Production of Ferric Hydroxide by Anodic Dissolution

of Carbon Steel

Luis Cifuentes1, Jorge Torrealba and Gloria Crisóstomo

Mining Engineering Dept., Universidad de Chile, Tupper 2069,

Santiago, Chile

Mauricio Bustamante and Barner Muñoz

CODELCO Chile, División Andina, Casilla 6 A, Saladillo, Quinta Región, Chile

Abstract

Ferric hydroxide has been produced by electrochemical dissolution of carbon steel in

aqueous NaCl solution at room temperature. Best results (yield = 56%) were obtained with a

4% NaCl concentration, pH = 5, a cell current density of 250 A/m2, periodic current reversal

at 60 second intervals and a stirring intensity of 2400 rpm.

Keywords: ferric hydroxide, iron anode, passivation, periodic current reversal, cell voltage

Subject area: applied electrochemistry

1
Corresponding author. E-mail: luicifue@ing.uchile.cl FAX (562) 672 3504
1. Introduction

It is well known that gelatinous hydroxide precipitates can be used to remove metals

from ionic solutions as the metal ions become attached to the gel. Ferric hydroxide (Fe(OH)3,

Fe2O3⋅3H2O or FeO⋅OH⋅H2O), which is usually produced via chemical reactions such as

FeCl3 + 3 H2O → Fe(OH)3 + 3 HCl [1]

has shown to be able to capture both cations and anions [2, 3].

An electrochemical preparation method for ferric hydroxide has been proposed by

Toma [4], based on anodic iron dissolution in an aqueous 1% NaCl solution. However, the

author gives no details of: a) the possible anodic and cathodic reactions; b) the cell current

density or cell voltage; c) the effect of the solution pH or degree of agitation. Moreover, no

mention is made of any experimental evidence of the actual presence of ferric hydroxide. In the

proposed procedure, the unidentified reaction product is heated in order to convert it to iron

oxides, which are the final product of the process. The present work aims to establish a

detailed set of conditions to obtain ferric hydroxide by electrochemical means.

2. Fundamentals

The electrolytic production of ferric hydroxide by anodic dissolution of iron in aqueous

NaCl solution may be explained as follows.

2.1 Anodic reactions

The main anodic reactions are:

a) single step oxidation of Fe into ferric ion

 Fe → Fe3+ + 3e E0 = -0.04 V

b) a two-step process where iron is firstly oxidized to ferrous ion which, depending on anode

potential, then oxidises to ferric ion

Fe → Fe2+ + 2e E0 = -0.44 V

Fe2+ → Fe3+ + e E0 = 0.77 V

The second step would take place at the anode, however, it can also be promoted by the

presence of other oxidants in aqueous phase:

O2 (gas) + 4 H+ + 4 e → 2 H2O (in acid solution) or

O2 (gas) + H2O + 4 e → 4 OH- (in alkaline solution) or

Cl2 (gas) + 2e → 2 Cl- .

The actual occurrence of these couplings depends on the availability of dissolved oxygen and

chlorine.

The applied current forces OH- ion migration to the anode, so the pH near the anode is

higher than in the bulk solution, thus favouring ferric hydroxide formation

Fe3+ + 3 OH- → Fe (OH)3

Fe(OH)3 forms as a red-brown colloid which, depending on pH and on the availability of

ferrous ions, can react with dissolved oxygen to give Fe 3O4 [2].

c) Other possible anodic reactions depend on the anode potential. Water decomposes at the

anode as H2O → O2 (gas) + 4 H+ + 4e E0 = 1.23 V

Chloride ions also migrate towards the anode giving

2 Cl- → Cl2 (gas) + 2e E0 = 1.36 V.

2.2 Cathodic reactions

The main cathodic reactions are:

a) H+ ions migrate to the cathode favouring the reaction

2H+ + 2e → H2 (gas) E0 = 0.0 V

b) an alternative cathodic reaction is

2 H2O + 2e → H2 (gas) + 2 OH- E0 = -0.83 V

c) other possible reactions are

Fe3+ + e → Fe2+, Fe2+ + 2 e → Fe, Fe3+ + 3e → Fe

The Na+ ion also migrates to the cathode, but its reduction is unlikely due to its very negative

standard equilibrium potential.

Na+ + e → Na E0 = - 2.71 V

2.3 Periodic current reversal

During the electrochemical production of ferric hydroxide periodic current reversal is

advisable for two reasons: a) to use two iron based (carbon steel) electrodes which alternate

as anode and cathode, both of them contributing to ferric hydroxide production. This way, they

are evenly consumed during the process; b) to avoid anode passivation by periodic removal of

excess ferrous and ferric ions from the vicinity of the anode and of loosely attached reaction

products from the anode surface. Passivation of the anode surface is possible in these systems

due to high current densities and high concentrations of Fe2+, Fe3+ and OH- ions at the anode

surface, despite the fact that the presence of chloride ions would limit the formation and/or

growth of the passivation layer [5, 6].

3. Experimental

A 1286 Solartron electrochemical interface with a 3-electrode cell was used in order

to characterize the electrode kinetics via potentiodynamic tests. The working electrode was

made of carbon steel; a platinum counter electrode and a Hg/Hg2SO4 reference electrode

were used. The electrolyte was 1% aqueous NaCl (pH = 6.7). The solution was at room

temperature (22 ±0.5°C). Sweep rate was 1 mV/s.

A 5 liter hard-glass reactor in the shape of an inverted bottle with an open top was

used to produce Fe(OH)3. The electrodes were 8 x 12 x 0.15 cm carbon steel plates with an

effective surface area of 96 cm2. An electrode holder kept the anode and cathode separated

by 9 cm. Anode and cathode were fully immersed. The solution was prepared with 99.5%

pure NaCl and its volume was 4 liters. Temperature was 23 ± 1 °C. A rectifier (–2 to +2 A,

30 V) with programmable periodic current reversal capability was used. The current was

periodically reversed in order to avoid anode passivation. The solution was agitated with a

mechanical stirrer (4 x 1 cm vane) at 2400 rpm, which was the maximum speed allowed by the

equipment. When required, the pH was adjusted with 0.37 % HCl. The solution was sampled

at 10 minute intervals. Ferrous ion and total Fe were determined by colorimetry and atomic

absorption respectively. Cell voltage and pH were monitored throughout the experiment. At

the end of each run, the suspension was sampled and filtered through a 2.5 µm pore size

membrane filter and the recovered solid was washed and submitted for analyses (see below).
 Decreasing the time interval between consecutive current reversals decreases the

likelyhood of anode passivation. Four current reversal intervals were evaluated: 180, 120, 90

and 60 seconds. The current density was 250 A/m2 in all cases.

The effect of NaCl concentration on cell voltage was determined with 0.5 , 2 and 4 %

(by weight) NaCl solutions. The electrolytic process was carried out at 150 A/m2 and the cell

voltage was monitored throughout.

In order to determine the optimum pH, the investigated values were 2, 4, 5, 6 and 8.

The aspect of the reaction product was observed in each case.

To establish the optimum current density, tests at 150, 200, 250, 300 and 400 A/m2

were performed. The cell voltage was monitored throughout.

The final product was analyzed by X-ray diffraction, X-ray photoelectron

spectroscopy and Mössbauer spectroscopy.

4. Results and discussion

4.1 Kinetics of cathodic and anodic reactions.

Figs. 2 and 3 show anodic and cathodic potentiodynamic plots. The curves show that

the anodic process does not exhibit a limiting current density within the studied potential range.

(Fig. 2) (Fig.3)
 At the beginning of the anodic sweep a yellow compound is observed near the anode

surface (probably FeCl3). Then, a red-brown colloid appeared, which corresponds to the

usual description of Fe (OH)3. Finally, the generation of a dark precipitate which becomes

black in a brief period of time (probably Fe3O4) was observed. The cathodic curve exhibits a

small plateau, which would indicate the electrodeposition of metallic Fe or the reduction of iron

oxides formed onto the cathode surface. At more negative potentials, a drastic current density

raise was observed. This represents hydrogen evolution, which was visually confirmed. The

kinetics does not show obvious limits to the cell current densities that can be applied to the

process, however, the brief period of time and variable current densities during the anodic

sweep do not favour anode passivation, which may take place at longer periods of operation

and constant, high current densities.

4.2 Ferric hydroxide production

4.2.1 Effect of the current reversal interval on anode passivation

Table 1 shows the operation time at which the anode passivates as a function of

current reversal interval. This interval is defined as the time which elapses between two

consecutive current reversals.

(Table 1)

As seen, a shorter current reversal interval permitted longer times of operation before

the anode passivates. This effect can be attributed to the remotion of the excess ferrous and

ferric ions from the vicinity of the anode by iron metal deposition, thus decreasing the
probability of precipitation of iron hydroxides or oxides on the anode surface, which could

lead to passivation. The strong hydrogen evolution, which takes place on the electrode when it

turns cathodic, may have also helped to remove loosely attached iron oxidation products that

could also promote passivation of the electrode. Accordingly, to avoid passivation, a 60

seconds interval was used for the rest of this work. For long operation times, such as those

common in industrial practice, a shorter interval (e.g. 30 s) and/or a lower current density (e.g.

150 or 200 A/m2) would be required.

4.2.2 Effect of NaCl concentration on cell voltage

Average cell voltage values at various NaCl concentrations in the process solution are

given in Table 2.

(Table 2)

The cell voltage is made up of the difference between the equilibrium potentials of the

main anodic and cathodic reactions, their overpotentials, the ohmic potential drop in solution

and other potential losses. NaCl concentration strongly influences the cell voltage, as it affects

the electrical conductivity of the solution and the IR drop in the electrolyte. Four per cent NaCl

provided an appropriate value for the cell voltage (2.3 V) and it was used for the rest of this

work. No concentrations higher than 4 % were tested, as they would increase the cost of the

process.
4.2.3 Determination of the optimum pH value

When the precipitation test was carried out at pH values above 6 a dark compound

precipitated, which became black at longer operation times. This precipitate exhibited a strong

magnetic response, which was detected by placing a magnet near the outside wall of the

reactor. The only black and magnetic product of iron dissolution is Fe3O4 (magnetite). At pH

values lower than 4, ferric ion would be reduced to its ferrous state. This is shown in Table 3.

(Table 3)

From these results, it can be concluded that the optimum pH range is 6 > pH > 4, so

pH = 5 was used for the rest of this work. The results also show that ferric ion concentration in

solution at the optimum pH is less than one tenth of the ferrous ion concentration. This is

related to the fact that ferric ions are precipitating as ferric hydroxide, i.e., the solution is

constantly being depleted of ferric ions.

4.2.4 Determination of the optimum current density

At pH = 5, NaCl concentration = 4 % and current reversal interval = 60 seconds, the

following results were obtained for the average cell voltage (Table 4):

(Table 4)
 The cell voltage increase was small in the studied current density range, but passivation

of the anodes took place at 300 and 400 A/m2. At the latter two current densities the rate of

production of ferrous and ferric ions was high and the solubility product constant for the

respective hydroxides was quickly attained in the anolyte, causing precipitation on the anode

surface and passivation. From these results a current density of 250 A/m2 was selected. Given

the fact that operation times are much longer in industrial practice, this c.d. value should be

considered as an upper limit.

4.2.5 Characterization of the reaction product

The reaction product is a red-brown colloid which does not exhibit magnetic

properties. This description is in full agreement with those given in the literature for ferric

hydroxide. The colloid was filtered under vacuum, dried at room temperature and analyzed. X-

ray diffraction did not detect significant amounts of crystallized products. X-ray photoelectron

spectroscopy found ferrous and ferric ions as well as Fe oxides and hydroxides, but produced

no quantification. Mössbauer spectroscopy measured over 95% FeO·OH·H2O. The chemical

composition of the process product was thereby established.

4.2.6 Process yield, energy requirements and iron balance.

The best set of conditions for ferric hydroxide production were: pH = 5,

icell = 250 A/m2, [NaCl] = 4%, periodic current reversal interval = 60 s and stirring intensity =

2400 rpm.
 After 20 minutes of operation under such conditions, the amount of produced

hydroxide was 0.56 g. The theoretical amount (Faraday's law), assuming Fe dissolution to

ferric ion, is 1.00 g. The yield is then about 56%.

The energy required by the process is 14.8 MJ per kilogram of Fe (OH)3.

The mass balance for iron is given in Table 5. The amounts of ferric and ferrous ions

are those remaining in solution after separating the hydroxide by filtering .

(Table 5)

5. Conclusion

A detailed method has been proposed to produce ferric hydroxide by an

electrochemical process at room temperature. The yield was about 56%. The pH is very

critical, as ferric hydroxide is only produced within a narrow pH band around 5. The cell

voltage strongly depends on NaCl concentration. Periodic current reversal and solution

agitation were carried out to avoid anode passivation. For an industrial operation, the optimum

current density (250 A/m2) and the current reversal interval (60 s) given here should be

considered as upper limits.

Acknowledgements

The authors would like to thank CODELCO-Chile, Andina Division, for funding this work.

References
[1] Cotton, F.A. and Wilkinson, G., Advanced Inorganic Chemistry, 2nd Ed., Wiley (1966),

chapter 29, section E

[2] Esmadi, F. and Simm, J., Colloids Surf., 104 (1995), 265

[3] Miltenburg, J.C and Golterman, H.L., Hydrobiologia, 364 (1997), 193

[4] Rumanian Patent RO 93974, 29.02.88 (1988), Toma, A.P.

[5] Vetter, K.J., Elektrochemische Kinetik, Springer Verlag (1961), p. 633

[6] Uhlig, H.H., Corrosion and Corrosion Control, 2nd Ed., Wiley (1971), p. 75
Table 1. Current reversal interval vs. time to passivation at 250 A/m2

_____________________________________________________________

Current reversal interval, s Time to electrode passivation, minutes

_____________________________________________________________

180 12

120 14

90 23

60 <30

____________________________________________________________
Table 2. Cell voltage vs. NaCl concentration

_________________________________________

[NaCl], % Cell voltage, V / SHE

_________________________________________

0.5 12.0

2.0 4.5

4.0 2.3

_________________________________________
Table 3. pH vs. ferric to ferrous ratio

_____________________________

pH [Ferric] : [Ferrous]

_____________________________

5 1 : 11

4 1 : 500

_____________________________
Table 4. Current density vs. cell voltage

___________________________________

C.d., A/m2 Cell voltage, V / SHE

___________________________________

150 2.3

200 2.5

250 2.6

300 passivation

400 passivation

___________________________________
Table 5. Mass balance for iron

____________________________________________________________________

Dissolved Fe Fe as Fe (OH)3 Fe as ferric ion Fe as ferrous ion

g g g g

____________________________________________________________________

0.52 0.29 0.02 0.21

____________________________________________________________________
Fig. 1 Anodic potential sweep
Fig. 2 Cathodic potential sweep