CORROSION SCIENCE

Use of Mössbauer Spectroscopy to Study

Reaction Products of Polyphenols
and Iron Compounds✫

J. Gust* and J. Suwalski**

ABSTRACT INTRODUCTION

Mössbauer spectroscopy was used to study parameters of The formation of colored complexes as a result of a
the reaction products of iron compounds (FeIII) and reaction between iron salts (FeIII) and polyphenols
polyphenols with hydroxyl (OH) groups in ortho positions. having hydroxyl (OH) groups in ortho positions is
Polyphenols used in the reaction were catechol, pyrogallol, characteristic of these organic compounds. Such
gallic acid, and oak tannin. The Fe-containing compounds
complexes also are formed by reactions of Fe and
were hydrated ferric sulfate (Fe2[SO4]3·nH2O), lepidocrocite
(␥-FeOOH), goethite (␣-FeOOH), magnetite (Fe3O4), and the steel corrosion product phase components and poly-
carbon (C) steel corrosion products containing ␥-FeOOH, phenols, including the tannins used for rust conversion.
␣-FeOOH, and Fe3O4. Within a pH range of 1 to 7, all the This reaction enables rusted steel surfaces to be
polyphenols were shown to form with FeIII sparingly soluble protected with tannin-containing agents.
complexes that were mixtures of mono- and bis-type The complexes formed in aqueous solutions as a
complexes with different Mössbauer parameters. Parameters result of a reaction of Fe3+ and polyphenols with OH
of each of the complex types were similar irrespective of the groups in ortho positions and low molecular masses
structure of the polyphenol used. A mixture of the mono- and were investigated previously.1-6 Results indicated
bis-type complexes also formed as a result of a reaction
structures of the polyphenol-iron complexes were
between rust-phase components and oak tannin in an
aqueous solution. When the reaction occurred on a surface of dependent on pH of the solution in which they
the rusted steel coated with an oak tannin solution, mainly formed.1-3
mono-type complexes were formed. These complexes One study indicated catechol formed monocom-
imparted anticorrosive properties to the converted rust. plexes of FeL+ (where L is a catechol ligand) in the
presence of oxygen (O2) in acidic solutions.1 At pH of
KEY WORDS: catechol, gallic acid, goethite, iron,
~ 4 to ~ 6, bis-type complexes of the FeL2– type
lepidocrocite, magnetite, Mössbauer spectroscopy, oak
tannin, pyrogallol, rust conversion, tannins, polyphenol-iron formed, whereas tris-type complexes of the FeL33– type
complexes, steels formed at pH > 7. Gallic acid (GA) formed complexes
of the Fe(LH)23– type (where L was the GA ligand) at
pH 7.5, Fe(LH)23– and Fe(LH)36– complexes at pH 7.5 to
10.5, and Fe(LH)36– complexes at pH 10.5.1
Avdeef, et al., investigated Fe complexes with
catechol; 4,5-dihydroxy-m-benzene disulfonate; and
✫
4-nitrocatechol.2 They found these complexes to be
Submitted for publication June 1993; in revised form, November 1993.
* Building Research Institute, Filtrowa 1, 00-950, Warsaw, Poland. formed in the mono-, bis-, and tris-types in the pH
** Atomic Energy Institute, 05-400, Otwock-Swierk, Poland. ranges of 3.3 to 4.5, 6.0 to 7.0, and > 8.5; < 2.8, 4.1 to
0010-9312/94/000083/$5.00+$0.50/0
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(a) (b)

FIGURE 1. Structures of tannins isolated from oak wood: (a,b) gallotannins and (c,d) catechin tannins;
(a) castalagin, (b) vescalagin, (c) catechin polymers, and (d) gallocatechin polymers.

5.2, and > 6.8; and 1.8 to 2.4, 3.5 to 4.2, > 5.4; and catechin tannins) or a carboxyl group (COOH) at
respectively. Electron spin resonance spectra indicated the aromatic ring in the meta position relative to one of
catechol ligands were oxidized by Fe3+ at pH 4. the OH groups (in gallotannins). Structures of the basic
Hider, et al., investigated the Mössbauer polyphenols composed in oak tannin (isolated from oak
parameters of the compounds formed at various pH wood) that contain both gallotannins6-7 and catechin
values as a result of Fe3+ reacting with catechol; tannins7 are presented in Figure 1.
2,3-dihydroxybenzaldehyde; and 2,3-dihydroxybenzoic The structure of tannins indicates that tannin-iron
acid (DHBA).3 Compounds dissolved in water were complexes may be of the catecholate mode (Figure
investigated after black precipitates were removed 2[a]), however they may not be of the salicylate mode
from the aqueous solutions. FeIII was reduced to FeII in (Figure 2[b]), which can be formed as a result of
the acidic media in the presence of those compounds. reaction of FeIII and DHBA.2,8
The pH at which FeIl reoxidized to FeIII depended The structure of tannin-iron complexes has been
strongly on the nature of the catechol ligand.3 discussed previously.9-17 Complexes have been
In other studies, a reaction mechanism between presented as tris complexes (Figure 2[c]).10-13 Tannin-
Fe3+ and catechol in the presence of hydrogen iron complexes formed in an acidic medium have been
peroxide (H2O2) was proposed.4-5 By that mechanism, presented as mono-type complexes (Figure 2[a]),9 bis-
the reaction products comprised catechol-iron type complexes (Figure 2[d]),14 or mono- and bis-type
complexes and ortho-quinone as a result of the complexes.15-16
oxidation of catechol via the semiquinone radicals. Seavell presented the possibility of bis-chelate and
FeIII reduced to FeII, which oxidized back to FeIII. polymeric bis-chelate structures formed by the reaction
Tannins also are polyphenols with OH groups in of hydrated ferrous sulfate (FeSO4·7H2O) and mimosa
ortho positions. The molecular masses of tannins tannin in the presence of hydrated sodium acetate
are much higher than those of the other polyphenols (CH3COONa·3H2O).17 These formulas allow for the
(500 kDa to 3,000 kDa). various possible ratios of the amount of Fe3+aq formed
Two basic tannin types are the gallotannins and as a result of the oxidation of Fe2+ to the average
the catechin tannins. Tannins may have an additional flavonoid units occurring in mimosa tannin.
third OH group at the aromatic ring in a position ortho Despite these investigations, however, the
to one of the mentioned OH groups (in gallotannins structure of the complexes formed in the rust layer

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subjected to the action of tannins has not been

determined accurately. Whether the converted rust
comprises one or more kinds of tannin-iron complexes
also has not been determined.
The objective of the present work was to present
results of Mössbauer analysis of the complexes formed (a)
by the reaction of oak tannin and hydrated ferric sulfate
(Fe2[SO4]3·nH2O), lepidocrocite (␥-FeOOH), goethite
(␣-FeOOH), magnetite (Fe3O4), and the corrosion
products of the carbon (C) steel containing ␥-FeOOH,
␣-FeOOH, and Fe3O4. The Mössbauer parameters for
the complexes formed by the reaction of catechol,
pyrogallol, and GA (C7H6O5) with Fe2(SO4)3·nH2O also
were determined.

EXPERIMENTAL
(b)
The following substances were investigated by
Mössbauer spectroscopy:
— Reaction products of catechol (Pc), pyrogallol
(Pg), gallic acid (GA), and oak tannin (OT) with
Fe2(SO4)3·nH2O formed at pH ranging from 1 to 7;
— Ferric oak tannates (FOT) formed at pH 2.6 to
3.6 and then separated into three fractions (soluble in
water at room temperature [RT], soluble in boiling
water, and insoluble in boiling water) by extraction with
water at RT and then with boiling water;
— ␥-FeOOH, ␣-FeOOH, Fe3O4 and rust converted
in the powdered form for 12 months in 15% aqueous
ethanolic OT solution at 25°C (the converted ␣-FeOOH
then was separated into soluble and insoluble fractions
by boiling water extraction, and the converted rust was
separated into three fractions by extraction with water
(c)
at RT and with boiling water); and
— Rust converted on the C steel surface after the
rusted surface was coated twice with 15% aqueous
ethanolic OT solution. The conversion took 30 days in
air at 100% relative humidity (RH) and 25°C. The
converted rust was removed from the steel surface and
separated into three fractions by extraction with water
at RT and with boiling water.
Ferric catecholates (FPc), ferric pyrogallolates
(FPg), and FOT were obtained using 15% aqueous Pc, (d)
Pg, and OT and 20% aqueous Fe2(SO4)3·nH2O
solution. They were precipitated with an aqueous FIGURE 2. Polyphenol-iron complexes: (a,b) mono-complexes;
sodium hydroxide (NaOH) solution at pH 1 to 7. (a) catecholate mode, (b) salicylate mode; (c) tannin-iron tris-
Similarly, ferric gallates (FG) were obtained using a complexes; and (d) tannin-iron bis-complexes. R = residue of
15% GA solution in dimethylformamide (DMF) with the polyphenol ligand.
10% water added and by precipitating FG at pH 1 to 4.
The solution was used because of the low solubility of
GA in water. Except for OT, all compounds used for
preparing ferric polyphenolates were commercial, method described previously.19 Rust was obtained
analytically pure reagents. using a previous laboratory method and a solution
OT was obtained using a method described containing 0.07% sodium sulfate (Na2SO4) and 0.03%
previously.18 ␥-FeOOH, ␣-FeOOH, and Fe3O4 and the sodium chloride (NaCl).20 Analytically pure compounds
conversion with OT also were prepared using a were used in preparing this solution.

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TABLE 1
Mössbauer Parameters of the Reaction Products of Pc, Pg, and GA with Fe2(SO4)3·nH2O
Formed at Various pH Values
Substance Used Mössbauer Parameters
for Reaction with Temp. QS(A) IS(A) I(A) Identified
Fe2(SO4)3·nH2O pH (K) (mm/s) (mm/s) (%) Compounds

Pc 1.0 to 4.0 78 0.81 ± 0.04 0.56 ± 0.02 44 CI type

1.20 ± 0.05 0.57 ± 0.03 40 CII type
3.18 ± 0.17 1.39 ± 0.06 16

300 0.80 ± 0.07 0.45 ± 0.04 38 CI type

1.12 ± 0.06 0.45 ± 0.03 47 CII type
3.07 ± 0.18 1.28 ± 0.09 16 FeSO4·7H2O

3.0 to 7.0 300 0.83 ± 0.03 0.43 ± 0.02 57 CI type

1.23 ± 0.04 0.44 ± 0.02 43 CII type

5.5 to 7.0 78 0.82 ± 0.02 0.59 ± 0.01 72 CI type

1.26 ± 0.06 0.59 ± 0.01 28 CII type

Pg 1.0 to 2.5 300 0.87 ± 0.03 0.45 ± 0.01 38 CI type

1.24 ± 0.04 0.45 ± 0.01 31 CII type
3.24 ± 0.04 1.24 ± 0.02 31 FeSO4·7H2O

4.0 to 5.5 78 0.78 ± 0.03 0.56 ± 0.02 42 CI type

1.19 ± 0.04 0.56 ± 0.02 32 CII type
3.05 ± 0.13 1.26 ± 0.06 26

300 0.78 ± 0.04 0.45 ± 0.02 46 CI type

1.17 ± 0.06 0.45 ± 0.02 33 CII type
3.05 ± 0.13 1.26 ± 0.06 21 FeSO4·7H2O

3.0 to 7.0 300 0.83± 0.04 0.44 ± 0.02 57 CI type

1.22 ± 0.05 0.45 ± 0.03 43 CII type

GA 1.0 to 4.0 78 0.78 ± 0.03 0.54 ± 0.02 26 CI type

1.12 ± 0.02 0.54 ± 0.01 39 CII type
0.35 ± 0.02 0.55 ± 0.01 35

300 0.72 ± 0.04 0.36 ± 0.02 23 CI type

1.07 ± 0.03 0.37 ± 0.02 41 CII type
0.28 ± 0.02 0.39 ± 0.02 36 Fe2(SO4)3·nH2O

(A)
QS = quadrupole splitting, IS = isomer shift, and I = relative intensity.

For extractions with water at RT and with boiling spectrum lines. Mössbauer parameters were ex-
water, distilled water in an amount 20 times exceeding pressed as velocities with respect to high-purity Fe at
the mass of the extracted substances was used. The RT. Effective magnetic fields (Heff) measured in ferro-
extracts obtained were evaporated, and the fractions magnetic compounds were done in magnetic units kilo-
–
remaining after the water extractions were dried to Oersted (kOe). Relative intensity (I) of the spectrum of
constant mass. the given compound was expressed as a percentage
Mössbauer measurements were made using a of the total Mössbauer absorption on Fe atoms.
standard-acceleration spectrometer operating in the Also determined were the Mössbauer parameters
transmission mode in 256 channels. The source used known from the literature21-22 for ␥-FeOOH, ␣-FeOOH,
was 25 mCi cobalt-57 in palladium at RT. and Fe3O4 and for analytically pure FeSO4·7H2O and
The Mössbauer spectra were recorded for Fe2(SO4)3·nH2O used in this work.
samples maintained at RT (300 K) and liquid nitrogen
(78 K) temperature. For statistical reliability, the spectra RESULTS AND DISCUSSION
were recorded with several million counts per channel.
Assuming Lorentian shape lines profiles, the least- Table 1 presents the Mössbauer parameters of the
squares routine was used to calculate the theoretical reaction products of Pc, Pg, GA with Fe2(SO4)3·nH2O.

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TABLE 2
Mössbauer Parameters of the Reaction Products of OT and Fe2(SO4)3
Obtained at Various pH Values
Mössbauer Parameters
Temp. QS(A) IS(A) I(A) Identified
pH (K) (mm/s) (mm/s) (%) Compounds

1.2 to 2.4 78 0.81 ± 0.03 0.54 ± 0.01 57 CI type

1.27 ± 0.04 0.54 ± 0.02 37 CII type
2.82 ± 0.16 1.68 ± 0.08 8

300 0.77 ± 0.03 0.44 ± 0.01 55 CI type

1.17 ± 0.04 0.45 ± 0.02 36 CII type
3.16 ± 0.19 1.27 ± 0.09 8 FeSO4·7H2O

2.6 to 3.6 78 0.78 ± 0.04 0.54 ± 0.03 58 CI type

1.22 ± 0.09 0.57 ± 0.03 42 CII type

300 0.80 ± 0.03 0.43 ± 0.02 60 CI type

1.25 ± 0.05 0.44 ± 0.02 40 CII type

3.7 to 5.3 78 0.71 ± 0.17 0.56 ± 0.10 60 CI type

1.14 ± 0.16 0.57 ± 0.08 40 CII type

300 0.80 ± 0.07 0.43 ± 0.04 67 CI type

1.29 ± 0.10 0.43 ± 0.04 33 CII type

5.3 to 7.0 78 0.79 ± 0.03 0.52 ± 0.02 53 CI type

1.28 ± 0.05 0.52 ± 0.02 40 CII type
2.60 ± 0.30 1.60 ± 0.10 7 Partially oxidized
Fe(OH)2

300 0.74 ± 0.03 0.42 ± 0.02 55 CI type

1.18 ± 0.05 0.42 ± 0.02 41 CII type
2.45 ± 0.50 1.23 ± 0.25 4

(A)
QS = quadrupole splitting, IS = isomer shift, and I = relative intensity.

Table 2 presents parameters of the reaction products CII-type complexes. These parameters did not depend
of OT with Fe2(SO4)3·nH2O. on whether the polyphenol ligand had two or three
Two FeIII compounds occurred in all substances phenolic groups at the aromatic ring (if at least two
tested and were considered to be polyphenol-iron were ortho to one another) and did not depend on the
complexes. Because of marked similarity of the structure of the residue (R) rest (Figures 2[a] through
Mössbauer parameters of the compounds occurring in [d]) of that ligand, i.e., whether R was an H atom as in
all the substances tested, those compounds were the case of Pc and Pg, a COOH group as in the case
designated conventionally as CI- and CII-type of GA, or R had a much developed structure as for OT
complexes. Table 3 provides the mean Mössbauer (Figure 1). This also indicated tannin-iron complexes
parameters of the CI- and CII-type compounds, as should have had the same kind of bonds between FeIII
calculated from the data in Tables 1 and 2. Figure 3 and the ligand irrespective of whether the ligands came
shows the Mössbauer spectrum for FOT obtained at from gallotannins or catechin tannins.
pH 2.6 to 3.6 and containing 60% of Fe atoms in the The CI- and CII-type compounds formed at pH 1
CI-type compound and 40% of Fe atoms in the CII- to 4 in the case of FPc, 1 to 5.5 in the case of FPg, and
type compound. 1.2 to 2.4 in the case of FOT were accompanied by
Two kinds of bonds (of the CI- and CII-types) were FeSO4·7H2O identified on the basis of the data in
assumed to appear in the complexes between FeIII and Table 4. Reaction products of GA and Fe3+, as
their nearest neighbors, irrespective of the differences obtained at pH 1 to 4, were accompanied by
in structures of further parts of the polyphenol ligands. Fe2(SO4)3·nH2O, also identified on the basis of the
These differences slightly affected the Mössbauer data in Table 4.
parameters of tannin-iron complexes. During the reaction of polyphenols and Fe3+,
The mean Mössbauer parameters presented in formation of the complexes was accompanied by
Table 3 were taken as characteristic for the CI- and reduction of FeIII to FeII. At low pH values (1 to 4, 1 to

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TABLE 3 Pritchard and Mould determined the Mössbauer

Mean Mössbauer Parameters of the CI- spectra of Fe(OH)2 and nemalite, which may contain
and CII-Type Compounds Fe as Fe3O4 and Fe(OH)2.25 They found that, as the
degree of Fe(OH)2 oxidation increased, the value of the
Temp. QS(A) IS(A)
(K) Compound (mm/s) (mm/s) quadrupole splitting decreased, with a similar isomer
shift value being retained. The Mössbauer parameters
78 CI type 0.78 ± 0.07 0.55 ± 0.03 of these compounds, as obtained by Pritchard and
CII type 1.21 ± 0.08 0.56 ± 0.04
Mould, are presented in Table 4.25
300 CI type 0.80 ± 0.06 0.43 ± 0.02 Stratmann and Hoffmann investigated the
CII type 1.19 ± 0.08 0.44 ± 0.02 reduction of ␥-FeOOH to Fe(OH)2 and found that
␥-FeOOH at a potential lower than –0.2 VSHE was
(A)
QS = quadrupole splitting and IS = isomer shift. reduced partially to Fe(OH)2.24 After reoxidation
potentiostatically or by contact with air, Fe(OH)2 was
reoxidized to ␥-FeOOH. In their study, the Mössbauer
spectra of partially reduced ␥-FeOOH corresponded to
those obtained in the present work (Figures 4 through
6) for the substances containing admixtures of the
compound identified as partially oxidized Fe(OH)2.
Analysis of previous data24-25 and a comparison of
the Mössbauer parameters obtained in this work for the
compound accompanying FOT and obtained at pH 5.3
to 7.0 and those of partially oxidized Fe(OH)2 and
partially reduced ␥-FeOOH led to a conclusion that the
compound accompanying FOT was partially oxidized
Fe(OH)2.
Table 5 presents results of the Mössbauer
investigation of the individual FOT fractions obtained at
pH 2.6 to 3.6 and separated by extraction with water at
RT and with boiling water. The Mössbauer spectrum of
the compounds (that could be defined as those of the
CI type) extracted with water at RT is shown in Figure
7. During the extraction, ~ 0.3% solution of the CI-type
FIGURE 3. Mössbauer spectrum measured at 300 K for FOT compounds was obtained. During the boiling water
obtained at pH 2.6 to 3.6 for: (1) CI-type complexes and extraction, ~ 1.2% solution of the CI-type compounds
(2) CII-type complexes. and ~ 0.8% solution of the CII-type compounds were
obtained. This testified to low solubility of the com-
pounds in water. However, the CI-type compounds
were slightly more soluble.
5.5, and 1.2 to 2.4 with the use of Pc, Pg, and OT, In a previous work, the Mössbauer parameters of
respectively), the precipitate also contained water-soluble catechol-iron complexes were
FeSO4·7H2O that formed as a result of the reduction of determined.3 Small amounts of these complexes
Fe2(SO4)3·nH2O. The occurrence of Fe2(SO4)3·nH2O in accompanied FeII compounds at pH 6. The precipitate
the precipitate was found only when FG precipitated obtained during a reaction of Pc and FeIII were
from the DMF-H2O solution. However, this related to separated from the solution investigated. The
the low solubility of Fe2(SO4)3·nH2O and good solubility Mössbauer parameters of these complexes and
of FeSO4·7H2O in such a solution. FeSO4·7H2O catechol-iron complexes formed at pH 5.4 corre-
probably remained in the solution. sponded exactly to those of the CI-type complexes
At pH 3 to 7, using Pc and Pg and at pH 2.6 to 5.3 determined in this work.27 This confirmed a slight water
using OT, FeII was found to be absent in the precipi- solubility of the CI-type complexes. The CII-type
tate. FeSO4 thus probably reoxidized to Fe2(SO4)3. complexes probably occurred in the filtrated precipi-
The FOT formed as a result of the reaction of tate.3,27 At pH < 6, only FeII compounds appeared in the
OT and Fe3+ at pH 5.3 to 7.0 was accompanied by solution. FeIII compounds appeared at pH 7.7 to 12.3
partially oxidized ferrous hydroxide (Fe[OH]2). This Table 6 lists the Mössbauer parameters of the
compound was identified on the basis of data in compounds occurring in the ␥-FeOOH, ␣-FeOOH, and
previous works.24-25 The Mössbauer spectrum of the Fe3O4 converted by means of OT. All the converted
reaction products is shown in Figure 4. synthetic rust phase components contained CI- and

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TABLE 4
Mössbauer Parameters of the Inorganic Compounds Identified in the Substances Investigated
Temp. QS(A) IS(A) Heff(A) I(A)
Compound (K) (mm/s) (mm/s) (kOe) (%) Reference

␥-FeOOH 78 0.66 ± 0.02 0.50 ± 0.01 100 This work(B)

78 0.58 ± 0.01 0.50 ± 0.01 76 This work(C)
0.97 ± 0.03 0.50 ± 0.01 24
300 0.60 ± 0.02 0.38 ± 0.01 100 This work(B)
300 0.54 ± 0.01 0.38 ± 0.01 80 This work(C)
0.93 ± 0.05 0.38 ± 0.01 20

␣-FeOOH 78 0.12 ± 0.03 0.48 ± 0.03 494.8 ± 2.4 100 This work(B)

Fe3O4 78 0.01 ± 0.04 0.46 ± 0.04 516.5 ± 3.2 This work(D)

0.07 ± 0.19 0.80 ± 0.19 475.4 ± 14.6
300 0.00 ± 0.03 0.33 ± 0.03 492.8 ± 2.3 This work(D)
0.00 ± 0.03 0.64 ± 0.05 460.0 ± 4.0

FeSO4·7H2O 300 3.20 ± 0.03 1.27 ± 0.02 100 This work(B)

RT 3.217 1.261 22

FeSO4 80 3.104 1.390 22

RT 2.726 1.270 22

Fe2(SO4)3·nH2O 300 0.34 ± 0.03 0.44 ± 0.02 100 This work(B)

Fe2(SO4)3 RT 0.60 0.39 23

Fe(OH)2(E) 85 2.92 24
88 3.02 ± 0.1 1.49 ± 0.05 25
90 3.00 1.25 26
298 2.6 1.2 24
298 2.92 1.44 25

Nemalite(F) 95 3.02 1.65 25

298 2.18 1.68 25
298 3.12 1.44 25
298 0.70 0.45 25

(A) –
QS = quadrupole splitting, IS = isomer shift, I = relative intensity, Heff = magnetic splitting, and kO3 = kilo-Oersted.
(B)
Calculated using one doublet.
(C)
Calculated using two doublets.
(D)
Calculated using two sextets.
(E)
Fe(OH)2, ferrous hydroxide.
(F)
Containing 7% Fe as Fe(OH)2 and FeIII.

CII-type compounds. The greatest amount of those in the rust converted by means of OT in the powdered
compounds was in converted ␥-FeOOH (100% of form in an aqueous ethanolic solution of that tannin
converted compound), less in the converted Fe3O4, and on the surface of steel. Table 7 also specifies the
and the least in the converted ␣-FeOOH (10% by composition of the rust investigated. The compounds
weight of the converted compound). This confirmed extracted with water at RT and with boiling water and
results of previous work in which it was found that OT the residue after those extractions accounted for
reacted fastest with ␥-FeOOH, slower with Fe3O4 and 8 wt%, 31 wt%, and 62 wt%, respectively, for the rust
slowest with ␣-FeOOH.19 The ratio of moles of all converted in an OT solution and 7 wt%, 16 wt%, and
compounds of the CI type to those of the CII type was 77 wt%, respectively, for the rust converted on the
highest in the converted ␣-FeOOH (1.78:1) and lowest surface of steel.
in converted ␥-FeOOH (1:1). This indicated the kind of As was evident from data in Table 7, the CI-type
polyphenol-iron complex formed also was affected by compounds passed into solution in both cases during
reagents that contained Fe. the water extraction at RT. During the boiling water
Table 7 details Mössbauer parameters of the extraction of the rust converted in the OT solution, the
compounds extracted with water at RT and with boiling CI- and CII- type compounds and the partially oxidized
water and the compounds remaining after extractions Fe(OH)2 passed into solution (Figure 5). However, an

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FIGURE 5. Mössbauer spectrum measured at 300 K for the

FIGURE 4. Mössbauer spectrum measured at 78 K for the compounds extracted with boiling water from the rust converted
reaction products of OT and Fe2(SO4)3·nH2O obtained at pH for 12 months in 15% OT solution at 25°C: (1) CI-type
5.3 to 7.0 for: (1) CI-type complexes, (2) CII-type complexes complexes, (2) CII-type complexes, and (3) partially oxidized
and (3) partially oxidized Fe(OH)2. Fe(OH)2.

FIGURE 6. Mössbauer spectrum measured at 300 K for the

compounds extracted with boiling water from the rust converted
on a steel surface after coating with 15% OT solution and
storage for 30 days at 100% RH and 25°C for: (1) CI-type FIGURE 7. Mössbauer spectrum measured at 300 K for FOT-
complexes and (2) partially oxidized Fe(OH)2. iron complexes of the CI-type.

analogous extract obtained by extraction of the rust CII-type complexes formed when rust conversion
converted on the steel surface contained only the occurred in aqueous OT solution, while the CI-type
CI-type compound and the partially oxidized Fe(OH)2 complexes formed mainly in the rust converted on a
(Figure 6). In the last of these cases, the converted steel surface.
rust was not found to contain the CII-type compounds, It was assumed that the CI-type complexes
neither the water-extracted compounds nor the water- corresponded to the formula in Figure 2(a) and the CII-
extraction residue. It followed that both the CI- and type complexes to the formula in Figure 2(d). It

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TABLE 5
Mössbauer Parameters of the Fractions of the Reaction Products of OT and Fe2(SO4)3·nH2O
Formed at pH Values of 2.6 to 3.6
Fraction Content
Temp. in Reaction Products QS(A) IS(A) I(A) Compounds Occurring
(K) Fraction (%) (mm/s) (mm/s) (%) in the Fraction

300 Soluble 7 0.79 ± 0.15 0.43 ± 0.08 100 CI type

in water
at RT

78 Soluble 42 0.76 ± 0.05 0.53 ± 0.03 59 CI type

in boiling 1.27 ± 0.08 0.53 ± 0.04 41 CII type
water

300 Remaining after 51 0.82 ± 0.03 0.44 ± 0.01 55 CI type

extractions(B) 1.24 ± 0.04 0.44 ± 0.01 45 CII type

(A)
QS = quadrupole splitting, IS = isomer shift, and I = relative intensity.
(B)
With water at RT and boiling water.

FIGURE 8. Reactions between polyphenols and Fe compounds at pH 1 to 7. (Pc: R1 = R2 = R3 = H. Pg: R1 = OH,

R2 = R3 = H. GA: R1 = OH, R2 = COOH, R3 = H. OT: R1 = H or OH, R = residues of oak tannin molecules,
R3 = H or residues of oak tannin molecules in accordance with Figure 1.

appeared that monocomplexes should form easier on The water-extraction residue of the rust converted
the surfaces of the rust phase components than should in OT solution was found to contain the CI-type
bis-type complexes because of spatial hindrance. compounds, ␥-FeOOH and Fe3O4, and also a low
However, bis-type complexes may form easily in an admixture of a compound whose parameters
aqueous solution in addition to monocomplexes. The accurately corresponded to those of Fe(OH)2, in
imposition of certain anticorrosive properties20 to the agreement with the literature data presented in Table
rust converted by means of tannins probably was 4. In the opinion of Stratmann and Hoffmann, the
related to formation of the complexes. oxidation of Fe(OH)2 may lead to various products

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TABLE 6
Mössbauer Parameters of the Phase Components of the Rust Converted for 12 Months in OT Solution
Compounds
in the
Investigated Temp. QS(A) IS(A) Heff(A) I(A) Substance
Substance (K) (mm/s) (mm/s) (kOe) (%) Investigated

Converted 78 0.70 ± 0.05 0.49 ± 0.03 50 CI type

␥-FeOOH 1.20 ± 0.05 0.51 ± 0.03 50 CII type

Converted 78 0.81 ± 0.12 0.56 ± 0.05 15 CI type

Fe3O4 1.36 ± 0.16 0.56 ± 0.05 13 CII type
0.02 ± 0.03 0.43 ± 0.04 507 ± 3 73 Fe3O4

Compounds extracted 300 0.81 ± 0.04 0.43 ± 0.02 64 CI type

with BW(A) from 1.31 ± 0.08 0.43 ± 0.02 36 CII type
converted ␣-FeOOH(B)

Compounds remaining 78 0.12 ± 0.02 0.48 ± 0.02 490 ± 2 100 ␣-FeOOH

after the extraction of
converted ␣-FeOOH(C)

(A)
QS = quadrupole splitting, IS = isomer shift, I = relative intensity, Heff = magnetic splitting, and BW = boiling water.
(B)
10 wt% of the converted ␣-FeOOH.
(C)
90 wt% of the converted ␣-FeOOH.

depending on whether Fe(OH)2 was formed by from aqueous solution as a result of the reaction of
dissolution of the crystalline phases of FeOOH, Fe2(SO4)3·nH2O and OT (mono- and bis-type
followed by precipitation of Fe(OH)2, or by reduction of complexes).
FeOOH through a solid-state reaction.24 In the latter ❖ Where the reaction of tannins and rust-phase
case, a Mössbauer spectrum similar to that of Fe(OH)2 components occurred in a rust layer on a steel surface,
was obtained. This could account for a discrepancy in only monocomplexes were formed, increasing the
results obtained in this work for the substance corrosive resistance of the converted rust.
determined as a partially oxidized Fe(OH)2 and ❖ The complexes had low solubility in water, with
identified as an admixture accompanying FOT when monocomplexes being somewhat more soluble than
they were formed in an aqueous solution containing bis-type complexes. These complexes also had low
OT and Fe2(SO4)3·H2O and when they were formed solubility in DMF.
during the conversion of the rust extracted with boiling ❖ All the polyphenol-iron monocomplexes of the
water. The degree of oxidation of the compounds catecholate mode showed similar Mössbauer
investigated also may have differed. parameters regardless of the kind of ligand. The kind of
On the basis of the data presented and of the ligand only slightly affected the parameters.
literature,4-5,28-30 the course of the reaction between the Similar Mössbauer parameters were shown by all
polyphenols and Fe compounds within pH of 1 to 7 can polyphenol-iron bis-type complexes of the catecholate
be presented in the form shown in Figure 8. mode. The kind of ligand also slightly affected the
parameters.
CONCLUSIONS ❖ FOT precipitated from an aqueous solution
containing OT and Fe2(SO4)3·nH2O at pH 1.2 to 2.4 and
❖ During a reaction between Fe3+ and polyphenols, 5.3 to 7.0 were accompanied by FeSO4·7H2O and
inclusive of tannins, complexes were formed and a partially oxidized Fe(OH)2, respectively.
redox reaction occurred, resulting in FeIII being The compounds were obtained as a result of FeIII
reduced to FeII. being reduced by tannins and, for partially oxidized
❖ When this reaction occurred in a concentrated Fe(OH)2, being reoxidized partially by means of O2 in
(15%) aqueous polyphenol solution at pH 1 to 7, the air.
mono- and bis-type complexes were precipitated from ❖ The Fe-containing compounds that occurred in the
the solution. composition of the rust converted by means of tannins
❖ The reaction of rust-phase components and OT were original rust components, ferric tannates,
occurring in an aqueous solution resulted in the Fe(OH)2, partially oxidized Fe(OH)2, and products of
formation of the same complexes as those precipitated tannin oxidation.

364 CORROSION–MAY 1994

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TABLE 7
Mössbauer Parameters of the Compounds Occurring in the Rust Converted by Means of OT
Compounds
Investigated Temp. QS(A) IS(A) Heff(A) I Occurring in the
Substance (K) (mm/s) (mm/s) (kOe) (%) Substance

Original rust 78 0.59 ± 0.02 0.50 ± 0.02 59 ␥-FeOOH

0.11 ± 0.07 0.49 ± 0.07 489 ± 7 9 ␣-FeOOH
0.01 ± 0.09 0.46 ± 0.09 515 ± 7 32 Fe3O4

Compounds extracted 78 0.81 ± 0.11 0.53 ± 0.07 100 CI type

with water at RT from
the rust converted(B) in
OT solution

Compounds extracted 78 0.73 ± 0.04 0.52 ± 0.02 50 CI type

with BW(A) from the rust 1.21 ± 0.06 0.50 ± 0.03 33 CII type
converted(B) in OT solution 2.75 ± 0.13 1.46 ± 0.07 17 Partially oxidized
Fe(OH)2

Compounds remaining 78 1.26 ± 0.11 0.57 ± 0.05 17 CII type

after extractions(C) of the 0.68 ± 0.05 0.49 ± 0.03 32 ␥-FeOOH
converted rust(B) 0.03 ± 0.05 0.62 ± 0.08 486 ± 10 49 Fe3O4
3.00 ± 0.75 1.26 ± 0.05 2 Fe(OH)2

Compounds extracted 300 0.74 ± 0.04 0.39 ± 0.02 100 CI type

with water at RT from
the rust converted on
steel surface by means
of OT solution

Compounds extracted 300 0.78 ± 0.03 0.40 ± 0.02 79 CI type

with BW from the rust 2.39 ± 0.17 1.09 ± 0.09 21 Partially oxidized
converted on steel surface Fe(OH)2
by means of OT solution

Compounds remaining 300 0.65 ± 0.04 0.37 ± 0.03 36 ␥-FeOOH

after extractions(C) of the 0.49 ± 0.67 0.15 ± 0.67 197 ± 49 5 ␣-FeOOH
converted rust(D) 0.02 ± 0.08 0.32 ± 0.08 490 ± 6 59 Fe3O4

(A)
QS = quadrupole splitting, IS = isomer shift, I = relative intensity, Heff = magnetic splitting, and BW = boiling water.
(B)
Rust converted in the powdered form (in OT solution).
(C)
With water at RT and boiling water.
(D)
Rust converted on steel surface by treatment with OT solution.

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