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Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 566 (2004) 111121
www.elsevier.com/locate/jelechem
a,*
Programa de Ingeniera Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, San Bartolo Atepehuacan,
C.P. 07730 Mexico DF
b
Departamento Ingenieria Metalurgica, Facultad Quimica, UNAM, Ciudad Universitaria, 04510 Mexico DF
Received 7 March 2003; received in revised form 21 August 2003; accepted 14 November 2003
Abstract
The electrochemical behavior of 1-(2-ethylamino)-2-methylimidazoline (imidazoline), its precursor N-[3-(2-amino-ethylaminoethyl)]-acetamide (amide) and its derivative 1-(2-ethylamino)-2-methylimidazolidine (imidazolidine), is evaluated by using potentiodynamic polarization curves and electrochemical impedance spectroscopy, EIS, techniques in deaerated acid media to compare
their corrosion inhibition eciency. The experimental results suggest that imidazoline is a good corrosion inhibitor at dierent
concentrations whereas amide shows low eciency values; however, the properties of a corrosion inhibitor were not found in
imidazolidine. The reactivity of these compounds was analyzed through theoretical calculations based on density functional theory
(DFT) to explain the dierent eciencies of these compounds as corrosion inhibitors both in the neutral and protonated form. The
theoretical results indicate that imidazoline is the more ecient corrosion inhibitor because of its two very active sites (two nitrogen
atoms) and the plane geometry of the heterocyclic ring, thus promoting coordination with the metal surface.
2003 Elsevier B.V. All rights reserved.
Keywords: Amide; Corrosion inhibitors; Imidazoline; Imidazolidine; EIS; DFT calculations
1. Introduction
Nowadays the study of carbon steel corrosion phenomena has become an important industrial and academic topic [1]. The use of corrosion inhibitors is one of
the most eective methods to protect metal surfaces
against corrosion, especially in acid media [2,3].
The development of corrosion inhibitors is based on
organic compounds containing nitrogen, oxygen, sulfur
atoms, and multiple bonds in the molecules that facilitate adsorption on the metal surface [4]. The corrosion
inhibition eciency of organic compounds is related to
their adsorption properties. Adsorption depends on the
nature and the state of the metal surface, on the type of
corrosive medium and on the chemical structure of the
inhibitor [4]. Studies report that the adsorption of the
*
Corresponding author.
E-mail address: eochoa@imp.mx (E. Garca-Ochoa).
0022-0728/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2003.11.018
organic inhibitors mainly depends on some physicochemical properties of the molecule, related to its functional groups, to the possible steric eects and electronic
density of donor atoms; adsorption is suppose also to
depend on the possible interaction of p-orbitals of the
inhibitor with d-orbitals of the surface atoms, which
induce greater adsorption of the inhibitor molecules
onto the surface of carbon steel, leading to the formation of a corrosion protecting lm [1,5].
Dierent derivatives from imidazoline are employed
as steel corrosion inhibitors. Even though they have
been specially employed in the oil industry, only recently
have many studies been undertaken to understand how
they work [6]. The availability of sophisticated computational tools and electrochemical techniques and a
better understanding of corrosion inhibitors and their
mechanisms can now be achieved [79]. Ramachandran
et al. [10], Wang et al. [11], and Cruz et al. [12] have
published important papers concerning the molecular
112
2. Experimental procedure
Electrochemical tests were carried out with an electrochemical interface Solartron 1287 connected to a
frequency response analyzer (FRA) Solartron 1255B,
which was controlled by CorrWare and Zplot software.
The cell assembly consisted of a carbon steel working
electrode (WE), two-graphite counter electrodes (CE),
and a saturated calomel electrode (SCE) as the reference
electrode. The test material was carbon steel (composition, wt%: 0.18 C, 0.35 Mn, 0.17 Si, 0.025 S, 0.03 P, and
bal. Fe). Prior to exposure, it was polished with 400-grit
silicon carbide (SiC) paper wetted with deionized water,
then polished with 600-grit SiC paper wetted with ethanol (C2 H6 O), and then rinsed with C2 H6 O. Twice
distilled water and analytical reagent-grade hydrochloric
acid, 0.5 M HCl, were used to prepare the test solutions,
which were de-aerated by means of nitrogen during a
period of 45 min. The samples were exposed at static
conditions and room temperature.
Polarization curves were recorded potentiodynamically at a rate of 0.5 mV/s in the range )300 to +300 mV
versus the open circuit potential. Impedance was measured over a frequency range of 100 kHz10 mHz. All
the impedance experiments were carried out after dipping the working electrode into 0.5 M HCl solution
containing the inhibitor at the open-circuit potential,
Ecorr , with respect to a SCE reference electrode, with a
10 mV peak-to-peak perturbation. Two independent
experiments have been recorded for each inhibitor
concentration value.
N-[3-(2-amino-ethylamino-ethy)]-acetamide (amide)
and 2-methyl-N-(2-etihylamino)-imidazoline (imidazoline) were synthesized as follows. A solution of 10 ml of
xylene in glacial acetic acid solution (6.0 g, 0.1 mol) was
slowly added to a diethylenetriamine solution previously
heated at 50 C (10.3 g, 0.1 mol) in a closed system
under a nitrogen atmosphere and constant agitation.
The addition having been completed, the solution was
heated until the azeotropic distillation of xylene/water
produced amide (93%). After this stage was completed,
the reaction was progressively heated to 190 C at reduced pressure (3 mm Hg) until all the water was distilled. The product obtained was puried in a
chromatographic column of silica-gel using petroleum
ether as an eluant, imidazoline (91%) was obtained.
Scheme 1.
113
3. Computational details
Calculations were performed with the Gaussian 98
program [21]. Exchange and correlation calculations
were carried out with the functional hybrid B3LYP
[22,23] and the 6-311+G** orbital basis sets for all atoms. In all cases, total structure optimization together
with the vibrational analysis of the optimized structures
was carried out in order to determine whether they
corresponded to a maximum or a minimum in the potential energy curve. The frontier molecular orbitals,
namely, the highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital
(LUMO) and chemical reactivity were evaluated by
taking into account the Fukui indexes [24], which were
obtained by addition or subtraction of one electron,
N 1 and N 1.
Fig. 1. Corrosion rate against time for carbon steel in 0.5 M HCl
containing dierent concentrations of: (a) amide; (b) imidazoline; (c)
imidazolidine.
114
Rp
a:
1 jxCdl Rp
Fig. 2. Nyquist impedance plot for carbon steel in 0.5 M HCl containing dierent concentrations of: (a) amide; (b) imidazoline; (c) imidazolidine.
terpreted as an indication of the degree of inhomogeneity of the metal surface, corresponding to a small
depression of the double-layer capacitance semicircle,
and a has almost a constant value (0.9).
The impedance spectra of carbon steel in 0.5 M HCl
in the presence of the dierent inhibitors studied are
115
Rp inh Rp
100;
Rp inh
Table 1
Inhibition eciency for amide, imidazoline and imidazolidine
104 jcorr /A cm2
Ejcorr /%
r/s
Rp =X cm2
ERp /%
[Amide]/ppm
0
10
25
50
100
7.41
4.08
2.56
5.41
2.17
0
45
65
27
70
2.74
1.93
1.81
7.23
1.61
0.913
0.917
0.917
0.924
0.917
0.40
0.47
0.59
1.95
0.67
23
38
51
42
65
0
39
54
45
64
[Imidazoline]/ppm
0
10
25
50
100
7.41
4.10
2.77
2.21
1.92
0
44
63
70
74
2.74
1.76
1.54
1.40
1.16
0.913
0.905
0.909
0.896
0.905
0.40
0.48
0.60
0.73
0.76
23
43
62
82
103
0
46
62
71
77
0
)48
0
13
12
2.74
3.27
3.02
3.12
2.38
0.913
0.885
0.891
0.885
0.894
0.40
0.39
0.39
0.48
0.21
23
19
20
24
29
0
)21
)15
4
20
[Imidazolidine]/ppm
0
7.41
10
11.0
25
7.40
50
6.48
100
6.54
116
1
:
Rp Cdl
117
Fig. 6. The time constant against time for carbon steel in 0.5 M HCl
containing dierent concentrations of: (a) amide; (b) imidazoline; (c)
imidazolidine.
118
Fig. 7. Optimized B3LYP/6-311+G** structures of amide, imidazoline and imidazolidine and its more stable protonated forms. The NH hydrogen
bridge is also indicated. (For colours see online version of this article.)
119
Table 2
bond angles and dihedral in
Geometric parameters (bond length in A,
degrees) of amide, imidazoline and imidazolidine
Bond
Amide
Bond length/
A
C1N2
N2C3
C3C4
C4N5
N5C1
N5C6
C6C7
C7C8
Bond angle/
C1N2C3
N2C3C4
C3C4N5
C4N5C1
C4N5C6
Imidazoline
1.36
1.45
1.53
1.45
1.28
1.47
1.54
1.47
1.40
1.45
1.50
1.46
1.46
1.52
1.46
122.1
113.8
110
106.3
105.9
101.2
105.6
118.2
113.8
Dihedral angle/
C1N2C3C4
N2C1N5C4
94.4
12
13.4
Imidazolidine
1.47
1.48
1.56
1.48
1.50
1.47
1.54
1.48
103.7
106.5
104.1
105.7
113.7
26.7
36.27
N2
N5
N8
O
Charge distribution
Amide
Imidazoline
Imidazolidine
)0.640
)0.684
)0.845
)0.644
)0.528
)0.553
)0.837
)0.668
)0.595
)0.847
Fig. 8. Molecular orbital HOMO for the amide, imidazoline and imidazolidine. (For colours see online version of this article.)
120
Table 4
Calculated Fukui indices (nucleophilic)
Atom
N2
N5
N8
O
Fukui indices
Amide
Imidazoline
Imidazolidine
0.009
0.358
0.290
)0.038
0.252
0.271
0.090
0.035
0.477
0.084
5. Conclusions
The relative inhibition eciencies of the three compounds studied, including their protonated forms, in a
deaerated 0.5 M HCl solution is found to be in the
following order: imidazoline amide imidazolidine.
With respect to imidazolidine, this compound showed a
very low corrosion inhibition eciency at high concentrations, being able to promote the corrosion even at
low concentrations.
The electrochemical techniques of EIS and Tafel
extrapolation provided consistent results during the
evaluation.
The EIS data provided additional information with
regard to the protective nature of the inhibitor lm.
The reasons for which imidazoline was the better
corrosion inhibitor are, among others, the plane geometry of the heterocyclic ring, thus favoring adsorption
through the double iminic bond N@C. The iminic nitrogen seems to be directly involved in the coordination
of the cycle with the metal surface.
The experimental results could be corroborated with
that obtained by means of the rst principles theoretical
calculations using the computational methodologies of
quantum chemistry, showing an electronic density more
important on the iminic nitrogen N2 in the imidazoline,
with respect to the analogous nitrogen in amide and
imidazolidine. The inhibitor eciencies of these compounds seem to be determined by the conjugation of
electronic factors and molecular geometry.
Acknowledgements
J. Cruz, R. Martnez and E. Garca thank S. Cruz for
his observations and the Molecular Engineering Program from the Instituto Mexicano del Petr
oleo support
for this research, as well as the access to the supercomputer Silicon Graphics Origin 2000/48 of IMP. J.
Cruz gratefully acknowledges a grant from CONACYT.
The authors also wish to thank Pedro Rebollar for his
technical assistance.
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