Mechanism and kinetics of wollastonite fibre dissolution in the aqueous solution of acetic acid

The dissolution of fibrous wollastonite (CaSiO₃) in the aqueous solution of acetic acid (3 mol dm^− 3) was investigated in the temperature interval from 25 to 50 °C using mixed batch-type reactor. An incongruent dissolution of wollastonite proceeds under applied acidic condition. The pH of solvent was increasing during leaching of calcium and its actual value depended on the concentration of Ca²⁺ ions in the solution according to the Henderson buffer equation. That enabled the monitoring of dissolution kinetics via concentration of Ca in the dispersion medium of suspension of wollastonite measurement. The kinetic parameter of the process was evaluated from measured dissolution rates of wollastonite at constant temperature using the empirical Arrhenius equation. The apparent activation energy and pre-exponential factor estimated from the Arrhenius plot are 47 ± 1 kJ mol^− 1 and (1.8 ± 0.9) × 10³ s^− 1. The kinetics analysis of the process indicates that the process is driven by the stationary two-dimensional diffusion (D₂).     

Effect of phosphate,calcium, and pH on the dissolution of a phosphate rock in soil

The effect of phosphate (P), calcium (Ca), and pH on the dissolution of Sechura phosphate rock (SPR) in a Typic Dystrochrept was investigated in an incubation study over 90 days. Increasing the P status of the soil had little effect on either the rate or extent of dissolution of SPR, as measured by a single extraction with 0.5M NaOH, or on the amount of plant-available P in the soil as measured by the Bray procedure. This suggests that a reactive PR such as SPR could be effective as a maintenance P fertilizer on soils of medium and high P status.The dissolution of SPR at pH 6.4 was only 4% of total P added, compared to 33.6% of total P added at pH 5.2. Addition of Ca as CaCl₂, at the same rate of Ca as that added in Ca(OH)₂ to raise soil pH from 5.2 to 6.4, reduced the dissolution of SPR to 11% of total P added. The large effect of Ca on the dissolution of SPR contrasts with the small effect of soil P status and probably reflects the fact that the concentration of Ca in the soil solution is generally several orders of magnitude higher than that of P. The results obtained suggest that pH, per se, is of less importance in the dissolution and subsequent plant availability of P from phosphate rock in soil than previously thought.     

Dissolution and rheological behaviour of hematite and quartz particles in aqueous media at pH 1

In this study we investigate isothermal, atmospheric acid dissolution behaviour of quartz and hematite minerals which constitute two of the predominant host gangue phases of typical low grade limonitic laterite ores. Batch dissolution tests were carried out on 57 wt.% solid dispersions for 4 h at pH 1 and 25 and 70 °C to establish the influential role of oxide mineralogy/chemistry on rheology and leaching behaviour. The results show that the two minerals displayed a weakly temperature and time-independent, non-Newtonian rheological behaviour with low shear yield stresses (<4 Pa) and viscosities (9–17 mPa s). Hematite dissolution rate was significantly higher compared with that of quartz under similar conditions. Quartz dissolution mechanism was substantially volume diffusion controlled at lower agitation rate (600 rpm) whilst for hematite it was both volume diffusion and chemical reaction controlled. These mechanisms reflected activation energies of 17.7 ± 0.9 and 28.5 ± 1.4 kJ/mol, respectively, for quartz and hematite. At 800 and 1000 rpm, dissolution of both minerals was chemical reaction-controlled with similar activation energies (32.6 ± 1.7 and 32.2 ± 1.6 kJ/mol). The findings underscore the need for higher agitation rates and elevated temperatures, to overcome both volume diffusion and chemical reaction limitations for enhanced acid leaching of these two fairly refractory oxides studied herein.     

Dissolution of phosphate rocks in soils. 2. Effect of pH on the dissolution and plant availability of phosphate rock in soil with pH dependent charge

The effect of soil pH on the dissolution of phosphate rocks (PRs) and the subsequent availability of the dissolved inorganic phosphorus (Pi) to plants was examined in a volcanic soil adjusted to different pH values. Potassium dihydrogen orthophosphate (KH₂PO₄) and three PRs, Nauru (NPR), Jordan (JPR) and North Carolina (NCPR) were incubated with the pH-amended soils at a rate of 800µg P g^–1 soil for 84 days. The extent of PR dissolution was determined by measuring the increases in the amount of 0.5 M NaOH extractable Pi (NaOH-P) in the PR treated soil over the control soil. The amount of plant available P was measured either by extracting with 0.5 M NaHCO₃ or by growing ryegrass in soil samples incubated with the phosphate sources.At each pH the order of the extent of PR dissolution followed NCPR > JPR > NPR, which was consistent with the decreasing order of their chemical reactivities. As the pH decreased from 6.5 to 3.9 the dissolution of PRs increased from 29.3% to 83.5%, from 18.2% to 78.9%, and from 12.5% to 60.3% for NCPR, JPR and NPR, respectively. In contrast, as the soil pH decreased from 6.5 to 3.9, the proportion of the dissolved P extracted by 0.5 M NAHCO₃ decreased from 38% to 5% and the proportion taken up by ryegrass plants decreased from 46% to 7%. This decrease in plant available P corresponded to an increase in the adsorption of inorganic P with a decrease in pH. However, the uptake of P from PR relative to that from KH₂PO₄ was higher at low pH than at high pH. Further, the amount of P taken up by plants was more closely related to the amount of NaHCO₃ extractable P than to the amount of dissolved P present in the soil.     

Influence of pH,time and rate of application on phosphate rock dissolution and availability to pastures

Soil Samples were collected from a field experiment conducted to evaluate the agronomic effectiveness of a reactive phosphate rock (PR), Sechura sand, relative to that of monocalcium phosphate (MCP) at different soil pHs and rates of application. The samples were analysed for P soluble in the soil solution and bicarbonate extractable P. The rate of dissolution of PR was calculated from the data on the fractionation of inorganic P. In MCP plots P in the soil solution decreased sharply with time especially at low pHs and high rates of fertiliser application. In PR plots the concentration remained with time at the same as or a slightly higher level than that was found one month after application. Solution concentration of P was lower at very high rates of PR application than at intermediate rates. In both MCP and PR plots bicarbonate extractable P decreased with increasing pH. Bicarbonate extractable P was linearly related to MCP but not to PR applied. The rate of dissolution and the proportion of PR dissolved decreased with increasing rates of PR application but the amount dissolved increased. Phosphate dissolved at high level of PR application did not seem to enhance proportionately either the concentration of P in soil solution or bicarbonate extractable P.     

Bone bonding ability behavior of some ternary borate glasses by immersion in sodium phosphate solution

Some ternary borate glasses of varying compositions were prepared and corrosion behaviors of such ternary borate glasses after immersion in aqueous dilute phosphate solution were studied using different immersion times. Fourier transform infrared (FTIR) absorption spectral measurements were done before and after immersion in the mentioned solution for extended times up to 3 days to justify the appearance of the characteristic FT infrared bands due to calcium phosphate (hydroxyapatite (HA)) which is considered as the potential indication of bone bonding ability.Experimental IR data confirm the beginning of the appearance of FTIR bands at about 580 and 650 cm⁻¹ after 1 day and the complete resolution with its characteristic split form after 3 days and more.The corrosion behavior of the studied borate glasses is explained in relation to a suggested hydrolysis and direct dissolution mechanism. The ease of dissolution of all the borate glasses constituents explains the rapid conversion and formation of hydroxyapatite within the borate glass matrix as indicated and confirmed by X-ray diffraction.     

A test for phosphate rock reactivity in which solubility and size are combined in a dissolution rate function

A test for phosphate rock (PR) reactivity has been developed based on a representation of certain fundamental properties of the rocks designated the Dissolution Rate Function. The function and properties have been shown to be those important in models of the dissolution rate of PRs in soil. The properties are size or mass distribution with size, solubility product, P content and particle density. In practice the solubility product is measured in terms of the P concentration attained in a standard solution, simulating that in an average soil with respect to pH, Ca and ionic strength.The test compares favourably with those using citric and formic acids, using published results for the relative agronomic effectiveness of 11 PRs, both unground and ground. The agronomic data also indicated that particle sizes < 0.15 mm can be regarded as equivalent to the size range of 0.10 to 0.15 mm.     

Synergistically reinforcement of a self-setting calcium phosphate cement with bioactive glass fibers

Calcium phosphate cements (CPCs) are highly promising for clinical uses due to their in situ-setting ability, excellent osteoconductivity and bone-replacement capability. However, the low strength limits their uses to non-load-bearing applications. In the present research, first, bioactive glass fibers (BGFs) in the ternary SiO₂-CaO-P₂O₅ system were prepared, and then the fiber composites with compositions based on CPC and BGFs were prepared and characterized. Then, the effect of structure and amount of BGF incorporation into the CPC system, and the effect of mechanical compaction on the fiber-modified system were investigated. The results showed that the compressive strength of the set cements without any BGFs was 0.635 MPa which was optimally increased to 3.69 MPa by applying 15% BGF and then decreased by further addition of it. In addition, both the work-of-fracture and elastic modulus of the cement were considerably increased after applying the fibers in the cement composition. Also, the setting time slightly decreased by applying the fibers. In summary, processing parameters were tailored to achieve optimum mechanical properties and strength. The prepared composite may be useful in surgical sites that are not freely accessible by open surgery or when using minimally invasive techniques.     

Inhibition of cobalt active dissolution by benzotriazole in slightly alkaline bicarbonate aqueous media

The efficiency of benzotriazole as inhibiting agent for the corrosion of cobalt was probed at pH ranging from 8.3 to 10.2 in a sodium bicarbonate solution, chosen to simulate mild natural environments. From electrochemical, Raman spectroscopy, atomic force microscopy and ellipsometry experiments, we have demonstrated that benzotriazole markedly affects the electrodissolution reactions, which become modeled by the formation of a [Co(II)(BTA)₂·H₂O]_n film according to two different mechanisms. Surface-enhanced Raman spectroscopy has shown that the polarization of a cobalt electrode at cathodic potentials with respect to its potential of zero charge allows a mechanism of specific adsorption of the neutral form of benzotriazole to take place through a suspected metal-to-molecule electron transfer and which follows Frumkin's adsorption isotherms. At the onset of the anodic dissolution, some experimental evidence suggests that these adsorbed neutral benzotriazole molecules deprotonate to yield a very thin [Co(II)(BTA)₂·H₂O]_n polymer-like and water-insoluble protective film, responsible for the inhibition of active dissolution processes occurring at slightly more anodic potentials. In the anodic dissolution region, deprotonated benzotriazole species present in the bulk solution favors the formation of a multilayered [Co(II)(BTA)₂·H₂O]_n film, which also contributes to the inhibition of any further cobalt dissolution usually observed at higher electrode potentials.     

Cogrinding as an approach to enhance dissolution rate of a poorly water-soluble drug (gliclazide)

Gliclazide is practically insoluble in water. In order to improve the drug dissolution rate, cogrinding method was used as an approach to prepare gliclazide coground/solid dispersions (SDs) in the carriers such as povidone (PVP-K30), crospovidone and microcrystalline cellulose (Avicel PH 101) with different drug to carrier ratios. The dissolution rate of gliclazide from the SDs was measured at two physiological pH values of 1.2 and 7.2 simulating gastric and intestinal fluids using USP dissolution apparatus II. The concentration of the dissolved drug in the medium was determined by direct or first-derivative UV spectroscopy. The dissolution rates of the formulations were dependent on the nature and ratio of drug to carriers in SDs and the corresponding physical mixtures as well as the pH of the medium. At a higher pH the drug has a faster dissolution than at a lower pH. The fastest dissolution rates were observed from coground formulations with the drug to carrier ratio of 1:5. The amount of drug dissolved in 15 min from these SDs was varied from 96% in the case of Avicel SD to 100% for SD of PVP. Whereas the amount of drug released in the same time from unground drug powder (UD), ground drug powder (GD) and all physical mixtures was between 60 and 80%. These results indicate that the dissolution rate is highly enhanced from the SDs. DSC as well as X-ray diffraction showed reduced drug crystallinity in SDs. Scanning electron microscopy and particle size analysis revealed significant decreased particle size of the drug in SDs. FT-IR spectroscopy demonstrated no detectable interactions between the drug and carriers. In addition to latter evidence, increased wettability and hydrophilicity of drug particles and deaggregation brought about by the carriers are the reasons for enhanced drug dissolution from the SDs. One of the possible advantages of formulating an insoluble drug such as gliclazide is that if it is used in preparation of capsules or tablets of the drug, its dose might be reduced which is economically beneficial.     

On the variable dissolution kinetics of zinc ferrite in acid media

Different magnetic fractions of narrow-sized industrial residues of zinc ferrite [(Zn_1-x, Fe)FeO₄, x ≤ 0.4] have been leached with 1 mol/L H₂SO₄ at temperatures ranging from 348 to 368 K. Fractions with excess iron, which exhibit higher magnetic susceptibility, are found to dissolve faster. It is believed that the lattice substitution of Zn by Fe²⁺ in the more magnetic ferrite fractions creates crystal defects and renders the ferrite more chemically reactive. An interfacial electrochemical reaction mechanism has been advanced to account for the effects of solid state composi tion and solution composition on the variation of the dissolution kinetics of zinc ferrite. Finally, the practical implications of these findings on the industrial leaching of zinc ferrite are briefly addressed.     

钠钙氯化物在乳糖水中热力学性质的确定

在298.15 K时利用电动势法确定四元体系氯化钠-氯化钙-乳糖-水不同组成(乳糖质量分数分别为0,5%,10%和15%)时的热力学性质。利用Pitzer离子作用模型拟合实验数据,获得了氯化钠和氯化钙在乳糖水混合溶剂中的Pitzer模型参数。进一步计算了氯化钠和氯化钙从纯水到乳糖水混合溶剂中的迁移吉布斯函数。获得了氯化钠和氯化钙混合电解质在乳糖水混合溶剂中的混合参数θ(Na Ca)和ψ(Na Ca Cl)。计算了298.15 K时四元体系中氯化钠和氯化钙的平均离子活度系数。结果发现:利用Pitzer高阶静电作用模型计算混合电解质在混合溶剂中的平均离子活度系数,能获得较为满意的结果。     

Evaporation rate as a function of water salinity

Water evaporation is an important physical phenomenon that occurs in nature and in several industrial applications. Many researchers are working in this area to establish a good correlation that can be used to measure evaporation rates precisely. In this article, we review previous experience by describing the instrument used, method of measurement, conditions of experimentation and correlations resulting from these experiments. Then, an experimental test that was constructed to measure the evaporation rates of distilled water, seawater (34,000 ppm) and two brine solutions with different salinities (56,000 and 69,000 ppm) is presented. A new correlation for measuring evaporation rate was established taking into account the effect of salinity on evaporation rate, which was not done by any other investigator before. Finally, a comparison is made between our correlation and a previous one for distilled water. The results show a decrease in the evaporation rate with an increase of the water salinity because of the reduction in the water vapor pressure at the water surface.     

Corrosion of Si3N4-ceramics in aqueous solutions: Part 2. Corrosion mechanisms in acids as a function of concentration,temperature and composition

The corrosion behaviour of Si₃N₄-ceramics with different grain boundary compositions was investigated in H₂SO₄ with different concentrations at 90 °C and was compared with the corrosion behaviour of glasses. In part I of this paper the influence of temperature was investigated [Schilm, J., Gruner, W., Herrmann, M. and Michel, G. Corrosion of Si3N4-ceramics in aqueous solutions, J. Eur. Ceram. Soc., 26 (2006) 3909–3917] The investigation showed that the corrosion rate as well as the corrosion mechanisms strongly depend on the concentration and temperature of the acid and the composition of the grain boundary phase. The observed dependencies allow the prediction of the corrosion behaviour of silicon nitride ceramics in acids. The investigation of the morphology of the corrosion layers by SEM and TEM proves that the observed passivation of the materials during corrosion in H₂SO₄ with concentrations higher than 0.5 mol/l is caused by the formation of SiO₂-rich layers inside the corroded triple junctions.The experimental results were discussed in terms of corrosion mechanisms allowing a qualitative prediction of the corrosion behaviour at least. The corrosion resistant Si₃N₄-materials can be reached by tailoring the amount and composition of the grain boundary phase.     

Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and surface charge properties

Chitosan, a natural biopolymeric cation, is a candidate to modify montmorillonite for the adsorption of anions. As an anionic organic pollutant the adsorption of tannic acid was studied. Because of protonation/deprotonation reactions of both chitosan-montmorillonite and tannic acid, the adsorption process is strongly pH-dependent. The objective of this work is to characterize the pH dependency of adsorption in combination with surface charge determinations.Montmorillonite was modified with different amounts of chitosan, corresponding to 20–1000% of the cation exchange capacity (CEC). The deacetylation degree of chitosan was determined by polyelectrolyte titration and was found to be 74%. The uptake of chitosan was determined by the C-content. The interlayer expansion was investigated by X-ray powder diffraction. The adsorption capacity for tannic acid was investigated with the batch technique at pH 3, 4, 5 and 8. As a measure for the adsorption properties, the electrokinetic surface charge was determined with a particle charge detector.The uptake of chitosan by montmorillonite is up to 152% (1.69 mol_c kg^− 1) of the CEC. The resulting anion exchange capacity of chitosan-montmorillonite calculated from C-content is 0.43 mol_c kg^− 1. At low loadings with chitosan (24.7 and 49.5% uptake), a monolayer is formed in montmorillonite. At an uptake of 96.8%, a bilayer structure is observed, which becomes more dominant at higher loadings. On the external surface, a monolayer of chitosan was formed. From pH 4 to 8, the surface charge of all modified montmorillonites is with − 9 to 8 mmol_c kg^− 1 close to the point of zero charge. The maximal adsorption capacity for tannic acid is found with 240 g kg^− 1 (0.14 mol_c kg^− 1) at pH 4. The adsorption process fits in well with the Freundlich isotherm. At lower as well as higher pH values the adsorption capacity decreases up to about 25%. Most probably the exchange sites in the interlayer do not contribute to the adsorption of tannic acid. The observed surface charge is lower than the adsorbed amount of tannin. It is thought that tannin is adsorbed also by van der Waals forces besides ionic forces.     

The effects of cationic polymers on flocculation of a coal thickener feed in washery water as a function of pH

The flocculation of a thickener feed using three cationic polyacrylamide copolymers of high molar mass and different charge densities was studied at three pHs in washery water. The binding capacities were very dependent on pH but only slightly dependent on the polymeric charge density. The reverse was true for the settling rates. At pH 7, all three polymers were equally effective at clarifying the suspensions, but there were marked differences at pH 4 and 9. For the polymers of highest charge density, reducing the pH increased their effectiveness; for the polymer of lower charge density, changing the pH had little effect on the residual turbidity. © l997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 783–789, 1997     

The stability of 12-molybdosilicic, 12-tungstosilicic, 12-molybdophosphoric and 12-tungstophosphoric acids in aqueous solution at various pH

The stabilities of the solid superacids H₃Mo₁₂O₄₀, H₃PW₁₂O₄₀, H₄SiMo₁₂O₄₀ and H₄SiW₁₂O₄₀ in aqueous solution have been measured at various values of pH by use of ion chromatographic analyses. The aforementioned acids are completely decomposed at values of pH, 4.0, 5.2, 7.0 and 11.0, respectively. The stabilities in aqueous solution with respect to pH follow the order H₄SiW₁₂O₄₀ > H₃PW₁₂O₄₀ > H₄SiMo₁₂O₄₀ > H₃PMo₁₂O₄₀.