Pentoxide

The reaction uses a fixed-bed vanadium pentoxide-titanium dioxide catalyst which gives good selectivity for phthalic anhydride, providing temperature is controlled within relatively narrow limits. The reaction is carried out in the vapor phase with reactor temperatures typically in the range 380 to 400°C. 

Dehumidification may be effected by cooling. Where small quantities of dry air are required dehumidification can be carried out using chemical absorbents, e.g. calcium chloride, phosphorus pentoxide, sulphuric acid, etc. 

Dinilrogen pentoxide, N2O5. White solid (HNO3 plus P2OJ) readily decomposes to NO2 and O2, sublimes 32-5 "C. In solid slate (N02) (N03) gaseous molecules O2NONO2... 

Dinitrogeri pentoxide is the anhydride of nitric acid and is prepared by removing water from pure nitric acid by means of phosphorus (V) oxide. It is a crystalline solid having the ionic structure of (N02) (N03) , nitronium nitrate (the nitronium ion is mentioned later). It decomposes above 273 K, thus ... 

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. 

This oxide was originally given the formula P2O5 and called phosphorus pentoxide but the vapour density and structure indicate the formula P40,q. It is prepared by burning phosphorus in a plentiful supply of air or oxygen ... 

Phosphorus(V) oxide will remove water from acids to give the acid anhydride. For example, if nitric acid is distilled with it. dinitrogen pentoxide is formed ... 

Unlike phosphorus pentoxide, this oxide cannot be made directly. Arsenic(V) acid, H3ASO4 (strictly, tetraoxoarsenic acid), is first prepared by oxidising arsenic(III) oxide with concentrated nitric acid or some other strong oxidising agent ... 

There appears to be only one true oxide of iodine, diiodine pentoxide, IjOs- It is a white solid prepared by heating iodic acid(V) to 450 K ... 

As the equation indicates, it is the anhydride of iodic-acid(V), which is re-formed when water is added to the pentoxide. Mixed with concentrated sulphuric acid and silica, it is a quantitative oxidising agent for carbon monoxide at room temperature ... 

The iodic acid may then be dehydrated by heat, giving iodine pentoxide... 

Vanadium pentoxide, vanadium(V) oxide, V2O5, is the most important compound in this oxidation state. It is a coloured solid (colour due to charge transfer, p. 60), the colour varying somewhat (red -> brown) with the state of subdivision it is formed when vanadium (or some of its compounds) is completely oxidised, and also by heating ammonium vanadate)V) ... 

Cobaltilll) nitrate Co(N03)3 has been prepared by the reaction of dinitrogen pentoxide with cobalt(III) fluoride. 

Dehydration of the corresponding acid amides. This process usually requires phosphorus pentoxide (correctly termed phosphoric anhydride) as a dehydrating agent. 

The crude acetonitrile contains as impurity chiefly acetic acid, arising from the action of phosphoric acid on the acetamide. Therefore add to the nitrile about half its volume of water, and then add powdered dry potassium carbonate until the well-shaken mixture is saturated. The potassium carbonate neutralises any acetic acid present, and at the same time salts out the otherwise water-soluble nitrile as a separate upper layer. Allow to stand for 20 minutes with further occasional shaking. Now decant the mixed liquids into a separating-funnel, run off the lower carbonate layer as completely as possible, and then pour off the acetonitrile into a 25 ml, distilling-flask into which about 3-4 g. of phosphorus pentoxide have been placed immediately before. Fit a thermometer and water-condenser to the flask and distil the acetonitrile slowly, collecting the fraction of b.p. 79-82°. Yield 9 5 g. (12 ml.). 

Phosphorus pentoxide. This is an extremely efficient reagent and is rapid in its reaction. Phosphoric oxide is difficult to handle, channels badly, is expensive, and tends to form a syrupy coating on its surface after a little use. A preliminary drying with anhydrous magnesium... 

Alkyl halides Aryl halides Anhydrous calcium chloride anhydrous sodium, magnesium or calcium sulphate phosphorus pentoxide. 

Saturated and aromatic hydrocarbons Ethers Anhydrous calcium chloride anhydrous calcium sulphate metallic sodium phosphorus pentoxide. 

By the dehydration of primary amides with phosphorus pentoxide or with thionyl chloride, for example ... 

Commercially, maleic anhydride is prepared more cheaply by the catalytic vapour phase oxidation (in the presence of vanadium pentoxide at about 400°) of benzene with atmospheric oxygen ... 

Fumaric acid is conveniently prepared by the oxidation of the inexpensive furfural with sodium chlorate in the presence of a vanadium pentoxide catalyst ... 

C. Fumaric acid from furfural. Place in a 1-litre three-necked flask, fitted with a reflux condenser, a mechanical stirrer and a thermometer, 112 5 g. of sodium chlorate, 250 ml. of water and 0 -5 g. of vanadium pentoxide catalyst (1), Set the stirrer in motion, heat the flask on an asbestos-centred wire gauze to 70-75°, and add 4 ml. of 50 g. (43 ml.) of technical furfural. As soon as the vigorous reaction commences (2) bvi not before, add the remainder of the furfural through a dropping funnel, inserted into the top of the condenser by means of a grooved cork, at such a rate that the vigorous reaction is maintained (25-30 minutes). Then heat the reaction mixture at 70-75° for 5-6 hours (3) and allow to stand overnight at the laboratory temperature. Filter the crystalline fumaric acid with suction, and wash it with a little cold water (4). Recrystallise the crude fumaric acid from about 300 ml. of iif-hydrochloric acid, and dry the crystals (26 g.) at 100°. The m.p. in a sealed capillary tube is 282-284°. A further recrystaUisation raises the m.p. to 286-287°. 

The vanadium pentoxide catalyst Is prepared as follows Suspend 5 g. of pure ammonium vanadate in 50 ml. of water and add slowly 7 5 ml. of pure concentrated hydrochloric acid. Allow the reddish-brown, semi-colloidal precipitate to settle (preferably overnight), decant the supernatant solution, and wash the precipitate several times by decantation. Finally, suspend the precipitate in 76 ml. of water and allow it to stand for 3 days. This treatment renders the precipitate granular and easy to 6lter. Filter the precipitate with suction, wash it several times with cold 5 p>er cent, sodium chloride solution to remove hydrochloric acid. Dry the product at 120° for 12 hours, grind it in a mortar to a fine powder, and heat again at 120° for 12 hours. The yield of catalyst is about 3 - 5 g. 

Benzoquinone ( quinone ) is obtained as the end product of the oxidation of aniline by acid dichromate solution. Industrially, the crude product is reduced with sulphur dioxide to hydroquinone, and the latter is oxidised either with dichromate mixture or in very dilute sulphuric acid solution with sodium chlorate in the presence of a little vanadium pentoxide as catalyst. For the preparation in the laboratory, it is best to oxidise the inexpensive hydroquinone with chromic acid or with sodium chlorate in the presence of vanadium pent-oxide. Naphthalene may be converted into 1 4-naphthoquinone by oxidation with chromic acid. 

---