Phosphorus with Oxygen

Many different kinds of instantaneous lights are made with phosphorus, owing to its ready combustibility by friction, especially when chlorate of potash is used. 

Vve are acquainted with four compounds of phosphorus and oxygen. 

This oxide is obtained by causing a current of oxygen to come in contact with phosphorus under boiling water. Combustion takes place, and some phosphoric acid is formed but a part of the phosphorus forms an insoluble cinnabar red powder, which is oxide of phosphorus, P, O. 

It bums, if heated nearly to redness, in the air if heated in close vessels, it is resolved into phosphorus and phosphoric acid, SP,0=P,05-f-P, It is oxidised with combustion by nitric acid, and takes fire in chlorine gas. 

In the separate, or hydrated state, P,0, 3HO, or P,0, H,. This acid is formed when phosphurets of the alkaline metals act on water, or when phosphorus is boiled with alkalies and water, phosphoric acid and phosphuretted hydrogen gas being formed at tne same time. The two acids combine with the base and if this be lime or baryta, the hypophosphite being soluble, is easily separated from the insoluble phosphate. From the hypophosphite of baryta sulphuric acid removes the baryta, and the hypophosphorous acid is left, dissolved in water. By gentle evaporation it may be obtained as a deliquescent crystalline mass, which is the hydrated acid. 

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A simple way of preparing hydroxyethylidene-diphosphonic acid which is an excellent chelating agent for Mg and Ca-ions consists in the reaction of white phosphorus with oxygen in acetic acid first at 80 °C and then heating the mixture to 150 °C i). 

High thermal stability enables P-red to withstand an extrusion temperature of up to 320 °C without decomposing and be particularly suitable for polyamides. During combustion, the combination of the phosphorus with oxygen and nitrogen in the polymer produces intermediates that then recombine to make an extended char layer as the flame retardant proponent. 

Discussed polymers are derived from the phosphorus atoms at two different level of oxidation, namely, pentavalent (P ) and trivalent (P ). Structurally, these compounds can be penta-, tetra-, or tricoordinated with direct bonding of phosphorus with oxygen or carbon atoms. 

Phosphorus(III) oxide reacts slowly with oxygen at ordinary temperatures to give the pentoxide, P40,g. The reaction is rapid if the oxide is heated in air. It is oxidised vigorously by chlorine and bromine which form the oxidehalides, POX3. 

The trichloride is obtained as a liquid, boiling point 349 K, when a jet of chlorine burns in phosphorus vapour. Care must be taken to exclude both air and moisture from the apparatus since phosphorus trichloride reacts with oxygen and is vigorously hydrolysed by water, fuming strongly in moist air. The hydrolysis reaction is ... 

The reaction with oxygen converts phosphorus trichloride to phosphorus trichloride oxide (oxychloride), POCI3 the trichloride is able to remove oxygen from some molecules, for example sulphur trioxide... 

Ihese reactions (and those of the irichloride) indicate the great tendency of (pentavalent) phosphorus to unite with oxygen (cf. silicon). 

Zinc and cadmium tarnish quickly in moist air and combine with oxygen, sulfur, phosphorus and the halogens on being heated. Mercury also reacts with these elements, except phosphorus and its reaction with oxygen was of considerable practical importance in the early work of J. Priestley and A. L. Lavoisier on oxygen (p. 601). The reaction only becomes appreciable at temperatures of about 350° C, but above about 400°C HgO decomposes back into the elements. 

The initial step of olefin formation is a nucleophilic addition of the negatively polarized ylide carbon center (see the resonance structure 1 above) to the carbonyl carbon center of an aldehyde or ketone. A betain 8 is thus formed, which can cyclize to give the oxaphosphetane 9 as an intermediate. The latter decomposes to yield a trisubstituted phosphine oxide 4—e.g. triphenylphosphine oxide (with R = Ph) and an alkene 3. The driving force for that reaction is the formation of the strong double bond between phosphorus and oxygen ... 

Phosphorus reacts with oxygen to produce different kinds of oxides. One of these oxides is formed when 1.347 g of phosphorus reacts with 1.744 g of oxygen. What is the simplest formula of this oxide Name the oxide. 

There are many methods for the preparation of ethane-1-hydroxy-1,1-diphosphonic acid including reacting phosphorus trichloride and acetic acid in the presence of tributylamine [106], phosphorus with acetic acid and oxygen [108], acetic anhydride with phosphorous acid and acetyl chloride [80,84-86,109,110], and acetic anhydride with phosphoric acid and acetic acid [111]. By another method ketene and phosphorous acid can be used [112], as shown in Eq. (68) ... 

It is interesting to point out that the same kind of arylation of this methoxyethanol with arylbromide, performed in the same reactions conditions, but now in presence of copper(I) or (II) catalysts with oxygen, phosphorus or nitrogen ligands give very poor yields no higher than 12 % in aryl ether (Fig. 10). 

Japanese workers have prepared diethyl phosphite in 43% yield from the reaction of white phosphorus with ethanol and oxygen. 

The phosphinic isocyanates (116) and isothiocyanates (117) react with oxygen, nitrogen, and phosphorus nucleophiles by attack at carbon rather than phosphorus. Phenyl phosphonodichloridate has been recommended as a useful reagent for the activation (presumably by mixed anhydride formation) of carboxylic acids for conversion to amides and hydrazides. ... 

The formation and reaction of peroxyl radicals derived by reaction of tervalent phosphorus compounds with oxygen have attracted interest. Photolysis of trialkyl phosphites in oxygenated solutions of aromatic hydrocarbons gives phenols. " Phosphorus trichloride reacts with 1,2-dichloroethylene, in the presence of oxygen, to give (17). It is tempting to suggest that both reactions occur via similar intermediates, e.g. (15) and (16). 

A chemist is about to synthesize tetraphosphorus decoxide by combining X grams of phosphorus with sufficient oxygen to react completely with the phosphorus. If he wants to determine the amount of tetraphosphorus decoxide that will be produced, all of the following need to be answered before initiating the experiment EXCEPT —... 

Thus it has so far proved possible to isolate stable derivatives of monomeric metaphosphoric acid and of metathio- and metaselenophosphoric acid, which, understandably, generally bear tert-butyl and/or trimethylsilyl substituents u. Specifically, we know aminobisiminophosphoranes (3, Z = NR2, X = Y = NR)2,3,4), aminoiminothio (or seleno)phosphoranes (5, Z = NR2, X = NR, Y = S or Se)5), and aminoiminomethylenephosphoranes (1, R = NR2, X = NR)6>. Conspicuously, no stable phosphorus(V) three-coordinate compounds have been synthesized with oxygen as divalent ligand. 

Several unusual cycloaddition reactions of 9 with unsaturated ketones should be mentioned in conclusion the heterocumulene generated photolytically from 7 undergoes [8 + 2]-cycloaddition with tropone to form 33 (40%) the structure of the product has been unequivocally established by X-ray structure analysis 22,23). Once again, the affinity of phosphorus for oxygen is manifested an entirely analogous cycloaddition reaction is known for diphenylketene 26). 

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