ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces, 2009, Vol. 45, No. 1, pp. 46–53. © Pleiades Publishing, Ltd., 2009.
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INTRODUCTION
Acidic solutions are used in many industrial areas.
The most important application are acid pickling,
industrial acid cleaning, acid descaling, and oil well
acidising [1, 2]. Various methods are investigated to
protect the metals from corrosion in acidic solutions.
The studies of inhibitive effect of organic molecules are
progressive. Organic molecules rich in heteroatoms as
oxygen, sulfide and nitrogen provide the best protection
from metal corrosion [3–13]. Various organic com-
pounds used as inhibitors in industrial applications
blockade the metal surface by adsorbing on the metal
surface physically and chemically. Adsorbed inhibitors
prevent the occurrence of cathodic or anodic reactions
or both of them.
The adsorption effect of inhibitive molecules
depends on the structure of a molecule, corrosion envi-
ronment, the charge and nature of metal surface, and
the interaction type between metal surface and organic
molecule [7–11].
In recent studies, the search on compounds such as
azol, aminoacids, aminoesters, and pyridine, contain-
ing nitrogen and sulfur, are in progress [7–15]. Oguzie
et al. found methionine functions as an inhibitor of mild
steel corrosion in 0.5 M H
2
SO
4
solution. A mixed-
inhibiting mechanism is proposed for the protective
effect increased with concentration [16]. On the other
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The text was submitted by the authors in English.
hand, quantum chemical studies have been successfully
performed to link the corrosion inhibition efficiency
with molecular structure levels for some kinds of
organic compounds, e.g. imidazole [17], amides [18,
19], etc.
The aim of the present study was to examine inhib-
itive action of the afore mentioned inhibitors toward the
corrosion of iron in HCl solution and to investigate
structure and inhibitor relationship.
EXPERIMENTAL
Hydrocloric acid (HCl, Merch, 35–37%) methion-
ine, and tyrosine (Sigma Aldrich) were used as
received. Armco iron was used for the electrochemical
measurements. Iron electrode was armored in polyes-
ter, with a surface area of 0.785 cm
2
in contact with the
corrosive media. The electrode was first polished suc-
cessively with metallographic emery paper up to 600
grits. The electrode was then washed with distilled
water, degreased with acetone, washed using distilled
water again, and then inserted immediately into the
glass cell containing 250 ml of the electrolyte solution.
Polarization experiments were carried out in a con-
ventional three-electrode electrochemical cell. Pt elec-
trode was the counter one, Saturated Calomel Electrode
(SCE) was as the reference one, and iron electrode was
the working. Polarization curves were recorded by
changing the electrode potential from –250 to +250 mV
MOLECULAR AND SUPRAMOLECULAR
STRUCTURES AT THE INTERFACES
Inhibition Effects of Methionine and Tyrosine on Corrosion
of Iron in HCl Solution: Electrochemical, FTIR,
and Quantum-Chemical Study
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S. Zor, F. Kandemirli, and M. Bingul
Department of Chemistry, Kocaeli University, Kocaeli, 41380, Turkey
Received October 26, 2007
Abstract—The inhibiting effect of methionine and tyrosine on the corrosion of iron is researched electrochem-
ically in 0.1M HCl, Quantum chemical calculations were performed. The level of HF with the 6–311G(d,p)
basis set for methionine and tyrosine. Corrosion current density has been determined by polarization measures
and the inhibition effect was calculated. With an increase in the concentration of inhibitor, the effectiveness of
inhibition increases. The highest inhibition is determined as 97.8% at 100 ppm methionine. The effect of tem-
perature is determined by chronoammetric measures. Surface analysis is performed with FTIR spectroscopy.
Methionine and tyrosine adsorb on the iron surface according to Langmiur isotherm. The highest occupied and
the lowest unoccupied molecular orbital energy, as well as Mulliken and atomic charges with hydrogens
summed into heavy atoms of C, N, O, S atoms and of methionine, tyrosine, and protonated forms have been
examined.
PACS numbers: 81.65.Kn, 68.43.-h
DOI: 10.1134/S2070205109010079