Sunday 16 August 2015

Carbon monoxide (CO) - colorless, odorless, and tasteless gas

Carbon monoxide (CO) is a colorless, odorless, and tasteless gas that is slightly less dense than air. It is toxic to humans when encountered in concentrations above about 35 ppm, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal biological functions. In the atmosphere, it is spatially variable and short lived, having a role in the formation of ground-level ozone.

Carbon monoxide consists of one carbon atom and one oxygen atom, connected by a triple bond that consists of two covalent bonds as well as one dative covalent bond. It is the simplest oxocarbon and is isoelectronic with the cyanide anion, the nitrosonium cation and molecular nitrogen. In coordination complexes the carbon monoxide ligand is called carbonyl.

Carbon monoxide is produced from the partial oxidation of carbon-containing compounds; it forms when there is not enough oxygen to produce carbon dioxide (CO2), such as when operating a stove or an internal combustion engine in an enclosed space. In the presence of oxygen, including atmospheric concentrations, carbon monoxide burns with a blue flame, producing carbon dioxide.Coal gas, which was widely used before the 1960s for domestic lighting, cooking, and heating, had carbon monoxide as a significant fuel constituent. Some processes in modern technology, such as iron smelting, still produce carbon monoxide as a byproduct.

Worldwide, the largest source of carbon monoxide is natural in origin, due to photochemical reactions in the troposphere that generate about 5×1012 kilograms per year.Other natural sources of CO include volcanoes, forest fires, and other forms of combustion.

In biology, carbon monoxide is naturally produced by the action of heme oxygenase 1 and 2 on the heme from hemoglobin breakdown. This process produces a certain amount of carboxyhemoglobin in normal persons, even if they do not breathe any carbon monoxide. Following the first report that carbon monoxide is a normal neurotransmitter in 1993, as well as one of three gases that naturally modulate inflammatory responses in the body (the other two being nitric oxide and hydrogen sulfide), carbon monoxide has received a great deal of clinical attention as a biological regulator. In many tissues, all three gases are known to act as anti-inflammatories, vasodilators, and promoters of neovascular growth. Clinical trials of small amounts of carbon monoxide as a drug are ongoing.Carbon monoxide has a molar mass of 28.0, which makes it slightly lighter than air, whose average molar mass is 28.8. According to the ideal gas law, CO is therefore less dense than air.

The bond length between the carbon atom and the oxygen atom is 112.8 pm. This bond length is consistent with a triple bond, as in molecular nitrogen (N2), which has a similar bond length and nearly the same molecular mass. Carbon–oxygen double bonds are significantly longer, 120.8 pm in formaldehyde, for example. The boiling point (82 K) and melting point (68 K) are very similar to those of N2 (77 K and 63 K, respectively). The bond dissociation energy of 1072 kJ/mol is stronger than that of N2 (942 kJ/mol) and represents the strongest chemical bond known.

The ground electronic state of carbon monoxide is a singlet state since there are no unpaired electrons.

Bonding and dipole moment
Carbon and oxygen together have a total of 10 valence electrons in carbon monoxide. To satisfy the octet rule for the carbon, the two atoms form a triple bond, with six shared electrons in three bonding molecular orbitals, rather than the usual double bond found in organic carbonyl compounds. Since four of the shared electrons come from the oxygen atom and only two from carbon, one bonding orbital is occupied by two electrons from oxygen, forming a dative or dipolar bond. This causes a C ← O polarization of the molecule, with a small negative charge on carbon and a small positive charge on oxygen. The other two bonding orbitals are each occupied by one electron from carbon and one from oxygen, forming (polar) covalent bonds with a reverse C → O polarization, since oxygen is more electronegative than carbon. In the free carbon monoxide, a net negative charge δ- remains at the carbon end and the molecule has a small dipole moment of 0.122 D.

The molecule is therefore asymmetric: oxygen has more electron density than carbon, and is also slightly positively charged compared to carbon being negative. By contrast, the isoelectronic dinitrogen molecule has no dipole moment.

If carbon monoxide acts as a ligand, the polarity of the dipole may reverse with a net negative charge on the oxygen end, depending on the structure of the coordination complex. See also the section "Coordination chemistry" below.

Bond polarity and oxidation state
Theoretical and experimental studies show that, despite the greater electronegativity of oxygen, the dipole moment points from the more-negative carbon end to the more-positive oxygen end.The three bonds are in fact polar covalent bonds that are strongly polarized. The calculated polarization toward the oxygen atom is 71% for the σ-bond and 77% for both π-bonds.

The oxidation state of carbon in carbon monoxide is +2 in each of these structures. It is calculated by counting all the bonding electrons as belonging to the more electronegative oxygen. Only the two non-bonding electrons on carbon are assigned to carbon. In this count, carbon then has only two valence electrons in the molecule compared to four in the free atom.

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