures A, 4. 4. 1.1 through A. 4. 4. 1.4. The tests can be performed in a
ceramic spotplate or by transferring small portions of the test, mixture to
small test tubes.
1. Sodium pellets in mineral oil.
2. Methanol .
A few classes of organic compounds such as nlcroaikanes,
azides, diazo esters3 diauonium salts, and some aliphatic
polyhalides (chloroform, carbon tetrachloride) react expl
with hot sodium or m^gne^ium. Safety £
ons »&
Notes:
1. This test must, be carried out 1r a wel i-ventilated area behind a
safety shield.
2. It is recommended that explosive materials not b^- sutj^c'.ed to ;.,a
sodium fusion
113
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A.4.4.1.1 Cyanide test for nitrogen (N)--
Pjyceduire:
Nitrogen is determined by treating 2 to 3 drops of the fusion extract
with 1 drop of chloramine T solution followed by 1 drop of pyridine-
barbituric acid solution. If the mixture turns a dark red or carmine after
10 to 30 sec, it is a positive response,
jteac[ents_;
1. Chloramine T solution: Ig of chloramine T is dissolved in 100 ml of
distilled water.
2. Pyridine-barbituric acid: 1.5g of barbituric acid (Aldrich Chemical
Company) is mixed with 5 ml of water and 7.5 ml of pyridine. The
mixture is treated with 1.5 ml of hydrochloric acid (concentrated),
and diluted to 25 ml.
3. Ferric chloride: 13.5g of ferric chloride (Feds) is dissolved in
100 ml of distilled water and 2 ml of concentrated hydrochloric
acid.
_Note:
1. Some organic materials containing both nitrogen and sulfur form
thiocyanate and give a negative cyanide test. Therefore, if a
negative cyanide test and a positive sulfide test are obtained, the
fusion extract is tested for thiocyanate. Two drops of fusion
extract are treated with one drop of dilute hydrochloric acid and
one drop of ferric chloride. Red indicates a positive test.
A.4.4.1.2 Sulfide test for sulfur (S)--
Procedure:
The presence of sulfide is determined by placing a strip of lead-
acetate paper moistened with 1 drop of water over the spotplate cavity
containing 2 to 3 drops of the test solution and 1 to 3 drops of 3M
hydrochloric acid. The test paper turns black after 0.5 to 1 min if sulfur
is present.
Reajjentjj,:
I. 3M HCL: 25 ml of concentrated hydrochloric acid is diluted to
100 ml with distilled water.
2, Lead-acetate paper: (VWR Scientific)
A.4*4.1.3 Silver nitrate test for halogen (X)--
Procedure:
To the acidified (1 to 2 drops nitric acid) filtrate a few drops of
silver nitrate solution are added. A precipitate indicates the presence of
119
-------
Cl'(white)5 Br~(light brown), or I"(pale yellow). If sulfide or cyanide is
present In the fusion extract it is removed by boiling 1 ml of the fusion
extract with a few drops of 3M HN03 before carrying out the halogen test.
Reagenlts:
1. Silver nitrate solution: 1.69g of silver nitrate dissolved in
100 ml of distilled water.
2. 3M HN03
A.4.4.1.4 Phosphate test for phosphorus (P)--
_Procedure:
To 2 to 3 drops of the test solution, 2 drops of ammonium molybdate
solution are added. A bright yellow precipitate indicates the presence of
phosphate. The test result might be obscured when the fusion filtrate 4s
colored.
R^eajent;
1. Ammonium molybdate solution: 6g of ammonium molybdate,
(NH4)6Mo/024 • ^HgO (J. T. Baker Chemical Company) are dissolved in
150 ml of water and 35 ml of concentrated hydrochloric acid.
A.4.4.1.5 Alternate phosphate test for phosphorus—
P£p_ced_ure:
To about 2 ml of the test solution, 8 drops of molybdate solution ere
added in a test tube. After addition of 1 drop of stannous chloride the
mixture turns deep blue after 10 to 30 sec in the presence of phosphate, it
is very important to use the reagents in the correct proportions and order
described.
jteagerrtsj
1. Ammonium molybdate/H^SO/i: 5g of (^84)5^07024 • 4H20 are dissolved
in 35 ml of HgO. Then 15.5 ml of" concentrated H;>S04 is added and
the solution is diluted with #ater to ?00 ml after cod ing.
2. Stannous chloride; l.Og of slanneus chloride ^ 2H£G is dissolved -t:
40 ml of warmed (approximately 60°C in a net wdier bai'h) glycerol,
A.4,4.2 Ferrox Test For Organic Compounds Containing Oxygon--
f£ocedjj£e:
A glass stirring rod is dipped into the ether solution of the reaoenl ro
a depth of about 0.5 cm. The ether is allowed to evaporate In to the a-ir, A
few drops of the test solution or an equivalent amount of solid ^ith a f;:i»
drops of methy^ene chloride, chloroform, or hexane ^re placed In the
120
-------
depression of a spotplate. The sample is stirred with the reagent-coated
stirring rod,
A positive test is indicated if the test solution turns red.
Occasionally, some red scratches will appear on the spotplate with a negative
test. (It is advisable to test a small portion of the solvent alone as a
control .)
JReagent;
1.
Ferric hexathi ocyanatoferri ate (ferrox): A solution of 4g of
potassium thiocyanate (KCNS) in 20 ml of water is mixed with a
solution of 5g of ferric chloride (FeCl3 • 6^0) in 20 ml of water.
The solution is extracted with 30 ml of ether. The ether (upper)
layer is stored in a dark container prior to use, and has been found
to be stable for several weeks when stored at room temperature.,
otes
1. Negative tests were obtained for some compounds containing oxygen
bound to nitrogen (i.e., picrates)
2, A positive test that fades was obtained for some easily oxidized
compounds (i.e., mercaptans)
A . 4 . 5 PJLJL -- Organic Functional i ty Tests
A. 4. 5.1 PS 5A -- Hydrocarbon Classification Tests--
A. 4. 5. 1.1 Friedel -Crafts test for aromatic hydrocarbons (RGN 16) --
Procedure:
A small amount of anhydrous aluminum chloride is placed in a 4-in.
test tube and heated with a small hot flame to sublime the A1C13 on the test
tube wall. A small amount of the test material is dissolved in 0.5 ml CHC13
and a few drops of this solution is run down the side of the test tube. On
contact with the sublimed A1C13, aromatic hydrocarbons form brightly colored
products , which range from yellow, orange or red, to blue.
Jteajervtsj
1. Aluminum chloride: anhydrous powder (Aldrich Chemical Company)
2. Chloroform
A sufficiently large amount of A1C13 should be used to cover a
1 to 2 cm2 area of the test tube wall with sublimed Aids to make
the color formation easily visible.
1.
121
-------
2. It is often desirable to determine the presence of the aromatic
structure in the presence of other functional groups (especially
chloride),, This test can be performed in the presence of many
functional groups with little interference,
3. The specific color produced in the test can often be used as an
indicator of the type of aromatic structure present. Some general
guidelines are as follows:
Color Structure Indicated
Yellow, orange, red Monocyclic (benzene)
Blue Bicyclic (naphthalene)
Green Complex aromatic (anthracene)
A. 4. 5. 1.2 Baeyer (Permanganate) test for unsaturated aliphatic hydrocarbons
(RGN 28) —
P_rocedu££:
Five drops of a small amount of the test material in acetone are added
to 2 to 3 drops of KMn04 reagent. If the test material contains unsaturated
hydrocarbonss the reagent is decolorized (with formation of brown MnCh), Tte
reaction occurs instantaneously or after 0.5 to 1 min of stirring.
1. KMn04 reagent: 0.5g KMn04 in 50 ml of acetone
2 . Acetone
Jtote:
1, It is advisable to prepare the reagent immediately prior to use,
This is most conveniently accomplished by piecing 0,,5g of KHnO,] in
an erapcy dropping bottle and adding acetone upon arrival at Lhe te
site.
A. 4. 5. 2 PS 5B — Tests for Functional Groups Conteining Oxygen--
A.4,5.2.1 Peroxide Te~,t (RON 30)-*
One drop of the liquid lest substance or a few crystals of tire lest
material dissolved in water s alcohol, cr acetone is placed on -a peroxide u. -~t
strip. The development of a blue color indu:dles the presence of psr-ox iaes,
the color intensity is an indicator of tlu peroxide concentration,
. Peroxide test strip EM Cuav.t (Merck)
-------
Notes:
1. Oxidizing ions can interfere but they turn the test strip grey to
brown instead of the characteristic blue.
2. The color development requires the presence of traces of water,
which can be achieved by adding a drop of water to the nonaqueous
test solution or by exposing the strip to humid air for 1 to 3 min.
A.4.5.2.2 Vanadate test for alcohols (RGN 4) —
P rocedu re:
A small amount of the solid test material or 1 drop of the liquid test
material are placed in a test tube with 1 to 2 drops of toluene. Five drops
of the vanadate-quinolinol reagent are added and the mixture is wanned with
repeated shaking for about 2 min at about 60°C in a water bath. The mixture
turns a light red-orange in the presence of alcohols.
jteacjerrt:
1. Vanadate-quinolino!: 1.25g of 8-hydroxyquinoline are dissolved in
50 ml of 6 percent acetic acid. One ml of this solution is mixed
with 1 ml of a 0,1 percent aqueous solution of Na3\/04 and then
extracted with 30 ml of toluene. The toluene (upper) layer
containing the quinoline-vanadate reagent is separated from the
aqueous phase and can be used for analysis for 1 to 3 hr.
jjgtes:
1. Some nonalcoholic compounds give a purplish-brown which is not
easily distinguished from the color of a positive reaction. Only
light red-orange with a definite red tint should be considered as
positive.
2. SH~ groups may interfere by shifting the color to a more vellow
tint.
3. Some alcohols containing basic nitrogen or carboxyl groups give a
negative response.
A.4.5,2.3 2,4-Dinitrophenylhydrazine (DNPH) test for aldehydes and
ketones (RGN's 5 and 19)--
P_rocedjjre:
A small amount of the test material is dissolved in ethanol , and
1 drop of this solution is added to 5 to 10 drops of 2,4-dinitrophenylhydra-
zine reagent in a porcelain spotplate. When aldehydes or ketones are present
a thick yellow precipitate appears after 10 to 20 sec which is easily visible
even though the reagent is yellow.
123
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1. 2,4-dinitrophenylhydrazine: Saturated in 2N HCL.
Note:
1. It is important to observe the ratio of reagent to test solution;
the precipitate forms best at excess reagent concentrations.
A. 4. 5. 2. 4 Schiff's test for aldehydes (RGN 5)--
Procedure:
One drop of the test material in ethanol is added to 2 tc 3 drops cf
fuchsin-sulfurous acid reagent. A bright deep-violet indicates the presence
of an aldehyde .
jteajent:
1. Fuchsin-sulfurous acid reagent: O.lg of fuchsin (p-rosam'Hne •
HCL), 1.8g of NaHSOa, and 2 ml of HCL are diluted with water to
100 ml. The reagent should be almost colorless.
2. Ethanol
.Note:
1. Some compounds produce various shades of pink with the reagent,
Only a definite violet is to be considered a positive test,
A. 4.5.2. 5 Hydroxamate test for esters (RGN 13)--
A few drops or equivalent amount of solid is added to 0.5 ml of
hydroxy] ami ne thymol phthalein solution. Then 2N potassium hydroxide in
methane'! is added dropwise until the solution turns blue. After addition 01
5 droos excess NaOH, the solution Is heated tu boiling in a water bath and 2N
HCL is added until the blue disappears, Tnen 1 to ? drops of a 10 percent
ferric chloride solution are added. The solution turns purple- red in the
presence of esters. If & b^own precipitate Is formed ?. to 3 additional drops
of ferric chloride are added. The color will then chang*: to uurcle r" r"^."^
are present.
1. Hydroxylar.rine thympphthalein solution: 7g of hydroxylaTiine * HCL
Is dissolved in IOC* ml of methane! anr! 0.02g of thymo'Iphthaloin are
added,
2. 2N potassium hydroxide: 11«2g of KOH is dissolved in 100 Ti. of
metharso!.
-------
3. 2N HCL: 16 ml of concentrated hydrochloric acid is diluted to
100 ml.
4. 10 percent ferric chloride: lOg of ferric chloride is dissolved in
100 ml of water.
A.4.5.2.6 Iodine test for ethers (RGN 14)--
Procedure;
Five drops of iodine-carbon/disulfide solution are placed in a
spotplate and 1 drop of the liquid or dissolved test material is added. In
the presence of ethers, the purple color of the reagent changes immediately
to a pale yellow or completely colorless. A change of color from purple to
dark yellow or brown is not considered a positive result.
1. A few crystals of iodine are dissolved in carbon disulfide. The
reagent, should be light violet.
Note:
1. A decolorization of the reagent is _not to be considered positive if
later in PS 5D mercaptans are found to be present.
A. 4. 5.2. 7 Ferric chloride test for phenols (RGN 31) —
One to two drops of the test material dissolved in chloroform are
added to 1 drop of FeCl3/pyridine reagent in a spotplate. A strong red,
purple, blue, or green color indicates the presence of phenols. Excess
reagent should be avoided.
1. Fed 3 reagent: Ig of FeCla is dissolved in 100 ml of CHCla. Then,
8 ml of pyridine are added and the mixture is filtered.
2. Chloroform
1. Sulfide or sulfhydryl groups interfere by producing a purple or
green color also. Nitrophenols give a negative test.
125
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A.4.5,3 PS 5C — Tests For Functional Groups Containing Nitrogen--
A.4.5.3.1 Diphenylcarbonhydrazine test for carbamates (RGN 9)~~
£rocedure:
One drop of test solution or equivalent amount of solid is treated
with 1 drop of phenylhydrazine in a small test tube, The mixture is heated
to 195°C in an oil bath for 5 min. After cooling,, 5 drops of nickel su'iface
solution and 10 drops of chloroform are added and the mixture is shaken. A
positive response is indicated by a red color In the chloroform (lower)
layer. The color is best observed by holding the tube to a light.
_Re_ac[einit_s:
1. Nickel sulfate: 5g of nickel sulfate (N1S04) is dissolved in 50 ?ri
of water and 50 ml of concentrated aqueous ammonia is added,
2. Phenylhydrazine: Obtained from Aldrich Chemical Company.
N_otes:
1. Many organic compounds turn brown when they are heated to 19E°C.
Therefore, care must be taken to distinguish a red color froin
charring of an organic material.
2. Isocyanat.es and certain other orgarncs give a positive test,
3. Chloroform
A.4.5=3e? Glutaconic aldehyde test for hydrazines (RGN 8)—
procedure:
One drop of test solution (or an equivalent amount of solid with 3 Co
4 drops of etner) in a expression of a porcelain snotplate I1- treated (v-
order) with I drop of pyridylpyridinium chloride, I drop of IN sodium
hydroxide, and I drop of concentrated hydrochloric acid. A bHod-red spc-h
that appears a few seconds after the addition of the hydrochloric acid is a
positive test (see note).
!„ Pyridylpyridliiii'Pi chloride: Ig of pyr:d> i pyrrJiniun; cHondo
(Aldrich Chemical Company) is dissolved in 100 ,nL of -/later,
2, IN sodium hydroxide: 4g of sodium hydroxide (NaOH) pellets are
dissolved in 100 ml of vater.
3. Hydrochloric aci<1: Concentrated (36 percent) hydrochloric f.cin
(HCL) is used.
4. Ether
-------
1. Some compounds, most notably substituted phenols, turn dark upon
treatment with sodium hydroxide or hydrochloric acid. If a positive
test is observed, refer to the results of solution/reactivity tests
(PS 2) to determine whether the material darkens with acid or base.
If the material darkens with acid or base alone, the test for
hydrazine is not positive.
A«4.5.3,3 Dimethylaminobenzaldehyde (DMAB) test for azo compounds (RGN 8)--
Procedure:
A drop of test solution or equivalent amount of solid in the
depression of a porcelain spotplate is treated with a drop of 4 percent
hydrochloric acid and a few granules of zinc and allowed to stand for 15 minu
The resulting test solution is spotted onto filter paper and allowed to air
dry (10 to 15 min). The paper is then spotted with a drop of
f.-dimethyl-aminobenzaldehyde. An orange to red spot indicates a positive
test (see note).
Reagents:
1. 4 percent hydrochloric acid: 10 ml of 36
is diluted to 100 ml with water.
Notes:
percent hydrochloric, acid
2. P~dimethylaminobenzaldehyde: Benzene is saturated with
p-dimethyl-aminobenzaldehyde (Aldrich Chemical Company),
3. Zinc: Granular zinc (fine) is used.
1. Azo compounds are intensely colored,, If the test material is
colorless, it does not contain an azo compound in appreciable
quantity and the test need not be performed.
2. Certain other compounds give colored products with
p-dimethylaminobenzaldehyde. To confirm a positive test response,
the test should be repeated without the treatment with zinc and
hydrochloric acid. A similar response to
p-dimethylaminobenzaldehyde indicates that the material is not an
azo compound.
3. A decolorization of the test material will normally occur during the
reaction with zinc and hydrochloric acid if the compound is an azo
compound.
4. Benzene is a
caution!
carcinogen and must be handled with appropriate
127
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A.4.5.3.4 Oxamide test for amides and nitriles (RGN's 6 and 26)--
Procedure:
A small portion (2 to 3 drops or equivalent) of test material is nr.ixed
with approximately twice the bulk amount of oxalic acid (^204 * ZHgG) in a
3-in. test tube. The tube is heated carefully in a gentle flame until
melting of the oxalic acid and subsequent bubbling occurs,, Gentle heating Is
continued for an additional 10 to 15 sec, and sublimed oxalic acid is removed
from the upper portion of the test, tube by heating the upper part of the tube
directly. The tube is cooled, and a small portion (about the size of a pea)
of thiobarbituric acid is mixed with the contents of the tube, using a glass
stirring rod. The mixture is heated in an oil bath at 120° to 14Q°C for 5 to
10 min. A positive response is indicated by a dark oreinge or red color,
Reagents:
1, Oxalic acid: Obtained from Aldrich Chemical Company.
2. Thiobarbituric acid: Obtained from Tridon (Fluka) Chemical
Company.
JNotejs:
1. Care^must be taken not to heat the mixture too strongly in the
initial heating step.
2. Thiobarbituric acid is light orange but is easily distinguished from
the dark orange of a positive test.
3. Many organics turn brown when heated. Care must be taken not to
confuse this with a positive test,
4. Concurrent running of a blank with oxalic acid is recommended.
A, 4.5.3,5 Ietj^baj>e__fj^ij3^^ ^ZJjj
" ' ~ ~ ' '
A drop of test solution or equivalent portion of solid test material
is treated with s drop of tetraha.se solution in a 3-"in, test tube. If the
material does not dissolve in the reagent solution, the test material 55
dissolved in a few drops of ethanol before addition of th0 '•eaooni.-
is placed in a container of hoiiing water for 2 to 3 mio9 then v,ilhd
positive response is indicated by a yellow to orange color in the bottom af
the tube.
teagervt:
1, Tetrabase solution: Sg of 4,4'-methyl3nebis (N.N-dimethylam'1 irt-:1
(tetrabase -- Tridon-Flu^a Chemical Company) in K:0 ml of tolu^e,
-------
Note:
1, Care should be taken to ensure that water does not enter the test
tube while heating in the water batho
A,405.3*6 p-Nitrobenzene-diazonium Tetraf luoroborate lest, for Phenol •. and
Amines (RGN 31) —
Procedjjre:
A small amount of the test material is added to 3 to 4 drops of
p-ni trobenzerte-di azoni urn tetraf luoroborate reagent. A reds orange, or yellow
precipitate indicates the presence of phenols or amines,,
Reagent:
1. p»Nitrobenzene-diazoniuni tetrafluoroborate; ly in 100 ml of water,
_NjJte:
lc Ortho- and para-substituted phenols ana amines give a neyatv-e
reaction with the exception of picric acid and dipicrvlcniiine which
show a positive reaction since they form yellovi to orange
precipitates at the reaction pH» Interferences are: a.'onia-t ic
SH-groups and isocyanates that hydro lyze at acidic, conditions to
amines, p-Hydroxyacetophenone gives a negative reaction,
A. 4. 5, 4 PS 5D — Tests for Functional Groups Containing Sulfur--
A. 4. 5. 4.1 Cupric chloride Lest for dithiocarbamates (RGN 12)--
P_roceduj'_e:
To a mixture of 1 drop of the liquid test material or a small amoum:
of the solid test material and 2 drops of methanol in a spotplate, 2 drops of
cispric chloride acetic acid reagent are added., A brown precipitate or brow.''
coloration indicates the presence of dithiocarbomat.es. When it is difficult
to decide whether the precipitate or brown color constitutes a positive
react.ions the addition of 1 to 2 drops of CHCi3 will extract the brown
product from the aqueous phase and even small amounts of dithiocarbontates co.'i
be observed.
.Reagent :
Notes:
Cupric chloride acetic acid: Ig of CuCl? is dissolved in 50 rnL
water and 50 ml of acetic acid,
The test can also be carried out. in a test tube with larger amounts
of test material and this is preferable when the addition of
is required for better color observation.
129
-------
2, Copper nitrate (Cu(N03)2) can be substituted for copper chloride for
this test,
A. 4.5.4.2 Lead acetate test for mercaptans (RGN 20)--
Procedure^:
One drop of the dissolved test material is added to 1 to 2 ml of a
saturated solution of lead acetate in ethanol . A lemon-yellow precipitate
appears immediately when thiol groups are present.
1. Lead acetate: Saturated solution of lead acetate in ethanoL,
_Note:
1. The test can also be carried out in a spotplate with 0.5 to i ml cr.
reagent and 1 drop of a more dilute solution of the test material
2. Disulfide groups can be detected with this test after reducing the
test material with 1 mL of 3 IN solution of hydroxylamine * HC1 in
metharsol and some zinc powder,
3. A white precipitate may be formed, but. this should not be
interpreted as a positive test,
A. 4. 6 fSJLj^iJLn^LS^^
A. 4.6.1 Zirconium Alizarinate Tesr, For Fluorides (RGN 15)---
.Procedure :
four drops of a mixture of equal amounts of zirconium nitrate and sodium
alizarin sulfonata solution are placed in a spotpiate and 1 to 2 drops cf r,n«
test mal'rnol dissolved in water or a'coiio1, or a snail amount of so1 id -ir-e
added. In the presence of fluoride ions the burgundy reagent turns yellow.
1., Zirconium nitrate so'lutio.T: G,05q oi £r{N03)p disseised *n 50 ml r
-------
of sodium alizarin sulfonate. The paper is then washed with water
and dried.
2. Fluoride from organic fluoro compounds can be detected only after
fusion with sodium.
A. 4. 6. 2 Tests for Metals and Metal Compounds--
A. 4.6. 2.1 Phosphomolybdate test for metals (RGN 21, 22, 23)--
Procedure:
A small amount of test material is added to 2 drops of phosphomolybdic
acid and placed on a spotplate. When elemental metals are present a deep-
blue color develops around the test material forming a blue solution after
0.5 to 1 min and/or after stirring with a glass rod.
1. Saturated phosphomolybdic acid (Aldrich Chemical Company)
_Note:
1. Aluminum did not give a positive reaction.
A. 4.6. 2. 2 Sulfide test for metal ions (RGN 24)--
Two drops of the test solution, acidified with nitric acid (5 percent)
are placed in a spotplate. After adding a few grains of zinc sulfide a
black, grey, or yellow precipitate indicates the presence of metal ions. If
the response is negative, ammonium sulfide is added until the solution turns
slightly alkaline. A precipitate indicates the presence of heavy metal ions.
Metallic elements or salts, which may be present in waste materials, must be
dissolved (i.e., in nitric acid) prior to conducting this test.
JReajjents:
1. Zinc sulfide powder (Chem-Service)
2. Nitric acid 5 percent
3. (NH4)2$ 30 percent in water (Chem-Service)
Note:
1. Strong oxidizing agents interfere by converting the sulfide ion to
sulfur.
131
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A. 5 DEVICE FOR TEST MIXING HAZARDOUS WASTE MATERIALS
Two Important criteria for evaluating the compatibility of two or more
substances when mixed together are heat generation and gas evolution. Both
can create hazards in the form of pressure increases and formation of toxic
gases. They are measured with a simple mixing device which is easy to
assemble and use under field conditions. A functional diagram of the device
is shown in Figure A-9.
A. 5.1 Description
The device consists of a 120-mL glass reaction vessel equipped witn a
rubber stopper with holes for a hand-operated glass stirring rod with a
Teflon paddle, a thermocouple (K-type stainless steel, Omega), a buret for
adding liquids, and Teflon tubing which is connected to a 50-mL impinger
bottle. The temperature is measured with a battery-operated digital
thermometer (Omega Model 727C) . The reaction vessel and the impinger bottle
are held in a wooden block; the cavity for the reaction vessel is deep enough
to provide protection in the event of glass breakage but still permits visual
observation of the reaction. The reaction vessel is held by a clamp and
metal stand.
A . 5 , 2
Violent reactions during mixing can be avoided by mixing sma'M amounts
of the test materials in a test tube before carrying out the reaction in the
mixing device. If the mixture creates heat or forms gases or fumes in test
tube quantities no mixing with larger quantities is necessary. In case of
unpredicteds high pressure buildup inside the mixing vessel, the release? of
the stopcock will prevent the glass vessel from shattering. The experiment
should be carried out behind a safety shield to avoid accidents.
A . 5 . 3 £rocedjjre
The mixing tests are carried out by placing 3 to 5g of the solid or 3 t
5 ml of the liquid test material in the reaction vessel, then closing the
stopper, and adjusting the thermocouple so it reaches into the test mater a1
The impinger is filled with 10 ml of water and connected tc the reaction
vessel. The temperature of 'che test fnatef ial is recorded before the sacor--;
liquid) test material is acLle-;1 from a bur;-:-,, the stopcock Is closed
both materials are mixed by turning the stirrint. roc* The reaction ic
observed for foaming s color changes, fumes, and temperature changes,, Gus
evolution is observed as bubbles appearing 5n the iinp":nger solution. If
desired,, the impinger solution c^n be analyzed for Ss, CM", C03~, CV", Br" ,
I", SCN~9 and pH» The procedures outlined in Section A, 4 and below art i»se-~
substituting the impinger solution in each case for the test soKit/'O'v Sc>
Table A-5 for references.
132
-------
Addition
buret
Thermocouple
120-mL
reaction
vessel
Digital
thermometer
Midget
impinger
(ground
glass seal)
Support block
Figure A-9. Test mixing device.
133
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TABLE A-5. REFERENCES FOR ADDITIONAL TESTS OF IMPINGER SOLUlIONS
Sulfide (S=) A. 4, 4. 1.2
Cyanide (CN~) A. 4. 4. I.I
Carbonate (C03=) A. 5. 4.1
Halide (CT, Br"s I~) A.4.4.1.3
Thiocyanate (SCN") A. 5. 4, 2
_I.ndic_at_or_JestLS for Carbpnate and Thiocyanate
The two following tests can be performed on the mixing device implnger
solution to determine if carbon dioxide or thiocyanate IMS been evnlvecL
Reagents for these tests are not, ir. general, in the kit. These lasts do net
identify RGN's but add information to the results of mixing wastes.
A. 5, 4,1 Barium Nitrate Test for Evolution of Carbon dioxide—
P rocedu re :
Approximately i ml of the 'mixing device impinger solution is treated
with 2 to 3 drops of 0.1N barium nitrate solution in a 3-in. test tube, if
the solution turns cloudy or a white precipitate- forms iha,n cirboaate is
pre£umed t:c be present. Compare with a blank (unused) portion or frnpraje,'
solution. The presence of carbonate indicates that carbon dioxide has been
evolved,,
I. Banum/nitrate solution: 2,6y o:
100 ffl of water,,
»2 Ferric Chloride Test *',or Th^cc/--auue-"
Test the impinger solution for p!!. Hclf fi";i a 3 in. test tube with
solution, If the solution is acidic, adjust the pH to si '-ji.-1. ty basic v,^
to 2 drops sodium hydroxide r/nutiOit. Acid approximately r drop^ of iuM
sodium carbonate. Warm gently, it' riGce-isary,, to Dissolve. Aridifv t^e
solution with 6K hyd^GcMofic" ei/;J. Add I 'to 2 drops ferric chic-rldr-
solution, A blood red solution is a positive test for1 thicc^^a'.^,
i34
-------
JReacjerrt:
1. Saturated sodium carbonate solution: Add sodium carbonate with
stirring to warm water until no more dissolves. Decant solution
into storage container.
2. Ferric chloride: 1.35g of ferric chloride (FeCls) is dissolved in
100 ml of distilled water and 2 ml of concentrated hydrochloric
acid.
A . 5 . 5 EjjiJJj?ment LJMai hit ejna n_ce and Reagent Ref i 1 1
Ae5«5.1 Equipment Cleaning--
Test tubes, spatulas, spotplates, and watchgl asses are cleaned between
tests with acetone, methanol , or detergent (Alconox) and water. For this
purpose, 2,000 ml acetone, 2,000 ml methanol, about lOOg of Alconox, test
tube brushes, and cleaning tissue (Kimwipes®) are included in the test kit.
!' no deionized water is available at the test site it can be either carried
in the test kit or a deionizing cartridge (Barnstead DB950) can be attached
with plastic tubing to a tapwater outlet. Deionized water is sometimes
available at local supermarkets. Sufficient quantities of test tubes were
carried during field testing so that used ones needed to be rinsed only at
the site. Final cleaning could be carried out in a laboratory after return
from the test site. Disposable Pasteur pipets are used for sample transfer
and spot testing.
Depending on the solubility of the materials used in the mixing test,
the reaction vessel, stirring rod, addition buret, and thermocouple are
cleaned with acetone or methanol. They are then rinsed with deionized water
and wiped dry with cleaning tissue. The impinger and the connecting tube are
rinsed with deionized water. After completion of the mixing tests all
equipment belonging to the mixing device is cleaned and returned to its
case.
A. 5,5. 2 Reagent Refill-
Several of the reagents used in the kit are stable for only a few weeks
and need to be prepared fresh before each field trip. These are the
pyridine-barbituric acid and iodine-carbon disulfide reagents. It is also
necessary that all reagent bottles be at least half full, which is sufficient
for about 100 specific tests. Some of the reagents have to be prepared fresh
for each test (vanadate-quinolinol , potassium permanganate, acetone), their
components are included separately in the reagent cases and are mixed
according to the instructions given in the respective sections of the
instruction manual. Reagents which degrade in less than 3 weeks are
discarded and prepared fresh. These reagents and their observed degradation
characteristics are:
• Fuchsin-sulfurous acid -- fading of color or color change to brown
• Ferric chloride-pyridine -- precipitation
135
-------
® P-dimethylaminobenzaldehyde ~ appearance of crystals
@ Tetrabase — appearance of crystals or darkening of color
• P-nitrobenzene-diazonium tetrafluoroborate — large amount of
precipitation
e Zirconium alizarinate -- fading or darkening of color
In general it is advisable to prepare fresh reagents if color changes or
precipitates are observed and not to use reagents 3 to 4 months after
preparation. All reagents are easily prepared according to the instructions
given 1n the test manual.
1.36
-------
ATTACHMENT A
REAGENTS FOR HAZARDOUS WASTE FIELD TEST KIT
Reagents
Peroxide test strips
pH paper
Methyl ene blue paper
2,6-dichloroindophenol paper
Kl-starch paper
Lead acetate paper
Sulfuric acid (concentrated)
Hydrochloric acid (concentrated)
Nitric acid (concentrated)
Sodium hydroxide (3M)
Hexane
Toluene
Methanol
Acetone
Hydrochloric acid (3M)
Nitric acid (3M)
Sodium pellets
Chloramine T reagent
Pyridinebarbituric acid
Ferric chloride
Sodium pellets
Silver nitrate solution (0.1M)
Ammonium molybdate — HC1
Stannous chloride -- glycerol reagent
Sodium vanadate solution
Quinol inol/acetic acid
Toluene
Ethanol
D'initrophenyl hydrazine reagent
Fuchsin/sulfurous acid reagent
Hydroxyl ami ne-thymol phthal ei n reagent
Potassium hydroxide/methane!
Ferric chloride (10%)
Quantity
1 vial
2 vials
2 vials
2 vials
2 vials
2 vials
50 mL
50 mL
50 ml.
50 mL
100 mL
100 mL
100 mL
250 ml
100 mL
100 mL
SOg
25 mL
25 mL
25 ml
lOOg
25 mL
25 mL
25 mL
50 ml.
50 mL
250 mL
150 mL
25 mL
25 mL
25 mL
25 mL
25 mL
Section3
(4,5.2,1)
(4.1.2)
(4.1,2)
(4.2.2)
(4.2.2)
(4.4.1.1)
(4.4,1.3)
(4.4.1.4)
(4.4.1.5)
(4.5,2.2)
(4.5.2.2)
(4.5.2.3)
(4.5.2.4)
(4.5.2.5)
(4.5.2.5)
(4.5.2.5)
Indicates section in which directions for preparation are given
137
-------
Reagents Quantity Section2
Iod1ne/C$2 25 ml (4.5,2.6)
ferrox reagent 25 ml (4.4,2)
Ferric chloride/pyridine reagent (4.5.2.'')
Phenylhydrazine 25 ml (4.b.3.1)
N1S04 reagent 25 ml (4.5.3.1)
Chloroform 150 ml
Pyridylpyridinium chloride 25 ml (4.5.3.2)
Sodium hydroxide (1M) 25 mL (4.5.3.2)
Hydrochloric acid (4 percent) 25 ml (4,5,3.3)
Dimethyl ami nobenzaldehyde solution 25 ml (4,5.3.,3)
Granulated zinc 25g
Oxalic acid (solid) 50g
Thlobarbitun'c acid (solid) 50g
Tetrabase solution 50 ml (4.5.3,5;
Cupric chloride-acetic acid solution 25 ml {4.5£«J}
Lead acetata-ethanol reagent 25 ml (4.5.4.2)
Hydroxylamine hydrochloride (1M) 25 ml (4 ,,5.4.2)
Zirconium-alizarin test, paper 1 vial (4.6.1)
Potassium permanganate/acetone 50 ml (4,5.1.1)
Aluminum chloride 50g (4.5.U2)
p-Nitrobenzenediazonium tetrafluoroborate 50 nil (4«592«,8)
Phosphomolybdlc acid bG ml (4.6.2.1)
Zinc sulflde 2bg
Ammonium sulfide "~ 25 m!. (4,6.2.2)
a!naicates section In which directions for preparation are g'«ven
138
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ATTACHMENT B
EQUIPMENT FOR HAZARDOUS WASTE FIELD TEST KIT
Equipment
Porcelain spotplates
Spatulas (stainless steel)
Ceramic spoon
Pasteur pi pets
Wire loops
Glass rods
Beakers (250 ml)
Beakers (150 ml)
Lighter for propane torch
Propane torch
Extra flame tips
Extra propane cylinders
Forceps
Test tubes (4 in.)
Test tubes (3 in.)
Test tube racks
Test tube holder
Funnels
Pi pet bulb (large)
Pasteur pi pet bulbs
Bottle with oil (glycerol)
Filter paper (4 in.)
Kimwipes
Large wipes
Watchgl asses
Separatory funnels (30/60/125 ml)
Graduated pi pets (5 ml)
Graduated pi pet (10 ml)
Scissors
Screwdriver
Pliers
Parafilm
Sample vials
Rack for vials
Clamps
Quantity
6 each
3 each
3 each
2 boxes
3 each
15 each
3 each
6 each
2 each
I each
3 each
1 each
2 each
2 boxes
2 boxes
2 each
4 each
10 each
2 each
12 each
1 each
2 boxes
2 boxes
1 box
6 each
1 each
2 each
1 each
1 each
1 each
1 each
1 roll
30 each
1 each
2 each
Cooler
2
1
1
2
1
i
i
2
2
1
1
1
3
1
3
3
1
1
2
2
2
3
2
2
2
2
2
2
2
1
1
1
2
3
3
2
Box
B
A
A
A
A
A
D
D
B
B
B
K
C
H
I
CSD
A
C
A
A
L
B
D
D
B
D
D
D
B
B
B
8
G
G
D
139
-------
Equipment
Ring support
Stand
Wire screens
Acetone
Methanol
Glycerol
Tyvac coveralls
Safety shield
Latex gloves
Solvent gloves
Safaty glasses
Safety goggles
Respirator
Haste solvent container
Garbage bag(s) for disposal
of contaminated pi pets, etc.
M1xing__device
Glass vessels
Buret
'Stopper no, 10 with 4 holes
Tygon/Teflon tubing
(approximately 8 in. long)
Impinger bottle
31 ess stirring rod/paddle
Thermocouple , digital readout
Support/wooden racfc
S^SI=MJ=.S*=aK^E=SK=3e=SE*^S=3--!pi=S
Quantity
1 each
1 each
3 each
29000 ml
2S000 ml
250 ml
3 each
1 each
1 box
1 pair
2 pairs
2 pairs
1 each
1 each
As needed
2
2
2 or 3
2 pieces
2
1
A
i
1
Cooler
2
2
1
3
3
3
3
2
3
3
3
3
3
3
Bo*
D
D
B
C
G
L
A
D
E
E
E
8
Pencil?, pens
Labels9 forms
-------
ATTACHHENT C
KIT ORGANIZATION
VA\\ \V\ \\\ A \ \ \\\\A\\
A Spatulas, ceramic spoons, hire loops, glass rods, test tube
holders, pipet bulbs
B Lighter, flame tips, stand for propane torch, forceps, wire
screens, scissors, pliers, screwdriver
C Test tube rack and 4-1n. test tubas
D Test tubs rack and 3-1n. test tubes
E Reagents for PS 1, PS 2, PS 6
F Reagents for PS 4, PS 5A
G Reagents for PS SB
H Reagents for PS 5C, PS 50
Equipment organization — cooler 1.
141
-------
A Pasteur pi pets
8 Sptt.pl a tas
C Separatory furinals
0 Beakers
I Safety shield
tqui prisent orqani 7.a11 or> -~ coo i 2r H
p^l.
tii "
N[ R
-•HM
i i\ >
A '-'IpstE- ?(\>tr i.sf;,1 , !'ti-'!?5(; !•>, bei^er,-
B Filtar parjer, wstc jjjSuJC'.^, par;;fi!i«iv sxtra ..ai
C Ppr'ci".-, ptri'ij i-.i 'if-;. ',-j:rt-]s, tsiss
' "' "<' • • r-' .--'Tt- -
-------
A Latex gloves
B Mixing device
C Wash solvents (acetone, methane!)
D Acid gloves
£ Respirators, goggles
F Safety suits
6 Rack with sample rials
h Test tubes, 4 ir*.
I Test tubes, 3 in.
J Sodium hydroxide and barium nitrate solutions
X Propane tanks (2)
Glycerol
Behind cutaway
Equipment organization — cooler 3.
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