Allotropes of phosphorus
solid forms of the element phosphorus
Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus.
White phosphorus
White phosphorus, yellow phosphorus or simply tetraphosphorus (P4) exists as molecules of four phosphorus atoms in a tetrahedral structure, joined by six phosphorus—phosphorus single bonds. The free P4 molecule in the gas phase has a P-P bond length of rg = 2.1994(3) Å as was determined by gas electron diffraction. Despite the tetrahedral arrangement the P4 molecules have no significant ring strain and a vapor of P4 molecules is stable. This is due to the nature of bonding in the P4 tetrahedron which can be described by spherical aromaticity or cluster bonding, that is the electrons are highly delocalized. This has been illustrated by calculations of the magnetically induced currents, which sum up to 29 nA/T, much more than in the archetypical aromatic molecule benzene (11 nA/T).
Molten and gaseous white phosphorus also retains the tetrahedral molecules, until 800 °C (1,500 °F; 1,100 K) when it starts decomposing to P2 molecules.
White phosphorus is a translucent waxy solid that quickly yellows in light, and impure white phosphorus is for this reason called yellow phosphorus.
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