Chemical Properties
colourless liquid with a musty odour
Uses
In organic synthesis; production of high-purity nickel powder and continuous nickel coatings on steel and other metals.
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.
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
Vapor forms explosive mixtures with air. Vapor is heavier than air and may travel a considerable distance to source of ignition and flash back. Liquid may explode when heated under confinement. Vapor explosion and poison hazard indoors, outdoors, or in sewers. Runoff to sewer may create fire and explosion. May explode at 68F in presence of air or oxygen. Avoid contact with heat, acid or acid fumes as these cause the emission of highly toxic fumes. Avoid contact with air, ignition sources and vapors entering a confined space.
Hazard
Flammable, dangerous fire risk, explodes
at 60C (140F). A lung irritant and confirmed carcinogen.
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.
First aid
If this chemical gets into the eyes, remove any
contact lenses at once and irrigate immediately for at least
15 minutes, occasionally lifting upper and lower lids. Seek
medical attention immediately. If this chemical contacts the
skin, remove contaminated clothing and wash immediately
with soap and water. Seek medical attention immediately.
If this chemical has been inhaled, remove from exposure,
begin rescue breathing (using universal precautions, including
resuscitation mask) if breathing has stopped and CPR if
heart action has stopped. Transfer promptly to a medical
facility. When this chemical has been swallowed, get medical
attention. Give large quantities of water and induce
vomiting. Do not make an unconscious person vomit. Medical observation is advised for 3 days or more; delayed
lung effects including pulmonary edema may occur.
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.
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.
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.
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.
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.
