Catalysis by some metal oxides modified with phosphate ions

Surface acidity of phosphate modified La2O3,CeO2 and SnO2 has been estimated by titrimetric Method using Hammett Indicators.Mixed Oxides of tin and lanthanum have also been prepared and subjected to phosphate modification.Surface characterizartion of the samples has been carried out using XRD, surface area,thermal analysis and IR spectroscopy. Phosphate content in the samples has been chemically estimated. The catalytic activity for benzylation and esterification reaction has also been investigated.

Surface properties and catalytic activity of phosphate modified zirconia

Preparation and physico-chemical characterization or phosphate modified zirconia systems and their application to Friedel-Crafts benzylation and benzoylation of toluene have been reported. The influence of transition metals on the surface properties and catalytic activity has also been discussed.

Glucoamylase immobilized on montmorillonite: Synthesis, characterization and starch hydrolysis activity in a fixed bed reactor

Glucoamylase from Aspergillus Niger was immobilized on montmorillonite clay (K-10) by two procedures, adsorption and covalent binding. The immobilized enzymes were characterized using XRD, surface area measurements and 27Al MAS NMR and the activity of the immobilized enzymes for starch hydrolysis was tested in a fixed bed reactor (FBR). XRD shows that enzyme intercalates into the inter-lamellar space of the clay matrix with a layer expansion up to 2.25 nm. Covalently bound glucoamylase demonstrates a sharp decrease in surface area and pore volume that suggests binding of the enzyme at the pore entrance. NMR studies reveal the involvement of octahedral and tetrahedral Al during immobilization. The performance characteristics in FBR were evaluated. Effectiveness factor (η) for FBR is greater than unity demonstrating that activity of enzyme is more than that of the free enzyme. The Michaelis constant (Km) for covalently bound glucoamylase was lower than that for free enzyme, i.e., the affinity for substrate improves upon immobilization. This shows that diffusional effects are completely eliminated in the FBR. Both immobilized systems showed almost 100% initial activity after 96 h of continuous operation. Covalent binding demonstrated better operational stability.

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Electrical conductivity, dielectric constant and phase transitions in pure and doped diammonium hydrogen phosphate

DC and AC electrical conductivity measurements in single crystals of diammonium hydrogen phosphate along the c axis show anomalous variations at 174, 246 and 416 K. The low-frequency dielectric constant also exhibits peaks exactly at these temperatures with a thermal hysteresis of 13 degrees C for the peak at 416 K. These specific features of the electrical properties are in agreement with earlier NMR second-moment data and can be identified with three distinct phase transitions that occur in the crystal. The electrical conductivity values have been found to increase linearly with impurity concentration in specimens doped with a specific amount of SO42- ions. The mechanisms of the phase transition and of the electrical conduction process are discussed in detail.

High‐temperature phase transitions in pure and deuterated ammonium dihydrogen phosphate: Conductivity and dielectric measurements

Results of axiswise measurements of the electrical conductivity (dc and ac) and dielectric constant of NH4H2PO4 confirm the occurrence of the recently suggested high‐temperature phase transition in this crystal (at 133 °C). The corresponding transition in ND4D2PO4 observed here for the first time takes place at 141.5 °C. The mechanism involved in these transitions and those associated with the electrical conduction and dielectric anomalies are explained on the basis of the motional effects of the ammonium ions in these crystals. Conductivity values for deuterated crystals give direct evidence for the predominance of protonic conduction throughout the entire range of temperatures studied (30–260 °C).

Effects of Tithonia diversifolia, farmyard manure and urea, and phosphate fertiliser application methods on maize yields in western Kenya

Maize production in western Kenya is often limited by deficiencies of nitrogen and phosphorus. We assessed the effectiveness of Tithonia diversifolia green manure (tithonia), farmyard manure (FYM) and urea as sources of nitrogen (N) for maize when inorganic phosphorus (P) fertiliser was either broadcast (BR) or spot-placed in the planting hole (SP) for two consecutive seasons; October to December of 1998 and April to August of 1999 at two sites; Nyabeda and Khwisero in western Kenya. A randomised complete block design with four replications was used. Maize yields were higher at Nyabeda and responded to P application better than at Khwisero. At the same N rate, tithonia and FYM were as effective as urea in increasing maize yields at both sites. There were no significant differences in maize yields when phosphate fertiliser was either BR or SP regardless of the N source used in the first season. However, in the second season, the residual yields for the BR treatments were consistently higher than those of the SP. Our results suggest that tithonia and FYM can substitute for urea as N sources and that fertiliser P should be broadcast and incorporated together with the organic materials at the time of planting to save on labour costs.

Assessment of the effect of time and temperature on the availability of residual phosphate in a glasshouse study of four soils using the Olsen method

The Olsen method is an indicator of plant-available phosphorus (P). The effect of time and temperature on residual phosphate in soils was measured using the Olsen method in a pot experiment. Four soils were investigated: two from Pakistan and one each from England (calcareous) and Colombia (acidic). Two levels of residual phosphate were developed in each soil after addition of phosphate by incubation at either 10degreesC or 45degreesC. The amount of phosphate added was based on the P maximum of each soil, calculated using the Langmuir equation. Rvegrass was used as the test crop. The pooled data for the four soils incubated at 10degreesC showed good correlation between Olsen P and dry matter yield or P uptake (r(2) = 0.85 and 0.77, respectively), whereas at 45 degreesC, each soil had its own relationship and pooled data did not show correlation of Olsen P with dry matter yield or P uptake. When the data at both temperatures were pooled, Olsen P was a good indicator of yield and uptake for the English soil. For the Pakistani soils, Olsen P after 45 degreesC treatment was an underestimate relative to the 10 degreesC data and for the Colombian soil it was an overestimate. The reasons for these differences need to be explored further before high temperature incubation can be used to simulate long-term changes in the field.

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.

Arsenate-induced phosphate release from soils and its effect on plant phosphorus

Adsorption of arsenic onto soil was investigated as a means of understanding arsenic-induced release of phosphate. In batch adsorption experiments As adsorption was accompanied by P desorption. At low As additions, the ratio As adsorbed: P desorbed remained constant. At higher As additions, P desorption reached a maximum while As adsorption continued to increase. The P desorption maximum coincided with an increase in pH. Barley plants were grown on soils spiked with arsenate (0-360 mg As kg(-1)) to investigate the effect on plant growth and P uptake. As arsenic concentration increased, above ground plant yield decreased and the plants showed symptoms typical of As toxicity and P deficiency. At low As additions to the soil, uptake of As and P by barley increased. At higher As additions P uptake decreased. It is argued that this was due to the change in As:P ratio in the soil solution. It is concluded that input of arsenic to the soil could mobilise phosphate. Crop yield is likely to be affected, either due to reduced phosphate availability at low arsenic additions or arsenic toxicity at higher additions.

Factors influencing the dissolution of phosphate rock in a range of high P-fixing soils from Cameroon

A laboratory incubation experiment was conducted to evaluate the soil factors that influence the dissolution of two phosphate rocks (PRs) of different reactivity (Gafsa, GPR, reactive PR; and Togo-Hahotoe, HPR, low reactivity PR) in seven agricultural soils from Cameroon having variable phosphorus (P)- sorption capacities, organic carbon (C) contents, and exchangeable acidities. Ground PR was mixed with the soils at a rate of 500 mg P kg 21 soil and incubated at 30 degrees C for 85 days. Dissolution of the PRs was determined at various intervals using the Delta NaOH-P method ( the difference of the amount of P extracted by 0.5 M NaOH between the PR-treated soils and the control). Between 4 and 27% of HPR and 33 and 50% of GPR were dissolved in the soils. Calcium (Ca) saturation of cation exchange sites and proton supply strongly affected PR dissolution in these soils. Acid soils with pH-(H2O), < 5 (NKL, ODJ, NSM, MTF) dissolved more phosphate rock than those with pH-(H2O) > 5 (DSC, FGT, BAF). However, the lack of a sufficient Ca sink in the former constrained the dissolution of both PRs. The dissolution of GPR in the slightly acidic soils was limited by increase in Ca saturation and that of HPR was constrained by limited supply in protons. Generally, the dissolution of GPR was higher than that of HPR for each soil. The kinetics of dissolution of PR in the soils was best described by the power function equation P At B. More efficient use of PR in these soils can be achieved by raising the soil cation exchange capacity, thereby increasing the Ca sink size. This could be done by amending such soils with organic materials.