Protection of Metals, Vol. 38, No. 1, 2002, pp. 17–21. Translated from Zashchita Metallov, Vol. 38, No.

1, 2002, pp. 22–26.

Original Russian Text Copyright © 2002 by Andreeva, Bulgakova, Kuznetsov, Sokolova.

Adsorption of Monoethanolamine on Iron

from a Carbon Dioxide Atmosphere
N. P. Andreeva, R. A. Bulgakova, Yu. I. Kuznetsov, and N. P. Sokolova
Institute of Physical Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117915 Russia
Received June 20, 2001

Abstract—The adsorption of carbon dioxide on Armco iron at a pressure of 1 atm was revealed and studied by
ellipsometry and IR spectroscopy. The conditions of the formation of adsorbed VCI layers were found to be
important for steel protection. The surface preliminarily exposed to an atmosphere of CO2 is covered with a thin
(about 2 nm) adsorbed layer which significantly changes its properties. The layers of VCI adsorbed from a CO2
atmosphere differ only slightly in thickness from those formed in air. However, the adhesion of the former is
better, as evidenced by its lower Kd.

Lower amines and amino alcohols are well known
as neutralizing agents for steel protection from carbon
dioxide corrosion in power generation and in oil and
gas industry [1, 2]. However, now it has been shown
that they contribute to metal protection not only by reg-
ulating pH of the medium, but also by their adsorption
[3]. Although a great number of such compounds are
known to be volatile corrosion inhibitors (VCIs) [4],
their adsorption on iron from a vapor phase is studied
inadequately [5]. For this reason, we investigated the
adsorption and desorption of a known VCI, namely,
monoethanolamine (MEA), on iron from an atmo-
sphere of carbon dioxide at p CO2 = 1 atm.
EXPERIMENTAL
The adsorption–desorption kinetics of VCI was
studied ellipsometrically. The ∆ and ψ angles charac-
terizing a surface under study were measured on a Gart-
ner manual ellipsometer. A halogen lamp with a
540-nm filter was used as a radiation source. The ellip-
someter scheme included a polarizer, a compensator, a
surface, and an analyzer. The ∆ and ψ angles were
determined using a zero scheme, i.e., the polarizer and
the analyzer were rotated alternately to minimize the
intensity on the recording device. The ∆ and ψ values
were calculated from the angles of the polarizer and the
analyzer in a suppression position.
An Armco iron specimen was ground, polished with
alumina, kept in a dry atmosphere for two days to sta-
bilize the oxide film, and placed in a hermetically
sealed Teflon cell for ellipsometric measurements. The
specimen surface was oriented perpendicular to the cell
bottom containing a drop of VCI. The distance between
the specimen center and the cell bottom was 30 mm.
The cell cover was equipped with a manometer and
ground openings for gas inlet.
Changes in the ellipsometric angles during the
experiments, δ∆ = ∆ – ∆0 and δψ = ψ – ψ0 (where ∆0 and
ψ0 refer to the initial specimen surface), were attributed
to the adsorption or desorption of the test compound
alone. As a rule, δ∆ < 0 when a film grows. For small
film thicknesses (d < 10 nm), the thickness is a linear
function of ∆ [6]: d = – α(∆ – ∆0) = – αδ∆, where α is a
proportionality factor. The δψ values can be both posi-
tive and negative. The thickness d and the complex
refractive index N = n – ik (n and k are its real and imag-
inary parts, respectively) of the adsorbed film were
determined using the McCrackin program. The initial
data were the medium refractive index n0 , the angle of
light incidence (68.5°), the radiation source wavelength
(540 nm), and Ns of the base (2.7 – 2.9i).
Three sets of experiments were carried out: (1) the
adsorption and desorption of VCI in air, (2) the adsorp-
tion and desorption of VCI in an atmosphere of carbon
dioxide, and (3) the same as in (2) with preliminary
exposure of an iron specimen to a CO2 atmosphere for
14 days.
To determine a desorbed portion of VCI in an atmo-
sphere of carbon dioxide, the cell was opened and, after
removal of the drop of the inhibitor, closed again and
filled with CO2 to p CO2 = 1 atm.
The Armco iron plate surface exposed to the corro-
sive medium was examined by diffuse reflection IR
spectroscopy. Spectra were recorded on a Perkin-Elmer
1720 Fourier spectrometer equipped with a Harrick

0033-1732/02/3801-0017$27.00 © 2002 MAIK “Nauka /Interperiodica”

18
+δ∆, deg
4 To interpret the experimental data, the specific fea-
2 be considered. The adsorption on a polycrystalline iron
3 T = 196, 273, 300, and 370 K. They revealed a low con-
0 at T ≥ 273 K adsorption involves dissociation. It was
10 20 30
τ, days
1
–4
– δ∆, deg
Fig. 1. Changes in the ellipsometric ∆ angle during the
adsorption and desorption of MEA on Armco iron (1) in air,
(2) in an atmosphere of CO2 , and (3) during the adsorption
of CO2 on a scattered iron film.
attachment for diffuse reflection in a range of 400–
4000 cm–1.
RESULTS AND DISCUSSION
The kinetics of the growth of an adsorbed film can
be determined from changes in ∆ (Fig. 1). Earlier, such
measurements revealed that MEA adsorbs on iron from
air to form a 2.5 to 3-nm film during the first two to
three days; its final thickness reaches 6 nm [5]. For
comparison purpose, we also determined the film thick-
nesses for other, more effective VCIs, namely,
IFKhAN-70 and amine A (3 and 6 nm, respectively)
[7, 8]. When VCIs were removed from the cell, the
films always became thinner, suggesting the desorption
of VCI from specimens. The ability of VCI to adsorb
irreversibly can be judged from the desorption factor
Kd, which is the fraction of the desorbed amount of VCI
(in percent). Thus, in air, Kd was found to be ≈80% for
MEA, 30% for IFKhAN-70, and 10% for amine A.
In an atmosphere of CO2 , the adsorption of these
VCIs changes. As can be illustrated with MEA (Fig. 1),
δ∆, in the initial segment of the curve increases rather
than decreases with time. Insofar as the same effect was
also observed in the adsorption of IFKhAN-70 or
amine A from a carbon dioxide atmosphere, it can obvi-
ously be attributed to a specific interaction of CO2 with
the iron surface. Indeed, such an unusual dependence of
∆ on time (δ∆ > 0) for film growth was also obtained in
ANDREEVA et al.
the absence of VCI (Fig. 1, curve 3). Carbon dioxide
adsorbs in such a way for nearly two days, whereupon
δ∆ begins to decrease.
tures of the adsorption of carbon dioxide on iron should
film was studied by volumetric and resistometric tech-
niques [9]. Along with measuring work function data at
tent of adsorbed CO2 . Molecular adsorption of carbon
dioxide occurs only at low temperatures (196 K), while
assumed in [10] that CO2 reacts with iron to give the
– –
following species: CO2 + CO 2 , CO 2 , CO + O, and C + O.
–
The CO 2 ion is detected on polycrystalline iron films
even at 120 K, while CO2 dissociates into CO + O at
180 K. The vibrational frequencies for carbon dioxide
chemisorbed on different faces of an iron single crystal
are reported in [11]. Bands at 1232 and 1634 cm–1 (car-
bonates) are observed on Fe(100) face and bands at
800, 1064/1160, and 1360/1600 cm–1 on Fe(111).
Using Fourier IR spectroscopy, we compared the
interactions of CO2 and MEA with the air-oxidized iron
surface under different conditions. Thus, the spectrum
of an iron specimen exposed to an atmosphere of CO2
for eight days shows, along with interference bands
caused by a small film thickness, bands from adsorbed
CO2 molecules (2213 cm–1) and from the carbonate ion
coordinated in a mono- and bidentate manner (Fig. 2b,
curve 4) [11, 12].
Comparing spectra of MEA itself (Fig. 2a, curve 1)
with those of the iron surface having adsorbed MEA,
one can easily see that the adsorption changes both
stretching and deformation vibrations in MEA and
gives rise to a new adsorption band at 2700–2000 cm–1
characteristic of amino salts [13]. When MEA adsorbs
from a carbon dioxide atmosphere, the spectrum con-
tains a number of weak bands at 1740–1680 cm–1,
which can be due to the formation of carbamates
(1739–1719, 1728–1722, 1722–1705, and 1691–
1683 cm–1) (Fig. 2a, curve 3). However, the adsorption
of MEA on a specimen preexposed to an atmosphere of
pure CO2 changes this spectral range only slightly, i.e.,
no carbamates are apparently formed.
On the other hand, the band of adsorbed CO2 mole-
cules, which is observed after an 8-day contact with the
gas, disappears once such a specimen interacts with
MEA in a carbon dioxide atmosphere. Its spectrum
shows, along with bands characteristic of adsorbed
MEA, new bands at 2140 and 1880 cm–1. Although they
can be interpreted ambiguously, one can suppose that
the band at 2140 cm–1 is related to physically adsorbed
molecules of carbon monoxide, while the band at
1880 cm–1 is either to a carbonyl complex on the elec-
trode surface or to an organic carbonate yielding from
PROTECTION OF METALS Vol. 38 No. 1 2002
 ADSORPTION OF MONOETHANOLAMINE ON IRON 19

(a)

3
2140.05 1644.75

2929.97 2873.94

1641.95
2

2128.85

1600.00

4000 3600 2800 2000 1600 1200 800 400

ν, cm –1
(b) 4
1015.38

2212.88
1655.94

1913.28
3165.26

1888.11
2145.65
3

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400
ν, cm –1

Fig. 2. IR spectra of (1) MEA, (2) iron in an atmosphere of MEA, (3) iron in an atmosphere of both MEA and CO2 , (4) iron pre-
liminarily exposed to an atmosphere of CO2 for eight days, and (5) iron preliminarily exposed to an atmosphere of CO2 for ten days
and then to an atmosphere of MEA.

the reaction of MEA with CO2 [12]. This assumption is
also supported by the previously mentioned formation
of CO in the reaction of CO2 with metallic iron [10, 11].
Our spectroscopic data offer a clearer view of how
the adsorption of CO2 changes the surface state of an
iron specimen. A model in which carbon dioxide is
assumed to form a homogeneous adsorbed layer with a
real refractive index 0.2 < n < 4.8 does not describe the
experimental dependence of δ∆ on the exposure time.
The change in δ∆ could be influenced by a variation of
the medium refractive index n0 as the cell is filled with

PROTECTION OF METALS Vol. 38 No. 1 2002

20 ANDREEVA et al.
+ δ∆, deg
2 rally oxidized iron is ≈2 nm.
2 The thicknesses of adsorbed VCI layers were calcu-
3 lated using a model of multilayer film. The refractive
5 with n0 , passes through homogeneous layers, and
1 reflects against the base: n0/N(inhibitor)/N(carbonate
1
14
0 0.2 0.4
+δψ, deg
Fig. 3. Changes in the ellipsometric ∆ and ψ angles of the
iron surface in an atmosphere of CO2 . The experimental
curve is given in solid line. The points (䊉) and (䊊) refer to
theoretical curves for Nf = 2.2 – 3.8i and Nf = 1.7 – 0.4i,
respectively. The numbers at the points indicate the days
when the corresponding measurements were performed.
CO2 . However, its value (1.0029, 1.0043, and 1.0083 at
p CO2 = 1.00, 14.84, and 28.58 atm, respectively [14]) is
virtually independent of the pressure, approximating to
the refractive index of air (1.000). Such changes in n0
are too little to affect δ∆ and cannot cause, by them-
selves, the reverse of its dependence in time.
In connection with this, attention should be given to
a study [15], in which the specific adsorption of carbon
monoxide on ruthenium was explained by a complex
refractive index of the adsorbed layer. We also consid-
ered the possibility of using such an interpretation of
ellipsometric data for the adsorption of CO2 and MEA.
For this purpose, the experimental and theoretical
adsorption curves of CO2 were drawn in δ∆ vs. δψ
coordinates (Fig. 3).
With time as a parameter, the experimental curve is
given in solid line (the numbers at the points denote the
days of the corresponding measurements) and shows a
breaks point indicating that the film changes its refrac-
tive index at this δψ value. Such changes are often
attributed to structural changes in films. The best theo-
retical fits are obtained on the assumption that CO2
adsorbs on the surface to give a film with Nf = 2.2 – 3.8i
(see Fig. 3, dotted curve to the left of the breaks point).
This film is covered by surface carbonate complexes
with Nf = 1.7 – 0.4i [15], which is shown by the theo-
retical curve to the right of the inflection point.
Thus, the supposition of a complex refractive index
of an adsorbed film provides a good agreement between
a theoretical model and experimental data. Based on
this model, our ellipsometric measurements revealed
that the thickness of an adsorbed film of CO2 on natu-
indices of N-containing VCIs usually fall in the range
of 1.5 to 1.6 [16]. A light beam comes from a medium
complexes)/N(CO2)/N(air-formed oxide)/N(base). The
thickness of the VCI film in an atmosphere of carbon
dioxide reaches 5 nm for MEA, 3 to 70 for IFKhAN-70,
and 7.5 nm for amine A.
VCIs adsorbed from an atmosphere of CO2 adhere
more strongly than those formed in air. The desorption
factor Kd was found to be ≈14% for MEA, 21% for
IFKhAN-70, and 7% for amine A, suggesting their
enhanced adsorption on the iron surface with pread-
sorbed CO2 .
CONCLUSIONS
(1) The conditions of the formation of adsorbed
MEA (and other VCIs) layers can play an important
part in steel protection from carbon dioxide corrosion.
According to the IR data, the iron surface preliminarily
exposed to CO2 provides an enhanced adsorption of
VCI.
(2) An increase in the angle phase shift during the
adsorption of CO2 on iron cannot be described by the
model of non-absorbing homogeneous layer, but the
problem is solved by using an optical model of a multi-
layer film with complex refractive indices. According
to this model, the thickness of an adsorbed layer equals
≈2 nm.
(3) The VCI layers adsorbed from an atmosphere of
CO2 differ insignificantly in thickness from those
formed in air, but the former adhere to the surface more
firmly.
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