CARBON MONOXIDE Chemical Properties
- Melting point:−205 °C(lit.)
- Boiling point:−191.5 °C(lit.)
- Density d4-195 (liq) 0.814; d (gas) 0.968 (air = 1.000); d40 at 760 mm: 1.250 g/liter
- vapor density 0.97 (vs air)
- vapor pressure >760 mmHg at 20 °C
- refractive index 1.0003
- solubility At 20 °C and at a pressure of 101 kPa, 2.266 volumes of carbon monoxide dissolve in 100 volumes of water.
- form colorless gas
- OdorOdorless gas
- explosive limit74%
- Water Solubility mL/100mL H2O: 3.3 (0°C), 2.3 (20°C) [MER06]
- Merck 13,1823
- BRN 3587264
- Exposure limitsTLV-TWA 50 ppm (～55 mg/m3) (ACGIH, MSHA, and OSHA); STEL 400 ppm (ACGIH); IDLH 1500 ppm (NIOSH).
- CAS DataBase Reference630-08-0(CAS DataBase Reference)
- EPA Substance Registry SystemCarbon monoxide (630-08-0)
- Hazard Codes F+,T
- Risk Statements 61-12-23-48/23
- Safety Statements 53-45
- RIDADR UN 1016 2.3
- WGK Germany 1
- RTECS FG3500000
- Autoignition Temperature609 °C
- HazardClass 2.3
- ToxicityLC50 inhal (rat) 1807 ppm (2065 mg/m3; 4 h)
LCLO inhal (man) 4000 ppm (4570 mg/m3; 30 min)
PEL (OSHA) 50 ppm (55 mg/m3)
TLV-TWA (ACGIH) 25 ppm (29 mg/m3)
CARBON MONOXIDE Usage And Synthesis
- DescriptionCarbon monoxide is a colorless, odorless, tasteless, flammable, toxic gas.Carbon monoxide is produced when carbon and carbon compounds undergo incomplete combustion. The inefficient combustion of carbon fuels for heating results in the production of carbon monoxide, which may result in high CO concentrations in indoor environments. The use of carbon fuel heaters without adequate ventilation can result in deadly conditions. Each year several hundred people in the United States die from CO poisoning, and 10,000 patients are treated in hospitals for CO exposure.Cars and other forms of transportation are a major source of carbon monoxide pollution in cities.
- Chemical PropertiesCarbon monoxide, CO, is a colorless,odorless, toxic gas. It is soluble in alcohol and cuprix chloride solutions, but insoluble in water. Carbon monoxide is formed by the incomplete oxidation of carbon. It is found in mines and carexhaust. Carbon monoxide is used in metallurgy as a reducing agent in smelting operations, in the production of carbony is for the separation of various metals, as an ingredient in the synthesis of phosgene,and as an intermediate in the production of methanol.
Because it is only slightly less dense than air, it mixes readily without stratification. Because it is only slightly less dense than air, it mixes readily without stratification. Because of its low boiling point, carbon monoxide is shipped as a nonliquified compressed gas. It is also known as carbon oxide, flue gas, and monoxide. Carbon monoxide is a flammable gas and is incompatible or reactive with strong oxidizers, such as bromine trifluoride, chlorine trifluoride, and lithium.
- Physical propertiesColorless, odorless and tasteless gas; density 1.229 g/L; very flammable,burns in air with a bright blue flame; liquefies at -191.5°C; solidifies at -205°C; critical temperature -140°C, critical pressure 34.53 atm, critical vol ume 93 cm3/mol; soluble in chloroform, acetic acid, ethyl acetate, ethanol, and ammonium hydroxide; sparingly soluble in water (2.3 mL/100 mL water at 20°C).
- OccurrenceCarbon monoxide is found in varying concentrations in unventilated and confined spaces resulting from partial oxidation of carbonaceous matter. Burning wood, paper, kerosene, or other organic materials in inadequate air can produce this gas. It also is found in automobile exhaust and tobacco smoke emissions.
Carbon monoxide has many important industrial applications. It is used in Fischer-Tropsch process to produce liquid or gaseous hydrocarbons, synthet ic fuels and many oxygenated derivatives. This process was applied before and during World War II to produce synthetic fuels. Probably the most important application of this compound involves production of oxygenated organics in the Synthol process and in oxo synthesis. Many aliphatic alcohols, alehydes and ketones are produced by catalytic hydrogenation of carbon monoxide. Oxo synthesis produces aldehydes from olefins. Carbon monoxide also is the start ing material for preparing metal carbonyls. In metallurgy, it is used as a reducing agent to reduce oxides. In the Mond process it recovers nickel.
- HistoryCarbon monoxide is a colorless, odorless, tasteless, flammable, toxic gas. It was first identified by the Spanish alchemist Arnold of Villanova (1235–1313), who noted the production of a poisonous gas when wood was burned. The formal discovery of carbon monoxide is credited to the French chemist Joseph Marie Fran?ois de Lassone (1717–1788) and the British chemist Joseph Priestley (1733–1804). The former prepared carbon monoxide by heating carbon in the presence of zinc, and for a time the compound was incorrectly identified as hydrogen. William Cumberland Cruikshank (1745–1800) correctly determined that carbon monoxide was an oxide of carbon in 1800.
- UsesCarbon monoxide bonds to the iron in hemoglobin to form carboxyhemoglobin, which interferes with oxygen’s ability to bind to hemoglobin to form oxyhemoglobin. Thus carbon monoxide is a chemical asphyxiant, which prevents oxygen from reaching body tissues.
Carbon monoxide is an important industrial chemical. It is produced, along with hydrogen, by steam reforming. Carbon monoxide is a basic feedstock in these processes.
Carbon monoxide is also useful as a reducing agent. It is used in metallurgy to obtain metals from their oxides. For example, during iron and steel production coke in a blast furnace is converted to carbon monoxide. The carbon monoxide reduces the Fe3+ in the iron (III) oxide contained in the iron ore to produce elemental iron according to the reaction: Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g).
- UsesCarbon monoxide is used in the oxo processor Fischer–Tropsch process in the produc tion of synthetic fuel gas (producer gas, watergas, etc.); as a reducing agent in the Monodprocess for the recovery of nickel; in car bonylation reactions; and in the productionof metal carbonyls and complexes. It is pro duced by incomplete combustion of organicmaterials. Risk of exposure to this gas arisesunder fire conditions; from a burning stoveor from burning wood or candles in a closedroom; in the exhausts of internal combustion engines; in a closed garage with theautoengine on; and from oil or gas burners,improperly adjusted.
- UsesAs reducing agent in metallurgical operations especially in the Mond process for the recovery of nickel; in organic synthesis especially in the Fischer-Tropsch processes for petroleum-type products and in the oxo reaction; in the manufacture of metal carbonyls.
- DefinitionA colorless flammable toxic gas
formed by the incomplete combustion of
carbon. In the laboratory it can be made by
dehydrating methanoic acid with concentrated
HCOOH – H2O → CO
Industrially, it is produced by the oxidation of carbon or of natural gas, or by the water-gas reaction. It is a powerful reducing agent and is used in metallurgy.
Carbon monoxide is neutral and only sparingly soluble in water. It is not the anhydride of methanoic acid, although under extreme conditions it can react with sodium hydroxide to form sodium methanoate. It forms metal carbonyls with transition metals, and its toxicity is due to its ability to form a complex with hemoglobin.
- Production MethodsCarbon monoxide is formed during combustion of carbonaceous materials in oxygen (when carbon is in excess), or it can be formed (with oxygen) by thermal decomposition of carbon dioxide (>2000° °C). It can be generated by improperly vented cooking and heating appliances including coal stoves, furnaces, and gas appliances when the oxygen supply is insufficient. Other sources include exhaust of internal combustion engines, structural fires, and tobacco products. Carbon monoxide can also be formed endogenously by normal heme turnover or during the metabolism of selected hydrocarbons, such as methylene chloride. Not surprisingly, CO is one of the most common agents of inadvertent human intoxication in both occupational and nonoccupational environments.
- ReactionsChemically, carbon monoxide is (1) reactive with oxygen to form CO2 accompanied by a transparent blue flame and the evolution of heat, but the fuel value is low (320 Btu per ft3), (2) reactive with chlorine, forming carbonyl chloride COCl2 in the presence of light and a catalyzer, (3) reactive with sulfur vapor at a red heat, forming carbonyl sulfide COS, (4) reactive with hydrogen, forming methyl alcohol, CH3OH or methane CH4 in the presence of a catalyzer, (5) reactive with nickel (also iron, cobalt, molybdenum, ruthenium, rhodium, osmium, and iridium) to form nickel carbonyl, Ni(CO)4 (and carbonyls of the other metals named), (6) reactive with fused NaOH, forming sodium formate, HCOONa, (7) reactive with cuprous salt dissolved in either ammonia solution or concentrated HCl, which solutions are utilized in the estimation of carbon monoxide in mixtures of gases, e.g., flue gases of combustion, coal gas, exhaust gases of internal combustion engines, (8) reactive with iodine pentoxide at 150 °C. For the reaction of carbon monoxide with oxygen to form CO2 finely divided iron or palladium wire is used as a catalyzer; for the reaction of carbon monoxide with H2O vapor to form CO2 plus hydrogen (“water gas reaction”) important studies have been made of the conditions; and for the reaction of CO2 plus carbon (hot) similar important studies have been made (at 675 °C, 50% CO2 plus 50% CO; at 900°C, 5% CO2 plus 95% CO). The reaction of carbon plus oxygen at such a temperature as produces carbon monoxide (say 900 °C, 95% CO plus 5% CO2) and evolves heat; while the reaction of carbon plus CO2, producing carbon monoxide at the same temperature absorbs heat. Accordingly it is possible to arrange the oxygen (free or as air) and CO2 supply ratio in such a way that the desired temperature may be continuously maintained. The reduction of CO2 by iron forms carbon monoxide plus ferrous oxide.
- General DescriptionA colorless cryogenic liquid. Prolonged exposure to carbon monoxide rich atmospheres may be fatal. Contact with the liquid can cause severe frostbite. Less dense than air. Easily ignited and a flame can flash back to the source of a leak very easily. Burns with a violet flame. Under prolonged exposure to fire or intense heat the containers may rupture violently and rocket. CARBON MONOXIDE is used in organic synthesis, metallurgy, and a fuel.
- Air & Water ReactionsHighly flammable.
- Reactivity ProfileContact of very cold liquefied gas with water may result in vigorous or violent boiling and extremely rapid vaporization. If the water is hot, a liquid "superheat" explosion may occur. Pressures may build to dangerous levels if the liquid contacts water in a closed container [Handling Chemicals Safely 1980]. Reacts explosively with bromine trifluoride at high temperatures or concentrations [Mellor 2, Supp. 1:166 1956]. The same is true for various oxidizers such as: chlorine dioxide, oxygen (liquid), peroxodisulfuryl difluoride. Reacts with lithium to give lithium carbonyl, which detonates violently with water, igniting the gaseous products [Mellor 2, Supp 2:84 1961]. Potassium and sodium metals behave similarly. Cesium oxide, iron(III) oxide, and silver oxide all react, in the presence of moisture, at ambient temperatures with carbon monoxide causing ignition, [Mellor, 1941, vol. 2, 487].
- HazardHighly flammable, dangerous fire and explosion risk. Flammable limits in air 12–75% by volume. Toxic by inhalation. Note: Carbon monox- ide has an affinity for blood hemoglobin over 200 times that of oxygen. A major air pollutant.
- Health HazardCarbon monoxide is a highly poisonous gas.The acute toxic symptoms include headache,tachypnea, nausea, dizziness, weakness, con fusion, depression, hallucination, loss ofmuscular control, and an increase and thena decrease in pulse and respiratory rate. Ifthe dose is high, these symptoms progressto collapse, unconsciousness, and death.The severity of toxic effects depends on theconcentration of carbon monoxide and theduration of exposure. Prolonged exposure toa concentration of 50 ppm does not resultin adverse health effects in humans, but a6-hour exposure to 100 ppm may produceperceptible effects. A 10-minute exposure to5000 ppm is lethal to humans
LC50 value, inhalation (rats): 1800 ppm/4 h
The biochemical action of carbon monox ide involves its reaction with hemoglobin(Hb) in the blood. It enters into thebloodstream through the lungs and com bines with hemoglobin to form carboxyhe moglobin (COHb). Hemoglobin is essentialfor the transportation of oxygen into the tis sues. The affinity of carbon monoxide tocombine with hemoglobin is about 300 timesgreater than that of oxygen (Meyer 1989).Thus, the CO molecule readily displaces oxy gen from the oxyhemoglobin (O2Hb) to formthe more stable adduct, carboxyhemoglobin
Thus the hemoglobin is tied up. It cannot,therefore, supply oxygen to the tissues, thusresulting in hypoxia and death
Therapy involves artificial respirationusing a compression chamber at about 2atmospheres of oxygen, or a 95% O2/5%CO2 mixture, thus supplying more oxygento compete for the hemoglobin and increasethe solubility of oxygen in the blood plasma.
- Fire HazardEXTREMELY FLAMMABLE. May be ignited by heat, sparks or flames. Flame may be invisible. Containers may explode when heated. Vapor explosion and poison hazard indoors, outdoors or in sewers. Vapors from liquefied gas are initially heavier than air and spread along ground. Vapors may travel to source of ignition and flash back. Runoff may create fire or explosion hazard.
- Flammability and ExplosibilityCarbon monoxide is a flammable gas. It forms explosive mixtures with air in the range of 12.5 to 74% by volume.
- Industrial usesCarbon monoxide (CO) is a product of incompletecombustion, and is very reactive. It is oneof the desirable products in synthesis gas formaking chemicals; the synthesis gas made fromcoal contains at least 37% CO. It is also recoveredfrom top-blown O2 furnaces in steel mills.It reacts with H2 to form methanol, which is then catalyzed by zeolites into gasoline. Aceticacid is made by methanol carbonylation, andacrylic acid results from the reaction of CO,acetylene, and methanol.
- Safety ProfileMddly toxic by inhalation in humans but has caused many fatalities. Experimental teratogenic and reproductive effects. Human systemic effects by inhalation: changes in psychophysiological tests and methemoglobinemiacarboxyhemoglobinemia. Can cause asphyxiation by preventing hemoglobin from bindmg oxygen. After removal from exposure, the half-life of elimination from the blood is one hour. Chronic exposure effects can occur at lower concentrations. A common air contaminant. Acute cases of poisoning resulting from brief exposures to hgh concentrations seldom result in any permanent dtsability if recovery takes place. Chronic effects as the result of repeated exposure to lower concentrations have been described, particularly in the Scandinavian literature. Auditory disturbances and contraction of the visual fields have been demonstrated. Glycosuria does occur, and heart irregularities have been reported. Other workers have found that where the poisoning has been relatively long and severe, cerebral congestion and edema may occur, resulting in long-lasting mental or nervous damage. Repeated exposure to low concentration of the gas, up to 100 ppm in air, is generally believed to cause no signs of poisoning or permanent damage. Industrially, sequelae are rare, as exposure, though often severe, is usually brief. It is a common air contaminant. flame. Severe explosion hazard when exposed to heat or flame. Violent or explosive reaction on contact with bromine trifluoride, bromine pentafluoride, chlorine doxide, or peroxodsulfuryl difluoride. Mixture of liquid CO with liquid O2 is explosive. Reacts with sodurn or potassium to form explosive products sensitive to shock, heat, or contact with water. Murture , , . with copper powder + copper(Ⅱ) perchlorate + water forms an explosive complex. dime of liquid CO with liquid dinitrogen oxide is a rocket propellant combination. Ignites on warming with iodine heptafluoride. Ignites on contact with . cesium oxide + water. Potentially explosive reaction with iron(IⅡ) oxide between 0' and 150℃. Exothermic reaction with CIF3, (Li + H2O), NF3,OF2, (K + 04, Ag2O, (Na + NH3). To fight fire, stop flow of gas. A dangerous fire hazard when exposed to
- Potential ExposureCarbon monoxide is used in metallurgy as a reducing agent, particularly in the Mond process for nickel; in organic synthesis, especially in the FischerTropsch process for petroleum products, and in the oxo reaction; and in the manufacture of metal carbonyls. It is usually encountered in industry as a waste product of incomplete combustion of carbonaceous material (complete combustion produces CO2). The major source of CO emission in the atmosphere is the gasoline-powered internal combustion engine. Special industrial processes which contribute significantly to CO emission are iron foundries, particularly the cupola; fluid catalytic crackers; fluid coking; and moving-bed catalytic crackers in thermal operations in carbon black plants; beehive coke ovens; basic oxygen furnaces, sintering of blast furnace feed in steel mills; and formaldehyde manufacture. There are numerous other operations in which a flame touches a surface that is cooler than the ignition temperature of the gaseous part of the flame where exposure to CO may occur,e.g., arc welding, automobile repair; traffic control; tunnel construction; firefighting; mines, use of explosives, etc.
- storagecylinders of carbon monoxide should be stored and used in a continuously ventilated gas cabinet or fume hood. Local fire codes should be reviewed for limitations on quantity and storage requirements.
- ShippingUN1016 Carbon monoxide, compressed, Hazard class: 2.3; Labels: 2.3-Poisonous gas; 2.1- Flammable gas, Inhalation Hazard Zone D. NA9202 Carbon monoxide, refrigerated liquid (cryogenic liquid), Hazard class: 2.3; Labels: 2.3-Poisonous gas; 2.1- Flammable gas, Domestic (United States), Inhalation Hazard Zone D. Cylinders must be transported in a secureupright position, in a well-ventilated truck. Protect cylinder and labels from physical damage. The owner of the compressed gas cylinder is the only entity allowed by federal law (49CFR) to transport and refill them. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner.
- Purification MethodsIron carbonyl is a likely impurity in CO stored under pressure in steel tanks. It can be decomposed by passing the gas through a hot porcelain tube at 350-400o. Passage through alkaline pyrogallol solution removes oxygen (and CO2). Removal of CO2 and water are effected by passage through soda-lime followed by Mg(ClO4)2 or P2O5 and collected over Hg. Carbon monoxide can be condensed and distilled at -195o. It is sparingly soluble in H2O but is readily absorbed by a solution of CuCl in HCl to give the white crystalline adduct CuCl.CO.2H2O. It burns in air with a bright blue flame but a mixture of 2volumes of CO and 1volume of O2 explode when kindled, although in a small jar the combustion is not violent. HIGHLY POISONOUS gas as it reacts with haemoglobin to form bright red carboxyhaemoglobin which is stable and not readily decomposed by oxygen. [Gilliland & Blanchard Inorg Synth II 81 1946, Glemser in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I p 645-646 1963.]
- IncompatibilitiesForms extremely explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. In the presence of finely dispersed metal powders the substance forms toxic and flammable carbonyls. May react vigorously with oxygen, acetylene, chlorine, fluorine, nitrous oxide.
- Waste DisposalReturn refillable compressed gas cylinders to supplier. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Carbon monoxide can also be recovered from gas mixtures as an alternative to disposal.
- PrecautionsCarbon monoxide poisoning, prevention, occupational safety Install a CO alarm on each level of your home. Home heating systems, chimneys, and fl ues must be inspected and cleaned by a qualifi ed technician every year. Keep chimneys clear of bird and squirrel nests, leaves, and residue to ensure proper ventilation. Make sure that the furnace and other appliances, such as gas ovens, ranges, and cooktops are inspected for adequate ventilation. Do not burn charcoal inside the house even in the fi replace. Do not operate gasoline-powered engines in confi ned areas, such as garages or basements. Do not leave your car, mower, or other vehicle running in an attached garage, even with the door open. Do not block or seal shut exhaust fl ues or ducts for appliances such as water heaters, ranges, and clothes dryers.
CARBON MONOXIDE Preparation Products And Raw materials
- Preparation ProductsEthyl acrylateAnthraquinoneSodium formatePivaloyl chlorideCalcium carbideDimethyl carbonateFluorobenzenePropionaldehydeCalcium hypochloriteDimethylcarbamoyl chloride Diethyl chlorothiophosphateCalcium cyanamideketene Sodium fluorosilicateSilicon carbideCalcium fluorideChlorotoluronSodium fluorideIsoprocarbCARBONYL SULFIDEPivalic acidHexythiazoxDiphenyl carbonateThiobencarbCalcium formate 4,4'-Diphenylmethane diisocyanateN-MethylformamideKRYPTONSeedavay(Uniroyal)Disodium oxalateAluminum dihydrogen phosphate2-[(2-METHYL-2-PROPENYL)OXY]-PHENOLSodium diacetate4-Methylvaleric acidSODIUM A-CYANOPHENYL ALDOXIMEMethyl 2-methylbutyrateIsobutyl formateEthyl 2-methylbutyrateAMYL FORMATE2-isopropyl cyclopentanone
- Raw materialsAmmoniaCarbon BlackWhite phosphorusCoke (coal)
- DICHLORODICARBONYLBIS(TRIPHENYLPHOSPHINE)RUTHENIUM (II) BIS(TRIPHENYLPHOSPHINE)DICARBONYLNICKEL CYCLOPENTADIENYLIRON DICARBONYL DIMER CYCLOOCTATETRAENE IRON TRICARBONYL Molybdenum hexacarbonyl TRICARBONYL(CYCLOHEPTATRIENE)CHROMIUM DICARBONYLCYCLOPENTADIENYLIODOIRON CARBONYLCHLOROBIS(TRIPHENYLPHOSPHINE)IRIDIUM(I) (METHYL BENZOATE)TRICARBONYLCHROMIUM METHYLCYCLOPENTADIENYLMANGANESE TRICARBONYL TRICARBONYL(1,2,3,4-TETRAHYDRONAPHTHALENE)CHROMIUM CYCLOPENTADIENYLMANGANESE TRICARBONYL (TOLUENE)TRICARBONYLCHROMIUM DICARBONYLCYCLOPENTADIENYLCOBALT Dicarbonylacetylacetonato rhodium(I) CYCLOPENTADIENYLMOLYBDENUM TRICARBONYL DIMER CYCLOHEPTATRIENE MOLYBDENUM TRICARBONYL (ANISOLE)TRICARBONYLCHROMIUM, 99
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