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Electrochimica Acta 53 (2008) 3484–3492

Molecular simulation, quantum chemical calculations and

electrochemical studies for inhibition of mild steel by triazoles
K.F. Khaled ∗
Electrochemistry Laboratory, Chemistry Department, Faculty of Education, Ain Shams University, Roxy, Cairo, Egypt
Received 19 October 2007; received in revised form 5 December 2007; accepted 6 December 2007
Available online 15 December 2007

Abstract
The inhibition performance of three triazole derivatives on mild steel in 1 M HCl were tested by weight loss, potentiodynamic polarization
and electrochemical impedance spectroscopy (EIS). The adsorption behavior of these molecules at the Fe surface was studied by the molecular
dynamics simulation method and the quantum chemical calculations. Results showed that these compounds inhibit the corrosion of mild steel
in 1 M HCl solution significantly. Molecular simulation studies were applied to optimize the adsorption structures of triazole derivatives. The
iron/inhibitor/solvent interfaces were simulated and the charges on the inhibitor molecules as well as their structural parameters were calculated in
presence of solvent effects. Aminotriazole was the best inhibitor among the three triazole derivatives (triazole, aminotriazole and benzotriazole).
The adsorption of the inhibitors on the mild steel surface in the acid solution was found to obey Langmuir’s adsorption isotherm.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Molecular simulation; Quantum chemical calculation; Mild steel; Corrosion inhibition; Triazoles; EIS

1. Introduction occurred between the adsorbed molecules and metal surfaces. A

practical route to study these complex processes are computer
Iron and its alloys are widely used in many applications, simulations of suitable models. In recent years, the quantum
which have resulted in research into the corrosion resistance in chemistry computing method has become an effective way to
various aggressive environments. In efforts to mitigate electro- study the correlation of the molecular structure and its inhibi-
chemical corrosion, the primary strategy is to isolate the metal tion properties and much achievement was reached [3–8]. The
from corrosive agents. Among the different methods available, quantum chemistry computing method is often used to study
the use of corrosion inhibitors is usually the most appropriate the simple systems. For more complex systems, such as systems
way to achieve this objective [1]. Corrosion inhibition occurs involving a relatively large number of molecules, the quantum
via adsorption of the organic molecule on the corroding metal chemistry computing method is not suitable anymore. Khaled
surface following some known adsorption isotherms with the et al. [9] concluded that the quantum mechanical approach may
polar groups acting as the reactive centers in the molecules. well be able to foretell molecule structures that are better for cor-
The resulting adsorption film acts as a barrier that isolates rosion inhibition purposes if it is taken into account that (i) the
the metal from the corroding environment and efficiency of effect depends only on the inhibitor molecule properties and (ii)
inhibition depends on the mechanical, structural, and chemical everything else in its vicinity is uninvolved either with respect
characteristics of the adsorption layers formed under particular to competition for the surface or with respect to itself. Also, it
conditions. Although various experimental and theoretical tech- is clear that there is no general way for predicting compound
niques [2] have been developed to study the structural properties usefulness to be good corrosion inhibitor or find some univer-
of inhibitor molecules, little is known about the interactions that sal type of correlation. A number of excluded parameters that
should be involved as effect of solvent molecules, surface nature,
adsorption sites of the metal atoms or oxide sites or vacancies,
∗ Present address: Chemistry Department, Faculty of Science, Taif University,
competitive adsorption with other chemical species in the fluid
888 Hayia, Saudi Arabia. Tel.: +966550670425; fax: +9667255529. phase and solubility give at least simplified inspection. In this cir-
E-mail address: [email protected]. cumstance, a molecular simulation method is the best choice in

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.12.030
 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492 3485

an attempt to take into account the effect some of these excluded All compounds investigated were obtained from Aldrich
parameters. Chemical Co. They were put in the 1 M HCl (Fisher Scientific)
Molecular simulation has been used to investigate the forma- without pretreatment at concentrations of 10−4 , 10−3 , 5 × 10−3
tion of adsorption layers on metals and provide some valuable and 10−2 M.
information about the microstructures of the surfaces [10,11].
It maybe has a potential application towards the design and 2.2. Modeling calculations
development of organic corrosion inhibitors in corrosion field.
Molecular modeling has not been used widely for inhibition The molecular simulation product called MS Modeling 4.0
studies. Edwards et al. [12] investigated the adsorption of the oil was used to perform MS Modeling using the amorphous cell
field pipeline inhibitor oleic imidazoline using both molecular module which provides a comprehensive set of tools to per-
orbital and molecular mechanics methods whilst Fitzwater [13] form atomistic simulations on complex systems containing
employed molecular mechanics and molecular dynamics to sim- dense amorphous polymers, liquids and other non-crystalline
ulate the adsorption of both poly(acrylic acid) and poly(aspartic materials. Using these tools, one can construct systems con-
acid) on various CaCO3 surfaces. Ramachandran et al. [14] stud- taining bulk solvent and phases, perform structural analysis
ied the oleic imidazolines and reported on the use of molecular and property calculation to obtain estimates of experimen-
orbital calculations and subsequent molecular dynamics simu- tally measurable quantities and parameters, including estimates
lations to investigate the adsorption of 1,2-dimethylimidazoline of properties that are sometimes difficult or even impossi-
on an Fe(OH)3 (H2 O)2 surface. These methods were also used to ble to obtain in the laboratory. Also, the study was carried
simulate the adsorption of imidazolines to the Fe site of Fe2 O3 out using Dewar’s linear combinations of atomic orbitals–self-
[15], whilst in another article [16] molecular mechanics was consistent field–molecular orbital (LCAO–SCF–MO) [27,28].
employed to model the interactions between imidazolines and Semi-empirical PM3 method [29,30] with commercially avail-
Fe3 O4 surface. Further work on the adsorption of imidazolines able quantum chemical software HyperChem, Release 7.5 [31].
has been done by Wang et al. [17]. These workers designed three A full optimization of all geometrical variables without any sym-
imidazoline derivatives and their MO predictions as to inhibition metry constraint was performed at the restricted Hartree–Fock
efficiency were in good agreement with experimental corrosion (RHF) level [32,33]. It develops the molecular orbitals on a
studies. Triazole derivatives have been studied extensively in the valence basis set and also calculates electronic properties, opti-
literature as corrosion inhibitors for iron and copper in acidic mized geometries and total energy of the triazoles molecules.
media [18–22]. Relation between inhibition performance and Molecular structures were optimized to a gradient <0.01 in
quantum chemical calculations have been reported by several the solvent phase. As an optimization procedure, the built-in
authors [23–26]. Polak–Ribiere algorithm was used [34].
In this study, molecular simulation studies were performed
to simulate the adsorption of some triazole derivatives on iron 2.3. Weight loss measurements
surface and advance the understanding of interactions between
these molecules and iron surface. In essence molecular mechan- The experiments were carried out using mild steel (99.14%)
ics has been coupled with molecular dynamics to simulate specimens. The steel coupons of 3.0 cm × 1.0 cm × 0.20 cm
adsorption of triazoles with a clean (1 1 0) iron surface. In each with an exposed total area of 7.6 cm2 were used for weight loss
case interaction of a single, triazole derivatives molecule only measurement studies. A mild steel rod of the same composition
has been considered. The aim of this work is to investigate was mounted in Teflon with an exposed area of 0.28 cm2 used
the inhibition mechanism of these molecules on mild steel in for polarization and electrochemical impedance EIS measure-
an aerated solution of 1 M HCl, using chemical (weight loss) ments the coupons were polished, dried and weighted and then
electrochemical techniques such as electrochemical impedance suspended in a 100-cm3 aerated solution of 1 M HCl with and
spectroscopy (EIS) and potentiodynamic polarization as well as without the different concentrations of triazoles for exposure
molecular modeling of the corrosion system which allow deter- period (8 h). After the designated exposure to the test solution,
mining the possible anchoring site suitable for the inhibitor to the specimens were rinsed with distilled water, washed with
bond with steel surface. acetone to remove a film possibly formed due to the inhibitor,
dried between two tissue papers, and weighted again. Weight
2. Experimental loss measurements were made in triplicate and the loss of weight
was calculated by taking an average of these values.
2.1. Structure of triazole derivatives Prior to all measurements, the steel samples are abraded with
a series of emery paper up to 0000 grit size. The specimens are
The structure of the studied compounds are listed below: washed thoroughly with bidistilled water, degreased and dried
with acetone.

2.4. Electrochemical measurements

Electrochemical experiments were carried out using a con-

ventional electrolytic cell with three-electrode arrangement:
3486 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492

saturated calomel reference electrode (SCE), platinum mesh

as a counter electrode, and the working electrode (WE) had
the form of rod. The counter electrode was separated from the
working electrode compartment by fritted glass. The reference
electrode was connected to a Luggin capillary to minimize IR
drop. Solutions were prepared from bidistilled water of resis-
tivity 13 M cm, Prior to each experiment, the specimen was
polished with a series of emery papers of different grit sizes up
to 0000 grit size, polished with Al2 O3 (0.5 mm particle size),
washed several times with bidistilled water then with acetone
and dried using a stream of air. The electrode potential was
allowed to stabilize 30 min before starting the measurements.
The aggressive environment used was 1 M HCl solution with
different concentrations of triazole derivatives. All experiments
were conducted at 300 K. The exposed electrode area to the
corrosive solution is 0.28 cm2 .
Potentiodynamic polarization curves were obtained by
changing the electrode potential automatically from (−1100 to
+400 mV vs. SCE) at open circuit potential with scan rate of
3 mV s−1 .
EIS measurements were carried out in a frequency range of
100 kHz to 50 mHz with amplitude of 5 mV peak-to-peak using
ac signals at open circuit potential.
Measurements were performed with a Gamry Instrument
Potentiostat/Galvanostat/ZRA. This includes a Gamry Frame-
work System based on the ESA400, Gamry applications that
include DC105 for dc corrosion measurements, EIS300 for elec-
trochemical impedance spectroscopy measurements to calculate
the corrosion current and the Tafel constants along with a com-
puter for collecting the data. Echem Analyst 4.0 Software was
used for plotting, graphing and fitting data.

3. Results and discussions

3.1. Molecular modeling Fig. 1. The amorphous cell containing the iron substrate, the solvent molecule
and the triazole derivatives.
Here, molecular simulation studies were performed to sim-
ulate the adsorption structure of the triazole derivatives and was constructed using the amorphous cell module, the whole
press on the understanding of interactions between these tria- system was energy optimized and the possibility of triazoles
zoles and iron surface. Molecular structure of triazoles shows adsorption on the iron surface were simulated as in Fig. 1.
that it is likely for these molecules to adsorb on iron surface Fig. 1 shows that the close contact between aminotriazole is
by sharing the electrons of nitrogen atoms with iron to form more efficient than triazole and bensotriazole, respectively. The
coordinated bonds with nitrogen and ␲-electron interactions of charges on nitrogen atoms and other quantum chemical param-
the aromatic rings [35]. Both interactions can make it possi- eters for the three triazoles are presented in Fig. 2 and Table 1,
ble for the triazoles to form coordination bond with iron. The respectively. Fig. 2 shows the molecular orbital plots (Fig. 2c) as
adsorption progress of triazoles on iron surface is investigated
by performing molecular mechanics (MM) using MS Modeling Table 1
Software. As the three kinds of Fe surfaces (1 1 0, 1 0 0, 1 1 1), The calculated quantum chemical properties for triazole derivatives
Fe (1 1 1) and Fe (1 0 0) surfaces have relatively open struc-
Compound
tures while Fe (1 1 0) is a density packed surface and has the
most stabilization, so we choose Fe (1 1 0) surface to simulate Aminotriazole Triazole Benzotriazole
the adsorption process [36]. The periodic boundary conditions EHOMO (eV) −10.395 −9.309 −8.433
(PBC) are applied to the simulation cell. The size of simulation ELUMO (eV) 0.438 0.1057 −0.571
box is 23.0 Å × 23.0 Å × 19.79 Å. The force field used in the E (total energy) (kcal mol−1 ) −29341.47 −21824.7 −17724.14
current MM is COMPASS (condensed phase optimized molec- Maximum charge on N atoms −0.795 −0.51 −0.204
Dipole moment (D) 1.2 2.9 3.8
ular potentials for atomistic simulation studies) force field. All Molecular weight 84.8 69.07 119.13
molecules are energy optimized, iron surface and solvent layers
 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492 3487

Fig. 2. Structure of triazole derivatives, molecular orbital plots and the charge density distribution.

well as the charge density distribution (Fig. 2d) on the three tri- inhibitor) increases with lower dipole moments, with decreasing
azoles. It is worth noting that the charge density distribution on molecular size and with increasing nitrogen charge, respectively
aminotriazole are more intense than triazole and benzotriazole [38,39]. EHOMO is often associated with the electron donating
which enhance the possibility of aminotriazole to adsorb more ability of a molecule, whereas ELUMO indicates its ability to
strongly on iron surface than triazole and benzotriazole. It is con- accept electrons.
firmed that the more negative the atomic charges (Fig. 2b) of the As EHOMO is often associated with the electron donating abil-
adsorbed centre, the more easily the atom donates its electrons ity of the molecule, high values of EHOMO are likely to indicate
to the unoccupied orbital of metal [37]. So these negative atomic a tendency of the molecule to donate electrons to appropri-
charges indicated that nitrogen atoms are the active adsorption ate acceptor molecules with low energy and empty molecular
sites. The electronegativity of the nitrogen atoms and the con- orbital. From Table 1, it is clear that EHOMO in case of aminotria-
jugated ␲-electrons of the triazoles make it possible to form zole is higher than both triazole and benzotriazole which enhance
coordination bond with iron surface as can be seen in Fig. 1. the assumption that aminotriazole will adsorb more strongly on
The structure and electronic parameters can be obtained iron surface than both triazole and benzotriazole. Fig. 2 shows
by means of theoretical calculations using the computational the molecular orbital distribution of triazole compounds. The
methodologies of quantum chemistry. The geometry of the negative sign of the EHOMO indicates that the adsorption is
inhibitor in its ground state, as well as the nature of their molec- physisorption [39].
ular orbitals, HOMO (highest occupied molecular orbital) and
LUMO (lowest unoccupied molecular orbital) are involved in 3.2. Weight loss measurements
the properties of activity of inhibitors.
Table 1 shows the calculated quantum chemical properties for The corrosion parameters such as inhibition efficiency, EI (%)
triazole compounds, EHOMO (eV), ELUMO (eV), dipole moment, and corrosion rate (mg cm−2 h−1 ) at different concentration of
μ (D) total energy. In fact the adsorption power (efficiency of the triazoles in 1 M HCl at 300 K are presented in Table 2. As can
3488 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492

Table 2
Corrosion rate and efficiency data obtained from weight loss measurements for
mild steel in 1 M HCl solutions in absence and presence of different concentra-
tions from triazole derivatives
Concentration CR (mg cm−2 h−1 ) Coverage Ew (%)
(M) ()

0 2.15 0 0.0000
10−4 1.21 0.44 44.0000
Benzotriazole 10−3 0.98 0.54 54.0000
5 × 10−3 0.45 0.79 79.0000
10−2 0.27 0.87 87.0000
10−4 0.75 0.65 65.0000
10−3 0.47 0.78 78.0000
Triazole
5 × 10−3 0.23 0.89 89.0000
10−2 0.17 0.92 92.0000
10−4 0.60 0.72 72.0000
10−3 0.41 0.81 81.0000
Aminotriazole Fig. 3. Potentiodynamic polarization curves of the mild steel electrode in 1 M
5 × 10−3 0.13 0.94 94.0000
HCl without and with various concentrations from benzotriazole.
10−2 0.06 0.97 97.0000

be seen in Table 2, triazoles inhibit the corrosion of mild steel at

all concentrations in 1 M HCl. From the determined weight loss
values, the inhibition efficiencies, Ew (%) and coverage θ, were
calculated using the following equations [40]:
 
w
Ew (%) = 1 − × 100 (1)
w0
 
w
θ = 1− (2)
w0
where w0 and w are the weight loss in absence and in the
presence of triazoles, respectively. Inspection of these data
in Table 2, reveal that the inhibition efficiency increases
with increasing the concentration of triazoles, and aminotri-
azole is better inhibitor than both triazole and benzotriazole.
The corrosion inhibition can be attributed to the adsorption
of triazoles molecules at mild steel acid solution interface Fig. 4. Potentiodynamic polarization curves of the mild steel electrode in 1 M
. Adsorption of triazole derivatives can be explained on the basis HCl without and with various concentrations from triazole.
that adsorption of these compound are mainly via the nitrogen
atoms in the triazole ring, in addition to the availability of ␲-
electrons (by resonance structures) in the aromatic system. In
case of aminotriazole, the presence of an amino group enhances
its adsorption more than triazole itself, while the presence of
benzene ring in benzotriazole lower the efficiency of benzotri-
azole than triazole compound due to the electron withdrawing
ability of benzene ring.

3.3. Polarization measurements

Figs. 3–5 are showing typical polarization curves for the

inhibition characteristics of triazole derivatives. These curves
show anodic and cathodic polarization plots recorded on mild
steel electrode in 1 M HCl at various concentrations in the pres-
ence and absence of triazole derivatives. As would be expected
both anodic and cathodic reactions of mild steel electrode cor-
rosion were inhibited with the increase of triazole derivatives
concentration. This result suggests that the addition of tria- Fig. 5. Potentiodynamic polarization curves of the mild steel electrode in 1 M
zole derivatives reduces anodic dissolution and also retards the HCl without and with various concentrations from aminotriazole.
 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492 3489

Table 3
Electrochemical kinetic parameters obtained form potentiodynamic polarization curves shown in Figs. 3–5 for the mild steel electrode in 1 M HCl in different
concentrations of triazole derivatives
Concentration (M) icorr (␮A cm−2 ) −Ecorr (mV) −βc (mV dec−1 ) βa (mV dec−1 ) Ep (%)

0.00 489 450 117 114 0.00

10−4 381 459 119 100 22.1
Benzotriazole 10−3 320 458 128 100 34.6
5 × 10−3 130 465 130 102 73.4
10−2 80 469 137 108 83.6
10−4 331 459 138 119 32.3
10−3 280 468 139 120 42.7
Triazole
5 × 10−3 101 463 143 124 79.3
10−2 65 475 142 121 86.7
10−4 309 460 149 101 36.8
10−3 220 475 149 110 55.1
Aminotriazole
5 × 10−3 85 476 151 114 82.6
10−2 48 475 160 115 90.2

hydrogen evolution reaction. Table 3 shows the electrochemi- the impedance behavior of steel in 1 M HCl solutions are given
cal corrosion kinetic parameters, i.e., corrosion potential (Ecorr ), in Figs. 7–9.
cathodic and anodic Tafel slopes (βc , βa ) and corrosion current These curves show a typical set of Nyquist plots for mild steel
density icorr obtained by extrapolation of the Tafel lines. The in 1 M HCl in the absence and presence of various concentra-
calculated inhibition efficiency, Ep (%) are also reported from tions of triazole derivatives. It is clear from these plots that the
the following equation: impedance response of mild steel has significantly changed after
  the addition of triazole derivatives in the corrosive media. This
icorr
Ep (%) = 1 − 0 × 100 (3) indicates that the impedance of an inhibited substrate increases
icorr with increasing concentration of inhibitor in 1 MHCl. It is worth
where i0corr and icorr correspond to uninhibited and inhibited cur- noting that the change in concentration of triazole derivatives
rent densities, respectively. The best inhibition efficiency was did not alter the profile of the impedance behavior, suggest-
about 90.2% at concentration 10−2 M. It can be seen that by ing similar mechanism for the corrosion inhibition of mild steel
increasing inhibitor concentration, the corrosion rate decreased by triazole derivatives, Figs. 7–9. The impedance parameters
and inhibition efficiency Ep (%), increased. No definite trend derived from Figs. 7–9 are given in Table 4. The charge trans-
was observed in the shift of Ecorr values, in the presence of fer resistance Rct , double layer capacitance Cdl and inhibition
various concentrations of triazole derivatives, suggesting that efficiency EI (%) are calculated from the following equations:
these compounds behave as mixed-type inhibitors. Moreover,  
R0
these inhibitors cause no change in the anodic and cathodic Tafel EI (%) = 1 − ct × 100 (4)
slopes, indicating that the inhibitors are first adsorbed onto steel Rct
surface and therefore impedes by merely blocking the reaction
sites of iron surface without affecting the anodic and cathodic
reaction mechanism [40].

3.4. Electrochemical impedance measurements

Results obtained from EIS can be interpreted in terms of

the equivalent circuit of the electrical double layer shown in
Fig. 6, which was used previously to model the iron/acid inter-
face [41]. The effects of triazole derivatives concentrations on

Fig. 7. Nyquist plots for mild steel in 1 M HCl in absence and presence of
Fig. 6. Suggested equivalent circuit model for the studied system. different concentrations of benzotriazole.
3490 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492

Table 4
Electrochemical kinetic parameters obtained by EIS technique for mild steel in 1 M HCl in absence and presence of various concentrations of triazole derivatives
Concentration (M) Rs ( cm) Rct ( cm) Cdl (␮F cm−2 ) EI (%)

0.00 2.3 112.5 93.12

10−4 2.5 173.2 73.55 35.04
Benzotriazole 10−3 2.3 214.4 74.27 47.52
5 × 10−3 2.9 475.6 52.89 76.34
10−2 3.0 717.5 49.76 84.32
10−4 2.1 272.5 46.74 58.71
10−3 2.5 400.0 39.81 71.87
Triazole
5 × 10−3 2.1 637.0 39.49 82.33
10−2 1.9 1084.0 32.93 89.62
10−4 1.7 306.0 41.63 63.23
10−3 1.9 432.0 36.86 73.95
Aminotriazole
5 × 10−3 2.1 848.0 29.66 86.73
10−2 2.6 1446.0 24.69 92.21

zole derivatives, respectively, −Zimg is the maximum imaginary

component of the impedance.

The Nyquist plots obtained in the real system represent a
general behavior where the double layer on the interface of
metal/solution does not behave as a real capacitor. On the metal
side electrons control the charge distribution whereas on the
solution side it is controlled by ions. As ions are much larger than
the electrons, the equivalent ions to the charge on the metal will
occupy quite a large volume on the solution side of the double
layer [42]. From Table 4, it was clear that charge transfer resis-
tance Rct values were increased and the capacitance values Cdl
decreased with increasing inhibitors’ concentration. Decrease
in the capacitance, which can result from a decrease in local
dielectric constant and/or an increase in the thickness of the
electrical double layer, suggests that the inhibitor molecules act
Fig. 8. Nyquist plots for mild steel in 1 M HCl in absence and presence of by adsorption at the metal/solution interface [43].
different concentrations of triazole. The addition of triazole derivatives provides lower Cdl
values, probably as a consequence of replacement of water
 1 molecules by triazoles at the electrode surface. Also the
f (−Zimg )= (5)
2πCdl Rct inhibitor molecules may reduce the capacitance by increasing
where R0ct and Rct are the charge transfer resistances in 1 M the double layer thickness according to the Helmholtz model
HCl solution without and with different concentrations of tria- [44]:
εε0 A
Cdl = (6)
δ
where ε is the dielectric constant of the medium, ε0 is the vacuum
permittivity, A is the electrode surface area and δ is the thickness
of the protective layer. The value of Cdl is always smaller in the
presence of the inhibitor than in its absence, as a result of the
effective adsorption of the triazole derivatives.
The results obtained from EIS measurements are in good
agreement with that obtained from potentiodynamic polarization
and weight loss measurements.

3.5. Adsorption isotherm

It has been assumed that organic inhibitor molecules establish

their inhibition action via the adsorption of the inhibitor onto
Fig. 9. Nyquist plots for mild steel in 1 M HCl in absence and presence of the metal surface. The adsorption processes of inhibitors are
different concentrations of aminotriazole. influenced by the chemical structures of organic compounds, the
 K.F. Khaled / Electrochimica Acta 53 (2008) 3484–3492 3491

nature and surface charge of metal, the distribution of charge in The obtained plots of the inhibitors is linear with corre-
molecule and the type of aggressive media. lation coefficient higher than 0.99. The intercept permits the
In general, two modes of adsorption can be considered. The calculation of the equilibrium constant b which are 9980.1,
proceeding of physical adsorption requires the presence of elec- 9615.38 and 2898.5 M−1 for aminotriazole, triazole and benzo-
trically charged metal surface and charged species in the bulk triazole, respectively. The values of b which indicate the binding
of the solution. Chemisorption process involves charge shar- power of the inhibitor to the steel surface can lead to calculate
ing or charge transfer from the inhibitor molecules to the metal the adsorption energy. Values of Gads = −14.323, −14.283,
surface. The presence, with a transition metal, having vacant, −12.984 kJ mol−1 .
low-energy electron orbital, of an inhibitor molecule having rel- The negative value of Gads means that the adsorption of
atively loosely bound electrons or heteroatoms with lone-pair triazoles on mild steel surface is a spontaneous process, and
electrons facilitates this adsorption [45,46]. furthermore the negative values of Gads also show the strong
Assuming the corrosion inhibition was caused by the adsorp- interaction of the inhibitor molecule onto the mild steel surface
tion of triazole derivatives, and the values of surface coverage [48,49].
(θ) for different concentrations of inhibitors in 1 M HCl were Generally, values of Gads around −20 kJ mol−1 or lower are
evaluated from weight loss measurements from Eq. (2). consistent with the electrostatic interaction between the charged
Adsorption isotherms are very important in determining the molecules and the charged metal (physisorption). Those more
mechanism of organic electrochemical reactions. The most fre- negative than −40 kJ mol−1 involve charge sharing or transfer
quently used adsorption isotherms are Langmuir, Temkin and from the inhibitor molecules to the metal surface to form a coor-
Frumkin. So several adsorption isotherms were tested for the dinate type of bond (chemisorption) [50,51]. For investigated
description of adsorption behaviour of studied compounds and aminotriazole inhibitor, one can see that the calculated Gads
it is found that adsorption of triazoles on mild steel surface in values, equals −14.323 kJ mol−1 , indicating, that the adsorp-
HCl solution obeys the Langmuir adsorption isotherm given by tion mechanism of the aminotriazole on mild steel in 1 M HCl
the following equations [47]: solution was typical of physisorption.
Cinh 1
= + Cinh (7) 4. Conclusions
θ b
 
1 Gads The following results can be drawn from this study:
b= exp − (8)
55.5 RT
• This study is unique in that the simulation included the pres-
Cinh is the inhibitor concentration, θ is the fraction of the surface
ence of solvent molecules; traditionally the solvent has been
covered, b is the adsorption coefficient and Gads is the standard
ignored to save computational time. The work is a good exam-
free energy of adsorption.
ple of how computational chemistry can not only be used as
Fig. 10 shows the dependence of the fraction of the surface
a screening tool to test several different molecules, but more
covered C/θ as a function of the concentration (C) of triazole
importantly to develop an understanding on the behavior of
derivatives.
different systems as a function of their molecular character-
It should be explained that other adsorption isotherms
istics. This reduces the number of experiments required and
(Frumkin and Temkin) were checked and Langmuir adsorption
allows one to do more intelligent experiments.
isotherm is the best approximate between them. This is why the
• Molecular modeling techniques incorporating molecular
assumption is true for Langmuir adsorption isotherm.
mechanics and molecular dynamics can be used to simu-
late the adsorption from 1 M HCl solution of a single target
molecule from triazole derivatives on iron (1 1 0) surface.
• The quantum mechanical approach may well be able to fore-
tell molecule structures that are better for corrosion inhibition.
• Double layer capacitances decreases with respect to the blank
solution when these inhibitors are added. This fact may be
explained on the basis of adsorption of these inhibitors on the
steel surface.
• In determining the corrosion rates, electrochemical studies
and weight loss measurements give similar results.
• Triazole derivatives can be used as corrosion inhibitors for
mild steel in 1 M HCl.

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