ECS Transactions, 6 (9) 1-15 (2007)

10.1149/1.2790397, © The Electrochemical Society

Electrochemistry behind Electrocoagulation using Iron Electrodes

H. A. Moreno C.a, D. L. Cockea, J. A. G. Gomesa, P. Morkovskyb, J. R. Pargac, E.

Petersona and C. Garciad
a
Gill Chair of Chemistry and Chem. Eng. Lamar University, Beaumont, Texas 77710,
USA
b
Kaspar Electroplating Corporation, Shiner, Texas 77984, USA
c
Department of Metallurgy and Materials Science, Instituto Tecnológico de Saltillo,
Saltillo, Coahuila 25280, México
d
Chemical Engineering , Instituto Tecnológico de La laguna, Torreon, Coahuila 27000,
México

Electrocoagulation (EC) has been known for more than a century.

Applications in industries as a water and wastewater treatment
process have been adapted for the removal of metals, non metals,
suspended solids, organic compounds, COD and BOD. Iron
electrodes have been preferred over aluminum due to their
durability and cost. However, the electrochemical reactions
occurring with EC using iron electrodes have not been
systematically studied. For a better understanding of the
mechanism and reactions for EC using iron electrodes, we present
a review of the concept of green rust (GR) and its relationship to
the current theory of EC. Experimental results obtained by
measuring pH at different zones near the iron electrodes during the
EC process are detailed, and are used to illustrate the mechanism
and reactions that occur at both, the anode and cathode.
Mechanism and reactions presented explain phenomena associated
with EC and are congruent with solubility and Pourbaix diagrams.

Introduction

Electrocoagulation (EC) is an electrochemical water and wastewater treatment

technology that in its simplest form uses an electrochemical cell where a dc voltage is
applied to electrodes, usually made of iron or aluminum, and water or wastewater is the
electrolyte.

EC involves the generation of coagulant in situ by dissolution of metal from the

anode with simultaneous formation of hydroxyl ions and hydrogen gas at the cathode.
This process produces the corresponding aluminum or iron hydroxides and/or
polyhydroxides. The generated gas also helps to float the flocculated particles at the
water surface.

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EC has been proposed since before the turn of the 20th century. A plant was built in
London in 1889 for the treatment of sewage mixing it with seawater and electrolyzing it.,
EC was first patented by A. E. Dietrich in 1906and used to treat bilge water from ships.
In 1909, J.T. Harries received a patent in the United States for wastewater treatment by
electrolysis using sacrificial aluminum and iron anodes (1). Matteson et al. described a
device of the 1940’s, the “electronic coagulator” which electrochemically dissolved
aluminum (from the anode) into solution, reacting this with the hydroxyl ion (from the
cathode) to form aluminum hydroxide (2). The hydroxide flocculates and coagulates the
suspended solids and thereby purifies water. A similar process was used in Britain in
1956 in which iron electrodes were used to treat river water (3, 4).

Treatment of wastewater by EC was practiced for most of the 20th Century with
limited success and popularity. However, in the later years its usage has increased as
evidenced with a larger number of companies selling EC units. This is because the
technology has been optimized to minimize electrical power consumption and maximize
effluent throughput rates. It has also proven to be competitive and effective in the
treatment of water and wastewater to remove heavy metals such as Pb, Cd, Cr, and As,
metals such as Mn, Cu, Zn, Ni, Al, Fe, Co, Sn, Mg, Se, Mo, Ca, and Pt. It has also seen
applications in removing anions such as CN-, PO4-3, SO4-2, NO3-, F- and Cl-, non metals
such as P, organic compounds such as total petroleum hydrocarbons (TPH), toluene,
benzene and xylenes (TBX), methyl tert-butyl ether (MTBE), COD, BOD, suspended
solids, clay minerals, organic dyes, and oil and greases from a variety of industrial
effluents (1, 2, 5, 6, 7, 8, 9).

Green rust & current theory of EC

Rust

Rust is a reddish-brown corrosion product of iron ideally consisting of three layers of

iron oxide in different states of oxidation:

• Hydrous ferrous oxide FeO.nH2O (or ferrous hydroxide Fe (OH)2)

2Fe + O2 + H2O → 2Fe (OH)2 [1]

Fe(OH)2 +(n-1)H2O → FeO*nH2O [2]

Fe(OH)2 whose color is normally green turns to greenish-black because of incipient

oxidation by air.
• Hydrous ferric oxide or ferric hydroxide
At the outer surface of the corrosion layer, access to dissolved oxygen converts
ferrous oxide to hydrous ferric oxide or ferric hydroxide according to the following
reaction:

4Fe(OH)2 + O2 → 2Fe2O3*H2O + 2H2O [3]

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This oxide is orange to red-brown in color and comprises most of ordinary rust. It
exists as non-magnetic α-Fe2O3 (hematite) or magnetic δ-Fe2O3 (maghemite). The α-
form possesses greater negative free energy of formation (10).
• Magnetic hydrous ferrous ferrite
A magnetic hydrous ferrous ferrite, Fe3O4.nH2O, often forms a black intermediate
layer between hydrous Fe2O3 and FeO.

Fe2O3 + FeO → Fe3O4 [4]

Green rust (GR)

GRs are layered Fe(II)-Fe(III) hydroxides having a pyroaurite-type structure

consisting of alternating positively charged hydroxide layers and hydrated anion layers.
Some of the Fe(II) of the octahedral sheets of Fe(OH)2 is replaced by Fe(III). This results
in positive layers of charge that are balanced by the inclusion of anions between the
layers (Bernal et al., 1959). Its exact nature depends on the interlayer anion. Various
forms have been synthesized and studied. Results of many studies have shown that GR
conform to a general chemical composition and stoichiometry, that can be represented
with the general formula: [FeII(6-x) FeIII x(OH)12]x+[(A)x/n.yH2O]x-, Where x ranges from
0.9 to 4.2, A is an n-valent anion (typically CO32-, Cl- or SO42- and y denotes the varying
amounts of interlayer water (typically y ranges from 2 to 4 for most GRs) (11).

The literature distinguishes between GR-I (An- = F-, Cl-, Br-, I-), GR-II (An- =
SO4 ) and GR-CO3 (An-= CO32-). This division is due to a crystallographic classification
2-

of the mineral structures by which GR-I is described as rhombic obtained with "planar"
anions such as chlorides, carbonate, etc. GR-II and GR-CO3 are hexagonal; obtained with
three-dimensional tetrahedral anions such as sulfate or selenate (12).

GR, unlike most iron oxides forms, have an internal surface area; so these
minerals have both large specific surface areas and reactivity. Most of the work reported
to date has focused on the reactivity of sulfate GR rather than the chloride or carbonate
forms (13). They represent reactive ion exchangers and sorbents (14). The amphoteric
surface hydroxyl groups lead to both sorption of heavy metals (cations) as well as organic
anions, e.g. linear alkyl benzene sulfonates (LAS), the major synthetic surfactant used in
laundry detergents and cleaning products worldwide, and inorganic anions, e.g. silicate,
arsenate and selenate. Furthermore, polar non-charged compounds are sorbed into the
interlayer. Cations as Cu(II), Ni(II), Zn(II), Cd(II), Co(II) and Mg(II), may
isomorphically substitute for Fe(II) during GR formation (co precipitation). For example,
nickelous-ferric GR rusts, the end products obtained by substitution of Fe(II) ions by
Ni(II) ions, have been reported (15, 16, 17 18). This incorporation of cationic inorganic
contaminants into the structures of GR could provide an effective means of sequestering
contaminants in the subsurface.

GR is now recognized as an important intermediate phase in corrosion of Fe(0).

The oxidation of the Fe2+ ions in GR results in the formation of ferrihydrite

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(Fe5HO8.4H2O), goethite (α-FeOOH), akaganeite (β-FeOOH), and lepidocrocite (γ-

FeOOH) in well-aerated systems, and hematite (α-Fe2O3) maghemite (δ-Fe2O3) or
magnetite (Fe3O4) in oxygen-depleted systems. Conversion depends on pH, solution
composition, oxidant, rate of oxidation, and the degree and rate of dehydration (19, 20).
Rust composition, therefore, changes with time (and metal composition). On pure iron, γ
-FeOOH transforms to the more stable goethite (α-FeOOH) and some spinel. With
increasing time, goethite converts to either maghemite or hematite. Conversion to
hematite usually requires higher temperatures.

GRs are formed by a number of abiotic and biotic processes under circumneutral
to alkaline conditions in suboxic environments. GRs are believed to play a central role in
the redox cycling of Fe in aquatic and terrestrial environments.

Various processes have been developed to synthesize GR in the laboratory. Two

primary procedures were envisioned, one by partial oxidation of Fe(II) hydroxides or
Fe(II) solutions, the other by mixing Fe(II) and Fe(III) aqueous solutions or suspensions
(co-precipitation). The anion associated with Fe(II) or Fe(III) in the salt is thus present in
solution and induces the formation of the corresponding GR, e.g. using FeSO4 leads to
GR-SO4. Géhin et al. (2002) reported that the composition of GR-SO4 prepared by co-
precipitation is the same as that observed for GR-SO4 samples prepared by other
methods. Legrand et al. (2001) has reported about new carbonate green rust obtained
electrochemically. GR can also be produced with EC. Composition of pollutants in water
or wastewater affects both the generation and the type of GR formed (21).

Figure 1. Green Rust generated with EC using Fe electrodes.

Current Theory of EC. Current theory of EC states several successive stages [22, 23]:

From sections 1.1 and 1.3, it can be recognized that there are many similarities in
reactions that can be achieved, and pollutants that can be removed with GR and EC. One

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 ECS Transactions, 6 (9) 1-15 (2007)

of the factors often used to visually determine the success of pollutant(s) removal with
EC using Fe electrodes is the formation of a dark green floc (Fig. 1).

1 Generation of metal ions.

Anode: Fe ↔ Fe+2 + 2e- [5]

Fe ↔ Fe+3 + 3e- [6]

2 Hydrolysis of metal ions and generation of metal hydroxides and polyhydroxides. This
has been studied and explained repeatedly for coagulation processes in water treatment.

Fe + 6H2O → Fe(H2O)4(OH)2 (aq) + 2H+1 + 2e-1 [7]

Fe + 6H2O → Fe(H2O)3(OH)3 (aq) + 3H+1 + 3e-1 [8]

3 Electrolysis of water. Water is also electrolyzed in a parallel reaction, producing small

bubbles of oxygen at the anode and hydrogen at the cathode, and as a result, flotation of
the coagulated particles occurs.

Anode: 2H2O(l) → O2(g) + 4H+ + 4 e- [9]

Cathode: 2H++ 2 e-→ H2(g)↑ [10]

Although the presence of magnetite and maghentite identified in EC sludge when

using iron electrodes can suggest oxygen evolution at the anode, this is not what happens.
Rather, the iron oxides present are dehydrated iron hydroxides, and some of the rust
formation occurs on the surface of the floated sludge. It can also occur during filtration
and preparation of the sample. The experimental evidence for not formation of oxygen
during EC with iron electrodes have been reported elsewhere (9).

4 Destabilization and aggregation: Destabilization of the contaminants, particulate

suspension, breaking of emulsions, and aggregation of the destabilized phases to form
flocs through compression of the diffuse double layer and charge neutralization of the
ionic species present. Therefore, suspended solids and colloids in small quantities are
easily removed by EC.

5 Physicochemical reactions: The following physicochemical reactions may also take

place in the EC cell: chemical reaction and precipitation of metal hydroxides with
pollutants, cathodic reduction of impurities or metal ions present, electrophoretic
migration of ions, oxidation of pollutants to less toxic species, and other electrochemical
and chemical processes.

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Experiments

Three set of experiments were performed to determine the electrochemical

reactions for EC using a 125x65mm Pyrex crystallizer as the cell, 30x60x2 mm iron
plates as electrodes, five pH meters (Oakton pH 10 series, Fisher digital 107, Fisher
Accumet 125, Barnant Co. model 500-2324 and a Cole Parmer model 607), a UL–CSA
direct plug-in transformer unit (with 120V, 60Hz & 6W input and 12 DCV and 300 mA
output), and two multimeters (Cen-tech p-30756 and a CSI/SPECO DMR-2012A). 0.02N
sulfuric acid solution and 0.5 g/L of NaCl were used as electrolytes. Reagent grade
chemicals and buffers were used.

Experiment 1

Experiment 1 was performed using the set-up as shown in figure 2. This

experiment was carried out without stirring, and with three replicates. All three replicates
were made under the same conditions for voltage and current.
pH Electrodes

Out In In Out

Cathode Anode

Figure 2. Diagram of the setup used for the first set of experiments showing the position
of the pH electrodes in the EC reactor.

Experiment 2

Based upon conclusions derived from the first set of experiments, some modifications
were made to track the pH at different locations on the surface of both anode and cathode
to indicate the expected electrochemical reactions taking place in the EC reactor
according to the iron Pourbaix diagram. The setup is shown in figure 3. Two electrodes
(1 and 2) were located on the outside of both anode and cathode, three electrodes (3, 4,
and 5) were located on the inside of the anode, and four (3, 4, 5 and 6) by the cathode.

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6
2 5

1 4 3

Figure 3. Diagram of the setup of pH electrodes on the iron plate (anode and cathode).

Experiment 3

Since there was no stirring during experiments 1 and 2, it was possible to observe
a migration and electrophoretic current in the reactor as shown in figure 4. A third
experiment was completed to measure the pH along the current path. The pH electrodes
were located as shown in figure 4.
pH Electrodes

3 4
2 1

Cathode Anode

EC pH
Figure 4. Current established in the EC reactor, and location of the pH electrodes.

Results and Discussion

Since graphic results are similar to those from experiment 2, first, observations for
experiment 1 are stated. It is found from experiment 1 that for the cathode, pH vs.
residence time curves were different, implying that pH varies with position of the pH
electrode over the iron plate, and oscillatory behavior of pH is observed. For the anode,
there is similar effect on pH curves, but no oscillatory behavior is observed, curves
approximate the same trend. At the anode but external to the electric field of the cell, the
pH increases slowly up to a value of 4, corresponding to the neutralization of strong

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acids. After that, pH increases significantly faster. Finally, the sludge generation occurs at
the surface of the electrolyte around the cathode.

Results from experiment 2 are shown in figures 6 and 7. Figure 6 shows a plot of
pH vs. residence time at different locations on the anode. Two ranges or areas of pH are
well defined; one that goes from negative pH to pH 0, and the other that begins at pH 4
and slowly increases to pH 10. It is also known that there is no oxygen evolution at the
anode. These two areas have been highlighted in the iron Pourbaix diagram (Figure 8).
The region of negative pH, parallel to the oxygen evolution line; but below it, indicates
that only Fe(III) ions are being released from the anode, while the corresponding region
from pH 4 to pH 10, indicates that Fe(III) hydroxide is also being formed.

From figure 7, a plot of pH vs. residence time at different locations on the cathode,
two different ranges or areas are defined; one that goes from negative pH to pH 2, and the
other that begins at pH 2, oscillates from low acid to high alkaline values showing an
increasing trend. The plot may not accurately represent the actual behavior because
readings were taken within ten minutes intervals, with only the uppermost and lowest
values recorded, and another issue is the different sensitivity of the pHmeters used.
Knowning that there is hydrogen evolution at the cathode, these areas have been
highlighted in the iron Pourbaix diagram as shown in Figure 10. The region
corresponding to negative pH to pH 2, parallel and in contact with the hydrogen
evolution line, indicates that only Fe(II) ions are being released from the cathode in that
part of the electrode. The region corresponding from pH 2 to pH >14, indicates that both
Fe(II) ions and Fe(II) hydroxide are being generated.

EC - pH
pH

11

5 1
2
3 3
4
1
5

-1 0 20 40 60 80 100 120

-3

-5

-7 time (min)

Figure 6. Plot of pH vs. Residence time at different locations on the anode.

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pH
EC - pH Cathode

15

10

1
5 2
3
1
4
0 5
6
0 20 40 60 80 100 120

-5

time (min)
-10
Figure 7. Plot of pH at different locations on the cathode.

Figure 8. Pourbaix diagram showing the regions in which the anode operates.

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Figure 9. Pourbaix diagram showing the regions in which the cathode operates. After
(24).

Position 1

14 Position 2
Position 3
12
Position 4
10 Position 5

6
pH

0
0 20 40 60 80 100
-2

-4
tim e (m in)

Figure 10. Plot of pH vs. residence time for experiment 3.

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Results from experiment 3 are presented in figure 10. The plot in figure 10
corroborates the observation concerning the migration and electrophoretic current. The
curve for electrode 1 indicates that there is a high concentration of acidic ions (Fe(III)
and [H+]) near the anode. Data for electrodes 2 and 3, both closer to the cathode,
indicates a high concentration of acidic ions but less than that for electrode 1. This
suggests that some of them are being neutralized in that region. Examining the plot for
electrode location 4, shows a pH value of 4 and greater, indicating that strong acid [H+]
has been neutralized. Electrode 5 was located on the surface of the electrolyte close to the
cathode, precisely where sludge generation takes place. The corresponding curve shows
oscillatory behavior from acid to high alkaline, presenting appropriate pH conditions for
precipitation of iron hydroxides.

Electrochemical reactions in the EC cell

Electrochemical reactions in the EC reactor must match the observations and data
described in the preceding section. Although all reactions are simultaneous, it is easier to
explain them if they are presented in sequential order.

Anode: Fe Æ Fe+3 + 3e- 0.04 V [6]

Oxidation of Fe to Fe(II) has a standard electrode potential of 0.44 V, so reaction

(6) is thermodynamically favored and more likely to occur. According to the results of
experiment 2, and Pourbaix diagram in figure 10, that is exactly what happens. Fe+3 ions
are generated at the anode and they are strongly attracted to the cathode, causing them to
move in that direction.

Bulk solution (on the way to the cathode): If there is a strong acid present Fe(III) ions
will first react the anions associated with the acid. In this particular case:

2Fe+3 + 3SO4-2 → Fe2(SO4)3(aq) [11]

After neutralization of strong acids via hydrogen evolution, hydrolysis of Fe(III)

will occur:

Fe+3 + H2O → Fe(OH)+2 + H+ [12]

Fe(OH)+2 + H2O → Fe(OH)2+ + H+ [13]

Fe(OH)2+1 + H2O → Fe(OH)3 + H+ [14]

According to the density-functional theory study (25), the hydrated form of

Fe(OH)2+ was found to be the most stable species among Fe(III) hydrolysis products.
Therefore, we assume that mainly this species migrates to the cathode along with the
generated H+ ions.

Cathode: Hydrogen evolution, 2H++ 2 e-→ H2(g)↑ [10]

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Electrochemistry depends on thermodynamics and kinetics. EC can be considered

as an accelerated corrosion process. The rate of reaction depends on the removal of [H+]
via H2 evolution. This reaction will occur fast for low pH values (strong acids) (26).

If a strong acid is present (sulfuric acid in this case), it will provide the hydrogen
ions for the hydrogen evolution reaction until it is completely reacted. After
neutralization of strong acids, the hydrogen ions are provided by hydrolysis of iron, and
maybe by weak acids if present. Oscillatory behavior is produced by hydrogen evolution
and formation of iron (II) hydroxide (high pH), and new H+ ions attracted to the cathode
(low pH).

At the cathode, in addition to hydrogen evolution according to experiment 2, and

the Pourbaix diagram in figure 9, generation of Fe(II), and Fe(II) hydroxide occur as
explained by the following reactions.

Fe(OH)2+ + e-→ Fe(OH)2 (aq) [15]

If the pH is high enough it may precipitate:

Fe(OH)2 (aq) → Fe(OH)2 (s) [16]

But hydrolysis could go further:

Fe(OH)2(aq) + H2O → Fe(OH)3- + H+ [17]

Reaction [17] is favored by the hydrogen evolution reaction [10], and the
Fe(OH)3-1 ion will be attracted to the anode where:

Anode: Fe(OH)3-1 → Fe(OH)3 (aq) + e- [18]

Experiment 2, and the Pourbaix diagram in figure 8 show that there is generation
of Fe(III) hydroxide at the anode. Reactions [13] and [14] describes this generation.

Cathode: As mentioned before, a migration and electrophoretic current is established that

vacillates between the anode and cathode. This current also carries the Fe(OH)3 (aq) and
mixes it with the Fe(OH)2 (aq) . Since both are neutral, they are not repelled from the
cathode and find the proper pH conditions at the top of the cathode (figure 5) to form iron
poly-oxyhydroxides. In the appropriate conditions, they combine in the following
proportion to generate GR. A complete sketch of formation of green rust is reiterated.

(anode) Fe ↔ Fe+3 + 3e- [6]

(bulk solution) Fe(OH)+2 + H2O → Fe(OH)2+1 + H+ [13]

(cathode) 2H++ 2 e-→ H2(g)↑ [10]

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(cathode) Fe(OH)2+1 + e-→ Fe(OH)2 (aq) [15]

(cathode) Fe(OH)2(aq) + H2O → Fe(OH)3-1 + H+ [17]

(anode) Fe(OH)3-1 → Fe(OH)3 (aq) + e- [18]

Overall reaction:

6Fe + (12+x) H2O → ½ (12-x)H2(g)↑ + x Fe(OH)3 * (6-X) Fe(OH)2 (s) [19]

If pH conditions are too acidic or alkaline for the bulk solution, EC will not lead
to GR formation and the removal efficiency of pollutants will be small.

Formation of rust (dehydrated hydroxides) occurs as shown in the following:

2Fe(OH)3 ↔ Fe2O3 + 3H2O (hematite, maghemite) [20]

Fe(OH)2 ↔ FeO + H2O (wüstite) [21]

2Fe(OH)3 + Fe(OH)2 ↔ Fe3O4 + 4H2O (magnetite) [22]

Fe(OH)3 ↔ FeO(OH) + H2O (goethite, lepidocrocite) [23]

Hematite, maghemite, wüstite, magnetite, lepidocrocite and goethite have been

identified as EC by-products (27, 28), EC experiments were performed in stirred or
turbulent conditions. This indicates the applicability of the proposed electrochemical
reactions for the system with stirred or continuous reactors.

Conclusions

The following conclusions can be drawn from the experimental data obtained:
• Oxygen evolution does not take place during EC when using iron electrodes.
• EC is an accelerated corrosion process that may be explained with the iron
Pourbaix diagram.
• Observations and data from experiments measuring pH at different locations of
both cathode and anode, while running EC without stirring, together with the iron
Pourbaix diagram explain the proposed electrochemical reactions occurring in an
EC reactor.
• EC is a cyclic dynamic process: pH, concentrations and species are different in
almost every zone of the EC reactor.
• The relationship between GR and EC has been confirmed.
• Same electrochemical reactions occur in stirred and continuous reactors.

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Acknowledgments:

We are greatly thankful for financial support from USDA (2004-38899-02181),

Texas ATP (Grant No. 003581-0033-2003), and the Welch foundation (Grant No. V-
1103).
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