ISSN 0036-0295, Russian Metallurgy (Metally), Vol. 2008, No. 4, pp. 294300. Pleiades Publishing, Ltd., 2008.

. Original Russian Text Yu.A. Lainer, I.G. Gorichev, A.S. Tuzhilin, E.G. Gololobova, 2008, published in Metally, 2008, No. 4, pp. 2937.

Dissolution Mechanism of Aluminum Hydroxides in Acid Media

Yu. A. Lainera, I. G. Gorichevb, A. S. Tuzhilina, and E. G. Gololobovab
aBaikov

Institute of Metallurgy and Materials Science, Russian Academy of Sciences, Moscow, Russia e-mail: lainer4@yandex.ru bMoscow State Pedagogical University, Moscow, Russia
Received April 14, 2008

AbstractThe effects of the concentration, temperature, and potential at the hydroxide/electrolyte interface on the aluminum hydroxide dissolution in sulfuric, hydrochloric, and perchloric acids are studied. The limiting stage of the aluminum hydroxide dissolution in the acids is found to be the transition of the complexes that form on the aluminum hydroxide surface from the solid phase into the solution. The results of the calculation of the acidbase equilibrium constants at the oxide (hydroxide)/solution interface using the experimental data on the potentiometric titration of Al2O3 and AlOOH suspensions are analyzed. A mechanism is proposed for the dissolution of aluminum hydroxides in acid media. PACS number: 64.70.Dv DOI: 10.1134/S0036029508040046

INTRODUCTION When studying the kinetics and mechanism of aluminum hydroxide dissolution, one can solve a challenging chemical technology problem, namely, the optimization of the complex technological process of leaching aluminum-containing raw materials [1, 2]. The effects of various conditions on the dissolution kinetics of aluminum oxides and hydroxides in acid media were studied in many works [210]. However, the main kinetic parameters that can be used to reveal the nature of the limiting stage of the dissolution of aluminum hydroxide have not been found. The mechanism of aluminum hydroxide dissolution is also unknown; as a result, the process cannot be simulated and optimized. The purpose of this work is to study the effects of the temperature, the acid (HClO4, HCl, H2SO4) concentrations, and the acidbase equilibria appearing at the aluminum hydroxide/electrolyte interface on the dissolution rate of aluminum hydroxide in acid media in order to reveal the nature of the limiting stage and the mechanism of aluminum hydroxide dissolution. EXPERIMENTAL We used an aluminum hydroxide powder produced according to the technique in [11]. The initial material was identied by IR spectroscopy (SPECORD-751R), thermogravimetry (Q-150D derivatograph (MOM)), and X-ray diffraction (DRON-3). With the results obtained, we determined the exact formula and structure of the initial compound: it corresponded to Al(OH)3 (bayerite). As follows from the thermogravimetric results, the water losses at temperatures of 192,

268, and 510C were caused by transformations in the substance, which corresponds to the data in [12]. To determine the initial particle radius, we performed granulometric fractional analysis using a COTAM apparatussoftware setup, which includes an optical television image acquisition system of microobjective lenses and the Scientic Image Processing software. The statistical results were obtained in the form of tables and the length, width, area, perimeter, and shapefactor histograms of the particles. The average particle size was calculated; for an initial radius of dissolving particles R0 = 0.05 0.02 mm, it was found to be R = 4 106 m. In experiments, we used solutions of sulfuric, hydrochloric, and perchloric acids in twice-distilled water. A 60 5-mg aluminum hydroxide sample was introduced into a thermostatically controlled reactor containing a 500 10-ml aqueous solution of acid. The experiments were carried out at various acid solution concentrations and various temperatures. To eliminate diffusion difculties, we maintained free particle motion conditions ( = 500 min1). During dissolution, we took 1-ml samples from the reactor in certain time intervals to determine the Al3+ concentration on a KFK-2-UKhL spectrometer with aluminon using the technique in [13]. Figures 13 show the main results on the dissolution kinetics of -Al(OH)3 in perchloric, sulfuric, and hydrochloric acids. To study the acidbase properties, we used puregrade aluminum oxide (-Al2O3) and the and modications of aluminum oxyhydroxide (-AlOOH, -AlOOH). The X-ray diffraction analysis demonstrated that the lattice parameters of the aluminum oxide and oxyhydroxides corresponded to the tabulated

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295

values [1116]. For studies, we screened the fraction with an average particle size R = (90 10) 106 m. 0.1 N hydrochloric acid was prepared using a TU 6-09-254072 titration standard. After preparation, the pure-grade potassium hydroxide was standardized by the titration of a solution of hydrochloric acid. As the base electrolyte, we used pure-grade potassium chloride. All solutions were prepared using twice-distilled water. To study the acidbase equilibria appearing at the aluminum hydroxide/solution interface, we employed potentiometric titration. The pH measurements were carried out on an electronic MV 870 R pH meter with chlorinesilver and glass electrodes. To determine the coefcients of active ion [H+] and [H3O+] concentrations, we obtained the base curve of the titration of hydrochloric acid by an alkali at various base KCl electrolyte concentrations and a total electrolyte volume of 50 ml. The aluminum hydroxide suspension was then titrated in KCl-containing hydrochloric acid with a concentration 0.01 mol/l. The aluminum hydroxide sample weight was 5.00 g per 50 ml solution. The experimental data on the kinetics of aluminum hydroxide dissolution were processed in the form of () dependences. The fraction of dissolved aluminum was calculated by the equation = Ai/A, (1) where Ai is the ltrate optical density at time i and A is the same upon complete dissolution of the sample. RESULTS AND DISCUSSION The kinetic curves of aluminum hydroxide dissolution in HClO4, H2SO4, and HCl shown in Figs. 1 and 3 have - and s-type shapes. To process such results, researchers usually apply the equations for a compressible volume and a plane in [9]. However, these equations describe the kinetic curves with an insufcient accuracy, and we have to take into account an induction period or to introduce a correction for diffusion [9]. When analyzing the kinetic laws of aluminum hydroxide dissolution, we should also take into account changes in the surface of the dissolving particles. To analyze the curves, we use fractal geometry [17]. To nd the dependence of the fraction of dissolved aluminum hydroxide on time , we divided the volume of a dissolving particle with initial radius R0 into layers of thickness dx located at a distance R0 dx. We also assumed that the fraction of each dissolved layer at time is (x, ). Then, we have S() ( x, ) = ----------dx, V0 (2)

In the general form, the dissolving volume of any particle V0 can be represented as a multidimensional space of fractal dimension q [17]; i.e., V 0 = f R0 , (3) where V0 is the initial volume of the fully dissolved particles (cm3), f is the particle shape factor, R0 is the initial particle radius (cm), and q is the fractal dimension of the dissolving particles. The particle volume at time is (cm3) V = qf(R0 x)q 1dx, (4) where x is the decrease in the radius that characterizes the dissolution (x = W, where W is a dissolution rate constant (cm/min)) and dx is the layer thickness of the dissolving particle. For convenience, we introduce dimensionless parameters = W/R0 and = x/R0. We take into account the limits of integration from zero to R for and from zero to for and nd the () dependence, q ( R0 x ) q x q1 = ----------------------------- d x = ----- 1 ----- d x q R0 R 0 R0 0 0
R0 q

q1

q q1 q = ----- ( 1 ) d = 1 ( 1 ) R0

or (5) 1 (1 )1/q = . The oxide phase dissolution rate d/d can be written in the form d/d = q(1 )(q 1)/q. (6) To determine the fractal dimension of the dissolving volume of the particle, we present the experimental data in the /0.5 coordinates (Fig. 3) and compare them with the calculated versus /0.5 curves [17].
0.8 0.6 0.4 0.2 3 4

1 2

where S() is the sphere surface at time and distance x (cm2), V0 is the initial volume of the fully dissolved particles (cm3), and dx is the layer thickness of the dissolving particle (cm).
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10 , min

Fig. 1. Fraction of dissolved aluminum hydroxide -Al(OH)3 as a function of time at a perchloric acid concentration C HClO = (1) 9, (2) 6, (3) 4, and (4) 2 mol/l.
4

296 0.8 1 2 3 4

LAINER et al. 5 6 7 8 9 10

0.6

0.4

0.2 (a) 0 20 40 60 80 , min 0 0.5 1.0 (b) 1.5 10 2, min

Fig. 2. Dependence () for the dissolution of aluminum hydroxide in (a) 5 M H2SO4 at a temperature of (1) 343, (2) 338, (3) 333, (4) 328, and (5) 323 K and in (b) 10 M HCl at a temperature of (6) 358, (7) 353, (8) 348, (9) 343, and (10) 333 K.

We experimentally found q = 0.7 0.2. The fact that q < 1 indicates that the process proceeds on active centers. To rene the chosen model, we present the kinetic curves in the 1 (1 )1/q coordinates. The use of the 1 (1 )1/3 or 1 (1 )1/2 coordinates was shown to require the introduction of an induction period, whose physical meaning is unclear [9]. When taking into account fractality, we failed to correctly describe the kinetic curves; therefore, we propose a model that takes into account the diffusion law of the removal of aluminum ions. In this case, to describe the kinetic curves, we use an equation of the type [9] / 0.5 = [ ( 1 3 1 ) ( 1 + 2 3 1 ) + (1 1 ) ](1 + ) ,
3 1 2

(7)

0.6 0.4 0.2

where /0.5 is the reduced time, is the dissolution time (min), t0.5 is the dissolution time of half the sample (min), = W/D is the ratio of the kinetic to diffusion process rates (min), and D is the diffusion coefcient (min/cm2). As follows from an analysis of the kinetic curves in Fig. 3, they are well described by heterogeneous kinetic equations corrected for diffusion [9]. To determine the anion reaction order, we presented the experimental data in the log W log C HA coordinates (Fig. 4). As follows from the results obtained, the approximate reaction order is 1.43 0.05 for the dissolution of -Al(OH)3 in sulfuric acid, 1.28 0.05 in hydrochloric acid, and 1.1 0.05 in perchloric acid. The dissolution reaction order calculated for hydrogen ions is 0.5. To determine the dissolution activation energy, the experimental data were processed in the log W 1/T coordinates. The calculated activation energies Ea are given in the table. The empirical equation for the -Al(OH)3 dissolution rate has the form Ea Ea n 0.5 m W = WC HA exp ------- = WC H+ C A exp ------- , (8) RT RT where W is the dissolution rate constant (cm/min), CHA is the concentration of the HA acid (mol/l), Ea is the activation energy (kJ/mol), R is the universal gas constant (J/(mol K), n is the acid-related dissolution rate order, and m is the anion-related dissolution rate order. According to the experimental data, the anionrelated order for dissolution in various acids is n SO2+ = 0.9;
4

1 2 3 4 3.0 /0.5

0.5

1.0

1.5

2.0

2.5

Fig. 3. Fraction of dissolved oxide vs. the reduced time /0.5 at various perchloric acid concentrations: (points 14) experimental data (the same as in Fig. 1), (curves) calculated dependences at various diffusion and kinetic constants.

n Cl = 0.7;

n ClO = 0.6.
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To explain the empirical dependences, we propose an acidbase model for the dissolution of aluminum hydroxides. The rst stage in this model of the dissolution of aluminum hydroxide consists in proton sorption [18]. When discussing absorption properties, researchers most often use the acidbase model of the structure of the electrical double layer [1621]. During ion adsorption, active dissolution centers, which can be + represented as [AlO H 2 A s ] surface compounds, are assumed to appear [20, 21]. To calculate the number of active dissolution centers and to analyze the acid base equilibria appearing at the oxide/solution interface, we should take into account the acid characteristics of aluminum hydroxides. The potentiometric titration of a suspension [21, 22] was shown to be effective for the calculation of the acidbase constants of the Brensted acids in aqueous solutions. At the oxide/solution interface, equilibria of four types are established, and they are described with ther0 0 modynamic equilibrium constants K 1 K 4 [14, 15, 19]. In particular, we have AlOH 2, s
0 +

logW H2SO4 1.0 HCl 0.5 0.2 0 0.4 0.6 0.8 logCHA HClO4

0.5

1.0
Fig. 4. Logarithm of the dissolution rate vs. the logarithm of the acid concentration CHA (H is the hydrogen ion and A is an acid anion).

AlOH s + H ,
+ 0 [ AlOH s ] [ H ] ------------------------------------, 0 [ AlOH 2.9 ] +

K 1 = K 1 exp ( 0 F/RT ) = AlOH s

0

(9)

AlO s + H ,
+

[ AlO s ] [ H ] 0 K 2 = K 2 exp ( 0 F/RT ) = -------------------------------- , 0 [ AlOH s ] AlOH 2 Cl s

+

(10)

[Al O s ], [AlO H 2 Cl s ], and [AlO K s ] (C/cm2); 0 and q0 are the potential drop (V) and the surface charge (C/cm2), respectively, at the oxide/solution interface; and K01 is the integrated capacitance of the electrical double layer between the oxide surface and the internal Helmholtz plane (F/cm2). Based on numerous reported results, we describe a procedure for the calculation of the logarithms of the constants using the experimental data on potentiometric titration in [19] and present the calculation results. Calculation of the Constants of the AcidBase Equilibria Using the Data on the Potentiometric Titration of an -AlOOH Suspension Results of the titration of the base electrolyte. To calculate the constants, we used the potentiometric curves presented in the pHVi coordinates (Fig. 5). The base curves (which will then be described by Eq. (14)) were calculated at KCl concentrations from 0.01 to

AlOH s + Cl + H ,

0 + q0 [ AlOH s ] [ Cl ] [ H ] (11) 0 K 3 = K 3 exp ------- F/RT = -------------------------------------------------- , + K 01 [ AlOH 2 Cl s ] 0 AlOH s

+K

AlO

+ K s

+H ,

+ + q0 [ AlO K s ] [ H ] (12) 0 K 4 = K 4 exp ------- F/RT = --------------------------------------------- , + 0 K 01 [ AlOH s ] [ K ]

where subscript s stands for absorbed ions with a + surface concentration of the particles [AlO H 2, s ],

Effective activation energy Ea and the specic rate of aluminum hydroxide dissolution W (T = 343 K) in hydrochloric and sulfuric acids Parameter at the acid concentration (mol/l) Parameter 10 Ea, kJ/mol W 104, cm/min 70.0 1.22 8 70.01 1.07 CHCl, mol/l 5 55.9 0.69
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C H2 SO4 , mol/l 3 54.4 0.24 5 66.3 2.26 4 70.9 2.14 3 78.9 1.67 2 68.7 1.20

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298 q0 105, C/cm2

LAINER et al. Vi 103, l

titration curves presented in the pHVi coordinates using the equations from [1921], Ve V 2 + a H+ a H+ ----------------i [ KOH ] [ H s ] K w = 0, (14) V0 + Vi Ve V 1 a H+ K w = ----------------i [ KOH ] -- ------------------- , a H+ V0 + Vi
+ 2

2 0 2 4 3 4 5 6 pH 7 8 9

+ [ Hs ]

(15)

where [ H s ] is the surface concentration of hydrogen ions (mol/l) and is the activity coefcient calculated from the base titration curves. The found value of [ H s ] (mol/l) was converted into the value of charge q0 (C/m2) using the equation q 0 = [ H s ] ( F/mS ) = [ H s ] 1.5 10 ,
+ + 3 +

Fig. 5. Dependence of hydrogen index pH on the volume Vi of added alkali KOH and charge q0 during the potentiometric titration of an aluminum hydroxide suspension.

1 mol/l (before the calculations, we analyzed the base titration curves) [20, 21] Ve V 2 a H+ a H+ ----------------t [ KOH ] K w = 0, V 0 + V t (13)

(16)

where a H+ is the active hydrogen ion concentration in the solutions (mol/l), Vi is the volume (l) of the introduced alkali with a given concentration [KOH], Ve is the equivalent volume (l) of the alkali with the concentration [KOH] (mol/l) consumed for the titration of HCl with a given concentration (mol/l), V0 is the initial system volume (l), is the activity coefcient of hydrogen ions, and Kw is the ionic product of water. When using Eq. (13), we can substitute the values of Vi, Ve, V0, and [KOH] into it and obtain a theoretical titration curve. To determine Ve, we doubly differentiate the pHVi curves (using Grans method) and construct pH - 2a linear ---- ------ Vi dependence. Vi
2

where F is the Faraday number (C/mol), m is the suspension concentration (100 g/l), and S is the oxide surface. The main results of the dependence of charge q0 on pH at various base electrolyte concentrations Cel are shown in Fig. 5. To calculate the constants, we have to know the values of q0 and 0 for each value of pH at a certain value of Cel. Calculation of Potential 0 The authors of [1921] proposed the following semiempirical equation to describe the dependence of potential 0 on the charge at the oxide/solution interface: H0 RT 0 = 2.3 ------- ln ----- , + F H
+

(17)

The calculated values of are used to analyze the experimental data on the potentiometric titration of suspensions at given [KCl] concentrations and current values of pH and Vi. Results of the titration of aluminum oxide suspensions. After the determination of the = f(pH, Vi) dependences for base solutions, we titrated AlOOH suspensions. The potentiometric titration results are given in Fig. 5. The calculation of the constants of acidbase equilibria was reduced to the determination of the concen+ trations of adsorbed [ H s ] ions from the suspension

where is the coefcient of ion passage through the + interface, [ H 0 ] is the hydrogen ion concentration in the solution at the pH value corresponding to the zero charge point (mol/l), and [H+] is the hydrogen ion concentration in the solution at a given value of pH (mol/l). Estimation of Ns We determined the limiting concentration Ns of all surface centers using the geometric sizes of the unit cells [15]. For example, for Al2O3, 7.6 centers are located in 100 2 (1 nm2); that is, Ns = 7.91 nm2 = 7.91 1014 cm2 = 1 109 mol/cm2 = 125 106 C/cm2 [3].
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DISSOLUTION MECHANISM OF ALUMINUM HYDROXIDES

299 103

Calculation of the Constants of the AcidBase Equilibria We calculated constants K i using the equation 38.301 q 0 = B 0 B 1 C sinh 2.303 ( pH k pH 0 ) + q --------------- K 01 c + sin ( 38.301 0 + 2.303 ( pH k pH 0 ) )- 38.301 B 1 C cosh 2.303 ( pH k pH 0 ) + q --------------- K 01 c -- + cos ( 38.301 0 + 2.303 ( pH k pH 0 ) ) + B 2 , -. and B2 = -----------+ 2 [ H0 ] We obtained the acidbase equilibrium constants, which can be used to calculate the distribution of aluminum hydroxide surface complexes. The negative logarithms of the thermodynamic acidbase equilibrium constants at the aluminum hydroxide/solution interface that were determined from the potentiometric titration data are as follows: where B0 = Ns, B1 =
pK 1 6.5 pH 8.8
0 0 K1 ----- , 0 K3 0 K1 1

0.8 1 0.6 2 3 4 5

1.5

1.0 0.4

(18)

0.2

0.5

2.5

5.0

7.5 pH
+

10.0

12.5

Fig. 6. Distribution of the relative fraction of (1) AlOH+ A s , (2) AlO H 2, s (3) AlO H s , (4) Al O s , and (5) AlOHKs in the anion particles adsorbed on the surface of aluminum hydroxide.
0

or (20) dissolution products. To describe the dissolution mechanism quantitatively, we assume that the limiting stage is represented by the transition of the intermediate complex + [AlO H 2 A s ] from the solid phase to the solution at a rate (21) W = k21,
k2

[ 0 AlOH s ] + H + A
0 +

k1

[ 1 AlOH 2 A s ]
+

pK 2 11.1 K01, F/cm2 100

pK 3 8.4

pK 4 9.2 Ns 106, C/cm2 125

Figure 6 shows the calculated distribution of anion particles adsorbed on the surface. An analysis of the curves in Fig. 6 demonstrates that the main type of particles that controls the aluminum hydroxide dissolution rate is represented by + AlO H 2 A s ions. To reveal the mechanism, we should take into account the effect of anions. According to our preliminary experiments, the adsorption of A = Cl, 2 S O 4 anions is described by Langmuir isotherms [19 22], and adsorption constant B depends on potential 0, /(1 ) = BCHAexp(0F/(RT)), (19) where is the coverage of the surface by the complex + [AlO H 2 A s ], B is the absorption constant (l/mol), and CHA is the acid concentration (mol/l). The processes of proton and anion adsorption and the subsequent dissolution can be represented in the form [23] [ AlOH s ] + H + A = [ AlOH 2 A s ]
0 + +

where k2 is the limiting stage rate constant (min1) and 1 is the coverage of the surface by the complex + [AlO H 2 A s ]. To calculate 1 and W, we use the kinetic analysis proposed by Rozovskii [22]. It is based on the application of the principles of stationary approximation and detailed equilibrium to the stages preceding the limiting stage. The dependence of the specic aluminum hydroxide dissolution rate on the hydrogen-ion concentration can be derived by the joint solution of rate equations (with allowance for the stationarity principle) for the rate constants of the forward (k1, k2) and reverse (k1) reactions, (22) d0/d = k11 k1[H+][A]0 0, d1/d = k1[H+][A]0 (k1 + k2)1 0 and the material balance equation = 0 + 1.
+

(23) (24)

After manipulations with Eqs. (22)(24), we have

+ k1 [H ][ A ] ----------------- = 0 ---------------------------------- , (25) 1 = [ H ] [ A ] + k 1 + k 2 [H ][ A ] + K1 where K1 = (k1 + k2)/k1.

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LAINER et al. 3. E. Yu. Nevskaya, O. V. Kuchkovskaya, A. M. Kutepov, et al., Dissolution of Aluminum Hydroxide -Al(OH)3 in Acid media, Teor. Osn. Khim. Tekhnol. 34 (3), 327332 (2000). 4. W. J. Alford and D. L. Stephens, Chemical Polishing and Etching Techniques for Al2O3 Single Crystals, J. Am. Ceram. Soc. 46, 193 (1963). 5. D. N. S. Rao, K. E. Wycherley, and G. A. Kumsah, Kinetics of Dissolution of Iron from Bauxite Slimes, Rev. Chim. Minerale 9, 877882 (1973). 6. R. C. McVickers, S. D. Ford, and R. A. Dygdale, Polishing and Etching Techniques for Dense Alumina, J. Am. Ceram. Soc. 45, 199 (1962). 7. B. Siesmayer, R. Heimann, R. Lacmann, and W. Franke, The Dissolution Form of Single Crystal Spheres: V. Dissolution of Al2O3, J. Cryst. Growth 28, 757 (1975). 8. V. Zutic and W. Stumm, Effect of Organic Acids and Fluoride on the Dissolution Kinetics of Hydrous Alumina: A Model Study Using the Rotating Disc Electrode, J. Geochim. Cosmochim. Acta 48, 1493 (1984). 9. B. Delmon, Introduction a la Cinetique Heterogene (Technip, Paris, 1969; Mir, Moscow, 1972). 10. W. Stumm, B. Wehrli, and E. Wieland, Surface Complexation nd Its Impact on Geochemical Kinetics, Croat. Chem. Acta 60 (3), 429 (1987). 11. A. V. Filonov, A. N. Kharlamov, and E. V. Lunina, AcidBase Properties of Aluminum Oxide Modied by Orthoboric Acid, Zh. Fiz. Khim. 70 (6), 1027 (1996). 12. E. L. Paukshtis, Infrared Spectroscopy in Heterogeneous AcidBase Catalysis (Nauka, Novosibirsk, 1992) [in Russian]. 13. K. Wefer and C. Misra, Oxides and Hydroxides of Aluminum (Wiley, New York, 1987). 14. K. B. Lippens and I. I. Steggerdi, in Physical and Chemical Aspects of Adsorbents and Catalysts, Ed. by B. Linsen (Academic Press, London, 1970; Mir, Moscow, 1973). 15. V. N. Tikhonov, Analytical Chemistry of Elements: Aluminum (Nauka, Moscow, 1971) [in Russian]. 16. I. G. Gorichev, A. M. Kutepov, A. I. Gorichev, et al., Dissolution Kinetics and Mechanism of Iron Oxides and Hydroxides in Acid Media (Ros. Univ. Druzhby Narodov, Moscow, 1999) [in Russian]. 17. J. A. Davis, R. O. James, and J. O. Leckie, Surface Ionization and Complexation at the Oxide/Water Interface, J. Colloid Interface Sci. 63 (3), 480 (1978). 18. R. J. Sprycha, Electrical Double Layer at Alumina/Electrolyte Interface, J. Colloid Interface Sci. 127 (1), 110 (1980). 19. J. Westall and H. Hohl, A Comparison of Electrostatic Models for the Oxide/Solution Interface, J. Colloid Interface Sci. 65 (12), 265 (1980). 20. V. V. Batrakov, I. G. Gorichev, and N. A. Kipriyanov, Effect of the Electrical Double Layer on the Metal Dissolution Kinetics, Elektrokhimiya 30 (4), 444 (1990). 21. I. G. Gorichev, V. V. Batrakov, N. S. Shaplygin, et al., Complexation of the Surface of iron Hydroxides, Neorg. Mater. 30 (10), 1203 (1994). 22. A. Ya. Rozovskii, Heterogeneous Chemical Reactions (Nauka, Moscow, 1980) [in Russian]. 23. K. Tanabe, Solid Acids and Bases. Their Catalytic Properties (Academic Press, New York, 1970; Mir, Moscow, 1973).

We substitute Eq. (25) into Eq. (21) and nd [H ][ A ] W = W ---------------------------------- , + K1 + [H ][ A ]

+

(26)

where the dissolution rate constant is W = k20. To analyze the experimental data, it is more convenient to use the transformation K1 1 1 1 -, - + ---- = ------ + ------ --------------------W W W [ H ] [ A ] (27)

where [H+] is the hydrogen-ion concentration in an aluminate solution at a given value of pH (mol/l). Thus, if our considerations are valid, the experimental data represented in the 1/W1/CHA coordinates should fall on a straight line, which is supported by the experimental data. The slope of the straight line is K1/W, and the abscissa intercept is 1/W. As follows from the experimental data, the values of K1 and W depend on the nature of the acid. CONCLUSIONS (1) We experimentally studied the kinetics of aluminum hydroxide dissolution in acid media and, thus, were able to obtain an empirical dependence of the specic dissolution rate on pH, the process time , and the acid concentration CHA. (2) We proposed an acidbase model for the dissolution of aluminum hydroxide; it takes into account heterogeneous dissolution processes, the diffusion of aluminum ions, and the acidbase characteristics of aluminum hydroxides. (3) With potentiometric titration, we determined the acidbase equilibria at the hydroxide/electrolyte interface and their constants. (4) We experimentally revealed the nature of the limiting stage and used it to describe the empirical dependences of the dissolution rate on pH, the process time, and the acid concentration. (5) We found theoretically and experimentally that the dissolution rate is described by the equation + [H ][ A ] W = W ---------------------------------- . + K1 + [H ][ A ] REFERENCES
1. A. I. Lainer, N. I. Eremin, Yu. A. Lainer, and R. Z. Pevzner, Alumina Production (Metallurgiya, Moscow, 1978) [in Russian]. 2. A. Pacter and H. S. Dhillon, The Heterogeneous Reaction of Gibbsite Powder with Aqueous Inorganic Acid Solutions: Kinetics Mechanism, J. Chem. Soc. 15, 25882592 (1969).

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