EPA 670/2-73-053-1
August 1973
Environmental Protection Technology Series
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY OR
DISPOSAL OF HAZARDOUS WASTE
Volume XII Inorganic Compounds
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
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EPA-670/2-73-053-1
August 1973
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY
OR DISPOSAL OF HAZARDOUS WASTE
Volume XII. Industrial and Municipal Disposal
Candidate Waste Stream Constituent Profile Reports
Inorganic Compounds
By
R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto
G. I. Gruber, M. J. Santy, and C. C. Shih
TRW Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-03-0089
Program Element No. 1D2311
Project Officers
Norbert B. Schomaker
Henry Johnson
Solid and Hazardous Waste Research Laboratory
National Environmental Research Center
Cincinnati, Ohio 45268
Prepared .for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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REVIEW NOTICE
The Solid Waste Research Laboratory of the National Environmental
Research Center - Cincinnati, U.S. Environmental Protection Agency has
reviewed this report and approved its publication. Approval does not
signify that the contents necessarily reflect the .views and policies of
this Laboratory or of the U.S. Environmental Protection Agency, nor does
mention of trade names of commercial products constitute endorsement or
recommendation for use.
The text of this report is reproduced by the National Environmental
Research Center - Cincinnati in the form received from the Grantee; new
preliminary pages and new page numbers have been supplied.
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FOREWORD
Man and his environment must be protected from the adverse
effects of pesticides, radiation, noise and other forms of pollu-
tion, and the unwise management of solid waste. Efforts to protect
the environment require a focus that recognizes the interplay between
the components of our physical environment—air, water, and land.
The National Environmental Research Centers provide this multidisci-
plinary focus through programs engaged in:
» studies on the effects of environmental
contaminants on man and the biosphere, and
« a search for ways to prevent contamination
and to recycle valuable resources.
Under Section 212 of Public Law 91-512, the Resource Recovery
Act of 1970, the U.S. Environmental Protection Agency is charged
with preparing a comprehensive report and plan for the creation of
a system of National Disposal Sites for the storage and disposal of
hazardous wastes. The overall program is being directed jointly by
the Solid and Hazardous Waste Research Laboratory, Office of Research
and Development, National Environmental Research Center, Cincinnati,
and the Office of Solid Waste Management Programs, Office of Hazard-
ous Materials Control. Section 212 mandates, in part, that recom-
mended methods of reduction, neutralization, recovery, or disposal
of the materials be determined. This determination effort has been
completed and prepared into this 16-volume study. The 16 volumes
consist of profile reports summarizing the definition of adequate
waste management and evaluation of waste management practices for
over 500 hazardous materials. In addition to summarizing the defini-
tion and evaluation efforts, these reports also serve to designate a
material as a candidate for a National Disposal Site, if the material
meets criteria based on quantity, degree of hazard, and difficulty of
disposal. Those materials which are hazardous but not designated as
candidates for National Disposal Sites, are then designated as candi-
dates for the industrial or municipal disposal sites.
A. W. Breidenbach, Ph.D., Director
National Environmental Research Center
Cincinnati, Ohio
m
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TABLE OF CONTENTS
VOLUME XII
INDUSTRIAL AND MUNICIPAL DISPOSAL CANDIDATE
WASTE STREAM CONSTITUENT PROFILE REPORTS
Inorganic Compounds
Page
ALKALI AND AMMONIUM FLUORIDES - Ammonium Bifluoride (544),
Ammonium Fluoride (23), Potassium Bifluoride (545), Potassium
Fluoride (346), Sodium Bifluoride (546), Sodium Fluoride (389) ... 1
Aluminum Fluoride (16), Barium Fluoride (470), Cadmium
Fluoride (478) 23
Aluminum Oxide (465), Asbestos (468), Calcium Phosphate (95),
Coal (488), Magnesium Oxide (247), Sulfur (413), Vanadium
Pentoxide (513), Zinc Oxide (460) . . 33
Aluminum Sulfate (17), Calcium Chloride (90), Calcium
Hydroxide (94), Calcium Oxide (483), Potassium Sulfate (352),
Potassium Sulfide (353) 55
Ammonium Chloride (20), Ammonium Nitrate (24), Dehydrated
Borax (381), Potassium Phosphate (351), Sodium Carbonate (383),
Sodium Nitrate (396), Sodium Orthophosphates (401) 73
Ammonium Hydroxide (19), Boron Chloride (62), Carbon Monoxide (99),
Hydrochloric Acid (aq) (214), Hydrofluoric Acid (aq) (216),
Hydrogen Chloride (g) (217), Hydrogen Peroxide (aq., >52%),
Iodine (tincture) (223), Mixed Acids (277), Nitric Acid (299),
Nitrous Oxide (313), Silicon Tetrachloride (369), Sulfur
Dioxide (414), Sulfuric Acid (415), Sulfurous Acid (416),
Sulfuryl Fluoride (417), Sulfur Trioxide (509) . . . 91
Ammonium Perchlorate (25), Ammonium Persulfate (26), Calcium
Hypochlorite (482), Magnesium Chlorate (246), Sodium Carbonate
Peroxide (384), Sodium Hypochlorite (222), Sodium
Perchlorate (399), Zinc Chlorate (455) . . 129
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TABLE OF CONTENTS (CONTINUED)
Ammonium Sulfide (29), Antimony Pentachloride (35), Antimony
Trichloride (41), Calcium Carbide (39), Calcium Hydride (93),
Lithium Aluminum Hydride (244), Potassium Binoxalate (342),
Potassium Hydroxide (347), Potassium Oxalate (348), Sodium
Amide (375), Sodium Hydride (391), Sodium Hydrosulfite (392),
Sodium Sulfide (404), Sodium Thiocyanate (406), Stannic
Chloride (408), Thiocyanates (432) 145
Antimony (33), Antimony Trioxide (45) 175
Antimony Pentasulfide (37), Antimony Sulfate (39), Antimony
Trisulfide (40), Arsenic Pentaselenide (467), Calcium
Fluoride (92), Metallic Mixture of Powdered Magnesium and
Aluminum (260), Silica (368), Tantalum (510) 187
Antimony Potassium Tartrate (38) 207
Arsenic (46) 213
Arsenic Trichloride (50) 219
Barium Carbonate (52), Barium Chloride (53), Barium Cyanide (469),
Barium Nitrate (471), Barium Sulfide (472) 227
Beryllium Carbonate (473), Beryllium Chloride (474), Beryllium
Hydroxide (475), Beryllium Oxide (476), Beryllium Powder (59),
Beryllium Selenate (477) 243
Boric Acid (60) 259
Boron Trifluoride (63) 267
Bromic Acid (64) 275
Bromine (65) 281
Chlorosulfonic Acid (112) 289
Chrome (113) 295
Cobalt Chloride (489), Cobalt Nitrate (116), Ferrous Sulfate (198),
Stannous Chloride (409) 301
Copper Nitrate (121), Copper Sulfate (122) 313
Hydrazine (212) 327
VI
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PROFILE REPORTS ON
THE ALKALI AND AMMONIUM FLUORIDES
Ammonium Bi fluoride (544
Potassium Bi fluoride (545
Sodium Bi fluoride (546
, Ammonium Fluoride (23),
, Potassium Fluoride (346),
, Sodium Fluoride (389)
1. GENERAL
Introduction
The alkali and ammonium fluorides are similar in their chemistry,
toxicology, and other hazards. Because of this, ammonium fluoride, ammonium
bifluoride, potassium fluoride, potassium bifluoride, sodium fluoride, and
sodium bifluoride are included in a combined Profile Report.
Ammonium Fluroide
Ammonium fluoride is a colorless, crystalline deliquescent solid, sup-
1492
plied commercially as a granular powder. The salt decomposes on
1433 1492
heating, and corrodes glass. The physical and chemical properties
of NH.F are summarized in the attached worksheet.
The salt is prepared by the reaction of anhydrous ammonia and ice-cold
40 percent hydrofluoric acid:
HF
NH4F
The major uses of ammonium fluoride are:
(1) etching and frosting glass,
(2) as antiseptic in brewing beer,
(3) as mothproofing agent,
(4) in preserving wood
(5) in printing and dyeing textiles.
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Ammonium fluoride has been suggested as an intermediate in the
manufacture of acid-grade CaF2 (fluorspar) from -by-product fluosilicic
acid produced in very large quantities by the wet phosphoric acid process.
The proposed reactions, which have been investigated on a laboratory and
pilot scale are:
H2SiF6 + 6 NH3 + 2 H20
Ca(OH)2 + 2 NH4F 4 "CaF^ + 2 NH3*.+ 2
Ammo n i urn Bi f 1 uo r.i de
Ammonium bifluoride is a white, crystalline, transparent solid.
Solutions of the salt are acid, and the dry crystals have an acid odor. The
commercial product is marketed in flake form, and is hygroscopic at
humidities above 50 percent. Ammonium bifluoride corrodes glass readily.;
it should be stored in a tightly closed plaslis;, rubber, wood or parafinned
container.. The attached worksheet contains a summary of physical and chemical
properties.
Ammonium bifluoride is prepared on a large scale by reacting anhydrous
1433
ammonia and anhydrous HF:
NH3 + 2 HF •* NH4 HF2
The gases are injected into a cooled, packed tower, and the resultant
liquid NH* HF2 is flaked on a cooled rotary drum. An alternative process,
used for the production of crystalline NH» HF2, is the batch reaction of
ammonium hydroxide solution with aqueous hydrofluoric acid, followed by
evaporation, cooling, crystallization, and centrifugation. The mother liquor
from the crystallization is recycled to the evaporation step of the process
with the next batch of dilute NH. HF2 solution.
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The major uses of ammonium bifluoride are:
(1) in combination with hydrofluoric acid, as a commercial glass
frosting and etching agent,
(2) as a laundry sour, because of its capability to decolorize
iron stains,
(3) in the removal of silica scale from steam boilers and
automoti ve radi ators,
(4) in the manufacture of magnesium and magnesium alloys,
(5) in brightening aluminum,
(6) in oil well treatment,
(7) in washing glass television tube blanks and faceplates,
greenhouses, and factory windows,
(8) as a fungicide, in treating wood,
(9) in breweries and distilleries.
Potassium Fluoride
Potassium fluoride is a white, transparent, hygroscopic crystalline
powder, available commercially as either the anhydrous salt, or the
dihydrate. Two hydrates are known - KF.2H90, and KF.4H90. The salt is
1492
very freely soluble in boiling water. The anhydrous salt may be
stored in aluminum containers. Aqueous solutions of KF corrode glass
and porcelain. The physical and chemical properties are summarized in
the attached worksheet.
Potassium fluoride is prepared commercially by reacting potassium
carbonate with aqueous hydrofluoric acid. Extreme care is necessary in
judging the neutralization point, since in concentrated solutions both
potassium bifluoride and potassium bicarbonate are stable in the
presence of the other. The resultant neutral solution is concentrated
and cooled. The anhydrous salt is obtained by arresting the cooling at
50 to 55 C and removing the crystals by centrifuging at this temperature.
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If the dihydrate is desired, the solution is cooled to room temperature
and the resulting crystals are centrifuged and packaged as moist crystal.
The anhydrous salt is also prepared in flake form by passing the hot
concentrated solution over a heated rotary drum dryer. Extreme care is
necessary in handling the anhydrous salt to prevent rehydration.
The major uses of KF are:
(1) in the fluorination of organic compounds,
(2) in flux for hard solder (silver solder),
(3) to prevent fermentation
(4) in insecticide formulations,
(5) for frosting glass,
(6) as a solvent, in preparing barium titanate crystals,
(7) as a fire extinguisher in alkali metal fires.
Potassium Bifluoride
Potassium bifluoride is a white, crystalline salt, which assumes one
of two solid forms, dependent upon temperature. Between 194 and 239 C, the
3-form--a soft white solid—is the stable phase. At 195 C, the g-form
changes to the a-form, a hard white solid, stable below 195 C.
Potassium bifluoride is manufactured commercially from potassium
carbonate and hydrofluoric acid. A slight excess of HF over the stoichio-
metric amount is used. The solution is concentrated to a specific gravity
of 45 Baume and cooled to form the crystals. The crystals are separated
by centrifugation, dried, ground and packaged in polyethylene-lined fiber
1433
drums containing 100 or 400 Ibs. The commercial salt contains about
0.5 percent KF.
The major uses of KHFp are:
(1) as an electrolyte, in conjunction with HF, in the preparation
of F2,
(2) as the basis for most silver soldering fluxes,
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(3) in frosting glass,
(4) in the preparation of pure anhydrous HF in the laboratory,
(5) as a co-catalyst, with BF7, in the alkylation of benzene
with olefins.1433
Sodium Fluoride
Sodium fluoride is a white crystalline powder, available commercially
in three grades--90, 95 and 98 per cent purity-- and two densities--
light (37 cubic in./lb), and dense (23 cubic in./lb). Aqueous solutions
are alkaline, and etch glass.
Sodium fluoride is manufactured commercially by reacting soda ash with
40 percent hydrofluoric acid.
Na2C03 + 2 HF -> 2NaF + H20 + CCy
1492
The crystals precipitate immediately, are separated and dewatered,
dried, sized and packaged. The reactors are usually rubber or carbon
brick-lined steel. Process piping is rubber hose, stainless steel, or
plastic-lined steel. Valves are rubber or plastic-lined diaphragm valves,
or plastic-lined plug cocks
The commercial material is packaged in 100 Ib multiwall bags and
125 and 400 Ib fiber drums. Sodium fluoride for insecticidal purposes
must be colored blue. Some states require that the word "Poison", together
with information on appropriate antidotes, appear on the labels of the
packages. Sodium fluoride shipped in interstate commerce must carry a
Manufacturing Chemists Association (MCA) warning label.
The major uses of sodium fluoride are:
(1) as insecticide,
(2) in other pesticide formulations,
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(3) in the fluoridation of water,
(4) in soldering and metallurgical fluxes,
(5) in the manufacture of rimmed steel,
(6) in electroplating,
(7) as a constituent of vitreous enamel and opal glass mixes,
(8) in heat treating salts,
(9) for pickling stainless steel,
(10) as a disinfectant in breweries and distilleries,
(11) as a glue and paste adhesive preservative,
(12) in the manufacture of coated papers.
Sodium fluoride solution is applied topically to the teeth as a 2.percent
solution, for prevention of dental cavities. Sodium fluoride has been
responsible for more lethal and acute cases of fluoride poisoning than all
1988
other fluorides combined.
Sodium Bifluoride
Sodium bifluoride is a white, free-flowing granular material supplied
at a commercial purity of about 99 percent. The material has limited
solubility in water, and decomposes into NaF and HF above 150 C. The
attached worksheet summarizes the chemical and physical properties of
sodium bifluoride.
NaH Fp is made by reacting soda ash or caustic soda with hydrofluoric
acid. An adequate concentration of excess HF is maintained, in order to
crystallize the bifluoride. The slurry is dewatered, dried, screened and
packaged. Spray drying has been used to some extent. Cooling of the
reaction is necessary to avoid self-heating to an undesirably high
temperature. The reactors are usually rubber- or carbon brick-lined steel.
Process piping is rubber hose, stainless, or plastic-lined steel, with
rubber or plastic-lined diaphragm valves or plastic-lined plug cocks.
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Sodium bifluoride is available in 100 Ib multiwall bags and 125, 375
and 400 Ib fiber drums. The salt hydrolyzes readily, and can cause
hydrofluoric acid burns to the skin.
Major uses of sodium bifluoride are:
(1) as a laundry sour and stain remover,
(2) in bleaching leather and treating hides.
(3) in plating tin,
(4) etching and frosting glass,
(5) cleaning stone and brick building faces.
2. TOXICOLOGY
Human Toxicity
The use of the fluorides as insecticides and rodenticides is so
widespread that sodium fluoride is almost a common household preparation.
Because of the innocuous appearance of sodium fluoride prior to the law
requiring that it be colored blue, the white powder was easily mistaken for
powdered milk, baking powder, powdered sugar, corn starch, or pancake flour.
This, coupled with the custom of keeping insecticides in the cupboard along
with soaps and washing powders, produced many tragic cases of fluoride
poisoning.
The alkali and ammonium fluorides, like the other soluble fluorides
can cause both acute and chronic poisoning. Fatal human poisonings
generally have taken place after the ingestion, accidentally or by suicidal
intent, of a large quantity (5 to 10 grams) of sodium fluoride. The course
is violent and brief, with death occurring within two to four hours. The
symptoms of acute fluoride poisoning include extreme nausea and vomiting,
perspiration, salivation, burning, cramp-like abdominal pains, diarrhea,
dehydration and thirst, muscle weakness; hemorrhagic gastroenteritis,
muscle weakness, central nervous depression, cyanosis, shock, weak and
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thready pulse, shallow unlabored respiration, weak heart tones, paralysis
of the muscles of deglutation, carpopedal spasm, spasm of the extremities,
1OQQ
and, in extreme cases, death. Lethal dosages of 1-1/2 to 2 grams (25
1 ggo
to 30 grains) expressed as F, of soluble fluorides have been reported.
Prompt treatment has averted death in one case where 50 to 80 grams
of NaF was ingested.1988 Sevei
as 66 mg (about 1 grain) of F.
I QOO
of NaF was ingested. Severe illness can follow ingestion of as little
Fluoride kills by a blockage of the normal metabolism of the cells,
inhibiting the enzymes involved in essential processes. Vital functions—
e.g., the origin and transmission of nerve impulses—cease. Necessary
bodily functions controlled by calcium, such as blood clotting and membrane
permeability, are interfered with. Cell damage and necrosis produce
massive impairment in the function of vital organs. There is a characteristic
I QOQ
shock-like syndrome terminally.
Treatment of acute fluoride poisoning emphasizes intravenous and
intramuscular injections of 10 percent calcium gluconate solution,
intravenous injection of glucose in isotonic saline, gastric lavage with
lime-water or 1 percent CaClp solution, treatment for shock and dehydration,
and the absolute necessity for quick response.
The bifluorides hydrolyze, and cause hydrofluoric acid burns in contact
with the skin, the mucosa, or the eyes. These burns are extremely painful
and unless treated promptly may result in permanent damage, including loss
of sight.
Chronic industrial fluorosis, called crippling fluorosis, has been
reported in England, Scotland, the mainland of Europe, and Africa; crippling
IQfift
fluorosis, however, has never been seen in the United States. 9 The
disease is not rapidly reversible, and develops after exposures to
relatively large amounts of fluoride over protracted periods. Exposures
such that 20 to 80 mg or more of fluoride are ingested daily for periods
of 10 to 20 years produce the full-blown disease. Crippling effects are
1 QOQ
limited to the skeleton,1300 and include "poker, back," painful and disabled
joints, generalized osteoscleroses, calcification in the tendons and
8
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ligaments, and synostosis. Mottled teeth are a frequent sympton.
Threshold Limit Value (TLV) for fluoride dusts is 2.5 milligrams per
cubic meter as reported by the American Conference of Governmental Industrial
Hygienists (ACGIH). The Federal Water Pollution Control Administration
(FWPCA) Water Quality Criteria recommends permissible limit criteria for
fluoride in drinking water ranging from 1.7 mg/liter to 0.8 mg/liter, for
average daily maximum temperatures ranging from 50 to 90.5 F, and recommends
that water for livestock use contain less than 2.4 mg/liter of fluoride
ion. .The same source indicates a quality requirement of a maximum of
1 mg/liter of fluoride ion in water intended for use by the canned, dried,
and frozen fruits and vegetable industry.
Animal Toxicity
Because of the well-documented history and economic effects of fluorosis
of farm animals, ingestion of fluoride has been investigated extensively in
many species of animals. In general, symptoms of acute and lethal fluorine
poisoning in animals follow those exhibited in man. Sub-acute dosages
produce the symptoms of loss of appetite and starvation. Chronic effects,
listed in order of appearance on exposed animals are:
(1) dental lesions (primarily damage to incisor teeth),
(2) hyperostosis,
(3) lameness,
(4) loss of appetite,
(5) decreased milk production,
(6) diminution in reproduction.
Herbivorous animals will exhibit the symptoms of acute fluorine
poisoning on eating vegetation containing in excess of 5000 parts per million
(ppm) of fluoride. Sub-acute effects were observed in cattle experimentally
fed with vegetation containing 500 to 1200 ppm of fluoride, for time periods
l fififi
ranging from four months to six months.
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Chronic effects, leading to economic losses occur on the continuous
ingestion of food by dairy cattle containing 40 to 50 ppm of fluoride.
Exposure terms of 5 years or more may be required for the maximum economic
loss to occur. Susceptibility varies amongst animal species, ranging from
maximum in dairy cattle, to the lower range in turkeys. The farm animals
affected include dairy cattle, beef cattle, sheep, chickens, and turkeys.
Plant Toxicity
There are, in general, four types of fluoride effects on vegetation:
Visible effects such as necrosis (injured portions of leaves die and become
discolored); diminution in the growth or in the yield of fruit or seeds;
changes in physiological activities, metabolic activities, and cellular
structure with or without visible injury; and deposit or accumulation of
fluoride in the plant with increasingly higher fluoride concentrations in
ififift
its tissues. Plant species vary very widely in sensitivity to soluble
fluorides. Sorghum, citrus, fruit trees, conifers and corn are relatively
sensitive crops. Alfalfa is quite insensitive.
Comparatively little information is available for relating particulate
fluoride levels to vegetation damage in contrast to the large collection
of data on the effects of gaseous fluorides. Generally, the fluoride dusts
are less toxic than the gaseous fluorides. Dissolved fluorides (NaF)
have produced injury resembling that caused by HF in air. Fluoride damage
to vegetation through fluoride contamination of the soil, while possible,
has not been observed in the field, possibly because of the presence of
l fififi
sufficient calcium and aluminum in the soils to inactivate the fluoride
3. OTHER HAZARDS
The alkali and ammonium bifluorides, when moist or in solution, are
extremely corrosive to glass, porcelain, and most common metals of
construction. The bifluorides are non-flammable, but are easily decomposed
on heating, yielding highly toxic HF fumes.
10
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The alkali and ammonium fluorides and bifluorides are toxic to all
life--yeast, other microorganisms, plant life, both harmful and beneficial--
insects, fish and all higher vertebrates. Their use as economic poisons
is based on this toxicity.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, Transportation
Care must be exercised in handling the alkali and ammonium fluorides
to prevent contact of the materials with the skin or eyes, and to avoid
ingestion by inhalation of dust or other means. Food should not be handled
in proximity to the soluble fluorides. In case of contact with the
bifluorides, the skin and eyes should be flushed with cold water for at
least 15 minutes, and prompt medical attention should be secured. In the
case of contact with the normal fluorides, the skin should be washed
thoroughly; contact with the eyes requires medical attention in addition
to thorough flushing with cold water. Contaminated clothing should be removed
and washed before re-use.
The alkali and ammonium fluorides are shipped in screw cap bottles,
for quantities up to 5 Ib; for quantities from 5 Ib to 400 Ib, polyethylene
bag-lined drums or fiber drums are used. In accordance with current
manufacturers liability laws, the containers carry a "Poison" warning label,
and information on treatment and antidotes for accidental contact and
poisoning. The containers should be stored in a cool, dry area, and should be
kept tightly closed.2093' 2094' 2095> 2096
Sodium fluoride shipped in interstate commerce must, as noted earlier,
be colored blue, and must carry a Manufacturing Chemists Association (MCA)
warning label. There are no current Department of Transportation or Coast
Guard regulations which cover shipment or labeling of the other fluorides.
Recommended criteria for acceptable disposal of the alkali and ammonium
fluorides, defined in terms of the recommended provisional limits in the
atmosphere, water, and soil are as follows:
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Basis for
Contaminant in Air Provisional Limit Recommendation
Alkali and Ammonium 0.025 mg/M3 as F 0.01 TLV
Fluori des
Contaminant in Basis for
Hater and Soil Provisional Limit Recommendation
Alkali and Ammonium 0.6-1.7 ppm (mg/1) Drinking Water
Fluorides ' as F Standard
The stringency of the recommended criteria are due to both the acute
and chronic toxicity of the soluble fluorides. Any excess of soluble flu-
orides released to a watercourse will not be decreased by natural action
to acceptable levels for potable water supply, or for farm animal use un-
less the stream percolates through or runs over a limestone bed.
Particulate fluorides, released as aerosol fume, can cause both acute
and chronic fluorosis in plant employees, and can cause economic damage to
crops and farm animals in surrounding areas.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The keystone of any economically feasible process for the minimum
environmental impact disposal of any of the alkali or ammonium fluorides
must involve either recovery of the fluoride portion of the compound for
re-use, or precipitation of the fluoride as calcium fluoride, followed by
separation and impact-free disposal of the calcium fluoride via use as a
fluorspar substitute, or land burial. With the exception noted under
Option No. 1, below, current practice in disposal of the alkali and am-
monium fluorides is to vent the material without capture from high tem-
perature operations such as glass manufacture, vitreous enamel processes,
1 coo
and brick manufacutre, or to flush the fluoride wastes down the sewer
after recovery of the economically valuable metal present. These
practices are unacceptable. Two current disposal practices, and some
possible future options are discussed in the following paragraphs.
12
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Option No. 1 - Tin and Fluoride Pollution Control Process.
A patented process exists for the removal of both the tin and fluoride
contents of plating, wash and tin recovery wastes from halogen tin lines
used in tin plating. Basis for the process is the two-stage addition
of lime slurry to the wastes in two sequential, compartmented reaction and
settling tanks. The underflow from each tank is in part recycled to the
feed, or reaction, compartment of the first tank. Most of the tin is pre-
cipitated in the first tank, and the part of the underflow from the first
tank which is not recycled is sent to tin recovery operations. The major-
ity of the fluoride is precipitated as calcium fluoride in the second tank.
That portion of the underflow from the second tank which is not recycled
is diverted to disposal operations. The overflow from the second tank is
discharged to sewer.
The disposal system employed for the calcium fluoride waste product is
not stated. To allow economic recovery, the discharged, alkaline CaFp slurry
should be lagooned, and the clarified, fluoride-stripped overflow discharged
to sewer. The separated CaF2 should then be dried, and re-used as metal-
lurgical grade CaF2 in steel mill operations. Where economic recovery is
not feasible, the sludge should be added to a landfill.
Option No. 2 - Reaction with Slaked Lime.
The disposal procedure given for package lots of the soluble in-
organic fluorides in the laboratory is to add the fluorides slowly to a
large container of water. Stir in a slight excess of soda ash and slaked
lime. Allow the slurry to stand, settling, for 24 hrs. The supernatant
liquor is then dicanted or siphoned into another container, and neutralized
with dilute hydrochloric acid before being washed into the sewer, with
large quantities of water. The sludge is added to landfill.
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Option No. 3 - Discharge to the Environment
The majority of the sodium fluoride emitted by the glass industry
is vented to the atmosphere. In those few cases where wet cyclones are
employed, the sludge is frequently discharged to sewer. Both of these
practices are undesirable. Glass industry discharged to sewer in 1968 from
wet and dry cyclones contained an estimated 1,700 Ib of NaF. About 80 per-
cent of the NaF thus disposed of was discharged in some 300 tons of dilute
aqueous waste, with the approximate composition 0.2 percent NaF, 4.7 percent
HF, and 95 percent water. The balance of the glass industry NaF wastes were
in the form of slightly over 3,000 Ib of a mixture of NaF and Na2C03, con-
taining slightly over 10 percent NaF.
In the enamel frit industry, about 80 percent of the plants discharge
1 fififl
their NaF fume directly to the atmosphere. The remaining plants fre-
quently discharge material recovered from stack gas to the sewer, without
treatment. These practices are undesirable, and are not recommended. In
1968, the enamel frit industry disposed of an estimated 200 tons of NaF in
waste streams sent to sewer. Over half of the fluoride wastes were in the
form of dilute solutions in water!' The remainder were mixtures of solids —
45 percent NaF and 55 percent Na,,C03.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The alkali and ammonium fluorides are not candidate waste stream con-
stituents for National Disposal Sites. Their treatment by either of the
techniques listed below as recommended procedures is not hazardous, does not
require costly or sophisticated apparatus, and is economically feasible and
technologically practical for waste generation site use.
The procedure recommended for treatment of large quantity, continuous
discharges of the alkali and ammonium fluorides is that of Option No. 1 —
i.e., continuous reaction with an excess of lime, followed by lagooning,
and either recovery or landfill disposal of the separated CaF^. The pro-
cedure recommended for the treatment of package lots and spills of the
14
-------
alkali and ammonium fluorides is that of Option No. 2— i.e., reaction in
solution with an excess of slaked lime, followed by separation of CaF2,
and reuse or landfill disposal of the separated CaFp.
15
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 3d ed. Washington, Manufacturing Chemists,
Association, 1970. 176 p.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards,
Aug. 1971. p. 35-40.
0536. Water quality criteria. Report of the National Technical
Advisory Committee to the Secretary of the Interior.
April 1, 1968. Washington, Federal Water Pollution Control
Administration. 234 p.
0653. Jones, H. R. Environmental control in the inorganic chemical
industry. Park Ridge, New Jersey, Noyes Data Corp., 1972.
249 p.
0766. Sax, N.I. Dangerous properties of industrial materials, 3d
ed. New York, Reinhold Publishing Corp., 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d. ed. v. 9.
New York, Wiley-Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway,
New Jersey, Merck Co., Inc., 1960. 1,634 p.
1668. Robinson, J. M., G. I. Gruber, W. D. Lusk, and M. J. Santy.
v. 1. Engineering and cost effectiveness study of fluoride
emissions control. January, 1972. McLean, Virginia, Office
of Air Programs, Environmental Protection Agency. 356 p.
1988. Simons, J. H. Editor, v. 1. and v. 4. Fluorine Chemistry.
New York, Academic Press, 1940, 1965. 615 p., 786 p.
2093. Product Information Data Sheet. Ammonium Fluoride, crystal,
technical. NH.F DA-32672 New York, General Chemical
Division, Allied Chemical. 2 p.
2094. Product Information Data Sheet. Potassium Fluoride, anhydrous
purified. KF DA-40913 Morristown, New Jersey, Industrial
Chemicals Division, Allied Chemical, 1967. 2 p.
2095. Product Information Data Sheet, Potassium Fluoride, crystal,
purified. KF 2H20. DA-41042 New York, General Chemical
.Division, Allied Chemical. 2 p.
2096. Product Information Data Sheet. Potassium Bifluoride, crystal,
technical. KF. HF DA-41462 New York, General Chemical
Division, Allied Chemical, 1961. 2 p.
16
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H H Name Ammonium Fluoride (23)
~ Structural Formula
IDC Name Ammonium Fluoride
Common Names
Neutra1 Ammonium Fluoride
NH4F
Molecular Wt. 37'04 Melting Pt. Sub1itnes(1) Boiling Pt.Sub1l'mes (1).
Density (Condensed) 1.315 P 25 C^ Density (gas) @ _^ '
A
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 41.8 g/lOOg soln@0 C Hot Water 54.1g/100q soln@0 Ethanol Slightly Sol.
Others:
Acid, Base Properties Aqueous solution acid . •
Highly Reactive withQuinine salts; soluble calcium salts
Compatible with iron (dry)
Shipped in Plastic (polyethylene) bag lined drum; fiber drum
ICC Classification _ None _ Coast Guard Classification _ None
Comments r»ait js deliquescentr Coimiprcial gait ic granular pnu/Hcr — Used in etching
frosting glass; as antiseptir in hrpuing hp>»r; prpgpruing wood; moth proofing agent
References (1) 0766
(2) 1433
(3) 2093
17
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Ammonium 8j fluoride (544)
IUC Name Ammonium Hydrogen Fluoride
Structural Formula
Common Names
Ammonium Acid Fluoride
Molecular Wt.
57.05
u;
Density (Condensed) 1.503
Vapor Pressure (recommended 55 C and 20 Q)
Melting Pt. 126.1 C
_ -_ Density (gas)
Boiling Pt.Subl.
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water 28.45g/100gsolnPO C
Others:
Hot Water85.55g/100gso1neiOO C Ethanol Slightly sol.
Acid, Base Properties Strongly acid in solution
Highly Reactive with glass; silica
Compatible with polyethylene; plastics; rubber; wood; parafjnned paper and fibertoard
Shipped in polyethylene lined drums
ICC Classification None
Coast Guard Classification
None
Comments Used to etch/frost glass; as antiseptic in brewing beer; moth proofing* ';removal
of silica scale (boilers. etc.);oil well treatment: fungicide: laundry soap; in
manufacture of Mg and Mg alloys.
References (1) 1433
(2) 1492
18
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Potassium Fluoride (544)
IUC iMame Potassium Fluoride
Common Names
Structural Formula
Potassium Fluoride
KF
Molecular Wt. 58.10
Oensity (Condensed )2.48r
Melting Pt.
860 C
;_ Density (gas)
Boiling Pt.1505
@ -
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
F 1 ammab i 1 i ty Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper
Upper
Solubility
Cold Water 92.3 g/100
Others: Sol liquid
Hot Water Very sol.
Ethanol
Insol.
Acid, Base Properties
Highly Reactive with
glass, porcelain (corrodes)
Compatible with Aluminum (anhydrous)
Shipped in Polyethylene Dag ]lned drums; screw cap
(3)
ICC Classification
None
Coast Guard Classification None
_ _
Comments Used as silver soldering flux, preparation of ba»-ium titanate crystals'2'
Hydrates very readily to KF.2H?0 _ .
References (1) 1492
(2) 1433
(3) 2094
19
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Potassium Bifluoride (545)
Potassium Hydrogen Fluoride Structural Formula
IUC NaTO K,,F2
Common Names Potassium Acid Fluoride
F ^einy' s salt
Molecular Wt. 78-10 Melting Pt. 239 c (B) Boiling Pt.__Decomposes
Density (Condensed) 2.37 @ 2_ Density (gas) _" P ° "
Vapor Pressure (recommended 55 C and 20 Cj
3 @ " @
Flash Point ~ _ Autoignition Temp.
Flammability Limits in Air (wt %) Lower _ Upper _ - _
Explosive Limits it Air (wt. %) Lower _ Upper _ "
Solubility
Cold Water 24. 5g/ 100m/ go C Hot Water "4g/100m/p80 C Ethanol Inso1
Others: _ ~ _
Acid, Base Properties Strongly acid ___
Highly Reactive with Glass; silica
Compatible with Plastics; rubber
Shipped in Polvethvlene-lined drums : screw cap bottles
(3) '
ICC Classification Coast Guard Classification
Comments Used in silver soldering fluxes; frosting glass; anti-fungal agent for wood;
C' Irolyte for fluorine manufacture. Decomposes on heating, into KF and \\f\_.'
References (1) 1433
(2) 1492
(3)2096
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium_EJUJOride (389)
IUC Name Sodium Fluoride
Common Names Villiaumite
Structural Formula
NaF
Molecular Wt. 42.00
Density (Condensed) 2.78
Melting Pt. 993 C
" Density (gas)
(1)
Boiling PtJ?04 C
&
(1)
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
r 1,4 L, . 4g/100mlG>0 C u «.,,«. 5g/100ml p 100 C V. slight, sol.
Cold Water Hot Water_ Ethanol
Others:
Acid, Base Properties Solution in water is basic
Highly Reactive with_
Compatible with plastics; rubber; paper
multiwall bags and 125 and 400 Ib fiber drums
Coast Guard Classification
None
Shipped in 10(
ICC Classification^0 warning label
Comments Used as insecticide; pesticide: in vitreous enamel and glass mixes; ^
degassing agpnt ; in flux in fluoridating water; in electroplating.—Spdigm fluoride sold
for insprtin'dp imps must HP rnlnroH hliiP Pnicnn lahpl rigq^iro^ by Some States.(2)
References (1)
(2) 1433
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Sodium B1 fluoride (546)
Structural Formula
IUC Name Sodium Hydrogen Fluoride
Common Names Sodium Acid Fluoride
NaHF
2
Molecular Mt. ^-P* Melting Pt. Decomposes Boiling Pt.Decomposes
Density (Condensed) g Density (gas) 9 = ;_
Vapor Pressure (recomended 55 C and 20 0
Flash Point Autolgnltlon Temp.
FlammablHty Limits in A1r (wt X) Lower Upper_
Explosive Limits 1n A1r (wt. X) Lexer Upper_
Solubility*1*
Cold Water 3.25g/100mlg20 C Hot Mater 7.5g/100ml@90 C Ethanol.
Others: ; ,
Acid, Base Properties Solution is acid •
Highly Reactive with &a&s: steel
Compatible with
Shipped in 100 Ib multiwall bags; 125.375 and 400 lb fiber drums
ICC Classification Coast Guard Classification
Comments Used as laundry "sour", In bleaching leather; disinfecting hides; plating tin;
etching/frosting glass; cleaning stone and brick^ Decomposes on heating, to
NaF and HF.
References (1) 1433
-------
PROFILE REPORT
Aluminum Fluoride (16), Barium Fluoride (470), Cadmium Fluoride (478)
o
1. GENERAL
Aluminum Fluoride
Aluminum fluoride is a white crystalline solid, used principally as
an electrolyte component in the electrolytic reduction and refining of
aluminum and as a modifier of glass and enamels in the ceramic industry.
Pure anhydrous aluminum fluoride is extremely difficult to prepare; the
commercial product contains oxyfluoride. The only simple aluminum fluoride
compound occuring in nature is the rare mineral fluellite A1F3 • H20.
Aluminum fluoride used commercially is manufactured by one of the following
processes. In one process used currently aluminum fluoride is prepared
batchwise by solution of alumina hydrate in 15 percent hydrofluoric acid,
followed by continuous crystallization, filtration, and calcination. In
another process, alumina trihydrate is heated to between 400 and 700 C
and allowed to react with gaseous hydrogen fluoride or the HF evolved in
the electrolytic production of aluminum. The recovered aluminum fluoride
is recycled to the molten electrolyte used in the cell. In still another
process an ammonium fluoaluminate intermediate is decomposed to aluminum
1433
fluoride by heating to 700 C. The physical/chemical properties for
aluminum fluoride are summarized on the attached worksheet.
Barium Fluoride
Barium fluoride forms colorless cubic crystals. It is prepared by
treating barium carbonate with hydrofluoric acid. Its principal uses are
as a flux and opacifier in enamel frits and as a white pigment in record
compositions. It is also used to some extent in metal heat-treating baths
and in the manufacture of carbon brushes for electrical generators for
aircraft. The physical/chemical properties for barium fluoride are
23
-------
shown on the attached worksheet.
Cadmium Fluoride
Cadmium fluoride forms white cubic crystals. It is prepared by dis-
solving cadmium, cadmium carbonate, or cadmium oxide in a solution of hydro-
gen fluoride and evaporating to dryness. It may also be made by the addi-
tion of ammonium fluoride to a solution of cadmium chloride. -Cadmium
fluoride is used as a fluoride phosphor in cathode-ray-beam tubes and as
an impregnating agent in carbon brushes of dynamoes to prevent excessive
1433
wear of the brushes. The physical/chemical properties for cadmium
fluoride are summarized in the attached worksheet.
2. TOXICOLOGY
For detailed discussion of fluoride toxicology please refer to the
Profile Reports on the alkali and ammonium fluorides (23, etc.). The Thresh-
hold Limit Value (TLV) for fluoride dusts is 2.5 milligrams per cubic meter.
nope
The recommended permissible limit criteria for fluoride in drinking
water is from 1.7 mg/liter to 0.8 mg/liter, and the recommended maximum con-
centration for fluoride in water for livestock use is less than 2.4 mg/1.
The aluminum ion does not contribute to the toxicity of aluminum fluo-
ride. The toxicity of barium fluoride combines the effects of the fluoride
and barium ions. The toxicity of barium compounds is discussed in the Pro-
file Report on barium compounds (53, etc.). The permissible maximum for
barium in public water supplies is 1.0 mg/liter. Cadmium fluoride toxic
effects are due to both fluoride and cadmium ions. Cadmium is moderately
toxic to all organisms and is a cumulative poison in mammals. The recom-
mended permissible limits for cadmium in drinking water and for farmstead
use is 0.01 mg/1.0536
3. OTHER HAZARDS
The fluorides of aluminum, barium and cadmium, when moist or in
-------
solution, are corrosive to glass, porcelain, and most common metals of con-
struction except nickel.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Care must be exercised in handling aluminum, barium or cadmium fluo-
rides to prevent contact of the materials with the skin or eyes, and to
avoid ingestion or inhalation of dust. Food should not be handled in prox-
imity to these soluble fluorides. There are no current Department of Trans-
portation or Coast Guard regulations which cover shipment or labeling of
these fluorides.
Recommended criteria for acceptable disposal of these fluorides, in
terms of recommended provisional limits in the atmosphere and in water
and soil are as follows:
Contaminant in Air
A1F3
BaF2
CdF0
Provisional Limit
0.025 mg/M3 as F
0.005 mg/M3 as Ba
0.002 mg/M3 as Cd
Basis for
Recommendation
0.01 TLV
0.01 TLV
0.01 TLV
Contaminant in
Water and Soil
A1F3
BaF2
CdFo
Provisional Limit
0.6-1.7 mg/1 as F
1.0 mg/1 as Ba
0.01 mg/1 as Cd
Basis for
Recommendation
Drinking Water
Standard
Drinking Water
Standard
Drinking Water
Standard
25
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
As previously indicated in the Profile Report on alkali and ammonium
fluorides (23, etc.) current practice in disposal of many fluorides, except
aluminum fluoride in aluminum manufacturing processes, is to vent the mate-
rial without capture from high temperature operations such as glass manu-
facture, vitreous enamel processes, and brick manufacture, or to flush the
fluoride wastes down the sewer without treatments where wet collection
1
devices are used for fume abatement. In the primary aluminum industry,
aluminum fluoride recovered from process vent streams is disposed of as a
mixed cryolite-aluminum fluoride slurry, when the material is not suitable
for recycle and reuse in the electrolytic process. These practices are un-
acceptable. In contrast to these current disposal practices, some environ-
mentally acceptable options are discussed in the following paragraphs.
Option No. 1 - Collection and Return to Process
Aluminum fluoride dusts generated in the handling of the material in the
aluminum reduction industry are recovered by mechanical collection devices
(cyclones and centrifugal collectors) and returned for reuse to the process
system. Aluminum fluoride fumes volatilized from molten electrolyte baths,
or mechanically entrained and carried in the vent gases from the electrolytic
cells are frequently collected in dry dust abatement devices such as centri-
fugal collectors, multitube cyclones, and electrostatic preci pita tors, and
recycled to the process for use in the electrolyte. The dusts generated in
the preparation of feed for enamel frit furnaces are also frequently recovered
by mechanical collectors, and returned for further process use. These abate-
ment and recycle disposal techniques are recommended for use with all
mechanically generated aluminum fluoride, barium fluoride and cadmium fluo-
ride dusts. They are also recommended for use9 where economically feasible,
on thermally generated metal fluoride fumes.
Option No. 2 - Reaction with Slaked Lime
The Manufacturing Chemists Association recommends packaged lots of solu-
ble or slightly soluble fluorides be slowly added to a large container of
-------
water. Then a slight excess of soda ash or slaked lime is stirred into the
0955
solution. The slurry formed is allowed to settle for 24 hours. If
aluminum fluoride is being treated, the supernatant liquid is decanted or
siphoned into another container, and neutralized with dilute hydrochloric
acid before being washed into a sewer or stream with large quantities of
water. The sludge is placed in a landfill. If cadmium fluoride is the
fluoride being treated, cadmium hydroxide (solubility is 0.0026 g/100 g of
water) will be precipitated with the slurry formed upon addition of lime.
The mixed calcium fluoride-cadmium hydroxide sludge from treatment of cadmium
fluoride should be sent to a landfill of the California Class 1 category.
The supernatant liquid will require treatment via another process such as
ion exchange, reverse osmosis, or activated carbon adsorption to« reduce the
cadmium content of discharge solutions to less than 0.01 mg per liter of
cadmium (see Profile Report on cadmium and cadmium compounds [81, etc.]).
If barium fluoride is being treated, the supernatant liquid may be neu-
tralized with sulfuric acid, instead of hydrochloric acid, to form the
insoluble barium sulfate. After removal of the barium sulfate by settling,
the effluent will contain about 2 ppm of barium. This effluent may be di-
luted with additional water to meet the permissible criteria of 1.0 ppm for
barium in public water supplies (see Profile Report on barium compounds
[53, etc.]).
Variations on the above technique should be employed where it is nec-
essary to use wet collection techniques to abate metal fluoride fumes
generated thermally.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Aluminum and barium fluorides are not candidate waste stream
constituents for National Disposal Sites. Their treatment by either Option
No. 1 or Option No.2, is not hazardous, does not require costly or sophis-
ticated apparatus not available to the users, and is economically feasible
and technologically practical for waste generation site use. The two dis-
posal options are equally acceptable and selection of the option .to be
used should be based on economics. Although cadmium fluoride wastes are
generated in relatively small quantities and are not considered National
-------
Disposal Site candidates on this basis, the presence of cadmium in those
wastes dictates the use of an acceptable treatment. The only treatment
deemed adequate is Option No. 2, reaction with slaked lime and subsequent
disposal in designated California Class 1 type landfills.
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual
2d ed. Washington, Manufacturing Chemists Association, Sept. 1969.
174 p.
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Washington, Federal
Water Pollution Administration, Apr. 1, 1968. 234 p.
1668. Robinson, J. M., G. I. Gruber, W. D. Lusk, and M. J. Santy. Engi-
neering and cost effectiveness study of fluoride emissions control.
v. 1. McLean, Virginia, Office of Air Programs, Environmental
Protection Agency, Jan. 1972. 356 p.
1988. Simons, J. H., ed. Fluorine chemistry, v. 1. and v. 4. New York,
Academic Press, Inc., 1940, 1965. 615 p. 786 p.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Aluminum Fluoride (16)
IUC Name Aluminum Fluoride
Common Names
Structural Formula
A1F,
Molecular Wt. 83.97
(1)
Melting Pt. man
Boiling Pt. 1291
Density (Condensed)
Density (gas)
Vapor Pressure (recommended 55 C and 20 Q
16.4 torr & 1098 C^ fin T torr 9 1144 C*
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
254.7 torre 1218 C
(1)
Upper_
Upper_
.0)
Solubility
Cold Water °-559 g/1009 at 25 Ctu Hot Hater_
Others: aqueous hydrnfliinHr arirf _ soluble
Acid, Base Properties •
Ethanol Insoluble
0)
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments •
none
Coast Guard Classification none
References (1) 1433
30
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Barium Fluoride (470)
IUC Name
Common Names
Barium Fluoride
Structural Formula
BaF,
Molecular Wt. 175.36
(1
Melting Pt. 1287 C
(1)
Boiling Pt.
Density (Condensed) 4-89g/cc @ 25_C Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
@ 9
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water 1.586g/l at 10 C(1) Hot Water 1.620g/l at 30 C(1) Ethanol.
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification none
Comments
Coast Guard Classification
none
References (1) 1433
31
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Cadmium Fluoride (478)
IUC Name Cadmium Fluoride
Common Names
Structural Formula
CdFn
Molecular Wt. 150.41
Melting Pt. 520 C
(1)
Density (Condensed )j^64g/cc _ @ _ 23 £__ Density (gas)
Boiling Pt.>i2QQ
&
Vapor Pressure (recommended 55 C and 20 Q
(?
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water soluble
Others:
Hot Water
Ethanol
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
ICC Classification_
Comments
none
Coast Guard Classification none
References (1) 1433
32
-------
PROFILE REPORT
Calcium Phosphate (95), Magnesium Oxide (247).
Sulfur (413). Zinc Oxide (460). Aluminum Oxide (465).
Asbestos (468). Coal (488). Vanadium Pentoxide (513)
1 . GENERAL
Introduction
The inorganic materials treated in this report are part of the materials
previously identified as probable candidate waste stream constituents for
municipal -type disposal. These materials are generally produced in large
tonnage. They are basically nontoxic. Physically, they are all virtually
insoluble in water and hence trace concentrations in water supplies would
not constitute a hazard. These properties provide a common ground for the
disposal of these materials. Therefore, they are discussed here as a group
even though chemically, they are not a homogeneous group.
Calcium Phosphate
Calcium phosphate, Ca^PO^K. occurs in nature as the minerals
oxydapatite, voelicherite, and whitlockite. In pure state, it is a white,
amorphous, odorless powder. The technical grade product is also known as
"bone ash". Commercially, it is produced from phosphate rock which is
1492
essentially a complex salt of calcium phosphate and other calcium salts.
For example, the principal mineral in the domestic phosphate rock is
fluorapatite which can be expressed as CaF2'3Ca3(PO.)2. By heating the
phosphate rock with silica, calcium phosphate is produced as shown in the
following reaction:
CaF2-3Ca3(P04)2 + H20 + Si02 — - — -3Ca3(P04)2 + 2HF + CaSi0
3
33
-------
The uses of calcium phosphate are:
(1) in the manufacture of fertilizers, phosphoric acid, and other
phosphorus compounds;
(2) in the manufacture of milk-glass, polishing and dental powders,
porcelains, pottery;
(3) in enameling and in clarifying sugar syrups;
(4) in animal feeds;
:
(5) as a noncaking agent;
(6) in textile industry;
(7) as antacid for humans and animals.
Magnesium Oxide
Magnesium oxide, MgO, occurs in nature as the mineral periclase. In
pure state, it is a colorless crystal of cubic form. It takes up CCL and
moisture from air. It reacts with water to yield magnesium hydroxide. It
is manufactured by calcination of magnesium carbonate or magnesium
1433
hydroxide. The oxide produced below 900 C is known as caustic-burned
magnesia which can be easily hydrated with water and is chemically reactive.
It is used for preparation of MgCl2, oxychloride cements, decolorizing
agents, etc. The magnesium oxide produced above 900 C is called dead-
burned or sintered magnesia which is a dense, highly refractory product
used almost exclusively in the manufacture of basic refractory bricks.
Magnesium oxide can also be produced economically by decomposition of
magnesium chloride or magnesium sulfate. Magnesium chloride can be
completely decomposed in the temperature range of 1,300 to 1,700 C. In
1963, the total U.S. production of magnesia was 2.8 million tons. Its
uses are:1433' 1492
(1) in the manufacture of refractories, magnesium metal and
oxychloride cements; ,
(2) as an ingredient in mixed fertilizers (impure grade magnesia);
34
-------
(3) in the manufacture of magnesium salts;
(4) as a neutralizing agent and vulcanization accelerator in the
compounding of neoprene and other rubbers (reactive grade
Magnesia);
(5) as a decolorizing agent for solvents in drycleaning industry;
(6) as an absorbent and a catalyst;
(7) as an ingredient of various pharmaceutical and cosmetic
formulations such as dentifrices and powders;
(8) as an antacid and laxative for man and as a laxative for young
foals, calves, pigs and dogs.
Sulfur
Abundant literature has been published regarding the physical and
chemical properties of sulfur, its manufacturing processes and uses. It
is suffice to say that sulfur exists in several forms and occurs widely
in nature, both as sulfur deposit and in various minerals. Commercially,
it is produced from the well-known Frasch process and as a recovered
by-product from sour natural gas, refinery gas and coal as a result of
pollution control requirements. In 1967, the U.S. production of sulfur
by Frasch process amounted to 7 million tons. Its uses are: '
(1) in the manufacture of sulfuric acid, carbon disulfide and
sulfites;
(2) in vulcanization of natural rubber;
(3) in the manufacture of black gunpowder and matches;
(4) in the manufacture of fungicide, insecticides, plastics,
enamels, and metal-glass cements;
(5) in the manufacture of sulfite paper and other papers;
(6) in organic sulfur drugs and various medicinal and veterinary
uses;
35
-------
(7) in bleaching of dried fruits, wood pulp, straw, wool, silk,
felt, and linen;
(8) in the syntheses-of dyes.
Zinc Oxide
Zinc oxide, ZnO, is a white, hexagonal crystal. It occurs naturally
as the mineral zincite. It is also known as flower of zinc or zinc white.
Industrially, it is produced by vaporization of metallic zinc by indirect
heating in the presence of CO gas and oxidation of the zinc vapor with
preheated air. It may be also prepared from the zinc ore, franklinite
(ZnFe204), or from zinc blende (ZnS). Lead blast furnace slag usually
contains 10 to 18 percent zinc which can also be recovered as zinc oxide
by carbon reduction process. In 1968, the U.S. production of zinc oxide
was 213,826 tons.1433 Its uses are:1492
(1) as a pigment in white paints;
(2) in cosmetics, driers, quick-setting cements;
(3) in dental cements (with syrupy phosphoric acid or ZnCl2);
(4) in the manufacture of opaque glass and certain types of
transparent glass;
(5) in the manufacture of enamels, automobile tires, white glue,
matches, white printing inks, porcelains, zinc green;
(6) as an analytical chemical reagent;
(7) as an astringent, antiseptic, protective in skin diseases;
(8) in veterinary applications as dressing in moist eczema and on
wounds, otorrhea in dogs.
Aluminum Oxide
Aluminum oxide, Al^O.,, also known as alumina, occurs abundantly in
nature. However,1 there are so many structural varieties of alumina, their
properties, preparations and uses are correspondingly diversified.
36
-------
1433
of bauxite, amounted to approximately 8 million tons in 1960. The
Physically, it varies from the amorphous alumina gels to various crystalline
forms of alumina and its hydrates. Industrially, aluminum oxide is
produced from aluminum hydroxide such as bauxite. For example, a-alumina
trihydrate, AlpOvSHpO, is produced by the Bayer process in which the
bauxite is treated with alkali, under pressure, to yield a sodium aluminate
solution. The latter is decomposed by dilution and seeding with already
formed alumina trihydrate. Similarly, the amorphous alumina gels can also
be produced from a solution of aluminum salts or alkaline aluminates. The
world consumption of alumina which is produced from about 18 million tons
of bauxite, amounted to approxi
uses of alumina are:1433' 1492
(1) as an adsorbent and desiccant for drying gases and liquids;
(2) as a catalyst for various chemical reactions such as
dehydrogenation, oxidation, polymerization, petroleum cracking
and reformings etc.;
(3) as abrasives;
(4) in the manufacture of refractories;
(5) in adsorption chromatography;
(6) as filler for paints and varnishes;
(7) in the manufacture of alloys, ceramic materials, electrical
insulators and resistors, dental cements, glass, artifical gems;
(8) in coating for metals,
Asbestos
0
Asbestos is a broad term applied to a number of fibrous mineral
1433
silicates which differ in their chemical compositions. They may be
classified into two large groups:
(a) serpentine
(b) amphibole
'37
-------
Belonging to group (a) is the mineral chrysolite, Mg3Si205(OH)4. Group (b)
contains such minerals as anthophyllite ([Mg, Fe]^S1 g022[OH « F^ ' amosite
(ferroanthophyllite), crocidolite, tremolite (CagSitOH, Fi), and
actinolite (Ca2[Mg, Fe]5Sig022[OH, F]2).
In general, they are fine, slender and flexy fibers; resist fire and
most solvents. Canada produces about 42 percent of the world's supply of
asbestos and the United States imports about 22 percent of the world's
output. In 1961, the total world production of asbestos was estimated to
be 2.8 to 3.0 million tons, of which 53,000 tons were produced in the
1433
United States and 1.2 million tons in Canada. Its uses are:
(1) in the manufacture of asbestos cement products such as pipes,
sheets, shingles, electrical panels, etc.;
(2) in asphalt and vinyl floor tiles;
(3) in the manufacture of asbestos papers, millboards, roofing
felts, fire-proof gloves and clothing;
(4) as brake linings, clutch facings, packings, etc., in automobile
industry;
(5) as an inert filter medium for filtering wine, fruit juice, beer,
whisky and Pharmaceuticals;
(6) in missile work, satellites, special packings for atomic energy
equipment and reinforced plastics.
Coal
Voluminous publications have been lavished on coal covering every
topic of interest from deposit reserves to mining and cleaning processes.
It is sufficient to say that coal and steel are the two most important
and basic industries in the United States. Its most important use is, of
course, as a fuel. It is also used to produce coke, carbon or graphite,
fuel gas, coal tar and light oils. In recent years, attempts and processes
have been designed to liquefy and to gasify coal in order to circumvent
the air pollution problem caused by S02, a product of sulfur bearing
coal combustion.
38
-------
Vanadium Pentoxide
Vanadium pentoxide, V205, is a yellow to red crystal of rhombic form.
It is prepared by heating vanadium compounds in air. Industrially, ammonium
vanadate, NHLVO-j, is carefully ignited in air to yield vanadium pentoxide.
The operation is carried out in stages to lessen the chance of lower
vanadium oxides being formed. It can also be prepared by slightly
acidifying an alkaline, aqueous solution of ammonium vanadate. Its uses
are:1492
(1) as a catalyst for various chemical reactions, particularly
those involving oxidation such as oxidation of S02 and S03
in making sulfuric acid;
(2) in the manufacture of yellow glass, and for inhibiting
ultraviolet light transmission in glass;
(3) as a developer in photography;
(4) in the manufacture of aniline black.
Sources and Types of Waste
The main sources of wastes for the materials treated in this report
may include the following:
(1) manufacturers of these materials;
(2) commercial and industrial operation and processes using them
as starting materials or as catalysts;
(3) users of these materials or other products containing these
materials(such as paints, cosmetics, asbestos papers and
boards, fertilizers, etc.);
(4) chemical laboratories and plants using these materials as
chemical reagents.
39
-------
The wastes are mainly of the concentrated type, because they are all
insoluble in water. Most of the wastes are unused or contaminated materials
or products containing these materials.
Physical and Chemical Properties
The physical arid chemical properties of the materials in this report
are given in the attached worksheets.
4>
2. TOXICOLOGY0766'0643'0225'1312
The materials discussed in this report are nontoxic in nature.
However, inhalation of the solid particles could cause some physical damage.
Inhalation of fumes of freshly formed magnesium oxide may cause metal
fume fever. There is no evidence however that it can produce any true
systemic poisoning.
Similarly, inhalation of fresh fume of zinc oxide can cause a disease
known as "brass founders' aque" or "brass chills". However, there is no
cumulative effect to the inhalation of zinc fume. The zinc oxide dust
which is not freshly formed is virtually innocuous. But it can block the
ducts of sebaceous glands and give use to a papular, pustular eczema in
men engaged in packing this compound into barrels.
Aluminum oxide is nontoxic in nature. It has been reported however
that inhalation of finely divided aluminum oxide particles can cause
physical damage to the lung.
Vanadium compounds act chiefly as irritants to the conjunctivae and
respiratory tracts. Prolonged exposures may lead to pulmonary involvement.
Responses are acute, but never chronic. Symptoms and signs of poisoning
are pallor, greenish black discoloration of tongue, paroxysmal cough,
conjunctivitis, dyspnea and pain in the chest, bronchitis, rales and ronchi,
broncho-spasm, tremor of fingers and arms, radiographic reticulation.
40
-------
^ Sulfur, coal, and calcium phosphate are basically nontoxic.
Inhalation of asbestos may cause a diffuse fibrosis known as
asbestosis and/or cancer. The asbestosis probably begins as a "collar"
about the terminal bronchiols. Usually, at least 4 to 7 years of exposure
to high concentrations of asbestos dust are required before a serious
degree of asbestosis results. Once established, it would continue to
progress even after the exposure to asbestos dust ceases. Clinically,
the most striking sign of asbestosis is the shortness of breath of
gradually increasing intensity, often associated with a dry cough. In
the early stages physical signs are absent or slight; in the later stages
rales may be heard, and in long-standing cases there is frequently clubbing
of the fingers. In the early stages of the disease a chest X-ray
reveals a ground glass or granular change, chiefly in the lower lung
fields. As the condition worsens, the heart outline becomes "shaggy"
and regular patches of mottled shadowing may be seen. Asbestos bodies
may also be found in sputum.
Although asbestos has been found to be carcinogenic, the exact
causes are not yet clearly understood. The most common form of cancer
caused by asbestos is the lung cancer which may appear unaccompanied by
asbestosis. The latent period between exposure and evidence of
carcinoma may be even longer than that for asbestosis. Another form of
cancer caused by asbestos is the mesothelioma of the pleura and peritoneum.
This is a very rare form of cancer which is now considered a frequent
cause of death among asbestos workers. The interval between first
exposure and the development of the terminal illness from mesothelioma
ranged between 16 and 55 years. Finally, extrapulmonary cancer has also
been reported as a cause of death among asbestos workers.
41
-------
The Threshold Limit Value (TLV) recommended by the American Conference
of Governmental Industrial Hygienists (ACGIH) and the lethal doses or
concentration reported are tabulated as follows:
Contaminant in Air
Calcium Phosphate
Magnesium Oxide
Sulfur
Zinc Oxide
Aluminum Oxide
Asbestos
Coal
Vanadium Pentoxide
TLV
15 mg/M-5 (fume)
5 mg/M (fume)
5 fibers/ml* >
5 y in length
2 mg/M3
0.5 mg/M? (dust)
0.1 mg/M*5 (fume)
Lethal Dose or Concentration
ih LCCA: 2500 mg/M , rat
Sulfur and aluminum oxide are generally considered as inert or nuisance
particulates when they are present as dusts in air. The proposed ACGIH
TLV for these particulates is 10 mg/M or 30 million particles per cubic
0225
foot, whichever is smaller.
3. OTHER HAZARDS
With the exception of sulfur and coal, all materials in this report
are very stable with respect to fire and explosion hazards. Sulfur and
coal are fire hazards when exposed to flame or heat. In the form of dust,
sulfur and coal could cause explosion hazard when exposed to flame.
*As determined by the membrane filter method at 430X magnification
phase contrast illumination. Concentrations between 5 and 10 fibers/ml
may be permitted for 15 minute periods each hour up to five times daily.
42
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
The chief concern in handling and storage for the materials in this
report is to maintain adequate ventilation and dust control to avoid
inhalation of the fume and dust by the workers and fire and explosion
hazards. For example, in the asbestos industries, the dusty air should be
passed from the ventilators through fabric sleeve filters before discharged
to the atmosphere. The filtration is very effective because the asbestos
fibers form a mat which becomes an absolute filter. To control the
asbestos in the exhaust gases, bag filters are used. Some operations are
carried out in wet processes to keep the dust from becoming airborne.
Dust-tight casings should be used for conveyor buckets, elevators, etc.,
which may be equipped with explosion relief vents, if necessary. Since
sulfur and coal are combustible, they should be stored in cool and well-
ventilated areas and kept away from heat, or flame, or oxidizing materials.
In shipping, only sulfur is classified by the Coast Guard as a hazardous
article. Dusty material like asbestos may be shipped in plasti'c-coated
bags to prevent pollution during transportation.
Disposal/Reuse
Contaminated materials are generally disposed of rather than
reprocessed for reuse. The safe disposal of these materials is here
defined in terms of provisional limits given below:
Basis for
Contaminant in Air Provisional Limit Recommendation
Calcium Phosphate 0.01 mg/M3 as H3P04 0.01 TLV for H3P04
Magnesium Oxide (fume) 0.10 mg/M3 0.01 TLV
* Whichever is the smaller.
43
-------
(Continued)
Contaminant in Air
Sulfur
Zinc Oxide (fume)
Aluminum Oxide
Asbestos
Coal
Vanadium Pentoxide (fume)
(dust)
Provisional Limit
0.1 mg/M3 or
0.3 m.p.p.c.f.*
0.05 mg/M3
0.1 mg/M3 or
0.3 m.p.p.c.f.*
0.05 fibers/ml >
5y in length
0.02 mg/M3
0.005 mg/M3
0.001 mg/MJ
Basis for
Recommendation
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
Contaminant in
Water and Soil
Calcium Phosphate
Magnesium Oxide
Sulfur
Zinc Oxide
Aluminum Oxide
Asbestos
Provisional Limit
0.05 ppm (mg/1)
125 ppm (mg/1) as Mg
500 ppm (mg/1)
5 ppm (mg/1) as Zn
0.5 ppm (mg/1)
500 ppm (mg/1)
Basis for
Recommendation
Stokinger and
Woodward Method
Drinking Water
Standard
Drinking Water
Standard for
total dissolved
solids
Drinking Water
Standard
Stokinger and
Woodward Method
Drinking Water
Standard for
total dissolved
solids
* Whichever is the smaller.
m.p.p.c.f. is million particles per cubic foot
44
-------
(Continued)
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
Coal 500 ppm (mg/1) Drinking Water
Standard for
total dissolved
solids
Vanadium Pentoxide 0.05 ppm (mg/1) as V Chronic toxicity
drinking water
studies
5. EVALUATION OF WASTE DISPOSAL PRACTICES
Option No. 1 - Landfill
For the waste disposal of the materials in this report, the landfill
method is recommended because the waste materials are all insoluble in
water and nontoxic in nature. In fact, most of them originally come from
the land as naturally-occurred minerals. Should they be washed into any
water source, by rainfall, for instance, they can be easily removed from
water by filtration. If a trace concentration of the material remains in
the water supply, it would not constitute a hazard. Also, they are in
general, chemically stable and will not degrade to yield air or water
pollutants. The landfill method therefore offers a convenient and
economic way to dispose of the waste materials.
Option No. 2 - Incineration
Combustible materials such as coal and sulfur can also be disposed of
by incineration. For coal, the combustion must be complete to insure that
no carbon monoxide is produced. For sulfur and coals with high sulfur
contents, the exhaust gas must be scrubbed off the sulfur dioxide formed.
One convenient way to scrub off the S02 is the wet limestone method, where
the. exhaust gas is scrubbed with an aqueous suspension of finely ground
limestone. The limestone suspension usually contains an organic acid
stronger than carbonic acid but weaker than sulfuric acid to accelerate
45
-------
the dissolution of the limestone and thereby increase the scrubbing effi-
ciency. This method is naturally more costly than Option No. 1, particularly
in view of the fact that pollution controls for S02 are becoming more stringent.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES :-
As landfill provides a convenient and adequate means for the disposal
of the materials included in this Profile Report, it is concluded that
consideration for waste treatment at the National Disposal Site is not
warranted.
46
-------
7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit value for 1971. Occupational Hazards, Aug. 1971. p. 35-40.
0643. Sullivan, R. J. and Y. C. Athanassiadis. Air pollution aspects of
asbestos. Bethesda, Maryland, Litton Systems, Inc., 1969. 105 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971.
Washington, U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Chemical Rubber Company, 1969. 2,100 p.
1662. Shreve, R. N. The chemical process industries. 3d. ed. New York,
McGraw-Hill, Inc., 1967. 905 p.
47
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium phosphate (95)
IUC Name
Common Names
Structural Formula
Ca3(P04)
2
Molecular Wt. 310.18
(1)
Density (Condensed) 3.14'
Melting Pt. 1670 C
Density (gas)
(1)
Boiling Pt.
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flanmability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Solubility
Cold Water 0.002 grams/100 m
1
Hot Water decomposes
Upper_
Upper_
' ]
Ethanol insoluble
(1!
Others: soluble in acids *
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
48
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Magnesium Oxide (247)
1UC Name
Common Names
Structural Formula
Molecular Wt.
40-311}
Density (Condensed) 3.58^ @
Melting Pt. 2800 C*1* Boiling Pt. 3600 C(1)
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
I?
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Lower
Upper_
Upper_
Solubility
Cold W
Others: soluble in acids and ammonium salts 0)
m 9 30 CO)
Cold Water 0.00062 grams/100 ml v "Hot Water 0.0086 grams/100 ml Ethanol insoluble (])
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classificat1on
References (1) 1579
49
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sulfur (413)
Structural Formula
IUC Name
Common Names <-
8
aTI278 C
Molecular Wt. 256.512 (1) Melting Pt. ? iTi?^ Boiling Pt. 444.6
Density (Condensed) ° ^'96 & __ Density (gas) _ @
Vapor Pressure (reconKnende2d 55 C and 20 Q^
1 mm Hg @ 183'8 _ * _ e'
. _ _
Flash Point 207.2 C tz) Autoignitlon Temp. 232.2 C*2*
Flamnability Limits in Air (wt %) Lower _ Upper
Explosive Limits in Air (wt. %) Lower _ Upper
Solubility (1)
Cold Water insoluble Hot Water insoluble Ethanolslightly soluble
Others: soluble in CS^. CC1.
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification Coast Guard Classification hazardous article
Comments I :
References (1) ^570
(2) 0766
50
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Zinc Oxide (460)
Structural Formula
IUC Name
Common Names
ZnO
Molecular Wt. 81.37 "' Melting Pt. 1975 C*1* Boiling Pt.,
Density (Condensed) 5.606^' @ Density (gas) 9-
Vapor Pressure (recommended 55 C and 20 Cj
0 9 (
Flash Point Autolgnition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. X) Lower Upper
Solubility .^
Cold Water 0.00016 grams/100 ml g 2n0t Water Ethanol insoluble*
Others: soluble in acids, alkalis. NH.C1 ' '
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification Coast Guard Classification_
Comments
References (1) 1579
51
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Aluminum Oxide (465)
IUC Name
Common Names
Structural Formula
Molecular Wt. 101.96
(1)
Melting Pt. 2045 C
or
(1)
Boiling Pt. 2980 C (1)
Density (Condensed) 3.965 & 25 C Vl/ Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower_
Upper
Upper_
Solubility
Cold Water insoluble
Others:
(1)
Acid, Base Properties -
Hot Water
Ethanol insoluble1
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) ^570
52
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Vanadium Pentoxide (513)
1UC Name
Common Names
Structural Formula
,„,„
Molecular Wt. 181. 88
(!)
v '
Density (Condensed) 3. ?57U) @
Melting Pt. 690 CV
Density (gas)
decomposes (1)
Boiling Pt. @ 1750 C
9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper
Upper
Solubility
Cold Water °-8 grams/IPO ml @ 20
Others:
Acid, Base Properties
Water
Ethanol insoluble
(1)
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments ^_____
Coast Guard Classification
References (1) 1570
53
-------
PROFILE REPORT
Aluminum Sulfate (17), Calcium Chloride (90),
Calcium Hydroxide (94). Potassium Sulfate (352),
Potassium Sulfide (353). Calcium Oxide (483)
1. GENERAL
Introduction
The inorganic chemicals in this Profile Report are basically nontoxic.
However, they may react violently with water and/or dissolve in water in
sufficiently large concentrations to constitute a hazard or nuisance. They
are grouped together here in one report because they can be handled by
similar disposal processes.
Aluminum Sulfate
Aluminum sulfate, A12(SOJ_, is a white lustrous crystal or powder.
The commercial grade is usually produced in the United States directly
from bauxite or clay. Finely ground bauxite is digested with sulfuric
acid near the boiling point of the solution. The solids are removed by
sedimentation. Unless the bauxite or clay is sufficiently low in iron,
the solution may also be treated for iron removal by precipitation of iron
compounds, using sulfides of potassium or calcium, hydroxides of calcium
or ammonium, etc. In 1960, 1.5 million tons were produced in the United
1433 1492
States. Its uses are listed as follows:IH<"' IW£
(1) close to two-thirds of total A12(S04)3 production is used in the
paper industry for clarification of process waters, pH control
of pulp slurries, setting of certain dyes and setting of size
in paper;
55
-------
(2) water treatment applications account for another one-fourth of
the total production;
(3) the remainder AlpCSO,)., goes into manufacture of chemicals,
pharmaceutical preparations, dyeing operations, soaps and grease,
fire-extinguishing solutions, tanning leather, waterproofing
concrete, fireproof ing and waterproofing cloth, deodorizing and
decolorizing petroleum.
Calcium Chloride
Calcium chloride, CaClp, is a colorless cubic crystal, very hygroscopic.
When dissolved in water, much heat is liberated. Commercially, about
50 to 60 percent of the calcium chloride sold in the United States is
manufactured from natural brines. In 1961, total U.S. production of
CaCl? was 558,352 tons flake (77-80%) and 226,636 tons liquor (40-45%).
1433
Its uses are:1^"'
(1) as a drying and dehydrating agent for organic liquids and in
desiccators;
(2) drying gases in chemical analyses'4,
(3) in bri'ne making in refrigeration plants;
(4) in control of snow and ice on highways, streets;
(5) in dust control on secondary roads, unpaved streets and highway
shoulders;
(6) in freezproofing of coal and ores, both in shipping and
stockpiling;
(7) in concrete mixes to give quicker initial set, high early
strength and greater ultimate strength.
56
-------
Calcium Hydroxide
Calcium hydroxide, Ca(OH)2, also known as slaked lime, is a colorless
orthorhombic or trigonal crystal, or soft, odorless powder and granules.
It readily absorbs C0~ from air. When ignited, it loses water to form
1433
CaO. Commercially, it is prepared from brine, CaO.
CaO + H20
1492
Its uses are:
(1) manufacture of mortars, plasters, and cements;
(2) manufacture of soda ash by the Solvay process;
(3) in dehairing hides;
(4) in water paints;
(5) as antiemetic and in infant feeding formulas to decrease sizes
of curds formed from cows' milk.
Potassium Sulfate
Potassium sulfate, K2SO,, is a colorless crystal of rhombic or
hexagonal form. It occurs in nature as the mineral arcanite. Commercially,
it is obtained from the langbeinite ore, K2SCv2MgS04. It is also one of
the many products recovered from the Searles Lake brine. In an unusual
situation where HC1 is valuable, it can be prepared as shown in the
following reaction:
2KC1 + H2S04 - *-K2S04 + 2HC1
Finally, it can also be produced by burning sulfur with excess of air mixed
with steam and then passing the gaseous mixture through a bed of porous KC1
briquets.
4KC1 + 2S02 + 02 + 2H20 - ^2K2$04 + 4HC1
The U.S. production of potassium sulfate is about 500,000 tons/year. Its
uses are:
57
-------
(1) as fertilizers (technical grade product);
(2) in the manufacture of potassium alum (KA1(SOJ4'12H20),
potassium carbonate, and glass;
(3) in the manufacture of SBR latex rubber;
(4) in smokeless powder;
(5) as analytical reagent.
14Q?
Potassium Sulfide
Potassium sulfide, K2$, is a yellow to brown crystal of cubic form.
It is very hygroscopic and unstable. It discolors in air. It may be
prepared from reaction of potassium with sulfur in liquid ammonia.
Commercially, it is manufactured by (1) heating potassium sulfate with
coal:
K2S04 + 4C -K2S + 4CO
or (2) reacting potassium hydroxide with hydrogen sulfide:
KOH
KOH
Potassium sulfide has little use except as a laboratory reagent and as a
depilatory.
Calcium Oxide
Calcium oxide, CaO, also known as lime or quicklime, is white or
grayish-white lumps or granular powder. On exposure to air it absorbs
C02 and water becomes air-slaked. With a little water it generates much
heat and is converted to Ca(OH)2, the slaked lime. Industrially, it is
manufactured from calcination of limestone (CaCO^) in a kiln.
CaC03
58
-------
In 1964, 13.5 million tons of CaO were produced in the United States. Its
uses are:1433'1492
(1) in the manufacture of mortar and plaster;
(2) in various metallurgical processes, for example, as a flux and
in forming a molten slag which purifies the metal in the
production of pig iron and steel
(3) in the manufacture of slaked lime, Ca(OH)2;
(4) as a desiccant;
(5) in the manufacture of bleaching agents, pesticides, inorganic
and organic salts of calcium, and chlorinated lime;
(6) in water purification and treatment for potable and industrial
purposes;
(7) in paper pulp processing;
(8) in the manufacture of glass and ceramics;
(9) in deodorizing vegetable oils and dehairing hides.
Sources and Types of Wastes
The main sources of wastes for the materials in this report are:
(1) manufacturers of these materials;
(2) the paper and water treatment industries;
(3) various metallurgical operations and processes;
(4) highway and streets maintainence operations;
(5) construction industry;
(6) fanning operation;
(7) chemical laboratories and plants using these materials as
chemical reagents;
(8) textile, rubber, glass and ceramics industries.
The wastes may include contaminated materials and process wastes in
the form of solid or aqueous solution.
59
-------
Physical and Chemical Properties
The physical and chemical properties of the inorganic chemicals
treated in this report are given in the attached worksheets.
2. TOXICOLOGY0225'0766'1312'1492
The materials treated in this report are in general nontoxic. However,
they are all soluble in or reactive with water to yield solutions or
products which may be corrosive or toxic.
When dry, aluminum sulfate is harmless. When dissolved in water, it
hydrolyzes readily to form sulfuric acid which is corrosive and would
cause rapid destruction of body tissue on contact.
Generally speaking, calcium compounds are nontoxic. In fact, many
calcium compounds are used medicinally. Calcium chloride is completely
innocuous. Calcium hydroxide and oxide, on the other hand, may be
considered as moderately toxic. They have caustic reaction and therefore
are irritating to the skin and respiratory system. In the form of dust,
calcium hydroxide can cause dermatitus and irritation of the eyes and
mucous membranes.
Potassium sulfate is nontoxic. Potassium sulfide is similar to
alkali in action: It causes softening and irritation of the skin. If
taken by mouth, it is corrosive and irritant through the liberation of
hydrogen sulfide and free alkali. Hydrogen sulfide is toxic.
The Threshold Limit Value (TLV) recommended by the American Conference
of Governmental Industrial Hygienists and the lethal doses reported are
given in the following table:
60
-------
3
Contaminant TLV, mg/M Lethal Dose
Aluminum Sulfate -- or LD5Q 770 mg/kg mouse
Calcium Chloride -- or ID™ 4000 mg/kg rat
Calcium Hydroxide — or ID™ 7340 mg/kg rat
Potassium Sulfate -- sc LD~ 3000 mg/kg guinea pig
Potassium Sulfide
Calcium Oxide 5
3. OTHER HAZARDS
Potassium sulfide may explode on percussion or rapid heating. When
exposed to flame or by spontaneous chemical reaction, it may cause moderate
fire hazard.
Calcium chloride and calcium oxide generate much heat when dissolved
in water due to the heat of solution and the reaction to calcium hydroxide
in the latter case.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
In storage, the materials in this report should be kept tightly closed
and dry, because most of them would absorb moisture and/or carbon dioxide
from the air. Adequate ventilation and dust control should be maintained
particularly for storing and handling calcium hydroxide. In shipping,
potassium sulfide is classified by the U.S. Coast Guard and the U.S.
Department of Transportation (DOT) as flammable solid.
61
-------
Disposal/Reuse
Industrially, contaminated materials probably will not be considered
for reprocessing for reuse based on economic considerations. For the
safe disposal of these waste materials, the acceptable criteria for their
release into the environment are defined in terms of the following
provisional limits:
Contaminant in Air
Aluminum sulfate
Calcium chloride
Calcium hydroxide
Potassium sulfate
Potassium sulfide
Calcium oxide
Provisional Limit
0.01 mg/M3 as H2$
0,07 mg/M3 as HC1
0.05 mg/M3
0.01 mg/M3 as H2$
0.15 mg/M3 as H2S
0.05 mg/M3
Basis for
Recommendation
0.01 TLV for H2S04
0.01 TLV for HC1
0.01 TLV for CaO
0.01 TLV for H2S04
0.01 TLV for H2S
0.01 TLV
Contaminant in Water
and Soil
Aluminum Sulfate
Calcium Chloride
Calcium hydroxide
Potassium sulfate
Potassium sulfide
Calcium oxide
Provisional Limit
250 ppm (mg/1) as S04
250 ppm (mg/1) as Cl
0.25 ppm (mg/1)
250 ppm(mg/1) as S04
0.75 ppm (mg/1) as H2S
0.25 ppm (mg/1)
Basis for ,
Recommendation
Drinking water
standard
Drinking water
standard
Stokinger and
Woodward method
Drinking water
standard
Stokinger and
Woodward method
Stokinger and
Woodward method
5. EVALUATION OF WASTE DISPOSAL PROCESSES
Since the materials in this report do not all belong to the same
chemical family, slightly different processes are required for their
disposal.
62
-------
Option No. 1 - Hydrolysis and Neutralization for Aluminum Sulfate
Aluminum sulfate can be readily hydrolyzed to yield aluminum
hydroxide and sulfuric acid.
A12(S04)3 + 6H20 - -2A1(OH)3 + 3H2$04
The sulfuric acid formed is neutralized by NaOH and the insoluble
aluminum hydroxide is removed by filtration. The latter may be heated
to decomposition to yield alumina which has valuable industrial applications.
2A1(OH)3 — — -A1203 + 3H20
The neutral solution of sodium sulfate may then be safely discharged into
sewers or waterways as long as its concentration is below the recommended
provisional limit of 250 mg/liter.
Option No. 2 - Carbonate Precipitation for the Chlorides
Calcium chloride can be treated with soda ash to yield the insoluble
calcium carbonate.
CaCl2 + Na2C03 • • CaC03 + 2 NaCl
After removing the carbonate precipitate by filtration, the remaining
brine solution, when its sodium chloride concentration is below 250 mg/
liter, may be discharged into sewers or any other waterways. Calcium
carbonate may be calcined to yield the quicklime, CaO.
CaC03 - 800 C " Ca° + C02
Lime has many industrial uses and therefore is a valuable by-product.
63
-------
Option No. 3'- Neutralization and Carbonate
Precipitation for CaO and Ca(OH)o
Contaminated calcium oxide and hydroxide can be neutralized by
hydrochloric acid to yield calcium chloride.
Ca(OH) + 2HC1 -
The calcium chloride formed can now be treated as described in Option No.
2. Since calcium chloride is nontoxic, the neutral aqueous calcium chloride
solution could also be diluted to a concentration below 250 mg/liter and
discharged directly to sewers, rivers, lakes, oceans, or any other waterways.
Option No. 4 - Sulfide Precipitation for KpS
Potassium sulfide can be converted into insoluble FeS by ferric
chloride solution. After removing the FeS precipitate by filtration, the
i
remaining potassium chloride solution can be diluted to a concentration
level below 250 mg/liter and discharged to sewers, rivers, lakes, oceans,
.or any other waterways. If excess ferric chloride solution has been used
to precipitate out FeS, the remaining solution should be neutralized with
soda ash followed by filtration and discharge of the waste liquid.
Option No. 5 - Dilution and Discharge
Potassium sulfate and calcium chloride are relatively harmless.
Dilute solutions of these two chemicals can be released into streams and
bays under careful monitoring and control to ensure that their concentration
levels are below the recommended maximum of 250 mg/liter.
In summary, the materials in this report are generally innocuous and
soluble in water. The contaminated waste can be dissolved in water to
form a dilute solution and discharged into streams or bays under careful
control. If the waste solution is acidic (as that of aluminum sulfate)
or caustic (as that of calcium hydroxide), they should be neutralized
with soda ash or hydrochloric acid, filtered to remove the solid, diluted,
and then discharged.
64
-------
6.. APPLICABILITY TO NATIONAL DISPOSAL SITES
As mentioned at the beginning of this report, the chemical compounds
discussed here have been preliminarily classified as probable candidate
waste stream constituents for municipal disposal. Based on the discussion
of disposal processes, it may be concluded that the waste treatment for
these compounds can be adequately handled locally and no consideration
for National Disposal Site is warranted.
65
-------
7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards, Aug. 1971.
p. 35-40.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971.
Washington, U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed., 22 v. and
suppl. New York, Interscience Publishers, 1966.
<
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ecL Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1752. Public Health Service. Drinking water standards, 1962.
Washington, U.S. Department of Health, Education, and Welfare,
1969.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Aluminum Sulfate (17)
Structural Formula
IUC Name
Common Names
A12(S04).
Molecular Wt. 342.15* ' Melting Pt. decomposes @ 770 C*fe0iling
Density (Condensed) 2.7TU @
Vapor Pressure (recommended 55 C and 20 C)
Density (Condensed) 2.7r @ Density (gas) &
Flash Point Autolgnition Temp.
Flammability Limits in Air (wt %) Lower Uooer_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility(1)
Cold Water 31.3 grams/100 ml @ 0 C Hot Water 98.1 grams/100 ml 3 ^hanol slightly soluble
Others: soluble in dilute acids
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification Coast Guard Classification
Comments :
References (1) 1570
67
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium Chloride (90)
IUC Name
Common Names
Structural Formula
CaCl,
Molecular Wt. 110.99
(U
Melting Pt. 772 C
(1)
Boiling Pt.>
r(D
Density (Condensed) 2.15
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
(1)
Cold Water 74-5 grams/100 ml @ 20 CHot Water 159 grams/100 ml g1Q°E^hanol soluble
Others: soluble in acetic acid, acetone
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1579
68
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium Hydroxide (94)
IUC Name
Common Names
Structural Formula
Ca(OH)
Molecular Wt. 74. 09
^
Density (Condensed) 2.24
Melting Pt. - H^O @ 580
Density (gas)
Boiling Pt. decomposes
&
^
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Upper
Upper
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility(1)
Cold Water 0.185 grams/100 ml (j> 0 CHot Water 0.077 grams/100 ml
Others: soluble in acids and ammonium salts
Acid, Base Properties _
insoluble
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classificatio
References (1) 157Q
69
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Potassium Sulfate (352)
IUC Name
Common Names
Structural Formula
K2S04
Molecular Wt. 174.27
(1)
Melting Pt. 1069
Boiling Pt. 1689 C
(D
Density (Condensed) 2.662 @
Vapor Pressure (recommended 55 C and 20 C)
Density (gas)
Flash Point
Autolgnltlon Temp.
Upper_
Upper_
Flammability Limits in Air (wt X) Lower
Explosive Limits in Air (wt. X) Lower
Solubility^1*
Cold Water 12 grams/100 ml @ 25 C Hot Water24.1 grams/100 ml Q^tSianol insoluble
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification^
Comments
Coast Guard Classification
References (1) 1570
70
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Potassium Sulfide (353)
IUC Name
Common Names
Structural Formula
Molecular Wt. 110.27
(1)
Melting Pt. 840 C
(1)
Boiling Pt.
Density (Condensed) 1.805
Density (gas)
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. J)
(1)
Lower
Upper,
Upper_
Solubility
Cold Water soluble
Hot Water very soluble
Ethanol soluble
Others: soluble in glycerin
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
rrr ri »** *• flammable solid
ICC Classification yellow label
inflammable
Coast Guard Classification sgljd. y,
*21
Comments.
References (1) 1570
(2) 0766
71
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium Oxide (483)
UK. Name
Common Names
Structural Formula
CaO
Molecular Wt. 56.08
(1)
Melting Pt. 2580 C
(1)
Boiling Pt. 2850 C
(1)
Density (Condensed) 3.25-3.38 @
Density (gas)
v.jpor Pressure (recommended 55 C and 20 C)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubi11ty decomposes decomposes m .
Cold Water 0-131 grams/100 mg Q IQTIot Water 0.07 grams/100 mg @°" Ethanol
Others: soluble in acids
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification_
Comments
Coast Guard Classification
References (1)
-------
PROFILE REPORT
Ammonium Chloride ^20), Ammonium Nitrate (24), Potassium Phosphate (351).
Dehydrated Borax (381). Sodium Carbonate (383). Sodium Nitrate (396),
Q Sodium Orthophosphates (401)
1. GENERAL
Introduction
The inorganic chemicals in this Profile Report are basically nontoxic.
However, when dissolved in water, they may be present in sufficiently large
concentrations to constitute a hazard or nuisance. They are grouped
together here because they can be handled by similar disposal processes.
Manufacture and Uses
Ammonium Chloride. Ammonium chloride, NH.C1, is a white crystalline
substance that has a saline taste and is somewhat hygroscopic. The
commercial grade is usually produced as a by-product of the Solvay Ammonia-
Soda Process (discussed in the paragraph on sodium carbonate). The
ammonium chloride is collected from the other products of the ammonia-soda
process by crystallization steps carried out under controlled temperature
gradients. Another method used for ammonium chloride manufacture is to
react ammonium sulfate with sodium chloride in aqueous solution and
crystallize ammonium chloride from the resultant mixture. It is used in
soldering flux, washing powders, pickling agents for zinc coating and
tinning, electroplating and medicine, and in the manufacture of dyes,
various ammonia compounds, fertilizer and cement for pipe joints. '
Ammonium Nitrate. Ammonium nitrate, NH/I03, a colorless crystalline
material, is an important nitrogen fertilizer because of the high nitrogen
content (35%) and the simplicity and cheapness of manufacture. It is a
vital ingredient in many explosives. A minor, but important, application
73
-------
is in the manufacture of nitrous oxide, an anesthetic. There are four
basic processes for the manufacture of ammonium nitrate: prilling or
spraying, the Stengel process, crystallization, and graining. All
ammonium nitrate is made by neutralizing nitric acid with ammonia and
collecting a solid product from the reaction product. To decrease
deliquescence and caking and to obtain the best physical characteristics,
ammonium nitrate 1s produced by graining, or prilling. Graining Involves
batch cooling of a concentrated solution under proper agitation to produce
small rounded pellets or grains which can be used for fertilizer or as an
explosive. For fertilizer use the ammonium nitrate is prilled by spraying
hot concentrated ammonium nitrate solution from the top of a tower and.
allowing the droplets to cool and harden during the fall, forming solid
particles (prills) about 1/16 to 3/32 in. in diameter. After drying and
screening, the prills or grains are conditioned against moisture pickup
by coating them with a material such as diatomaceous earth.
Potassium Phosphate. Potassium phosphate, K-jPO^, is a white powder
that is soluble in water. It is prepared by the action of phosphoric
acid on potassium carbonate. It finds use in water treatment as a
sequestering agent. When dissolved in water, a strongly basic solution
results.1492
Dehydrated Borax. Dehydrated borax, NapB^O^, or sodium tetraborate,
is a hygroscopic white crystalline material. It 1s prepared either from
the mineral kernite found in the Mojave Desert or from the saline brines
of Searles Lake, California. Borax, ^B^CL'lOHpO is recovered from
kernite by dissolving the mineral in water, filtering the solution and
crystallizing the borax. Borax and potassium chloride are recovered from
Searles Lake. The borax is then collected by crystallization. By heating,
borax is dehydrated to the anhydrous form. It is used as a water softener
and in the manufacture of glass, enamels and other ceramic products.
74
-------
Sodium Carbonate. Sodium carbonate, N^CO^, or soda ash--the crude
sodium carbonate of commerce, is in the form of a grayish-white powder or
lumps that contain 99 percent sodium carbonate. Over 90 percent of the
world's production of soda ash is made by the Solvay ammonia-soda process
with the remaining quantities being recovered from natural deposits or
brines in California and Wyoming. The raw materials for the Solvay process
are coke, salt, lime and ammonia. The reactions of the process are as
follows:
Heat
NH4HCO
Cl
uau
c +
CaO + H
NH3 + H
I4OH + C
;03 + Na
+ Ca(OH
2NaHC
U3
n
U2
n —
2U
0 -
r
n -
U2
n -
\
2
n _
U3
« CO
fc NH OH
* "in^un
. * (HH } rn
* 1N"V2('U3
— .— *. ?MII urn
"nil4IIL03
,_ , __» MM n i M
_, ., ,_» Mil i rnP
Heat M ^n ,
r na2tu3
+ H20
dri wL/o
12 + H20
C02 + H2i
,0
Soda ash is used in large quantities by the glass, soap, water treatment,
chemical, pulp and paper, petroleum, nonferrous metals and textile
industries.1662
Sodium Nitrate. Sodium nitrate, NaNOo, is a colorless, transparent,
odorless crystalline material. It is prepared by reacting sodium carbonate
with nitric acid or by recrystallization of Chile saltpeter which is
impure natural sodium nitrate. It is widely used in the chemical industry,
1492
in fertilizers and in making explosives such as dynamite.
75
-------
Sodium Orthophosphates. The orthophosphates, such as
7H20, and Na3P04-12H00, with the general formula Na3_xHxP04(x = 0,1,2) are
used chiefly in packaged detergents and soaps and in water softening.
Sodium dihydrogen phosphate has been used as an ingredient in baking powder.
The orthophosphates are prepared by treating soda ash with the proper
1492
quantities of phosphoric acid.
Physical and Chemical Properties
The physical/chemical properties for the compounds covered by this
Profile Report are summarized on the attached worksheets.
2. TOXICOLOGY
The materials treated in this report are not considered particularly
toxic. However, soda ash and the basic orthophosphates because of their
alkalinity are irritating to the skin, and their dust is irritating to the
respiratory tract. Boron compounds such as borax may result in accidental
poisoning by oral ingestion and toxic reactions in small children may
result through skin absorption. The American Conference of Governmental
Industrial Hygienists has not established Threshold Limit Values (TLV)
poor
for any of the compounds listed in this report. The lethal doses
reported for the compounds are given below:
Contaminant Lethal Dose
Ammonium Chloride im LD5Q: 30 mg/kg, rat
Ammonium Nitrate
Potassium Phosphate or LD50: I600 ">9/kg. mouse
Borax
Sodium Carbonate or LD5Q: 4200 mg/kg, rat
Sodium Nitrate or LDC : 200 mg/kg, rat
Sodium Orthophosphate ip LD5Q: 326 mg/kg, rat
76
-------
3. OTHER HAZARDS
Ammonium and sodium nitrate are fire hazards when in contact with
organic materials or other readily oxidizable substances. Ammonium nitrate
may explode under confinement at high temperature. A mixture of ammonium
nitrate and diesel oil is used industrially as an explosive. Explosions
have occurred with ammonium nitrate in ship's holds. However, there have
been warehouse fires where ammonium nitrate burned and did not explode.
Upon heating, ammonium and sodium nitrate give off toxic fumes of nitrogen
qxides.0955
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
In storage, the materials in this report require special care only
with respect to protection from moisture, their alkaline or acid nature
when dissolved in water, and the fire or explosion hazards discussed in
Section 3. Na-jPO^ and sodium carbonate are alkaline when dissolved in
water and will attack aluminum. NaH^PO* is acid when dissolved and will
attack many metals. Both ammonium nitrate and sodium nitrate are
classified by the Coast Guard and Department of Transportation (DOT) as
oxidizing materials that require a Yellow Label.
Disposal/Reuse
Industrially contaminated materials may on occasion be reprocessed
for reuse. If disposal is to be carried out, safe disposal of these
materials is here defined in terms of the following recommended provisional
limits in air, potable water and in marine habitats:
77
-------
Contaminant in Air
Ammonium Chloride
Ammonium Nitrate
Potassium Phosphate
Borax
Sodium Carbonate
Sodium Nitrate
Sodium Orthophosphate
Contaminant in Water
and Soil
Ammonium Chloride
Ammonium Nitrate
Potassium Phosphate
Borax
Sodium Carbonate
Sodium Nitrate
Sodium Orthophosphates
Provisional Limit
0.10 mg/M3
0.05 mg/M3
0.01 mg/M3
0.02 mg/M3
0.02 mg/M3
0.05 mg/M3
0.01 mg/M3
Provisional Limit
250 mg/1 as Cl
45 mg/1 as N03
0.05 mg/1 as H3P0
0.10 mg/1
.10 mg/1
45 mg/1 as NO^
0.05 mg/1 as HP0
Basis for
Recommendation
.01 TLV
Data for Similar Compounds
Data for Similar Compounds
Data for Similar Compounds
Data for Similar Compoun'ds
Data for Similar Compounds
Data for Similar Compounds
Basis for
Recommendation
Drinking Water Standard
Drinking Water Standard
Stokinger and Woodward
Method
Drinking Water Standard
Stokinger and Woodward
Method
Drinking Water Standard
Stokinger and Woodward
Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Dilution and Discharge
The Manufacturing Chemists Association has recommended disposal of
all the materials in this report by discharge into sewers after
neutralization and dilution. If each of the materials are diluted to the
levels indicated in Section 4 as recommended provisional limits in
water and the pH is adjusted to between 6.5 and 9.1, the materials can be
discharged into sewers or natural streams.
This acid limit is not applicable directly to the phosphate salts,
however, eutrophication 1s encouraged by phosphate levels above 0;1
mg/1 in water. Reference to Section 2 indicates that the salts are
not very toxic to mammalian life.
78
-------
Option No. 2 - Treatment with Sodium Hydroxide
Both ammonium nitrate and ammonium chloride upon treatment with sodium
hydroxide liberate ammonia and form soluble sodium salts, either the
chloride or nitrate. The liberated ammonia can be recovered and sold.
After dilution to the limits noted in Section 4, sodium nitrate or sodium
chloride can be discharged into a stream or sewer.
Option No. 3 - Incineration
Ammonium nitrate and ammonium chloride after dilution with water can
be charged into a gas fed incinerator. The NO and/or HC1 formed must be
J\
removed by appropriate gas cleaning devices (scrubber for HC1 and NOp,
oxidation or reduction for NO). Though this method is possible, it is
not in wide use.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The materials discussed in this-report have been classified as
probable candidate waste stream constituents for muncipial disposal.
Based on the discussion of disposal in Section 5, it may be concluded
that the waste treatment of these compounds can be adequately handled
locally and no consideration for National Disposal Site treatment is
warranted.
79
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards. 35:35-40,
Aug. 1971.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sittig, Marshall. Inorganic chemical and metallurgical process
encyclopedia. Park Ridge, New Jersey, Noyes Development Corporation,
1968. 883 p.
1492. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Chemical Rubber Company, 1966. 1,500 p.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
SO
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Ammonium Chloride (20)
IUC Name Ammonium Chloride
Common Names Sal Ammoniac
Structural Formula
NH4C1
Molecular Wt.
53.50
(2)
V
Density (Condensed) 1.54V1) @
Melting Pt.
Density (gas)
0)
Boiling Pt. 350 C sublimes
9
Vapor Pressure (recommended 55 C and 20 C)
&
9
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %}
Lower
Upper_
Upper_
(2)
Solubility
Cold Water 29.7g/100g at 0 C
Others: soluble - NH4OH
Acid, Base Properties Acid in aqueous solution due to hydrolysis.
Hot Water 75. 8g/100g at 100 C^Ethanol slightly soluble
Highly Reactive with Liberates ammonia when treated with sodium hydroxide
Compatible with
Shipped in barrels, multiwall paper sacks
ICC Classification "Q™?
Comments
(
Coast Guard Classification none
*1'
References (1) 1492
(2) 1570
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Ammonium Nitrate (24)
IDC Name Ammonium Nitrate
Common Names Norway Saltpeter
Structural Formula
NH4N03
80.05
Melting Pt. 169-6
.(1)
Molecular Wt.
Density (Condensed) 1 -725g/cc @ 23 C Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
(1)
Boiling Pt. 210 decomposes
0
Flash Point
Autoignition Temp.
Fl amiability Limits in Air (wt X) Lower
Explosive Limits in Air (wt. X) Lower
Upper,
Upper_
Solubility
Cold Water HSg/lOOg at 0 C^
Others: -alkalies - soluble
(2) (2)
Hot Mater 871q/100q at 100 C Ethanol 2.8q/100g at 20 C
Acid, Base Properties_
Highly Reactive with Reacts with strong alkalies to liberate ammonia. The mixture of
ammonium nitrate with diesel oil is used as an industrial explosive.
Compatible with
Shipped in Bags, carloads, truck loads
ICC Classification Oxidizing material
Comments
Coast Guard Classification Oxidizing material
References (1)1492
(2)1570
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Hams Potassium Phosphate (351)
IUC Hams Potassium Phosphate. Tribasic
Common Names
Structural Formula
Molecular Wt. 212.31
(2)
Melting Pt. 134(1 E
Density (Condensed)
Density (gas)_
Boiling Pt.
9
Vapor Pressure (recommended 55 C and 20 0
G>
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Solubility
Cold Hater Soluble^1\
Others:
Acid, Base Properties Strong base in water
Hot Mater Soluble
(1)
Upper_
Upper_
Ethanol Insoluble
(1)
Highly Reactive with
Compatible with
Shipped in 275. 300. 400-1b drumsH)
None
ICC Classification
Comments Hygroscopic'*'
(1)
Coast Guard Classification None
(1)
References (1) 1492
(2) 1570
-------
HAZARDOUS WASTES PROPERTIES
• WORKSHEET
H. M. Name Borax Dehydrated (381
IUC Name Sodium Tetraborate
Common Names
Structural Formula
Molecular Wt. 201. 27
^
Melting Pt. 741
Density (Condensed) 2.367g/cc P 23
Density (gas)
Boiling Pt. 1575
&
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 1.49g/1QOg at 0
Others:
Hot Water 8.79g/100g at 40 C Ethanol Insoluble
^
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in 100 lb paper bags, boxcars^
ICC Classification None
(
Coast Guard Classification None
(1)
Comments Hygroscopic^1
References (1) 1492
(2) 1570
84
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Carbonate (383)
IUC Name Sodium Carbonate
Common Names Soda Ash
Structural Formula
Molecular Wt. 106. 00
^
Melting Pt. 851
Boiling Pt. decomposes
Density (Condensed) 2.509 _ @ 0 c(2) _ Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Mater 7.1g/100 ml at 0
Others:
(2)
Hot Water 45.5g/100 ml at 100 CEthanol Insoluble
Acid, Base Properties Alkaline '
Highly Reactive with Acids * '
Compatible with
Shipped in Bags, barrels, drums.
ICC Classification None* '
Comments
Coast Guard Classification None
*
References (1) 1492
(2) 1570
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Nitrate (396)
IUC Mama Sodium Nitrate
Common Names Chile Saltpeter
Structural Formula
NaNO,
Molecular Wt. 85.01
(2)
Density (Condensed) 2.267
020 C
Melting Pt. 308 C
(2)
Boiling Pt. Decomposes
(2)
Density (gas)
Vapor Pressure (reconended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper.
Upper_
Solubility
Cold Mater 73g/100 ml at 0 C
Others:
(2)
(2)
(1)
Hot Water 180g/100 ml at 100 C Ethanol Slightly Soluble
Glycerol - soluble
Acid, Base Properties_
Highly Reactive with Organic matter
Compatible with_
Shipped in Tins, glass bottles, bags up to 100 Ib. bulk'
I ICC Classification ozidizing material
Comments
(1)
Coast Guard Classification oxidizing material
References (1) 1492
(2) 1570
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Phosphate (401)
IUC Name Sodium Phosphate. Monobasic
Common Names
Structural Formula
Molecular Wt. 138.05
(1)
(1)
Melting Pt. 200C-H?0
Density (Condensed )2.04ng/rr (?_20_c|_J__ Density (gas)
Vapor Pressure (recommended 55 C and 20 Q
_ 0 9
Boiling Pt.?00 C-2H20
& •
(1)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X) Lower
Upper
Upper_
Solubility fl)
Cold Water 59.9g/100 ml at 0 C(1^ Hot Water 427g/100 ml at 100 C Ethanol insoluble
Others:
Acid, Base Properties Acid' .
*1
Highly Reactive with
Compatible with
Shipped in Bags, drums, barrels
ICC Classification None
Comments
*2'
Coast Guard Classification
References (1) 1570
(2) 1492
87
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sodium Phosphate (401)
IUC Name Sodium Phosphate, Dibasic
Common Names
Structural Formula
Na2HP04 • 2H20
Molecular Wt. 178-05 .
Density (Condensed) 2-066
_ Melting Pt. 92-5 C-H20
@ _ 15 c^ Density (gas)
Boiling Pt.
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autbignition Temp.
Flammabili ty Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubil ity
Cold Water 82.5g/100 ml at 50
Others:
/, *
Hot Water 96.6q/100 ml at 80 C Ethanol slightly soluble
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in Bags, fiber drums, barrels^ '
ICC Classification "Q"e
Comments :
(2)
Coast Guard Classification none
(2)
References (1) 1570
(2) 1492
88
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Phosphate (401)
Structural Formula
IUC Name Sodium Phosphate, Tribasic
Common Names
Na3P04 • 10H20
Molecular Wt. 344.17* _ Melting Pt. 100 C^ Boiling Pt.
Density (Condensed) 2. 536g/cc & 175 C^ Density (gas) _ & _
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air,(wt. %) Lower Upper_
Solubility (1)
Cold Water 1.5g/100 ml at 10 Cu; Hot Water 157g/100 ml at 100 C Ethanol_
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in 1, 5-lb bottles, barrels,, bags'
ICC Classification Noneu; Coast Guard Classification,
Commen ts -
References (1) 1570
(2) 1492
89
-------
PROFILE REPORT
Ammonium Hydroxide (19), Boron Chloride (62), Carbon Monoxide (99) Hydro-
chloric Acid (ag) (214). Hydrofluoric Acid (aq) (216), Hydrogen Chloride
(g) (217), Hydrogen Peroxide (aq., >52%) (219). Iodine (tincture) (223),
Mixed Acids (277). Nitric Acid (299). Nitrous Oxide (313). Silicon Tetra-
chloride (369). Sulfur Dioxide (414). Sulfuric Acid (415), Sulfurous Acid
(416). Sulfuryl Fluoride (417), Sulfur Trioxide (509)
1. GENERAL
Introduction
The inorganic chemicals discussed in this Profile Report have been pre-
liminarily identified as probable candidate waste stream constituents for
industrial disposal. The grouping is based on broad chemical and/or physical
similarities and covers both gases and liquids.
Manufacture and Uses
The industrial processes of manufacturing and uses of the materials in
this report are summarized briefly as follows.
Ammonium Hydroxide. Ammonium hydroxide, NH,OH, also called ammonia
water, is essentially ammonia dissolved in water. Ammonia is a very
important and basic raw material for modern chemical industry. It is
produced in large tonnage by the well-known Haber process in which hydrogen
and nitrogen gases react catalytically under elevated temperature and
pressure to yield ammonia. In 1965, 8.4 million tons of ammonia were
ififi?
produced in the United States. The weaker ammonia water (10%) has
been used as a reflex stimulant. The stronger ammonia water (28-29%) may
1492
be used for the following purposes:
(1) as a detergent and in removing stains, bleaching, calico printing,
, and extracting plant colors (cochineal, archil, etc.) and alkaloids;
91
-------
(2) in the manufacture of ammonium salts, aniline dyes;
(3) as a chemical reagent and in a wide variety of other uses.
Boron Chloride. Boron chloride, BC13, is a colorless gas produced
commerically by chlorination of a mixture of boron trioxide and carbon at
a temperature range of 1,600 to 1,800 F. It can also be prepared according
to the reactions shown below:
(1) 7B203 + 6NaCl 8QO to 100° C ^2BC13 + SNa^
(2) 2NaBF4 + 3MgCl2 500 to 1000 C ^2Bcl3 + 2NaF + 3MgF2
(3) 2B203 + 3SiC13 600 to 1000 C ^BC^ + 3S102
Its uses are:
(1) in the manufacture of other boron compounds;
(2) as an acidic catalyst for organic reactions;
(3) in the purification of aluminum, magnesium, zinc and copper
alloys to remove nitrides, carbides, and oxides.
1492
Carbon Monoxide. Carbon Monoxide, CO, is a colorless and odorless
gas, highly poisonous and flammable. It is produced by partial oxidation
of hydrocarbon gases from the natural gas or by the gasification of coal
or coke. Its uses are:
(1) as a reducing agent in various metallurgical processes;
(2) in organic synthesis, especially in the Fischer-Tropsh process;
(3) in the manufacture of acids, esters, hydroxy acids, and metal
carbonyls;
(4) in the preparation of some catalysts.
Hydrochloric Acid. Hydrogen chloride, HC1 (g), is a colorless gas.
Its aqueous solution is the hydrochloric acid. It is produced from four
l fifi?
major processes:
-------
(1) as a by-product in the ch Tori nation of both the aromatic and
aliphatic hydrocarbons;
(2) from the reaction between sulfuric acid and salts of hydrochloric
acid such as the common salt, NaCl ;
(3) from the combustion of hydrogen and chlorine;
$
(4) from the Hargreaves type reactions such as
4NaCl + 2S02 + 02 + 2H20 - ^ 2Na2S04 + 4HC1
In 1969, 1.8 million tons were produced in the United States. Its
major uses are:
(1) in the manufacture of pharmaceutical hydrochlorides, various
inorganic and organic chlorides, and chlorine;
(2) in chlorination, isomerization, polymerization and alkylation
processes;
(3) as a chemical reagent.
1433
Hydrofluoric Acid. Hydrofluoric acid, HF, is a colorless, fuming,
corrosive liquid or gas. It is produced in heated kilns by reacting
fluorspar, CaF2, with sulfuric acid.
CaF2 + H2S04 - 20° to 25° C - ^CaS04 + 2HF
The U.S. production of hydrofluoric acid amounted to about 310,000 tons in
1969. Its uses are:
(1) in the manufacture of fluorinated organics;
(2) in the manufacture of synthetic cryolite, fluorides, fluoborates,
fluorosilicon products;
(3) in producing nuclear energy feed materials;
(4) in petroleum industry as an alkylation catalyst;
(5) in stainless steel industry;
(6) in etching and polishing glasses.
93
-------
1433 1492
Hydrogen Peroxide. ' Hydrogen peroxide, H202, is a colorless,
heavy liquid or at low temperatures a crystalline solid. It is manufactured
by:
(1) autoxidation of anthraquinone;
(2) oxidation of a lower secondary alcohol, preferably isopropyl
alcohol, to yield H202 and ketone;
(3) electrolysis through ammonium persulfate.
In 1969, 70,000 tons of H202 were produced in the United States. Its
uses are:
(1) as a bleaching agent of cotton textiles (largest uses);
(2) as an oxidizing agent for organic compounds (second largest
application);
(3) as an oxidizing agent for inorganic compounds;
(4) in the manufacture of organic and inorganic peroxides;
(5) in the plastics industry;
(6) in pharmaceutical preparations, mouth washes, dentifrices,
sanitary lotions;
(7) as a topical antiseptic;
(8) in rocket propulsion (using 90 percent solution).
Iodine (tincture).1433' 1662 Iodine is a violet-black rhombic crystal
with metallic luster. It is soluble in water and organic solvents such as
alcohol, ether, etc. It is produced by extraction from (1) the nitrate-
bearing earth known as caliche in Chile, (2) brine, and (3) seaweed.
The U.S. consumption of iodine amounts to about 3,500 tons a year. Its
main uses are:
(1) in the production of potassium iodide for photography (about
38 percent of total iodine is for this purpose);
94
-------
(2) in the manufacture of other iodine compounds, germicides,
antiseptics;
(3) as a catalyst in alkylation and condensation of aromatic amines,
sulfations, and sulfonations;
(4) as an additive to salt to meet the requirements of the thyroid
gland;
(5) as an analytical reagent;
(6) in various nutritional, medicinal and sanitary applications;
(7) in making artiftcal isotopes for biochemical, biological and
chemical structure research.
1433
Mixed Acids. Mixed acids are mixtures of sulfuric acid and
nitric acid in various proportions. The standard mixed acid contains
36 percent of concentrated nitric acid and 61 percent of concentrated
sulfuric acid. It is mainly used for nitrating purposes such as in
producing the nitrated cotton. The presence of concentrated sulfuric
acid increases the efficiency of the nitration by absorbing the water
which is the product of nitration reaction.
1 A *3 O
Nitric Acid. Nitric acid, HNCL, is a colorless or yellowish,
fuming suffocating, corrosive liquid. Virtually all nitric acid produced
commercially is obtained by the ammonia oxidation process. Despite the
many variations in the manufacturing details, the basic steps are as
fol1ows:
(1) Oxidation of ammonia to nitric oxide;
4NH3 + 502 * 4NO + 6H20
(2) Oxidation of nitric oxide to dioxide;
2NO + 0
95
-------
(3) Absorption of nitrogen dioxide in water to yield nitric acid and
release additional nitric oxide;
3N00 + H00 «~2HN00 + NO
J2 "2
3
In 1969, the total U.S. production of nitric acid was about 6.14 million
tons. Its main uses are summarized as follows:
(1) "About 70 to 85 percent of nitric acid produced is used to
produce ammonium nitrate which is used as fertilizer;
(2) About another 5 to 10 percent is used to produce cyclohexanone
which is. the raw material for making the monomers for nylon;
(3) The remaining nitric acid is used for manufacturing various
inorganic and organic nitrates and nitro compounds.
1433 1492
Nitrous Oxide. ' Nitrous oxide, NpO, more commonly known as
laughing gas, is a colorless gas with a slight sweet odor and taste. It
is prepared by thermal decomposition of ammonium nitrate at a temperature
range of 170 to 260 C. It can also be prepared by reaction between
hydroxylamine (NH2OH) and nitrous acid (HN02). Its uses are:
(1) as inhalation anesthetic and analgesic;
(2) as an oxidizing agent for organic compounds;
(3) in the manufacture of nitriles;
(4) in rocket fuel formulation;
(5) in the preparation of whipped cream.
1433
Silicon Tetrachloride. Silicon tetrachloride, SiCK, is a
colorless, fuming liquid with a suffocating odor. It is decomposed
by water into silicic and hydrochloric acids with much heat liberated.
Commercially, it is produced by reacting silicon carbide with chlorine
gas. The production in the United States is about 35 to 40 million Ib
a year. Its main uses are:
96
-------
(1) in producing smoke screen (fumed silica) in warfare;
(2) in the manufacture of high purity silicon;
(3) in the synthesis of silicon esters;
(4) in making special glass for the electronic industry.
Sulfur Dioxide. Sulfur dioxide, SOp, is a colorless gas with a
strong pungent, suffocating odor. It is mainly produced by the oxidation
of sulfur, and also an undesirable by-product in the exhaust streams of
petroleum refining, natural gas processing and coal-burning power plants.
About 85 percent of SOo produced goes into manufacturing sulfuric acid.
The other uses are:
(1) in the manufacture of pulp and paper;
(2) as a bleaching agent, refrigerant, and liquid solvent;
(3) in the manufacture of other chemicals;
(4) in preserving fruits, vegetables, etc., and as a disinfectant
1492
in breweries and food factories.
1 ceo
Sulfuric Acid. Sulfuric acid, HpSO,, is a colorless, oily,
corrosive liquid. It is so widely used that it may be considered as the
foundation of the modern chemical and petrochemical industries. In 1969,
28 million tons were produced in the United States. Its main uses are
given as follows:
(1) 44 percent of the sulfuric acid produced in the United States is
used to manufacture superphosphate (36%) and phosphate-type (8%)
fertilizers;
(2) 21 percent is used in the chemical industry for making phosphoric
acid, aluminum sulfate, paper, etc.;
(3) 10 percent is used in the petroleum industry, mainly in the
alkylation process (55%);
(4) Other major uses are in the manufacture of titanium pigments,
steel pickling, rayon, dyes and intermediates, detergents, etc.
97
-------
Sulfurous Acid. * Sulfurous acid, H2$03> is a colorless
liquid with the suffocating odor of sulfur. It is made by dissolving
sulfur dioxide in water. It is used mainly as sulfur dioxide in aqueous
solution. It is an excellent low cost reducing agent. In acid solution,
sulfurous acid will ,a1so act as an oxidizing agent in the presence of ,
reducing agents such as nydrogen sulfide, hydrogen iodide, reduced metal
salts, and zinc. Medicinally, sulfurous acid has been used externally
in parasitic skin diseases, as a swab in tonsillitis, and as a gastric
antiseptic?in pyrosis. *
Sulfuryl Fluoride. ' Sulfuryl fluoride, S02F2, is a colorless and
odorless gas. It is prepared according to the following reactions:
(1) BaCl2 + 2HS03F - -Ba(S03F)2 + 2HC1
(2) Ba(S03F)2 45QC »S02F2 + BaS04
(3) 2AgF2 + S02 - ^S02F2 + 2AgF
Sulfur Tri oxide. * Sulfur tri oxide, S03> exists in more than
one form. a-S03 is a silky, fibrous, needle- like crystal. 3-S03 is
metastable asbestos-like fiber. Y-S03 is a metastable, vitreous,
orthorhombic crystal or colorless liquid (melting point, 16.8 C). It is
prepared by catalytic oxidation of sulfur dioxide. Its major use is as
an intermediate in the manufacture of sulfuric acid. Other uses are:
(1) in sulfonation;
(2) in the manufacture of explosives;
(3) in the formation of addition compounds with the amines.
Sources and Types of Wastes
A large number of chemicals are covered in this report. Some of the
chemicals are the basic raw materials in the chemical industry. Hence,
the sources of the wastes are very widespread. Generally, they include
98
-------
coal-burning power plants, manufacturers and users of these chemicals in
various industrial plants, laboratories, and their distributors. For the
same reason, the types of wastes to be expected will include both
concentrated and dilute wastes in the exhaust gas and liquid streams.
Physical and Chemical Properties
Physical and chemical properties of the chemicals in this report are
given in the attached worksheets.
2. TOXICOLOGY0766'1492
Ammonium hydroxide or ammonia water is an irritant to the eyes and
mucous membranes. Corneal ulcers have been reported following splashing of
ammonia water in the eye. When heated, it emits toxic fumes. Inhalation
of concentrated fumes would cause edema of the respiratory tract, spasm
of the glottis, and asphyxia.
The toxic effect of boron chloride is not too well known. However,
when heated to decomposition, it would emit toxic fumes of chlorides.
Carbon monoxide is highly poisonous due to its strong affinity for
hemoglobin (210 times that of oxygen). It combines with hemoglobin to
form the carboxyhemoglobin which is useless as an oxygen carrier. The
effect on the body is therefore predominantly that of asphyxia. The
symptoms are headache, dizziness, nausea, vomiting, loss of muscular
control, unconsciousness, and death.
Hydrochloric acid is strongly corrosive. It is irritant to the
mucous membranes of the eyes and the respiratory tract. On contact,
concentrated solution would cause severe burns; permanent visual damage
may occur. Inhalation of the fume results in cough, choking, and
inflammation and ulceration of the respiratory tract. However, in general,
hydrochloric acid causes little trouble in industry, other than from
accidental splashes and burns.
99
-------
Hydrofluoric acid is corrosive and poisonous. External contact with
liquid or vapor causes severe irritation of the eyes and eyelids which
may result in prolonged or permanent visual defects or total destruction
of the eyes. Skin contact results in severe burns. Inhalation of vapor
may cause extreme irritation of respiratory tract, pulmonary inflammation,
congestion, and fluorosis. The symptoms are weight loss, malaise, anemia,
leukopenia, and osteosclerosis.
Hydrogen peroxide is not a toxic material. It is, however, a strong
v
oxidizer. Strong solutions can cause burns of skin and mucous membranes.
Iodine is one of few elements required by the human body. A normal
person needs about 75 mg of iodine a year to satisfy the requirement of
the thyroid gland. Lack of iodine in the body is the cause of goiter.
It is also an antidote to alkaloid poisoning. Iodine vapor is irritating
to the lung. But serious exposures are seldom due to the low volatility
of the solid. Ingestion of large quantities of iodine would cause
abdominal pain, nausea, vomiting and diarrhea.
Mixed acid is a mixture of nitric and sulfuric acids, and its
corrosive and toxic effects are those of the constituent acids.
Nitric acid is very corrosive. Its vapor is highly irritating to
the skin and the mucous membranes of the eyes and respiratory tract.
Continued exposure to the vapor may cause chronic bronchitis and chemical
pneumonia. Ingestion of nitric acid causes burning and corrosion of
mouth, esophagus, stomach, abdominal tenderness, shock, and death.
Nitrous oxide 'is not a toxic gas. In fact, it is used as inhalation
anesthetic and analgesic. However, in high concentrations, it is narcotic.
It is also an asphyxiant.
100
-------
Silicon tetrachloride may be an irritant to the eyes and respiratory
tract but is basically nontoxic. However, when heated to decomposition,
it will emit highly toxic fumes of hydrochloric acid. It will also react
with water or steam to produce toxic and corrosive fumes.
Sulfur dioxide is corrosive and poisonous. It is dangerous to the
eyes because it causes irritation and inflammation of the conjunctiva. It
affects the upper respiratory tract and the bronchi. It may cause edema of
the lungs or glottis, and can produce respiratory paralysis. Excessive
exposure to high enough concentrations of sulfur dioxide can be fatal.
Sulfuric acid is very corrosive to all body tissues. Contact with
eyes may result in total loss of vision and skin contact may produce severe
necrosis. Inhalation of concentrated vapor may cause serious lung damage.
Ingestion may cause severe injury and death.
Sulfurous acid is also corrosive. When heated to decomposition, it
emits the toxic fume of sulfur dioxide.
Sulfuryl fluoride is highly irritant and toxic. Inhalation may cause
nausea, vomiting, abdominal distress, diarrhea, muscular weakness,
convulsions, collapse, respiratory and cardiac failure and death.
Sulfur trioxide is irritant and corrosive to mucous membranes. It may
cause coughing, choking, and severe discomfort. When heated to
decomposition, it emits highly toxic fumes of oxides of sulfur. It will
also react with water or steam to produce toxic and corrosive fumes of
sulfuric acid.
101
-------
The Threshold Limit Value (TLV) recommended by the American Conference
of Governmental Industrial Hygienists and the reported lethal doses or
concentrations for the chemicals are given below. *
Contaminant
Ammonium Hydroxide
Boron Chloride
Carbon Monoxide
Hydrochloric Acid (g)
Hydrofluoric Acid (aq)
(g)
Hydrogen Peroxide
Iodine
Mixed Acids
Nitric Acid
Nitrous Oxide
Silicon Tetrachloride
Sulfur Dioxide
Sulfuric Acid
Sulfurous Acid
Sulfuryl Fluoride ...
Sulfur Trioxide
TLV
35 mg/M3 (NH3)
55 mg/M*
7 mg/M3
2 mg/M°
1.4 mg/M-
1.0 mg/M^
5 mg/M°
asphyxiant
13 mg/M3
1.0 mg/M3
20 mg/W
Lethal Dose or Concentration
or LD: 250 mg(NH3)/kg, rat
in LCCg: 20 ppm, rat
ih LC~ : 2000 ppm, mouse
ih LCCa: 1000 mg/M3, rabbit
ih LC5Q: 1310 ppm, rat
ih LCp : 1000 mg/M , guinea pig
or LD~ : 30 mg/kg, man
ih LC
Ca'
ih LC
or LD
50"
50:
8000 ppm, rat
ih LCCg(: 1000 ppm, rat
500 mg/M , rat
2140 mg/kg, rat
or LDCa: 100 mg/kg, rat
102
-------
3. OTHER HAZARDS
Boron chloride hydrolyzes readily in moist air or water to yield
corrosive hydrochloric acid. Carbon monoxide is very flammable. Hydrogen
peroxide is a powerful oxidizer, particularly the concentrated solution.
Heat is generated during hydrogen peroxide decomposition, and hence it is a
fire hazard when heated or contacted with flammable materials. Nitrous
oxide supports combustion and can form an explosive mixture with air. A
shock can shatter the nitrous oxide container with explosive force. Nitric
acid is a powerful oxidizing agent, and can cause a moderate fire hazard by
chemical reaction with reducing agents. It can also explode on contact
with powerful reducing agents. Similarly, sulfuric acid is also a
powerful oxidizing agent and can ignite upon contact with combustibles.
Also, sulfuric acid has a strong affinity for water, generating much heat
in mixing.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transporation
Corrosive materials such as sulfuric and hydrochloric acid must be
handled carefully. Contact with skin and inhalation of the fume should be
avoided. They should also be kept away from feed and food products. Flam-
mable chemicals, such as carbon monoxide, should be kept away from heat and
stored in cool and well-ventilated areas. Powerful oxidizers such as
hydrogen peroxide, nitric acid, etc., should be kept away from reducing
agents or combustible materials. Practically every chemical treated in
this report should be kept tightly closed in its original container. Ut-
most care must be excercised to prevent the leaking of carbon monoxide from
its containers, because it is highly poisonous and odorless. It should be
stored in a very well-ventilated area.
103
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Disposal/Reuse
In general, the chemicals discussed in this report could not be
economically reprocessed for reuse when they are contaminated or present
in the process waste stream. The notable exceptions are iodine, nitric
acid, and under certain conditions, sulfuric acid. Iodine is a valuable
commodity. Nitric and sulfuric acid wastes are often in concentrated
forms and are susceptible to regeneration. For the safe disposal of these
chemicals, the acceptable criteria for their release into the environment
are defined in terms of the following provisional limits:
Contaminant in Air
Ammonium Hydroxide
Boron Chloride
Carbon Monoxide
Hydrochloric Acid
Hydrofluoric Acid
Hydrogen Peroxide
Iodine
Mixed Acids
•
Nitric Acid
Nitrous Oxide
Silicon Tetrachloride
Sulfur Dioxide
Sulfuric Acid
Sulfurous Acid
Sulfuryl Fluoride
Sulfur Trioxide
Maximum Exposure Limit
0.02 mg/M3 as NH3
0.03 mg/M3
0.55 mg/M3
0.07 mg (vapor)/M3
0.02 mg (vapor)/M3
0.014 mg/M3
0.01 mg/M3
0.01 to 0.05 mg/M3
0.05 mg/M
0.09 mg/M3
0.1 mg/M3 as Si
0.13 mg/M3
0.01 mg/M3
0.01 mg/M3
0.20 mg/M3
0.01 mg/M3
Basis for
Recommendation
0.01 TLV for
NaOH
0.01 TLV for
BF3
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV for
H2S04 and HNO.
0.01 TLV
0.01 TLV for
N02
0.01 TLV for
Si
0.01 TLV
0.01 TLV
0.01 TLV for
H2S04
0.01 TLV
0.01 TLV for
H2S04
104
-------
Contaminant in Water
and Soil
Ammonium Hydroxide
Boron Chloride
Carbon Monoxide
Hydrochloric Acid
Hydrofluoric Acid
Hydrogen Peroxide
Iodine
Mixed Acid
Nitric Acid
Nitrous Oxide
Silicon Tetrachloride
Sulfur Dioxide
Sulfuric Acid
Sulfurous Acid
Sulfuryl Fluoride
Sulfur Trioxide
Provisional Limit
0.01 ppm (mg/1)
0.15 ppm (mg/1)
2.75 ppm (mg/1)
0.35 ppm (mg/1)
0.1 ppm (mg/1)
0.07 ppm (mg/1)
.0.05 ppm (mg/1)
0.05 to 0.25 ppm
(mg/1)
0.25 ppm (mg/1)
0.45 ppm (mg/1)
0.50 ppm (mg/1)
0.65 ppm (mg/1)
0.05 ppm (mg/1)
0.05 ppm (mg/1)
1.00 ppm (mg/1)
0.05 ppm (mg/1)
Basis for
Recommendation
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stckinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
105
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Neutralization
Waste streams containing acids, acidic oxides, or bases can be
treated by neutralization (1) to form a neutral solution which can then be
discharged safely, or (2) to yield an> insoluble precipitate which can be
removed by filtration. Belonging to this group are:
(1) acids: hydrochloric, hydrofluoric, nitric, sulfuric, sulfurous,
and mixed acid;
(2) acidic oxides: sulfur dioxide and trioxide;
(3) bases: ammonium hydroxide.
In addition, certain halides, such as boron chloride, silicon tetrachloride,
and sulfuryl fluoride, can be treated in the same manner.
For the acids, acidic oxides and halides, soda ash-slaked lime solution
is most commonly used. In the case of sulfuric and hydrofluoric acids,
the insoluble calcium sulfate or fluoride is precipitated out and removed
by filtration. In the case of nitric and hydrochloric acids, the neutral
solution of nitrate or chloride of sodium and calcium is formed and can be
discharged after dilution with water. In the case of halides, the
corresponding sodium and calcium salt solution is formed. For example,
in the case of boron chloride, a solution of chloride and borate of sodium
and calcium is formed.
For the removal of sulfur dioxide from a gas stream, there exists a
number of processes involving either regenerative or nonregenerative
alkaline absorption. These include, among others, various wet limestone
scrubbing processes, scrubbing with an aqueous solution of sodium carbonate,
106
-------
sodium sulfite, potassium formate or ammonia, suspension of magnesium
oxide, molten carbonate salt solutions, alkaline water, and furnace
injection of lime, limestone, and dolomite.*
Ammonium hydroxide may be neutralized by nitric acid to form a
solution of ammonium nitrate-which can be used as fertilizer.
Option No. 2 - Fractionation
Iodine is a volatile material and can be easily recovered by fraction-
ation. Fractionation is a convenient and economic way to reclaim the waste
materials, and is particularly recommended for recovering expensive items
such as iodine.
Option No. 3 - Incineration
Combustible materials can also be disposed of by controlled inciner-
ations. In this group are carbon monoxide and nitrous oxide. However,
burning of nitrous oxides can produce the undesirable oxides of nitrogen,
NO and N02, and therefore uncontrolled incineration is not recommended for
the disposal of nitrous oxide. Nitrous oxide can be incinerated in a unit
designed and operated to produce nitrogen and oxygen products.
Option No. 4 - Dilution and Decomposition by Water
Concentrated hydrogen peroxide is a powerful oxidizing agent. Rapid
decomposition is hazardous. Wasted concentrated hydrogen peroxide can be
disposed of by dilution with water to release the oxygen. .Agitation would
*The relative merits and the stages of development of the various
sulfur dioxide removal processes have been discussed extensively in
various technical journals. An excellent papar published recently is
"Sulfur Recovery" by G. M. Meisel, in Journal of Metals, May 1972.
107
-------
accelerate the decomposition. After decomposition, the waste stream may
be discharged safely.
Option No. 5 - Acid Regeneration
The recovery of sulfuric acid from inorganic and organic wastes for
1 fifi?
reuse are generally not economical, unless the following specific
9A7R
conditions can be s-atisfied:
(1) An existing sulfuric acid - producing plant is available at •
the site where the waste stream is being generated.
(2) Concentration of sulfuric acid in the waste must exceed
70 percent.
(3) The waste stream to be processed must exceed 50 tons/day.
(4) The organic impurities in the waste must not cause excessive
consumption of oxygen.
(5) The inorganic impurities must be very minor.
In the regeneration process , the spent sulfuric acid stream is thermally
decomposed to sulfur dioxide which is then converted back to sulfuric
acid in the acid plant by the contact process. If the spent sulfuric acid
stream is sufficiently clean but dilute (as in the case of the mixed acid
where sulfuric acid is used mainly to absorb the water formed during the
nitration process), it can be sent to the acid plant to be fortified for
reuse, even though this does not remove the impurities.
Nitric acid forms a constant-boiling azeotrope with water (68%
32% H20). The normal boiling point of the azeotrope is 120.5 C. Hence,
under certain conditions, spent nitric acid can be recovered by steam
distillation to yield concentrated acid. On the other hand, the hydrochloric
acid-water constant-boiling azeotrope contains only 20.24 percent of HC1 .
Therefore, regeneration of spent hydrochloric acid by steam distillation
is much less desirable.
108
-------
Option No. 6 - Gas Adsorption
Recovery of gases may be made by adsorption. The most commonly used
gas adsorbents are activated carbon, alumina, silica gel, and various
molecular sieves. The adsorption may be carried out in fixed or fluidized
beds in single- or multi-stage units. After adsorption, the gases can be
regenerated from the adsorbents either under reduced pressures or upon
heating by a carrier gas or vapor. For gases which do not react or
decompose on contact with water, steam is commonly used as the heating
medium. By simple condensation, the steam can be easily separated and
removed from the gas-steam mixture. Several activated carbon adsorption
processes have been developed to adsorb the sulfur dioxide and convert it
into sulfuric acid. None of these processes, however, has reached the
commercial production stage.
In addition, regenerative organic absorption processes have also been
considered for the removal of sulfur dioxide from the waste gas streams.
These include the use of dimethyl aniline, xylidine, hydrazine, sodium
citrate and other proprietary organic absorbents. All these processes
are still under development and have not been commercialized.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The waste stream constituents discussed in this report can be adequately
disposed of or recovered in the industrial sites by conventional means.
Therefore, it does not appear that consideration for their disposal at the
National Disposal Sites is warranted. However, some capacity for sulfur
dioxide disposal is required at the National Disposal Sites to handle, for
example, a secondary waste gas stream containing S02 generated as the re-
sult of processing sulfur-containing wastes or burning of sulfur-containing
fuels. Currently, the only proven and applicable commercial S02 removal
process is the Wellman-Lord process of scrubbing the waste gas stream with
an aqueous solution of sodium sulfite. Therefore, this process is recom-
mended for the removal of sulfur dioxide at National Disposal Sites.
109
-------
7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit va.lues for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0766. Sax, N. I. Dangerous, properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971.
Washington, U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1662. Shreve, R. N. Chemical process industries. 3d ed. New York,
McGraw-Hill, Incorporated, 1967. 905 p.
1752. Public Health Service. Drinking water standards, 1962. Washington,
U.S. Department of Health, Education, and Welfare, 1969. 61 p.
2478. Personal communication. G. I. Gruber, TRW Systems, to S. S. Kwong,
TRW Systems, Oct. 26, 1972.
110
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Ammonium Hydroxide
IUC Name
Coimion Names
Structural Formula
NH4OH
Molecular Wt. 35.05
(1)
Melting Pt. -77 C(
Boiling Pt.
Density (Condensed) &
Vapor Pressure (recommended 55 C and 20 Cj
Density (gas)
Flash Point
Autolgnition Temp.
FTammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water soluble
Others:
Acid, Base Properties
Hot Water
Ethanol
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments MCA warning label
Coast Guard Classification
References (1) 1570
111
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Boron Chloride (62)
IUC Name
Common Names
Structural Formula
BC1.
Molecular Wt. 117.17
(1)
Density (Condensed) 1.349
Melting Pt. -107.3 C
JJ_C Density (gas)
(1)
Boiling
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
L)pper_
Upper_
Solubil ity
Cold Water_
Others:
Hot Water decomposes
Ethanol decomposes
Acid, Base Properties^
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1 )
j/0'
112
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Carbon Monoxide (99)
Structural Formula
1UC Name
Common Names
CO
Molecular Wt. 28.01(1) Melting Pt. -207 C(1) Boiling Pt. -191.3 C(1'
Density (Condensed) 0.793 & Density (gas) 1.25 grams/1 & 0 C
Vapor Pressure (recommended 55 C and 20 C)
0 & 0
Flash Point Autoignition Temp. 1204 C
Flammability Limits in Air(vol %r Lower 12 Upper 75
Explosive Limits in Air (wt. %) Lower 12.5 Upper 74.2
Solubility
Cold Water ; Hot Water Ethanol
Others:
Acid, Base Properties •
Highly Reactive with
Compatible with
Shipped in
ICC Clas;
Comments
(!) i~\\ flammable gas,
ICC Classification v 'flammable gas, red gas labeKoast Guard Classification * I;rpd gas lahpl
References (1) 0766
(2) 1492
113
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrochloric Acid (214)
IUC Name
Common Names
Structural Formula
HC1 (aq.)
Molecular Wt.
Density (Condensed)
Melting P.t.
Boiling Pt.
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt *) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water_
Others:
Hot Water
Ethanol
Acid, Base Properties strongly acidic
Highly Reactive with
Compatible with_
Sh i pped i n
M\corrosive liquid,
ICC Classification white label
/^corrosive liquid,
Coast Guard Classification ''white label
Comments.
References (1) 0766
114
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrofluoric Acid (216)
IUC Name
Common Names
Structural Formula
HF (aq.)
Molecular Wt.
Density (Condensed)
Melting Pt.
Boiling Pt.
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
G>
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Upper_
Upper
Solubility
Cold Water_
Others:
Hot Water
Ethanol
Acid, Base Properties acidic
Highly Reactive with_
Compatible with
Shipped in
,,} corrosive liquid,
ICC Classification { ' white label
M)corrosive liquid
Coast Guard Classification white label
Comments.
References (1) 0766
115
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrogen Chloride (217)
Structural Formula
IUC Name
Common Names
(g)
Molecular Wt. 36.46(1) Melting Pt. -H4.8 C(1) Boiling Pt. -84.9 C(1)
Density (Condensed) @ Density (gas) _@
Vapor Pressure (recommended 55 C and 20 Q
a @ . a
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubil ity
Cold Water 82-3 grams/100 ml g 0 CHot Water 56.1 grams/100 ml @60 Ethanol _soluble
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
/?\noninflammable
ICC Classification Coast Guard Classification^ 'gas, green gas
r . label
Comments :
References (1) 1570
(2) 0766
116
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrogen Peroxide (219)
1UC Name
Common Names
Structural Formula
(aq. >52%)
Molecular Wt.
Density (Condensed)
Melting Pt.
Density (gas)
Boiling Pt.
G>
Vapor Pressure (recommended 55 C /md 20 C)
0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits.in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water_
Others:
Hot Water
Ethanol
Acid, Base Properties
Highly Reactive with reducing agent
Compatible with
Shipped in
ICC Classification
Comments
/^corrosive liquid
Coast Guard Classification white label
References (1) 0766
117
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Iodine (tincture) (223)
IUC Name
Common Names
Structural Formula
Molecular Wt. 253.809v
(1)
Melting Pt. 113.5 C
(1)
Boiling Pt. 184.35 C
1)
Density (Condensed) 4.93
Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flanmability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility - - ,a, 20.5 grams/lOOml
Cold Mater 0.029 grams/100 mg 3 20LHot Hater 0.078 grams/100 ml ga!tTiano1 @ 15 C
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
118
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Mixed Acids (277)
IUC Name J
Common Names
Structural Formula
H2S04 + HN03
Molecular Wt.
Density (Condensed)
Melting Pt.
Boiling Pt.
Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
9
Flash Point
Autoignition Temp.
Flanmability Limits in Air (wt %) Lower_
Explosive Limits in Air {wt. %) Lower
Upper.
l)pper_
Solubility
Cold Water_
Others:
Hot Water
Ethanol
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
/^corrosive liquid
Coast Guard Classificationv 'white label
ICC Classification
Comments Mixed acid is a mixture of nitric acid and sulfuric acid in various proportions.
References (1) 0766
119
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitric Acid (299)
IUC Name
Common Names
Structural Formula
HNO-
Molecular Wt. 63-01
Density (Condensed) 1.50
Melting Pt. -42 C
Density (gas)
(1)
Boiling Pt.__8
Vapor Pressure (recommended 55 C and 20 C)
@
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility^]*
Cold Water
Others:
Hot Water
Ethanol
Acid, Base Properties strongly acidic
Highly Reactive with_
Compatible with
Shipped in
ICC Classification
corrosive liquid,
white label _
corrosive liquid
/?\corrosve
Coast Guard Classification' 'white label
Comments Nitric acid is a powerful oxidizing agent.
References (1) 1570
(2) 0766
120
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitrous Oxide (313)
IUC Name
Common Names
Structural Formula
Molecular Wt. 44.Or
Density (Condensed)
Melting Pt. -90.8 C
Density (gas)
(1)
Boiling Pt. -88.5
&
Vapor Pressure (recommended 55 C and 20 0
Flash Point
. Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility (1)
Cold Water
Hot Water
Ethanol soluble
Others : soluble in ether.
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in
/2\ nonflammable gas,
ICC Classification green label
Comments ;
/2%noninflanimable
'
/2%nonnanimae
Coast Guard Classification' gas, green gas
label
References (1) 1570
(2) 0766
121
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Silicon Tetrachloride (369)
IUC Name
Common Names
Structural Formula
SiCl,
169.90
(1)
Molecular Wt.
Density (Condensed) 1.483
Melting Pt. -70
20 C
r(D
Boiling Pt. 57.57 C
(1)
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
&
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower '
Explosive Limits in Air (wt. %) Lower
Solubility '
Cold Water decomposes Hot Water decomposes
Others:
Acid, Base Properties
Upper_
Upper_
Ethanol decomposes
Highly Reactive with
Compatible with
Shipped in
/,»corrosive liquid,
ICC Classification u;white label
,9icorrosive liquid
Coast Guard Classification^'white label
Comnents.
References (1) 1570
(2) 0766
122
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sulfur Dioxide
IUC Name
Common Names
Structural Formula
SO-
(1!
Molecular Wt. 64-06
Density (Condensed) 1.434 @
Melting Pt. -75.5 C
_On_C Density (gas)
(1)
Boiling Pt. -10.0 C
(1)
Vapor Pressure (recommended 55 C and 20 Q
2538 mm Hg g 21.1 C
(1)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Solubility
Cold Water
Others:
Lower
Upper_
Upper
Hot Water
Ethanol
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
/,v nonflammable gas,
ICC Classification u; green label
/,\noninflammable
Coast Guard Classification' 'gas, green gas
Comments.
label
References (1) 0766
123
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sulfuric Acid (415)
IUC Name
Structural Formula
Common Names
98.98
1)
Molecular Wt.
Density (Condensed) 1.841
(96-98%)
Vapor Pressure (recommended 55 C and 20 Q
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sulfurous Acid (416)
IUC Name
Common Names
Structural Formula
H2S03
(1)
Molecular Wt. 83.08
Density (Condensed) Ca 1.03 0
Melting Pt.
Density (gas)
Boiling Pt.
&
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper
Upper_
Solubility
Cold Water Soluble
Others:
Hot Water
Ethanol Soluble
Acid, Base Properties Acidic
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Coast Guard Classification
Comments Sulfurous acid exists in solution only. No free sulfurous acid has been
isolated.
References (1) 0766
125
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Sulfuryl Fluoride (417)
Structural Formula
IUC Name
Common Names
S00F
22
Molecular Wt. 102.06^ Melting Pt. -136.7 C^ Boiling Pt. -55.4 C(1)
Density (Condensed) 1.7 @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
G> 9
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sulfur Trioxide (509)
IUC Name
Common Names
Structural Formula
Molecular Wt.
80.06
(1)
a 62.3 C
8 32.5 C
Melting Pt. y 15.8 C
SO,
1)
Boiling Pt. 44.8 C
(i;
Density (Condensed) a 1.97^) @ 20. C
Y 1.92 20 C
Vapor Pressure (recommended 55 C and 20 Q
Density (gas)_
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility*1*
Cold Water decomposes
Others:
Hot Water decomposes
Ethanol
Acid, Base Properties
Highly Reactive with SO-, combines with water with explosive violence to form sulfuric acid.
Compatible with
Shipped in
ICC Classification_
Commen ts
Coast Guard Classification
References (1) 1570
127
-------
PROFILE REPORT
Ammonium Perchlorate (25), Ammonium Persulfate (26),
Sodium Hypochlorite (222). Magnesium Chlorate (246),
Sodium Carbonate Peroxide (384), Sodium Perchlorate (399),
Zinc Chlorate (455), Calcium Hypochlorite (482)
1. GENERAL
Introduction
The inorganic chemicals in this Profile Report are basically nontoxic.
However, they are oxidizing agents that constitute fire or explosion hazards.
They are grouped together because they can be handled by similar disposal
processes.
Manufacture and Uses
Ammonium Perchlorate. Ammonium perchlorate, NH^CIO*, is a white
crystalline material, which is made by a six-operation process which involves
reacting sodium perchlorate, ammonia, and hydrochloric acid in an aqueous
medium. After cooling and concentrating the reaction mixture by flash
evaporation, ammonium perchlorate comes out of solution in a crystallizer,
under closely controlled conditions. The NH.C10, crystals are separated
from the slurry by centrifugation, washed, and reslurried in saturated
solution. The second NH^CIO, slurry is centrifuged, and the
cake produced is washed, dried and sized. The filtrate from the
first centrifugation is concentrated to permit crystallization of the
excess NaCl present. The slurry produced is centrifuged, and the filtrate
returned to the first operation as a raw material. The crystalline NaCl
2489
is washed and dried for sale as a by-product. Ammonium perchlorate is
used as an ingredient of explosives, in solid propellant compositions, in
pyrotechnic compositions, and as a raw material for the production of
perchloric acid and numerous metallic perchlorates.
129
-------
Ammonium Persulfate. Ammonium persulfate, (NH^kS^Og, is a strong
oxidizing material that occurs as white crystals. It is prepared by
electrolysis of acid solutions of ammonium sulfate using electrolytic
cells having a stationary catholyte. Usually platinum anodes and graphite
cathodes are employed. Tne ammonium persulfate is recovered by
crystallization. Its uses include the manufacture of hydrogen peroxide,
the oxidation of inorganic and organic compounds, and electroplating.
Sodium Hypochlorite. Sodium hypochlorite, NaOCl , exists only in
aqueous solution. The aqueous solutions generally contain sodium hydroxide.
It is employed as a disinfectant and deodorant in dairies, creameries,
water supplies, sewage disposal and as a bleaching agent for cotton, linen,
jute, paper pulp and oranges. The most common method of manufacture is
the reaction between sodium hydroxide solution and gaseous chlorine.
C12 * 2NaOH * NaCI + H20 + NaOCl
Another method formerly in wide use was the electrolysis of a concentrated
salt solution. The electrolytic cells used to manufacture NaOCl did not
have any diaphragm and were operated at high current density in nearly
neutral solution. The cells were designed with the chlorine given off at
the anode.1662
Magnesium Chlorate. Magnesium chlorate, Mg(C10o)p> is a white
hygroscopic powder that has a bitter taste. It is prepared by reacting
magnesium chloride and sodium chlorate followed by crystallization of
magnesium chlorate. It is used in medicine, as a defoliant and as a
desiccant.
Sodium Carbonate Peroxide. Sodium carbonate peroxide,
is a white crystalline powder that is stable at room temperature when dry
but decomposes rapidly at 100 C. It is prepared by crystallization from
a solution of soda ash and hydrogen peroxide. It is used in household
detergents, dental cleansers, bleaching and dyeing compounds, and in
formulations for the modification of starch. 16'166
130
-------
Sodium Perch 1 orate. Sodium perchlorate, NaCIO,, forms white
deliquescent crystals. It is prepared by the electrolysis of sodium in
steel electrolytic cells which have smooth platinum anodes or lead dioxide
anodes and operate at 6.5 to 7.0 volts, 2,500 amps., and at a temperature
2489
of 35 to 50 C. The solution is concentrated and crystallized. NaCIO*
is used as analytical reagent and to a limited extent in explosives.
The major use is in the preparation of ammonium perchlorate.
Zinc Chlorate. Zinc chlorate, Zn(C103)2'4H20, is a color-less to
yellow deliquescent crystalline material. It decomposes at 60 C. It is
prepared by reacting zinc chloride with a solution of sodium chlorate
followed by crystallization.
Calcium Hypochlorite. Calcium hypochlorite, CafOCl)^ is a white,
crystalline solid. It is prepared by chlorination of a slurry of lime and
caustic soda with subsequent precipitation of calcium hypochlorite
dihydrate which is dried under vacuum. It is used as an algicide, fungi-
1 ceo
cide and bleaching agent. *"
Physical/Chemical Properties
The physical/chemical properties of the compounds covered by this
Profile Report are summarized on the attached worksheets.
2. TOXICOLOGY
The materials treated by this report are not considered particularly
toxic. The Amercian Conference of Government Industrial Hygienists has
not established Threshold Limit Values (TLV) for any of the compounds
listed in this report nor have any maximum allowable concentrations (MAC)
in water for man been established.0225'1536 Perchlorates are irritating
to the skin and mucous membranes. Chlorates and persulfates can irritate
the gastrointestinal tract. If absorbed, chlorates can cause hemolysis
131
-------
of red blood cells, methemoglobinemia, liver and kidney damage. Five
1142
grams of chlorate salt is considered a toxic dose for adults.
Hypochlorites and peroxides are irritating to the skin and mucous membranes.
3. OTHER HAZARDS
All of the materials included in this report are oxidizing materials
and contact with combustible material should be avoided. The perchlorates
are powerful oxidizers that explode violently when heated with sulfur,
organic matter, or finely divided metal, particularly magnesium and
aluminum. Large exotherms occur upon heating. The chlorates explode
when exposed to heat or shock and when rubbed in the presence of organic
1142
or reducing materials.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
All the materials in this report must be handled in such a manner
that they do not come into contact with reducing substances. They should
not be exposed to heat. Contact with the skin should be avoided. Ammonium
perchlorate, magnesium chlorate, sodium perchlorate, zinc chlorate, and
calcium hypochlorite are classified by Department of Transportation (DOT)
and the U. S. Coast Guard as oxidizing materials that require a Yellow
Label.0776
Disposal/Reuse
Industrially, contaminated materials discussed in this report are not
usually reprocessed for reuse since these materials are oxidizing agents
that may ignite or explode easily when contaminated with organic or re-
ducing materials. When disposal of wastes containing these materials is
required, the acceptable criteria for their release into the environment
are defined in terms of the following provisional limits:
132
-------
Contaminant in Air
Ammonium perch!orate
Ammonium persulfate
Sodium hyprochlorite
Magnesium chlorate
Sodium carbonate
peroxide
Sodium perch!orate
Zinc chlorate
Calcium hypochlorite
Provisional Limit
0.01 mg/M3
0.01 mg/M
0.02 mg/M3
0.01 mg/M3
0.02 mg/M3
0.02 mg/M3
0.01 mg/M3
0.025 mg/M:
Basis for
Recommendation
Provisional limit
for(NH4)2S04
0.01 TLV for NaOH
Provisional limit
for MgS04
0.01 TLV for NaOH
0.01 TLV for NaOH
0.01 TLV for ZnCl,
Provisional limit
for CaF0
Contaminant in Water
and Soil
Ammonium perch!orate
Ammonium persulfate
Sodium hypochlorite
Magnesium chlorate
Sodium carbonate
peroxide
Sodium perchlorate
Zinc chlorate
Calcium hypochlorite
Provisional Limit
0.05 ppm (mg/1)
0.05 ppm (mg/1)
0.10 ppm (mg/1)
125 ppm (mg/1) as Mg
0.10 ppm (mg/1)
0.10 ppm (mg/1)
5 ppm (mg/1) as Zn
0.125 ppm (mg/1)
Basis
Recommendation
Stokinger and Woodward
Method
Drinking Water
Standard
Stokinger and Woodward
Method
Stokinger and Woodward
Method
Drinking Water
Standard
Stokinger and Woodward
Method
133
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Reduction
Disposal of oxidizing agents covered by this report may be accomplished
by dissolving the material, adding the resultant solution to a large volume
of a concentrated solution of reducing agent (sodium thiosulfate, sodium
bisulfite, or a ferrous salt), and then acidifying the mixture with SM-HpSO*.
When reduction is complete, soda ash is added to make the solution alkaline.
(If an ammonium salt is present, ammonia will be liberated and will require
recovery.) The alkaline liquid is decanted from any sludge produced,
neutralized, and diluted before discharge to a sewer or stream. The
sludge (if magnesium or zinc are present) is added to a landfill. This
process is considered satisfactory for treatment of the materials covered
by this report.
Option No. 2 - Open Burning
Uncontaminated oxidizers, particularly the perchlorate reject materials,
process fines, or overruns from grinding or blending operations, are
collected and transported to "burn sites" in open-top 30-gal. drums with
lids attached. At the burn sites the oxidizers are spread thinly over a
layer of excelsior or other flammable dry materials. The flammable
materials are ignited by a squib, fired electrically, with the controls
at a safe distance. Contaminated materials are left in the containers in
which they are collected and the material burned in the container in a
similar manner. Though this process is widely used at solid propellent
manufacturing sites, it is not considered satisfactory because large
quantities of NO and HC1 are liberated.
A
134
-------
Option No. 3 - Incineration
Though not in wide use, dilute aqueous solutions of all the materials
covered by this report can be destroyed by injection into an incinerator
supported by a gas flame. Scrubbers are required to remove HC1, NOV,
X
and metal oxide particles from the incinerator vent gases. Properly
designed and operated incineration is considered a promising near-future
method for the disposal of aqueous wastes containing oxidizing materials
but additional research is required before the process could be employed
on a large scale.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Wastes streams containing hychlorites, chlorates, perchlorates, and
persulfates are found in only small quantities, are basically nontoxic,
and can be adequately disposed of by the simple reduction technique dis-
cussed under Option No. 1. For these reasons, the oxidizing materials
included in this Profile Report are not considered as candidate waste
stream constituents for national disposal.
135
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 2d ed. Washington, 1969. 176 p.
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards. 35:35-40. Aug. 1971.
0625. Sathl, Q. R. Air pollution aspects of chlorine gas. Technical
Report, Bethesda, Maryland, Litton Systems, Inc., Sept. 1969.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sittig, M. Inorganic chemical and metallurgical process encyclopedia.
Park Ridge, New Jersey, Noyes Development Corporation, 1968. 883 p.
1142. JANAF Hazards Working Group, JANAF Propulsion Committee. Chemical
Rocket Propellant Hazards. Vii CPIA Publication 194, May 1970.
Chemical Propulsion Information Agency, John Hopkins University,
Silver Spring, Maryland.
1416. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Ohio, Chemical Rubber Company, 1966. 1,500 p.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
2489. Schumacher, J. C. Perchlorates, their properties, manufacture and
uses. New York, Reinhold Publishing Corporation, 1960. 257 p.
136
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ammonium Perchlorate (25)
Structural Formula
IDC Name Ammonium Perchlorate
Common Names
NH4C104
Molecular Wt. 117-5 Melting Pt. 150 C decomposes Boiling pt. decomposes
Density (Condensed) 1.95g/cc @ 20 t__ Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
0 ' Q on« n/nnn nv' I
Cold Water 20g/100 ml at 25 C(1) Hot Water 88 g/100 ml at 100 C Ethanol 9'908 g/10Q g
Others: Acetone 2.2 6 g/100 g
Acid, Base Properties
Highly Reactive with reducing material
Compatible with
Shipped in metal drums with polyethylene liners.
ICC Classification oxidizing material^ Coast Guard Classification material*9
Comments.
References (1) 1142
137
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Magnesium Chlorate (245)
Structural Formula
IUC Name Magnesium Chlorate
Common Names
Mg(C103)2'6H20
Molecular Wt. 299.33 Melting Pt. 251 C decomp". Boiling Pt._
Density (Condensed) 180 g/cc 3 25 C ' ' Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt ») Lower Upper_
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
(1)
Cold Water 49.90 g/100 ml at 25 C Hot Water ver> soluble Ethanol,
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in glass bottles'2'
ICC Classification oxidizing material ^ Coast Guard ClassificationOxidizing Material '
Comments _^______
References (1) 1570
(2) 1416
138
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Carbonate Peroxide (384)
Structural Formula
IUC Name
Common Names
2Na2C03'3H202
decomposes
Molecular Wt. not a true compound Melting Pt. above 10° c Boiling Pt.
Density (Condensed) & Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
G> &
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water soluble Hot Water Ethanol.
Others:
Acid, Base Properties
Highly Reactive with reducing substances
Compatible with
Shipped in TOO 1b fiber drums
ICC Classification None coast Guard Classification None
Comments __________^___
References (1) 1416
139
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sodium Perchlorate (399)
Structural Formula
IUC Name Sodium Perchlorate
NaC104
Common Names
Molecular *Wt. 122.45^ Melting Pt. 482 C Decomp. Boiling Pt.
Density (Condensed) 2.0 2g/cc (j>20 C^ Density (gas) @
Vapor Pressure (recommended 55 C and 20 Q
Flash Point Autoignition Temp.
Flanmability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. X) Lower Upper
Solubility /I \
Cold Water 2Q9g/10Q ml at 15 C Hot Water 284 9/10° m1 at 5° C Ethanol Soluble
Others:
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in bottles, drums, kegs
ICC Classification°xidizin9 material Coast Guard classification Material
Comments
References (1) 1570
(2) U16
140
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Chlorate (455)
IUC Name Zinc Chlorate
Common Names
Structural Formula
2n(C]0-,)0'4H90
Molecular Wt.
3°4'36
Melting Pt.
60 C decomp-
Density (Condensed) 2.15 g/cc p 20
Density (gas)
Boiling Pt. _______
@
Vapor Pressure (recommended 55 C and 20 C)
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium Hypochlorite (482)
IDC Name Calcium Hypochlorite
Common Names
Structural Formula
Ca(OCl)2'4H20
Molecular Wt. 215.06
Melting Pt.
Boiling Pt.
Density (Condensed)
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Solubility
Cold Water very soluble
Others:
Hot Water decomposes
Upper_
Upper_
Ethanol decomposes
Acid, Base Properties_
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification
Commen ts
Coast Guard Classification none
References (1) 1570
142
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ammonium Persulfate (26)
IUC Name
Ammonium Persulfate
Structural Formula
Common Names
Molecular Wt. 228-20
(!
(1)
Melting Pt. 120 C decomposes Boiling Pt.
( '
Density (Condensed) T-982 9/cc @ 20 C v ; Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
G» 9
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility 100 C
Cold Water 70.6 g/100 ml at OC^ Hot Water 103.8 g/100 ml at Ethanol Insoluble
Othe rs : Acetone - insoluble * '
Acid, Base Properties
Highly Reactive with reducing materials^ '
Compatible with
Shipped in bottles, drums
ICC Classification None
Comments
(2)
Coast Guard Classification None
(2)
References (1)1570
(2) 1416
143
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H M Name Sodium Hypochlorite (222)
Structural Formula
IUC Name Sodium Hypochlorite
Common Names NaOC1
Molecular Wt. 74-45 Melting Pt. " Boiling Pt.
Density (Condensed) @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Soluble Hot Water Ethanol
Others:
Acid, Base Properties Solution is strongly basic
Highly Reactive with reducing agents
Compatible with
Shipped in glass carboys, drums ^ '
ICC Classification None ^ ' Coast Guard Classification
Comments present only in solution
References (1) 1416
144
-------
PROFILE REPORT
Ammonium Sulfide (29), Antimony Pentachlon'de (35), Antimony Trichloride (41),
Calcium Carbide (89), Calcium Hydride (93), Lithium Aluminum Hydride (244),
Potassium Binoxalate (342), Potassium Hydroxide (347), Potassium
Oxalate (348), Sodium Amide (375), Sodium Hydride (391). Sodium
Hydrosulfite (392). Sodium Sulfide (404), Sodium Thiocyanate (406)
Stannic Chloride (408). Thiocyanates (432)
1. GENERAL
. •••,
Introduction
The inorganic materials included in this Profile Report have been
preliminarily identified as probable candidate waste stream constituents
for industrial disposal. These materials either dissolve readily in water
or react with water violently. Their toxicities vary from irritating and
corrosive to skin to highly toxic. Many of them emit corrosive and/or toxic
fumes when heated to decomposition or by chemical reactions on contact with
water or moisture in air. Most of them are not produced in large tonnage.
1433, 1492
Manufacture and Uses
Ammonium Sulfide. Ammonium sulfide, (NHJ^S, is a colorless crystal at
temperatures below -18 C. -At higher temperatures, it decomposes into ammonia
and ammonium hydrosulfide (NH^HS). Ammonium sulfide is prepared by reacting
excess of ammonia with hydrogen sulfide. It has limited uses in (1) the
application of patina to bronze; (2) photographic developers; and (3) textile
manufacture.
Antimony Pentachloride. Antimony Pentachloride, SbCl,-, is a yellow, oily
liquid. It loses chlorine readily. The decomposition is appreciable even
at 12 C. It is prepared by passing chlorine gas into molten antimony
trichloride. It is used as a catalyst when replacing a fluorine substituent
with chlorine in organic compounds.
145
-------
Antimony Trichloride. Antimony trichloride, SbCl^, is a colorless,
rhombic, and deliquescent crystal. It fumes in air. It is prepared by
direct chlorination of antimony trioxide, antimony trisulfide or antimony.
Its uses are:
(1) as a catalyst;
(2) as a mordant in calico printing;
(3) in the manufacture of other antimony salts and organic syntheses;
(4) as a chemical reagent.
Calcium Carbide. Calcium carbide, CaC2, is a colorless, orthorhombic
crystal or 1n grayish-black, irregular lumps. It decomposes readily on
contact with water, producing acetylene gas. It is produced by heating
lime and carbon (usually coke or anthracite) in an electric furnace at
2000 to 2200 C. In 1969, 920,000 tons of calcium carbide were produced
1929
in the United States. Its uses are:
(1) in generating acetylene for lighting (largest use), and welding
and cutting metals;
(2) in the manufacture of calcium cyanamide and lampblack;
(3) as a reducing, dyhydrating or desulfurizing agent in various
chemical and metallurgical processes;
(4) in signal fires for marine services.
Calcium Hydride. Calcium hydride, CaH2, is a white rhombic crystal.
It decomposes on contact with water. Commercially, it is produced by
reacting calcium with hydrogen at atmospheric pressure and a temperature
of 300 C. Its uses are:
(1) in the production of rare metals such as titanium, zirconium,
vanadium, niobium, uranium, and thorium from their oxides;
(2) as a drying agent for drying esters, ketones, halides, air,
hydrogen, other gases, etc.;
(3) as a source of hydrogen.
,46
-------
Lithium Aluminum Hydride. Lithium aluminum hydride, LiAlH^, is a
white crystalline powder. It is stable in dry air at room temperatures,
but it will decompose at a temperature above 125 C or in moist air. It
is prepared by the addition of an ether solution of aluminum chloride to
a slurry of lithium hydride in ether. It can also be prepared from its
elements at 2000 psi and 100 C. It is used as a reducing agent and in the
preparation of other hydrides and organic compounds.
Potassium Binoxalate. Potassium binoxalate, KHCpO*, also called
potassium acid oxalate, is a colorless, odorless, monoclinic crystal. It
is used in removing ink stains, scouring metals, cleaning wood, photography,
bleaching stearin, and as a mordant in dyeing.
Potassium Hydroxide. Potassium hydroxide, KOH, is in the form of
white or slightly yellow lumps, rods or pellets. It rapidly absorbs
moisture and carbon dioxide from the air and deliquesces. Commercially,
it is produced by electrolysis of potassium chloride. About 180,000 tons
1QPQ
of KOH (90% basis) were produced in the United States in 1969.'*" Its
uses are:
(1) in the manufacture of "soft" soap;
(2) in producing other potassium compounds and organic syntheses;
(3) in electroplating, photoengraving and lithography;
(4) as a chemical reagent;
(5) as a mordant for wood;
(6) as a paint and varnish remover;
(7) in mercerizing cotton.
Potassium Oxalate. Potassium oxalate, I^C^^O, is a colorless,
odorless, monoclinic crystal, efflorescent in warm, dry air. Its uses are:
(1) in cleaning and bleaching straw
(2) in removing stains in photography;
147
-------
(3) in examination of blood to prevent its coagulation;
(4) as a reagent in analytical chemistry.
Sodium Amide. Sodium amide, NaNhL, also known as sodamide, is a white
to olive-green solid with seashell structure. It reacts violently with
water to form sodium hydroxide and ammonia. It is produced by reacting
ammonia gas with molten sodium or liquid ammonia with sodium in presence
of ferric nitrate as a catalyst. Its uses are:
(1) as a dehydrating agent;
(2) in the production of indigo, sodium azide, and hydrazine;
(3) as an intermediate in the preparation of sodium cyanide;
(4) in ammonolysis, Claisen condensation, alkylation of nitriles and
ketones;
(5) in the synthesis of ethynyl compounds, acetylenic carbinols.
Sodium Hydride. Sodium hydride, NaH, is a silvery needle. The
commercial product is a gray-white powder. It reacts explosively with
water. It is prepared by passing hydrogen gas into molten sodium dispersed
in oil or mixed with a catalyst such as anthracene at a temperature above
250 C. Its uses are:
(1) in the reduction of oxide scale of metals (sodium hydride used
is in solution with molten sodium hydroxide);
(2) as a reducing agent and reduction catalyst in high temperatures.
Sodium Hydrosulfite. Sodium hydrosulfite, Na2S204, is a white or
grayish-white crystalline powder, with a slight characteristic odor. It
oxidizes in air (more readily so in the presence of moisture or when in
solution) to bisulfite and bisulfate. It is prepared by the reduction of
sodium sulfite, sodiuto bisulfite, or sulfur dioxide with a reducing agent
such as iron or zinc powder, sodium or zinc amalgam or sodium suspension.
148
-------
The U.S. production of sodium hydrosulfite amounted to about 74 million
,lb in 1967. Its applications are based mainly on its powerful reducing
action. The main uses are:
(1) as a reducing agent, particularly in dyeing of textiles with
indigo and vat dyes;
(2) in bleaching soaps, straw, ground wood pulp, sugar, molasses and
glues.
Sodium Sulfide. Sodium sulfide, Na2S'9H20, is a colorless, tetragonal,
deliquescent crystal, with the odor of hydrogen sulfide. Exposure of the
crystals to air produces the toxic hydrogen sulfide. Industrially, it
may be prepared by (1) heating sodium sulfate with coal, or (2) reacting
hydrogen sulfide with sodium hydroxide according to the following equations:
H2S + NaOH
NaHS + NaOH
Estimated U.S. production of sodium sulfide in 1965 was 46,000 tons (as
60 to 62 percent solution). Its uses are:
(1) in dehairing hides (in leather industry), and wool pulling;
(2) as a reducing agent in the production of ami no compounds;
(3) in desulfurizing viscose rayon;
(4) in the manufacture of sulfur dyes and rubber;
(5) as a raw material or intermediate for the preparation of other
compounds such as sodium hydrosulfide and polysul fides;
(6) in ore flotation, metal refining, engraving and lithography,
cotton printing;
(7) as a chemical reagent.
149
-------
Sodium Thiocyanate. Sodium 'thiocyanate, NaSCN.'is a colorless, rhombic
deliquescent crystal. It is prepared by fusing sodium cyanide solid or
boiling a solution of sodium cyanide with sulfur or a polysulfide.
NaCn + S— * - -NaCNS
4NaCN + Na-Sr - ^4NaCNS + Na9S
£ D £
Its uses are:
(1) in the manufacture of other thiocyanates, -especially organic;
(2) as a drying agent for wool;
(3) as a stabilizing agent in photography.
Stannic Chloride. Stannic chloride, SriCl., is a colorless, fuming,
caustic liquid. It is prepared by the direct chlorination of tin which
can be in molten state or finely divided suspension in stannic 'chloride.
Its uses are:
(1) as a mordant;
(2) in dyeing of fabrics, weighing silk, tinning vessels; ,
(3) as a dehydrating agent in organic syntheses;
(4) reviving colors.
Thiocyanates. Inorganic thiocyanates arc, in general, deliquescent
crystals which are freely soluble in water and alcohol. Some would
decompose on heating. They find some -applications in photography,', textile
industry, and pyrotechnic. Some also find medical uses because they
possess anti thyroid properties.
Sources and Types of Wastes
The wastes from the materials discussed in this report come from a
variety of sources. They include the manufacturers of these chemicals
and various industrial plants which use these chemicals in their processes
150
-------
or operations. The wastes are generally of the concentrated type in the
form of unused or contaminated materials. For the majority of materials
in this group, there is normally no dilute aqueous waste because they
decompose very readily on contact with water.
Physical and Chemical Properties
The physical and chemical properties of these inorganic materials are
given in the attached worksheets.
2. TOXICOLOGY0766'1492
The toxicity of these materials varies from irritating and corrosive
to the skin and mucous membranes to highly toxic.
Ammonium sulfide is stable only at temperatures below -18C. At higher
temperatures it decomposes into ammonia and ammonium hydrosulfide (NH.HS).
The latter also decomposes easily at room temperatures to yield ammonia
and hydrogen sulfide which is highly toxic. Consequently, under normal
conditions, ammonium sulfide is irritating to the skin and emits highly
toxic fumes.
Antimony pentachloride decomposes easily at room temperatures to
produce chlorine gas which is highly toxic. When heated to decomposition,
it emits the toxic fumes of antimony and hydrochloric acid. It will also
react with water or steam to produce toxic or corrosive fumes. Antimony
trichloride is poisonous and irritating to the skin. In general, antimony
and its compounds can cause dermatitis, keratitis, conjunctivitis and
nasal septal ulceration by contact with fumes or dust.
Calcium carbide itself is nontoxic. However, it generates acetylene
on contact with water. When inhaled, acetylene is toxic.
Similarly, calcium hydride is basically nontoxic. Again, it reacts
readily with water to yield hydrogen gas and calcium hydroxide.
151
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3. OTHER HAZARDS
The hydrides (sodium, calcium, and lithium aluminum) react violently
with water to generate hydrogen gas. Similarly, calcium carbide reacts
very rapidly with water to yield acetylene. Both, hydrogen and acetylene
are highly flammable. They can cause fire and explosion hazards.
Ammonium sulfide is unstable at room temperatures. It decomposes
readily to yield hydrogen sulfide. On contact with water or moisture in
the air, sodium sulfide also decomposes easily to generate hydrogen, sulfide.
The hydrogen sulfide evolved can cause a fire hazard or form an explosive
mixture with air.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Most of the materials in this group react rapidly with water or
moisture in air, producing either flammable or toxic vapors. Therefore,
they must be kept tightly closed in dry and cool areas with adequate
ventilation. In general, they should not be handled with bare hands.
Some also decompose readily upon heating and should be kept, away from heat
or flame. Toxic substances such as the oxalates should be stored away
from food and feed products. In shipping, sodium amide, sodium hydride and
sodium hydrosulfite are shipped under the Yellow Label, indicating flammable
solids.
Disposal/Reuse
The chemicals discussed in this report are either so reactive with
water or unstable with respect to heat that it is normally impractical to
attempt to recover them for reuse with the possible exceptions of antimony
and stannic chlorides. For the safe disposal of these materials, the
acceptable criteria for their release into the environment are defined in
terms of the recommended provisional limits.
152
-------
Lithium aluminum hydride is generally not considered a toxic material.
A large dose of lithium compounds has caused dizziness and prostration.
Potassium oxalate and binoxalate are both toxic substances. In general,
they are corrosive and produce local irritation. When ingested, they are
readily absorbed from the gastro-intestinal tract and can cause severe damage
to the kidneys.
Potassium hydroxide is a strong alkali. It is very caustic and
corrosive to the body tissue. Ingestion may produce violent pain in the
throat and epigastrium, hematemesis, and collapse. If not immediately
fatal, stricture of esophagus may develop. Dilute acetic acid may be
used as an antidote.
On contact with water or moist air, sodium amide and sodium hydride
hydrolyze readily to yield sodium hydroxide and ammonia (from sodamide)
or hydrogen (from the hydride). Sodium hydroxide is a strong alkali
having.the same corrosive and toxic effects as that of potassium hydroxide
described in the previous paragraph. Inhalation of ammonia gas would
cause edema of the respiratory tract, spasm of glottis, and asphyxia.
The toxic effects of sodium hydrosulfite are similar to those of
sulfites. Fairly large doses of sulfites can be tolerated by the human
body because they are readily oxidized to sulfates. However, if swallowed,
the sulfites may cause irritation of the stomach by liberating free
sulfurous acid.
Sodium sulfide is similar to alkali in actoion. It causes softening
and irritation of the skin. If taken by mouth, it is corrosive and
irritant through the liberation of free alkali and hydrogen sulfide. Also,
exposure of the sodium sulfide crystals to moist air produces hydrogen sulfide
which is highly toxic.
Thiocyanates, including sodium thiocyanate, are not normally
dissociated into cyanide. They have a low acute toxicity. Prolonged
153
-------
absorption of thiocyanates may cause various skin eruptions, coryza,
occasional dizziness, cramps and convulsions, nausea * vomiting, and mild
to severe disturbances of the nervous system.
Stannic chloride may be highly irritating to the mucous membranes of
the eyes and the respiratory tract. More severe exposures may result in
pulmonary edema and often laryngeal spasm.
The Threshold Limit Value (TLV) recommended by the American Conference
of Governmental Industrial Hygienists and lethal doses reported for the
0225 1312
materials in this report are tabulated as follows: '
Chemicals
Ammonium Sulfide
Antimony Pentachloride
Antimony Trichloride
Calcium Carbide
Calcium Hydride
Lithium Aluminum Hydride
Potassium Binoxalate
Potassium Hydroxide
Potassium Oxalate
Sodi urn Ami de
Sodium Hydride
Sodium Hydrosulfite
Sodium Sulfide
Sodium Thiccyanate
Stannic Chloride
Thiocyanate
TLV
0.5 mg as Sb/NT
0.5 mg as Sb/M*
Lethal Dose
or LDCa: 2 mg/kg, mouse
or LD • 675 mg/kg, rat
or LD5Q: 1230 mg/kg, rat
ip LD5Q: 53 mg/kg, mouse
or LD5Q: 764 mg/kg, rat
i.p LD5Q: 2}/mg/kg, mouse
154
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Contaminant in
Air
Provisional Limit
Basis for Recommendation
Ammonium sulfide
Antimony pentachloride
Antimony trichloride
Calcium carbide
Calcium hydride
Lithium aluminum hydride
Potassium binoxalate
Potassium hydroxide
Potassium oxalate
Sodium amide
Sodium hydride
Sodium hydrosulfite
Sodium sulfide
Sodium thiocyanate
Stannic chloride
Thiocyanate
Contaminant in
Water and Soil
Ammonium sulfide
Antimony pentachloride
Antimony trichloride
Calcium carbide
Calcium hydride
Lithium aluminum hydride
Potassium Binoxalate
Potassium hydroxide
Potassium oxalate
Sodium amide
Sodium hydride
0.15 mg/ir as H£S
0.005 mg/M3 as Sb
0.005 mg/M3 as Sb
0.025 mg/M3
0.025 mg/M3
0.00025 mg/M3
0.02 mg/M3
0.02 mg/M3
0.01 mg/M3 as oxalic
0.02 mg/M3
0.02 mg/M3
0.02 mg/M3
0.15 mg/M3 as H2S
0.02 mg/M3
0.02 mg/M3 as Sn
Variable
0.01 TLV for H2S
0.01 TLV for Sb
0.01 TLV for Sb
Data on similar compounds
Data on similar compounds
0.01 TLV for lithium
hydride
Data on similar compounds
Data on similar compounds
acid o.Ol TLV for oxalic acid
0.01 TLV for NaOH
0.01 TLV for NaOH
0.01 TLV for NaOH
0.01 TLV for H2S
0.01 TLV for NaOH
0.01 TLV for Sn
Depending on the thio-
cyanate compound
Provisional Limit Basis for Recommendation
0.75 ppm (mg/1) as H2
0.05 ppm (mg/1) as Sb
0.05 ppm (mg/1) as Sb
0.125 ppm (mg/1)
0.125 ppm (mg/1)
0.00125 ppm (mg/1)1
0.10 ppm (mg/1)
0.10 ppm (mg/1)
0.05 ppm (mg/1)
0.10 ppm (mg/1)
0.10 ppm (mg/1)
Stokinger & Woodward Method
Chronic toxicity
drinking water studies
Chronic toxicity
drinking water studies
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
155
-------
Contaminant in
Water & Soil
Sodium hydrosulfite
Sodium sulfide
Sodium thiocyanate
Stannic chloride
Thiocyanate
Provisional Limit
0.10 ppm (mg/1)
0.75 ppm (mg/1) as
H2S
0.10 ppm (mg/1)
Basis for Recommendation
Stokinger & Woodward Method
Stokinger & Woodward Method
Stokinger & Woodward Method
0.05 ppm (mg/1) as Sn Chronic toxicity
drinking water studies
Variable
Depending on the thio-
cyanate compounds
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Hydrolysis and Combustion
Calcium carbide and the hydrides of calcium, sodium, and lithium
aluminum all hydrolyze very readily producing combustible gases. For the
disposal of the calcium carbide waste, the material is slowly added to a
large container of water. The acetylene gas liberated is burned off with
a pilot flame. The remaining residue is lime and can be sent to landfill.
For the hydrides, the waste materials may be first mixed with dry sand to
minimize the fire hazard before they are added to water. Again, the
hydrogen gas liberated is burned off with a pilot flame. The remaining
residues are hydroxides and they should be neutralized by an acid before
being disposed of.
t
Option No. 2 - Hydrolysis and Neutralization
Sodium amide hydrolyzes rapidly to form sodium hydroxide and ammonia,
both of which can be neutralized by hydrochloric or sulfuric acid. The
neutral solution can be safely discharged if the salt content is below the
limits set to maintain water quality. Salt mixtures containing antimony
chlorides or stannous chlorides will form the very slightly soluble oxides
of these metals when dissolved in water and neutralized. Removal of the
156
-------
oxides is followed by sulfide precipitation described below to ensure
removal of the metal ions from solution. The antimony oxides can be sent
to a refiner if justified by market conditions or placed in drums and
stored at a National Disposal Site. The tin oxides can be refined or
landfilled.
Option No. 3 - Sulfide Precipitation
The soluble sodium and ammonium sulfides can be converted into the
insoluble ferrous sulfide by reaction with ferrous chloride solution. The
ferrous sulfide precipitate may be removed by filtration and reclaimed.
Similarly, antimony pentachloride and trichloride can be converted to the
corresponding insoluble sulfides by saturating the chloride solutions with
hydrogen sulfide. After filtering out the sulfide precipitate, the
filtrate solution is neutralized with soda ash and then discharged. The
recovered sulfide may be sent to refiners for reprocessing if economically
feasible or placed in containers and shipped to a National Disposal Site
for storage.
Option No. 4 - Oxidation
When ignited, potassium binoxalate and oxalate are converted into
carbonates. The carbonates, particularly sodium carbonate, have many applications
Since they are nontoxic, they may also be sent to landfill or simply sewered.
Sodium hydrosulfite is a reducing agent. It can be easily oxidized
to yield sodium sulfate with the liberation of sulfur dioxide. The exhaust
gas is therefore scrubbed with an aqueous suspension of finely-ground
limestone to absorb the sulfur dioxide gas. The soluble sodium sulfate is
also converted to the insoluble calcium sulfate which is removed by
filtration and sent to landfill. The filtrate is diluted and discharged.
157
-------
Option No. 5 - Neutralization
Disposal of contaminated potassium hydroxide (solid) can be carried
out by first dissolving it in water followed by neutralization with an
acid and finally sewered. Similarly, sodium thiocyanate which has a low
acute toxicity can be disposed of by dissolving it in a large quantity of
water, buffered with slight excess of soda ash and finally neutralized
by an acid and sewered.
In summary, the majority of materials in this group can be easily
disposed of by reacting with water or by ignition or by neutralization.
These procedures are all simple and quite adequate.
6. APPLICABILITY TO NATIONAL DISPOSAL SITE
The disposal processing described herein is of a level that can be
quite easily performed adequately in an industrial environment. Most of
the treated materials which cannot be economically recovered can be dis-
charged to sewer systems or landfilled. An exception is the stable anti-
mony product, either the oxide or sulfide, which must be carefully con-
trolled and returned to the antimony producers or reclaimers for the
recovery of its antimony value. Secondary antimony recovered from various
manufacturers and foundries while reprocessing scrap material amounted to
23,664 tons in 1967, about twice as much as the primary antimony produced
in the United States for the same year. The depletions of high grade
antimony oxide ores indicate that even greater attention should be focused
on the secondary recovery of antimony from waste streams containing
antimony compounds.
158
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual
(revised May, 1970). Washington, Manufacturing Chemists Association,
1970. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971.
Washington, U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1929. Datagraphics, Inc. Inorganic chemical industry profile (updated).
Washington, D. C., U.S. Government Printing Office, 1971. 211 p.
159
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Ammonium Sulfide (29)
IUC Name
Common Names
Structural Formula
(NH4)2S
Molecular Wt. 68-14
(1!
Density (Condensed)
Melting Pt. decomposes Boiling Pt.
Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water Very soluble
Others : very soluble in
Acid, Base Properties
Hot Water decomposes
Ethanol soluble
Highly Reactive with_
Compatible with
Sh i pped i n
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
160
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Antimony Petachloride (35)
IUC Name
Common Names
Structural Formula
SbCl,
Molecular Wt. 299.02
(1)
Melting Pt.
2.8 C
(1)
Boiling Pt. 14° c
(2)
Density (Condensed) lig. 2.336 @ 20_ C Density (gas)
/2\
Vapor Pressure (recommended 55 C and 20 C) '
: 1 mm Hg (a 22.7 C 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water decomposes
Hot Water decomposes
Ethanol
Others: soluble in HC1. tarta. CHC1 -
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification
Commen ts
corrosive liquid, white (2) corrosive
label _ Coast Guard Classification 1 iquid. white label
References (1) 1570
(2) 0766
161
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Antimony Trichloride (4])
IUC Name
Common Names
Structural Formula
SbCl.
Molecular Wt. 228.11
(1)
Melting Pt. 73-4 C_
(1)
Density (Condensed) 3.14
9 25 C
Density (gas)
Boiling Pt.
&
283 C
(1)
Vapor Pressure (recommended 55 C and 20 0
l.rcm Hg _ @ 49.2 G
9
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility }
Cold Hater 601.6 grams/100 ml @ PC Hot Mater " a
Others: soluble in HC1 . CHC13> benzene, acetone
Acid, Base Properties
Upper_
Upper_
80 C
Ethanol soluble
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
(2) 0766
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Calcium Carbide (39)
IUC Name
Common Names
Structural Formula
CaC,,
Molecular Wt. 64-10
(1)
Stable
Melting Pt. 25-477
C(D
.Boiling Pt. 2300 C
(1)
Density (Condensed) 2.22 @
Vapor Pressure (recommended 55 C and 20 Q)
Density (gas)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X)
Solubility
Cold Water decomposes
Others:
Lower_
Acid, Base Properties
Hot Water decomposes
Upper_
Upper_
Ethanol
Highly Reactive with water
Compatible with
Shipped in
ICC Classification
Comments
(2)
Coast Guard Classification 'hazardous artic
References (1) 1570
(2) 0766
163
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium Hydride (93)
IUC Name
Common Names
Structural Formula
CaH,,
Molecular Wt. 42.10
/,»
V ;
Density (Condensed) 1.9
decomposes
Melting Pt. Ca 600 C _ Boiling Pt.
@ __ Density (gas) __ @ _
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility (1)
Cold Water decomposes
Others:
Acid, Base Properties
Upper_
Upper_
Hot Water
Ethanol decomposes
Highly Reactive with water, lower alcohols and carboxylic acids
Compatible with
Shipped in_
ICC Classification
Comments _
Coast Guard Classification
References (1)
(2) 1492
164
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lithium Aluminum Hydride (244)
~ Structural Formula
IUC Name
Common Names
LiAlM.
. , ,-, ncO) decomposes 1-:
Molecular Wt. -*?.95 Melting Pt. (a 125 C Boiling Pt.
Density (Condensed) @ Density (gas) @ '
Vapor Pressure (recommended 55 C and 20 C)
g 9 g
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
(1)
Solubility
Ccld Water decomposes Hot Water Ethanol s1ight1* solubTe
Others' slightly soluble in liquid NH^
Acid, Base Properties
Highly Reactive with(2) water and a1coho1s
Compatible with
Shipped in
ICC Classification Coast Guard Classification
Commen ts :
References (1) 1570
(2) 1492
165
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Potassium Binoxalate (342)
Structural Formula
IUC Name
Common Names
KHC.,0
2"4
Molecular Wt. 128.ll^ Melting Pt. decoi"P°ses Boiling Pt..
Density (Condensed) 2.044 & Density (gas) 0
Vapor Pressure (recommended 55 C and 20 0
Flash Point _' Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility (1) 10Q
Cold Mater 2'5 g™"5/100 m1 Hot Hater 16'7 9ra"S/100 m1 Ethanol Insoluble
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification Coast Guard Classification
Commen ts . -
References (1) 1570
166
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Potassium Hydroxide (347)
Structural Formula
IUC Name
Common Names
KOH (S)
Molecular Wt. 56.11(1) Melting Pt. 360.4- 0.7 C Boiling pt. 1320-1324 C
Density (Condensed) 2.Q44 @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 Q)
(1)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility v '
Cold Water 107 g/100 ml & 15 C Hot Water 178 g/100 ml & 100 C Ethanol very soluble
Others:
Acid, Base Properties caustic
Highly Reactive with.
Compatible with_
Shipped in
(2) Hazardous
ICC Classification Coast Guard Classification article
Comments.
References (1) 1570
(2) 0766
167
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Potassium Oxalate (348)
Structural Formula
IUC Name
Common Names
Molecular Wt. 184.24^ Melting Pt. -H?Q & 1QQ C Boiling Pt.
Density (Condensed) 2.127 @ Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
0 @ __ (
Flash Point Autoignition Temp. '
Flammability Limits in Air (wt %) Lower - Upper_
Explosive Limits in Air (wt. %) Lower Upper_
(1)
Solubility
Cold Water Hot Water 33 g/100 ml @ 16 C Ethanol_
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
ICC Classification Coast Guard Classification_
Commen ts ,_
References (1)1570
168
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Amide (375)
IUC Name
Common Names
Structural Formula
NaNH,
Molecular Wt. 39.01
(1)
Melting Pt. 210 C
(1)
Density (Condensed)
G>
Density (gas)
Boiling Pt. 400 C
&
(1)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
(1)
Solubility
Cold Water decomposes Hot Water decomposes
Others:
Acid, Base Properties
Upper_
Upper_
Ethanol decomposes, hot
Highly Reactive with water
Compatible with
Shipped in
(2) flammable solid,
ICC Classification ; yellow label
Comments.
(2) inflammable
Coast Guard Classification solid, yellow
label
References (1) 1570
(2) 0766
169
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Hydride (391)
IUC Name
Common Names
Structural Formula
NaH
Molecular Wt. 24-°
(1)
Density (Condensed) 0-92
(D
Melting Pt. decomposes @ 800 C Boiling Pt.
_ Density (gas) »
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower,
Explosive Limits in Air (wt. X) Lower_
(1)
Upper_
Upper_
Solubility
Cold Water decomposes
Others:
Hot Water decomposes
Ethanol
in mnltpn
Acid, Base Properties
Highly Reactive with <3> Mater and 1ower alcohols
Compatible with_
Shipped in
(2) flammable solid,
ICC Classification yellow label
Comments.
References (1) 1570
(2) 0766
(3) 1492
(2) inflammable
Coast Guard Classification solid, yellow
label
170
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name
Sodium Hydrosulfite (392)
Structural Formula
Common Names
Molecular Wt. 174,13
(1)
Density (Condensed)
(2)
Melting Pt. decomposes v ' Boiling Pt.
Density (gas) 9
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flamnability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
(1)
Upper
Upper_
Solubility
Cold Water ™ry soluble
Others:
Hot Water decomposes
(2)
Ethanol slightly
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
(3) flammable solid, yellow
ICC Classification yellow label
Comments
References (1) 1492
(2) 1433
. (3) 0766
(^)inflairmable solic
Coast Guard Classification yellow label
171
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sodium Sulfide (404)
Structural Formula
IUC Name
Common Names
/,, decomposes
Molecular Wt. 240.18u; Melting Pt. at 920 C Boiling Pt.
Density (Condensed) 1.427 @ Density (gas) J?
Vapor Pressure (recommended 55 C and 20 C)
@ 9 (
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility ^
Cold Water 47.5 g/100 ml @ 10 C Hot Water 96.7 g/100 ml & 100 CEthanol slightly solubl
Others:
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in
ICC Classification Coast Guard Classification
Comments ____ :
References (1) 1570
172
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sodium Thiocyanate (4Q6)
IUC Name
Common Names
Structural Formula
NaSCN
Molecular-Wt. 81-07
Melting Pt. 287 C
(D
Density (Condensed)
Density (gas)
Boiling Pt.
(a
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water J39.31 g/100 ml @ 21.3CHot Water225 g/100 ml @ 100 C Ethanol very soluble
Others: verv soluble in acetone
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
173
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Staunic Chloride (4Q8)
Structural Formula
IUC Name
Common Names
SnCl
4
Molecular Wt. 260-50 • Melting Pt. ~33 c Boiling Pt. 114.1 C
Density (Condensed) & Density (gas) &
(2)
Vapor Pressure (recommended 55 C and 20 0
in inn Hg @ 10 C * 9 :
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
(1)
Cold Water soluble Hot Hater decomposes Ethflnol
Others: soluble in ether
Acid, Base Properties_
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Comments .
References (1) 1570
(2) 0766
174
-------
PROFILE REPORT
Antimony (33), and Antimony Trioxide (45)
1. GENERAL
The two major antimony producers in the United States are the Sunshine
Mining Company, Kellogg, Idaho and NL Industries (formerly National Lead),
who operate a smelter in Laredo, Texas to process ore originating in Mexico.
In 1971, Sunshine produced 1,708,000 Ib of antimony by electrowinning from
the NaOH leach of their Ag-Cu ore. The spent leach solution containing
400 Ib Sb/day is deposited in a tailings pond, from whence an effluent con-
taining 5 to 40 ppm Sb is emptied into the South Fork of the Coeur d'Alene
River. Within one year, continuous recycling based on evaporation of the
liquid and recovery of the solids will be instituted, thereby eliminating
the current antimony waste. .
NL employs conventional smelting in its Laredo, Texas facility.
No production figures are available, but a representative reports that
their slag contains 1 percent Sb of which 60 percent is present as antimony
metal. This slag is held in outdoor storage on their property.
Over 95 percent of all the antimony used in the United States is
alloyed at a 4 or 5 percent concentration with lead in bearings, type metal,
etc.0591'1433 Kirk-Othmer1433 reports that a large amount of the 13,500
tons of antimony used every year is recycled.
Antimony trioxide is an intermediate in the production of antimony metal
by smelting. The oxide is won from the ore by volatilization and then reduced
to metal. The principal use of antimony trioxide is as a fire-proofing
additive in plastics and cloth.0591'1433'0063 Also, it finds commercial
application as an opacifier for glasses and ceramics. Production was 6,518
1?R7 1?88
tons and consumption was 9,363 tons in 1968." '
175
-------
2. TOXICOLOGY0766'1312
The accepted Threshold Limit Value (TLV) of the American Council of
Governmental Industrial Hygienists (ACGIH) for antimony or antimony oxides is
0.5 mg/m air by inhalation. This represents approximately 10 percent of
3
a dose of 4.7 mg/m of antimony metal by inhalation, which had produced
clinical symptoms involving the skin, the pulmonary system, and the
gastrointestinal tract. LD 50 for antimony metal is 100 mg/kg body weight
for the rat for administration by means other than the respiratory tract.
Since antimony,pentoxide is chemically similar to antimony trioxide,
their toxicities should be approximately the same. Intraperitoneal admin-
istration of antimony pentoxide in rats indicates an LD 50 of 4000 mg/kg
body weight.
3. OTHER HAZARDS
\.
Finely divided antimony powder may explode; as may amorphous antimony
obtained by electrodeposition in an air or enriched oxygen environment.
Antimony has a fairly low boiling range of 1300 to 1640 C (depending on the
presence of metastable phases), and fumes released on heating are consider-
ably more toxic than the solid form. Antimony metal reacts with most acids
(except HC1) to form the highly toxic gas, SbHg. It also reacts with HC1
if zinc is present.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Hazardous exposures to the dusts and fumes of antimony and its oxides
have been reported and the use of goggles and respirators is recommended
for the handling of these compounds in powdered form. Antimony and anti-
mony trioxide are moderately toxic compounds and should be stored in cool
well-ventilated places; away from areas of high fire hazard, and should be
176
-------
periodically inspected and monitored. Antimony metal reacts with most
acids to form the extremely toxic gas stibine, SbH3 and caution should be
taken in isolating these materials from each other. Both antimony and
antimony trioxide are not classified by the Department of Transportation
as hazardous materials and there are no specific rules governing their
transportation.
Disposal/Reuse
Waste sludges containing antimony are not currently reclaimed for their
antimony value because of the soft antimony market for the past several
years. For the safe disposal of antimony and antimony trioxide, the ac-
ceptable criteria for their release into the environment are defined in
terms of the following provisional limits:
Basis for
Contaminant in Air Provisional Limit Recommendation
Antimony 0.005 mg/M3 0.01 TLV
Antimony Trioxide 0.005 mg/M3 as Sb 0.01 TLV for Sb
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
Antimony 0.05 ppm (mg/1) Chronic toxicity
drinking water
studies
Antimony Trioxide 0.05 ppm (mg/1) as Sb Chronic toxicity
drinking water
studies
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The present liquid effluent of the Sunshine Mining Company contains
5 to 40 ppm Sb and present plans call for this to cease when their new
1 coc
recycling system comes onstream sometime in 1972 (Figure 1). The
plant effluent of 9-12 tons/day containing 40 Ib Sb/ton and 150 g/1 alka-
linity equivalent Na,,S (the amount of Na2S which requires the same amount
of acid to titrate to Ph 7 as 150 g/1 CaCO., requires) is evaporated on a
177
-------
liquid
coke
)-*
vl
00
feedstream
9-12 tons/day contg.
40 Ib Sb/ton +
150 g/1 alkalinity
equiv. Na»S
2300 F
ELECTRIC
FURNACE
CLARIFIER
200 g/1 alkalinity
equivalent Na-S
solution contg.
soluble SbS ~
(to main plant
influent)
coke
sludge
(to smelter)
Figure 1. Recycle of Effluent from the Electrolytic Production of Antimony
-------
rotary flaker. The resulting crystals are mixed with liquid coke and re-
duced at 2,300 F in an electric furnace to Na2$ and other salts. The only
air emissions from the furnace are water vapor. Sufficient water is then
added to the reduced salts to make a 200 g/1 alkalinity equivalent Na^S
solution. This solution is then clarified to remove whatever coke sludge
may be present. It contains all the antimony present in the original ef-
fluent as soluble thioantimonate ion. In this form it is recycled to the
main plant to mix with the antimony plant influent, the NaOH leach of their
Ag-Cu ore. It is anticipated that the amount of coke sludge will be approx-
imately zero. Any which does result will be recycled back to the smelter.
The advantages of this recyling system include the recovery of the
40 Ib Sb/ton which had hitherto been lost in a settling pond and the
recovery of 95 percent of their caustic. From an environmental standpoint,
the elimination of settling ponds will stop the flow of 5 to 40 ppm Sb pond
effluent Into the South Fork of the Coeur d'Alene River and eliminate the
SOg gas presently venting from these ponds.
The capital cost for this system 1s $350,000.00 which is mostly for
the electric furnace. Operating costs are estimated to be 6
-------
TABLE 1
ANTIMONY SMELTER WASTE AT LAREDO, TEXAS (1971)
Waste Material
Amount Produced/Ton Sb Amount Produced (Total)*
A1 rborne
NO
S02
Hydrocarbons
CO
Parti culates"1
Solid
Slag
3.75 Ib/ton
3.75 Ib/ton
22.00 Ib/ton
0.64 Ib/ton
940.00 Ib/ton
62.00 Ib/ton
8.015 ton/ton
10.30 tons/yr
60.50 tons/yr
1.76 tons/yr
2,590.00 tohs/yr
171.00 tons/yr
44,000 tons/yr
*Based on assumed annual production of 5,500 tons Sb.
^Includes transient dust from ore unloading and other extraneous sources,
180
-------
The slag, an insoluble mixture of metals and oxides, contains one
percent Sb, of which 60 percent is in the metal form. The slag is held in
outdoor storage on the property pending possible reworking or disposal.
For the past several years the antimony market has been very soft and it
is doubtful that anything will be done with this slag in the foreseeable
future.
No information is available with regard to the antimony content of the
particulate emissions, but, if it is assumed to be one percent, there
would be an airborne emission of approximately 28.1 g Sb/ton Sb produced.
Data is available for the volume of stack gases produced as a function of
1 fifift
the metal production in a lead smelter. If it is assumed that this
data is directly correctable with antimony smelter production, the Sb
o
particulate emissions are 7.5 mg/m , or 15 times the accepted Threshold
Limit Value. While this represents a high level of airborne emissions,
it is nevertheless a substantial improvement. Only within the past year,
have four additional baghouses been installed to achieve this level.
Since virtually all the antimony metal used in the United States is
alloyed at a four or five percent concentration with lead in bearings, type
metal, etc., its disposal and recycling from secondary sources is a part of
the lead recycle-disposal system.
With respect to antimony trioxide, it is ubiquitous in very small
concentrations as a fire-proofing additive in plastics and cloth. It is
discarded in municipal systems and is not considered to be a pollution
problem at present.0615'0768 Its range of measurement as an air pollutant
in 58 urban areas was 0.042-0.85 yg/m3 which is roughly 1/1000 of the
Threshold Limit Value of 0.5 mg/m . No human retention has been demonstrated,
181
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Of the two major antimony producers in the United States ' '
', one is currently putting a recycling system into operation which will,
eliminate all waste emissions and the other may have an airborne emissions
problem in the form of participate emissions containing about one percent
antimony. It is recommended that a study be performed to determine precisely
what total amount of antimony is emitted in this way. The economics of the
mining and smelting industry today make it unlikely that this particulate
dross could be transformed into something of significant commercial value.
Extensive clinical studies I5»0768 indicate that antimony and antimony
trioxide are not generally environmental hazards at present and are not
likely to become so in the future.
This lack of hazard together with the very low concentrations present
in the smelting dross (airborne particulate and solid) make these unlikely
candidate waste stream constituents for national disposal. If emissions
are found to be above the acceptable level, they should be treated at the
industrial site with standard technology equipment such as scrubbers,
cyclones, etc.
182
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7. REFERENCES
0591. Personal communication. Sunshine Mining Company, to M. Appel, TRW
Systems, Feb. 10, 1972.
0615. Schroeder, H. A. Metals in the environment. Environment, 13(8):
18-24, Oct. 1971.
0663. Personal communication. N. Hornedo, NL Industries, to M. Appel,
TRW Systems, Feb. 11, 1972.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
0768. Murthy, 6. K., U. Rhea, and J. T. Peeler. Levela of antimony, cadmium,
chromium, cobalt, manganese, and zinc in institutional total diets.
Environmental Science and Technology, 5(5):436-442, May 1971.
1287. U. S. Bureau of Mines. Mineral facts and problems. Bulletin
No. 650. 1970. 1,291 p.
1288. U. S. Bureau of Mines. Metals, minerals, and fuels. In Minerals
Yearbook. 2 v. 1969. 1,208 p.
1312. Christensen, H. E. Toxic substances; annual list, 1971. Rockville,
Maryland, U. S. Department of Health, Education, and Welfare,
Health Services and Mental Health Administration, National
Institute for Occupational Safety and Health, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1535. Personal communication. L. Barr, Sunshine Mining Company, to M.
Appel, TRW Systems, Apr. 6S 1972.
1663. Personal communication. C. Hornedo, NL Industries, to M. Appel,
TRW Systems, Mar. 18, 1972.
1668. Robinson, J. M., G. I. Gruber, W. D. Lusk, and M. J. Santy.
Engineering and cost effectiveness study of fluoride emissions
control, v. 1. McLean, Virginia, Resources Research, Inc.,
Jan. 1972. 560 p.
183
-------
r~
J\. M. Name
HAZARDOUS WASTES PROPERTIES
WORKSHEET
IUC Name ANTIMONY (33)
Structural Formula
Common .Names ANTIMONY
Sb
Molecular Wt. 121.75 _ Melting Pt. 630.5 C
Density (Condensed) _ K f^g fj/cg _ 2Q C Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
1 mm __ 9 fififi r _ _ 9 _
Boiling Pt. 1380 C-1640 C
•Hash Point
Autoignition Temp. - Does, not antoignite
Flammability Limits in Air (wt %) Lower _ Upper _
Explosive Limits in Air (wt. %) Lower
Solubility
Cold Water
Hot Water 0
Upper
Ethanol_
Othe rs : h. cone. H. SO,, an. rpg
, 4 ' 3
Acid, Base Properties Verv slightly basic
Highly Reactive with ElectrodepositPd amnrphnnc «ih may
presence Of Zn + HC1, rpflct«; uinrnu^l Wjth Cl.
Sbll in
Compatible with
Air» moisture. HC1
Shipped in
Barrels, truck*:, rail mart
None
ICC Classification _
Comments _ No shipping resctrictions found
Coast Guard Classification
184
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
)i. M. Name
IUC Name ANTIMONY POWDER (34)
Common names ANTIMONY POWDER
Structural Formula
Sb Powder
Molecular Wt.
121.75
Melting Pt.
630.5 C
Boiling Pt. 1380 -1640 C
Density (Condensed) 6.6189/cig jQ C Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
1 mm (3 886 C §
Flash Point
Autoignition Temp. 415 C (cloud), 330 C (layer)
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. Z)
Solubility
Cold Water 0
Others:
Lower 420 rnq/1
Upper_
Hot Water
Ethanol
"• cone.
ag. reg.
Acid, Base Properties
very slightly basic
Highly Reactive with Electrodeposited amorphous Sb may explode
produces
in prpsenrp of .7n + Hf.l, reacts vigorously with Cl.,
Compatible with_
Air, moisture, HC1
Shipped in_
barrels, trucks, railroad cars
ICC Classification none
Comments No shipping^ restrictions found
Coast Guard Classification
185
-------
HAZARDOUS WASTES PROPLKTILS
WORKSHEET
1-1. Narce.
IUC Name ANTIMONY TRIOXIDE (45)
Common Names ANTIMONY TRIOXIDE
Structural Formula
Sb2o3
Molecular Wt.
29-1-.52
Melting Pt. 656 C
Density (Condensed) 5.2 g/cc P 20 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
1 mm @ 574 C @
Boiling Pt. 1550 C (subliV.
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower Not flam.
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water_
Others:
v. si.
Hot Water si
• Ethanol
HC1, KOH, HAc
Acid, Base Properties Slightly basic
Highly Reactive with
Nothing
Compatible with_
Shipped in_
Barrels, trucks, railroad cars
None
ICC Classification
Comments No shipping rescrictions found
Coast Guard Classification
186
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PROFILE REPORT
Antimony Pen t as ul fide (37), Antimony Sulfate (39), Antimony Trisulfide (40),
Calcium Fluoride (92), Metallic Mixture of Powdered Magnesium and
Aluminum (260), Silica (368), Arsenic Pentaselenide (467), Tantalum (510)
1. GENERAL
Introduction
The inorganic materials to be discussed in this report have been pre-
liminarily identified as probable candidate waste stream constituents for
industrial disposal. These materials are generally insoluble in water. Their
toxicity varies from nontoxic to poisonous. Most of them are not produced in
large tonnage and their industrial applications are, in general, rather
limited.
Manufacture and Uses
Antimony Pentasulfide. Antimony pentasulfide, Sb2$5, is an orange-
yellow, odorless powder. It is insoluble in water. The commercial product
is made by boiling antimony trisulfide with sulfur in alkaline solution
and decomposing the resulting mass with hydrochloric acid to liberate the
1433
antimony pentasulfide. It may also be prepared by reacting hydrogen
sulfide with hydrated antimony pentoxide suspended in water or a
2275 1492
hydrochloric acid solution of antimony pentoxide. It is used:
(1) as a pigment in paints;
(2) in vulcanizing and coloring rubber;
(3) in the manufacture of matches and fireworks.
Antimony Sulfate. Antimony sulfate, Sb2(S04)3, is a colorless crystal.
It deliquesces in moist air. With an excess of water, it is converted into
an insoluble basic salt. It can be prepared by dissolving antimony trioxide
in hot, concentrated sulfuric acid. On cooling, long, silky needles of
187
-------
antimony sulfate are precipitated from the solution. The precipitates
are then removed by filtration, washed free of sulfuric acid with xylene,
and finally dried to finished products. Antimony sulfate appears to have
little commercial application.
Antimony Trisulfide. Antimony trisulfide, Sb,,S3, is a yellow-
orange, amorphous solid which turns black upon standing. It is insoluble
in water. It may be prepared by:
(1) reacting hydrogen sulfide with antimony trichloride;
(2) heating sulfur with antimony or antimony trioxide under vacuum
conditions;
(3) reacting antimony trichloride with a sodium thiosulfate solution
saturated with sulfur dioxide.
Its uses are:
(1) in the manufacture of pyrotechnics, matches and explosives;
(2) as a pigment in paints;
(3) in the manufacture of ruby glass.
1433 1492
Calcium Fluoride. ' Calcium fluoride, CaFy* occurs naturally
in the minerals fluorite and fluorspar. The latter is a common mineral
found in widely differing deposits. It is mined and purified to yield
pure calcium fluoride. The U.S. consumption of fluorspar amounted to
about 900,000 tons in 1964. When pure, calcium fluoride is a colorless,
cubic crystal or powder. It is practically insoluble in water and becomes
luminous when heated. Its uses are:
(1) as a flux in the steel industry;
(2) as a primary source of fluorine in the chemical industry;
(3) in the manufacture of glass, ceramics, enamel, portland cement,
abrasives;
(4) as the light-emitting agent in most fluorescent lighting tubes;
(5) as a catalyst in dehydration and dehydrogenation processes.
188
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Metallic Mixture of Powdered Magnesium and Aluminum.0766'1492'1570
Magnesium is a light, silvery white and fairly tough metal. It is produced
by electrolysis of fused magnesium chloride derived from brines, wells, or
sea water. In fine powder, magnesium can be ignited by a spark or the
flame of a match and burns with a dazzling white flame. It is unsurpassed
for high intensity light effect. Therefore, it is used in flashlight
photography, flares, and pyrotechnics, including incendiary bombs.
Aluminum is also a light and silvery white metal. It is produced by
electrolysis of alumina dissolved in a fused bath of cryolite. The finely
divided aluminum powder can also be ignited easily and may cause explosions.
It also is used as a flashlight in photography,.and in fireworks and
explosives. The mixture of magnesium and aluminum metallic powder is
therefore used primarily in pyrotechnics.
1433 1492
Si 1ica. ' Silica, SiOp, occurs plentifully in nature as sand,
quartz, flint, chalcedony, opal, agate, and infusorial earth. It exists
in a variety of polymorphic crystalline and amorphous forms as well as a
liquid. Among the-crystalline forms of silica are quartz, tridymite, and
cristobalite in atmospheric pressure and keatite, coesite and stishorite
in high pressures. Each of these in turn has its polymorphic forms existing
in different temperature ranges. Among the amorphous forms of silica are
silica gel, colloidal silica, precipitated silica and fused silica. Its
uses are:
(1) in the manufacture of glass, ceramics, enamels, refractories,
abrasives, concrete, bricks, and building stones;
(2) as a desiccant, an adsorbent, or a catalyst;
(3) in the manufacture of water glass and soluble silicates, silicon
and its alloys, silicon carbide, silicon-based chemicals, and
the silicones.
1492
Arsenic Pentaselenide. Arsenic pentaselenide, As2Se5, is a black,
brittle solid with a metallic luster. It is insoluble in water and
decomposes when heated in air. It may be prepared by melting a mixture of
189
-------
arsenic and selenium in correct proportions at about 400 C in a sealed
tube filled with nitrogen gas and distilling the resulting mass under
reduced pressures to obtain pure arsenic pentaselenide. It may also be
prepared by the reaction of an arsenic salt with hydrogen selenide in
solution. Arsenic pentaselenide is of limited commercial importance.
Tantalum. ' Tantalum, Ta, is a gray, heavy, and very hard
metal. It occurs principally in the mineral columbite-tantalite. The
metal has a high melting point exceeded only by tungsten and rhenium. At
temperatures below 150 C, it is almost completely inert to chemical attack.
Commercial production of tantalum is carried out in two major steps:
(1) extraction and purification of a pure tantalum compound from the ore;
and (2) reduction of such a compound to pure metal. The extraction and
purification step may be accomplished by either (1) an alkali fusion of
the ore followed by acid treatment to remove most of the impurities and
fractional crystallization to obtain a pure potassium fluotantalate, KpTaF7;
or (2) extraction of the ore by hydrofluoric acid followed by liquid-
liquid extraction using methyl isobutyl ketone (MIBK) and precipitation
with ammonia to yield hydrated tantalum oxide. The reduction step may be
carried out by: x
(1) electrolysis of molten potassium fluotantalate;
(2) reduction of potassium fluotantalate by sodium pellets;
(3) reduction of tantalum oxide by carbon or tantalum carbide.
Its uses are:
(1) in making electrolytic capacitors, lightning arresters, surge
suppressors;
(2) in fabricating chemical process equipments, nuclear reactors;
aircraft and missile parts, surgical Instruments;
(3) as an implant metal for the human body in surgery;
(4) in special-purpose vacuum tubes.
190
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Sources and Types of Wastes
The wastes of materials discussed in this report may come from the
following sources:
(1) mining and metal refining facilities;
(2) industrial plants which either produce these materials or use
them in their manufacturing processes;
(3) users of products containing these materials.
Practically, all the wastes are in the form of unused or contaminated
materials.
Specifically, arsenic has been used to provide for more heat stability
in xerox drums, which normally contain selenium coatings 0.002 in. thick,
and this has been identified as a source of arsenic pentaselenide wastes.
The selenium and arsenic coated xerox drums are manufactured and
reconditioned at Xerox's Rochester, New York facility. About 1 million Ib
of solid wastes containing 95 percent cotton 1 inter, 5 percent aluminum,
and 300 ppm selenium and arsenic are generated each year during these
operations. Of the selenium and arsenic found in these wastes, there is
usually more selenium present than arsenic, and approximately 25 percent
of the selenium is combined with arsenic chemically (e.g., arsenic
pentaselenide), with the remaining selenium containing less than 1 percent
arsenic in them. In addition, there are 5 to 10 barrels acid wastes
containing 1 to 3 percent selenium and arsenic generated each year from
the same operations.
Physical and Chemical Properties
Physical and chemical properties of the materials in this report are
given in the attached worksheets.
191
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2. TOXICITY0766
The antimony compounds, including the sulfides and sulfate, generally
cause irritation and eczematous eruption of the skin, inflammation of the
mucous membranes of the nose and throat, metallic taste and stomatitis,
gastrointestinal upset with vomiting and diarrhea, and various nervous
..complaints such as irritability, sleeplessness, fatigue, dizziness, and
muscular and neuralgic pains.
The ,toxic effect of calcium fluoride comes from its fluorine component.
In general, inorganic fluorides are toxic and irritant to the eyes and
^respiratory tract. Acute effects resulting from exposure to fluorine
^cpmpouridsr are due to hydrogen fluoride. Among the chronic fluorinei ;
poisoning commonly encountered are loss of weight, anorexia, anemia^;
wasting and cachexia, and dental defects. The very low solubility of the
calcium fluoride, however, requires exposure to large quantities of the
material to produce these symptoms.
Magnesium, aluminum and tantalum are all nontoxic metals. However,
inhalation of magnesium powder may cause irritation of the respiratory
tract. Particles of magnesium which perforate the skin or gain entry
through cuts and scratches may produce a severe local lesion characterized
by the evolution of gas and acute inflammatory reaction, frequently with
necrosis. This condition has been known as "chemical gas gangrene". The
lesion is very slow to heal. Similarly, aluminum powder can be irritating
to the eyes. There are also reports in the European literature of chronic
pulmonary disease due to the inhalation of aluminum dust. Tantalum appears
to have no ill effect upon the human body. Tantalum metal embedded in the
abdominal wall and in the bones of dogs cause no physiological disturbances.
So far, the use of tantalum in human surgery has received favorable comments,
192
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Silica occurs abundantly in nature. Prolonged inhalation of silica
dusts may result in a diffuse fibrosis known as silicosis. The duration
of exposure required for the development of silicosis varies widely from
2 to 30 years. This fibrosis is, to a certain extent, progressive, and
may continue to develop for several years after exposure is terminated.
The first and most common symptom of silicosis is the shortness of breath
on exertion. The most common physical sign is a limitation of chest
expansion. There may be a dry cough with increased susceptibility to
tuberculosis. Further progress of the disease results in more severe
shortness of breath and cough, marked fatigue, extreme dyspnea and cyanosis,
loss of appetite, pleuritic pain and total incapacity to work. If
tuberculosis does not supervene, the conditions may eventually cause death
from either cardiac failure or destruction of lung tissue with resultant
anoxemia.
Arsenic pentaselenide is a toxic chemical. Selenium resembles arsenic
both chemically and toxicologically. Poisoning due to selenium compounds
generally results in gastrointestinal disturbances, respiratory irritation,
cough, edema of the lungs, vomiting, diarrhea, abdominal pain or cramps,
loss of reflexes, convulsions and ultimately death. Selenium salts also
often cause contact dermatitis. Poisoning due to arsenic compounds may
be acute or chronic. Acute poisoning, usually from ingestion, results in
marked irritation of the stomach and intestines with nausea, vomiting and
diarrhea. In severe cases the vomitus arid stools are bloody and the
patient goes into collapse and shock with weak, rapid pulse, cold sweats,
coma and death. Chronic arsenic poisoning, through ingestion or inhalation,
causes disturbances of the digestive system such as loss of appetite,
nausea, constipation or diarrhea, damage to the liver resulting in jaundice,
disturbances to the blood, kidneys and nervous systems. Arsenic can also
cause a variety of skin abnormalities including itching, pigmentation and
even cancerous changes.
193
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The Threshold Limit Value (TLV) recommended by the American Conference
of Governmental Industrial Hygienists and lethal doses reported for the
materials in this report are given as follows:
Chemicals
Antimony Pentasulfide
Antimony Sulfate
Antimony Trisulfide
Calcium Fluoride
Mixture Powdered
Magnesium and
Aluminum
Silica
Arsenic Pentaselenide
Tantalum
0225
TLV'
0.5 mg as Sb/M"
0.5 mg as Sb/Mc
0.5 mg as Sb/fT
2.5 mg as F/M3
0.5 mg as As/Mw
Lethal Dose1312
ip LD5Q: 1000 mg/kg, rat
14Q?
ip LD: 1000 mg/kg, rat1
ip LDCa: 1000 mg/kg, rat
or LD: 5000 mg/kg, guinea
Pig1492
c . 230 mg Mg/kg, dog
50:
or LD
or LDCrt: 3160 mg/kg, rat
3. OTHER HAZARDS
The antimony sulfides would undergo spontaneous chemical reactions
with powerful oxidizers to cause moderate fire and explosion hazards. In
addition, both antimony pentasulfide and sulfate would decompose when
heated, resulting in a mild fire hazard.
Metallic powder of magnesium and aluminum can be ignited easily.
Arsenic pentaselenide should not be heated to decomposition or have
contact with acid or acid fumes since it emits the highly toxic fumes of
arsenic and selenium.
194
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
In handling the materials discussed in this report, care must be
exercised to avoid inhaling silica dust particles and metallic powder of
aluminum and magnesium. In storage, the antimony sulfides and sulfate and
arsenic pentaselenide must be stored in cool areas and away from powerful
oxidizers and acids. All toxic materials should be kept away from food
and feed products. Metallic powder of aluminum and magnesium can be
ignited easily. Therefore, they should be kept away from flame, and
spark-proof tools should be used where they are being shoveled or otherwise
moved by hand. In addition, magnesium should be kept dry, because it will
react with water or steam to generate the combustible hydrogen gas.
Similarly, antimony sulfate deliquesces in moist air and hence should be
kept tightly closed in dry areas.
Disposal/Reuse
For the majority of the materials in this report, recovery of the
wastes for reuse appears to be desirable, because they are, in general,
not produced in large quantities and are relatively costly. For the safe
disposal of these materials, the acceptable criteria for their release
into the environment is defined in terms of the following provisional
limits:
Contaminant in Provisional Limit Basis for Recommendation
Air
Antimony pentasulfide 0.005 mg/M as Sb 0.01 TLV for Sb
Antimony.sulfate 0.005 mg/M3 as Sb 0.01 TLV for Sb
Antimony trisulide 0.005 mg/M3 as Sb 0.01 TLV for Sb
Calcium fluoride 0.025 mg/M3 as F 0.01 TLV for F
Powdered magnesium, 0.1 mg/M 0.01 TLV for inert or
aluminum mixture nuisance particulates
Silica 0.1 mg/M3 0.01 TLV for Si
3
Arsenic pentaselenide 0.005 mg/M as As 0.01 TLV for As
Tantalum 0.05 mg/M3 0.01 TLV
195
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(Cont'd)
Contaminant in
Water and Soil
Antimony pentasulfide
Antimony sulfate
Antimony trisulfide
Calcium fluoride
Powdered magnesium,
aluminum mixture
Silica
Provisional Limit
Basis for Recommendation
0.05 ppm (mg/1) as Sb Chronic toxicity drinking
water studies
0.05 ppm (mg/1) as Sb Chronic toxicity drinking
water studies
0.05 ppm (mg/1) as Sb Chronic toxicity drinking
water studies
0.6 - 1.7 ppm (mg/1) Drinking. Water Standard
as F for F
.25 ppm (mg/1) as Mg Drinking Water Standard
for Mg
Arsenic pentaselenide 0.05 ppm (mg/1) as As Drinking Water Standard for
As
Tantalurn
0.25 ppm (mg/1)
Stokinger & Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PROCESS
Option No. 1 - Landfill
The materials in this report are insoluble in water and therefore may
be conveniently disposed of by landfill. However, arsenic pentaselenide
and the antimony compounds are highly toxic and the disposal of dilute wastes
containing these constituents by landfill should only be in Class 1 sites
located over nonwater-bearing sediments or with only unusable ground water
underlying them. For particularly expensive metal such as tantalum and
for antimony sulfide and sulfate wastes, recovery should be considered and
preferred over disposal by landfill.
Option No. 2 - Long Term Storage for Arsenic Pentaselem'de
Large, weatherproof, and siftproof storage bins or silos are currently
being used for the storage of arsenic compounds, especially arsenic tri-
oxide. This approach is relatively costly. However, since arsenic penta-
selenide is highly toxic and its wastes only appear in small quantities,
136
-------
long term storage of concentrated arsenic pentaselenide waste may be the
only practical and adequate means of disposal. The small quantity of the
waste contraindicates its designation as a candidate for National Disposal
Site, however, this waste could be stored at such a site.
Option No. 3 - Sulfide Precipitation
The antimony sulfides and sulfate can be recovered from the wastes by
first dissolving the wastes in concentrated hydrochloric acid, filtering
the resulting solution if necessary, and finally saturating the solution
with hydrogen sulfide to precipitate out the antimony sulfide which is
then removed by filtration. The sulfides may be marketed or roasted and
reduced to recover metallic antimony.
Option No. 4 - Mechanical Salvaging
Expensive metal such as tantalum is worth salvaging, even in small
pieces, and should be sorted out mechanically. Since tantalum is chemically
inert at ordinary temperatures, scraps of tantalum can be cleaned by
removing the contaminants with strong acid.
Option No. 5 - Recovery of Metallic Antimony
Antimony sulfides may be roasted to yield the oxide which can be
reduced to metallic antimony by carbon or by salt and scrap iron. The
sulfur dioxide produced by the roasting must be scrubbed from the exhaust
gas stream. A great number of scrubbing processes are available for this
purpose. Among the commonly used processes are scrubbing the exhaust gas
containing sulfur dioxide with an acidified, aqueous suspension of finely
ground limestone or an aqueous solution of soda ash.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Adequate waste treatment for the waste stream constituents discussed in
this Profile Report is commonly found in an industrial environment and there-
fore, treatment facilities need not be present at a National Disposal Site.
The disposal of arsenic pentaselenide and antimony sulfide and sulfate wastes
197
-------
by landfill must be carefully regulated at approved Class 1 type sites. It
is recommended that wastes containing antimony sulfides and sulfate as
constituents be returned to the antimony producers or reclaimers for the
recovery of their antimony value. Secondary antimony recovered from
various manufacturers and foundries while reprocessing scrap material
amounted to 23,664 tons in 1967, almost twice as much as the primary
antimony produced in the United States for the same year. The depletions
of high grade antimony oxide ores indicate that even greater attention
should be focused on the secondary recovery of antimony from waste streams
containing antimony compounds.
198
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7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971.
Washington, U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22v. and
suppl., New York, Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
2275. Mellor, J. W. A comprehensive treatise on inorganic and theoretical
chemistry, v. 7. New York, John Wiley & Sons, Inc., 1963.
199
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Antimony Pentasulfide (37)
IUC Name
Structural Formula
Common Names
Sb2s5
Molecular Wt.
(1)
403.82
Density (Condensed) 4.12
rrr
/-,% decomposes
Melting Pt\ ' @ 75 C
Boiling Pt._
Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt 2) Lower_
Explosive Limits in Air (wt. X)
(1)
Lower
Upper.
Upper_
Solubility
Cold Water insoluble
Hot Water insoluble
Ethanol insoluble
Others: soluble in HC1. alkali. NH^HS
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments -
Coast Guard Classification
References (1) 1570
200
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Antimony Sulfate (39)
IUC Name
Common Names
Structural Formula
sb2(so4)3
Molecular Wt
'
531.68
^
Melting Pt decomposes
Density (Condensed) 3.625^ @
Boiling Pt.
Density (gas)
Vapor Pressure (recommended 55 C and 20 0
(3
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility v '
Cold Water
insoluble
Others: soluble in acid
Acid, Base Properties
Hot Water decomposes
Ethanol
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
201
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Antimony Trisulfide
IUC Name
Common Names
Structural Formula
Sb2s3
Molecular Wt.
(1)
339.69
(1)
Density (Condensed) 4.12
UT
Melting Pt. ' 550 C
Density (gas)_
Boiling Pt.^Ca 1150 C
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility (1)
Cold Water 0.000175 g/100 ml @ 18 CHot Water_
Others: soluble in HC1, K2S, NH4HS
Acid, Base Properties
Upper_
Upper_
Ethanol insoluble
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
202
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Calcium Fluoride (92)
IUC Name
Common Names
Structural Formula
CaF,
(1)
(1)
Molecular Wt. 78.08 Melting Pt.v'7 1360 C Boiling Pt.v " ca 2500 C
Density (Condensed) 3.18^ @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Upper_
Upper_
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility (1)
Cold Water 0-0016 g/100 ml @ 18 C Hot Water 0.0017 g/100 ml @ 26E^hanol
Others: soluble In ammonium salts
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments __
Coast Guard Classification
References (1) 1570
203
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Silica (368)
IUC Name
Structural Formula
Common Names
Molecular Wt.
(1)
60.08
Density (Condensed) 2.64-2.66(1)g
Melting Pt.(1* 1610 C
Boiling Pt.*1* 2230 C
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Hater insoluble
Hot Water insoluble
Ethanol insoluble
Others : soluble in HF
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
Coast Guard Classification
ICC Classification
Comments Silica exists in a variety of forms. The density and melting point given here
are those of quartz. .
References (1) 1570
204
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Arsenic Pentaselem'de (467)
Structural Formula
IUC Name
Common Names
Molecular Ht. 544.62 Melting Pt. decomposes Boiling Pt.
Density (Condensed) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point ___ _ Autoignition Temp.
Flairmability Limits in Air (wt %) Lower _ Upper_
Explosive Limits in Air (wt. %) Lower _ Upper_
Solubility
Cold Water insoluble Hot Water Ethanol insoluble
Others: soluble in alkali hydroxides and sulfides
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification Coast Guard Classification
Comments
References (1) 1492
205
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tantalum (510)
IUC Name
Structural Formula
Common Names
Ta
Molecular Wt.(1) 180.948 Melting Pt.(1) 2996 C
Density (Condensed) 16.6 @ Density (gas)
Boiling Pt(.1} 5425 C.
9
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flanmability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X)
Solubility }
Cold Water insoluble
Lower
Upper_
Upper_
Hot Water
insoluble
Ethanol
others: Soluble in HF. fused alkali, insoluble in acid
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
206
-------
PROFILE REPORT
Antimony Potassium Tartrate (38)
1. GENERAL
Introduction
Potassium antimony tartrate, K(SbO)C4H4Og • 1/4H20, occurs as
transparent, odorless crystals or as a white powder. It is manufactured
by heating antimony trioxide with a solution of potassium bitartrate
followed by crystallization. It is used as a textile and leather mordant,
1442
medicine (emetic), insecticide and in perfumery.
Physical/Chemical Properties
The physical/chemical properties for potassium antimony tartrate are
summarized on the attached worksheet.
2. TOXICOLOGY
Although potassium antimony tartrate is used medicinally as an emetic,
the therapeutic dose is close to the toxic dose. It can cause cough,
metallic-taste, salivation, nausea, and diarrhea. Large doses can cause
severe liver damage. The dose for an emetic is 30 mg by mouth. The
lethal dose for the mouse is reported as LDCn 600 mg/kg (as Sb). For man
1 "536
the LD^a is reported to be 2 mg/Kg as potassium antimony tartrate.
ca
3. OTHER HAZARDS
None.
207
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
There are no special handling or storage requirements. There are no
Department of Transportation (DOT) or U.S. Coast Guard shipping requirements
but a Manufacturing Chemists Association warning label which states "may
be fatal if swallowed" is applied to all containers. It is shipped in 25-,
50-, and 250-lb drums and in 425- and 625-lb barrels.1416
Disposal/Reuse
Contaminated potassium antimony tartrate is not normally reprocessed
for reuse, but instead is treated for disposal.
The safe disposal of potassium antiomony tartrate is defined in terms
of the recommended provisional limits in the atmosphere and in water and
soil environments. These recommended provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Potassium Antimony o
Tartrate 0.005 mg/M as Sb 0.01 TLV
Contaminant in Water Basis for
and Soil Provisional Limit Recommendation
Potassium Antimony
Tartrate 0.05 mg/1 as Sb 0.01 Drinking
Water Studies
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Potassium antimony tartrate is dissolved in water, 6M-HC1 is added to
the solution to make it acid and the solution is then saturated with
hydrogen sulfide. The precipitated Sb2S., is filtered, washed, dried and
packaged for shipment to a company which markets antimony sulfide.
If there is no market, the antimony sulfide is placed in storage in
containers protected from rain and snow.
208
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Potassium antimony tartrate wastes are easily treated by the process
described above in Section 5 at the site of origin. The toxicity of
antimony compounds requires that their disposal be controlled to protect
man and his environment. If a market for the antimony sulfide recovered
from the waste treatment process cannot be identified and permanent storage
is required, it is recommended that the antimony sulfide be stored at a
National Disposal Site.
309
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 2d ed. Washington, 1969. 176 p.
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards. 35:35-40, Aug. 1971.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d.,
New York, Reinhold Publishing Corporation, 1957. 1,457 p.
1416. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
210
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Antimony Potassium Tartrate (33)
Structural Formula
IUC Name
Common Names Tartar emetic
K(SbO)C4 H406-1/4H20
Molecular Wt. 333.94^ Melting Pt. -1/2H?0 at 100 c'1 'Boiling Pt.
Density (Condensed) & Density (gas) 9
Vapor Pressure (recommended 55 C and 20 0
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water soluble*2* Hot Water soluble*2* Ethanol insoluble*2*
Others:
Acid, Base Properties Aqueous solution slightly acid*2* :
Highly Reactive with
Compatible with
Shipped in drums and barrels
/?\ (2)
ICC Classification none* ' Coast Guard Classification none
Comments
References (1) 0766
(2)
211
-------
PROFILE REPORT
Arsenic (46)
1. GENERAL
Elemental or metallic arsenic, in contrast to most other arsenic com-
pounds, cannot be generally considered as a hazardous waste material.
Arsenic does not appear in nature in elemental form and its occurrence
as a waste, is insignificant. American Smelting and Refining identifies
itself as the only U.S. producer of metallic, elemental arsenic. It is
produced in ultra high purity and sold in gram lots. It is used for the
doping of semiconductor materials and in alloys of copper, lead and other
metals. The alloys are made by adding arsenic trioxide to the molten
metal thereby accomplishing the reduction in situ and producing no waste.
American Smelting and Refining is apparently the only U.S. commercial source
of these materials and their process details and production figures are
proprietary. It is believed that nearly all metallic arsenic is imported
and amounts to an estimated 400 tons yearly. Arsenic alloys are val-
uable commodities and their use patterns indicate that under the most
minimal controls, wastes containing elemental arsenic or arsenic alloys
will not be generated in significant quantities.
2. TOXICOLOGY
Metallic arsenic is highly toxic when ingested or inhaled. It emits
toxic fumes when heated. The Threshold Limit Value (TLV) recommended by
o
the ACGIH is 0.5 mg/M air. The vapor pressure data indicates that metallic
arsenic at room temperature is safe to leave in the open. Most arsenic
compounds are poisonous to both plants and animals. Acute arsenic
poisoning in man from ingestion is marked by irritation of the stomach
and intestines accompanied by nausea, diarrhea and vomiting. In severe
cases the vomitus and stool contain blood and the patient can go into
collapse and shock with a weak, rapid pulse, cold sweats, coma and death.
213
-------
Chronic arsenic poisoning, whether by ingestion or inhalation of airborne
arsenic compounds, is very difficult to diagnose because it can cause a
varied patten of symptoms. Included are loss of appetite, cramps, nausea,
disruptions of the digestive tract, liver damage and a variety of skin
abnormalities.0766
3. OTHER HAZARDS
Arsenic in the form of dust or vapor has a moderate fire hazard when
exposed to heat or flame or if allowed to react with powerful airborne
oxidizers. The explosion hazard for airborne arsenic when exposed to a
flame is considered slight.
Four artificial isotopes of arsenic have been prepared. The type of
radiation and their energy levels as well as other radiological in-
formatioi
Arsenic.
formation are presented briefly in Sax under the compound heading
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT .
Handling, Storage, and Transportation
Metallic arsenic v/hen being shipped, handled or stored should not be
subjected to heating which would cause it to vaporize. It should be •
shipped in sealed glass ampules to prevent oxidation and maintain its
purity. It is necessary that the outside container be adequately labeled
as to the dangerous properties of the contents. Adequate supervision and
education of all personnel are considered a must for people handling this
material.
Both the Department of Transportation and the U. S. Coast Guard
classify elemental arsenic as a Class B poison and require the poison
label on all shipping containers. As such, all regulations
governing the handling, storing, loading, and shipping of these materials
must be complied with.
214
-------
Disposal/Reuse
Elemental arsenic usually does not occur as a waste product and
any surplus or contaminated material can always be returned to the
manufacturer for reprocessing. For the safe disposal of wastes con-
taining small amounts of arsenic, the acceptable criteria for the release
of arsenic into the environment are defined in terms- of the following
provisional limits:
Contaminant and Basis for
Envimoment Provisional Limit Recommendation
Arsenic in air 0.005 mg/M3 0.01 TLV
Arsenic in water 0.05 ppm (mg/1) Drinking Water
and soil Standard
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Elemental or metallic arsenic does not occur in any significant
amount as a waste material. There are no treatment means by which this
material can be made nontoxic. Should it be necessary to dispose of the
small quantities of this material, it should be packaged according to
federal regulations and shipped back to the supplier or manufacturer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Elemental arsenic is not considered as a candidate waste stream con-
stituent for National Disposal Sites because: (1) the material does hot
normally occur as a waste product; and (2) the material will be accepted
for return shipment by supplier or manufacturer for reprocessing. There
are, however, significant quantities of wastes containing arsenic compounds,
such as arsenic trioxide, arsenates, arsenites, and organic arsenicals and
long term storage has been recommended as the preferred management method
for the concentrated arsenic wastes at National Disposal Sites. The dis-
posal of wastes containing elemental arsenic can therefore be adequately
handled at a National Disposal Site, if indeed such a need arises. Some
215
-------
commercial disposal organizations also accept this material for permanent
encapsulation in DOT 17-H (heavy wall steel drums) and disposal in land-
fills. However, in light of the availability of reprocessing, burial of
arsenic is neither economically nor environmentally adequate.
216
-------
7. REFERENCES
0458. Bureau of Mines. Mineral facts and problems. 1965 ed. Bulletin 630,
1,117 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1518. Personal communication. M. Hutchinson, Hutchinson and Son Disposal
Company, to J. Clausen, TRW Systems, Apr. 13, 1972. ^
1560. Personal communication. K. Nelson, American Smelting and Refining
Company, to J. Clausen, TRW Systems, Apr. 11, 1972.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
217
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Arsenic (46)
IUC Name
Common Names
Structural Formula
As
Molecular Wt. 299>64
0)
Density (Condensed) 5.727
(3 14
Melting Pt. 814 C P 36 Atm. Boiling pt. sub. 615
_C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
1 mm (8 372 C 10mm
Flash Point
437
100
mm
-------
PROFILE REPORT
Arsenic Trichloride (50)
1 . GENERAL
Arsenic trichloride, AsCl3, commonly known as butter of arsenic, is a
corrosive, highly poisonous, oily liquid at room temperature. Arsenic
trichloride can be prepared by a combination of the elements or by one of
the following reactions:
3 + 6S2C12 -> 4AsCl3 + 3S02 + 9S
As203 + 6NaCl + 3H2$04 -> 2AsCl3 + 3Na2$04 + 3H20
The only current producer of AsCK, Rocky Mountain Research, burns arsenic
in a chlorine stream using a proprietary process. Its uses, listed in
Merck, are found in ceramics, surface doping of semiconductors, and
chlorine containing arsenical s such as the chloro derivatives of arsine. 92
Investigation revealed that the Bodman Chemical Company of Narberth,
Pennsylvania is currently the only supplier of AsCl3 as agent for Rocky
Mountain Research. They reported that nearly all the produced
AsCK is going into the production of fungicides by Aerojet General Solid
Propel! ant Co. in Sacramento, California. The remainder is being sold
as Tab reagents and an extremely small amount is used for coating semi-
conductors. Rocky Mountain Research is manufacturing approximately
6,000 Ib per month for Aerojet General while shipping an additional
1644
small amount to Bodman Chemicals for laboratory reagents.
Aerojet is consuming AsCK in the custom production of the fungicide
oxy bis phenoxarsine(OBPA). The reactions are carried olit at the
barricaded Sacramento facilities on the same isolated site -where solid
propellants are manufactured. The synthesis i-s performed in a batch
operation with approximately 500 Ib of AsCl3 per charge. It was reported
that the only AsCl3 waste is contained in a pot residue from the distilla-
tion of the first step product of the two-step reaction.. This waste is
219
-------
currently being sealed in 55-gal. steel drums and is being stored on
site at Aerojet General. The amount of material that is being stored
there is,by Aerojet's opinion, very small and Aerojet feels no need to
dispose of the material immediately. Aerojet is waiting until the first
phase of this custom synthesis contract is completed so that all wastes
can be removed at the same time. Aerojet contemplates controlled incin-
eration and/or landfill for these waste materials by a commercial disposal
firm.1643
2, TOXICOLOGY
The Merck Index indicates that arsenic trichloride is an extremely
toxic material. It can cause death through inhalation or by direct appli-
cation to the skin. It is highly corrosive through release of HC1 when
exposed to water and can be a serious respiratory tract irritant.
Arsenic trichloride has vapor pressure of 10 mm at about room temperature
making air exposure prohibative in areas without ventilation control. The
Threshold Limit Value (TLV) is listed at 0.5.mg/m3. °225
Merck has indicated that the lethal short term concentration of
AsCl3 in air for cats is 27 ppm. No specific data on the harmful
effects of AsCl3 on plant life was found but in light of its corrosive
nature and the harmful effects of arsenic compounds in general, it is
believed that AsCl- is highly poisonous to plant life.
3. OTHER HAZARDS
The Laboratory Waste Disposal Manual indicates that AsCl3 does not
have any significant ignition temperature or flammability limits and can
be considered to be generally non-flammable and non-explosive.
Its vapor pressure is appreciable and therefore a potential disaster
hazard exists should large quantities of this material be spilled or
released into the air near habitation. The present producers of this material
1644
are shipping in 5-gal. cans to further minimize any disaster hazard.
220
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Because of the highly toxic nature of AsCl.,, special considerations
must be taken to prevent direct contact with personnel, animal or plant
life. It should be stored in isolated areas away from such items as food
products, heat sources, or combustible materials which could create a
hazard in case of fire. Arsenic trichloride hydrolyzes in water releasing
hydrochloric acid which is the basis for the corrosive nature of Asd3-
Therefore, AsCl3 should not be exposed to the atmosphere. In case of spills
of arsenic trichloride the area should be evacuated by all personnel
immediately. Soda ash or bicarbonate of soda should be applied to neutra-
lize the evolved HC1. The spill should be washed down with collection of
the washings which contain As^O-j.
The Department of Transportation (DOT) classifies AsCl3 as a Class B
poison, requiring a label, and limiting the size of shipping containers to
55 gallons. The use of rubber gloves, safety glasses, a respirator, labo-
ratory coat or equivalent protection must be used when handling this mate-
rial. All other DOT regulations regarding the storage, shipment, or
handling of this material must be followed.
Disposal/Reuse
Arsenic trichloride is a liquid at room temperature and can be
distilled for purification. Rocky Mountain Research has a policy of
accepting excess amounts of arsenic trichloride or contaminated arsenic
trichloride for reprocessing. The returned AsCK is fed into their
reactor for subsequent purification. They will also accept certain
waste materials containing arsenic trichloride which is reacted with
water to liberate HC1 and precipitate the arsenic trioxide.
The acceptable criteria for the release of very small quantities of
arsenic trichloride into the environment are defined in terms of the
following recommended provisional limits:
221
-------
Contaminant in Provisional Limit Basis for Recommendation
Air
Arsenic trichloride 0.005 mg/M as As 0.01 TLV for As
Contaminant in Water
and Soil Provisional Limit Basis for Recommendation
Arsenic trichloride 0.05 ppm (mg/1) as As Drinking Water Standard for
As
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Arsenic trichloride when handled by methods that prevent exposure
does not present a serious disposal problem. The two waste management
options are discussed below.
Option No. 1 - Recycling/Reprocessing
. Rocky Mountain Research, the only current producer of arsenic tri-
chloride, has indicated its willingness to accept excessive or waste
arsenic -trichloride for reprocessing, purification or disposal. It is
fed into their reactor and purified in the same manner as a normal batch.
Rocky Mountain Research was not willing to discuss the details of their
process and hence an evaluation of the process and the purification tech-
nique for AsCK were not available. Rocky Mountain Research's alternate
procedure would be to add water to the waste under ventilation control to
hydrolyze the arsenic trichloride to arsenic trioxide which is much
easier to handle. It is conceivable that any industry that handles AsCl3
in significant amounts would probably have special facilities available
to them for hydrolyzing the AsCl3 and scrubbing the evolved HC1.
Option No.2 - Landfill
Landfill ing of arsenic trichloride is not considered as an acceptable
disposal option because of: (1) the high degree of toxicity of the
compound; (2) the nondegradable nature of the toxic arsenic component of
arsenic trichloride, whereby the compound would not be converted to a less
222
-------
toxic or non-toxic form in the soil environment; and (3) the reactivity
of arsenic trichloride with water to yield arsenic trioxide and corrosive
hydrochloric acid. The corrosive potential of arsenic trichloride also
indicates that the land burial of arsenic trichloride wastes containerized
in metal drums is not an adequate method of disposal.
6. APPLICABILITY TO A NATIONAL DISPOSAL SITE
Considering the very small production and consumption of AsCl, as
well as provisions for return of waste AsCl- by the producer, it is felt
that AsCl, cannot in itself be considered as a candidate waste stream
constituent for national disposal. There are simple methods for hydro-
lyzing it to As^O, which is easier to handle and this can be performed
by many firms who have simple wash down equipment. However, the charter
of a National Disposal Site should include accepting any kind of arsenic
containing material and it is probable that such a site would in any case
have a simple wash down area for a number of materials. Thus AsCK might
be sent to a National Site for a routine hydrolysis. But it is emphasized
that processes for the exclusive treatment of arsenic trichloride wastes
are not recommended for inclusion in the National Disposal Site scheme.
223
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, Sept. 1969. 174 p.
0225. Occupational Hazards.. Threshold limit values for 1971. Occupational
Hazards, Aug. 1971. p. 35-40.
0766. Sax, N. I. Dangerous properties of/industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
1639. Personal communication. Mr. Burnham, Badman Chemicals Company, to
J. Clausen, TRW Systems, Apr. 21, 1972.
1643. Personal communication. T. Foster, Aerojet-General Solid Propellant,
to J. Clausen, TRW Systems, Apr. 21, 1972.
1644. Personal communication. G. Thompson, Rocky Mountain Research, to
J. Clausen, TRW Systems, Apr. 21, 1972.
224
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Arsenic Trichloride (50)
Structural Formula
IUC Name
Common Names Butter of Arsenic
AsCl
3
Molecular Wt. 181.28^) Melting Pt. -8.5 C^ Boiling Pt.
Density (Condensed)2.163 9/cc (j> 20 C1 Density (gas) 6.2J2* @
Vapor Pressure (recommended 55 C and 20 C)
10 mm (a 23.5 C^ 9
Flash Point N/A Autoignition Temp.N/A
Flammability Limits in Air (wt %) Lower N/A Upper
Explosive Limits in Air (wt. X) Lower N/A Upper N/A
Solubility
Cold Water Decomposes Hot Water _ Decomposes Ethanol Soluble
Others: HBr. HC1, ether
Acid, Base Properties
Highly Reactive with H00 to produce HC1 and As,0,
Compatible with_
Shipped in—stppl 5-gallon cant and 55-gaU
-------
PROFILE REPORTS ON
Barium Compounds
Barium Carbonate (52). Barium Chloride (53), Barium Cyanide (469)
Barium Nitrate (471), Barium Sulfide (472)
1. GENERAL
Introduction
Barium compounds exhibit a close relationship to the compounds of the
other alkaline earth metals, calcium and strontium. Barium behaves
generally as a bivalent element, as do the other.alkaline earth metals.
The solubilities of barium salts are typical of the alkaline earth group.
The halides and nitrate are quite soluble, whereas the carbonate and
sulfate are insoluble. With the exception of barium sulfate, the salts
dissolve partially in carbonic acid and completely in hydrochloric or
nitric acid. The sulfate is extremely insoluble and is useful for the
determination of the barium ion.
Precipitated oarium carbonate is the most important of the
manufactured pure barium chemicals. In production tonnage it is second
to the principal mineral, barite. The production of barium carbonate has
decreased considerably in the last few years. In 1969, there were 114,000
tons of barium carbonate produced in the United States. In 1970 the
production of barium carbonate declined to 61,083 tons. In that same year
the production of all other barium compounds totaled 57,000 tons. Of'that
total it is estimated that there were less than 10,000 Ibs of barium cyanide
produced. Individual production figures for the other barium compounds
discussed in this Profile Report are not available.
Manufacture
All major barium salts in the United States are produced from the
chemical grade of barite (BaS04). Since barite is highly insoluble, the
starting point of the barium-plant process is the reduction of barite to
227
-------
soluble barium sulfide or black ash. This is then converted to the various
barium compounds.
Barium Carbonate. Black ash is dissolved in water and its clear solu-
tion is the usual raw material for barium carbonate manufacture. There are
two basic methods of manufacture which differ mainly in the way the carbonate
ion is introduced.
BaS + Na2C03 - &»- BaC03 + Na2$ (1)
BaS + C02 + H20 - ®-BaC03 + H2S (2)
The product from the straight-gassing process (equation 2) is more impure
than the soda ash product (equation 1). Large scale commercial facilities
for the manufacture of barium carbonate include the following :
Barium and Chemicals Incorporated, Painesville, Ohio
Chemical Products Corporation, Cartersville, Georgia
FMC Corporation, Modesto, California
Sherwin-Williams 'Company, Coffeyville, Kansas.
Barium Chloride. Barium chloride is produced by treating a barium
sulfide solution with hydrochloric acid:
BaS + 2HC1 - B»- Bad + H$
Barium Cyanide. Barium cyanide (Ba(CN)2) is prepared by reaction of
hydrogen cyanide on barium hydroxide suspended in petroleum ether. The
di hydrate is formed and then dried carefully under vacuum to yield a pro-
duct of 95 percent purity. Barium cyanide is produced by Phillips Brothers
Chemicals, Incorporated, New York.
Barium Nitrate. Barium nitrate is made by the interaction of a suspen
sion of barium carbonate in a mother liquor with nitric acid, followed by
crystallization after filtration. "Another method is to dissolve sodium
nitrate in a saturated solution of barium chloride, with subsequent perci-
pitation of barium nitrate. The precipitate is centrifuged, washed and
228
-------
dried. Barium nitrate is produced by Barium and Chemicals, Incorporated,
Painsville, Ohio.
Barium Sulfide. Black ash is produced by reducing ground barite with
coal at high temperatures. The reaction is:
BaS04 + 2C ——»- BaS + 2C02
Barium sulfide is also produced by Barium and Chemicals, Incorporated,
Painsville, Ohio.
Uses
The principal application areas of the five barium compounds have been
summarized by Miner (Table 1).
Sources and Types of Barium Wastes
The sources of barium wastes may include the following: (1) barium
compound manufacturers, and (2) commercial and industrial processes including
those from paper manufacturing pi ants» ceramic and enamel manufacturing plants,
etc.
In general, barium wastes can be classified as either diluted or con-
centrated wastes. Diluted barium wastes include those generated in the
waste waters of manufacturers and uses of barium chemicals. Concentrated
barium wastes include any unused or contaminated barium compounds that require
disposal or recovery.
Physical and Chemical Properties
The physical and chemical properties of the five barium compounds are
included in the attached worksheets.
229
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TABLE I0646
APPLICATION AREAS OF BARIUM COMPOUNDS
Compound
Uses
Barium Carbonate, BaCO.
Barium Chloride, Bad.
Barium Cyanide, Ba(CN)2
Barium Nitrate, Ba(N03)2
Barium Sulfide, BaS
As rat poison; in ceramics, enamels; .
in manufacture of paper, barium salts,
optical glasses; in case-hardening
steels.
In manufacturing of blanc fixe
(precipitated BaSO.); as mordant for
acid dyes; in weighting and dyeing
textile fabrics; as boiler compounds
for softening water; as purifying agent
in brines; in manufacture of barium
colors and of chlorine and sodium
hydroxide; as flux for magnesium alloys,
in case hardened steels.
In electroplating processes.
In manufacture of Ba02; as pyrotechnic
for green fire; as green signal lights;
in the. vacuum tube industry.
As raw material for other barium
compounds.
230
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2, TOXICOLOGY
Soluble barium compounds are highly toxic when ingested, while
insoluble compounds, such as barium sulfate9 are generally nontoxic.
Inhaled barium compounds cause a benign pneumoconiosis, called baritosis.
Ingestion of soluble barium compounds results in strong stimulation of
the muscles, including the heart; irritation of the intestinal tract;
and irritation of the central nervous system.
The symptoms of barium poisoning are severe abdominal pain with
vomiting, dyspnoea, rapid pulse, paralysis of the right arm and leg, and
eventually cyanosis and death. The usual result of exposure to the sulfide
and carbonate is irritation of the eyes, nose and throat, and of the skin,
producing dermatitis.
The five barium compounds included in this Profile Report are all
highly toxic and exhibit similar toxicity symptoms. With barium cyanide,
however, the toxic effects of both elements of the compound must be
considered (refer to Profile Report on Cyanides).
The relative oral L.DCQ values to the rat are 50-200 mg/kg for barium
carbonate and 355-533 mg/kg for barium chloride. The estimated oral
LDgQ values for man are 55 mg/kg for barium carbonate and 80 mg/kg for
barium chloride. The American Conference of Governmental Industrial
Hygienists (1971) recommended a Threshold Limit Value (TLV) in air of
0.5 mg/M for all soluble barium compounds. For cyanides (Ba(CN)p) the
TLV in air is 5.0 mg/M3. °225 The U.S. Public Health Service established
the permissible criteria for barium in public water supplies as 1.0 ppm.
This agency also recommends that the concentration of cyanides be kept
1752
below .01 ppm for both fish and people.
3. OTHER HAZARDS
Barium nitrate is an oxidizing material. In contact with easily
oxidizable substances it may react rapidly enough to cause ignition,
231
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violent combustion, or explosion. It increases the flammability of any
combustible substance.
The fire hazard of barium sulfide by spontaneous chemical reaction
is moderate; air, moisture or acid fumes may cause it to ignite. Barium
sulfide may react violently and explosively on contact with powerful
oxidizers.0766
Other than the toxic effects, barium carbonate, barium chloride and
barium cyanide present no further hazardous problems.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, Transportation
Care should be exercised in handling barium compounds because of
their high toxicity. The use of rubber gloves is advisable. Any material
which comes in contact with the skin should be immediately removed with
plenty of soap and water.
Barium nitrate should be stored in an area where it will be separated
from combustible, organic or other readily oxidizable materials. Avoid
storage on wood floors. Any spilled nitrate should be immediately removed
and disposed of. All of the barium compounds discussed in this report
should be stored away from foodstuffs, feeds, or any other material intended
for consumption by humans or animals.
Adequate procedures for the transportation of barium cyanide and
0278
barium nitrate have been established by the Department of Transportation.
Label requirements, as well as the maximum quantities permitted to be
shipped in one outside container, are also specified.
232
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Disposal/Reuse
Disposal or reuse of waste barium compound streams must take into
account the toxic nature of these materials. The discharged barium compounds
must be treated by the methods described in Section 5 or diluted to a concen-
tration of 1 ppm (.01 ppm for Ba(CN)2).
The safe disposal of barium compounds is defined in terms of the recom-
mended provisional limits:
Contaminant in Air
Barium Carbonate
Barium Chloride
Barium Cyanide
Barium Nitrate
Barium Sulfide
Provisional Limits
.005 mg/M3
.005 mg/M3
.005 mg/M3
.005 mg/M3
.005 mg/M3
Basis for
Recommendation
.01 TLV
.01 TLV
.01 TLV
.01 TLV
.01 TLV
Contaminant in Water
and Soil
Barium Carbonate
Barium Chloride
Barium Nitrate
Barium Sulfide
Barium Cyanide
Provisional Limits
1 mg/1
1 mg/1
1 mg/1
1 mg/1
.01 mg/1
Basis for
Recommendation
U. S. Public Health
Service recommendation
for public drinking water.
It should be noted that the recommended provisional limit for the barium
compounds (except barium cyanide) in water are less than that of .01 of the
TLm for fish.
1752
The provisional limit of barium cyanide in public drinking
water (.01 mg/1) is also a safe level for fish. It was found that trout
could survive a cyanide concentration of .02 mg/1 for more than 27 days.
1752
233
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Waste
Option No. 1 - Precipitation. By far the most widespread method used
for removing barium from industrial waters is precipitation with sulfate
ion (usually sulfuric acid) in settling ponds. The precipitate formed,
BaSO^, is only slightly soluble in water and the resulting effluent from
the pond contains about 2 ppm of barium. This effluent would then be di-
luted with an equal amount of water to meet the permissible criteria for
barium in public water supplies (1.0 ppm). Precipitation and settling is
normally a slow procedure and with high effluent flow it is normally nec-
essary to have settling ponds or lagoons in which to allow the slow coag-
ulation process to occur, the clear effluent removed and the precipitate
dried. Since barium sulfate is important in the barium industry (see
section on Manufacturing) it can be economically recycled. This method can
be used for both concentrated and dilute barium wastes. In the case of
barium cyanide wastes, the cyanide must be removed first before precipitating
the barium with sulfuric acid. The primary method of removing cyanide is to
oxidize it to C02 and N2 with an alkaline chlorine solution. Other methods
for removing cyanide include ion exchange, electro-oxidation, and reaction
with aldehydes (refer to Profile Report on cyanides for additional informa-
tion). Barium could also be precipitated by chromate ion to form barium
chromate. This is a workable method but is not normally economically feas-
ible unless a market as pigments for the precipitate is available.
Option No. 2 - Ion Exchange. Ion exchange can be used to remove
barium from dilute aqueous waste streams. Barium will behave much like
calcium and magnesium and can be removed from an aqueous waste stream by
either a sulfonic acid type cation exchange resin or a carboxylic weak acid
1795
type resin, depending upon the pH of the stream. An ion exchange unit
cannot usually handle an influent concentration load above 1500 ppm. An
advantage of ion exchange is that due to the coricentrative effects it is
possible to apply this process in recycling barium materials or in concen-
trating wastes for transport to centralized disposal. The major difficulty
in ion exchange operation is the critical dependence on flow rate. The ion
234
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exchange system is designed to operate with a particular efficiency at a
certain set flow. Should this flow be exceeded for even short periods of
time, the efficiency for absorbing the barium ion decreases drastically
causing the effluent to exceed the permissible limit.
Option No. 3 - Reverse Osmosis. The effectiveness of reverse osmosis
1812
to remove barium from water has been investigated by Sourirajan. Follow-
ing passage of a barium waste stream through a porous cellulose acetate mem-
brane, it was found that the barium concentration was reduced from 34.35
g/liter to 7.35 g/liter. It is conceivable that "R.O." is applicable to
dilute barium salt solutions as well, but no data is available to support
this assertion. With an effluent concentration of 7.35 g/liter, the "R.O."
unit would have to be used in conjunction with some other process (ion ex-
change for example) to produce an effluent with a permissible concentration
of barium.
Option No. 4 - Adsorption on Activated Carbon. Activated carbon has
1813
been shown to remove barium from acetate solutions by Kuzin et al.
Although the laboratory investigation was principally directed towards the
separation of uranium from other metallic compounds; it was found in the
same study that activated carbon possessed a sorption capacity for soluble
barium compounds of 0.7 mg/g carbon, thus demonstrating the feasibility of
activated carbon adsorption as a near future process for removing soluble
barium compounds from water.
The processes mentioned above deal exclusively with barium wastes in
the conventional aqueous form. If, however, the barium wastes are present
in the particulate form in a gas stream, the usual methods for removal of
particulates, such as bag filters, electrostatic precipitation, and wet
scrubbers should prevent their escape to the atmosphere.
The best method for disposing of both dilute and concentrated aqueous
barium wastes is precipitation with sulfate ion. The technique is efficient
and adequate for large scale removal of barium.
235
-------
The other processes discussed (ion exchange, reverse osmosis, and
adsorption on activated carbon) will result in reduced amounts of waste
barium but are not applicable as primary treatment methods. These pro-
cesses should function mainly as a secondary treatment of the effluent
from a barium precipitative facility.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the provisions for the recycle and recovery of waste barium
by the producers, it is felt that waste streams containing barium compounds
do not warrant National Disposal Site treatment. The precipitation method
for the removal of barium from waste streams is inexpensive enough for even
the small barium manufacturers and users to operate.
In summary, the recovery and/or disposal of barium wastes can be cur-
rently handled adequately at the industrial site level and this mode should
be continued.
236
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7. REFERENCES
0096. National Fire Protection Agency. Fire protection guide on
hazardous materials, 3d ed. 1969. 950 p.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards, p 35-40,
Aug. 1971.
0278. Code of Federal Regulations. Title 49--transportation, parts 71
to 90. (Revised as of January ls 1967). Washington, U.S.
Government Printing Office, 1967. 794 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. April 1, 1968.
Washington, Federal Water Pollution Control Administration.
234 p.
0646. Miner, S. Air pollution aspects of barium and its compounds.
Technical Report, Litton Systems, Inc., Sept. 1969. 69 p.
0766. Sax, N.I. Dangerous properties of industrial materials. 2d ed.,
New York. Reinhold Publishing Corp. 1957. 1,467 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers. 1963-1971.
1506. Barium carbonate. Jji Chemical profiles. New York, Schnell
Publishing Company, 1967.
1752. Public Health Service. Drinking Water Standards, 1962. U.S.
Department of Health, Education and Welfare, 1962. 61 p.
1794. Personal communication. B. Blank, Sherwin Williams Co., to
D. Dal Porto, TRW Systems, June 2, 1972. Barium waste stream
treatment.
1795. Personal communication. C. T. Dickert, Rohm & Haas to D. Dal Porto,
TRW Systems, May 16, 1972. Ion exchange applications- to barium
waste treatment.
1812. Sourirajan, S. Separation of some inorganic salts in aqueous
solution by flow, under pressure through porous cellulose,
acetate membranes. Industrial and Engineering Chemistry
Fundamentals, 3(3):286-210, Aug. 1964.
1813. Kuzin, A., V. P. TaushkanoV, B. M. Leonov, and Y. A. Boganch.
Sorption of metals by SKT activated carbon from acetate solutions.
Journal of Applied Chemistry of the U.S.S.R. 39(2): 325-328,
Feb. 1966.
1814. Personal communication, Olsen, U.S. Tariff Commission to D. Dal
Porto, TRW Systems, May 18, 1972. Production data on barium compounds.
237
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Barium Carbonate(52)
Structural Formula
IUC Name
Common Names
BaCO
3
Molecular Wt. T97.37 Melting Pt. 1740 @ 90 atm Boiling Pt. Decomposes
Density (Condensed) 4.43 @ Density (gas}_ 9
Vapor Pressure (recommended 55 C and 20 C)
(a § @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 0.0022g/10Qg @ 18 C Hot Water 0.0065 g/lOQg & IQOCEthanol insoluble
Others:
Acid, Base Properties ••
Highly Reactive with
Compatible with_
Shipped in Bags, barrels and kegs
ICC Classification Coast Guard Classification
r . White powder
Comments
References (1) 0766.
238
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HAZARDOUS WASTES PROPERTIES
b&RKSHEET
H. M. Name Bar1um Chloride (53)
IUC Name
Coimton Names
Structural Formula
Bad.
Molecular Wt.
208.27
Melting Pt.
92S c
Density (Condensed) 3'856 g 24 c Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. 1560 C
§
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water 37.5g/100g @ 26 C
Others:
Hot Water 59 g/TQOg B inn r Ethanol
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in Bags, barrels and kegs
ICC Classification
Comments
Coast Guard Classification
References (1) 0766.
239
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Barium Cyanide (469)
Structural Formula
IUC Name
Common Names
Ba(CN)
2
Molecular Wt. 189.40 Melting Pt. Slowly decomposp": Boiling Pt.
Density (Condensed) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper.
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 1 gm/1.5ml Hot Water . Ethanol i gm/?nmi
Others:
Acid, Base Properties_
Highly Reactive with_
Compatible with
Shipped in Bags, barrels and kegs
ICC Classification Coast Guard Classification
Comments
240
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Barium Nitrate (471)
IUC Name
Common Names
Structural Formula
Ba(N03)2
Molecular Wt.
261.38
Melting Pt. 592 c
Density (Condensed) 3.24 @ 23_ _C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Boiling Pt. Decomposes
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water 8.7g/100cc
Others:
Hot Mater 34.2g/100cc
Ethanol Insoluble
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped in Bags, barrels, kegs, casks, drums
ICC Classification
Coast Guard Classification
Comments In contact with easily oxidizable substances it may react rapidly enough to cause
ignition, violent combustion or explosion.
References (1)0766.
0096.
241
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Barium Sulfide (472)
IUC Name
Common Names
Structural Formula
BaS
169.43
Molecular Wt.
Density (Condensed) 4.25
1200 C
_ Melting Pt. _
@ 1£ _C Density (gas)
Boiling Pt.
Vapor Pressure (recommended 55 C and 20 C)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X)
Solubility
Cold Water Soluble
Others:
Lower
Upper_
Upper_
Hot Water
Soluble
Ethanol Insoluble
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped jn Ba9s, barrels, kegs
ICC Classification Coast Guard Classification
Comm t ^a^ reac^ violently and explosively on contact with powerful oxidizers.
242
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PROFILE REPORTS
Beryllium Powder (59), Beryllium Carbonate (473),
Beryllium Chloride (474), Beryllium Hydroxide (475),
Beryllium Oxide (476), and Beryllium Selenate (477)
1. GENERAL
Production
There are two beryllium producers in the United States: the Brush
Beryllium Company, Elmore, Ohio °394 and KBI Industries (formerly
Kawecki-Berylco or the Beryllium Corporation of America), Reading,
Pennsylvania.0599 Production amounts to 50 to 75 tons/year (as beryl-
lium metal) divided approximately equally between the two companies.°^58
Each of the two producers has his own methods of winning the metal
from its principal ore, beryl, 3BeO.Al203.6Si02- The processes are dis-
cussed extensively in the literature. ^33,1417 y^y ^g^ involve the
production of Be(OH)2 as an intermediate step with a 90 percent extraction
efficiency (as beryllium metal), followed by calcining to BeO, conversion
to BeF2, and reduction by Mg to beryllium metal. The metal is then pul-
verized, sintered, and sawed or ground into desired shapes and parts. If
the popular Be-Cu alloys are desired (2-4 percent beryllium, remainder Cu),
the BeO is reduced with carbon in the presence of copper.1677
The French produce Beryllium directly by the electrolysis of Bed2.
but this process is regarded as uneconomical in the United StatesJ433-1720
Overall efficiency in going from beryl ore to sintered beryllium parts
is about 63 percent.0458 Because the metal is so valuable (about $60/lb)
every effort is made to recycle dross continuously at every step. Both
Brush and KBI actively seek their customers' scrap material, which they
0394
purchase for $10 to 20/lb contained beryllium and recycle. This recycled
243
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scrap accounts for approximately 6 percent of the total annual production.
The final waste and slag contains less than 1 percent beryllium as insoluble
0394
oxide and is stored currently on the refinery property.
Uses
It is anticipated that prices will remain strong at $60/lb contained
beryllium, so uses will remain limited to fairly exotic applications. Be-
Cu alloys have gained some popularity for applications where high electrical
conductivity is required together with high strength. These alloys account
for approximately half of all the beryllium used today. Another third is
used as metal in various applications involving the nuclear and aerospace
industries, almost exclusively in projects funded by the Federal Government.
While most beryllium metal is used for structural and machine parts, it is
also being considered as an additive in powder form to increase the thrust
of rocket engines. ' The amount used in this way is not known.
The high cost of beryllium is due to a number of factors which are not
likely to change in the foreseeable future: (1) the lack of mineral re-
sources, (2) the complexity of its extractive metallurgy, (3) the complexity
of its' fabrication technology, and (4) its toxicity.
0599 1720
Neither the beryllium producers ' nor a sampling of principal
1722 1723 1724
users ' ' report any significant sale or use of beryllium carbon-
ate, beryllium chloride, beryllium hydroxide, or beryllium selenate, although
the hydroxide is an intermediate in the production of metal and oxide. No
special problems are associated with this use as an intermediate.
Sources and Types of Beryllium Wastes
Since the beryllium users can practically resell all beryllium scrap
to the producer at $10 to $20/lb contained beryllium, there is very little
scrap material which is actually disposed of as waste. Most of the
beryllium wastes are in the form of solid parti.culates or in a dilute aqueous
solution (scrubber liquor), and are generated as a result of the attempts to
control the emission of beryllium dusts, fumes, and mists. The sources of
these beryllium wastes include beryllium extraction plants and beryllium
244
-------
users such as machine shops, foundries, ceramic plants, and propellent
plants.
2. TOXICOLOGY
Health and Safety Standards
Health and safety standards for beryllium workers and the general public
have evolved over a period of 30 years, ever since the first positive
diagnoses of beryl!iosis were made. Currently, the Environmental Protection
Agency is formalizing national emission standards, which are based on
conditions already observed by all AEC contractors. ' Almost
all beryllium producers, fabricators, and users already comply with these
standards, and "little economic impact on the industry" will result from
their implementation. An excerpt from the proposed standards is quoted
here:1678
"The proposed beryllium standards are designed to protect the
public from 30-day average atmospheric concentrations of
beryllium greater than 0.01 microgram per cubic meter (ug/m ).
Experience over more than 20 years has shown this to be a safe
level of exposure. For short-term, periodic exposures, the safe
3
level has been determined to be 25 ug/m for a maximum of 30
minutes. This periodic exposure limit is the basis for the
standard pertaining to rocket-motor firings.
"The proposed beryllium emission standards for extraction plants,
machine shops, foundries, ceramic plants, propel!ant plants, and
incinerators designed or modified for disposal of these substances
allow the operator to demonstrate compliance with either 1 or 2
below:
1. No more than 10 grams of beryllium emitted per 24-hour day.
2. No emission that will cause atmospheric concentrations of
beryllium to exceed an average of 0.01 microgram per cubic
meter of air for 30 days.
245
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"The beryllium emission standards given below are being proposed
for rocket-motor test facilities:
1. No emissions that will cause atmospheric concentrations of
beryllium to exceed 75 microgram-mlnutes per cubic meter
of air within the limit of 10 to 60 minutes.
2. No more than 10 grams of beryllium will be emitted per 24-
hour day when rockets are fired into a tank and the exhausts
are gradually released."
Epidemiology
Although annual beryllium consumption in the 20-year period 1948-1968
increased 500 percent, there have been no new cases except those currently
in incubation. '' Principal means of exposure include the
burning of coal. Coal contains 1 to 3 ppm beryllium with peak values of 31 ppm
having been reported. Approximately 500 million tons are burned annually.
To date, there is no evidence that anyone has ever contracted berylliosls
from handling beryl ore. There are 812 registered victims in the
United States, of which 60 are classified as "neighborhood victims", i.e.,
they had the misfortune to live near a beryllium plant, but never worked
with the material directly. However, they may have come in contact with
workers wearing contaminated clothing, etc.
The clinical manifestations of berylliosis are well documented. '
0276,1676,0641,1433,etc. Jn addnion to tne manifestations attributable to
all beryllium compounds, beryllium chloride, beryllium selenate, and other
soluble salts produce dermatitis on contact with the skin. Although
many berylliosis victims have contracted cancer, positive statistical
correlation is lacking. There is increasing circumstantial evidence for
246
-------
possible carcinogenic properties for beryllium in humans, since lung tumors
have been successfully induced in monkeys and rats and sarcomas have been
induced in rabbits. The 1971 Toxic Substances Annual List reports
that 0.1 mg/M have produced toxic effects in man by inhalation. Reported
50th percentile lethal doses (LD50) for beryllium compounds are:
Beryllium Carbonate: 150 mg/kg in the guinea pig injected
intraperitoneally
Beryllium Chloride: 86 mg/kg in the rat administered orally
Beryllium Hydroxide: 0.35-2.5 mg/kg in the rat injected
intravenously, depending on the
crystalline form of the hydroxide.
Recent laboratory studies1720'1721'1725'1744 in which rats and rabbits
were injected intratrachea!ly with BeO of respirable particle size (1 to
5y) indicate that there is a definite inverse correlation beween the toxicity
of the BeO and the temperature at which it is calcined. Beryllium oxide
calcined at 500 C produced severe pneumonitis and the eventual development
of adenocarcinomas. The pathological changes associated with, the intra-
tracheal injection of BeO calcined at 1100 C were qualitatively similar,
but quantitatively less severe. In contrast, BeO calcined at 1600 C was
"almost inert" and produced "minimal" pathologies. Beryllium oxide obtained
from rocket firings produced symptoms characteristic of the 1600 C-calcined
material.
There is no preferential uptake or concentration of beryllium or
beryllium compounds from the environment by any animals or plants, includ-
ing humans.0615'0641'0276'1127
3. OTHER HAZARDS
Finely divided beryllium metal may explode to form beryllium oxide* an
exceptionally stable compound. All other beryllium compounds react non-
violently with varieties of gases, liquids, and solids to eventually form
the ultimately stable beryllium oxide.
247
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4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage, and Transportation
Procedures for the handling, storage, and transportation of beryllium
waste are well-documented.0039'1678'0278 Sintered beryllium ingots or fabri-
cated parts and hot-pressed beryllium oxide shapes require no special shipping
or packaging precautions. A label is usually attached to indicate that fumes
or dust of this material may be toxic if inhaled.
Beryllium metal powder has a weight limitation of 25 Ib net per metal
container, when shipped under Department of Transportation regulations.
It is classified as a Class B poison, and must be so labeled. No regula-
tions exist for beryllium compounds as such, but the 25 Ib rule is generally
followed on the theory that controlled ventilation (such as a common
laboratory hood) will be available for 25 Ib quantities, but may not be
available for larger quantities.
Disposal and Reuse
Since the beryllium producers eagerly purchase all available scrap at
$10 to $20/1b containing beryllium, all users capture as much waste as possible
0394 0460
for resale to the producers. ' There is therefore ,very little scrap
material which is actually disposed of as waste.
The means of collection and control of dust, fume, and mist have been
summarized in new regulations being promulgated by the Environmental Protec-
tion Agency. 75'1678 Standard collection techniques such as scrubbers,
packed towers, cyclones, and fabric-filter units are currently in use on an
industry-wide basis to bring essentially everyone within the new target
emission concentration of OiOl yg/m . Scrubber liquors, etc. are disposed
of adequately with other liquid wastes.0275'0460'0461'1678
248
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Recommended provisional limits for beryllium and beryllium compounds
in the environment are as follows:
Basis of
Contaminant and Environment Provisional Limits Recommendation
Beryllium and beryllium 0.0001 mg/M EPA proposed
compounds in air standard
Beryllium and beryllium 1 ppm (mg/1) Drinking water
compounds in water standards
and soil
For the disposal of beryllium and beryllium compounds, an alternate
emission standard of no more than 10 gm of beryllium per 24-hour day for
each beryllium producing or beryllium using plant has also been proposed
by EPA, and operators have the option of complying with this standard instead
of the recommended provisional limits. For rocket-motor test facilities,
special beryllium emission standards have been proposed by EPA and these
are: (1) no more than 75 yg-min/M within the limit of 10 to 60 min; or
(2) no more than 10 gm per 24-hour day, provided the exhausts are trapped
and gradually released.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Recycling to Primary Producers
This is most desirable from the standpoints of users, producers, and
environmentalists. Beryllium and beryllium compounds are difficult to pro-
duce and the primary producers repurchase all available material at $10 to
$20/lb contained beryllium. ' This situation is expected to continue
indefinitely.0458
Option No. 2 - Burial
Liquid, solid, or particulate waste which is too dilute to recycle is
buried on private property or in public landfills. Often waste is first
burned to produce the insoluble, chemically inert oxide. This is easily
and safely done, providing the exhaust gases are scrubbed to remove any
249
-------
0394
particulates. These procedures were verified with KBI Industries,
two other large beryllium users, ' and the County of Los Angeles,
California, which operates several landfills which receive liquid
coolant wastes containing beryllium. All independently agreed with this
analysis.
Since there have been no new reported cases of berylliosis in 20 years
and demand is expected to remain static for the indefinite future, it may
be concluded that practices are adequate at present and for the foreseeable
future.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Since there have been no new reported cases of beryl!iosis contracted
within the past 20 years and essentially all producers and users already
comply with the proposed Environmental Protection Agency standards, it may
be concluded that beryllium and beryllium compounds are under adequate
control as hazardous wastes.
The continued high demand for scrap at $10 to $20/lb contained beryllium
makes its recovery extremely attractive for all users. Recovery systems
currently in operation keep ambient concentrations below the required 0.01
3
yg/m . The small amount that does not get recovered is disposed of by
burial, or dumping0461.0039,1678,0398,0460 at nQ great expen$e Qr danger>
Recent clinical and laboratory studies1720'1725'1721'1744 indicate that any
beryllium waste can be rendered virtually innocuous by heating to form the
oxide and then firing at 1600 C for 16 hr. The resulting material produces the
mild symptoms generally associated with dusts of clays, iron oxides, etc.
While it is not known how much beryllium is released to the environment
by the burning of coal, investigations in urban and rural areas show a
negligible uptake by humans, animals,, or plants. 64'»0615>
In summary, the recovery and/or disposal of beryllium wastes is
currently handled very adequately at the industrial site level and this
mode should be continued.
250
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7. REFERENCES
0039. National Safety Council. Beryllium. National Safety Council Data
Sheet 562, 1965.
0275. Environmental Protection Agency. National emission standards for
hazardous air pollutants, proposed standards for asbestos,
beryllium, and mercury. Federal Register, v. 36, No. 235,
Dec. 7, 1971. p. 23,239-23,256.
0276. Stokinger, H. E., ed. Beryllium: its industrial hygiene aspects.
American Industrial Hygiene Association for the Division of
Technical Information, U. S. Atomic Energy Commission, Academic
Press, New York, 1966. 394 p..
0278. Code of Federal Regulations, Department of Transportation. Title 49,
Parts 71-90. Washington, Superintendent of Documents, U. S.
Government Printing Office, 1967. 794 p.
0394. Personal communication. KBI, to M. Appel, TRW Systems, Jan. 12, 1972.
0398. Personal communication. Dr. M. E. Remley, Atomics International, to
M. Appel, TRW Systems, Jan. 12, 1972.
0458. Bureau of Mines. Mineral facts and problems. 1965 ed. Bulletin 630,
1,117 p.
0459. Personal communication. Brush Beryllium Company, to M. Appel, TRW
Systems, Jan. 21, 1972.
0460. Personal communication. North American Rockwell, to M. Appel, TRW
Systems, Jan. 21, 1972.
0461. Personal communication. County Sanitation Department, Industrial
Wastes Section, to M. Appel, TRW Systems, Jan. 21, 1972.
0599. Personal communication. P. Wilson, Brush Beryllium Company, to
M. Appel, TRW Systems, Feb. 7, 1972.
0615. Schroeder, H. A. Metals in the environment. Environment, 13(8):
18-24, Oct. 1971.
0641. Durocher, N. L. Air pollution aspects of beryllium and its compounds.
Technical Report PB-188-078. Bethesda, Maryland, Litton Systems,
Inc., Sept. 1969. 92 p.
1127. Meechan, W. R., and L. E. Smythe. Occurrence of beryllium as a trace
element in environmental materials. Environmental Science and
Technology, 1(10):839-844, Oct. 1967.
251
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REFERENCES (CONTINUED)
1312. Christensen, H. E. Toxic substances; annual list 1971. Rockville,
Maryland, U. S. Department of Health, Education, and Welfare,
Health Services and Mental Health Administration, National
Institute for Occupational Safety and Health, 1971, 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1668. Robinson, J. M., G. I. Gruber, W. D. Lusk, and M. J. Santy. Engineering
and cost effectiveness study of fluoride emissions control, v. 1.
McLean, Virginia, Resources Research Inc., Jan. 1972. 560 p.
1675. Cholak, J. Toxicity of beryllium. ASD-TR-62-7-665. Illinois,
Apr. 1972. 69 p.
1676. Zielinski, J. F. Nature and incidence of beryllium associated diseases.
Brush Beryllium Company, Nov. 1962. 16 p.
1677. Beryllium-hazardous air pollutant. Environmental Science Technology,
5(7):584-585, July 1971.
1678. Environmental Protection Agency. Background information—proposed
national emission standards for hazardous air pollutants—asbestos,
Be, Hg. Research Triangle Park, North Carolina, Dec. 1971.
1719-. Personal communication. Dr. C. R. Sharp, NAPCA, to M. Appel, TRW
Systems, Feb. 11, 1972.
1720. Personal communication. J. P. Butler, KBI Industries, Inc., to
M. Appel, TRW Systems, May 11, 1972.
1721. Personal communication. H. C. Spencer, DOW Chemical Company, to
M. Appel, TRW Systems, May 15, 1972.
1722. Personal communication. Dr. M. E. Remley, Atomics International, to
M. Appel, TRW Systems, May 13, 1972.
1723. Personal communication. G. Port, NAR, Los Angeles Division, to
M. Appel, TRW Systems, May 13, 1972.
1724. Personal communication. H. Weiss, NAR, Rocketdyne, to M. Appel,
TRW Systems, May 13, 1972.
1725. Spencer, H. C., R. H. Hook, et al. Toxicological studies on beryllium
oxides and beryllium-containing exhaust products. AMRL-TR-68-148.
Wright Patterson Air Force Base, Ohio, Aerospace Medical Research
Laboratory, Dec. 1968.
1744. Personal communication. Dr. L. Scheel, National Institute for
Occupational Safety and Health, to M. Appel, TRW Systems, May 22, 1972.
252
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Ponder (59)
Common Names Beryllium Powder
Be
Molecular Wt. 9-013
Melting Pt. ^82 C
Density (Condensed) 1 .85 g/cc @ _ 4^ J| _ Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. 2970 C
9
Flash Point mnn F
Autoigm'tion Temp. N.A.
Flammability Limits in Air (wt %) Lower Moderate
Explosive Limits in Air (wt. %) Lower Slight
Upper_
Upper
Solubility
Cold Water
0
Hot Water Slightly
Ethanol
0?
Others: Dilute acid, base
Acid, Base Properties Slightly basic
Highly Reactive with H2S04' HC1 • Ailing water to evolve H?
Compatible with other metals, oxides, air
Shipped in •
ICC Classification Meta1 P°wder» Poison B. 200 1ttoast. 6uard classification metal powder,
Conrnents c°de °f Federal Regulations (Transportation). Sec. 73-363-73-365 poison B
253
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name :
Structural Formula
IUC Name Beryllium Carbonate (474)
Common Names Basic Beryl!ium Carbonate
BeC03 + Be(OH)2
Molecular Wt. 112.05 Melting Pt. Boiling Pt.
Density (Condensed) @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
Flash Point N'A' Autoigr.ition Temp.N'A'
Flammability Limits in Air (wt %) Lower N.A. Upper_
Explosive Limits in Air (wt. %) Lower N.A. Upper_
Solubility
Cold Water °_ Hot Water Palates EthanQl 0?_
Others: Acids, bases
Acid, Base Properties Basic
Highly Reactive with Dissociates easily in acids
Compatible with Oxides
Shipped in_
ICC Classification Poison B,Poison label, 200 IbsCoast Guard Classification
Conine"tr Highly un^tahlp, pa^iiy rnpyoft'"1 to BpOtOH)-^ by heatin
Code of Federal Regulatinns (Transportation), Spr 7^ ?
254
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Beryllium Chloride (475)
Common Names Beryllium Chloride
Structural Formula
Bed.
79.93
Molecular Wt.
Density (Condensed) 1.899
Melting Pt. 399 C
25_ _C Density (gas)_
Boiling Pt. 483 C
Vapor Pressure (recommended 55 C and 20 0
1 mm @ 291 C(sublimes)
Flash Point
N.A.
Autoignition Temp .N.A.
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Lower_
Lower
N.A.
N.A.
Upper_
Upper_
very soluble
Solubility
Cold Water
Others: Ether. Benzene. Pyridine
Acid, Base Properties Basic
Hot Water dissociates
Ethanol very soluble
Highly Reactive with Dissociates readily in aqueous solution
Compatible with insoluble in acetone. NH-,
Shipped in
ICC Classification Poison B. Poison Label 200'tbast Guard Classification
Comments Code of Federal Regulations (Transportation). Sec. 73.363-73.365
255
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Hydrnxidp (47b)
Common Names Beryllium Hydroxide
Be(OH)2
Molecular Wt. 43-04 Melting Pt. 138 C (decomposes) Boiling Pt.
Density (Condensed) 1.909 @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
Flash Point N.A. Autoignition Temp .M. A.
Flammability Limits in Air (wt %) Lower N-A- Upper_
Explosive Limits in Air (wt. %) Lower N.A. Upper_
Solubility
Cold Water slightly Hot Water slightly Ethanol Q?
Others: Acids. Bases, (NH4)gCQ3
Acid, Base Properties Basic
Highly Reactive with Acid
Compatible with Bases, metals other than alkali metals
Shipped in
ICC Classification Poison B. Poison Label, 200 Ibfoast Guard Classification
Comments rw»rnmn«\goc ;»+ ita r »n p^n A u n
L-vu,,rUm ou D.-U u <-u uau nu
Code of Federal Regulations (Transportation). Sec. 73.363-73.365
256
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
!l. M. Name
n i,- r. -j lAn\ Structural Formula
Beryllium Oxide I4")
IUC Name
Common Names BromellHe, Beryllium Oxide
BeO
Molecular Wt. 25.0 __ Melting Pt. 2530 + 30 C Boiling Pt. 3900 C
Density (Condensed) 3.025 (? __ Density (gas) _ & ___
Vapor Pressure (recommended 55 C and 20 0
Flash Point N.A. _ Autoignition Temp. N. A.
Flammability Limits in Air (wt %) Lower _ N.A. _ Upper
Explosive Limits in Air (wt. %) Lower N.A. _ Upper
Solubility
Cold Water Insoluble Hot Water Insolube Ethanol Insoluble
Others: Cone. H2S04. Fused KOH
Acid, Base Properties Slightly Basic .
Highly Reactive with Very unreactive. extremely stable
Compatible with Metals. Oxides. Air. Water
Shipped in_
ICC Classification Pnisnn p Poisnn Label 200 lbsCoast Guard Classification
nnnd mafprial^ pY*T>pg>rt''^S . ¥pry toy*C
Of Fpdpral BoQiilatinnt (Trangpnrtatinn) , <:cr ?T Jf.Tt.Ti
257
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Selenate(478)
Common Names Beryllium Selenate
BeSe04-4H20
Molecular Wt. 224.04 _ Melting Pt. -2H?0 9 100 C ; '4 Wj 1310n°g
Density (Condensed) 2.03 @ 20 _c _ Density (gas) _ &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ Autoignition Temp.
Flamniability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %} Lower Upper_
Solubility
Cold Water Very soluble Hot Water ygry soluble Ethanol
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification Poison B. Poison Label. 200 Ibfoast Guard Classification
Comments Code of Federal Regulations (Transportation). Sec. 73.363-73.305
258
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PROFILE REPORT
Boric Acid (60)
1. GENERAL
Introduction
Boric acid is a white crystalline solid belonging to the triclinic
system. Its solubility in water is low at room temperature but is greatly
increased by heating.
Boric acid reacts with various pyridine bases to form soft, white,
crystalline solids, reported to be nonhygroscopic and, with the exception
of the piperidine-boric acid compound, completely hydrolyzed by dissolution
in water.1433
In 1969, there were 138,969 tons of boric acid produced in the
United States.1751
Manufacture
Boric acid is usually manufactured from borax or from colemanite.
Granulated borax or a hot saturated solution of borax from the borax
refining plant is charged into a reaction vessel. Sulfuric or hydrochloric
acid, concentrated or dilute, is added until the solution is acidic. The
solution is then cooled to the proper temperature, and boric acid crystals
are removed by filtration. If sulfuric acid is used, the mother liquor is
cooled further to recover sodium sulfate decahydrate. The crude boric acid
may be refined by one or more crystallizations from water to yield purified
boric acid.
When boric acid is made from colemanite, the colemanite is ground to
a very fine powder and added in proportions to dilute the mother liquor
and sulfuric acid at about 90 C. To prevent coating the unreacted colemanite
particles with the precipitated gypsum, the slurry is stirred vigorously.
259
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The excess acid is neutralized with lime, the iron is oxidized with
permanganate, and the solution is decolorized with activated carbon and
1433
filtered. The solution is cooled to crystallize the boric acid.
Large scale commercial facilities for the manufacture of boric acid
include the following:
U. S. Borax and Chemical Corporation; Des Plaines, Illinois
Ashland Chemical Company; Kansas City, Missouri
Baker Chemical Company; Charlotte, North Carolina
Uses
Boric acid has a wide variety of industrial uses. It is used in salt
glazing in ceramics and in making glazes and ceramic colors. It is a
raw material in making chemicals such as boron trifluoride, fluoborates,
i>orides, and boron carbide. It is used in making boron alloys and
ferroboron, which may be used for hardening steel. It is used in washing
fruit to inhibit mold. It is used in cosmetics, dye stabilizers,
solutions for electroplating nickel, electrolytes for electrolytic condensers,
enamels, flameproofing, welding and brazing fluxes, hardening steel by
heat treatment, fiber glass, optical glass, borosilicate glass, leather
finishing, deliming hides and skins, latex base paints, photography, sand
casting magnesium alloys, laundry starch and textile finishing, sizing,
and scouring compositions.
Boric acid is used in many pharmaceutical preparations as a nonirritant,
mildly antiseptic solution or in protective ointments for inflammations of
the skin and mucous membranes and minor cuts and injuries.
A weak solution of boric acid has for years been a standard household
remedy for washing the eyes. Boric acid is also used in hair rinses and
hand lotions.1433
260
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Physical and Chemical Properties
The physical and chemical properties of boric acid are included in
the attached worksheet.
2. TOXICOLOGY
Boron compounds,with the exception of hydrides are not highly toxic
and therefore are not considered to be an industrial poison. Fatal poisoning
of children has been caused in some instances by the accidental substitution
of boric acid for powdered milk. The medical literature reveals many in-
stances of accidental poisoning due to boric acid, oral ingestion of borates
or boric acid, and presumably absorption of boric acid from wounds and burns.
The fatal dose of orally ingested boric acid for an adult is somewhat more
than 15 or 20 grams and for an infact 5 to 6 grams.
Boron is one of a group of elements, such as lead, manganese and
arsenic, which effects the central nervous system. It is cumulative poison
and since its antiseptic value is weak, other more active and less harmful
therapeutic agents should be employed for medicinal use. Boron poisoning
causes depression of the circulation, persistent vomiting and diarrhea,
followed by profound shock and coma. The temperature is subnormal and a
scaletina from rash may cover the entire body. Boric acid intoxication
can come about from absorbing toxic quantities from ointments applied to
burned areas or wounds involving loss or damage to such areas of skin, but
it is not absorbed from intact skin. When a 5 percent acid solution is used
to irrigate body cavities most of the boric acid is absorbed by the tissues.
Repeated doses can produce pathological changes in the central nervous
system and kidneys.0766
The oral LD5Q value to the rat is 3.5 g/kg for boric acid. The boron
equivalent of this is .60 g/kg.
Rainbow trout were unaffected in a 30-minute test in 0.2 percent boric
acid (350 ppm boron); in 2 percent boric acid .the trout appeared distressed,
261
-------
but were alive after 30 minutes; after one-half hour exposure to a slurry of
solid boric acid (8%), they recovered if placed in running water. The LD5Q
to 15-month old rainbow trout is 339 ppm boron for 48 hours. Safe limits
are listed as 30 ppm for bass and 33 ppm for bluegill.2358
Boron is an essential element to plant growth but is toxic to many
plants at levels as low as 1 mg/liter. The Public Health Service has
established a limit of 1 mg/liter which provides a good factor of safety
physiologically and also considers the domestic use of water for home
gardening.
3. OTHER HAZARDS
Other than the toxic effects, boric acid presents no further problems.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
coat.
Workers handling boric acid should wear rubber gloves and a laboratory
0095
Boric acid should be stored in containers away from any material
intended for consumption by humans or animals.
Adequate procedures for the transportation of boric acid have been
0278
established by the Department of Transportation. Label requirements,
as well as the maximum quantities permitted to be shipped in one outside
container, are also specified.
262
-------
Disposal/Reuse
United States Borax and Chemical Corporation will accept contaminated
and degraded boric acid for reprocessing as long as there is a significant
OO
amount of the material to be reprocessed and it is in concentrated form.
U. S. Borax has a plant that manufacturers boric acid in Wilmington,
California. The effluent from the plant contains about 3,000 ppm of boron
and has been discharged directly into the ocean for many years. Although
U. S. Borax plans to discontinue this practice shortly, it is claimed that
the marine life around the discharge point has not been affected.
The acceptable criteria for the release of boric acid into the environment
are defined in terms of the following provisional limits:
Contaminant and Basis for
Environment Provisional Limits Recommendation
Boric acid in air 0.1 mg/M3 0.01 TLV for B203
Boric acid in water 1 ppm (itig/1) as B Drinking water
and soil standard
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Coagulation and Filtration.
U.S. Borax and Chemical Corporation indicates that boric acid
may be removed from aqueous waste streams by reacting the material with
appropriate quantities of lime. Lime will react with boric acid to deposit
calcium borates which can be filtered from solution. This will not remove
all of the borate, however, as calcium borates are soluble in water to the
extent of about 0.2 percent BgOg (620 ppm boron). The removal of this
residual amount will require more elaborate treatment methods such as
ion exchange or adsorption with selected clays. The borates contained
in the calcium borate sludge formed in this process are not easily
263
-------
recoverable, and are usually sent to Class 1 sanitary landfill areas
for disposal.2346
Option No. 2 - Ion Exchange
Rohm and Haas offers a boron specific ion exchange resin (Amberlite
XE 243) which will remove boron from solution to extremely low levels
(below 1 nig/liter). Since ion exchange systems operate best with dilute
solutions, this process could be used in conjunction with coagulation and
filtration (discussed above) to produce an effluent with an acceptable
concentration of boron. The major drawback affiliated with the use of
the Rohm and Haas resin is the high operating costs involved.
Option No. 3 - Adsorption with Clays.
Selected clays might be used for the removal of borate in low
concentrations. This process could be used in conjunction with coagulation
and filtration to further reduce the boron concentration. Clays, however,
are not specific and a large volume would be required per unit of liquor
passing the clay body.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the relatively low toxicity of boric acid, and the
provisions for the disposal of the major portion of waste boric acid
by the producers, it is felt that boric acid does not warrant National
Disposal Site treatment. The problem of small amounts of residual waste
boric acid being discharged in the plant effluent is currently being
solved by the manufacturers because of the stringent environmental
regulations recently imposed. U.S. Borax, for example, wilt soon connect
with a new industrial sewer line that will take the combined effluents
of the industries in the area to a secondary treatment plant before
discharge to the ocean.
In summary, the disposal of waste boric acid can be handled
adequately at the industrial site level and this mode should be continued.
264
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7. REFERENCES
0095. Laboratory waste disposal manual. Manufacturing Chemists
Association. (Revised as of May 1970). Washington, 1970.
175 p.
0278. Code of Federal Regulations. Title 49—transportation parts 71
to 90. (Revised as of Jan. 1, 1967). Washington, U. S.
Government Printing Office, 1967. 794 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Washington,
Federal Water Pollution Control Administration. Apr. 1, 1968. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. v. 2. New
York, Interscience publishers. 1966. 899 p.
1670. Chemical Week. 1972 Buyers guide issue, part 2. 109 (17):618,
Oct. 1971.
2346. Personal communication. Grover Collins, U. S. Borax and Chemical
Corporation to D. Dal Porto, TRW Systems, Sept. 25, 1972.
Boric acid waste treatment.
2358. Sprague, R. W. The ecological significance of boron. Los Angeles,
U. S. Borax and Chemical Corp., 1972. 58 p.
265
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. H. Name Boric Acid (60)
Structural Formula
IUC Name
Common Names Boric Acid
H3B03
(1)
Molecular Wt. 61.84 * ' Melting Pt.185 C (decomposes) Boiling Pt..1 1/2 HgO
Density (Condensed) 1.435(1) » 15 C ^ Density (gas) » ~^° C
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point ._ Autoignition Temp.
Flamiability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 6.35 g/100 a:*1) Hot Mater 27.6 g/100 CC (]) Ethanol.
Others: glycerine 28 g/100 CC; methyl alcohol 20.20 g/100 CC^)
Acid, Base Properties .
Highly Reactive with
Compatible with
Shipped in_
ICC Classification Coast Guard Classification
Commen ts '
References (1) 0766
266
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PROFILE REPORT
Boron Trlfluoride (63)
1. GENERAL
Boron trifluoride is a colorless gas which fumes in moist air and has
a pungent suffocating odor. It is nonflammable and does not support
combustion. It is normally packaged in cylinders as a nonliquified gas
at pressures of 2,000 psig at 70 F. It is very soluble in water with
decomposition (forming fluoboric and boric acids) and is heavier than
air.1301 I
worksheet.
air. Physical/chemical properties are summarized in the attached
Boron trifluoride is used extensively, industrially, as a catalyst
in isomerization, alkylation, polymerization, esterification and con-
densation reactions. Boron trifluoride is also used in gas brazing. Its
other uses are as a filling gas for neutron counters and in the preparation
of diborane. 1301
Boron trifluoride is manufactured commercially by adding borax to
hydrofluoric acid to yield water and Na20'(BF3)., or by treating boric
acid with ammonium fluoride to yield water, ammonia and the compound
(NH^JpO*(BF-J^. The boron trifluoride complex is transferred to a
generator and is treated with cold fuming sulfuric acid. The reaction
mass is slowly heated and the generation of boron trifluoride is controlled
by regulating the temperature.
267
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2. TOXICOLOGY
Human Toxicity
Boron tri fluoride is very irritating to the respiratory tract. Exposure
of the skin and eyes, and breathing of boron tri fluoride should be avoided.
The American Conference of Governmental Industrial Hygiem'sts in 1971 recom-
•J
mended a Threshold Limit Value (TLV) in air of 2 mg/M . No medical:
evidence of chronic effects has been found among workmen who have frequently
been exposed to small amounts for periods up to 7 years. In tests on mice,
a concentration of 15 ppm for 30 days produced dental fluorosis. The inha-
lation lethal concentration (LC) for rats is 750 ppm. At high concentra-
tions boron trifluoride causes burm &n the skin similar to, but not as
penetrating as those from hydrogen fluoride.
Toxicity Toward Plant Life
If allowed to escape, boron trifluoride will kill plant life in the;
nearby area. Trace amounts of boron trifluoride escaping from a reactor can
be detected by the white fumes produced. In Los Angeles, the Los'Angeles Air
Pollution Control District makes frequent inspections of any users-plant.
3. OTHER HAZARDS
Boron trifluoride is nonflammable and does not support combustion.
BF3 hydrolyzes in contact with water, forming fluoboric and boric acids.
The boric acid is extremely corrosive to iron, steel, and aluminum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Boron trifluoride is packaged and shipped, in steel cylinders
under Department of Transportation and Coast Guard regulations as a
nonflammable, compressed gas, taking a Green Label. The filled
cylinders have an internal pressure of 2,000 psig at 70 F. Boron
268
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trifluoride cylinders should be handled with all of the precautions ^used
with cylinders of high pressure compressed gases. The cylinders should
be protected against impact, assigned a definite dry cool well-ventilated
fire-resistant area for storage, and shielded from direct sunlight, the
extremes of weather, and temperatures above 125 F. In addition, due to
the reactivity of BF3 with water, amines, alcohol, ether and other compounds,
traps or check valves should be used in the piping system to prevent
suckback of liquid into the cylinder.
Personnel handling the BF3 should wear chemical safety goggles and
rubber gloves, and should be provided with a gas mask for acid gases,
or have an independent air/oxygen supply mask available. Dry boron
triffuoride can be handled in steel, stainless steel, copper,nickel,
monel, brass and aluminum and the more noble metals up to 200 C. At
low pressures and for temperatures up to 200 C Pyrex glass can be used.
Copper is recommended as the metal for handling the moist gas. Saran
tubing, hard rubber, Teflon, polyethylene, Pyrex glass and pure polyvinyl
chloride are not attacked at temperatures up to 80 C.
Disposal/Reuse
A definition of acceptable criteria for the disposal of boron
trifluoride must also take into account acceptable criteria for the
release or treatment of compounds formed during treatment of boron
trifluoride. Compounds formed and their disposition are as follows:
Compounds Formed Disposition
Calcium Fluoride Insoluble, place in landfill
Boric Acid See Profile Report on boric
acid (60)
Safe disposal of BF3 is defined in terms of the recommended provisional
limits in the atmosphere, water and soil. These are:
269
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Contaminant in Provisional Limit Basis for Recommendation
Air
Boron trifluoride 0.03 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Boron trifluoride 0.15 mg/1 Stokinger and Woodward
hydrolysis products Method
5. EVALUATION OF PRESENT MANAGEMENT PRACTICES
The manufacturers of boron trifluoride do not normally discharge
waste streams because the preparation is carried out in a closed system.
Boron trifluoride is usually recovered after its use as a Lewis acid
1415
catalyst in organic reactions by distillation, by chemical reaction,
or by combinations of the two methods. When amines or ammonia are used
to strip BF3 from spent catalyst, NH3'BF3 or RNH2'BF3 are formed; the boron
trifluoride is liberated from the complexes by treatment with sulfuric
acid. The amine or ammonia complexes can also be reacted with compounds
that form more stable complexes than the boron trifluoride complex, thus
liberating boron trifluoride. Selective solvents are sometimes used to
extract the spent boron trifluoride catalyst from the reaction media.
If a fluoride salt is added to the spent catalyst, a precipitate,
BFo'MF is formed which upon heating liberates boron trifluoride. The
regenerated BF3 from these processes is recycled for reuse.
The method currently employed to dispose of excess or contaminated
boron trifluoride, is to discharge the gaseous BF3 into a water spray.
The reaction first gives a precipitate of boric acid and then a solution
of fluoboric acid:
BF3 + 3H20 •* B(OH)3 + 3HF
BF3 + HF•* HBF4
270
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The fluoboric acid is treated with lime or limestone, and decomposes to
calcium fluoride and boric acid. The calcium fluoride produced is
either sent to a land fill, or lagooned. The boric acid produced is
discharged to sewer; it can be handled as discussed in the Profile
Report on boric acid (60).
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is expected that boron trifluoride will either be recovered for
reuse or destroyed by the satisfactory procedure discussed above. It is
our conclusion that boron trifluoride is not a candidate waste stream
constituent for National Disposal Sites.
271
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7. REFERENCES
1160. Durrant, P. J., and B. Durrani. Introduction to advanced inorganic
chemistry. 2d ed. New York, John Wiley and Sons, 1970. 1,249 p.
1301. Matheson gas data book. 4th ed. East Rutherford, New Jersey,
Matheson Co. Inc., 1966. 500 p.
1304. Personal communication. Mr. Stanfield, Allied Chemical Corporation,
to J. R. Denson, TRW Systems, Mar. 16, 1972.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
supplement. New York, Wiley-Interscience Publishers, 1963-1971.
272
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
i
H. M. Name Boron Trifluoride (63)
Structural Formula
IUC Name Boron Tri fluoride
Common Names
BF
3
Molecular Wt. 67-82 Melting Pt. -127.1C Boiling pt. -100-4 C
Density (Condensed) 1.57 0-100.4 C Density (gas) 3.077 @ Q c
Vapor Pressure (recommended £5 C and 20 0
139.7 Torr 9 -120.5 C 760 Torr 9 -1QQ.4 C 10 atmos. $ -54.4
Flash Point Autoignition Temp._
Flammability Limits in Air (vrt X) Lower Upper_
Explosive Limits in Air {wt. *> Lower Upper_
Solubility
Cold Mater' 369.4g/10Qq fe 6 C Hot Water Ethanol Forms Complex
Others: 1.94g/100g HoS04; soluble in most organic liquids such as saturated hydrocarbons
Acid, Base Properties Lewfs acid
Highly Reactive with HNOj 9 20 C; decomposes in aqueous bases
Compatible with Copper, iron, stainless steel, chromium, mercury
Shipped in SteeT cylinders under pressure. 1500-1800 psi
cylinders are either 6 or 62 Ib. BF, - in tube trailers 12,000-13,000 Ib.
ICC Classification Nonflammable coup, gas Coast ward Classification Nonflammable comp.
Consents.
Green label gas Green Label
Critical temp - 12.25
Critical Pressure - 12.25 C
References (1) 7301
273
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PROFILE REPORT
Bromic Acid (64)
1. GENERAL
Bromic acid is a colorless or slightly yellow liquid that turns yellow
on exposure to air. It is unstable except in dilute solutions and is
almost never sold as bromic acid. Bromic acid is used as an oxidizing
agent in the preparation of dyes, organic compounds, and Pharmaceuticals
and in the oxidation of mercaptan groups to disulfide groups in wool and
hair treatment. When required, it is usually prepared for immediate use
by adding sulfuric acid to barium or sodium bromate and the bromic acid
recovered as an aqueous solution by subsequent distillation and absorption
in water.
Potassium and sodium bromate, because of their use as "neutralizers"
in home permanent cold wave kits, are the major bromate wastes. They are
generally discharged as dilute solutions, directly to municipal or other
local sewer systems.
The limited physical/chemical properties reported for bromic acid
are summarized on the attached worksheet.
2. TOXICOLOGY
Bromic acid is not highly toxic, but because it is a strong oxidizing
agent it causes severe irritation of the skin, eyes and upper respiratory
tract.
Potassium and sodium bromate are the most common sources for bromate
ingestion. The mean lethal dosage for bromate has not been established;
rabbits succumbed to an oral dosage of 0.5 gm/Kg of NaBrO.,, while about
14.2 gm has been the cause of death in a 19 month old child.2376
275
-------
Upon heating or standing bromic acid decomposes with liberation of bromine
and oxygen. The toxicity of bromine then becomes the controlling factor
(See Profile Report on Bromine £65]). Bromine has a Threshold Limit Value
(TLV) of 0.7 mg/M3.
3. OTHER HAZARDS
Bromic acid produces a fire hazard on contact with organic matter. It
1138
will corrode most metals other than silver, platinum, and tantalum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Bromic acid is handled in the same manner as any aqueous solution of
a strong acid which is also a strong oxidizing agent. Contact with reducing.
substances is permitted only under controlled conditions. Solutions of HBrO^ .
should be stored in glass or Teflon, protected from sunlight and extremes
of temperatures.
Though bromic acid is almost never shipped it may be shipped under
Department of Transportation regulations for a corrosive liquid with a
White Label, in properly protected glass containers.
Bromic acid, because of its instability, will probably decompose to
bromine and bromides on release to the environment. Safe disposal of bromic
acid is defined, therefore, in terms of the recommended and provisional
limits for bromine in the atmosphere and in water and soil. These recommended
provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Bromine 0.007 mg/M3 0.01 TLV
Contaminant in Water Provisional Limit Basis for
and Soil r_ Recommenda ti on
Bromine 0.035 mg/L Drinking Water
Studies
276
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Reduction and Discharge
Small packaged lots of bromic acid may be decomposed by the addition of
reducing materials such as sodium thiosulfate, bisulfites or ferrous salts.
This method is recommended by the Manufacturing Chemists Association, but
procedures for recovery of the bromides produced are not provided. Instead,
when reduction is complete, the treatment solution is neutralized with soda
ash, and the solution is washed down the drain with a large excess of water.
This process is satisfactory for small quantities of bromic acid, but the
process is not recommended for larger quantities because valuable bromides
will be lost.
Option No. 2 - Reduction and Recovery as Bromide
Bromic acid, like bromine, is recovered from a dilute solution or
waste stream by passing an aqueous solution over iron turnings to produce
the so-called ferrosoferric bromide. This is decomposed by sodium carbonate,
the excess carbon dioxide boiled off and the sodium bromide crystallized
and sold.1138
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Bromic acid is not a candidate waste stream constituent for National
Disposal Sites because it is not stable, and therefore, requires treatment
at the site where the waste originates. Option No. 2 is the process re-
commended for treatment of wastes containing bromic acid. This process
is simple and can be performed by any plant using bromic acid.
277
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. v. 35. Occupational Hazards, Aug. 1971.
p. 35-40.
1138. Jolles, Z. E. Bromine and its compounds. New York, Academic Press,
1966. 640 p.
1305. Personal communication. Mr. Sharp, Dow Chemical Company, to
J. R. Denson, TRW Systems, March 16, 1972. Bromine, hydrogen
bromide and bromic acid disposal.
1416. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
2376. Gleason, M. W., R. E. Gosselin, H. C. Hodge, and R. P. Smith.
Clinical Toxicology of Commercial Products 3rd ed. Baltimore,
Williams and Wilkins Company, 1969. 1,428 p.
278
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Bromlc acid (64)
IUC Name Bromic acid
Common Names
Structural Formula
HBrO,
Molecular Wt. 128.92
(1)
Melting Pt.
(1)
Boiling Pt. decomposes 100C
Density (Condensed) 3.188 g/cc @ 20 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water completely miscible Hot Water
Others:
Acid, Base Properties strong acid ; strong oxidizing agent
Ethanol
Highly Reactive with Reducing substances; bases; most metals
Compatible with Glass
Shipped in Not usually shipped
ICC Classification Corrosive liquid
Comments White Label
Coast Guard Classification corrosive liquid
White Label
References (1) 1416
279
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PROFILE REPORT
Bromine (65)
1. GENERAL
Bromine is a member of the halogen family and is a brown-red, fuming,
heavy and highly corrosive liquid. It is the only non-metallic element
liquid at room temperature. Bromine is manufactured in the United States
principally at the Ethyl Dow plant at Freeport, Texas, built during the sec-
ond World War. Other production is from the Michigan brines. About 90
percent of the domestic output is used in the manufacture of ethylene di-
bromide, an anti-knock fluid, used in conjunction with tetra-ethyl lead in
gasoline. This demand is subject to change as lead is phased out of gasoline.
In the United States the chief raw material for bromine manufacture is
sea water in which bromine occurs in concentrations of 60 to 70 ppm. It is
also manufactured from natural brines. Sea water or brine is acidulated
with dilute sulfuric acid to a pH of 3, and chlorinated.
The chlorinated sea water (or brine) is stripped of bromine by air
blowing, and returned to the ocean (or re-injected via a deep well). The
moist bromine-containing air from the stripping tower, contaminated with
a small amount of vaporized chlorine, is reacted with less than stoichio-
metric quantities of sulfur dioxide and water in an absorption tower to
form a solution of bromine in mixed hydrobromic, hydrochloric and sulfuric
acids. The mixed solution is reacted with an excess of'chlorine and the
liberated bromine is steam-stripped from the solution, condensed as liquid,
and purified by distillation. Any excess chlorine is recycled, as is the
residual sulfuric and hydrochloric acid solution. This manufacturing
process creates as waste streams only the sea water or brine from which
1138
the bromine was removed.
281
-------
The physical/chemical properties for bromine are summarized in the
attached worksheet.
2. TOXICOLOGY
Human Toxidty
Liquid bromine rapidly attacks the skin and other tissues, producing
irritation and burns which heal slowly. Even very low concentrations of
the vapor are highly irritating to the respiratory tract. The chronic
effects of inhalation of bromine vapors include reduced red cell and
hemoglobin content of the blood. The leucocyte count may increase, some-
times up to fourfold.1138
The good warning properties of bromine (its pungent, irritating nature
and dark brown color) help in preventing dangerous exposure of humans to
the vapor. Concentrations as low as 0.3 ppm cause irritation of the eyes.
A concentration of 7 ppm of bromine in the air is thought to cause fatal
illness in man after exposure of half an hour to one hour. The TLV for
bromine, the highest concentration considered safe for 8 hours continuous
11 ^8
exposure, is 1 ppm.
Other Toxicity
Bromine reacts rapidly, at ambient temperatures in an aqueous media,
with many substances known to be constituents of living matter. With
unsaturated aliphatic acids, dibromides and bromohydrins are formed;
aromatic aminoacids such as tyrosine undergo ring substitution; amino
groups form bromamine derivatives; and thiols are oxidized to sulphinic
and sulfonic acids and disulfides. Specific toxic action is illustrated
by the rapid germicidal effect of trace concentrations, 0.1 ppm of bromine
or less, on the activity of various enzymes. Bromine is more effective
than chlorine in killing bacterial spores, yeasts, molds and algae.
Bromines toxicity to microorganisms has been put to good use, but like
282
-------
chlorine the concentration level must be controlled to avoid damage to
plants and fish. In swimming pools concentrations of 9 ppm bromine can be
1138
reached without irritation to the eyes to swimmers.
3. OTHER HAZARDS
Bromine may produce a fire on contact with organic matter such as
sawdust. Moist bromine reacts with most metals with lead being attacked
only slowly. Dry bromine can be contained by monel.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Storage, Handling, and Transportation
Drums for bromine storage are made of monel or of lead-lined steel.
Only very dry bromine can be stored in monel. Glass or glass lined con-
tainers are also used.
The chemical reactivity of elemental bromine with living matter presents
a serious hazard in handling. Prolonged exposure to even very low concen-
trations of the vapor must be avoided. Effective safety devices which should
be at hand when bromine is handled are: water safety showers and eye-wash
fountains, safety face shields and rubber gloves. Annydrous ammonia in
cylinders can be used to knock down bromine fumes. Liquid spills can be
decontaminated with saturated alkaline thiosulfate solution or a lime slurry.
Bromine is classified by the Department of Transportation (DOT) as a
corrosive liquid requiring a White Label. Due to the high cost of packing
and insurance, bromine is seldom transported overseas. Only small quantities
compared to the total production are shipped. Most of bromine produced is
consumed in the integrated chemical plants where it is manufactured. Drums
(monel or lead lined) with a capacity up to 225 Ib are in use for shipping
I I OQ
bromine; tank cars with a capacity up to 50 tons are used for bulk
shipment.
283
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Disposal/Reuse
Because the value of bromine is great, little is disposed of. The
recommended provisional limits for bromine in the atmosphere and in water
and soil are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Bromine 0.007 mg/M3 0.01 TLV
Contaminant in Basis for
Hater and Soil Provisional Limit Recommendation
Bromine 0.035 mg/1 Stokinger and
Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Bromine is a valuable commodity and is seldom disposed of as a waste.
If disposal of contaminated bromine or bromine solution is required, the
bromine or bromine solution is returned to the manufacturer for recovery.
The manufacturer will in most cases buy the bromine. If bromine vapor
is in a process waste stream, it can be condensed easily. If the bromine
is in an aqueous waste stream that is too dilute for shipment, concentra-
tion is required. Concentration is accomplished in the same manner used
to recover bromine from sea water, i.e., chlorine is used to oxidize any
bromide to bromine and the solution is air stripped of the bromine, which
is subsequently trapped in an ice cooled condenser. The impure bromine can
be used or returned to the manufacturer.
An alternate recovery process is to pass an aqueous waste stream con-
taining bromine over iron turnings to produce so called ferroso-ferric
bromide. This is decomposed by sodium carbonate, the excess carbon dioxide
1138
boiled off and the sodium bromide crystallized and sold.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
With the exception of the return of contaminated bromine or bromine
compounds to the manufacturer for purification, bromine waste streams can
284
-------
be best handled at the site where they originate. Designated sites (at
the primary bromine producers) should be identified for the economic
recovery of bromine from waste streams from .the few sources not equipped
with recovery systems.
285
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7. REFERENCES.,
1138. JolTes,, Z. E. Bromine and its compounds. New. York, Academic Press,
1966, 940. p.
1305. Personal' communication. M. Sharp, Dow Chemical Company,, to J. R.
Denson, TRW Systems, Mar. 16, 1972.
286
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Bromine
Structural Formula
IUC Nams Bromine
Common Names
Molecular Wt. 79.909 _ Melting Pt. -7.3 C Boiling Pt. 52.2 C
Density (Condensed) 3.119 g 25 C^ Density (gas) 3.5 _ (3 _ 20_ C
Vapor Pressure (recommended 55 C and 20 0
2 atm g 78.8 C 3 atm 9 110.3 C 10 atm p 139.8
Flash Point - Autoignition Temp. -
Flammability Limits in Air (wt %) Lower -_ Upper_
Explosive Limits in Air (wt. X) Lower - Upper_
Solubility
Cold Water 3.41 g/lOOg at 20 C Hot Water 3.33 q/IOOg at 40 C Ethanol freely soluble
Others: freely in chloroform, CS2, CCl^ H)
Acid, Base Properties
Highly Reactive with Alkali hydroxides, arsenites and other oxidizable materials'"'
Compatible with
Shipped in 1 and 6.5 Ib bottle, 10 gal drums, tank cars, trucks
ICC Classification corrosive liquid <1 qt^2^ coast Guard Classification *h1te label1
white
Comments
References (1) 1492
(2) 0766
287
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PROFILE REPORT
Chlorosulfonic Acid (112)
1. GENERAL
Chlorosulfonic acid is an important item of commerce, tank-car
quantities being used as an intermediate in the production of synthetic
detergents, drugs, ion exchange resins, and dyestuffs. It has also
been used as a smoke-forming agent in warfare. Chlorosulfonic acid may
be considered as a mono acid chloride of sulfonic acid, since one
chlorine atom has replaced one hydroxyl group. It is a clear, colorless,
mobile liquid which decomposes slightly when distilled. It reacts with
water with explosive violence and fumes strongly in moist air to form a
persistent, irritating aerosol of sulfuric and hydrochloric acids. It
also reacts with almost all organic materials; in some cases with
charring.
Chlorosulfonic acid is a strong acid containing a relatively weak
sulfurchlorine bond. It is a powerful sulfating and sulfonating agent,
a fairly strong dehydrating agent, and a specialized chlorinating agent.
In most of its applications it is used to form sulfates, sulfonates and
sulfonyl chlorides with such organic compounds as hydrocarbons, alcohols,
phenols and amines. Many salts and esters of Chlorosulfonic acid are
known, but most of them are relatively unstable or hydrolyze readily in
moist air.
Manufacture of Chlorosulfonic acid is accomplished by the direct
union of sulfur trioxide with dry hydrogen chloride gas. The sulfur
trioxide may be in the form of 100 percent liquid or gas, as obtained
from boiling oleum, or may be present as a dilute gaseous mixture obtained
directly from a contact sulfuric acid plant. The reaction of sulfur
trioxide and hydrogen chloride takes place spontaneously with evolution
1433
of a large quantity of heat. The chemical/physical properties for
Chlorosulfonic acid are given in the attached worksheet.
289
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2. TOXICOLOGY
Chlorosulfonic acid will cause severe acid burns on contact of the
liquid with the skin or mucose, and the vapor is very irritating to the
eyes, lungs, and mucous membranes. It can cause acute toxic effects in
either the liquid or vapor state. Inhalation of concentrated vapor may
cause loss of consciousness with serious damage to lung tissue. Upon
ingestion, it will burn and destroy the mucose of the mouth, esophagus
and stomach to a serious degree. Contact of the liquid with the eyes can
cause permanent destruction of the tissues involved. Even in the vapor
state it causes conjunctivitis. Chlorosulfonic acid does not have a
Threshold Limit Valve (TLV) established by the American Conference of
Governmental Industrial Hygienist (ACGIH) but the TLV of 5 ppm for
hydrochloric acid should be considered the maximum level of exposure for
0095
an 8-hr work day of a 40-hr work week.
3. OTHER HAZARDS
Chlorosulfonic acid is corrosive, functioning both as a strong acid
and as a dehydrating and charring agent. It has an appreciable vapor
pressure and through the action of moisture in air (or water) is
decomposed to hydrochloric acid and sulfuric acid. Good ventilation
should be provided, and goggles, gloves, protective clothing, and face
shields should always be worn when handling this material.
The acid itself is not flammable, but may cause ignition by contact
with combustible materials. The flammable and explosive gas, hydrogen,
is slowly generated by action of the acid on moist metals.
4. .DEFINITION OF ADEQUATE WASTE MANAGEMENT
When working with Chlorosulfonic acid waste or spills, in addition
to the protective devices indicated above, a self-contained breathing
apparatus should be employed. For small quantities work can be performed
in a fume hood, and a laboratory coat, goggles and gloves should be worn.
Spills of small quantities should be covered with excess sodium
290
-------
bicarbonate and the mixture diluted with a large quantity of water.
Spills of larger quantities should very carefully be diluted with a large
quantity of water and neutralized with lime.
Chlorosulfonic acid is shipped in bottles, 170-lb carboys, 1,600-lb
stainless steel drums and 8,000-gal tank cars. It is shipped under
Department of Transportation regulations as a corrosive liquid requiring
a White Label.1416
The safe disposal of chlorosulfonic acid is defined in terms of the
recommended provisional limits 1n the atmosphere and in water and soil
environments. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limits Basis for Recommendation
3
Chlorosulfonic Acid .01 mg/M Limit for hLSO.
Contaminant in
Water and Soil Provisional Limits Basis for Recommendation
H2S04 (hydrolysis .05 ppm Limit for H2SO.
product of chloro-
sulfonic acid in
water)
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The method of disposal of packaged lots of chlorosulfonic acid
recommended by the Manufacturing Chemists Association is satisfactory
if the effluent from the disposal process is within the limits for pH,
chloride ion» and sulfate ion.
In this procedure chlorosulfonic acid is decomposed by pouring small
quantities from behind a shield onto a dry layer of sodium bicarbonate.
After mixing thoroughly, the sodium bicarbonate, while being stirred, is
sprayed with 6M ammonium hydroxide. Then the sodium bicarbonate is covered
with a layer of crushed ice; and while continuing stirring, the sodium
bicarbonate mixture is again sprayed with 6M ammonium hydroxide. When
evolution of ammonium chloride (which must be trapped and disposed of) has
291
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partially subsided, the sodium bicarbonate solution is neutralized with
hydrochloric acid. Following dilution to the concentration permitted for
effluents (see Section 4), the treated solution is discharged into a stream
or storm sewer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that the great majority of chlorosulfonic waste
will continue to be best handled at the source of the waste generated.
Because the process requires little special equipment and, when performed
properly, no new very toxic materials are created, chlorosulfonic acid
does not appear to be a candidate waste stream constituent for a National
Disposal Site.
292
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 2d ed. Washington, 1969. 176 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22v. and
Supplement. New York, Wiley-Interscience Publishers, 1963-1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p..
0536. Federal Water Pollution Control Administration. Water quality
criteria, Washington, 1968. 234 p.
1416. Ross, A. and E. Ross. Condensed chemical distionary. 6th ed.
New York, Reinhold Publishing Corporation, 1966. 1,256 p.
293
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Chlorosulfonic Add
IUC Name Chlorosulfonic Acid
Common Names Sulfuric Chlorohydrin
Structural Formula
C1S03H
Molecular Wt. 11.653
Density (Condensed) 1.766
Melting Pt. -80C
18 _C Density (gas)_
Boi.ling Pt. 151.DC
Vapor Pressure (recommended 55 C and 20 C)
1 torr at 32 C
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. 3!) Lower_
Upper_
Upper_
Solubility
Cold Water_
Others:
reacts
Hot Water reacts violently Ethanol reacts
Acid, Base Properties
contact with water forms hydrochloric or sulfuric acid.
Highly Reactive with Most organic materials; water
Compatible with_
Shipped jn Carboys. 1600 pound drums. 8.000 gallon tank cars
ICC Classification corrosive liquid Coast Guard Classification corrosive liquid
Comments Extremely caustic, corrosive and toxic liquid.
References (1) 1416
294
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PROFILE REPORT
Chrome (113)
1. GENERAL
Introduction
Chromium is a metallic element with properties resembling iron
occurring mainly in chrome/iron ore (FeO • Cr203). It is a very
infusible, hard, gray metal which is incorporated in the manufacture of
stainless steel and other corrosion resistant alloys. Chrome is exten-
sively used as a plating on other metal surfaces to give a hard, corrosion
resistant, beautiful surface and also finds wide use as a catalyst.
The ferro chromium alloys are made by silicon reduction of chromite
ores in a two-stage process. Initially a high silicone ferro chromium is
produced in a submerged arc furnace. Then this product is treated in an
open arc type furnace with a synthetic slag containing Cr203> To
produce chromium metal either electrolytically or by the reduction of
chromium compounds, a chemical treatment is necessary to remove the iron
and other impurities from the starting materials. Reduction methods start
with chromium oxide Cr20o which has been obtained from chromite ore via
sodium bichromate. Commercial chromium metal is produced by reducing
Cr^Oo with aluminum, although silicon and carbon are sometimes also used
as reducing materials. The aluminum reaction is performed in a refractory
lined vessel which contains the exothermic, self-sustaining reaction.
Chromium metal can also be produced by the electrowinning of chromium from
1433
either chrome alum or chromic acid electrolytes. As far as can be
determined by a review of the literature, no significant amounts of chrom-
ium metal appear as wastes from the production processes.
In 1968 approximately 300,000 short tons of chromium were consumed in
chromium ferro allloys and chromium metal in the United States. The
greatest proportion was used in various ferro chromium alloys. This rep-
1975
resents 60 to 70 percent of the chromium ore processed in the United States.
295
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Occurrence as a Waste Product
Chromium, either as a ferro alloy, stainless steel, metallic catalyst
or plate, is relatively valuable and normally is not disposed of without
reuse. Stainless steel and other alloys have considerable value as scrap
metal and these are normally recycled. Chromium plate on scrap metal,
such as that coming from scrapped automobiles, normally is recycled, not
necessarily for the chrome plate but for the scrap steel. The chrome is
believed to be melted down without any prior removal of the chrome plate.
The occurrence of ferro chrome alloys and chrome plated metal as recycled
scrap is widespread in the United States. At the present time the amount
of chrome metal that is actually Tost in junk yards and trash dumps is
not known.
2. TOXICOLOGY
Zero valent chromium, as the pure metal or alloy, is considered to be
1492
essentially nontoxic to plants and animals.
3. OTHER HAZARDS
The dust of chromium metal is considered a moderate fire hazard.
Chromium metal does not exhibit any other hazards.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Chromium does not require special handling when it occurs as a waste
in alloys or as a decorative plate on other metal surfaces. The industries
that use large amounts of chrome and chrome alloy materials should have a
program by which the various types of chrome containing scrap materials
are collected and segregated for recycling. No safety precautions are
required for the handling of the scrap materials except those which would
normally be used for the handling of other common scrap metals. For chrome
dust particles, the recommended provisional limit is:
Contaminant in Air Provisional Limit Basis for Recommendation
Chrome 0.01 mg/M3 0.01 TLV
296
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The only feasible waste management option for chrome metal and chrome
metal alloys is that of recycling scrap for use in new products. There is
a considerable market for this type of scrap material and it is believed
that all major industries who work with these metals have a program by
which the scrap is segregated and saved for sale to a scrap dealer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Waste chromium metal and chrome alloys are not candidate waste stream
constituents for national disposal. They are essentially non-toxic to both
plant and animal life. Additionally, they are very corrosion resistant
and do not weather to produce harmful corrosion products. Waste chrome
metals and their alloys have inherent value and scrap recovery and recycle
1975
programs are widespread in the industry.
297
-------
7. REFERENCES
0766. Sax, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed., 22 v. and
suppl. New York, Interscience Publishers Inc. 1963-1971.
1492. The Merck Index of Chemicals and Drugs. 7th ed. Rahway, New Jersey,
Merck and Company, Inc., 1960. 1,634 p.
1570. Weast, R.C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Chemical Rubber Company, 1969, 2,100 p.
1975. Bureau of Mines. Mineral facts and problems. Bulletin 650.
Washington, Department of the Interior, 1970. 1,291 p.
298
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name
Chrome (113)
Structural Formula
Common Names
Cr
(1)
Molecular Wt.
C1
Density (Condensed) 7.20(1J @ 28
Melting Pt. 1890C
l\
J
Boiling Pt. 2482
(1)
Density (gas) N/A @
Vapor Pressure (recommended 55 C and 20 G)
1 mm
1616C
(2)
Flash Point N/A
Autoignition Temp.
Flammability Limits in Air (wt X) Loner N/A
Explosive Limits in Air (wt. X) Lower N/A
(1)
Upper_
Upper_
N/A
N/A
Solubility
Cold Water insoluble
Hot Water insoluble
(1)
Ethanol
Others : sol in dil
HC1
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Comments Moderate fire hazard in dust fornr '
Coast Guard Classification
References (1) 1570
(2) 0766
299
-------
PROFILE REPORT
Cobalt Nitrate (116). Ferrous Sulfate (198).
Stannous Chloride (409), Cobalt Chloride (489)
1. GENERAL
Introduction
The inorganic chemicals in this Profile Report are grouped together
because they can be handled by similar disposal processes. Concentrated
aqueous solutions of the salts constitute a hazard or nuisance.
Manufacture and Uses
Cobalt Nitrate. Cobalt nitrate, or cobaltous nitrate, Co(N03)2, is a
red crystalline material which is deliquescent in moist air. Cobaltous
nitrate is prepared by the action of nitric acid on cobalt hydroxide
1492
followed by purification through recrystallization. It is used in:
(1) sympathetic inks;
(2) cobalt pigments; 4
(3) preparation of cobalt catalysts;
(4) additives to soils and animal feeds;
(5) additives to vitamin preparations;
(6) hair dyes;
(7) decorations on porcelain.
Ferrous Sulfate. Ferrous sulfate, FeS04'7H20, crystals or granules
are green, and are often brownish-yellow in color from oxidation and
efflorescence. The sources of commercial ferrous sulfate are:
301
-------
(1) by-product production (from the pickling of steel and from
many other chemical operations);
(2) direct reaction between dilute sulfuric acid and iron;
(3) oxidation of pyrites in air, followed by leaching and treatment
with scrap iron;
(4) by-product production from ilmenite.
The uses for ferrous sulfate include:0955' 1492> 1662
(1) water purification;
(2) source for other iron salts and oxides;
(3) fertilizer;
(4) feed additive;
(5) writing inks;
(6) pigments;
(7) medicine;
(8) deodorizer;
(9) metallurgy;
(10) aluminum etching;
(11) wood preservative compositions.
Stannous Chloride. Stannous chloride, SnCU. is a white crystalline
mass that absorbs oxygen from the air to form the insoluble oxychloride.
1492
It is prepared by dissolving tin in hydrochloric acid. SnClp is used:
(1) as a reducing agent in the manufacture of chemicals and dyes;
(2) in tin galvanizing;
(3) as a reagent in analytical chemistry;
(4) as a stain remover;
(5) in anti sludging agents for lubricating oils;
(6) as a chemical preservative.
Cobalt Chloride. Cobalt chloride or cobaltous chloride,
is prepared by recrystallization of the crude material obtained by reacting
1492
hydrochloric acid with cobalt oxide. It is used:
302
-------
(1) as an absorbent for ammonia;
(2) in gas masks;
(3) in electroplating;
(4) in sympathetic inks;
(5) in hygrometers;
(6) in catalysts;
(7) in barometers;
(8) as a flux for magnesium refining;
(9) as a trace element in feeds and in vitamin B,2 preparation.
Physical/Chemical Properties
The physical/chemical properties for the compounds covered by this
Profile Report are summarized on the attached worksheets.
2. TOXICOLOGY
Stannous chloride is considered relatively nontoxic. Ferrous sulfate,
although used as a diet supplement, has caused death when excessive
OOTC
quantities were ingested. Lowest lethal dose was 0.5 gm. The cobalt
salts have LD50's which range from 100 to 400 mg/Kg for mouse and rabbit.
With the exception of FeSOy,, which has a Threshold Limit Value (TLV)
o 0025
of 1 mg/M as Fe, the American Conference of Governmental Industrial
Hygienists has not established TLV's for any of the compounds listed in
this report.
303
-------
3. OTHER HAZARDS
Cobaltous nitrate is an oxidizing material which, in contact with
organic or other readily oxidizable substances,may cause a violent reaction
or combustion. Ferrous sulfate in aqueous solution witiHg^drrode iron and
most steels.149 The iron, cobalt, and tin salts liste^aJlflhydrolyze to
produce acid solutions. wmci <•
i
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
As discussed in Section 3, cobaltous material is an oxidizing material
and must be handled and stored as such. It is classified by the Department
of Transportation (DOT) and the U.S. Coast Guard as an oxidizing material
that requires a Yellow Label. Ferrous sulfate etches iron and aluminum;
316 stainless steel is relatively unaffected by FeSO^, and is used in con-
tact with aqueous solutions. Other than protection from moisture there are
no additional handling, storage or transportation requirements for the
compounds included in this Profile Report.
Disposal/Reuse
The inorganic chemicals discussed in this report can be reprocessed
for reuse if both quality and quantity of the waste discharged are con-
sistent with economic recovery. If disposal is required,, the acceptable
criteria for the release of these compounds into the environment is defined
in terms of the following provisional limits:
304
-------
Contaminant in Air
Cobalt nitrate
Ferrous sulfate
Stannous chloride
Cobalt chloride
Provisional Limit
0.001 mg/M3 as Co
0.01 mg/M3 as Fe
3
0.02 mg/M as Sn
0.001 mg/M3 as Co
Basis for
Recommendation
0.01 TLV for Co
0.01 TLV for Fe
0.01 TLV for Sn
0.01 TLV for Co
Contaminant in Water
and Soil
Cobalt nitrate
Ferrous sulfate
Stannous chloride
Cobalt chrloride
Provisional Limit
0.05 ppm as Co
0.03 ppm as Fe
0.05 ppm as Sn
0.05 ppm as Co
Basis for
Recommendation
Chronic toxicity
drinking water
standards
Drinking water
standard
Chronic toxicity
drinking water
standards
Chronic toxicity
drinking water
standards
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The Manufacturing Chemists Association has recommended disposal of
packaged lots of the materials in this report as follows. The salts are
dissolved in a large excess of water, and treated with a slight excess of
soda ash which precipitates the cobalt, ferric and tin ions. When the
sulfate ion is present, slaked lime is also added to reduce the sulfate
ion concentration. After standing 24 hours, the supernatant liquid is
decanted into another container and neutralized with hydrochloric acid,
and the liquid is diluted further before discharge into a sewer or stream.
The sludge is added to a landfill.
305
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Based on the discussion of disposal in Section 5, it may be concluded
that after preliminary treatment with soda ash (and lime when sulfate ions
are present) the treated waste streams containing the materials discussed
in this report can be discharged into municipal sewers or streams. Because
waste treatment can be handled adequately locally, these compounds do not
merit consideration as candidate waste stream constituents for national
disposal.
306
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, 35:35-40, Aug. 1971.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sittig, Marshall. Inorganic chemical and metallurgical process
encyclopedia. Park Ridge, New Jersey, Noyes Development
Corporation, 1968. 883 p.
1492. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Chemical Rubber Company, 1966. 1,500 p.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
2376. Gleason, M. N., R. C. Gosselin, H. C. Hodge, and R. P. Smith.
Clinical toxicity of commercial products. 3d ed. Baltimore,
Maryland, The Williams and Wilkins Company, 1969.
307
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Cobalt Nitrate (116)
IUC Name Cobaltous Nitrate
Common Names
Structural Formula
Co(N03)2 • 6H20
Molecular Wt. 291.05
(1)
Melting Pt. <100 C
(1)
Boiling Pt. -3H00. 55
Density (Condensed) 1 .87g/cc @ _ 20 r' Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 138.8g/100 ml at 0
Others:
Hot Water very soluble
^1
Ethanol100 ml at 12 C
0).
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped jn Glass bottles, wooden barrels^ '
ICC Classification oxidizing material'
Cotnmen ts
Coast Guard Classification oxidizing material'
References (1) 1570
(2) 1492
308
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ferrous Sulfate (198)
IUC Name
Common Names Copperas, Iron SuTfate
Structural Formula
FeS04 • 7H20
Molecular Wt. 278-01 Melting Pt. 64 C. -6H?0
Density (Condensed)! .898q/cc @ 20 C Density (gas)
Boiling Pt. 300 C. -7H90
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 15.65g/100 ml
Others:
(1)
(1)
Hot Water 48.6g/100 ml at 50 C Ethahol Insoluble
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in Bottles, bags, barrels, bulk
ICC Classification None
Comments
(2)
Coast Guard Classification None
(2)
References (1) 1570
(2) 1492
309
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Stannous Chloride (409)
IUC Name Stannous Chloride
Common Names Tin Chloride
Structural Formula
SnCl.
Molecular Wt. 189.
Density (Condensed) 3.393g/cclT^d 245
Vapor Pressure (recommended 55 C and 20 0
Melting Pt. 264.0 C
(1)
Density (gas)
Boiling Pt. 623 C(1)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper
Solubility
iDinty ^j
Cold Water 83.9g/TOO-ml at 10 C^ Hot Water 269.8g/100 ml at 15 CEthanol soluble^1*
Others :
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in bottles, drums^ '
ICC Classification none
Comments
(2)
Coast Guard Classification none
(2)
References (1) 1570
(2) 1492
310
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Cobalt chloride (489)
IUC Name Cobaltous chloride
Common Names
Structural Formula
CoCI.
Molecular Wt.129.85
(1)
Density (Condensed) 3.356g/cc (8 30 C
Melting Pt. subl.
(1)
(1)
Boiling
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water 45g/100 ml at 7 C
(1)
Hot Water105g/100 ml at 96 C(1)£thanol 54.4g/100 ml(l)
Others: acetone 8.6g/100 ml*'}
Acid, Base Properties
Highly Reactive with
Compatible with
t2T
Shipped in Bottles, tins, drums
ICC Classification_None
Comments
(2)
Coast Guard Classification None
(2)
References (1) 1570
(2) 1492
311
-------
PROFILE REPORTS ON THE COPPER SALTS
Copper Nitrated21), Copper Sul fated 22)
1. GENERAL
The subject copper compounds, copper II nitrate, copper I sulfate,
and copper II sulfate, are moderately poisonous materials. It is believed
that only the copper II compounds, (cupric nitrate and cupric sulfate)
occur as waste materials to any significant extent.
Industries, besides producers, which utilize these materials in
various forms include metal plating, metal pickling, and circuit board
etching. Normally waste streams that contain these compounds do not exist
as pure solutions, but rather are contaminated with other inorganic and
organic material. There are cases, however, in which copper sulfate wastes
occur as reasonably pure materials. Copper sulfate wastes from pickling
have the. greatest volume of all sources by far and are fairly pure. Copper
nitrate does find uses in electroless plating, but waste volumes from this
source are relatively low.
Commercial grade copper sulfate is produced by the action of sulfuric
acid on copper ores and scrap copper. The copper sulfate which is formed
in the solution is transferred to settling tanks where foreign material is
removed. The product solution is then filtered, evaporated, recrystallized,
and finally dried. The mother liquor from evaporation/recrystallization is
returned to the evaporator, creating no liquid waste other than spills.
The sludge that is obtained from settling and filtration is dumped. The
process is 99 percent efficient which indicates that waste output is
approximately 1 percent of the total production. Production figures
for 1963 are estimated at 40,000 tons. Thus, 400 tons per year of waste
copper sulfate from production is the current estimate.
313
-------
There is a significant portion of copper and copper alloy pickling
11 in
industry where the acid used for copper pickling is still being dumped.
Included in this waste is an anhydrous copper sulfate sludge which can
and should be easily recovered. The actual pickling tanks are rarely
dumped since the copper sulfate concentration increases, with use, until
saturation and it precipitates out of solution. Additions of sulfuric
acid replace precipitated sulfate to "sharpen up" the baths for renewed
HP! r
efficiency."*1
The manufacture of printed circuit boards creates large amounts of
copper wastes. Commonly used etchants include ferric chloride, chromic
acid/sulfuric acid, a family of alkaline solutions, cupric chloride and
ammonium persulfate., The use of ammonium persulfate materials is decreasing
in large shops due to material costs and waste treatment difficulties. The
presence of the ammonium ion in spent solutions complicates the normal
waste treatment process of precipitation by pH adjustment. When the waste
solution is made alkaline, free ammonia is liberated. The ammonia, a
noxious air pollutant, also complexes the copper in solution thereby
preventing precipitation. Industrial Filters Corp. claims that
additions of ferric chloride to isolated concentrates of this problem
solution will break the complexes. The use of hexavalent chrome is also
discouraged because of the additional chemical reduction step required
in the treatment process, as discussed in the Profile Report on the
chromates (21,22,etc.).
The large shops.which are close to suppliers often have their spent
solutions picked up by the supplier or have in-plant precipitation and
flocculation equipment. The small or remote printed circuit board shop
must rely on tank truck pick-up, private scavengers, or diluted sewer
dumping. In addition, the small shop is more likely to use the chrome/
sulfuric and ammonium persulfate etchants, because they have general, all
around capability. However, these are the two wastes which are the most
difficult to treat. The industry was characterized as having no big
problem with bulk disposal of spent solutions. Their real difficulties
lie with dragout and rinse waters, which can contain 20 to 100 ppm
copper.2156'2352 This rinse effluent must be reduced to levels compatible
314
-------
with waste water treatment plants. A large firm was noted as having an
poco
effluent output of 12,000 gal. per hour.
There are additional printed circuit board copper wastes from the
electroless plating used to apply the first layer of copper on the bare
composite board. Ammonium and ethylenediaminetetracetic acid (EDTA) complexed
copper again present the difficult waste treatment problem in dragout
2352
described above. Small shops tend to make up these solutions, use them
until they are nearly depleted, and then dump them. The larger shops can
afford the analysis of the solutions and make additions required to maintain
them.2349'2350
Metal plating is another significant contributor of copper sulfate
and nitrate wastes. The primary source is dragout as the actual plating baths
can be maintained indefinitely. Estimates of generated wastes range from
0.1 to 5 percent of the total copper used depending on equipment, stream
segregation, shape of the plated part, etc. ' Booz-Allen indicates
that "finishing effluents from fabricated metal parts" can contain 6 to
300 ppm Cu.1623
Copper sulfate has enjoyed wide use as a fungicide (applied directly)
but this has more or less been replaced by the Bordeaux Mixture (CuSO^
and CaCOHjp make a flocculent copper hydroxide-calcium sulfate complex).
Copper sulfate is also used in fungicides for treating wood. These uses
result in small amounts of waste material in containers and preparation
equipment. Consumption in agriculture has been as high as 50 percent of
the total production.
Copper nitrate is a difficult compound to profile because most of
the production and consumption is on a captive basis where it is made and
consumed entirely within a company. Captive production is primarily for
catalyst manufacture. Commercial copper nitrate is also sought as a raw
.material for catalyst manufacture.2348 Most of the remainder appears to
be used in metal finishing as discussed earlier. Copper nitrate is used
in the preparation of a wide variety of chemicals and catalysts, many of
which are made at one plant. The types and uses of these catalysts are
highly proprietary and little information is available. The assumption
315
-------
is made that waste dissolved copper nitrate occurs in highly mixed,
diverse waste streams-.
2. TOXICOLOGY
The compounds of copper exhibit a general toxicity which is less
severe than some of the other heavy metals. Sax describes them as being
moderately toxic and says that they may cause both irreversible and
reversible damage not generally severe enough to cause death and injury.
However, it is also specifically stated that the ingestion of a large
quantity of copper sulfate has caused vomiting, gastric pain, dizziness,
exhaustion, convulsions, shock, and coma which can finally lead to death.
As little as 27 grams have caused death while others have recovered after
ingestions of up to 120 grams. Symptoms of nervous system, kidney, and
liver damage have also been reported. Copper nitrate is not mentioned as
having toxicological properties different from those exhibited by the
whole class of copper compounds. The sulfate and nitrate anions, are not
considered to be toxic insofar as the toxic properties of compounds
containing these anions are normally attributed to that of the cation with
which they are bound.
The-U.S. Public Health Service indicates that copper in small amounts is
generally regarded as nontoxic and is in fact considered essential for
human metabolism. In 1942 the maximum permissible concentration of copper
in drinking water was raised from 0.2 mg/1 to 3.0 mg/1. However, since
it does contribute to ,an undesirable taste, the U.S. Public Health Service has
1752
recommended a maximum concentration of 1.0 mg/1. The critical
concentration for fish has been established at 0.15 to 0.18 ppm.
Copper sulfate has also been used extensively as a fungicide and
its general toxicity towards plants is significant. It has also been
established that high concentrations of copper in waste streams will
seriously impair the microorganisms that are employed in secondary water
treatment processes. For this reason, large scale dumping of dissolved
copper in the municipal sewer lines is discouraged by sewage treatment
authorities.
316
-------
3. OTHER HAZARDS
No flammable explosive, or other hazard has been found to exist for
these compounds.
4, DEFINITION OF ADEQUATE WASTE MANAGEMENT
Since it is apparent that waste copper compounds can create serious
problems with plant and animal life in sewer systems and open waterways,
it is necessary to define waste management techniques which will minimize
these hazards. Plants and processes must be designed so that no untreated
wastes reach open waterways or contaminate the surroundings. Each firm
should have the facilities to treat and recover copper from waste streams
and temporarily hold any treatment products for ultimate disposal. If a
firm is permitted to discharge to municipal sewer systems, suitable
holding or pretreatment tanks are required on the plant premises.
Handling, Storage, and Transportation
Dried waste materials containing copper sulfate or copper nitrate can
be packed, stored, and otherwise handled as if one were handling the pure
compound. Barrels, drums, bags, boxes, and bottles can all be used
to store and ship these materials. Protective clothing such as aprons,
gloves, and eyewear should be worn to prevent contact with these wastes.
All Department of Transportation (DOT) regulations should be followed when
shipping or otherwise handling these compounds.
All personnel and supervisory staff who work with these materials
should be carefully educated as to the precautions that must be taken to
prevent hazardous exposure.
317
-------
Disposal/Reuse
The U.S. Public Health Service recommends a maximum copper level of
1752
1.0 mg/1 (ppm) in drinking water. The proper levels of copper waste
discharge to municipal sewage systems or cooperative industrial waste
treatment would of course vary with such parameters as waste water volume,
efficiency of the plant, etc. For the safe disposal of copper nitrate and
copper sulfate, the acceptable criteria for their release into the environ-
ment are defined in terms of the following recommended provisional limits:
Contaminant in Air Provisional Limit Basis for Recommendation
Copper ni-trate 0.01 mg/M3 as Cu 0.01 TLV for Cu
Copper sulfate 0.01 mg/M as Cu 0.01 TLV for Cu
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Copper nitrate 1 ppm (mg/1) as Cu Drinking water standard
Copper sulfate 1 ppm (mg/1) as Cu Drinking water standard
Copper sulfate and copper nitrate both have inherent value when present
as concentrates in wastes. Very large amounts of copper sulfate are produced
from the numerous copper and copper alloy pickling processes that are
carried out in the nation. Waste copper nitrate normally occurs in dilute
solutions and is not as likely a candidate for recovery and reuse as
copper sulfate. The same is true with any dilute copper waste solutions.
However, with increased utilization of solution concentrating equipment,
along with waste stream segregation, some dilute copper solutions are
being economically recovered. The various means by which solutions can
be concentrated and waste copper compounds recovered are discussed later.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
There are two basic waste management practices which involve copper
sulfate and copper nitrate. The first method, product recovery, is used
318
-------
primarily in industries where the waste can be kept pure through segregation
and concentration. The other basic waste management option is that of
destructive precipitation. This involves either pH adjustment or discharge
to sewers.
Option No. 1 '- Recovery of Copper Process Byproducts
Since copper sulfate has inherent value as a chemical commodity
(80 to 90 cents per pound for purified grades) it is advantageous for the
metal finisher to attempt recovery if it is economically feasible. There
are several approaches by which valuable copper or copper compounds can
be recovered.
As previously described with copper pickling, copper oxide removal
continues until the pickling bath becomes saturated with copper sulfate
and it settles out of the pickling solution. This nearly pure copper
sulfate can be mechanically removed from the tanks, packaged and sent to
a commercial reclaiming firm.
There are also in-plant processes for recovering copper metal from
pickling solutions. An example of an integrated recovery and waste
treatment system is described by Lancy and Pinner who have installed an
electrolytic copper removal unit through which is pumped the sulfuric acid
pickling solutions. Copper metal is electrolytically plated out thereby
regenerating the sulfuric acid to be returned to the pickling tanks. The
1119
system is said to be simple to operate and can be easily automated.
Copper sulfate and copper nitrate waste solutions that are generated
by the metal plating processes are nearly always dilute solutions (less
than 500 ppm copper). Any type of copper recovery process for these
dilute solutions will likely require some type of solution concentrating
equipment. The addition of this type of equipment is costly, but if the
value of chemicals being lost from large volume shops is larger than the
cost of installing and operating recovery equipment, then such an approach
is justified. The types of process which might be considered for
319
-------
concentrating a dilute but pure waste stream include reverse osmosis, ion
exchange, dialysis, and multiple effect 'evaporators. The solutions can be
concentrated to a point where electrolytic or other copper recovery can be
carried out. Alternatively, the concentrates can be returned to plating
baths, etc. or sent to a reclaiming firm.
Option No. 2 - Precipitation by pH Adjustment
Precipitation is most suitable for dilute mixed streams where copper
will not be recovered for reuse. Soda ash, caustic or other alkaline
chemicals can be added to copper bearing solutions to adjust the pH to
about 9.5. This precipitates copper as an insoluble hydroxide gel along
with the precipitates of other heavy metals which might be present in a
mixed solution. Alum or other suitable floccuating agents can also be
used to speed up settling, and clarification of the effluent. The treated
effluent has characteristic heavy metal levels of 0 to 5 ppm. The alkaline
effluent is neutralized before sewering and the resultant sludge is almost
always landfilled. This procedure can be carried out in either batch or
continuous processes. Turn key equipment systems are available for
performing the precipitation on an automated or semi-automated basis.
There are two major disadvantages for using this procedure. The first
is the problem of handling and disposing of the highly hydrated metal
hydroxide sludges. It is not unusual for these sludges to contain upwards
of 75 to 80 percent water by volume. Precipitation and settling is normally
slow and it is necessary to have settling ponds in which to allow the
coagulation process .to occur. The second major disadvantage of precipitation
methods is that no feasible process has yet been developed for the
recovery of chemical or metal credits from this type of precipitated waste.
The sludge often contains many other organic and inorganic materials which
are present in the waste stream before treatment and these hinder effective
purification and recovery. These mixed sludges can serve no useful purpose
and can only be ultimately disposed. The method is adequate when the pH
is made high enough to leave only low ppm traces of pollutants in the
effluent. The ultimate disposal of the sludges is discussed later.
320
-------
Option No. 3 - Dilute Discharge to Municipal Sewers
Much of the major metal finishing industry is located in highly
industrial and large metropolitan areas. Significant amounts of copper
waste solutions generated in pickling, plating and other related industries
are being discharged to existing municipal sewage treatment. '
The only pretreatment which is customarily given metal finishing wastes
before discharge into municipal sewers is neutralization. If the material
being discharged is of a considerable quantity, or if the discharge
point is close to the sewage treatment plant, it is necessary to closely
monitor the discharge to ensure that there will be no undesirable ill
effects on the sewage stream.
When discharged to sewers, most of the copper ion will precipitate
when it reacts with the sulfides that are found in normal domestic streams.
This precipitation occurs in transit to the waste treatment plant and
the solids are removed at the primary screening and settling facilities
or after secondary biological treatment processes. This method of
disposal is considerably widespread and may be considered environmentally
acceptable only if the waste water treatment plants receiving these
discharges can efficiently deal with the waste loads. In spite of the
increased emphasis on recovery and recycling of wastes with value, the
trend for using municipal sewers for industrial discharge is actually
increasing.
Ultimate Disposal of Sludges from Options 2 and 3
Three ultimate disposal options for these sludges are: (1) landfill,
(2) incineration, and (3) ocean disposal. Landfill is believed to be, by
far, the most prevalent final disposal procedure but the problem of
potential contamination of surrounding land or water tables, due to the
leaching of poisonous materials from the sludge, must be considered.
Incineration reduces the sludge to an ash residue which can be more
easily handled for ultimate disposal but at the same time could also lead
321
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to the formation of poisonous, soluble metal oxides. Incineration also
requires additional equipment and a combustible fuel source as well as
equipment for air pollution control. Ocean disposal is currently being
practiced to a considerable degree by municipal waste treatment plants
located near the coast where the primary and secondary sludges can be either
pumped or barged out to submarine disposal areas. This disposal approach
has been the subject of much recent debate and it is likely that it will
not long remain one of the significant sludge disposal options.
Summary of Available Waste Management Options
i
Recovery Waste copper is a valuable commodity and
can be easily recovered.
Precipitation by Best method for dilute streams, mixed
pH adjustment streams, or other cases where recovery
is not practical.
Dilute discharge to Adequate for dilute streams or mixtures
municipal sewers only if treatment facilities can
' operate to meet local discharge
•i standards.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The installation of waste treating equipment specifically for copper
sulfate and copper-nitrate is not recommended for National Disposal Sites
for the following .reasons: (1) the inherent value of copper and its
compounds has led-a large proportion of the firms handling these materials
to install the various types of copper recovery equipment; and (2) the
transport of huge volumes of non-recyclable dilute solutions is simply
too expensive. Industry will continue to treat the dilute wastes by
destructive precipitation, or discharge to municipal sewers.
As stated in other Profile Reports, it is very likely that a general
facility for pH adjustment and precipitation will be required to handle
the waste streams generated within the site itself. This same facility
could also be used to treat various heavy metal wastes which might
occasionally be sent to the site. These would include waste mixtures
containing chromium, zinc, nickel, lead, mercury, copper and other metals.
322
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7. REFERENCES
0225. Threshold limit values for 1971. Occupational Hazards, Aug. 1971,
p. 35-41. -
0766. Sax, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1119. Ceresa, M., L. E. Lancy. Metal finishing waste disposal. Metal
Finishing (3 parts) 66(4): 56-62; 66(5): 60-65; 66(6) :112-118;
Apr., May, June 1968
1121. Lancy, L. E., R. Pinner. Waste treatment and metal recovery in
copper and copper alloy pickling plant. Metallurgia 73(437)119-122;
Mar. 1966
1501. Faith, W. L., D. B. Keyes, and R. L. Clark. Industrial chemicals. 3d
New York, John Wiley and Sons, Inc., 1965. 824 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Chemical Rubber Company, 1969. 2,100 p.
1752. Public health drinking water standards. U. S. Department of Health
Education and Welfare, Public Health Service Publication No. 956,
Environmental Control Administration, Rockville, Maryland 1962.
2156. Graham, A. K., ed. Electroplating engineering handbook, 2d ed.,
New York, Reinhold Publishing Corp., 1962. 774 p.
2347. Personal communication. Fred Stewart, Lancy Labs, to J. F. Clausen,
TRW Systems, Sept. 15, 1972.
2348. Personal communication. W. Witzleben, Allied Chemical Co.,
to J. F. Clausen, TRW Systems, Sept. 28, 1972.
2349. Personal communication. Simon Gary, Scientific Control Labs, to
J. F. Clausen, TRW Systems, Sept. 26, 1972.
2350. Personal communication. Don Hutchinson, Harshaw Chemical Co., to
J. F. Clausen, TRW Systems, Sept. 26, 1972.
2352. Personal communication. Frank Gorman, Cinch-Graphik Inc., to
J. F. Clausen, TRW Systems, Sept. 29, 1972.
323
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. in. Name Copper sulfate (122)
Structural Formula
IUC Name Copper II sulfate pentahydrate
Conmon Names Blue Vitriol, Chalcanthite' ' CaSO. • 5H?0
Molecular Wt. 249.68(1) Melting Pt. -4HoO at 110C(1* Boiling Pt. -5HJ3 at 150 C
Density (Condensed) 2.284 @ --_ Density (gas) P
Vapor Pressure (recommended 55 C and 20 0
@ e @
Flash Point Autoignition
Flammability Limits in Air (wt %) Lower none Upper none
Explosive Limits in Air (wt. %) Lower none Upper none
y m 100 c*1*
Cold Water 31.6g/100 cc at 0 C" Hot Hater 203.3 g/100cc at Ethanol insoluble
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in Barrels, drums, boxes, bags, bottles
(2)
ICC Classification N° label reguiredv Coast Guard Classification,
Commen ts
References (1) 1570
(2) 0766
324
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H. M. Name Copper ni
IUC Name Copper II
HAZARDOUS WASTES PROPERTIES
WORKSHEET
(121)
tri hydrate
Structural Formula
Common Names
Cu(N0)
3'2 '
Molecular Wt. 241.60^ Melting Pt. 114.5 C
Oensity (Condensed) 2-3? 9/cc @ 25 C( ' Density (gas)
Vapor Pressure (recommended 55 C and 20 Q)
& 9
(1)
-HNO, at 1?0 .
Boiling Pt. J 1/0 C
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Solubility
Lower
Upper_
Upper_
(1) 100 g/100 cc
Cold Water 137.8 g/100 cc at 0 C^Aot Water 1270 g/lOOcc at IQo'cEthanol *' it~U5
Others: very soluble in liquid NH
3
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
(2) 0766
325
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
•). ;•!. Name Co'P'P'er Nitrate (121)
HJi Name Copper II Nitrate, hexahydrate
Structural Formula
Common '<(iiiu:s
Cu(N03)2 • 6H20
Molecular Wt. 295.64'
(1)
Melting Pt.-3H20 at 26.4
Density (Condensed) 2.074 g/ccv' '@ N/A Density (gas)
Boiling Pt. N/A
Vapor Pressure (recommended 55 C and 20 C)
Dash Co int.
Autoignition Temp.
Flammabi I i ty Limits in Air (wt %} Lower_
Limits in Air (wt. %) Lower
Solubili ty /^ \
Cold Water ?43.7 g/100 cc at 6 C Hot Water infinite
Othe rs:
Acid, Base Properties
Upper
Upper_
(1)
Ethanol soluble
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
326
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PROFILE REPORT
v^
Hydrazine (212)
1. GENERAL
Hydrazine is a clear, oily, water-white liquid with an odor
similar to that of ammonia. It is a strong reducing agent, weakly
alkaline and very hygroscopic. It will react with carbon dioxide and
oxygen in air. Exposure of hydrazine to air on a large surface (as
on rags) may result in spontaneous ignition from the heat evolved
by its oxidation with atmospheric oxygen. With water it forms the
diamide hydrate, H2NNH2 . H20.1300
Hydrazine is formed by reacting equimolar quantities of sodium
hypochlorite and ammonia in an alkaline solution to give chloroamine
(NHpCl). This reacts at elevated temperature with ammonia to give
hydrazine:
NH3 + NaOCl •+ NaOH + NH2C1
NH3 + NH2C1 + NaOH + N2H4 + NaCl + H20
A side reaction occurs which leads to the decomposition of
hydrazine:
2NH2C1 + N2H4 -* N2 + 2NH4C1
This side reaction is catalyzed by dissolved chloride. Gelatin, glue,
amino acids or simple peptides are added to complex the chlorides.
Hydrazine is recovered from aqueous solution by distilling water until
the still bottoms approach the composition of hydrazine hydrate. The
hydrate is either treated with sodium hydroxide at a temperature
above the boiling point of hydrazine and the hydrazine distilled and
collected, or treated with aniline which is used to effect removal of
the water by azeotropic distillation.
Hydrazine is used in jet and rocket fuels, intermediates for
327
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agricultural chemicals, antioxidants, textile chemicals, explosives,
photographic developers, blowing agents, scavengers for chlorine in
hydrogen chloride, corrosion inhibitors and scavengers for oxygen.
The chemical and physical properties for hydrazine are summarized
in the attached worksheet.
2. TOXICOLOGY
Hydrazine is a strong irritant and may damage the eyes and cause
respiratory tract irritation. If spilled on the skin or eyes, liquid
hydrazine can cause severe local damage or burns and can cause derma-
titis. It can penetrate the skin. If inhaled, the vapor causes local
(irritation of eye and respiratory tract) and systemic effects. For
long exposure, systemic effects involve the central nervous system.
On exposure to higher concentrations, convulsions and possibly death
follow. Repeated exposures may cause toxic damage to the liver and
1300 1993
kidney, as well as anemia. '
The exposure limits recommended are as follows:
Threshold limit (ACGIH) -1.0 ppm (1.3 mg/m3)
Emergency exposure limits -
10 min - 30 ppm (39 mg/m3)
30 min - 20 ppm (26 mg/m )
o
60 mih - 10 ppm (13 mg/m )
3. OTHER HAZARDS
Hydrazine is flammable over a broad range of concentrations: 4.7
to 100 percent. It is hypergolic with some oxidants, such as hydrogen
peroxide, nitrogen tetroxide, fluorine, halogen fluorides, and nitric
acid. A film of hydrazine in contact with metal oxides, such as those
of iron, copper, lead, manganese and molybdenum, may ignite owing to
the heat of chemical reaction. Hydrazine vapors in a closed system may
explode when exposed to air. In the presence of finely-divided or
other high surface area forms of some metal or metal oxides, hydrazine
dissociates into nitrogen, hydrogen and ammonia.
328
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Adequate procedures for the safe handling, transportation and storage
of hydrazine are described in two publications,1300'1993 and in the military
specification for hydrazine, MIL-P-2705.1995 Hydrazine is classified by
Department of Transportation (DOT) as a corrosive liquid and is shipped
under a White Label. Under DOT specifications hydrazine may be shipped in
1-gal. glass bottles packed in cans, in metal barrels or drums of 304 or
347 stainless steel, or in tank cars of 304L, 347 stainless steel,
aluminum 103A AL-W, or aluminum 111A100-W-6.
Hydrazine as a waste will generally be encountered as excess material,
as contaminated material from spills, or in aqueous streams from chemical
process industries. Because of the hazards involved (unpredictable
decomposition), hydrazine is usually not recovered in a concentrated form
from contaminated or dilute systems. In ponds or holding tanks dilute
hydrazine is decomposed by the air and bacteria into nitrogen, hydrogen,
water and ammonia. In a concentrated form, hydrazine is destroyed by
burning. .
The safe disposal of hydrazine is defined in terms of £he recommended
provisional limits in the atmosphere, water and soil. These recommended
provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Hydrazine 0.01 ppm 0.01 TLV
Contaminant in Water
and Soil Provisional Limit Basjs for Recommendation
Hydrazine 1.0 ppm Quantity will rapidly
oxidize to near-zero
concentration
329
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Hydrazine is generally destroyed by oxidation to water and nitrogen.
In dilute solution, dissolved oxygen, catalysis, or bacterial action con-
vert hydrazine to nitrogen, hydrogen, ammonia and water. Therefore, there
are no problems in dealing with the products from waste treatment. Current
disposal practices for hydrazine are briefly described in the following
paragraphs together with recommendations as to adequacy.
Option No. 1 - Open Pit Burning
Hydrazine poured into an open lined pit is burned to nitrogen and
water. The transfer of the hydrazine and the ignition must be accomplished
by a remote means. For drum quantities of hydrazine this method is
generally acceptable although since excessive NO might be generated
X
another option would be preferred.
Option No. 2 - Incineration
The Air Force has a minimum of ten trailer-mounted incinerators capable
of incinerating up to 6 GPM of hydrazine in a variety of mixtures with water
(from 100 percent hydrazine to 100 percent water). The effluents from the
19Q4
units is limited to 0.03 Ibs/min NO when incinerating hydrazine. These
/\
units are acceptable for disposing of large quantities of hydrazine.
Option No. 3 - Catalytic Decomposition
One of the applications for hydrazine is its use as a monoprope11 ant.
When hydrazine is passed over a support (usually aluminum oxide) coated with
certain metals or metal oxides, it is decomposed into nitrogen, hydrogen and
ammonia. The details of catalyst composition are usually found in the
classified literature. In most cases the catalyst is expensive, but TRW
Systems has preliminary data on a low cost catalyst that should be further
investigated.
330
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Option No. 4 - Diluting with Water and Holding
If hydrazine is diluted with water, e.g., after spills, and placed in
open lined ponds or holding tanks, the hydrazine is decomposed to water,
nitrogen, and ammonia by air oxidation and bacterial action. For small
quantities of hydrazine in aqueous solution this method is acceptable if
adequate space is available.
Option No. 5 - Chemical Treatment
Small quantities and dilute solutions are collected in open containers
and treated with oxidizing compounds such as 10 percent hydrogen peroxide or
calcium hypochlorite. The oxidizing agents should be applied slowly until
in excess. This method is not recommended except for small quantities
because considerable heat is liberated during decomposition.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Hydrazine does not appear to be a candidate waste stream constituent
for National Disposal Sites. It is anticipated that packaged hydrazine
and hydrazine in aqueous waste streams will continue to be treated at the
source of waste generation. The major products of combustion or decomposi-
tion are the elements, water, or ammonia which do not present a secondary
disposal problem.
331
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7. REFERENCES
1300. JANAF Hazards Working Group. Chemical rocket/propel 1 ant hazards,
Volume III, liquid propellent handling, storage and transportation.
CPIA Publication No. 194, May 1970.
1157. Astle, J. Industrial organic nitrogen compounds. American Chemical
Society Monograph, New York, Reinhold Publishing Co., 1961.
1433. Kirk-Othmer Encyclopedia of chemical technology. 2d ed. New York,
Interscience Publishers, 1963.
1662. Shreve, R.N. The chemical process industries. McGraw-Hill series
in chemical engineering, 2d ed. New York, 1956. 1,004 p.
1993. U. S. Air Force Medical Service. The handling and storage of
liquid propel 1 ants. Department of the Air Force, Air Force
Manual No. 160-39, Apr. 1, 1964.
1995. U. S. Air Force. Military specification, propellant, hydrazine.
MIL-P-26536C. Edwards Air Force Base, May 23, 1969.
1994. Coen Company. Liquid wastes. Chemical Engineering, 78 (14): 43,
June 21, 1971, Advertisement.
332
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrezine (212)
Structural Formula
IUC Name Hydrazine_
_ ,. Di ami n e
Common Names
Molecular Wt. 32.05 Melting Pt. 1.5 Boiling Pt.113.5
Density (Condensed) 1.008 g cc @ 20 C Density (gas) 1.1 § _0 C
Vapor Pressure (recommended 55 C and 20 C)
0.07 psia @ 40 F 0.36psia g 80 F 2.9psia & 160 F
Flash Point 52. c Autoignition Temp.270__ c
Flammability Limits in Air (wt %) Lower 4.7% Upper 100% at 100 C
Explosive Limits in Air ,(wt. %) Lower Upper
Solubility
Cold Water Miscible Hot Water Miscible Ethanol Miscible
Others: acetone - miscible
Acid, Base Properties NPHA + H90 _ N9H/ + OH" K = 8.5 x TO'7
Highly Reactive with Acids, metal oxides
Compatible with Stainless steel, aluminum
Shipped in Bottles, drums, tank cars
White Label
ICC Classification Corrosive Liquid.Hhite Label coast Guard Classification Corrosive Liquid
Comments
Kofertnces (1) 1300
333
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-1
3. Recipient's Accession No.
4. Tiiie and subtitle Recornmenc|ec| Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume XII, Indus-
trial and Municipal Disposal Candidate Waste Stream. Constituent
Profile Reports - Inorganic Compounds __
5- Report Date
Issuing date - Aug. 1973
6.
7. Author(s) R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
6. I. Gruber, M. J. Santy, and C. C. Shin
8- Performing Organization Rept.
No.
21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089 .
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
Volume XII of 16 volumes.
16. Abstracts
This volume contains summary information and evaluation of waste management methods in
the form of Profile Reports for inorganic compounds. These Profile Reports were pre-
pared for either a particular hazardous waste stream constituent or a group of related
constituents. Each Profile Report contains a discussion of the general characteristics
of the waste stream constituents, their toxicology and other associated hazards, the
definition of adequate management for the waste material, an evaluation of the current
waste management practices with regard to their adequacy, and recommendation as to the
most appropriate processing methods available and whether the waste material should be
considered as a candidate for National Disposal, Industrial Disposal, or Municipal
Disposal.
17. Key Words and Document Analysis. 17a.
Hazardous Wastes
Alkali and Ammonium Fluorides
Aluminum Compounds
Phosphates
Inorganic Compounds
Industrial Disposal Candidate
Municipal Disposal Candidate
Oxides
Ammonium Compounds
Sodium Compounds
Carbonates
17b. Identifiers/Open-Ended Terms
Descriptors
Hydroxides
Sulfur Compounds
Potassium Compounds
Beryllium Compounds
Sulfates
Cobalt Compounds
Barium Compounds
Antimony Compounds
Nitrates
Arsenic
Hydrazine
Acids
Magnesium Compounds
17c. COSATl Field/Group Qgp.
18. Availability Statement
Release to public.
- 334 -
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCl-ASSIFIKD
21. No. of Pages
340
22. Price
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