개요
White phosphorus is a colorless, white, or yellow waxy solid with a garlic-like odor. It does not occur naturally, but is manufactured from phosphate rocks. White phosphorus reacts rapidly with oxygen, easily catching fire at temperatures 10 to 15 degrees above room temperature. White phosphorus is used by the military in various types of ammunition, and to produce smoke for concealing troop movements and identifying targets. It is also used by industry to produce phosphoric acid and other chemicals for use in fertilizers, food additives, and cleaning compounds. Small amounts of white phosphorus were used in the past in pesticides and fireworks.
이름 및 식별자
- 우선 이름
- Phosphorus
- IUPAC
- phosphane
- 현지명
- 인
- 영어명
- Phosphorus
- 분자식
- P
- 분자량
- 30.97
이름 및 동의어
이름 더 보기
데이터베이스 식별자
- CAS
7723-14-0、7723-14-0; 12185-10-3、7723-14-0 (red, violet, and black)- PubChem CID
- 5462309
- UNII
- 27YLU75U4W
- EC Number
- 231-768-7
물성
구조 계산 물성
- 극성 표면적
- 0 Ų
- 수소 결합 공여자 수
- 0
- 수소 결합 수용자 수
- 0
- 회전 가능 결합 수
- 0
- 무거운 원자 수
- 1
- 형식 전하
- 0
- 복잡도
- 0
실험 및 물리화학적 성질
Chemical Classes
Hazardous Air Pollutants (HAPs)
Other Classes -> Phosphorus Compounds
Flammable agents - 4th degree
-> NIOSH Emergency Response Categories
Nutrient
Odor
Garlic-like
Acrid
Density
2.34 red, 2.36 violet; 2.70 black; 1.8 white-yellow (EPA, 1998)
2.691 at 68 °F (USCG, 1999) - Denser than water; will sink
1.83 (alpha-form); 1.88 (beta form)
Density = 1.74 g/cu cm at 50 °C (liquid)
Black: Orthorhombic crystalline forms: stable in air; resembles graphite in texture; density 2.691. Does not catch fire spontaneously. Amorphous form prepared at lower pressures. At higher pressure the orthorhombic form undergoes reversible transition to a rhombohedral structure, density 3.56, and a cubic structure, density 3.83.
Red: The properties of red phosphorus are intermediate between those of the white and black forms. Density 2.34. Insoluble in organic solvents. Soluble in phosphorus tribromide. Less active than the white form; reacts only at high temperature. Yields the white modification when distilled at 290 °C. Catches fire when heated in air to about 260 °C and burns with formation of the pentoxide. Burns when heated in an atmosphere of chlorine.
Color/Form
Exists in three main allotropic forms: white, black, and red. The same liquid is obtained from all forms on melting.
Colorless or white, transparent, crystalline solid; waxy appearance; darkens on exposure to light. Sometimes called yellow phosphorus; color due to impurities. Two allotropic modifications: alpha-form exists at room temperature; cubic crystals containing P4 molecules; beta-form hexagonal crystals. /White phosphorus/
Yellow /allotropic form/: Colorless to yellow, wax-like solid.
Black /allotropic form/: Polymorphic; orthorhombic crystalline form; amorphous form.
For more Color/Form (Complete) data for PHOSPHORUS, ELEMENTAL (6 total), please visit the HSDB record page.
Solubility
Black: Insoluble in organic solvents; White: Insoluble in water, slightly soluble in benzene, ethanol, and chloroform, soluble in carbon disulfide; Red: Insoluble in water and organic solvents.
Solubilities in water: one part/300,000 parts water; in abs alc: one g/400 mL; in abs ether: one g/102 mL; in CHCl3: one g/40 mL; in benzene: one g/35 mL; in CS2: one g/0.8 mL. Solubility in oils: one gram phosphorus dissolves in 80 ml olive oil, 60 ml oil of turpentine, about 100 mL almond oil.
0.33 mg/100 g water at 15 °C; 2.7 g/100 g benzene at 15 °C; 89.8 g/100 g carbon disulfide at 10 °C
Boiling Point
536 °F at 760 mmHg ; white-yellow ignites at 86 °F in moist air; red ignites at 500 °F. (EPA, 1998)
838.9 °F at 760 mmHg (USCG, 1999)
280 °C
536 °F
280.5 °C @760 [mm Hg]
Melting Point
111.2 °F white-yellow; 1094 °F violet; 1094 °F red (EPA, 1998)
44.1 °C
Black: Melting point = 610 °C
44.1 °C
111.4 °F
44.15 °C
Vapor Density
4.77 red; 4.42 white-yellow (EPA, 1998) (Relative to Air)
Red: 4.77; White: 4.42 (Air = 1)
물리화학적 성질
- 녹는점
- 280 °C · 280 °C (white)(lit.)
- 끓는 점
- 280 ℃ · 280℃
- 밀도
- 2.34 g/mL · 2.34 g/mL at 25 °C(lit.)
- 증기 밀도
- 0.02 · 0.02 (vs air)
- 증기압
- 0.03 mm · 0.03 mm Hg ( 21 °C)
- 인화점
- 30 °C · 30°C
- 저장 조건
- 2 · 2-8°C
- 용해도
- 불용성
- 물리적 상태
- 가루 (빨간색)
- 색상
- 적갈색
- Specific Gravity
- 2.34 · 2.34
- 수소이온지수(pH)
- 3 at · 3 at 37℃ and 500-10000mg/L
- 냄새
- 공기에 노출되면 매운 연기가 납니다.
- Flame Color
- Pale blue-green
- 수용성
- 불용성
- 비열
- 0.68 J/ · Cp(crystal): 0.68 J/(g·K), at 25℃
- Merck
- 13 · 13,7433
- Dielectric constant
- 4.1 · 4.1(34℃)
- 안정성
- 안정적인. 가연성이 높습니다. 강한 산화제, 강한 염기와 호환되지 않습니다. 빛과 열에 민감합니다.
- InChI
- 1S/H3P/h1H3
- InChIKey
- XYFCBTPGUUZFHI-UHFFFAOYSA-N
- SMILES
- P
- NIST
- Phosphorus atom(7723-14-0)
- EPA
- Phosphorus (7723-14-0)
화학적 성질
Yellow or white phosphorus ignites spontaneously in air at 34 °C. It should be stored under water. Under this condition, however, it may form phosphoric acid. Stainless steel containers should be used to hold the corrosive material. White phosphorus fires can be controlled by using water or sand or by excluding air.
안전 및 규제
GHS 분류
GHS Classification
Danger
H228: Flammable solid [Danger Flammable solids]
P210, P240, P241, P273, P280, P370+P378, and P501 (click each P-code to see the statement)
This chemical does not meet GHS hazard criteria for 9.9% (108 of 1090) of reports.
Danger
H228 (72.5%): Flammable solid [Danger Flammable solids]
유해성 정보
Regulatory Information
Chemical: Phosphorus
Hazard Traits - Environmental tox; Respiratory Toxicity
Phosphorus is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Phosphorus are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)
Status: Active Update: 24-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/15360
Phosphorus, white, yellow, dry or in solution: HSNO Approval: HSR001451 Approved with controls
The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)
Other Safety Information
IMAP assessments - Phosphorus: Human health tier I assessment
- Indoor Air: White phosphorus can release into indoor air as smoke.
DOT Label
Flammable Solid
Flammable Solid
Fire Hazards
Will reignite itself after fire is extinguished. White/Yellow: Ignites at approximately 86F in air; ignition temperature is higher when air is dry. Black: Does not catch fire spontaneously. Red: Catches fire when heated in air to approximately 500F, and burns with formation of the pentoxide. Burns when heated in atmosphere of chlorine. Caution: Avoid contact with potassium chlorate, potassium permanganate, peroxides and other oxidizing agents; explosions may result on contact or friction. Upon heating Red releases toxic oxides of phosphorus and Yellow emits toxic gases and vapors such as phosphoric acid fumes. Red: Avoid uncontrolled contact with oxidizing agents, or with strong alkaline hydroxides. Can react violently with oxidizing agent in presence of air and moisture, liberating phosphorus acids and toxic, spontaneously flammable phosphine gas. White/Yellow: Avoid air, all oxidizing agents including elemental sulfur, strong caustics. White/Yellow: Darkens on exposure to light. Gives off acrid fumes on exposure to air. Ignites spontaneously in air at or above 86F. Black: stable in air. Avoid heat. Red: burning yields toxic oxides of phosphorus. White/Yellow: toxic gases and vapors such as phosphoric acid fumes are released. (EPA, 1998)
Excerpt from ERG Guide 133 [Flammable Solids]:
Fire Potential
White: ignites at approx 30 °C in moist air; ignition temp is higher when air is dry. Black: does not catch fire spontaneously. Red: catches fire when heated in air to approx 260 °C and burns with formation of the pentoxide. Burns when heated in atmosphere of chlorine.
Health Hazards
It is classified as super toxic. The probable lethal dose is less than 5 mg/kg (a taste or less than 7 drops) for 70 kg (150 lb.) person. Poisonous if swallowed or if fumes are inhaled. Yellow: Fumes are irritating to the respiratory tract and cause severe ocular irritation. On contact with the skin it may ignite and produce severe skin burns with blistering. Red: Irritates eyes. (EPA, 1998)
Excerpt from ERG Guide 133 [Flammable Solids]:
Hazards Summary
White phosphorus is a colorless, white, or yellow waxy solid with a garlic-like odor. It does not occur naturally, but is manufactured from phosphate rocks. White phosphorus reacts rapidly with oxygen, easily catching fire at temperatures 10 to 15 degrees above room temperature. White phosphorus is used by the military in various types of ammunition, and to produce smoke for concealing troop movements and identifying targets. It is also used by industry to produce phosphoric acid and other chemicals for use in fertilizers, food additives, and cleaning compounds. Small amounts of white phosphorus were used in the past in pesticides and fireworks.
White phosphorus is used in the manufacture of munitions, pyrotechnics, explosives, smoke bombs, in artificial fertilizers, and rodenticides. White phosphorus is extremely toxic to humans, while other forms of phosphorus are much less toxic. Acute (short-term) oral exposure to high levels of white phosphorus in humans is characterized by three stages: the first stage consists of gastrointestinal effects; the second stage is symptom-free and lasts about two days; the third stage consists of a rapid decline in condition with gastrointestinal effects, plus severe effects on the kidneys, liver, cardiovascular system, and central nervous system (CNS). Inhalation exposure has resulted in respiratory tract irritation and coughing in humans. Chronic (long-term) exposure to white phosphorus in humans results in necrosis of the jaw, termed "phossy jaw." EPA has classified white phosphorus as a Group D, not classifiable as to human carcinogenicity.
See Phosphorus (yellow).
Reactive Group
Reducing Agents, Weak
Reducing Agents, Weak
Special Reports
Department of Health and Human Services /ATSDR; Toxicological Profile for White Phosphorus PB/98/101090/AS (September 1997). Available from: http://www.atsdr.cdc.gov/toxprofiles/tp103.html as of November 29, 2005.
Stula RT et al; Airborne Emission Control Technology for the Elemental Phosphorus Industry; NTIS Report Order No PB84-156421, 412 pp (1984). A report on airborne emission control technology for the elemental phosphorus industry.
WHO; Diseases Caused by Phosphorus and Its Toxic Compounds; Early Detection of Occupational Diseases pg 53-62 (1986). Review of diseases and health related effects resulting from exposure to phosphorus or phosphorus cmpd.
TSCA Requirements
Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. Phosphorus is included on this list.
Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, use, and exposure to EPA as cited in the preamble in 51 FR 41329. /White phosphorus (12185-10-3)/
안전 및 보호
Fire Fighting
White/Yellow: Deluge with water, taking care not to scatter, until fire is extinguished and phosphorus has solidified, then cover with wet sand or dirt. Red: Flood with water and when fire is extingushed, cover with wet sand or dirt. Extreme caution should be used during clean up since reignition may occur. Under certain conditions at high temperature, red phosphorus reverts to more hazardous white phosphorus.
Excerpt from ERG Guide 133 [Flammable Solids]:
- White phosphorus is extremely flammable.
First Aid
Signs and Symptoms of Acute Phosphorus Exposure: Signs and symptoms of acute exposure to phosphorus may be severe and occur in three stages. The first stage will involve burns, pain, shock, intense thirst, nausea, vomiting, diarrhea, severe abdominal pain, and "smoking stools." The breath and feces may have garlicky odor. The second stage will be a symptom-free period of several days in which the patient appears to be recovering. The third stage may be severe and include nausea, bloody vomitus, diarrhea (may be bloody), jaundice, liver enlargement with tenderness, renal damage, hematuria (bloody urine), and either oliguria (little urine formation) or anuria (no urine formation). Headache, convulsions, delirium, coma, cardiac arrhythmias, and cardiovascular collapse may also occur. If phosphorus contacts the eyes, then severe irritation and burns, blepharospasm (spasmodic winking), lacrimation (tearing), and photophobia (heightened sensitivity to light) may occur. Eye contact may lead to a total destruction of the eyes. Victims may experience spontaneous hemorrhaging of phosphorus-contaminated skin and mucous membranes.
Excerpt from ERG Guide 133 [Flammable Solids]:
Firefighting Hazards
White phosphorus may be present as a contaminant or formed in fire situations. Fumes from phosphorus fires are highly irritating to lungs, skin, eyes. /Phosphorus, amorphous/
Fumes from phosphorus fires are highly irritating to lungs, skin, eyes. /Phosphorus, white, molten/
Fire Fighting Procedures
Flood with water to control flames, then smother with wet sand, clay, ground limestone. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. Where access to the area is strictly controlled, it may be best to allow the release to burn itself out. Fire situations may require evacuation. Fight fire from protected location or maximum possible distance. /Phosphorus, white, molten/
Flood with water to control flames, then smother with wet sand, clay, ground limestone. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. /Phosphorus, amorphous/
Storage Conditions
Separate from air, oxidizing materials, combustibles. Always keep container closed, with material under water or inert gas. /Phosphorus, white, molten/
Store in a cool, dry, well-ventilated location. Separate from oxidizing materials. Always keep container closed. /Phosphorus, amorphous/
Nonfire Spill Response
Caution : Flammable solid. Avoid sources of extreme heat or ignition including sparks or fire. White (or yellow) phosphorus may spontaneously ignite on contact with damp surfaces, including water or skin. Phosphorus will liberate toxic gases and vapors when heated.
Excerpt from ERG Guide 133 [Flammable Solids]:
Disposal Methods
Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number D003, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.
Phosphorus (white or yellow) is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration.
Cover with wet sand, shovel into bucket and remove to safe, open, isolated area where the phosphorus can be burnt off under supervision after drying out. Small spillages of phosphorus can be burnt off in a fume cupboard. Recommendable methods: Incineration & open burning. Not recommendable method: Landfill. Peer-review: Spontaneously flammable if dry. Mix with wet earth, allow to dry, ignite at a remote place. (Peer-review conclusions of an IRPTC expert consultation (May 1985))
White and yellow phosphorus is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration. Controlled incineration followed by alkaline scrubbing and particulate removal equipment.
Preventive Measures
SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.
White: Caution: handle with forceps.
SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.
The worker should immediately wash the skin when it becomes contaminated.
For more Preventive Measures (Complete) data for PHOSPHORUS, ELEMENTAL (6 total), please visit the HSDB record page.
Isolation and Evacuation
Excerpt from ERG Guide 133 [Flammable Solids]:
Excerpt from ERG Guide 133 [Flammable Solids]:
독성 정보
Interactions
... Liquid petrolatum is said to retard absorption and decrease phosphorus toxicity.
It has been demonstrated that intragastric administration of cysteine hydrochloride in a dose of 50 mg/kg and sodium sulfate in a dose of 25 mg/kg with reference to sulfate ion reduced the circulatory disturbances, dystrophic and sclerotic changes in the rat liver caused by intragastric administration of yellow phosphorus at a dose of 1 mg/kg. Admin of the drugs interfered with the development of liver cirrhosis, stimulated regeneration, and raised the adaptive abilities of hepatocytes. Cysteine protected hepatocyte mitochondria from phosphorus and activated their function.
The interactive effects of copper sulfate associated with dermal absorption are equivocal. Information was located suggesting antagonistic effects of copper sulfate solutions in water, glycerol, and oil with respect to phosphorus absorption. Emulsions of 3% copper sulfate (with 1% hydroxyethyl cellulose, 5% sodium bicarbonate, and 1% lauryl sulfate) applied to white phosphorus burns also appeared to demonstrate an antagonistic interaction in one study by preventing white phosphorus-induced death in rats. However, the same emulsion solution had no beneficial effect in a later repeat of the experiment. The mechanism by which copper sulfate theoretically impedes dermal absorption of phosphorus following white phosphorus burn is the formation of a copper-phosphorus complex (Cu3P2) that will not be absorbed, is unstable and may decompose to ionic copper and phosphate when in contact with oxygen in the air
A safer and potentially more reliable antagonist to white phosphorus dermal absorption is a solution of silver nitrate (AgNO3). The mechanism is not known with certainty but is hypothesized to be formation of Ag3P, the toxic properties of which are not reported.
For more Interactions (Complete) data for PHOSPHORUS, ELEMENTAL (9 total), please visit the HSDB record page.
Target Organs
Cardiovascular (Heart and Blood Vessels), Gastrointestinal (Stomach and Intestines, part of the digestive system), Gastrointestinal (Stomach and Intestines, part of the digestive system), Hepatic (Liver), Renal (Urinary System or Kidneys), Respiratory (From the Nose to the Lungs)
Dermal
Health Effects
Exposure to white phosphorus may cause liver, heart, or kidney damage. It can also result in death. Breathing white phosphorus for long periods may cause a condition known as 'phossy jaw', which involves poor wound healing of the mouth and breakdown of the jaw bone. Anemia and leukopenia in people chronically exposed to airborne white phosphorus. (L88)
Exposure Routes
White phosphorus absorbs into the body when inhaled, ingested, or through skin contact. It is unknown whether systemic exposure can occur from eye contact.
Inhalation; dermal; ingestion. (L88)
Toxicity Summary
Exposure to white phosphorus has been shown to damage the rough endoplasmic reticulum and cause a disaggregation of polyribosomes. This damage results in impairment of protein synthesis, in particular, a decrease in the synthesis of the apolipoprotein portion of very low density lipoproteins (VLDL), which are required for the transport of triglycerides. This causes an accumulation of triglycerides in the liver, resulting in steatosis and fibrosis. White phosphorus also damages the mitochondia, impairing a cell’s ability to produce ATP and resulting in necrosis. The mitochondrial damage may also inhibit fatty acid oxidation, which could result in an accumulation of fat in the organs. (L88)
Ecotoxicity Excerpts
/BIRDS and MAMMALS/ ... This study reports on the effects of white phosphorus on reproductive function in the mallard (Anas platyrhynchos) in captivity. Fertility, hatching success, teratogenicity, and egg laying frequency were examined in 70 adult female mallards who received up to seven daily doses of 0, 0.5, 1.0, and 2.0 mg/kg of white phosphorus. Measurements of fertility and hatchability were reduced by the white phosphorus. Teratogenic effects were observed in embryos from hens dosed at all treatment levels. Egg laying frequency was reduced even at the lowest treatment level; treated hens required a greater number of days to lay a clutch of 12 eggs than control hens. After two doses at 2.0 mg/kg, all females stopped laying completely for a minimum of 10 days, and laying frequency was depressed for at least 45 days. Fertility of 10 adult male mallards dosed with 1.0 mg/kg of white phosphorus did not differ from 10 controls, but plasma testosterone levels were significantly (p< 0.05) reduced in the treated males 1 day after dosing ended. These results provide evidence that productivity of free-ranging mallards may be impaired if they are exposed to white phosphorus at typical field levels.
/AQUATIC SPECIES/ Half the crustacean population died after 4.5 days exposure to water containing 20 mg phosphorus/L. Elemental phosphorus at 5-15 mg/L water disrupted feeding, reproduction, and body color among Daphnia magna Straus populations.
/FIELD STUDIES/ Extensive waterfowl mortality involving thousands of ducks, geese, and swans has occurred annually at Eagle River Flats, Alaska, USA, since at least 1982. The primary agent for this mortality has been identified as white phosphorus.
Signs and Symptoms
- White phosphorus fumes cause severe irritation and the sensation of a foreign body in the eye. This leads to excessive tear production (lacrimation), spasmodic blinking (blepharospasm), and increased sensitivity to light (photophobia).
- Stage 1:- Feeling of warmth or burning pain in the throat and abdomen accompanied by feelings of intense thirst;
- Expect eye and upper respiratory tract irritation.
- White phosphorus causes severely painful, partial (second degree) to full thickness (third degree) burns, which have a characteristic yellow color and garlic-like odor. Smoke may release from the burn site from the continued burning of white phosphorus or the formation of phosphoric acid.
Breathing white phosphorus for short periods may cause coughing and irritation of the throat and lungs. Eating or drinking small amounts of white phosphorus may cause stomach cramps, or drowsiness. (L88)
EPA IRIS Information
White phosphorus
Dermal
2 x 10 ^-5 mg/kg-day
Medical Surveillance
Indicators of occupational exposure to phosphorus include depressed erythrocyte concn, elevated monocyte concn and elevated phospholipid concn in blood.
... Employment medical examination should include X-ray studies of the teeth and jaw ... . Routine dental examination should be made monthly if exposure is high or prolonged.
TSCA Test Submissions
In a one-generation reproduction study, male and female Sprague Dawley rats (15 males and 30 females/group) were orally exposed by gavage to elemental yellow phosphorus in corn oil vehicle at dose levels of 0, 0.005, 0.015 or 0.075 mg/kg/day for 80 days prior to mating (2 females/male), and continued throughout mating, gestation and lactation periods. Due to low fertility in the first litter, the study was extended to 2 litters and dosing continued throughout the entire study. All pups were sacrificed at weaning and parental animals were sacrificed after weaning of the F1b litter. There were significant differences between treated and control animals in the following: decreased F0 male body weights (high-dose group, after 15 weeks of the study). There were no significant differences between treated and control animals in the following: parental mortality, food consumption, fertility indices, mean length of gestation, numbers of viable pups and pup survival, pup body weights, and gross or microscopic examinations at necropsy.
규제 정보
TSCA Requirements
Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. Phosphorus is included on this list.
Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, use, and exposure to EPA as cited in the preamble in 51 FR 41329. /White phosphorus (12185-10-3)/
FIFRA Requirements
As the federal pesticide law FIFRA directs, EPA is conducting a comprehensive review of older pesticides to consider their health and environmental effects and make decisions about their future use. Under this pesticide reregistration program, EPA examines health and safety data for pesticide active ingredients initially registered before November 1, 1984, and determines whether they are eligible for reregistration. In addition, all pesticides must meet the new safety standard of the Food Quality Protection Act of 1996. Pesticides for which EPA had not issued Registration Standards prior to the effective date of FIFRA, as amended in 1988, were divided into three lists based upon their potential for human exposure and other factors, with List B containing pesticides of greater concern and List D pesticides of less concern. Phosphorus is found on List C. Case No: 3111; Case Status: No products containing the pesticide are actively registered ... The case /is characterized/ as "cancelled." Under FIFRA, pesticide producers may voluntarily cancel their registered products. EPA also may cancel pesticide registrations if registrants fail to pay required fees or make/meet certain reregistration commitments, or if EPA reaches findings of unreasonable adverse effects.; Active ingredient (AI): phosphorus; AI Status: The active ingredient is no longer contained in any registered pesticide products ... "cancelled."
Atmospheric Standards
Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. Phosphorus is included on this list.
CERCLA Reportable Quantities
Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 1 lb or 0.454 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).
Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Phosphorus is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 100 lbs.
Clean Water Act Requirements
Phosphorus is designated as a hazardous substance under section 311(b)(2)(A) of the Federal Water Pollution Control Act and further regulated by the Clean Water Act Amendments of 1977 and 1978. These regulations apply to discharges of this substance. This designation includes any isomers and hydrates, as well as any solutions and mixtures containing this substance.
DHS Chemicals of Interest (COI)
Phosphorus
A Commercial Grade
400
Explosive/Improvised Explosive Device Precursor material that, if stolen or diverted, can be converted into weapons using simple chemistry, equipment, or techniques.
안전 데이터
- OEB
- D
- OEL
- TWA: 0.1 mg/m3
- wgk
- 2
- IDLA
- 5 mg/m3
- tsca
- TSCA listed
- rtecs
- TH3495000
- ridadr
- UN 1338
- 독성
- LD50 oral (rat) 3 mg/kg PEL (OSHA) 0.1 mg/m3 TLV-TWA (ACGIH) 0.02 ppm (0.1 mg/m3)
- HS 번호
- 28047000
- risk_code
- 11-16-52/53-50-35-26/28-17
- hazard_code
- F,N,C,T+
- safety_code
- 7-43-61-43C-45-38-26-5-27-6
- 포장분류
- III
- 위험 등급
- 4.1
- 기존화학 물질
- KE-28713
- F 고인화성물질
- 10-21
- 자연 발화 온도
- White phosphorus: 29 °C Red phosphorus: 260 °C
- Hazard Classifications
- Aquatic Chronic 3Flam. Sol. 2
- 스토리지 클래스
- 4.1B - Flammable solid hazardous materials
- 유해 물질 데이터
- 7723-14-0(Hazardous Substances Data)
화학 및 산업
약리 정보
Mechanism of Action
Phosphorus apparently decreases the absorption of intercellular calcified cartilage matrix by osteoclasts, in the metaphyseal region of growing bones. Administration of phosphorus to growing animals or children produces "phosphorus bands" of increased bone density and thickness that are visible grossly or from radiograms. The "phosphorus bands" are observed in the metaphyseal region of growing bones, and represent areas of decreased absorption of the calcified cartilage matrix.
Exposure to white phosphorus has been shown to damage the rough endoplasmic reticulum and cause a disaggregation of polyribosomes. This damage results in impairment of protein synthesis, in particular, a decrease in the synthesis of the apolipoprotein portion of very low density lipoproteins (VLDL), which are required for the transport of triglycerides. A significant decrease in protein synthesis has been detected as early as 3 hours after oral exposure. The smooth endoplasmic reticulum is also involved in the formation of the VLDLs, and damage to the smooth endoplasmic reticulum also impairs the formation of VLDLs. The net result of these ultrastructural changes is an accumulation of triglycerides in the liver. This results in steatosis and fibrosis, which is one of the mechanisms involved in the hepatotoxicity of white phosphorus. The mechanism behind the damage to the endoplasmic reticulum is not known; also, it is not known whether white phosphorus itself or a metabolite of white phosphorus is the damaging agent. In addition to these damages, white phosphorus or a metabolite causes damage to the mitochondria and nuclei in the livers of animals orally exposed to white phosphorus. The damage to the mitochondria may impair the cell's ability to produce ATP, thus resulting in necrosis of the cell. Fatty infiltration and/or cellular damage has also been observed in the kidney, brain, and heart. It is possible that white phosphorus (or a metabolite) also impairs the ability of cells in these organs to produce ATP. The mitochondrial damage may also inhibit fatty acid oxidation (also contributing to the decreased availability of ATP) which could result in an accumulation of fat in the organs.
Metabolism/Metabolites
Some phosporus is thought to be slowly oxidized to harmless acids, which are gradually excreted by kidneys.
In the body, phosphorus is converted to phosphates.
... It appears that it is metabolized to hypophosphoric acid via oxidation.
...Urinary metabolites of 32P-labeled white phosphorus /were qualitatively studied/ in rats. ...Thin-layer chromatography (TLC) /was used/ at 4 and 24 hours after a single oral dose to show that radioactive urinary metabolites consisted of two classes of compounds. One of the compounds corresponded to inorganic phosphate, the other compound was less polar and suggested an organic phosphate, although the composition of this class of metabolites was not determined. TLC analysis of liver extract also showed two classes of compounds with similar properties.
Since phosphate is a metabolite of the breakdown of white phosphorus and since phosphate is incorporated into a variety of organic molecules, these biomolecules may be considered molecular successors (or secondary metabolites of white phosphorus) and may provide information regarding the fate of white phosphorus after absorption. ...The effect of acute oral administration of white phosphorus /was studied/ in male Wistar rats on hepatic microsomal glucose-6-phosphatase activity. The activity was reported as milligram inorganic phosphate split from glucose-6-phosphate in 20 minutes per equivalent gram of microsomes. Glucose-6-phosphatase activity was significantly increased by 29% (p<0.025; n=6) and 39% (p<0.01%; n=6) over control values at 12 and 24 hours post-dosing, respectively. Activity was not significantly different from controls at 4 hours post-dosing (p value not reported; n=6).
Since white phosphorus is highly reactive in the presence of oxygen, it is likely rapidly converted to its oxidation products prior to absorption into the body. Little is known about the metabolism of white phosphorus in the body, although the oxo acids of phophorus are known to be found in the bloodstream.
Absorption, Distribution and Excretion
Phosphorus (white-yellow) can be absorbed through skin, by ingestion, and through respiratory tract ... . Phosphorus is excreted chiefly in urine in combined forms, such as phosphates. ... In phosphorus poisoning, insignificant amounts of phosphorus may be excreted in exhaled breath ... in sweat. Elemental phosphorus may be found in breath, blood, and feces, but not in urine.
Elemental yellow phosphorus is well absorbed from the skin and gastrointestinal tract ... . The lung and gut excrete yellow phosphorus, but little elimination occurs via the kidneys. Red phosphorus is practically unabsorbable.
Unreacted elementary phosphorus may be demonstrated in the tissues of people who die several days after ingesting phosphorus but not in those who die after longer periods.
Red phosphorus is nonvolatile, insoluble, not absorbed through the gastrointestinal tract, and, therefore, relatively harmless when ingested.
For more Absorption, Distribution and Excretion (Complete) data for PHOSPHORUS, ELEMENTAL (6 total), please visit the HSDB record page.
용도 및 제조
Uses
Most phosphorus is used in the production of phosphoric acid and phosphates, which are used in the fertilizers industry.
The active ingredient is no longer contained in any registered pesticide products ... "cancelled."
For phosphorus (USEPA/OPP Pesticide Code: 66502) there are 0 labels match. /SRP: Not registered for current use in the U.S., but approved pesticide uses may change periodically and so federal, state and local authorities must be consulted for currently approved uses./
White phosphorus has been used as insecticide in pastes made by grinding yellow phosphorus in presence of water and mixing with flour. Phosphorus paste was used to control American cockroach, also as rat poison.
Most (85%) of the elemental phosphorus is converted to phosphoric acid which is used directly or converted to phosphate compounds. Final applications include home laundry and automatic dishwasher detergents, industrial and institutional cleaners, food and beverages, metal cleaning and treatment, potable water and wastewater treatment, antifreeze and electronics. The remaining elemental phosphorus (15%) is used in P4-dependent applications which require the element as a direct reactant (P2S5, PCl3, POCl3, P2O5, and hypophosphite with smaller amounts leading to PH3, red phosphorus, phosphonates and other derivatives). Final applications include flame retardants, lubricant additives, insecticides, herbicides, water treatment, cleaning compounds, plasticizers, semiconductors, and surfactants.
For more Uses (Complete) data for PHOSPHORUS, ELEMENTAL (9 total), please visit the HSDB record page.
Impurities
Typical manufacturers' analysis for a straw yellow product: arsenic, 30-250 ppm; toluene insolubles, 0.01 - 0.05 wt %; oils (hydrocarbons), 30-100 ppm as carbon.
...White phosphorus contains boron, silicon, calcium, aluminum, iron, and arsenic in excess of 10 ppm as impurities... .
Because white phosphorus oxidizes rapidly, phosphorus fumes/vapors may contain phosphoric oxide and phosphorus oxide, in addition to phosphorus.
U.S. Exports
(1968) 1.55X10+10 G EXPORTED TO MEXICO
(1975) 3.27X10+10 G
(1984) 1.49X10+10 G.
1993: roughly 20,000 tons (elemental phosphorus and purified wet- acid on a phosphorus-equivalent basis)
U.S. Imports
(1968) 3.80X10+8 G ELEMENTAL PHOSPHORUS
(1975) 9.08X10+8 G
(1984) 2.12X10+9 G.
1993: 5,000 to 10,000 tons (elemental phosphorus and purified wet-acid on a phosphorus-equivalent basis)
U.S. Production
2023: 100,000,000 - <500,000,000 lb
(1968) 5.52X10+11 G ELEMENTAL PHOSPHORUS
(1975) 4.09X10+11 G
(1984) 3.50X10+11 g
(1989) 365,000 tons /Elemental, white (yellow), and red/
For more U.S. Production (Complete) data for PHOSPHORUS, ELEMENTAL (6 total), please visit the HSDB record page.
Consumption Patterns
77% IS USED IN THE PRODUCTION OF PHOSPHORIC ACID; 2% IS USED TO PRODUCE PHOSPHORUS TRICHLORIDE (FOR ORGANIC PHOSPHATES, PLASTICIZERS, GASOLINE & OIL ADDITIVES, FLOTATION AGENTS, FLAME RETARDANTS, & INSECTICIDES); 2% TO PRODUCE PHOSPHORUS PENTASULFIDE (FOR PHOSPHATE PESTICIDES, LUBRICATING OIL ADDITIVES, & FLOTATION AGENTS); 19% IN MISC APPLICATIONS (1968)
END USE PATTERN DERIVATIVE: PHOSPHORIC ACID, 85%; PHOSPHORUS PENTASULFIDE, 5%; PHOSPHORUS TRICHLORIDE, 5%; MISC, 5% (1984-ESTIMATE)
CHEMICAL PROFILE: Phosphorus. Thermal phosphoric acid, 82%; (sodium phosphates, 70%; direct phosphoric acid sales, 20%; calcium ammonium and potassium phosphates, 10%); direct reaction chemical production, including phosphorus trichloride, pentasulfide and pentoxide, 12%; exports, 6%.
CHEMICAL PROFILE: Phosphorus. Demand: 1987: 340,000 tons; 1988: 330,000 tons; 1992 /projected/: 310,000 tons (Includes exports; in addition, between 4,000 and 5,000 tons were imported in 1987, mostly from Canada).
Thermal phosphoric acid, 85% (sodium phosphates, 55%; direct phosphoric acid sales, 25%; calcium, ammonium and potassium phosphates, 20%); direct reaction chemical production, including phosphorus trichloride, pentasulfide and pentoxide, 15%.
Methods of Manufacturing
White phosphorus: (1) Produced in an electric furnace from phosphate rock, sand, and coke. The phosphorus vapor is driven off and condensed under water. (2) By reaction of phosphate rock with sulfuric acid, the resulting calcium sulfate being removed by filtration and the phosphoric acid concentrated by evaporation (wet process).
Red phosphorus is produced by heating white crystalline phosphorus to about 400 °C under an atmosphere of an oxygen-free inert gas, such as nitrogen or argon.
Black phosphorus: Produced from the white modification under high pressures.
Formulations/Preparations
Technical 99.9%; electronic grade 99.9999%
WHITE OR YELLOW IS THE SIGNIFICANT COMMERCIAL FORM OF ELEMENTAL PHOSPHORUS WITH A 99.8% MINIMUM PURITY.
응용 분야
용도성냥·연화(煙火) 등의 제조원료가 되는 외에 인화합물의 합성원료가 된다.
개요White or yellow white phosphorus is a yellow waxy or colourless, transparent, volatile crystalline solid, waxy appearance with a garlic-like odour. On exposure to light, it darkens and ignites in air. It is also called yellow phosphorus colour because of impurities. White phosphorus does not occur naturally but is manufactured from phosphate rocks. It is insoluble in water, slightly soluble in benzene, ethanol, and chloroform, and is soluble in carbon disulphide. White phosphorus reacts rapidly with oxygen, easily catching fire at temperatures 10°C–15°C above room temperature. White phosphorus is used by the military in various types of ammunition and to produce smoke for concealing troop movements and identifying targets. It is also used by industry to produce phosphoric acid and other chemicals for use in fertilisers, food additives, and cleaning compounds. Small amounts of white phosphorus were used in the past in pesticides and fireworks.White phosphorus is used mainly for producing phosphoric acid and other chemicals. These chemicals are used to make fertilisers, additives in foods and drinks, cleaning compounds, and other products. In the military, white phosphorus is used in ammunitions such as mortar and artillery shells, and grenades.
출처Phosphorus is the 12th most abundant element. It makes up about 0.1% of the Earth’s crust.Phosphorous occurs in nature in several forms, mostly as phosphates. The most commonsource is phosphate rock [Ca3(PO4)2] and a mineral called “apatite.” Phosphorus is found inall animal bones and teeth and in most living tissue. Phosphorous nodules are found on theocean floor along with manganese nodules.Most commercial phosphorus is produced in electric furnaces where the phosphate-richminerals are heated to drive off the phosphorus as a gas, which is then condensed under water.Another process uses sulfuric acid to remove the phosphorus.
용도It is used to make safety matches, incendiary shells,andsmokebombs;inpyrotechnics;and in the manufacture of fertilizers, pesticides, phosphoric acid, and phosphorus halides.
일반 설명A white or yellow colored semi-liquid. Transported at high temperatures. Insoluble in water and denser than water. Contact may cause burns to skin, eyes, and mucous membranes. May be toxic by ingestion, inhalation and skin absorption. May ignite upon exposure to air. Used to make other chemicals.
상·하류 제품 정보
상류 원료
하류 제품
공급사50 곳
추가 설명
정의phosphorus: Symbol P. A nonmetallicelement belonging togroup 15 (formerly VB) of the periodictable; a.n. 15; r.a.m. 30.9738; r.d.1.82 (white), 2.34 (red); m.p. 44.1°C(α-white); b.p. 280°C (α-white). It occursin various phosphate rocks,from which it is extracted by heatingwith carbon (coke) and silicon(IV)oxide in an electric furnace (1500°C).Calcium silicate and carbon monoxideare also produced. Phosphorushas a number of allotropic forms.The α-white form consists of P4 tetrahedra(there is also a β-white formstable below –77°C). If α-white phosphorusis dissolved in lead andheated at 500°C a violet form is obtained.Red phosphorus, which is acombination of violet and whitephosphorus, is obtained by heatingα-white phosphorus at 250°C with airexcluded. There is also a black allotrope,which has a graphite-likestructure, made by heating whitephosphorus at 300°C with a mercurycatalyst. The element is highly reactive.It forms metal phosphides andcovalently bonded phosphorus(III)and phosphorus(V) compounds. Phosphorusis an essential element forliving organisms. It is an importantconstituent of tissues (especiallybones and teeth) and of cells, beingrequired for the formation of nucleic acids and energy-carrying molecules(e.g. ATP) and also involved in variousmetabolic reactions. The elementwas discovered by Hennig Brand(c. 1630–92) in 1669.
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