Allotropes of 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. 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, yellow phosphorus or simply tetraphosphorus (P4) exists as molecules made up of four atoms in a tetrahedral structure. The tetrahedral arrangement results in ring strain and instability. The molecule is described as consisting of six single P–P bonds. Two different crystalline forms are known. The α form is defined as the standard state of the element, but is actually metastable under standard conditions. It has a body-centered cubic crystal structure, and transforms reversibly into the β form at 195.2 K. The β form is believed to have a hexagonal crystal structure. White phosphorus is a translucent waxy solid that quickly becomes yellow when exposed to light. For this reason it is also called yellow phosphorus. It glows greenish in the dark (when exposed to oxygen) and is highly flammable and pyrophoric (self-igniting) upon contact with air. It is toxic, causing severe liver damage on ingestion and phossy jaw from chronic ingestion or inhalation. The odour of combustion of this form has a characteristic garlic smell, and samples are commonly coated with white 'diphosphorus pentoxide', which consists of P4O10 tetrahedral with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is only slightly soluble in water and can be stored under water. Indeed, white phosphorus is safe from self-igniting only when it is submerged in water. It is soluble in benzene, oils, carbon disulfide, and disulfur dichloride. The white allotrope can be produced using several different methods. In the industrial process, phosphate rock is heated in an electric or fuel-fired furnace in the presence of carbon and silica. Elemental phosphorus is then liberated as a vapour and can be collected under phosphoric acid. An idealized equation for this carbothermal reaction is shown for calcium phosphate (although phosphate rock contains substantial amounts of fluoroapatite): White phosphorus has an appreciable vapour pressure at ordinary temperatures. The vapour density indicates that the vapour is composed of P4 molecules up to about 800 °C. Above that temperature, dissociation into P2 molecules occurs.