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a
Department of Human Biology, University of Cape Town, Rondebosch 7701, South Africa
b
Faculty of Civil and Environmental Engineering, Technion, Haifa 32000, Israel
Received 23 November 2006; received in revised form 6 February 2007; accepted 6 February 2007
Available online 21 March 2007
Abstract
The spontaneous chemical oxidation of Fe(II) to Fe(III) by O2 is a complex process involving meta-stable partially oxidized interme-
diate species such as green rusts, which ultimately transform into a variety of stable iron oxide end-products such as hematite, magnetite,
goethite and lepidocrocite. Although in many practical situations the nature of the end-products is of less interest than the oxidation
kinetics, it is difficult to find in the literature a description of all the basic steps and principles governing the kinetics of these reactions.
This paper uses basic aquatic-chemistry equilibrium theory as the framework upon which to present a heuristic model of the oxidation
kinetics of Fe(II) species to ferric iron by O2. The oxidation rate can be described by the equation (in units of mol Fe(II)/(l min)):
d½Fe2þ =dt ¼ 6 105 ½Fe2þ þ 1:7½FeðOHÞþ þ 4:3 105 ½FeðOHÞ02 . This rate equation yields a sigmoid-shaped curve as a function
of pH; at pH values below 4, the Fe2+ concentration dominates and the rate is independent of pH. At pH > 5, ½FeðOHÞ02 determines
the rate because it is far more readily oxidized than both Fe2+ and FeOH+. Between pH 5 and 8 the FeðOHÞ02 concentration rises steeply
with pH and the overall oxidation rate increases accordingly. At pH values > 8 ½FeðOHÞ02 no longer varies with pH and the oxidation
rate is again independent of pH. The paper presents a heuristic overview of the pH dependent kinetics of aqueous ferrous oxidation by
O2(aq) which we believe will be useful to professionals at both research and technical levels.
2007 Elsevier Ltd. All rights reserved.
Keywords: Ferrous iron; Oxidation rate; Oxygen; Kinetics; pH; Aqueous phase
0045-6535/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2007.02.015
Author's personal copy
d½Fe2þ 2
¼ k½Fe2þ ½OH pO2 ð1Þ
dt
pH
0 2 4 6 8 10
1 12 14
0
-
Fe2+ Fe(OH)3
-3
log [species]
-6 +
FeOH
-9
)2 0
H
O
-12
(
Fe
pH 0 FeðIIÞT
½FeðOHÞ2 ¼ þ þ 2
ð5Þ
0 2 4 6 8 10 12 14 1 þ KðH3 KþwÞ þ KðH2 K wÞ þ KðHK Þ
2
1 2Kw
0
FeðIIÞT
Fe2+ ½FeðOHÞ
3 ¼ þ 2 ð6Þ
þ
ðHþ Þ3
-2 1 þ KðH3 K wÞ þ KðH Þ
2K3Kw
þK 3
1K2K3Kw
log [species]
Fe(OH)2(s)
-4 where log K1 = 4.5, log K2 = 2.93, log K3 = 3.57 (Benjamin,
FeT 2002).
FeOH+ Eq. (2) implies that in the course of soluble ferrous spe-
-6
Fe(OH)02 cies oxidation, and in contrast with the approach presented
-8 in Eq. (1), more than one oxidation reaction occurs simul-
Fe(OH)3- taneously (Stumm and Morgan, 1996), viz.
-10 a Fe2þ ! Fe3þ þ e
þ 2þ
Fig. 4. Aqueous-solid phase equilibrium for soluble ferrous hydroxide b FeðOHÞ ! FeðOHÞ þ e
species at infinite dilution (in the absence of both inorganic carbon species
and ion pairing species such as Cl, SO2 3
4 , PO4 etc.). c FeðOHÞ02 ! FeðOHÞþ
2 þe
the free energy of the reaction (log K) and the rate (log k) aqueous-solid equilibrium. Here at pH 8 although Fe2+
0
of the reaction for the oxidation of Fe2+, FeOH+ and exceeds both FeOH+ and FeðOHÞ2 in concentration, the
0
FeðOHÞ2ðaqÞ . Based on the studies of Lowson (1982) and latter two species are far more easily oxidized due to the
Millero (1985) the following explicit rate equation for sol- presence of the hydroxyl groups. As one moves from pH
uble ferrous species oxidation can be written. Note that 8 to the right in Fig. 4, both the Fe2+ and FeOH+ concen-
0
no rate constant has been reported for the oxidation of trations drop steeply whilst the FeðOHÞ2 concentration is
FeðOHÞ 3 probably due to empirical limitations, however constant. As the pH increases above 8.0 the oxidation rate
the concentration of this species is exceptionally low at (Eq. (2)) therefore becomes dominated by FeOH02 . Since
pH values < pH 10 and thus from a practical standpoint this species is constant with respect to pH ‘throughout’
this rate constant is of a lesser importance. Also note that the range, the rate above pH 8 becomes independent of
the rate constants in Eq. (7) should probably be considered pH.
0
only with respect to their order of magnitude, rather than Note that although Fig. 4 shows the FeðOHÞ2 concen-
as accurate quantities. tration is constant below pH 8, in practice this never
0 arises for the reasons stated above, i.e. all Fe(II) solutions
d½Fe2þ @ 6 105 FeðIIÞT of concentrations of the order of 103 M are unsaturated
¼ 2 3 below pH 8 and single phase liquid equilibrium (Fig. 3)
dt 1 þ K 1 Kþw þ K 1 Kþ2 K2w þ K 1 Kþ2 K3w
ðH Þ ðH Þ ðH Þ rather than two phase aqueous-solid equilibrium (Fig. 4)
1:7 FeðIIÞT applies. As the pH moves below 8 the threshold for satu-
þ þ
1 þ KðH1 K wÞ þ KðH2 KþwÞ þ KðH
2K3Kw
2
ration rises logarithmically so that in practise saturated
þ 2
Þ Fe(II) solutions hardly ever occur at pH < 8.
1
5
4:3 10 FeðIIÞT A
þ þ þ 2
ð7Þ 2. A simple heuristic description
1 þ KðH3 KþwÞ þ KðH2 K wÞ þ KðHK Þ
2
1 2Kw
100 pH 4.0
• The rate constants of the three meaningful Fe(II) soluble
0
80 species (Fe2+, FeOH+, FeðOHÞ2 ) differ from each
pH 5.0 other by five orders of magnitude (6 · 105, 1.7, and
60
4.3 · 105 1/min), respectively. In practical terms this
pH 6.0
40 means that the overall oxidation rate depends dramati-
cally on the distribution of these three species in the
20 aqueous phase, which is mostly pH dependent, but to
pH 7.0 pH 6.3
0
a lesser degree also depends on temperature and ionic
0 pH 7.6 50 100 150 200 strength.
pH 7.75 Time (min) • No rate constant has been reported for the oxidation of
Fig. 5. Oxidation rate of soluble Fe(II) in a batch test as a function of pH FeðOHÞ3 probably due to empirical limitations, how-
(according to Eq. (7)). Assumptions: infinite dilution and DO saturated at ever the concentration of this species is exceptionally
25 C. Note that at pH 7.75 the curve starts at a ferrous concentration of low at pH values < pH 10 and thus from a practical
90.18 mg/l rather than 100 mg/l, because at this pH 9.82 mg/l precipitate
standpoint its rate constant is of a lesser importance.
as Fe(OH)2(s).
• Further empirical work is required in order to quantify
the rate constants of common complexes of Fe(II),
• It has been observed that catalysts such as Co2+ and encountered in natural waters. Such study is imperative
Cu2+ dramatically enhance the oxidation rate (Stumm for design purposes of, for example, oxidation reactors
and Lee, 1961). aimed at treatment of acid mine drainage, comprising
• The presence of anions such as Cl, CO2 and SO2 a variable, but always high SO2 4 concentration, or for
3 4
have been shown to retard the oxidation rate (Millero, Fe(II) containing groundwater that also includes a high
1985) because they form complexes with Fe(II) that Cl concentration.
are less favourably oxidized as compared to the hydrox-
ide complexes. The exact rate constants associated with References
each of these complexes have not been established to
Benjamin, M.M., 2002. Water Chemistry, International Edition.
date. Part of the difference in the rate curves for seawa-
McGraw-Hill series in Water Resources and Environmental
ter and water seen in Fig. 2 are a consequence of such Engineering.
anion effects, the other part being due to temperature. Lowson, R.T., 1982. Aqueous oxidation of pyrite by molecular oxygen.
• In water high in alkalinity (such as ground waters) the Chem. Rev. 82, 461–499.
overall solubility of Fe(II) is lower and controlled by Luther, G.W., 1990. The frontier-molecular-orbital theory approach in
geochemical processes. In: Stumm, W. (Ed.), Aquatic Chemical
siderite rather than by ferrous hydroxide. However,
Kinetics. Wiley-Interscience, New York, pp. 73–199.
the principles governing the rate equation (Eq. (7)) Millero, F.J., 1985. The effect of ionic interactions on the oxidation of
remain valid. metals in natural waters. Geochim. Cosmochim. Acta 49, 547–553.
Millero, F.J., Sotolongo, S., Izaguirre, M., 1987. The oxidation kinetics of
3. Conclusions Fe(II) in seawater. Geochim. Cosmochim. Acta 51, 793–801.
Prasad, T.P., Ramasastry, V.V., 1974. Oxidation of ferrous hydroxide
suspensions. Int. J. Appl. Chem. Biotechnol. 24, 769–775.
• The fundamental equilibrium and thermodynamic prin- Roekens, E.J., Van Grieken, R.E., 1983. Kinetics of iron(II) oxidation in
ciples governing the pH dependent (5 < pH < 8) and seawater of various pH. Mar. Chem. 13 (3), 195–202.
pH independent (5 > pH > 8) kinetics of oxidation Singer, P.C., Stumm, W., 1970. The solubility of ferrous iron in carbonate
of ferrous iron to ferric iron where oxygen is the oxidiz- bearing waters. J. Am. Water. Works Ass. 62, 198–202.
Stumm, W., Lee, G.F., 1961. Oxygenation of ferrous iron. Ind. Eng.
ing agent have been described. The result is a simple Chem. Res. 53, 143–146.
heuristic description of the oxidation kinetics as a func- Stumm, W., Morgan, J.J., 1970. Aquatic Chemistry: An Introduction
tion of pH. The visual simplicity of this model assures Emphasizing Chemical Equilibria in Natural Waters. Wiley-Inter-
that it can be easily remembered and applied to any sit- science, New York.
uation where it may be needed. Stumm, W., Morgan, J.J., 1996. Aquatic Chemistry: Chemical Equilibria
and Rates in Natural Waters. Wiley-Interscience, New York.
• The oxidation rate is both thermodynamically and Wehrli, B., 1990. Redox reactions of metal ions at mineral surfaces. In:
kinetically enhanced by adsorption of dissolved iron Stumm, W. (Ed.), Aquatic Chemical Kinetics. Wiley-Interscience, New
species to hydrous oxide surfaces. This is also because York, pp. 311–337.