Studies on recrystallised aluminium trihydroxide precipitates: The energetics of dissolution by sodium hydroxide solutions

Summary Aluminium hydroxide gels were recrystallised in high pH solution for 2–1000 hr to give a series of gibbsite powders of different surface areas, 1`11/2, P11/8, P11/48, P11/360 and P11/X; their average platelet lengths were 30, 60, 130, 260 and 450 nm. The dissolution equilibria of these powders in sodium hydroxide solutions of C=1-8 M were studied at 20° to 80°C.The equilibrium constants (for formation of diaquo-tetrahydroxoaluminate anion) increased with temperature and with increasing surface area; the K value for P11/2 was about four times that of P 11/X at 20 °C and about three times (that for P 11/X) at 80 °C. The dissolutions were endothermic; however, the value over this temperature range increased from –29.5 kJ mol<sup>–1</sup> (for P11/X) to –24.7 kJ (for P 11/2). This increase was related to the appreciable surface energies of the high surface-area materials.The (– G°) values increased with increasing temperature and in turn with increasing surface area; the (– G°) values for 1`11/2 dissolution at any temperature were about 4 kJ mol^–1 higher than those for P11/X dissolution.With 1 figure and 1 table     

Studies on recrystallised aluminium hydroxide precipitates

Summary Aluminium hydroxide gels were recrystallised in high pH solution for 2–1000 h to give a series of Gibbsite powdersP11/2,P11/8,P1/48,P11/360 andP11/X, consisting of hexagonal platelet crystals; their average platelet lengths (l ₀) were 0.03, 0.06, 0.13, 0.26 and 0.45 microns. The dissolution of dilute suspensions of these powders in well-stirred sodium hydroxide solutions were studied at 20–65°C Reaction solid and solution were analysed after different times by chemical and physical methods.Reaction occurred by two-directional dissolution of the platelet crystals. The reactions of GibbsiteP11/X (prepared by prolonged 1000 h crystallisation) were first order w.r.t. powder weight (and second order w.r.t. powder effective surface area); the reactions of the other Gibbsites were first order for the first twenty percent rapid dissolution and then slower. The initial rate constantsk _w1 (h^–1) and half-lifest _0.5 (h) for reactions ofP11/2,P11/8,P11/48.P11/360 andP11/X with sodium hydroxide solution of unit mean ionic activity at 20°C were 1.70, 0.9; 0.60, 2.2; 0.22, 5.5; 0.07, 14 and 0.02, 38 respectively.Rate constants increased linearly with the mean ionic activity of the hydroxide solution and increased exponentially with reciprocal absolute temperature, four to five times for 15°C temperature rise. Half-lifes decreased in a similar manner. Energies of activation varied from 76–83 kJ/mol. The rates of dissolution are determined by the rate of the chemical reaction between adsorbed hydroxyl ions and adjacent reactive aluminium hydroxide sites on the powder crystal surface.

---

Zusammenfassung Aluminiumhydroxydgele werden in Lösungen höher pH 2 bis 1000 Std. rekristallisiert und ergeben dabei eine Reihe von Gibbsit-PulverP11/2,P11/8,P11/48,P11/360 undP11/X. Sie bestehen aus hexagonalen plättchen-förmigen Kristallen. Die mittlere Dimension (l ₀) waren 0,03; 0,06; 0,13; 0,26 und 0,45 microns. Die Auflösung von verdünnten Suspensionen dieser Pulver wurden in stark gerührten Natriumhydroxyd-Lösungen bei 20 bis 65°C untersucht. Das feste Reaktionsprodukt und die Lösung wurden nach verschiedenen Zeiten mit chemischen und physikalischen Methoden analysiert.Die Reaktion erfolgte durch zwei-dimensionale Auflösung der Blättchen. Die Reaktion von GibbsitP11/X (präpariert durch eine auf 1000 Std. verlängerte Kristallisation) waren von 1. Ordnung hinsichtlich Pulver-gewicht, und von 2. Ordnung hinsichtlich effektiver Oberfläche. Die Reaktion der anderen Gibbsite waren von 1. Ordnung für die ersten 20% schnelle Lösung und wurden dann langsamer. Die anfänglichen Reaktionskonstanten und Halbzeiten der Auflösung für alle Gibbsite in Natriumhydroxyd-Lösungen der Ionenstärke 1 waren 1,70; 0,9, 0,60; 2,2; 0,22; 5,5; 0,07; 14 und 0,02, 38. Zahlen in der ReihenfolgeP11/2 bisP11/X.Die Geschwindigkeitskonstanten wachsen linear mit der mittleren Ionenaktivität der Hydroxylödung und wachsen exponentiell mit der reziproken absoluten Temperatur auf das Vier- oder Fünffache für 15°C Temperaturanstieg. Die Halblebensdauern nehmen in analoger Weise ab. Die Aktivierungsenergien variieren zwischen 76 und 83 kJ/mol. Die Geschwindigkeiten der Auflösungen. werden durch die Geschwindigkeit der chemischen Reaktion bestimmt. Zwischen den adsorbierten Hydroxyd-Ionen und den anhaftenden reaktiven Aluminiumhydroxydplätzen an der Kristall-Pulver-Oberfläche.

---

---

With 6 figures and 2 tables     

Kinetics of aluminium hydroxide dehydration

Non-isothermal thermogravimetric analysis was used for determination of the kinetics of aluminium hydroxide dehydration in an air atmosphere and for processing of the experimental results by the method due to Chatterjee.Aluminium hydroxide dehydration proceeds according to the following mechanism: Al(OH)₃AlOOH + H₂O 2 AlOOHAl₂O₃ + H₂OBoth reactions proceed in the diffusion region, the first up to 526 K and the second up to 700 K, and the corresponding activation energy values are 15.7 and 0.2 kJ/mole, respectively.

---

Zusammenfassung Die nicht-isotherme thermogravimetrische Analyse wurde zur Bestimmung der Kinetik der Dehydration von Aluminiumhydroxid in Luft-Atmosphäre eingesetzt und die Methode von P. K. Chatterjee zur Verarbeitung der Versuchsergebnisse angewendet.Der Dehydratisierungsvorgang von Aluminiumhydroxid verläuft nach folgendem Mechanismus: Al(OH)₃AlOOH + H₂O 2 AlOOHAl₂O₃ + H₂OBeide Reaktionen spielen sich in der Diffusionszone ab, die erstere bis zur Temperatur von 526 K und die zweite bis zur Temperatur von 700 K. Die entsprechenden Aktivierungsenergien sind 15.70 kJ/Mol für die erste und 0.20 kJ/Mol für die zweite Reaktion.Bei kontinuierlicher Erhöhung der Temperatur über 526 K im ersten und über 700 K im zweiten Fall werden die Geschwindigkeiten dieser Reaktionen durch kristallchemische Umwandlungen begrenzt und die Aktivierungsenergie beträgt 116.97 kJ/Mol für die erste und 91.92 kJ/Mol für die zweite Reaktion.

---

Résumé On détermine la cinétique de la déshydratation de l'hydroxyde d'aluminium dans l'air, par thermogravimétrie non-isotherme, en dépouillant les résultats suivant la méthode proposée par P. K. Chatterjee.Le processus de la déshydratation de l'hydroxyde d'aluminium s'effectue suivant le mécanisme: Al(OH)₃AlOOH + H₂O 2AlOOHAl₂O₃ + H₂OLes deux réactions ont lieu par diffusion, la première jusqu'à la température de 526 K et la seconde jusqu'à 700 K, les valeurs correspondantes des énergies d'activation étant 15.70 kJ · mol^–1 pour la première et 0.20 kJ · mol^–1 pour la seconde réaction.Lors d'une élévation continue de la température au-dessus de 526 K dans le premier cas et au-dessus de 700 K dans le deuxième cas, les vitesses de ces réactions deviennent limitées en raison des transformations cristallochimiques et les valeurs des énergies d'activation sont 116.97 pour la première et 91.92 kJ · mol^–1 pour la seconde réaction.

---

, — . : Al(OH)₃AlOOH + H₂O 2 AlOOHAl₂O₃ + H₂O , 526 , — 700 . 15,70 0,20 / . 526 700 — , - , , 116,97 91,92 /.

     

Zinc dissolution and passivation in buffered phosphate solutions: Part I. A comparative study with sodium hydroxide solutions

Zn dissolution and passivation in buffered phosphate electrolyte in the pH range between 7 and 13.5 has been studied under a wide variety of experimental conditions. The electrode rest potential shows three regions depending on pH. Between pH 7 and 10 a constant value was found while a slope of 60 mV is obtained from a plot of E_r vs. pH. In the pH range 10–11.5 a mixed potential could be established due to the minimum buffer capacity of the system. The necessary charge for passivation was found to be 1.5 mC cm^?2 and this was attributed to a monolayer film. From l.s.v. and RDE results a change on Zn dissolution mechanism from a dissolution precipitation to a solid phase process with pH can be postulated. Time and potential effects on product reduction would show that there are chemical transformations on the electrode surface as a second step on the electrode poassivation. From experimental kinetic parameters an empirical rate equation for Zn dissolution is found asi_a=2k_aFc_OH^?c_{(PO4^3?)t^0.5}exp[(3/2)EF/RT)]Accordingly a reaction mechanism is postulated where PO₄^3? ions act as dissolution promoters, while HPO₄^2?, through the formation of NaZnPO₄·H₂O glass, would act as a dissolution inhibitor.     

Spectrophotometric determination of sulphate in sodium hydroxide solutions by flow-injection analysis

A spectrophotometric flow-injection procedure is described for the determination of sulphate in sodium hydroxide solutions. Sulphate catalyses the reaction between zirconium and methylthymol blue to form a complex measured at 586 nm. Optimal reaction conditions are discussed. The calibration graph is linear over the range 0.05–0.5 g l^?1 sulphate with a relative standard deviation of 0.02. The sample throughput is 20 h^?1. Sulphate is easily determined in 1 M sodium hydroxide; the results agree with those obtained by the conventional gravimetric method and by ion chromatography.     

Anodic passivation of tin in sodium hydroxide solutions

The passivating processes at a tin anode in NaOH solutions have been investigated by voltammetry. The effects of varying sweep rate, rotation speed, concentration of NaOH and the potential limits have been studied. The results indicate that primary passivation is the results of a dissolution—precipitation mechanism involving the blocking of the electrode by Sn(II) species. There is evidence that during secondary passivation there is not only oxidation of Sn(II) to Sn(IV) species but alos the direct oxidation of Sn to Sn(IV) solution soluble species. At more positive potentials dehydration of the film may occur and result in a more efficient passivation. A possible explanation is advanced for observed current oscillations.     

Conductance and transport numbers of acidified sodium aluminate solutions and the zero point of charge of aluminium hydroxide

Summary Conductance measurements of acidified sodium aluminate solutions showed a gradual drop as the alumina content of the solution increases. This behaviour was explained by adsorption of H⁺ ions, as visualised from linear plots of ( ₀–) per mole of alumina against (where ₀ is the specific conductance of the corresponding (NaOH + HCl), is the specific conductance of (sodium aluminate + HCl) and is the amount of H⁺ ions adsorbed per mole of alumina). Transport number experiments showed that alumina behaves as a non-electrolyte and that the transport number of the Cl– ion increases with increase in alumina content. This behaviour was explained on the basis of aggregation of water molecules around alumina.The zero point of charge of colloidally dispersed aluminium hydroxide was determined from potentiometric and conductance measurements.

---

Zusammenfassung Leitfähigkeitsmessung von angesäuerten Natrium-Aluminat-Lösungen zeigen einen Abfall, wenn der Aluminat-Gehalt der Lösungen wächst. Dieses Verhalten wird durch Adsorption von Wasserstoff-Ionen erklärt, erkennbar aus der linearen Auftragung von ( ₀–) pro Mol/Aluminat gegen Dabei ist ₀ die spezifische Leitfähigkeit der entsprechenden (NaOH + HCl)-Lösung, die spezifische Leitfähigkeit vom Gemisch Natriumaluminat + HCl und der Betrag an Wasserstoffionen, adsorbiert pro Mol/Aluminat. überführungszahl-Experimente zeigen, daß Alumina sich nicht als Elektrolyt verhält und daß die überführungszahl für Cl^–-Ionen mit dem Alumina-Anteil wächst. Dieses Verhalten wird erklärt auf Grund einer Aggregation von Wassermolekülen um das Alumina.Der Neutralpunkt für Ladung von kolloidal dispergiertem Alumiumhydroxid wurde aus potentiometrischen und Leitfähigkeitsmessungen bestimmt.

     

Cyclic voltammetry of copper in sodium hydroxide solutions

The cyclic voltammograms of the Cu electrode were, obtained in NaOH solution as a function of the voltage scanning rate, electrolyte concentration and voltage range. A correlation was made between three well-defined anodic peaks and their corresponding cathodic ones. The anodic peaks were found to correspond successively to the formation of a monolayer of Cu₂O, formation of a thick multilayer film of CuO and finally Cu₂O₃ upon which O₂ is evolved. It is suggested that CuO is formed from the oxidation of Cu₂O and/or direct oxidation of metallic copper.Below 0.1 M NaOH the ratio of anodic to cathodic charges was found to be about unity, indicating the quantitative reduction of solid oxidation products, while at higher alkali concentrations higher charge ratios were obtained due to increasing proportions of soluble reaction products.The behaviour of the copper electrode in NaOH was found to be quite complicated. Thus, no simple relations were found between the voltage scanning rate and both the peak current and peak potential or between the peak current and the alkali, concentration. Further work is needed to obtain a definitive explanation of this behaviour.     

Kinetics of hydrogen absorption by porous nickel in an aqueous sodium hydroxide solution

Kinetic studies of hydrogen absorption by porous nickel catalyst establish that there are three regions on kinetic curves of the process differing in their regularities of adsorption. The dependence of the observed rate of hydrogen absorption on the adsorbate amount is formally described by a first order kinetic equation, and the absorption rate constants corresponding to distinct parts of the kinetic curve differ by 1–2 orders of magnitude. The obtained data are explained using the concept that hydrogen adsorption on nickel active centers proceeds with three forms of adsorption.     

Preconcentration of trace elements by aluminium hydroxide

Summary Coprecipitation of traces of cobalt, zinc, chromium, ruthenium and mercury with freshly precipitated aluminium hydroxide has been investigated by a radiotracer method. Investigations were performed over a wide range of pH. The results indicate that traces of cobalt, zinc and chromium could be almost completely coprecipitated between pH 6 and 10. On the other hand coprecipitation yield for ruthenium in this pH range do not exceed 95%, which is believed to be the consequence of the various physicochemical states of ruthenium. The coprecipitation yields for mercury are very low as a consequence of the presence of non-ionized HgCl₂.

---

Zusammenfassung Die Mitfällung von Spuren Kobalt, Zink, Chrom, Ruthenium und Quecksilber mit frisch gefälltem Aluminiumhydroxid wurde radiochemisch untersucht. Die dazu nötigen Experimente erstreckten sich über ein weites pH-Gebiet. Die Ergebnisse zeigen, daß Spuren Kobalt, Zink und Chrom zwischen pH 6 und 10 fast vollständig mitgefällt werden konnten. Andrerseits sind die Mitfällungsausbeuten für Ruthenium in diesem pH-Gebiet nicht größer als 95%, was vermutlich die Folge der verschiedenen physikalischchemischen Zustände des Rutheniums ist. Die Mitfällungsausbeuten für Queckilber sind infolge der nur geringen Dissoziation des HgCl₂ sehr gering.

     

Paramagnetic centers by X-ray-irradiation of aluminium hydroxide

EPR spectra of paramagnetic centers originating from X-ray-irradiation of aluminium hydroxide at room temperature have been measured. The EPR spectrum represents a superposition of EPR spectra of ionic centers O^–, holes of type and trapped electrons. Radiation chemical yield of paramagnetic centers observed at room temperature (293 K) is G(spins.)=4.4±0.6) spins per 100 eV absorbed energy. The decay of paramagnetic centers in irradiated Al(OH)₃ was oberved at 293 K. The rate constant of the paramagnetic centers decay in irradiated Al(OH)₃ is K₂=(0.0980±0.0019) kg·mol^–1·min^–1 and their half-life is 9.43±0.18 days.Dedicated to the memory of the late Genrikh Markovis Kolyiari.     

Electrical conductivity of aqueous sodium hydroxide solutions at high temperatures

Electrical conductivities of dilute sodium hydroxide aqueous solutions have been determined at 75, 100 and 150°C at 1.6 MPa using a recently developed DC-measuring technique especially suited for the study of aqueous solutions above room temperature. The data were analyzed with modern theories to obtain the infinite dilution conductivity and the association constant at the three temperatures.     

The dissolution of microcrystalline cellulose in sodium hydroxide-urea aqueous solutions

It has been reported that cellulose is better dissolved in NaOH-water when a certain amount of urea is added. In order to understand the mechanisms of this dissolution and the interactions between the components, the binary phase diagram of urea/water, the ternary urea/NaOH/water phase diagram and the influence of the addition of microcrystalline cellulose in urea/NaOH/water solutions were studied by DSC. Urea/water solutions have a simple eutectic behaviour with a eutectic compound formed by pure urea and ice (one urea per eight water moles), melting at −12.5 °C. In the urea/NaOH/water solutions, urea and NaOH do not interact, each forming their own eutectic mixtures, (NaOH + 5H₂O, 4H₂O) and (urea, 8H₂O), as found in their binary mixtures. When the amount of water is too low to form the two eutectic mixtures, NaOH is attracting water at the expense of urea. In the presence of microcrystalline cellulose, the interactions between cellulose and NaOH/water are exactly the same as without urea, and urea is not interacting with cellulose. A tentative explanation of the role of urea is to bind water, making cellulose-NaOH links more stable. Member of the European Polysaccharide Network of Excellence (EPNOE),     

Mercury passivation solutions of potassium chloride and sodium hydroxide and hypochlorite

Formation of anodic films on the surface of mercury in solutions of potassium chloride and sodium hydroxide and hypochlorite and the effect of these films on mercury passivation were studied by the potentiostatic method.     

The determination of hydroxide and carbonate in concentrated sodium chloride solutions

A computer method for the determination of carbonate and hydroxide in concentrated (2.89 M) sodium chloride solutions is described. The method is based on multiparametric curve-fitting and can also be applied to salts of dibasic acids with unknown equilibrium constants. The systematic error is not more than 1%. The titration and calculation takes less than 20 min.     

Kinetics of carbon steel dissolution in ammonium chloride solution containing sodium thiosulfate

The dissolution behavior of carbon steel in ammonium chloride (NH₄Cl) solution containing sodium thiosulfate (Na₂S₂O₃) of various concentrations (0.01 and 0.1 M) was investigated using electrochemical impedance spectroscopy (EIS) and other nonelectrochemical techniques. The weight loss and polarization measurements indicate a significant increase in the NH₄Cl corrosion rate of carbon steel on addition of Na₂S₂O_3. The EIS measurements exhibited two capacitive loops at multiple direct current (dc) potentials for both the concentrations. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to analyze the impedance data. A four-step mechanism with two intermediate adsorbate species of same charge was proposed to explain the dissolution behavior of carbon steel in the given system. The surface coverage values enumerated that the surface was entirely covered with adsorbed species unlike in the pure NH₄Cl system. Charge transfer resistance and polarization resistance values estimated from RMA parameters indicate the increase in a dissolution rate with dc potential. The surface morphology was inspected via field emission scanning electron microscopy, and the corrosion products including surface state of carbon steel electrode were analyzed using energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

Kinetics and mechanism of diethyl sulfide oxidation by sodium peroxoborate in aqueous solutions

The kinetics of diethyl sulfide (Et₂S) oxidation by aqueous sodium peroxoborate (Na₂[В₂(О₂)₂(ОН)₄]) solutions in a wide acidity range (from [HClO₄] = 1 mol/L to рН 12) has been studied using a kinetic distribution method. The kinetic data together with the results of ¹¹B NMR spectroscopy demonstrate that the monoperoxoborate B(O₂H) ₃ ^- (OH) and diperoxoborate B(O₂H)₂(OH) ₂ ^- anions are the active species in Et₂S oxidation by sodium peroxoborate at рН 8–12. It is assumed that, at a high acidity of the medium ([HClO₄] = 0.05–1.0 mol/L), peroxoboric acid (ОН)₂ВООН or its protonated form (OH)₂BOOH ₂ ⁺ are direct reactants along with Н₂О₂ and HOOH ₂ ⁺ .     

Influence of AgCl precipitates on the precipitation titration of sodium chloride by constant-current coulometry.

The precipitation titration of sodium chloride with electrogenerated silver ion was studied. The production of a precipitate of silver chloride had a significant effect on the titration results because the precipitate involved unreacted chloride or unreacted silver ion. The accuracy of the method was investigated by changing the introduction time of a sodium chloride solution to the coulometric cell during the process of electrolysis, and examining the dependency on the sample size. The accuracy of the measurement of the precipitation titration is discussed.     

Tribological behaviors of DLC films in sulfuric acid and sodium hydroxide solutions

Tribological behaviors of three typical kinds of diamond-like carbon (DLC) films (a-C, a-C:Cr, and a-C:H) in sulfuric acid and sodium hydroxide solutions were investigated. The a-C film showed the lowest stable coefficients of friction (COF) in both sulfuric acid and sodium hydroxide solutions but the worst wear resistance in sulfuric acid solution. The a-C:H film showed the highest COF in sulfuric acid solution and the best wear resistance in both sulfuric acid and sodium hydroxide solutions. The a-C:Cr film exhibited superior comprehensive tribological performance in sulfuric acid solution, while in sodium hydroxide solution, high COF and very poor wear resistance was observed. What is more, friction and wear mechanism was revealed by investigating the friction-induced material evolutions on the sliding surface.