NICKEL CARBONYL
- CAS No.
- 13463-39-3
- Chemical Name:
- NICKEL CARBONYL
- Synonyms
- Ni(CO)4;NICKEL CARBONYL;nickelcarbonyle;Carbonyl nickel;Nickel carbonyle;nickelcarbonyl11;Nikkeltetracarbonyl;rcrawastenumberp073;tetracarbonylnickel;nickel(II) carbonyl
- CBNumber:
- CB5739929
- Molecular Formula:
- C4NiO4
- Molecular Weight:
- 170.73
- MOL File:
- 13463-39-3.mol
- Modify Date:
- 2023/10/17 17:11:56
Melting point | -19°C |
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Boiling point | 43°C |
Density | 1,32 g/cm3 |
vapor pressure | 321 mmHg at 20 °C |
Flash point | <-20°C |
solubility | insoluble in H2O; soluble in ethanol, benzene,acetone, ctc |
form | liquid |
color | colorless |
Odor | Sooty odor detectable at 0.5 to 3 ppm |
Water Solubility | soluble in ~5000 parts air free H2O; soluble alcohol, benzene, chloroform, acetone, CCl4 [MER06] |
Sensitive | heat sensitive |
Exposure limits |
TLV-TWA: 0.05 ppm (0.35 mg as Ni/m3)
(ACGIH) PEL: 0.001 ppm (0.007 mg Ni/m3) (OSHA, MSHA and NIOSH) IDLH: 0.001 ppm (NIOSH, OSHA). |
Stability | Stable. Highly flammable and highly reactive. Explosion hazard. |
EPA Substance Registry System | Nickel carbonyl (13463-39-3) |
SAFETY
Risk and Safety Statements
Symbol(GHS) | GHS05,GHS07 |
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Signal word | Danger | |||||||||
Hazard statements | H314-H335 | |||||||||
Precautionary statements | P501-P261-P271-P264-P280-P303+P361+P353-P301+P330+P331-P363-P304+P340+P310-P305+P351+P338+P310-P403+P233-P405 | |||||||||
Hazard Codes | F,T+,N | |||||||||
Risk Statements | 11-26-40-50/53-61 | |||||||||
Safety Statements | 45-53-60-61 | |||||||||
RIDADR | 1259 | |||||||||
OEB | E | |||||||||
OEL | TWA: 0.001 ppm (0.007 mg/m3) | |||||||||
Autoignition Temperature | Explodes above 60 °C | |||||||||
HazardClass | 6.1(a) | |||||||||
PackingGroup | I | |||||||||
Toxicity | LD50 in rats (mg/kg): 39 i.p.; 63 s.c.; 66 i.v. (Hackett, Sunderman) | |||||||||
IDLA | 2 ppm | |||||||||
NFPA 704 |
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NICKEL CARBONYL Chemical Properties,Uses,Production
Description
Nickel carbonyl is a clear colourless to yellow volatile liquid, is flammable, and burns with a yellow flame. It is denser than water and insoluble in water but soluble in alcohol, benzene, chloroform, acetone, ethanol, carbon tetrachloride, and nitric acid. The vapours are heavier than air. In industries, nickel carbonyl is used in nickel coat steel and other metals and to make very pure nickel. Nickel carbonyl gets peroxidised by air as a solid deposit and decomposes to ignite.
Chemical Properties
Nickel carbonyl is a colorless, highly volatile, flammable liquid with a musty odor. The Odor Threshold is 1.3 ppm. It decomposes above room temperature producing carbon monoxide and finely divided nickel.
Physical properties
Colorless volatile liquid; diamagnetic; flammable; burns with a bright luminous flame; density 1.319 g/mL; freezes at -25°C; boils at 43°C; vapor pressure 320.6 torr at 20°C; vapor density 5.89 (air=1); critical temperature about 200°C; critical pressure 30 atm; practically insoluble in water, 180 mg/L at 10°C; miscible with most organic solvents including ethanol, acetone, and benzene; soluble in nitric acid and aqua regia.
History
Nickel tetracarbonyl was prepared first in 1888 by Mond and Langer by passing carbon monoxide over finely divided nickel. It is the most important zero valent compound of nickel and is used industrially to make high-purity nickel powder and pellets and to produce nickel coatings on steel.
Uses
Nickel carbonyl is used in nickel vapoplating processes in the metallurgical and electronics industry, and in the catalytic methyl- and ethylacrylate monomer synthesis. For many years it had been used to produce pure nickel by the Mond process, which has been considered to be outdated since around 1970.
Preparation
Nickel tetracarbonyl is made by passing carbon monoxide over finely divided nickel at 50 to 100°C. (The finely divided nickel is obtained from reduction of nickel oxide by hydrogen below 400°C.) Ni + 4CO → Ni(CO)4
In several commercial processes the reaction is carried out at a temperature of 200°C under 400 atm carbon monoxide pressure for obtaining high yield of nickel tetracarbonyl and also to prevent thermal dissociation.
Nickel tetracarbonyl may be prepared in the laboratory by the Hieber process, a disproportion reaction of several nickel compounds of organic thio acids, such as nickel(II) phenyldithiocarbamate, (C6H5—NH—C(=S)—S)2Ni, with carbon monoxide under controlled conditions. In such disproportionation reactions, the divalent nickel ion converts to a tetravalent nickel complex (Hieber. H. 1952. Z.anorg.Chem., 269, pp. 28). The overall reaction is: 2NiII + 4CO → NiIV(complex) + Nio(CO)4.
Production Methods
Nickel carbonyl is produced in a reaction of carbon monoxide and nickel metal. It may also be formed as a by-product in the industrial processes using nickel catalysts, such as coal gasification, crude oil refining, and hydrogenation reactions (293). Conditions for its formation occur in those processes where carbon monoxide is in contact with an active form of nickel under conditions of elevated pressure at 50–150°C.
Definition
nickel carbonyl: A colourlessvolatile liquid, Ni(CO)4; m.p.-25°C;b.p. 43°C. It is formed by direct combinationof nickel metal with carbonmonoxide at 50–60°C. The reaction isreversed at higher temperatures, andthe reactions are the basis of theMond process for purifying nickel.The nickel in the compound has anoxidation state of zero, and the compoundis a typical example of a complexwith pi-bonding ligands, inwhich filled d-orbitals on the nickeloverlap with empty p-orbitals on thecarbon.
General Description
A clear colorless to yellow liquid. Boiling point 43°C. Flash point below 0°F. Very toxic by ingestion and inhalation. Carcinogenic. Denser than water and insoluble in water. Vapors heavier than air. Used to nickel coat steel and other metals and to make very pure nickel.
Air & Water Reactions
Highly flammable over a wide range of vapor-air concentrations. Is peroxidized by air to give a solid deposit that tends to decompose and ignite. Insoluble in water.
Reactivity Profile
NICKEL CARBONYL is easily oxidized. Presents a very serious fire hazard if exposed to heat, flame, sparks, oxidizing agents. Explodes when heated to about 60°C. Reacts explosively with bromine (liquid), oxygen in the presence of mercury, or hydrocarbons (butane) mixed with oxygen. Undergoes violent reactions with air, oxygen, dinitrogen tetraoxide. Caused an explosion when added to an n-butane-oxygen at 20-40°C [J. Am. Chem. Soc. 70:2055-6. 1948]. Reacts with tetrachloropropadiene to form an extremely explosive dinickel chloride dimer. Emits highly toxic fumes of carbon monoxide when heated to decomposition or in contact with mineral acids or acid fumes [Bretherick, 5th ed., 1995, p. 1734]. Vapor explodes in air or oxygen at 20°C and a partial pressure of 15 mm.
Hazard
Flammable, dangerous fire risk, explodes at 60C (140F). A lung irritant and confirmed carcinogen.
Health Hazard
Probable oral lethal dose for a human is between 50 and 500 mg/kg, between one teaspoon and one ounce per 150 lb. person. NICKEL CARBONYL has also been estimated to be lethal in man at atmospheric exposures of 30 ppm for 20 minutes. Autopsies show congestion, collapse, and tissue destruction, as well as hemorrhage in the brain. Dermatitis, recurrent asthmatic attacks, and increased number of white blood cells (eosinophils) in respiratory tract are acute health hazards. NICKEL CARBONYL is poisonous. It can be fatal if inhaled, swallowed, or absorbed through skin. Vapors may cause irritation, congestion, and edema of lungs.
Fire Hazard
Nickel carbonyl is a highly flammable liquid (NFPA rating = 3) that may ignite spontaneously and explodes when heated above 60℃. Its lower flammable limit in air is 2% by volume; the upper limit has not been reported. Carbon dioxide, water, or dry chemical extinguishers should be used for nickel carbonyl fires.
Flammability and Explosibility
Nickel carbonyl is a highly flammable liquid (NFPA rating = 3) that may ignite spontaneously and explodes when heated above 60 °C. Its lower flammable limit in air is 2% by volume; the upper limit has not been reported. Carbon dioxide, water, or dry chemical extinguishers should be used for nickel carbonyl fires.
Potential Exposure
Nickel carbonyl is used as an intermediate product in the refining of nickel. The primary use for nickel carbonyl is in the production of nickel by the Mond process. Impure nickel powder is reacted with carbon monoxide to form gaseous nickel carbonyl which is then treated to deposit high purity metallic nickel and release carbon monoxide. Other uses include gas plating; the production of nickel products; in chemical synthesis as a catalyst, particularly for oxo reactions (addition reaction of hydrogen and carbon monoxide with unsaturated hydrocarbons to form oxygen-function compounds); e.g., synthesis of acrylic esters; and as a reactant.
storage
Work with nickel carbonyl should be conducted in a fume hood to prevent exposure by inhalation and splash goggles and impermeable gloves should be worn at all times to prevent eye and skin contact. Nickel carbonyl should only be used in areas free of ignition sources. Containers of nickel carbonyl should be stored in secondary containers in the dark in areas separate from oxidizers.
Shipping
UN1259 Nickel carbonyl, Hazard Class: 6.1; Labels: 6.1-Poisonous materials, 3-Flammable liquid, Inhalation Hazard Zone A. A United States DOT Severe Marine Pollutant.
Incompatibilities
May spontaneously ignite on contact with air. In the presence of air, oxidizes and forms a deposit which becomes peroxidized; this tends to decompose and ignite. May explode when heated above 60 C. Decomposes on contact with acids producing carbon monoxide. Violent reaction with oxidizers; may cause fire and explosions. Vapor may promote the ignition of mixtures of combustible vapors (such as gasoline) and air. Attacks some plastics, rubber and coatings. Store under inert gas blanket.
Waste Disposal
Incineration in admixture with a flammable solvent. Also, nickel carbonyl used in metallizing operations may be recovered and recycled. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal.