Essential phosphorus

PHOSPHOPROTEINS. These proteins have phosphate groups esterified to the hydroxyls of serine, threonine, or tyrosine residues. Casein, the major protein of milk, contains many phosphates and serves to bring essential phosphorus to the growing infant. Many key steps in metabolism are regulated between states of activity or inactivity, depending on the presence or absence of phosphate groups on proteins, as we shall see in Chapter 15. Glycogen phospho-rylase a is one well-studied example. 

Fe 5.0 Not toxic to plants in aerated soils, but can contribute to soil acidification and loss of availability of essential phosphorus and molybdenum. Overhead sprinkling may result in unsightly deposits on plants, equipment and buildings... 

Phosphorus compounds are very important as fertilizers (world use 1976/77 27-3 megatonnes as P2O5) but are widely used in matches, pesticides, special glasses and china ware, alloys (sleels. phosphor bronze), and metal treating (10%), detergents (40%), electrical components (e.g. GaP), foods and drinks (15%). Phosphates are an essential constituent of living organisms. U.S. production of phosphorus 1982 372 000 tonnes. 

Phosphorus, like nitrogen, is an essential constituent of living matter where it may be partly in combination (as phosphate groups) with organic groups, for example in lecithin and egg yolk, or mainly in inorganic form, as calcium phosphate(V), in bones and teeth. 

Phosphine is a colourless gas at room temperature, boiling point 183K. with an unpleasant odour it is extremely poisonous. Like ammonia, phosphine has an essentially tetrahedral structure with one position occupied by a lone pair of electrons. Phosphorus, however, is a larger atom than nitrogen and the lone pair of electrons on the phosphorus are much less concentrated in space. Thus phosphine has a very much smaller dipole moment than ammonia. Hence phosphine is not associated (like ammonia) in the liquid state (see data in Table 9.2) and it is only sparingly soluble in water. 

Nitrogen is unusual in forming so many oxides. The acidity of the Group V oxides falls from phosphorus, whose oxides are acidic, through arsenic and antimony whose oxides are amphoteric, to the basic oxide ofbismuth. This change is in accordance with the change from the non-metallic element, phosphorus, to the essentially metallic element, bismuth. The +5 oxides are found, in each case, to be more acidic than the corresponding + 3 oxides. 

White phosphorus may be made by several methods. By one process, tri-calcium phosphate, the essential ingredient of phosphate rock, is heated in the presence of carbon and silica in an electric furnace or fuel-fired furnace. Elementary phosphorus is liberated as vapor and may be collected under phosphoric acid, an important compound in making super-phosphate fertilizers. 

Phosphorus is also an essential ingredient of all cell protoplasm, nervous tissue, and bones. 

The pentahalides of phosphorus, PX, in the gas phase exhibit varying tendencies to dissociate into trihaUde and halogen. InstabiUty increases with increasing ionic radius of the halogen. The pentafluoride appears to be thermally stable. Dissociation of the pentachloride, a few percent at 100°C and 101.3 kPa (1 atm), is essentially completed at 300°C (36). The pentabromide is partially dissociated in the Hquid state and totally dissociated above ca 35°C (39). Pentaiodide does not exist. The molecules of PF and PCl in the vapor phase are trigonal bipyramids. In the crystalline state, both pentachloride and pentabromide have ionic stmctures, ie, [PClJ IPClg] and [PBr4]" PBrJ , respectively. The PX" 4 cations are tetrahedral and the PX anion is octahedral (36,37). 

Properties and Essential Information for S afe Handling and Use of Phosphorus Ouychloride, Chemical Manufacturers Association Chemical Safety Data Sheet SD-26, Washington, D.C., 1948. 

It is becoming increasingly clear that, in shallow lakes which have high rates of phosphorus sediment re-cycling, bio-manipulation is an essential element of successful restoration. 

Although previous experience indicates that phosphorus is not essential for these reductions, purification of the product is more difficult with its omission. With iiydrocarbons sensitive to further reduction, phosphorus can have a deleterious effect through promotion of hydrogenation of the desired product. Whether or not phosphorus should be employed in an indi-... 

Bromopyridine has been made by direct bromination of pyridine - from N-methyl-2-pyridone with phosphorus penta-bromide and phosphorus oxybromide from 2-aminopyridine by diazotization with amyl nitrite in 20% hydrobromic acid from sodium 2-pyridinediazotate by solution in concentrated hydrobromic acid and from 2-aminopyridinc by diazotization in the presence of bromine and concentrated hydrobromic acidd The method described here is essentially that of Craig. 

The method is essentially that discovered by Boeseken and Prins - and studied further by Prinsd Pentachloroethane can be used in place of tetrachlorethylene, as it is converted into the unsaturated compound in the presence of aluminum chloride. irwiyw.-Heptachloropropane has been obtained also by the action of phosphorus pentachloride on pentachloroacetone, and by treating dichloroacetyl chloride with aluminum chloride. ... 

Kinetic studies have shown that the enolate and phosphorus nucleophiles all react at about the same rate. This suggests that the only step directly involving the nucleophile (step 2 of the propagation sequence) occurs at essentially the diffusion-controlled rate so that there is little selectivity among the individual nucleophiles. The synthetic potential of the reaction lies in the fact that other substituents which activate the halide to substitution are not required in this reaction, in contrast to aromatic nucleophilic substitution which proceeds by an addition-elimination mechanism (see Seetion 10.5). 

Mixed fertilizers contain two or more of the elements nitrogen, phosphorus, and potassium (NPK), which are essential for good plant growth and high crop yields. This subsection briefly addresses the production of ammonium phosphates... 

Although most of the macrocycles that contain phosphorus or arsenic which have thus far been prepared, are primarily transition metals binders, two compounds have been prepared which are essentially crown ethers containing phosphorus. Kudrya, Shtepanek and Kirsanovhave prepared two compounds which are essentially polyoxygen macrocycles but which contain one or two methylphosphonic acid esters as part of the ring. These two macrocycles are shown below as 7d and 17 and are both prepared by the reaction of 2,2 [oxybis(ethyleneoxy)] bisphenolate with methylphosphonic dichloride in a mixture of acetonitrile and benzene. The crystalline monomer 16) and dimer 17) were isolated in 17% and 11% yields respectively as indicated in Eq. (6.13). 

The diphosphadithiatetrazocines 13.2 (E = S) and 13.3 (E = S) contain one more R2PN unit in the ring than 13.1. The structure of the orange-red 1,3-isomer (13.2, E = S, R = Ph) consists of an essentially planar N3S2 unit with the two phosphorus atoms located on opposite sides of the plane." Like 13.1 this isomer forms a 1 1 adduct with norbornadiene via 1,3-addition across the sulfur atoms. 

Phosphorus also occurs in all living things and the phosphate cycle, including the massive use of phosphatic fertilizers, is of great current interest.O 20) -pj.jg movement of phosphorus through the environment differs from that of the other non-metals essential to life (H, C, N, O and S) because it has no volatile compounds that can circulate via the atmosphere. Instead, it circulates via two rapid biological... 

Steel is essentially iron with a small amount of carbon. Additional elements are present in small quantities. Contaminants such as sulfur and phosphorus are tolerated at varying levels, depending on the use to which the steel is to be put. Since they are present in the raw material from which the steel is made it is not economic to remove them. Alloying elements such as manganese, silicon, nickel, chromium, molybdenum and vanadium are present at specified levels to improve physical properties such as toughness or corrosion resistance. 

In hospitals, chemical analysis is widely used to assist in the diagnosis of illness and in monitoring the condition of patients. In farming, the nature and level of fertiliser application is based upon information obtained by analysis of the soil to determine its content of the essential plant nutrients, nitrogen, phosphorus and potassium, and of the trace elements which are necessary for healthy plant growth. 

The most common selective detectors in use generally respond to the presence of a characteristic element or group in the eluted compound. This is well illustrated by the thermionic ionisation detector (TID) which is essentially a flame ionisation detector giving a selective response to phosphorus- and/or nitrogen-containing compounds. Typically the TID contains an electrically heated rubidium silicate bead situated a few millimetres above the detector jet tip and below the collector electrode. The temperature of the bead is maintained... 

The method can be applied to the determination of phosphorus in a wide variety of materials, e.g. phosphate rock, phosphatic fertilisers and metals, and is suitable for use in conjunction with the oxygen-flask procedure (Section 3.31). In all cases it is essential to ensure that the material is so treated that the phosphorus is converted to orthophosphate this may usually be done by dissolution in an oxidising medium such as concentrated nitric acid or in 60 per cent perchloric acid. 

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