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Phosphine

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Name

Phosphine

EINECS 232-260-8
CAS No. 7803-51-2 Density 1.15 (vs air)
PSA 13.59000 LogP 0.05810
Solubility 0.04 g/100 mL Melting Point -133.78oC
Formula H3P Boiling Point -87.5oC(lit.)
Molecular Weight 33.9976 Flash Point N/A
Transport Information UN 2199 Appearance colourless gas
Safety 28-36/37-45-61-63 Risk Codes 12-17-26-34-50
Molecular Structure Molecular Structure of 7803-51-2 (Phosphine) Hazard Symbols HighlyF+,VeryT+,DangerousN
Synonyms

Hydrogenphosphide;Phosphine (PH3);Phosphorus hydride;Phosphorus hydride (PH3);Phosphorus trihydride;TK-Gas;Vaporphos;

Article Data 774

Phosphine Synthetic route

371-74-4

bis(trifluoromethyl)arsane

31614-58-1

(CH3)3SnPH2

A

7803-51-2

phosphan

B

39185-14-3

trimethylstannylbis(trifluoromethyl)arsane

Conditions
ConditionsYield
20°C, 6 d;A n/a
B 100%
20°C, 6 d;A n/a
B 100%
371-74-4

bis(trifluoromethyl)arsane

20519-92-0

Trimethylphosphinogerman

A

7803-51-2

phosphan

B

39185-12-1

Trimethylgermanyl-bis-(trifluormethyl)-arsin

Conditions
ConditionsYield
20°C, 5 wk;A n/a
B 100%
20°C, 5 wk;A n/a
B 100%

calcium phosphide

A

12185-09-0

diphosphane

B

7803-51-2

phosphan

Conditions
ConditionsYield
In neat (no solvent) byproducts: Ca(OH)2; vac. (20-23 torr, 1.5 h, 0°C; 20°C, 10 torr); condensation (-78°C); (31)P NMR;A 90%
B n/a
12185-10-3

phosphorous

109-86-4

2-methoxy-ethanol

7803-51-2

phosphan

Conditions
ConditionsYield
With n-CH3C6H4SO3H In further solvent(s) Electrolysis; CH3OC2H4OH soln., cathode Pb, anode graphite, 20-25 °C, 0.01 A/cm**2, 5-8 V, 2.0 M CH3C6H4SO3H;89.3%
With HCl In further solvent(s) Electrolysis; CH3OC2H4OH soln., cathode Pb, anode graphite, 20-25 °C, 0.01 A/cm**2, 4.3-4.5 V, 2.0 M HCl;54.6%
With HCl In further solvent(s) Electrolysis; CH3OC2H4OH soln., cathode Pb, anode graphite, 20-25 °C, 0.05 A/cm**2, 9-12 V, 2.0 M HCl;45%
12185-10-3

phosphorous

64-17-5

ethanol

7803-51-2

phosphan

Conditions
ConditionsYield
With n-CH3C6H4SO3H In ethanol Electrolysis; cathode Pb, anode graphite, 20-25 °C, 0.01 A/cm**2, 4.5-6.0 V, 1.7-2 M n-CH3C6H4SO3H;80.7%
With n-CH3C6H4SO3H In ethanol Electrolysis; cathode Pb, anode graphite, 20-25 °C, 0.05 A/cm**2, 12-26 V, 1.7-2 M n-CH3C6H4SO3H;74.4%
With HCl In ethanol Electrolysis; cathode Pb, anode graphite, 20-25 °C, 0.05 A/cm**2, 6.5-6.7 V, 1.7-2 M HCl;60.5%
16853-85-3

lithium aluminium tetrahydride

7719-12-2, 52843-90-0

phosphorus trichloride

A

H(x)P(x)

B

7803-51-2

phosphan

Conditions
ConditionsYield
In diethyl ether reduction of PBr3 with LiAlH4 in ether at -115 °C;;A n/a
B 80%
In diethyl ether reduction of PBr3 with LiAlH4 in ether at -115 °C;;A n/a
B 80%
81744-45-8

3-diethylgerma 1,2-diphenyl 1,2-diphospholane

82312-29-6

Ge(C2H5)2C2H4P(C6H5)P(Ge(C2H5)2C6H5)

A

79301-90-9

phenyldiethylgermane

B

82312-33-2

2-(diethylgermyl)-1-(phenylphosphino)ethane

C

7803-51-2

phosphan

D

638-21-1

phenylphosphane

Conditions
ConditionsYield
With lithium aluminium tetrahydride In diethyl ether LiAlH4 (2-fold excess) added in portions to educts mixt. in Et2O, refluxed for 6 h; hydrolyzed, extd. (Et2O), dried (Na2SO4), distd.; elem. anal.;A 79%
B 73%
C n/a
D 68%
78665-55-1

trans-3,3-dimethyl-1,2-diphenyl-1,2,3-diphosphagermolane

82312-28-5

3,3-dimethyl-2-(dimethylphenylgermyl)-1-phenyl-1,2,3-diphosphagermolane

A

82312-32-1

2-(dimethylgermyl)-1-(phenylphosphino)ethane

B

7803-51-2

phosphan

C

7366-21-4

dimethylphenylgermane

D

638-21-1

phenylphosphane

Conditions
ConditionsYield
With lithium aluminium tetrahydride In diethyl ether LiAlH4 (2-fold excess) added in portions to educts mixt. in Et2O, refluxed for 6 h; hydrolyzed, extd. (Et2O), dried (Na2SO4), distd.; elem. anal.;A 78%
B n/a
C 52%
D 56%
12185-10-3

phosphorous

100-51-6

benzyl alcohol

7803-51-2

phosphan

Conditions
ConditionsYield
With HCl In benzyl alcohol Electrolysis; cathode Pb, anode graphite, 20-25 °C, 0.05 A/cm**2, 30-60 V, 3.5 M HCl;72.4%
7719-12-2, 52843-90-0

phosphorus trichloride

7803-51-2

phosphan

Conditions
ConditionsYield
With sodium In toluene reduction of PCl3 with Na in toluene;; heating, addn. of H2O;;70%
With Na In toluene reduction of PCl3 with Na in toluene;; heating, addn. of H2O;;70%
In water hydrolysis of PCl3;;

Phosphine Chemical Properties

Molecule structure of Phosphine (CAS NO.7803-51-2):

IUPAC Name: Phosphane 
Molecular Weight: 33.997581 g/mol
Molecular Formula: H3
Enthalpy of Vaporization: 14.6 kJ/mol 
Vapour Pressure: 27300 mmHg at 25 °C 
Boiling Point: −87.5 °C(lit.)
Stability: Stable, but pyrophoric - spontaneously flammable in air. Note the very wide explosion limits. Incompatible with oxidizing agents, halogens, nitric acid.
XLogP3-AA: -0.1
Exact Mass: 33.997237
MonoIsotopic Mass: 33.997237
Canonical SMILES: P
InChI: InChI=1S/H3P/h1H3
InChIKey: XYFCBTPGUUZFHI-UHFFFAOYSA-N
EINECS: 232-260-8
Product Categories: Inorganics;Compressed and Liquefied GasesPesticides;FumigantsMicro/Nanoelectronics;GasesCatalysis and Inorganic Chemistry;GasesVapor Deposition Precursors;Chemical Synthesis;Electronic Chemicals;Insecticides;Phosphorus Compounds;Phosphorus Precursors;Precursors by Metal;Synthetic Reagents

Phosphine History

 Phosphine was once regarded as a gaseous form of the element  because of its strong association with elemental phosphorus,but Lavoisier (1789) recognised it as a combination of phosphorus with hydrogen by describing it as "hydruyet of phosphorus, or phosphuret of hydrogen"
Later Ernst von Meyer (1891) described the early history of phosphine research thus: "The discovery of phosphuretted hydrogen (PH3) by Gengembre in 1783, and the examination of it by Pelletier (who was the first to prepare it pure), only became fruitful after Humphry Davy's investigations; and the last-named elucidated the composition of this gas, and pointed out its analogy to ammonia, this being emphasised still more sharply by H. Rose later on."
Then Thénard (1845) used a cold trap to separate diphosphine from phosphine which had been generated from calcium phosphide, so that demonstrating that P2H4 is responsible for spontaneous flammability associated with PH3, and also for the characteristic orange/brown colour that can form on surfaces, which is a polymerisation product. He considered diphosphine's formula to be PH2, and thus an intermediate between elemental phosphorus, the higher polymers, and phosphine.

Phosphine Uses

 Phosphine is commonly used for semiconductor manufacturing.

Phosphine Production

Industrially Phosphine can be made by the reaction of white phosphorus with sodium hydroxide, producing sodium hypophosphite and sodium phosphite as a by-product.

Phosphine Toxicity Data With Reference

1.    

ihl-hmn LCLo:1000 ppm

    GUCHAZ    Guide to the Chemicals Used in Crop Protection 6 (1973),412.
2.    

ihl-rat LC50:11 ppm/4H

    AIHAAP    American Industrial Hygiene Association Journal. 36 (1975),452.
3.    

ihl-mus LCLo:380 mg/m3/2H

    85GMAT    Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure Izmerov, N.F., et al.,Moscow, USSR.: Centre of International Projects, GKNT,1982,75.
4.    

ihl-cat LCLo:70 mg/m3/2H

    85GMAT    Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure Izmerov, N.F., et al.,Moscow, USSR.: Centre of International Projects, GKNT,1982,75.
5.    

ihl-rbt LCLo:2500 ppm/20M

    AEXPBL    Archiv fuer Experimentelle Pathologie und Pharmakologie. 27 (1890),314.
6.    

ihl-gpg LCLo:140 mg/m3/4H

    85GMAT    Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure Izmerov, N.F., et al.,Moscow, USSR.: Centre of International Projects, GKNT,1982,75.
7.    

ihl-mam LCLo:1000 ppm/5M

   

AEPPAE    Naunyn-Schmiedeberg’s Archiv fuer Experimentelle Pathologie und Pharmakologie. 138 (1928),65.

Phosphine Consensus Reports

EPA Extremely Hazardous Substances List. Reported in EPA TSCA Inventory.

Phosphine Safety Profile

Hazard Codes: HighlyF+, VeryT+, DangerousN
Risk Statements: 12-17-26-34-50 
R12:Extremely flammable. 
R17:Spontaneously flammable in air. 
R26:Very toxic by inhalation. 
R34:Causes burns. 
R50:Very toxic to aquatic organisms.
Safety Statements: 28-36/37-45-61-63 
S28:After contact with skin, wash immediately with plenty of soap-suds. 
S36/37:Wear suitable protective clothing and gloves. 
S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.) 
S61:Avoid release to the environment. Refer to special instructions / safety data sheets.
RIDADR: UN 2199 2.3
WGK Germany: 2
RTECS: SY7525000
HazardClass: 2.3 

Phosphine Standards and Recommendations

OSHA PEL: TWA 0.3 ppm; STEL 1 ppm
ACGIH TLV: TWA 0.3 ppm; STEL 1 ppm
DFG MAK: 0.1 ppm (0.14 mg/m3)
DOT Classification:  2.3; Label: Poison Gas, Flammable Gas

Phosphine Analytical Methods

For occupational chemical analysis use OSHA: #ID-180 or NIOSH: Phosphine S332.

Phosphine Specification

 Phosphine (CAS NO.7803-51-2) is also named as CCRIS 8578 ; ECO2FUME ; Fosforowodor ; Fosforowodor [Polish] ; Gas-Ex-B ; HSDB 1233 ; Hydrogen phosphide ; Phosphine (fumigant) ; Phosphoretted hydrogen ; Phosphorus hydride ; Phosphorus trihydride ; Phosphorwasserstoff ; Phosphorwasserstoff [German] ; RCRA waste number P096 ; UN 2199 . Phosphine (CAS NO.7803-51-2) is colourless gas. It is highly flammable. It usually ignites spontaneously in air. It is insoluble in water. Phosphine is a reducing agent. Liquefied Phosphine can be detonated. Forms explosive mixtures with even small amounts of oxygen. Ignites or reacts violently with boron trichloride, dichlorine oxide, halogens (bromine, chlorine, iodine), metal nitrates, nitrogen oxides, nitric acid, nitrous acid, nitrogen trichloride. Phosphine is a super- toxic gas. An air concentration of 3 ppm is safe for long term exposure, 500 ppm is lethal in 30 minutes, and a concentration of 1,000 ppm is lethal after a few breaths. 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. Phosphine emits highly toxic fumes of phosphorus oxides when heated to decomposition. It may become unstable at high temperatures.

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