Iron phosphates

Resorcinol Derivatives. Aminophenols (qv) are important intermediates for the syntheses of dyes or active molecules for agrochemistry and pharmacy. Syntheses have been described involving resorcinol reacting with amines (91). For these reactions, a number of catalysts have been used / -toluene sulfonic acid (92), zinc chloride (93), zeoHtes and clays (94), and oxides supported on siUca (95). In particular, catalysts performing the condensation of ammonia with resorcinol have been described gadolinium oxide on siUca (96), nickel, or zinc phosphates (97), and iron phosphate (98). 

Hydrogenis prevented from forming a passivating layer on the surface by an oxidant additive which also oxidizes ferrous iron to ferric iron. Ferric phosphate then precipitates as sludge away from the metal surface. Depending on bath parameters, tertiary iron phosphate may also deposit and ferrous iron can be incorporated into the crystal lattice. When other metals are included in the bath, these are also incorporated at distinct levels to generate species that can be written as Zn2Me(P0 2> where Me can represent Ni, Mn, Ca, Mg, or Fe. 

Metal Treatment. After rolling, the oxide scale on sheet steel is removed by acid treatment (pickling) (see Metal surface treatments). Phosphoric acid, a good pickling agent, leaves the steel coated with a thin film of iron phosphates. This process improves mst resistance but presents a problem if the steel is to be electroplated. 

The tertiary metal phosphates are of the general formula MPO where M is B, Al, Ga, Fe, Mn, etc. The metal—oxygen bonds of these materials have considerable covalent character. The anhydrous salts are continuous three-dimensional networks analogous to the various polymorphic forms of siHca. Of limited commercial interest are the alurninum, boron, and iron phosphates. Boron phosphate [13308-51 -5] BPO, is produced by heating the reaction product of boric acid and phosphoric acid or by a dding H BO to H PO at room temperature, foUowed by crystallization from a solution containing >48% P205- Boron phosphate has limited use as a catalyst support, in ceramics, and in refractories. 

The wash primer is a special type of vinyl coating. This material contains a poly(vinyl butyral) resin, zinc chromate, and phosphoric acid in an alcohol-water solvent. The coating is so thin it is HteraUy washed onto a freshly blasted steel surface, where it passivates the metal surface by converting it to a thin iron phosphate-chromate coating. The alcohol solvent makes it possible to apply the coating over damp surfaces. The coating forms the first coat of... 

Good quality steel is used and electrozinc is preferred for washing machines. Steel is pretreated with iron phosphate for economy electrozinc with a fine crystal zinc phosphate. No primer is normally used 25-40/im of finish is applied direct to metal. The required properties are best obtained with a thermosetting acrylic or polyester/melamine-formaldehyde finish. Self-reactive acrylics are usually preferred these resins contain about 15 Vo 7V-butoxymethyl acrylamide (CH2=CH —CO —NH —CHj—O —C4H,) monomer and cure in a manner similar to butylated melamine-formaldehyde resins. Resistance or anti-corrosive properties may be upgraded by the inclusion of small amounts of epoxy resin. Application is usually by electrostatic spray application from disc or bell. Shapes are complex enough to require convected hot-air curing. Schedules of 20 min at 150-175°C are... 

Very thin coatings of iron phosphate can be produced by treatment with solutions of alkali metal phosphate. These serve a useful purpose for the... 

Fig. 15.4 Effecl of heating on phosphate coatings for 16 h at various temperatures, showing loss of water of hydration. Curve A zinc phosphate, B iron phosphate and C iron manganese phosphate (courtesy y./.S./., 170, II (1952))...

The loss of water from conventional zinc and managanese phosphate coatings heated in air is from 10 to 20% higher than the loss on heating in the absence of air. It is thought that this greater loss may be due to oxidation of the iron phosphate present in the coatings. 

Manganese and/or iron phosphate coatings to be sealed with oil or grease 00125 0-5... 

Heavy phosphate coatings do not necessarily have better corrosion resistance than lighter coatings. Even with a single process, e.g. zinc/iron/ phosphate/nitrate, no consistent relationship has been found between corrosion resistance and either coating weight or weight of metal dissolved. 

The main value of salt-spray tests is in the evaluation of the effectiveness of phosphate coatings in restricting the spread of rust from scratches or other points of damage in a paint film. This feature is of particular interest to the motorcar industry, as vehicles are often exposed to marine atmospheres and to moisture and salt when the latter is used to disperse ice and frost from road surfaces. Great care is needed in the interpretation of a salt-spray test, as it has been found to favour thin iron phosphate coatings more than is justified by experience with natural weathering. In the motorcar industry the present custom is to use zinc phosphate coatings on the car bodies and all other parts exposed to the outside atmosphere. 

A Radiometric Study of the Iron Phosphating Process , US Dept, of Commerce, Office of Technical Services, Rep. No. PB 111, 400 (1953)... 

Conversion coating Conversion coatings are chemical solutions which react with the metal surface to create a corrosion-resistant layer onto which the coating can bond. For mild steel iron phosphate is used to attain good adhesion, but it does not give the underfilm corrosion resistance which can be obtained using zinc phosphate. Zinc coatings can be treated with either zinc phosphate or chromate. Aluminium is usually treated with chromate... 

Emerson, S. and Widmer, G. (1978). Early diagenesis in anaerobic lake sediments II. Equilibrium and kinetic factors controlling the formation of iron phosphate. Geochim. Cosmochim. Acta 42,1307-1316. 

Citraconic anhydride (Methyl maleic anhydride) was found to be produced from pyruvic acid by an oxidative decarboxy-condensation. The best catalyst is iron phosphate with a P/Fe atomic ratio of 1.2. The presence of oxygen is required to promote the reaction. The main side-reaction is formation of acetic acid and CO2 by oxidative C-C bond fission. The best results are obtained at a temperature of 200°C. The yield of citraconic anhydride reaches 71 mol% at a pyruvic acid conversion of 98%. 

Pyruvic acid is the simplest homologue of the a-keto acid, whose established procedures for synthesis are the dehydrative decarboxylation of tartaric acid and the hydrolysis of acetyl cyanide. On the other hand, vapor-phase contact oxidation of alkyl lactates to corresponding alkyl pyruvates using V2C - and MoOa-baseds mixed oxide catalysts has also been known [1-4]. Recently we found that pyruvic acid is obtained directly from a vapor-phase oxidative-dehydrogenation of lactic acid over iron phosphate catalysts with a P/Fe atomic ratio of 1.2 at a temperature around 230°C [5]. 

In the reaction of lactic acid to form pyruvic acid over the iron phosphate catalysts, formation of a new compound was observed. As the extent of reaction increased, the amount of pyruvic acid increased to a maximum and then decreased, while that of the new compound increased steadily. It was therefore concluded that the new compound is formed from pyruvic acid in parallel with acetic acid and CO2. According to gas-mass analyses, the molecular weight was determined as 112. However, there are many compounds with molecular weigth of 112. After the NMR analyses and X-ray diffraction analyses for the single crystal, the new compound was determined to be citraconic anhydride, i.e., mono-methyl maleic anhydride. 

An iron phosphate catalyst with a P/Fe atomic ratio of 1.2 used in this study was prepared according to the procedures described in the previous studies [6-8]. On the other hand, a V-P oxide catalyst with a P/V atomic ratio of 1.06 and pumice supported 12-molybdophosphoric acid (H3PM012O40) and its cesium salt (CS2HPM012O40) catalysts were the same as used in a previous study [9]. Pumice supported W03-based mixed oxide catalysts were the same as used in a previous study [10]. 

It should also be noted that the next best results are obtained with the iron phosphate catalyst under the reaction conditions used. 

The reaction was studied using the iron phosphate catalyst at 230°C with feed rates of pyruvic acid, air, and water = 10.5, 350, and 480 mmol/h. The main products were citraconic anhydride, acetic acid, and CO2. When the amount of catalyst used was lOg, that is, when the contact time is about 2.6 s, the conversion of pyruvic acid reached 95% and the yields of citraconic anhydride and acetic acid were 50 and 28 mol%, respectively the loss was about 17 mol%. The selectivity to citraconic anhydride is clearly lower and that to acetic acid is higher than in the case of the W-based oxide catalysts. However, the catalytic activity was very stable. No clear change in the yield of citraconic anhydride was observed during the reaction for 10 h. 

Effects of oxygen concentration on the reaction over iron phosphate catalyst... 

The reaction was performed over the iron phosphate catalyst by changing the feed rate of oxygen from zero to 350 mmol/h, while fixing the sum of feed rates of oxygen and nitrogen at 350 mmol/h. The feed rate of pyruvic acid was fixed at 10.5 mmol/h. The yields of citraconic anhydride obtained at a temperature of 230°C and a short contact time of 0.52 s (amount of catalyst used = 2 g) are plotted as a function of the feed rate of oxygen in Figure 3. 

As may be seen in Figures 5 and 6, when iron phosphate is used as the catalyst, the selectivity is dependent largely on the reaction temperature. Therefore, the activation energy for the citraconic anhydride formation is considered to be much lower than that for the acetic acid formation. Indeed, the selectivity to acetic acid decreases steadily with a decrease in the temperature. However, the selectivity to citraconic anhydride shows a maximum at about 200 C. Possibly, the vaporization of pyruvic acid may become difficult at temperatures below 200°C. 

N. S. Bolan, A. D. Robson, and N. J. Barrow, Effects of vesicular-arbuscular mycorrhiza on the availability of iron phosphates to plants. Plant and Soil 99 40l (1987). 

During the lifetime of a root, considerable depletion of the available mineral nutrients (MN) in the rhizosphere is to be expected. This, in turn, will affect the equilibrium between available and unavailable forms of MN. For example, dissolution of insoluble calcium or iron phosphates may occur, clay-fixed ammonium or potassium may be released, and nonlabile forms of P associated with clay and sesquioxide surfaces may enter soil solution (10). Any or all of these conversions to available forms will act to buffer the soil solution concentrations and reduce the intensity of the depletion curves around the root. However, because they occur relatively slowly (e.g., over hours, days, or weeks), they cannot be accounted for in the buffer capacity term and have to be included as separate source (dCldl) terms in Eq. (8). Such source terms are likely to be highly soil specific and difficult to measure (11). Many rhizosphere modelers have chosen to ignore them altogether, either by dealing with soils in which they are of limited importance or by growing plants for relatively short periods of time, where their contribution is small. Where such terms have been included, it is common to find first-order kinetic equations being used to describe the rate of interconversion (12). 

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