The coprecipitation of magnesium chromium hydroxide powders from aqueous solution: Precipitate compositions and coprecipitation mechanisms

Magnesium chromium (III) hydroxides were coprecipitated at ambient temperature from different mixed metal cation solutions — at C_Mtot = 0.1 M and Mg/Cr₂ ratios varying from 1 to 4 — with sodium hydroxide solution. The coprecipitations were monitored by potentiometric (pH) titration and the final precipitate compositions were examined by chemical analysis, i.r. spectrophotometry and thermal analysis. Generally, microcrystalline chromium(III) hydroxide was first precipitated at pH about 5; this material then redissolved on further addition of hydroxyl ion to form hydroxochromate(III) anion and magnesium chromium hydroxide coprecipitates were then formed continuously (at OH/Cr ratios from 4 to 10) at pHs from 9.5–10 to about 11. The coprecipitates from Mg/Cr₂ = 1 systems was predominately magnesium hydroxochromate hydrate. The coprecipitates from Mg/Cr₂ = 2 to 4 systems were mixture or solid solutions of magnesium hydroxochromate hydrate with increasing amounts of magnesium hydroxide. The ionic equilibria involved in different coprecipitations are discussed.     

The coprecipitation of magnesium hydroxide aluminium hydroxide powders from aqueous solution with sodium hydroxide: Precipitate compositions and coprecipitation mechanisms

Magnesium aluminium hydroxides were coprecipitated from different mixed metal cation solutions — at total C_M = 0.1 M and Mg/Al₂ ratios from 1 to 6 — with sodium hydroxide solution at ambient temperature, with different pre-ageing conditions for the aluminium hydroxide pre-precipitate. The coprecipitations were monitored by potentiometric (pH) titration and the final precipitate compositions were examined by chemical analysis, infrared spectrophotometry and thermal analysis. Magnesium hydroxide was coprecipitated onto completely recrystallised aluminium hydroxide as a simple mixture. Generally, with no to three days pre-ageing, microcrystalline aluminium hydroxide was first precipitated at pH about 4; this then partially redissolved on further addition of sodium hydroxide (to form hydroxoaluminate anion) and magnesium aluminium hydroxide coprecipitates were formed continuously at pHs from 8.0–8.7 to 12.0–12.5. Their compositions were similar to the magnesium hydroxoaluminate hydrates formed by direct precipitation from high pH sodium hydroxoaluminate solutions.      

The coprecipitation of magnesium hydroxoaluminate hydrates from aqueous solution with ammonium hydroxide: Precipitate compositions and coprecipitation mechanisms

Magnesium hydroxoaluminate hydrates were coprecipitated from different mixed metal cation solutions at Mg/Al₂ ratios from 1 to 4 by ammonium hydroxide. The coprecipitations were monitored by potentiometric titration and the final precipitate compositions were examined by chemical analysis, X-ray diffraction, infra-red spectrophotometry and thermal analysis. The process of coprecipitation was similar to that for coprecipitation with sodium hydroxide but large excess of ammonium hydroxide was required for complete reaction at pHs from about 8 to 10.

• At Mg/Al₂ = 1, the main phase was probably Mg(H₂O)_h [Al(OH)₄]₂;
• at Mg/Al₂ = 2, the main phase was probably Mg₂(H₂O)_h [Al₂(OH)₁₀];
• at Mg/Al₂ = 4, the main phase was probably (MgOH₄) (H₂O)^h [Al₂(OH)₁₀].

     

The precipitation of aluminium hydroxocarbonates powders from aqueous solution: Precipitate compositions and precipitation mechanisms

A series of aluminium hydroxocarbonate hydrates were prepared by precipitation from aluminium nitrate solution, with five sodium hydrogen carbonate-sodium carbonate solutions of different pH, at ambient temperature. The course of precipitation was monitored by pH measurement and the final precipitate compositions were determined by chemical analysis, infra-red spectrophotometry, X-ray diffraction and thermal analysis. Precipitation generally occurred through three stages, primary precipitation of materials with low carbonate content at low pH with evolution of carbon dioxide, their dissolution to form hydroxcarbonato anions and then secondary reprecipitation of the final products at higher pH. These materials were mixtures of polyhydroxoaluminium carbonate hydrates of general composition Al_n(OH)_3n-2CO₃ · hH₂O (where n = 2, 4, 6 and h = 6–8); their CO₃ content increased with increasing pH and carbonate anion content of the precipitant solution.     

The coprecipitation of magnesium nickel hydroxide solid solutions from aqueous solution: Precipitate compositions and precipitation mechanisms

Magnesium nickel hydroxides (solid solutions) were coprecipitated from different mixed metal cation solutions (overall concentration 0.1 M) and from hydroxide solution (0.1 M). The course of different coprecipitations was monitored by potentiometric (pH) titrations. Final Coprecipitate compositions were determined by chemical analysis, infra-red spectrophotometry and thermal analysis. The ionic equilibria involved in different coprecipitations and the precipitation mechanisms are discussed.     

The coprecipitation of calcium aluminium hydroxide (calcium hydroxoaluminate hydrate) powders from aqueous solution with sodium hydroxide: Precipitate compositions and percipitation mechanisms

Calcium aluminium hydroxides were coprecipitated from different mixed metal cation solutions — at total C_M = 0.1 M and Ca/Al₂ ratios from 1 to 4 — with sodium hydroxide solution at ambient temperature. The coprecipitations were monitored by potentiometric (pH) titration and the final coprecipitate compositions were examined by chemical analysis, infra-red spectrophotometry and thermal analysis Generally, microcrystalline aluminium hydroxide was first precipitated at pH about 4; this then redissolved on further addition of sodium hydroxide to form hydroxoaluminate anion and polyanion and calcium aluminium hydroxide coprecipitates were formed continuously at pHs from about 9 to above 12. Their compositions were similar to the calcium hydroxoaluminate hydrates formed by direct precipitation from high pH sodium hydroxoaluminate solutions. At Ca/Al₂ ratio = 1, the main phase was probably Ca₂(H₂O)_h[Al₂(OH)₄]₂ with some Al(OH)₃; At Ca/Al₂ ratio = 2, the main phase was probably Ca₂(H₂O)_h[Al₂(OH)₁₀] dehydrating to Ca₂[Al₂O(OH)₈]; At Ca/Al₂ ratios = 3–4, the main phase was Ca₂(H₂O)_h[Al₂(OH)₁₀] with increasing amounts of Ca₄(H₂O)_h(OH)₄[Al₂(OH)₁₀] and 5–10 percent adsorbed or post-precipitated Ca(OH)₂.     

The coprecipitation of zinc aluminium hydroxides (refractory-, absorbent-, and catalyst precursors) from aqueous solution with ammonium hydroxide: Precipitate compositions and coprecipitation mechanisms

Zinc aluminium hydroxide hydrates were coprecipitated from different mixed cation solutions at Zn/Al₂ ratios from 1/2 to 4/1. The coprecipitations were monitored by potentiometric titrations and the final coprecipitate compositions were examined by chemical analysis and atomic absorption spectrophotometry, X-ray diffraction and preliminary thermal analysis. The product from Zn/Al₂ = 1/2 solution was amorphous: at Zn/Al₂ = 1/1.5, the main phase (after drying at 95 °C) was a zinc hydroxoaluminate Zn[Al(OH)₄]₂ together with some gibbsite: at Zn/Al₂ = 1, the main phase was probably a solid solution (of Zn[Al(OH)₄]₂ with Zn₂[Al₂(OH)₁₀]) together with Zn₂[Al₂(OH)₁₀]: at Zn/Al₂ = 2, the main phase was a mixture of Zn₂[Al₂(OH)₁₀] with (ZnOH)₄ [Al₂(OH)₁₀] and some gibbsite: at Zn/Al₂ = 4, the main phase was (ZnOH)₄ [Al₂(OH)₁₀] with some zinc hydroxide.     

The coprecipitation of Magnesium Nickel Oxalate Dihydrate Powders (solid solutions) from aqueous solution: Precipitate compositions and Cporecipitate Mechanisms

The coprecipitation of magnesium nickel oxalate dihydrates from mixed metal cation solutions was monitored by conductivity measurements. A series of coprecipitates was then prepared from 0.2 M solutions with Mg contents varying from 0.2 to 0.9 total metal cation and their compositions and structures studied by chemical analysis, infra-red spectrophotometry, thermogravimetric analysis and detailed differential calorimetry. The coprecipitates with upto 20 percent Mg content were solid solutions with structures similar to nickel oxalate dihydrate, the coprecipitates with 20 to 80 percent Mg content were probably mixed solid solutions while the coprecipitates with over 80 percent Mg content were solid solutions with structures similar to magnesium oxalate dihydrate. The ionic equilibria in supersaturated magnesium nickel oxalate solutions were analysed and mechanisms are proposed for coprecipitations from solutions of different Mg/(Mg + Ni) ratios.     

The precipitation of magnesium hydroxoaluminate hydrate powders from sodium hydroxoaluminate solutions: Precipitate phases and precipitation mechanisms

Magnesium hydroxoaluminate hydrates were precipitated from different sodium hydroxoaluminate and hydroxoaluminate-hydroxide solutions at ambient temperature, at C_Al = 0.1 M, OH/Al ratios = 4–9 and XS OH/Al ratios = 1–6. The precipitations were monitored by potentiometric (pH) measurements while the final precipitate compositions were examined by chemical analysis, infra-red spectrophotometry and thermal analysis. At solution OH/Al ratio = 4, the main precipitate phase at 20°C was Mg(H₂O)_n[Al(OH)₄]₂ admixed with some Al(OH)₃; at solution OH/Al ratio = 5, the main phase was Mg₂(H₂O)₄[Al₂(OH)₁₀]; at solution OH/Al ratio = 7, the main phase was Mg₄(H₂O)_n(OH)₄[Al₂(OH)₁₀] while at solution OH/Al ratio = 9, the main phase was Mg₆(H₂O)_n(OH)₈[Al₂(OH)₁₀] admixed with some Mg(OH)₂. These hydrates were dehydrated at 60–100°C probably to the compounds Mg₂[Al₂O₃(OH)₄], Mg₄(OH)₄[Al₂O₃(OH)₄] and Mg₆(OH)₈[Al₂O₃(OH)₄], respectively.     

The precipitation of calcium hydroxoaluminate hydrate powders from sodium hydroxoaluminate solutions: Precipitate phases and precipitation mechanisms

Calcium hydroxoaluminate hydrates were precipitated from different sodium hydroxoaluminate and hydroxoaluminate-excess hydroxide solutions at ambient temperature (at C_Al = 0.1 to 0.3 M and at XS OH/Al = 0 to above 8). The precipitations were monitored by potentiometric (pH) measurements. Precipitate morphologies were examined by optical microscopy and precipitate compositions were determine by chemical analysis, infra-red spectrophotometry and thermal analysis. Generally at OH/Al ratios of 4 to 4.5 (XS OH/Al = 1 to 1.5), the compound 2 CaO · · Al₂O₃ · 8 H₂O (C₂AH₈) was precipitated with some aluminium hydroxide; then at OH/Al ratios of 5 to above 11 (XS OH/Al = 2 to above 8), the compound 2 CaO · Al₂O₃ · 8 H₂O was precipitated with increasing amounts of the compound 4 CaO · Al₂O₃ · 13 H₂O (C₄AH₁₃).     

The precipitation of barium hydroxoaluminate hydrate powders from sodium hydroxoaluminate solutions: Precipitate phases and precipitation mechanisms

Barium hydroxoaluminate hydrates were precipitated from different sodium hydroxoaluminate solutions at 20 °C; C_Al varied from 0.1 to 0.5 M and initial Ba/Al₂ ratios ( = excess OH/Al ratios) varied from 1 to 7. Precipitate compositions were determined by chemical analysis, infra-red spectrophotometry and thermal analysis. The compound BaO · Al₂O₃ · 7 H₂O was precipitated at initial Ba/Al₂ ratios of one to well above two while the compound 2 BaO · Al₂O₃ · 5 H₂O was only precipitated over a narrow range of concentrations. The compound Ba(OH)₂ · 8 H₂O was precipitated from solutions of high hydroxide and barium ion concentrations. The ionic equilibria and precipitation mechanisms in different solutions are discussed.     

The precipitation of alkaline-earth metal polymetaphosphate hydrate powders from aqueous solution. Nucleation and crystal growth processes,final precipitate compositions and crystal sizes

The precipitation of barium, strontium, calcium and magnesium polymetaphosphate hydrates was studied from aqueous solutions of initial metal salt concentrations from 0.001 to 3 M at 20 °C; equivalent sodium polymetaphosphate solutions were added to the alkaline-earth metal chloride solutions. Precipitate compositions were determined by chemical analysis, paper chromatography, potentiometric analysis, thermogravimetric and differential thermal analysis and infra-red spectrophotometry; final crystallite morphologies and sizes were studied by scanning electron microscopy and X-ray powder diffraction. Nucleation rates and nucleus numbers (at the end of the induction periods) were very high; crystal numbers varied from 10¹⁴ to 10¹⁵ at the critical concentrations to above 10¹⁷ per 1. solution. Crystal growth rates were also very high and varied as the fourth power of the initial metal salt concentration. High molecular-weight metal polymetaphosphate hydrates were precipitated from the more dilute solutions (0.001 to 0.025 M) while increasing amounts of the more soluble intermediate and low molecular-weight products were precipitated from the more concentrated solutions. Washing with cold water removed the tri- and tetralinear and cyclic phosphate products. The magnesium salts were not precipitated even from 3 M aqueous solutions. The precipitates from aqueous (NaPO₃(I))_n (n = 12) solutions had the compositions (BaP₂O₆ · 2.5 H₂O)₆, (SrP₂O₆ · 3 H₂O)_n and (CaP₂O₆ · 4 H₂O)_n while the magnesium salt precipitate from 20 percent aqueous acetone solution had the composition (MgP₂O₆ · 4 H₂O)_n, the precipitate n values varied from 19 to 13. The precipitates from aqueous (NaPO₃(II))_n (n = 20) solutions contained 0.5n to n additional adsorbed water molecules; these precipitate n values varied in turn from 40 to 26. The final precipitate powders consisted of ‘spherules’ of highly microcrystalline or amorphous polymer glass; the spherule diameters were about 0.2 μm at the critical concentrations and decreased to below 0.05 μm with increasing solution concentrations.     

The precipitation of transition metal oxalate powders from aqueous solution. Crystal numbers and final sizes

The precipitation of manganous, ferrous, cobalt, nickel and copper oxalate hydrates was studied from equivalent solutions of concentrations from 0.001 to 0.3 M at pHs 7 to 6, by optical microscopy and other methods. Crystals growth started after induction periods: the precipitations were heterogeneously nucleated at low supersaturations and homogeneously nucleated at medium to high supersaturations. The crystal numbers of the final precipitates depended on the number of nuclei (and crystallites) formed during the induction periods. At medium to high supersaturations, crystal numbers increased with increasing initial metal oxalate complex ion concentrations according to the relation. N = N₁C_mox^β, where β was 5. The N values increased in the order Mn ≪ Fe < Co < < Ni < Cu. The final crystal lengths, in this range, then decreased with increasing metal oxalate complex ion concentrations according to the relation l_fin = l₁/C_mox^γ, where γ was 1.3. For precipitations from solution of any concentration, smaller crystals were generally obtained in the precipitates of the metal oxalate of lower solubility; nickel oxalate precipitations were the exception to this.     

The precipitation of barium chromate powders from aqueous solution at different pHs: Nucleation,final crystal numbers and sizes

Barium chromate precipitations were studied from equivalent aqueous solutions of initial overall metal salt concentrations from 0.00013 to 0.010 M at ambient temperature and at pHs from 8 to 3. At pHs from 8 to 5, precipitation mainly occurred through homogeneous nucleation: the reciprocal induction periods (and nucleation rates) and the crystal numbers generally decreased with reduction of pH but the values at any effective mean metal salt concentration increased appreciably with increasing acidity. Presumably, both M⁺⁺A and M⁺⁺HA⁻ species were taking part in the nucleation process. – At pHs below 5, heterogeneous nucleation predominated in most precipitations: the crystal numbers and nucleus numbers at any effective metal salt concentration increased with reduction of pH in these systems. Presumably, more active sites for heterogeneous nucleation were developed.     

The precipitation of basic nickel carbonate powders from aqueous solution. Crystallite numbers,composition and final sizes

The precipitation of basic nickel carbonate hydrates was studied from nickel sulphate solutions (concentrations 0.05 M to 1 M) at 96°C, by addition of sodium carbonate, bicarbonate-carbonate and bicarbonate solutions. Precipitate compositions were determined by chemical analysis, thermogravimetric analysis, differential calorimetry and i.r. spectrophotometry; approximate final crystallite sizes and numbers were estimated from combined sedimentation and porosity measurements on precipitate aggregates. Nucleation, and then crystal growth, started after some ‘critical pH’ pH = 7.05 to 7.67 (at CO₃⁻⁻/Ni⁺⁺ ratio = 0.08–0.12); the solution pH then remained constant (until the CO₃⁻⁻/Ni⁺⁺ ratio = 0.8) and then rose to some final value. Nucleus numbers, and thence final crystallite numbers, decreased with increasing bicarbonate content of the precipitating solution and decreasing pH . Precipitate compositions did not vary significantly with reacting ion concentrations but the Ni(OH)₂/NiCO₃ ratios decreased from 2 to 1.4 with decreasing pH : thermal analysis and i.r. spectrophotometry confirmed that the final precipitates were mixtures of olated nickel carbonates and not nickel carbonate-nickel hydroxide mixtures. Final crystallite sizes of the precipitates from 1 M solutions varied approximately from 0.095 to 0.14 micron, for the above pH range.     

The precipitation of alkaline-earth metal molybdate powders from aqueous solution. Crystal numbers,final morphology and sizes

The precipitation of barium, strontium and calcium molybdates was studied from neutral equivalent solutions of concentrations from 0.0004 to 0.4 M at 25 °C. Crystal growth started after induction periods; the precipitiations were heterogeneously nucleated at low supersaturations and homogeneously nucleated at medium to high supersaturations. Barium molybdate was precipitated as tetragonal bipyramids, strontium molybdate generally as prisms and calcium molybdate as platelets. Crystal numbers at medium to high supersaturations increased with increasing inital metal molybdate concentrations according to the relation, The final crystal lengths in this range than decreased from maximum values (at the critical concentrations) with increasing initial metal molybdate concentrations according to the relation. Generally, for precipitation from solutions at any concentration, larger crystals were obtained in the precipitates of the salt of higher solubility.     

The precipitation and hydrothermal crystallisation of alkaline-earth. Metal aluminosilicate hydrates from aqueous solution: Crystalline phases and precipitation and recrystallisation mechanisms

The preparations, precipitations and recrystallisations of magnesium and calcium aluminosilicate hydrates, from aqueous suspensions of microcrystalline silica, aluminium hydroxide (and oxohydroxide) and magnesium (calcium) hydroxides at ambient temperatures to 400 °C, are surveyed. The phases reported in systems of different Mg(Ca)/(Al + Si) and Al/(Al + Si) composition ratios are tabulated and precipitation and recrystallisation mechanisms are proposed.     

The precipitation of barium sulphate and chromate powders from aqueous solution with slow development of supersaturation. Crystal numbers and final crystal sizes

The precipitations of barium sulphate and chromate were studied by slow addition of anion to metal cation solution at 20°C, to give final equivalent metal salt solutions; the final solute concentrations (C_fin) were varied from 0.002 to 0.30 mol l⁻¹ while the rates (R) of addition of anion were varied from 10⁻⁴ to 10⁻² ion l⁻¹. At first, mainly heterogeneous nuclei formed continuously during induction periods; then, as the metal salt concentration in solution increased, homogeneous nucleation soon predominated. This second nucleation process probably attained its maximum rate when the metal salt concentration in solution reached its maximum value (C_max) and then probably terminated quite rapidly. Some further nuclei also formed during the growth process when crystal growth was prolonged. The final nucleus numbers (N), and thence the crystal numbers for slow precipitations from very dilute solutions were then rather higher than the number N ∞ (het) of heterogeneous nuclei in solution: nucleus numbers then increased with increasing mixing rate according to the relation, (where β = 0.7–0.9) (where β = 0.7–0.9). The final average crystal lengths of any precipitate were then 2 to 40 times the sizes noted for rapid precipitation from equivalent solutions of the same concentration: generally, final lengths varied with mixing rate according to the relation, .     

The precipitation of calcium carbonate powders from aqueous solution with slow development of supersaturation. Induction periods,crystal numbers and final sizes

The precipitation of calcium carbonate was studied by slow addition of anion solution to excess cation solution and by slow mixing of equivalent cation land anion solutions at 20 °C: the final solute concentrations (C_fin were varied from 0.01 to 0.75 mole 1⁻¹ while the rates (R) of addition of ions were varied from 0.06 to 6 · 10⁻³ ion 1⁻¹ sec⁻¹. At first, mainly heterogeneous nuclei formed continuously during induction periods; then, as the metal salt concentration in solution increased, some more heterogeneous nuclei formed but homogeneous nucleation soon predominated. The second nucleation process probably attained its maximum rate when the metal salt concentratio in solution reached its maximum value (C_max) and then probably terminated quite rapidly. Some further nuclei also formed during the growth process when crystal growth was prolonged. The final nucleus numbers (N) (and thence the crystal numbers) for slow precipitations from dilute solutions were then rather higher than the optimum number N∞ (het) of heterogeneous nuclei in the solution; nucleus numbers then increased with increasing maxing rate according to the relations . These numbers were similar to those noted for rapid precipitation – onto homogeneous nuclei – from calcium carbonate solutions of concentrations somewhat lower than the C_max values. The final average crystal lengths of any precipitate then generally varied with mixing rate according to the relations, . where l₁ values increased with (C_fln)^0.33.     

The precipitation of alkaline-earth metal and transition metal ‘oxinate’ powders from aqueous solution. Crystal numbers and final sizes

The precipitation of barium strontium, calcium, magnesium, zinc, cadmium and lead, manganese, cobalt, nickel and copper 8-quinolinolates (‘oxinates’) was studied from equivalent solutions, at pHs from 4.5 to 10, by optical microscopy: the metal cation and overall ‘oxinate’ with ‘oxine’ concentrations were varied from 0.0002 to 0.020 M (while the mean metal oxinate concentrations varied from 10⁻⁷ to 0.001 M). Crystal growth started after induction periods; the precipitations were heterogeneously nucleated at low supersaturations and homogeneously nucleated at medium to high supersaturations. The final precipitate crystal numbers depended on the number of nuclei formed during the induction periods. Crystal numbers at medium to high supersaturations increased with increasing initial metal oxinate concentration according to the relation, The final crystal lengths in this supersaturation range then decreased (from maximum values) with increasing initial mean metal oxinate concentration according to the relation, For precipitation from solutions of any concentration at any pH, smaller crystals were generally obtained in the precipitates from solutions of the metal oxinate of lower solubility.