Chemistry of phosphorus

Phosphorus is the eleventh most abundant element in the crystal rocks of the earth. Elemental phosphorus does not exist in nature and all of its known terrestrial minerals are orthophosphates found in phosphate rocks which occur in vast deposits throughout the world. Phosphate rock is the starting material for the industrial manufacture of elemental phosphorus. White phosphorus is produced by heating phosphate rock with sand and coke in an electric furnace according to Equations 5.19  

The gaseous WP (P4) is distilled from the furnace by condensing with water. The WP allotrope that is formed by this process is a white waxy solid with a m.p. of 45 °C that should be kept under water to prevent its contact with air where it spontaneously ignites because of its extreme reactivity. It is also known as yellow phosphorus because most commercially-produced material exhibits yellow coloration. Red phosphorus (RP) is thermodynamically more stable than the white 

Appearance Crystalline waxy translucent Amorphous or crystalline opaque Crystalline resembling graphite 

Reprinted with permission from Peter J.D. Collins, Proc. 27th Inti. Pyrotech. Sem., 2000, pp. 191-205 2000, IPSUSA Seminars Inc, USA. 

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M. Halmann, Analytical Chemistry of Phosphorus Compounds, Wiley-Interscience, New York, 1972. 

MI1 L. D. Quin, The Heteroeyelie Chemistry of Phosphorus, Wiley Inter-... 

A. J. Kirby and S. G. Warren, The Organic Chemistry of Phosphorus, Elsevier, Amsterdam, 1967. 

This review concerns in the first part the works published during the last three years on the synthesis and reactivity of stabilized ylides C-substituted by electron-withdrawing groups (COR, CO2R, CN, etc.). The second part deals with the works published in the same period on the chemistry of phosphorus ylides mainly C-substituted by heteroatoms of groups 1-16 (metals, metalloids and nonmetal elements Li, Ba, Ca, Ti, Zr, Nb, Mo, Re, Fe, Ru, Rh, Pd, Pt, Au, Zn, Hg, B, Si, Sn, N, P, As, Sb, O, S, Te). 

P. B. Tinker, The chemistry of phosphorus and mycorrhizal effects on plant growth, Endoinycorrhizas (F. S. Saunders, B. Mosse, and P. B. Tinker, eds.). Academic Press, London, 1975, p. 353. 

Burg, A. B., and K. Modritzer Chemistry of Phosphorus Aluminium Bonding Dimethylphosphino-Aluminium Hydrides and Chlorides. J. Inorg. Nucl. Chem. 13, 318 (1960). 

Quin LD (1981) The heterocyclic chemistry of phosphorus systems based on the phosphorus-carbon bond. Wiley, New York... 

Recent work in the chemistry of phosphorus heterocycles derived from a-hydroxyalkylphosphines and vinylphosphines, much of which has appeared in the Russian language literature, is covered by B. A. Arbuzov and G. N. Nikonov (Kazan, Russia). 

All of the elements are important, and they are found in many common compounds. Some phosphorus compounds are among the most useful and essential of any element. As a result, there is a great deal more extensive chemistry of phosphorus, and more space will be devoted to it in this chapter. Much of the chemistry of the other elements can be inferred by comparison to the analogous phosphorus compounds but realizing the greater metallic character of As and Sb. 

The organic chemistry of phosphorus includes many compounds, but the phosphite esters are especially useful. These compounds can be prepared by the reaction of PC13 with an alcohol. 

Carbridge, D. E. C. (1974). The Structural Chemistry of Phosphorus. Elsevier, New York. An advanced treatise on an enormous range of topics in phosphorus chemistry. 

Although there exists a good understanding of the chemistry of phosphorus in soil-water systems, the hydrologic pathways linking spatially variable phosphorus sources, sinks, temporary storages, and transport processes in landscapes are less... 

Quin, L. D. The Heterocyclic Chemistry of Phosphorus, Wiley New York, 1981. 

From this brief review it will be realized that a new organic chemistry of phosphorus and fluorine arose during the war. Interest in these compounds now spreads far beyond the domain of chemistry, and the applications in agriculture and medicine have been particularly gratifying to those of us who worked on these substances initially as chemical warfare agents. Fortunately, they have not been used for the purpose for which they were originally designed. 

In view of the rapid growth of the organic chemistry of phosphorus since 1939, considerable attention has been paid to nomenclature. It has not always been easy to achieve agreement among workers in different parts of the world as to the most logical, convenient and simple system. It may not be out of place therefore to trace the inner history of some of the changes and developments that have taken place. However, the reader who is interested only in the details of the nomenclature as now accepted should turn at once to p. 25. 

Coates, H. The chemistry of phosphorus insecticides. Am. Appl. Biol, 36 156-159, 1949. 

In this and the following section the crystal structures of dithiophosphate compounds are summarized and compared to those of related compounds. As is obvious from Tables 5 and 6, dithiophosphate compounds comprise a fruitful area for structural research. Additional data for comparative purposes may be found in Corbridge s review of the structural chemistry of phosphorus compounds. 

The chemistry of phosphorus compounds with a delocalized P-C double bond proves to be very versatile. Whereas the physical properties of phosphamethin-cyanines are similar to the corresponding methin- or azamethin-cyanines, their chemical properties are distinguished by the higher reactivity of the phosphorus atom and the phosphorus-carbon double bond. 

J. Emsley and D. Hall, The Chemistry of Phosphorus, Wiley, Chichester, 1976. 

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