포스핀(기체)

Phosphine

HCID 24404CAS 13967-14-1

기본 정보

표준 SMILES
P
InChIKey
XYFCBTPGUUZFHI-UHFFFAOYSA-N
분자식
H3P
평균 분자량
33.998 g/mol
단동위원소 질량
33.99723673

개요

Phosphine is a colorless, flammable, and explosive gas at ambient temperature that has the odor of garlic or decaying fish. Small amounts occur naturally from the break down of organic matter. It is slightly soluble in water. Phosphine is used in semiconductor and plastics industries, in the production of a flame retardant, and as a pesticide in stored grain.

이름 및 식별자

우선 이름
Phosphine
IUPAC
phosphane
현지명
포스핀(기체)
영어명
Phosphine
분자식
H3P
분자량
34

이름 및 동의어

PHOSPHINEphosphaneHydrogen phosphidePhosphorus trihydride7803-51-2Phosphorus hydridePhosphorwasserstoffFosforowodorGas-Ex-BRCRA waste number P096Phosphoretted hydrogentrihydridophosphorus
이름 더 보기
포스핀포스핀(기체)포스파인인화수소PH3PHOSPHINE LIGANDPhospheneFosfanoFosfinaphosphine00
VAPORPHOSDTXSID2021157TK-GASPHOSPHINE (PH3)FW6947296ICHEBI:30278Phosphorated hydrogenRefChem:6131

데이터베이스 식별자

CAS
13967-14-1、29724-05-8、7803-51-2
PubChem CID
24404
DTXSID
DTXSID2021157
ChEMBL
CHEMBL2227836
ChEBI
CHEBI:30278
UNII
FW6947296I
EC Number
232-260-8
Nikkaji
J3.761C、J43.585F

물성

구조 계산 물성

XLogP
-0.1
극성 표면적
0 Ų
수소 결합 공여자 수
0
수소 결합 수용자 수
0
회전 가능 결합 수
0
무거운 원자 수
1

실험 및 물리화학적 성질

Chemical Classes · 4건

Hazardous Air Pollutants (HAPs)

Toxic Gases & Vapors -> Hydrides

Flammable agents - 4th degree

-> NIOSH Emergency Response Categories

pHSOLN ARE NEUTRAL
SpringerMaterials PropertiesCoriolis coupling
Pesticides · 3건

Pesticide -> EPA IRIS

Insecticides

Active substance -> EU Pesticides database: Approved

Odor · 4건

Disagreeable, garlic-like odor.

Almost odorless in purest form, but odor of decaying fish when occurring industrially.

Foul odor of decaying fish

Fish- or garlic-like odor [Note: Pure compound is odorless].

Density · 6건

0.746 at -130 °F (EPA, 1998) - Less dense than water; will float

1.390 g/L at 25 °C

Density: 1.529 g/L at 0 °C

Density (gas): 1.53 kg/m³

Relative density (water = 1): 0.8

0.746 at -130 °F

물리화학적 성질

녹는점
-133 ° · -133°
끓는 점
87.5 °C · −87.5 °C(lit.)
밀도
0.491 · 0.491 (estimate)
증기 밀도
1.15 · 1.15 (vs air)
증기압
3905 kPa · 3905kPa at 25℃
용해도
2 O; · insoluble in H2O; slightly soluble in ethanol, ethyl ether
화학적 성질 · 1건

Phosphine is a pyrophoric chemical and spontaneously flammable in air. It is incompatible with strong oxidising agents, halogens, nitric acid. It has the odour of garlic or decaying fish. It is slightly soluble in water. It is flammable and is an explosive gas at ambient temperature. Phosphine decomposes on heating or on burning producing toxic fumes including phosphorus oxides. It reacts violently with air, oxygen, oxidants such as chlorine and nitrogen oxides, metal nitrates, halogens, and other toxic substances, and causes fire and explosion hazard.

안전 및 규제

GHS 분류

GHS Classification · 6건

Danger

H220: Extremely flammable gas [Danger Flammable gases]

P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

Danger

H220 (100%): Extremely flammable gas [Danger Flammable gases]

P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, P410+P403, and P501 (click each P-code to see the statement)

유해성 정보

Hazards IdentificationToxic/poison by inhalation (TIH/PIH)
Regulatory Information · 6건

Chemical: Phosphine

Hazard Traits - Hematotoxicity; Hepatotoxicity and Digestive System Toxicity; Nephrotoxicity and Other Toxicity to the Urinary System; Neurotoxicity; Respiratory Toxicity

Council Directive (EEC) No 414/1991 (Repealed by Reg. EC No 1107/2009 (amended))

Phosphine is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Phosphine 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)

Dossier complete 08/566/EC, Reg. (EU) 2018/155, Reg. (EU) 2024/324, Reg. (EU) No 1043/2012, Reg. (EU) No 2023/114

Status: Active Update: 20-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/18616

Other Safety Information · 2건

IMAP assessments - Phosphine: Environment tier I assessment

- Indoor Air: Phosphine can be released into indoor air as a gas.

DOT LabelPoison Gas Flammable Gas
Fire Hazards · 3건

Phosphine can explode with powerful oxidizers. The gas is heavier than air and may travel along the ground to an ignition source. Container may explode in heat of fire. When heated to decomposition, it emits highly toxic fumes of phosphorus oxides. Reacts violently with: air; boron trichloride; bromine; chlorine; chlorine monoxide; nitric acid; nitric oxide; nitrous oxide; nitrogen trioxide; silver nitrate; nitrous acid; mercuric nitrate; nitrogen trichloride; oxygen; and (potassium plus ammonia). Stable up to 131F. May become unstable at high temperatures. (EPA, 1998)

· Flammable; may be ignited by heat, sparks or flames.

Extremely flammable. May ignite spontaneously on contact with air. Gives off irritating or toxic fumes (or gases) in a fire. Gas/air mixtures are explosive.

Fire Potential · 5건

Very dangerous fire hazard by spontaneous chemical reaction.

Moderately explosive when exposed to flame.

Pure phosphine does not spontaneously ignite in air below 150 °C unless it is thoroughly dried, when it ignites in cold air. The presence of traces (0.2%) of diphosphane in phosphine as normally prepared causes it to ignite spontaneously in air, even at below -15 °C ... Traces of oxidants promote pyrophoricity.

Spontaneously flammable in air if there is trace of /diphosphane/ present; burns with luminous flame.

Flammable gas. Pyrophoric; may ignite spontaneously in air or accumulate and explode in air without source of ignition.

안전 및 보호

Fire Fighting · 3건

Wear full protective clothing including self-contained breathing apparatus, rubber gloves, boots, and bands around legs, arms, and waist. No skin surface should be exposed. For massive fires in cargo areas, use unmanned hose holders or monitor nozzles. Move containers from fire area.

Shut off supply; if not possible and no risk to surroundings, let the fire burn itself out. In other cases extinguish with powder, carbon dioxide. In case of fire: keep cylinder cool by spraying with water. Combat fire from a sheltered position.

- Phosphine is extremely flammable and explosive.

First Aid Measures · 3건

Fresh air, rest. Half-upright position. Administration of oxygen may be needed. Artificial respiration may be needed. Refer immediately for medical attention.

ON FROSTBITE: rinse with plenty of water, do NOT remove clothes. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Accidental Release Measures · 2건

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area.

First Aid · 3건

Warning: Effects may be delayed for several hours. Caution is advised.

General First Aid:

(General first aid procedures)

Safe StorageFireproof. Keep in a well-ventilated room.
Firefighting HazardsEvolves hydrogen and ignites on contact with many materials. Vapors are heavier than air and may travel to a source of ignition and flash back. Closed containers may rupture violently when heated.

독성 정보

TreatmentAs there is no antidote for phosphine poisoning, treatment is mainly symptomatic. Artificial respiration, gastric lavage, and/or administration of activated charcoal may be necessary. (L982)
Target Organsrespiratory system
Health Effects · 1건

Inhalation of phosphine may cause severe pulmonary irritation leading to acute pulmonary oedema, cardiovascular dysfunction, CNS excitation, coma and death. Gastrointestinal disorders, renal damage and leukopenia may also occur. Chronic exposure to phosphine can result in anemia, bronchitis, gastrointestinal effects, and visual, speech and motor problems. (L980, L982)

Environmental Fate · 4건

TERRESTRIAL FATE: Phosphine is a gas(1) and, therefore, is expected to dissipate rapidly from both moist and dry soil(SRC). Studies have shown that sub-surface phosphine may bind to soil(2-3).

TERRESTRIAL FATE: The sorption and desorption of phosphine from wheat treated with a concentration of 0.5-5 mg/kg wheat were determined at 25, 45, and 85 °C. The desorbed phosphine was extracted from the air by passing through a cold trap. Most of the phosphine was desorbed in the first 2-3 days but small amounts continued to desorb for many weeks following treatment. After 220 days of aeration, phosphine was still present and desorbing. Even when the temp was increased to 85 °C for several days, unreacted phosphine still desorbed slowly from wheat. Corn aerated 26 days desorbed 0.004 ng/g in 2 days.

AQUATIC FATE: Phosphine is a gas and, therefore, is expected to dissipate rapidly from water surfaces(1). Biodegradation, hydrolysis and bioconcentration are not expected to be important fate processes when compared to dissipation(SRC).

ATMOSPHERIC FATE: Phosphine is a gas at ambient temperature(1). Gas-phase phosphine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals and has a reported atmospheric half-life of 5 hours(2).

Adverse EffectsNeurotoxin - Other CNS neurotoxin
Exposure Routes · 4건

The substance can be absorbed into the body by inhalation.

inhalation, skin and/or eye contact (liquid)

Phosphine can be absorbed into the body by inhalation. Direct contact with phosphine liquid may cause frostbite.

Oral (L1645) ; inhalation (L1645) ; dermal (L1645)

규제 정보

RCRA Requirements · 1건

P096; As stipulated in 40 CFR 261.33, when phosphine, as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to federal and/or state hazardous waste regulations. Also defined as a hazardous waste is any container or inner liner used to hold this waste or any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5(e)).

FIFRA Requirements · 5건

Tolerances are established for residues of phosphine in or on the following raw agricultural commodities (RACs) resulting from post-harvest fumigation for the control of insects with phosphine gas or phosphide compounds that produce phosphine gas.[Table#3029]

Tolerances are established for residues of the fumigant in or on all RACs resulting from preharvest treatment of pest burrows in agricultural and non-crop land areas.[Table#3030]

Residues resulting from fumigation of processed food:[Table#3031]

Residues resulting from fumigation of animal feed:[Table#3032]

For more FIFRA Requirements (Complete) data for Phosphine (6 total), please visit the HSDB record page.

Atmospheric Standards · 1건

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. Phosphine is included on this list.

CERCLA Reportable Quantities · 2건

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 100 lb or 45.4 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. Phosphine is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.

DHS Chemicals of Interest (COI) · 6건

Phosphine

1

10000

0.67

15

Flammable chemical that can be released at a facility.

State Drinking Water Guidelines(FL) FLORIDA 125 ug/L

안전 데이터

OEB
C
OEL
TWA: 0.3 ppm (0.4 mg/m3), STEL: 1 ppm (1 mg/m3)
wgk
2
IDLA
50 ppm
tsca
TSCA listed
rtecs
SY7525000

화학 및 산업

약리 정보

Mechanism of Action · 1건

... Phosphine-induced hemoglobin denaturation, oxidation to methemoglobin, and formation of a peculiar pigmented form of hemoglobin "Verdichromogen" /was described/. Studies of purified hemoglobin ... showed that with incr duration of exposure, phosphine in concn as low as 0.11 uM gradually resulted in the formation of hemichrome pigment. In intact red blood cells ... formation of Heinz bodies (hemoglobin protein aggregates) /was noted/ at PH3 concn as low as 2 ug/mL. The toxicant effects both in intact cells and in purified hemoglobin were abolished by incubation in a reduced oxygen atmosphere, indicating an oxygen requirement for phosphine hemoglobin toxicity.

Metabolism/Metabolites · 3건

... Absorbed phosphine is rapidly metabolized into phosphite and hypophosphite. ...

Metal phosphides are hydrolysed to phosphine and the corresponding metal cation. In rats, phosphine that is not excreted in the expired air is oxidized and appears in the urine, chiefly as hypophosphite and phosphite.

Phosphine and metal phosphides may be absorbed following ingestion or inhalation, then distribute to the nervous system, liver, and kidney. In the body, metal phosphides are hydrolysed to phosphine, and phosphine is oxidized to hypophosphite and phosphite. Metabolites are excreted in the urine, while unchanged phosphine is exhaled. (L982)

MeSH Pharmacological ClassificationPesticides designed to control insects that are harmful to man. The insects may be directly harmful, as those acting as disease vectors, or indirectly harmful, as destroyers of crops, food products, or textile fabrics.
Absorption, Distribution and Excretion · 1건

Studies with (32)P-phosphine showed that residues did remain in grain after proper ventilation ... Residues were ... incorporated into the tissues of mice that ate fumigated flour. The excreta were highly radioactive at first, but activity disappeared about 3 weeks after feeding was stopped.

용도 및 제조

Uses · 6건

Phosphine is used as an insecticide for the fumigation of grains, animal feed, and leaf-stored tobacco, and as a rodenticide. Phosphine is also used as an intermediate in the synthesis of flame retardants for cotton fabrics, as a doping agent for n-type semiconductors, a polymerization initiator, and a condensation catalyst.

Phosphine is used as a fumigant and as a dopant in microelectronics manufacturing. Also, law enforcement officers dismantling methamphetamine production labs have died from inhalation of phosphine. Veterinarians were exposed to phosphine gas while treating animals that ingested phosphide salts. [ACGIH] Phosphine is produced by reacting water or acid with metallic phosphides. It may be formed during the production of acetylene gas. Phosphine is used in the semiconductor industry to introduce phosphorus into silicon crystals as an intentional impurity. It also is used as a fumigant and a polymerization initiator. [ATSDR Medical Management] If phosphoric acid is used as a catalyst, phosphine can be formed in the strongly reducing atmosphere of the hot emissions. In air, phosphine rapidly oxidizes to phosphorus oxide. [IARC 2012: Iron and steel founding]

Molding and Core Making [Category: Foundry]

Insecticides

For phosphine (USEPA/OPP Pesticide Code: 66500) ACTIVE products with label matches. /SRP: Registered for 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./

The end-use product is a poisonous liquefied gas under pressure, and is a Restricted Use Pesticide (RUP) due to the acute inhalation toxicity of phosphine gas.

ImpuritiesThe presence of traces (0.2%) of diphosphane in phosphine as normally prepared ...
U.S. Production · 3건

2023: <75,000 lb

Non-confidential 2012 Chemical Data Reporting (CDR) information on the production and use of chemicals manufactured or imported into the United States. Chemical: Phosphine. National Production Volume: 140,652 lb/yr.

Non-confidential 2016 Chemical Data Reporting (CDR) information on the production and use of chemicals manufactured or imported into the United States. Chemical: Phosphine:

Consumer UsesSemiconductor and photovoltaic agent
Industry UsesIntermediate
Methods of Manufacturing · 5건

Prepared from white phosphorus and aqueous alkali hydroxide; also by treatment of /phosphonium iodide with potassium hydroxide/ ... ; by pyrolysis of phosphorous acid ... ; by hydrolysis of metal phosphide such as calcium phosphide.

By action of freshly formed hydrogen or of caustic potash on phosphorus.

By reaction of certain metal phosphides with water; hydrolysis of phosphorus in a base such as sodium hydroxide or calcium hydroxide, Ca(OH)2 (hydrated lime); and reduction of red phosphorus in hot phosphoric acid solution.

... Common industrial methods are based on disproportionation reactions of elemental phosphorus catalyzed by alkalies or acids.

... Generated from aluminum phosphide and ammonium carbamate in the presence of moisture.

응용 분야 · 3건

개요Phosphine is a colorless, flammable gas that is heavier than air and has a characteristic odor described as being similar to decaying fish. Pure phosphine is claimed to be odorless, even at a level of 200 ppm. The odor threshold for commercially available phosphine ranges from 0.02 ppm to 3 ppm. It has an autoignition temperature of 100°F (37.8°C) and ignites spontaneously when traces of other phosphorous hydrides such as diphosphine are present. For all practical purposes, phosphine should be handled both as a pyrophoric and highly toxic gas. Phosphine is stable at room temperature and begins to decompose at about 707°F (375°C), with complete decomposition at about 1100°F (593°C). Phosphine is readily oxidized by common oxidizers such as potassium permanganate and sodium hypochlorite. Unlike arsine, it will have some reaction with the alkalis. Phosphine is a strong reducing agent and can precipitate a number of heavy metals from solutions of their salts. It will react violently with oxidizers such as oxygen, chlorine, fluorine, and nitric oxide. Phosphine is shipped in the pure form as a liquefied gas, and is also commonly available as a mixture when blended with hydrogen or inert gases.

출처Phosphine is produced naturally in small amounts in marshy lands, especially in damp graveyards, resulting from bacterial decay of animal and vegetable matter containing phosphorus. The atmospheric oxidation of impure phosphine (containing trace amounts of diphosphine, P2H4) emits pale flickering lights, the so-called “Will o’ the wisps” or “corpse candles” seen on dark nights. The compound has very little commercial application. It is used to prepare phosphonium salts, which also can be made by other processes.

용도Phosphine is the most widely used fumigant for insect con-trol in the durable commodities throughout the world. It is increasingly used as a treatment to re-place methyl bromide especially because of its low cost, fast dispersion in the air and low residues. Versatility of use is a major advantage for phosphine, as it can be used in a variety of storage buildings, during transit (e.g. in ship holds) or in plastic sheet enclosures. It is close to an ideal fumigant except for few drawbacks: slow activity, the rapid increase in insect resistance, flammability at higher concentrations (>900 ppm) and corrosion of copper, silver and gold. The phosphine resistance among the insect populations was found to be the result of selection pressure caused by inadequate fumigations in the storage units; storage facilities not adequately sealed before fumigation; and fumigant concentrations not being monitored. The understanding of phosphine resistance mechanism, improved monitoring tactics and management of resistance are the priorities in tackling the problem (Rajendran, 2001). The other problems like corrosion and flammability were found to be limited by using the combination of heat (30–36℃), carbon dioxide (3–7%) and phosphine at 80–100 ppm, while achieving a complete insect control.

제조 방법 · 1건

생산 방법Phosphine, also known as phosphorated hydrogen or hydrogen phosphide (PH3), has no direct commercial use. However, it may be generated from aluminum or zinc phosphide and water for grain fumigation. It may be present in phosphorus as a polymer or generated at low rates under alkaline conditions and at a temperature of 85C. The generation of acetylene from calcium carbide containing calcium phosphide as an impurity and metal processing procedures in which phosphides are formed are the most frequent sources of industrial hygiene problems with phosphine.

추가 설명

정의ChEBI: The simplest phosphine, consisting of a single phosphorus atom with three hydrogens attached.

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