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Mechanisms of dissolution of iron oxides in

Mechanisms of dissolution of iron oxides in

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ELSEVIER Hydrometallurgy42 (1996) 257-265

Mechanisms of dissolution of iron oxides in aqueous oxalic acid solutions
D. Panias, M. Taxiarchou, I. Paspaliaris, A. Kontopoulos *
Laboratory of Metallurgy, National Technical University of Athens, P.O. Box 64056, GR-157 80 Zographos, Greece

Received 20 April 1995; accepted 30 October 1995

Abstract The dissolution of pure iron oxides by organic acids has been extensively reviewed. The mechanism of dissolution comprises three distinct steps: (1) adsorption of organic ligands on the iron oxide surface; (2) non-reductive dissolution; and (3) reductive dissolution. Reductive dissolution involves two stages: an induction period and an autocatalytic period. The overall dissolution process is affected by the pH of the initial solution, temperature, the exposure of solution to UV radiation and the addition of bivalent iron in the initial solution.

1. Introduction The dissolution of metal oxides is an important process in several fields, such as hydrometallurgy, the passivity of metals and cleaning of metal surfaces. Iron oxides are the most studied of the various metal oxides, due to their wide occurrence in natural systems. Many experimental studies have been reported in the literature concerning the dissolution of pure iron oxides by means of inorganic or organic acids. All studies aimed to identify: 1. the most promising acids (organic and inorganic) as solvent agents; 2. the conditions that intensify their action; 3. the probable mechanisms prevailing during the dissolution process. In hydrometallurgical processes, bacterially produced organic acids have been proposed as an alternative, and probably less expensive, leaching agent. Organic acids such as oxalic, citric, ascorbic, acetic, fumaric and tartaric acid, have been screened for their

* Corresponding author. E-mail: kontop@metal.ntua.gr. 0304-386X/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved. SSDI 0304-386X(95)00104-2

5-7. citric [4] and ascorbic [5] are the most used carboxylic acids. citrates and ascorbates. the higher the ionic strength of the solution. 2. The dissolution mechanism involves three different processes taking place simultaneously: 1. Adsorption o f organic ligands on the system interface It is generally accepted that the first step of the dissolution reaction is the adsorption of carboxylic acid on the surface of iron oxides. .H20 Surface complexation (3) The above is a competitive reaction between active surface hydroxyl groups and anions from the acidic solution.1. The above pathway plays an important role in oxide dissolution as the metal-oxygen bond is loosened due to the protonation process. / Hydrometallurgy 42 (1996) 257-265 ability to solubilise iron and other metal oxides. H + The surface of the oxide can behave as a Lewis base (electron pair donor) according to Eq. The greater the stability of [FenI-L] -(~ -2) complexes. When an iron oxide particle is suspended in an acidic solution an electrical double layer [15-20] is established on the system interface: H . Most of them have been conducted with pure iron oxides or synthetic ferrites [8-12] rather than with iron-bearing minerals. Of the above organic acids.10. Panias et al.19. 2. as the chelating capacity of a ligand increases. due to their effectiveness as solvent reagents.+ H + ~ [)FellI-L] -(n-2) q. At a given pH value of the initial solution. 3. such as oxalates. as described by: )Fern-OH + + L". oxalic [1-3]. adsorption of organic ligands from the solution on the system interface.13]. 2. the greater the yield of Eq.. the higher the surface charge associated with adsorbed protons [19].21-24]. The present review aims to collect literature data concerning iron oxide dissolution in organic solvents and is especially focused on the mechanisms prevailing in this process. the stability of [Fern-L] -~" -2) complexes also increases and the above reaction shifts to the right.14]. reductive dissolution [1-3. Mechanism of dissolution of iron oxides in organic acids Numerous kinetic studies have been performed on the dissolution of iron oxides with organic acids in order to reveal the reaction mechanism. non-reductive dissolution [6. consequently. (3). Iminodiacetic acid (IDA).258 D.. N-hydroxyethyl-iminoacetic acid (HIDA) and ethylenediaminotetraacetic acid (EDTA) have also been studied [6. the system interface appears positively charged.13. Generally. (2) and.10. In such systems interference by other metallic compounds on the dissolution process is excluded and attention to the real chemical pathways is given.7] as solvent reagents in aqueous solutions with satisfactory results. The surface hydroxyl groups (-OH) become active sites for the subsequent adsorption of organic ligands [1-4. L ~ nH+ + L "Acid ionisation Protonation of oxygen (1) (2) )Fem-O + H +~ )Fem-O.

13]. /Hydrometallurgy 42 (1996) 257-265 100% [#1 0 259 100"/o 6O% 4O% 20% 0% "~ o 0 2] 2- eO*/. the above pathway may become increasingly important and. It involves the desorption of adsorbed surface ferric complex ions and their transfer to the acidic solution: [)FeIII_L] -(n-2) + H + ~ .q) 1-(n-3) + )H - (4) The non-reductive dissolution mechanism removes only the more reactive sites of the oxide surface. eventually. 2). Non-reductive dissolution The non-reductive dissolution pathway is a simple desorption process. Adsorption of oxalates on the system interface A pH-dependent equilibrium is established between the two different surface > Fem-oxalate complexes [2.0 / +H + + HC:Oi OH c--c__--o II o The speciation of oxalate solutions as a function of pH is shown in Fig.1. 1. 1. 2. This figure also shows the speciation of Fe2+/oxalic acid solution. Speciation in bulk solution as a function of pH for (left) oxalic acid and (right) Fe 2+/oxalic acid [1].0 C---. As a result. As the temperature is raised. the desorption process is characterised by a high activation energy. .[Fe 3+-LJ(. Panias et al. override the reductive dissolution process as the most important pathway [13].2. As observed in the potential energy-reaction coordinate diagram (Fig.1. The number of the latter increases with decreasing pH and increasing temperature [6.0 I C ife-e-O~ 0 / ~-'-.24]: o OH II~ C'-.0 ~Pe-.D. 2.3. non-reductive dissolution at low temperature is not an operative pathway. 40*/0 o t~ 1~ 20% 0% 0 2 4 6 2 3 4 pH pH Fig.

_]-(n-2)~_~ [)Feli L(n_I)_]-(n-2) Electron transfer from the ligand to F e I11 DFen_L(n . In the absence of lattice Fe II ions.3. In general.1. the thermodynamic solubility.2) --o t e e 2+ -L. 2.1).10.o bond as compared to the FetII-o bond. It involves electron transfer [2. ferrous ions are dissolved [2. as described by the following equation: [)Fen r~ T 1-( ) L ] .} )rocees [Fe"lL]~-2~ot/ ~__ Reaction Coordinate Fig.2 ) [Fe (6) Dissolution (7) (8) Complexation .3.3. Fe~aq) + products of ligand oxidation 2+ _ ~-(n Fe(aq) + L n . Induction period During the induction period the generation of ferrous ions in the solution takes place. as in magnetite.~ " 2+ -L](aq) . 2. 2. Iron as a transition element appears in two oxidation states.2 ) (5) This observation is consistent with theories concerning the dissolution of metal oxides [19]. as in hematite.]-{n-2).7._.](aqn . Fe II can be transferred to the solution more readily than Fe III because of the greater lability (kinetic instability) of the F e l l . 2.5] and their concentration in the solution is slowly increased. the generation of Fe 2+ ions in the solution is a very slow process. the ionic character of the M . Reaction coordinate diagram for non-reductive dissolution process in acidic solution. / Hydrometallurgy 42 (1996) 257-265 activation energy of lesorption =4 Fe"l(~ [Fe'"L]~){. In the presence of lattice Fe n .13] from the adsorbed complex to surface Fe llI ions: DFeIII L .(n.25] and the rate of dissolution decrease as the charge of the cation increases and its radius decreases. autocatalytic dissolution period (second stage). Reductive dissolution Reductive dissolution can be divided in two different stages interacting with each other: 1. Panias et al.O bonds [2. induction period (first stage).260 D.

desorption of ferric complexes and transfer of trivalent iron in the solution._L]-(~-1) .3.3 ) . [)FeII_L]-(. a fast outer-sphere or inner-sphere electron transfer [18. (6).takes place over a wide range of wavelengths (visible and ultraviolet region) according to the following equation [1-3]: 2[ Fe3* ( C204 )3 ]~aq.( n .-(n-2) ~ DFelU-L] -(n-2) "" [Fe2+-L] -(n-2) [ ) F e m . .D. (8). the secondary reductive dissolution step becomes operative and the whole process is accelerated. 2. the factors affecting the rate of dissolution are: Temperature: It is reported [2.( n .3. at high temperature (150°C).. as a result. the above mechanism can be described by the following equations [10]: [)Fem-C20~ -] ~ [ ) F e n .26] and formation of Fe II on the system interface.-. the solution contains only Fe 2+ species generated by the reduction of Fe nl ions with oxalate ions.( n . When oxalic acid is used as solvent reagent.1.2 ) .l aq + )H Dissolution (15) The above reaction scheme can be divided into three elementary steps: 1. adsorption of aqueous solution ferrous complexes on the surface ferric complexes.+ 2)H 2.l ) .( ~ .-~-(n-2) [We2+_L]-(n-2)¢¢. [Fe3 + _ L ] . complete dissolution is rapidly achieved. Induction period in the Fetn-oxalates system. Visible light impacts: Photochemical electron transfer on surface > FeIn-oxalate complexes provides an additional pathway for the start of dissolution. Panias et a l .7. Autocatalytic dissolution period When a sufficient amount of ferrous oxalate ions has been formed.C 2 0 .) + [Fe3 +_L]-tn-3) Desorption (14) " 2+ . / Hydrometallurgy 42 (1996) 257-265 261 At this stage. "~ 2[ Fez * (C204) ] (aq) + 3C2 O2. . .+ 2CO2 ( 11 ) 2 [ ) F e ' I .~ [)Well L ] .-. . Photolysis of [Fe(C204)3] 3. (7) and Eq. ] Electron transfer (9) Dissolution as Fe 2 ÷ (10) At this stage. 3.1. through a partially or totally heterogeneous process. .10] that. (15) is easier in relation to Eq. This pathway is described by the following equations: .2..20. (12) [We3+ L] -(n-3) (13) H +'-" tFe -t. .L ] . the dissolution of iron takes place in the form of Fe 2+ rather than in the form of Fe 3+. 2. Electron transfer DFe. electron microscopy has shown that Fe n generated on the surface by electron transfer is more reactive than normal lattice Fe n [3].2 ) + [We2+ -Ll(aq) Adsorption of complex to surface [)FeIll L ] .c 2 0 4 ] + 2H +---> 2Fe(2aq)+ 2CO 2 + C 2 0 ~. its transfer to the solution by Eq. . (5) and Eq.

. . The most important are: pH of the initial aqueous solution: pH values in the range 2 .3 give satisfactory .1. temperature30°C. 3. Fe 3+-ox --.3. as a function of Fe(aq) concentration... / HydrometaUurgy 42 (1996) 257-265 60 50.[Fe 3+ OX](aq) ) F e n . Fe 3÷-ox (16) (17) (18) )FeI'-ox.3. (7) and (12).3.5 [ Fe(ll). Factors affecting reductive pathway The rate of reductive dissolution is affected by two factors: Addition of ferrous ions in the initial acidic solution: Addition of bivalent iron in the initial solution exerts a beneficial influence on the overall dissolution rate because it reduces the time-consuming induction period (Fig. Induction period. As can be understood by the previous reductive dissolution mechanism. .4. 2.262 D. . 3).o x ] + [Fe2+-oX]Caq)~ ) F e " I . "r.] (19) 2. As has been previously reported. [ ) F e " ' . (6).o x . Autocatalytic dissolution period in iron-oxalate system.o x . . ) F e l [ .expressed as its ratio respectiveto the concentrationof FeII originatedby total dissolutionof the solid (pH 4.1. Panias et al. ]l[Fe(ll)~d I I1 Fig. Fe2+-ox ) F e " I . Factors affecting the dissolution m e c h a n i s m The dissolution process is affected by several parameters. magnetite/oxalic acid solution) [2].27].o x q. UV radiation assists the reduction of surface ferric ions and accelerates the overall reductive pathway. the presence of Fe E+ ions in the initial solution favours the autocatalytic dissolution period according to Eqs. 40 E 30 20 10 ¸ 0 0 0.o x .o x --~ [Fe2+-oX](aq) where ox denotes any species derived from oxalic acid: [ox] = [H2C204] + [HC204] + [C2042. .3]. Illumination of iron oxides suspensions: The illumination of metal oxide suspensions with UV radiation gives exactly the same result [1.2. Fe 2+-ox ~ ) F e " . 3. In the case of dissolution in oxalic acid the above reductive dissolution pathway can be illustrated by the following equations [2.

enhance the dissolution of iron oxides [1. R0 ([Oxalic acid]= 0.28. Chelating capacity of polycarboxylic acids: Chelating capacity is the ability of polycarboxylic acids to form chelated compounds (chelates) with metal ions in the solution. This is a chemisorption rather than a physical sorption process. The overall dissolution process is affected by: 1.5.19]. It consists of two different stages: 3.10. Influenceof pH on the initial dissolution rate of magnetite.17.17. temperature. This process involves photochemical reduction of trivalent iron to bivalent. exerting a beneficial influence on the dissolution process.2.19]. Temperature: It is generally accepted that high temperatures. 4.16. It is well known that the dissolution process is assisted by chelating agents such as EDTA and oxalic acid [4-7. .5.1. the addition of bivalent iron to the initial solution. it is an important dissolution pathway only at high temperatures. It is characterised by high activation energy and.16. illumination of the solution with UV radiation. 2. / Hydrometallurgy 42 (1996) 257-265 2. pH of the initial solution.16. with the optimum value being 2. 3. 4. Reductive dissolution. therefore. The influence of pH on the dissolution rate of magnetite in the system oxalic acid-magnetite is plotted in Fig. This is a simple desorption process of surface iron-ligand complexes.5 g "- 1 0. 3. Panias et al. 0 I I I 2 3 pH 4 Fig. This is the main mechanism of iron oxides dissolution with organic acids.1 M.D. temperature 30oc) [3]. induction period.29].14. Photochemical effects: The dissolution of iron oxides suspended in organic acid solutions is promoted by ultraviolet and visible light radiation [1.27. 4. autocatalytic period.6 [1. The Lewis acid-base properties of surface iron oxides must be taken into account for the better understanding of this step. results. 4.5 263 m E 2 1. C o n c l u s i o n s The dissolution of iron oxides with organic acids comprises three distinct steps: 1. Adsorption of organic ligands on the iron oxide surface.30]. Non-reductive dissolution. above 90°C. 3.19.

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