Chemistry » Metals, Metalloids, and Nonmetals » Structure and General Properties of the Nonmetals



The name phosphorus comes from the Greek words meaning light bringing. When phosphorus was first isolated, scientists noted that it glowed in the dark and burned when exposed to air. Phosphorus is the only member of its group that does not occur in the uncombined state in nature; it exists in many allotropic forms. We will consider two of those forms: white phosphorus and red phosphorus.

White phosphorus is a white, waxy solid that melts at 44.2 °C and boils at 280 °C. It is insoluble in water (in which it is stored—see the figure below), is very soluble in carbon disulfide, and bursts into flame in air. As a solid, as a liquid, as a gas, and in solution, white phosphorus exists as P4 molecules with four phosphorus atoms at the corners of a regular tetrahedron, as illustrated in the figure below. Each phosphorus atom covalently bonds to the other three atoms in the molecule by single covalent bonds. White phosphorus is the most reactive allotrope and is very toxic.

Two photos and two diagrams are shown and labeled “a,” “b,” “c,” and “d.” Photo a shows a test tube that contains a solid yellow compound. Diagram b shows a four-sided pyramid shape that has an atom at each corner. Photo c shows a dark black powder in a watch glass. Diagram d shows two four-sided pyramid shapes that have an atom at each corner and are connected together by a single bond.

(a) Because white phosphorus bursts into flame in air, it is stored in water. (b) The structure of white phosphorus consists of P4 molecules arranged in a tetrahedron. (c) Red phosphorus is much less reactive than is white phosphorus. (d) The structure of red phosphorus consists of networks of P4 tetrahedra joined by P-P single bonds. (credit a: modification of work from

Heating white phosphorus to 270–300 °C in the absence of air yields red phosphorus. Red phosphorus (shown in the figure above) is denser, has a higher melting point (~600 °C), is much less reactive, is essentially nontoxic, and is easier and safer to handle than is white phosphorus. Its structure is highly polymeric and appears to contain three-dimensional networks of P4 tetrahedra joined by P-P single bonds. Red phosphorus is insoluble in solvents that dissolve white phosphorus. When red phosphorus is heated, P4 molecules sublime from the solid.

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