(Wuli Huaxue Xuebao)

October

Acta Phys. -Chim. Sin. 2013, 29 (10), 2221-2231

[Article]

doi: 10.3866/PKU.WHXB201307301

2221
www.whxb.pku.edu.cn

1,2,*

(1 , 650091;
:

, 650224)

(EIS)(2-

(HP) 2-(MP)) 1.05.0 molL 1 HCl (CRS). : HP MP

1.0 molL1 HCl , Langmuir .
, . ((K),
(G0))((Ea)(A)(k)(B)),
. , MP HP ; EIS ,
. MP>HP. ,
MP HP , .
:

; 2-; 2-; ; ; ;

O646

Inhibition Effect of Pyrimidine Derivatives on the Corrosion of

Steel in Hydrochloric Acid Solution
LI Xiang-Hong1,2,*

XIE Xiao-Guang1

(1School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. China;
2
Faculty of Science, Southwest Forestry University, Kunming 650224, P. R. China)
Abstract: The inhibition effect of two pyrimidine derivatives, 2- hydroxypyrimidine (HP) and 2mercaptopyrimidine (MP), on the corrosion of cold rolled steel (CRS) in 1.05.0 molL 1 HCl is investigated
by mass loss, potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and
quantum chemical calculations. The results show that HP and MP are both good inhibitors of corrosion of
CRS in 1.0 molL 1 HCl solution. The adsorption of these inhibitors onto the CRS surface obeys the Langmuir
adsorption isotherm. Inhibition efficiency increases with inhibitor concentration, and decreases with
hydrochloric acid concentration. The thermodynamic parameters of adsorption (adsorption equilibrium
constant (K) and adsorption free energy (G0)) and kinetic parameters of corrosion (apparent activation
energy (Ea), pre- exponential factor (A), corrosion rate constant (k), and kinetic reaction constant (B)) are
also calculated. Based on these parameters, the mechanism of inhibition is discussed. Potentiodynamic
polarization curves show that HP and MP act as mixed-type inhibitors. EIS exhibit one capacitive loop, and
the charge transfer resistance increases with inhibitor concentration. The results of quantum chemical
calculations indicate that MP exhibits higher adsorptive ability than HP, which is in good agreement with the
experimental data.
Key Words: Corrosion inhibitor; 2-Hydroxypyrimidine; 2-Mercaptopyrimidine; Steel;
Hydrochloric acid; Adsorption; Quantum chemical calculation
Received: May 22, 2013; Revised: July 25, 2013; Published on Web: July 30, 2013.

Corresponding author. Email: xianghong-li@163.com; Tel: +86-871-63863377.

The project was supported by the National Natural Science Foundation of China (51361027).
(51361027)

Editorial office of Acta Physico-Chimica Sinica

2222

Vol.29

Acta Phys. -Chim. Sin. 2013

1 Introduction
N-heterocyclic compounds are considered to be the most effective corrosion inhibitors for metals in acid media.1 They exhibit inhibition by adsorption on the metal surface, and the adsorption takes place through nitrogen, oxygen, and sulfur atoms, as well as those with triple or conjugated double bonds or
aromatic rings in their molecular structures. A stronger coordination bond formed between inhibitor and metal is always related to good inhibitive performance; as consequence, inhibition efficiency should increase in the order: O<N<S<P.2 If a
substitution polar group (NH2, OH, SH, etc.) is added
to the N-heterocyclic ring, the electron density of N-heterocyclic ring is increased, and subsequently, it facilitates the adsorption ability.3
As an important kind of N- heterocyclic compound, pyrimidine derivatives whose molecules possess the pyrimidine ring
with two N heteroatoms could also be deemed as good potential inhibitors. 2- Mercaptopyrimidine (MP) was reported as a
good corrosion inhibitor for non-ferrous metals in acid media,
such as zinc in HCl solution,4 aluminium in HCl solution,5 copper in H2SO4 solution.6 Besides non-ferrous metals, the inhibition effects of pyrimidine derivatives on the steel corrosion in
acid media were studied. In 1993, Zucchi et al.7 investigated
the corrosion inhibition of steel in H2SO4 solution by some pyrimidine derivatives. In 2001, Wang8 reported the corrosion inhibition by MP for steel in H3PO4 solution, and the maximum
inhibition efficiency () in 3.0 molL 1 H3PO4 solution is 98%
at 10.0 mmolL 1. According to our recent work,9 2-aminopyrimidne (AP) also acts as a good corrosion inhibitor on the corrosion of steel in 1.0 molL 1 HCl solution, and the is 92.4%
at 20 C when the concentration of AP is 10.0 mmolL1. However, another pyrimidine derivative of uracil (Ur) exhibits poor
inhibitive ability for steel in H3PO410 and H2SO411 solutions.
Through these studies, the efficiency of pyrimidine compound
mainly depends on the substitution group in the pyrimidine
ring. Accordingly, there is a great need to obtain the correlation
between the molecular structure and inhibitive performance.
Quantum chemical calculation has been proven to be a very
useful method in corrosion inhibitor studies.12 14 Using quantum chemical calculation, the theoretical parameters of inhibitor molecule can be obtained, and then, theoretically speaking,
the inhibitive mechanism can be directly accounted for the
chemical reactivity of the compound under study. It is found
that the inhibition activity of a given inhibitor is directly correlated with the theoretical parameters including the highest occupied molecular orbital energy (EHOMO), the lowest unoccupied
molecular orbital (ELUMO), dipole moment (), atomic charge,
and Fukui inces.15 However, many quantum parameters about
organic inhibitors are calculated in gas phase. In fact, acid inhibitors are used in acidic water solutions, and they could be
protonated. Thus, in the field of theoretical calculation of acid
inhibitors, the solvent effect and the protonated inhibitor molecules should be taken into account.

In this paper, the inhibition effect of two pyrimidine derivatives of 2-hydroxypyrimidine (HP) and MP on the corrosion of
cold rolled steel (CRS) in 1.0 molL 1 HCl solution is studied
using weight loss, potentiodynamic polarization curves, and
electrochemical impedance spectroscopy (EIS) methods. The
adsorption isotherm of inhibitor on steel surface and the standard adsorption free energy (G0) are obtained. Quantum
chemical calculation of density functional theory (DFT) including the solvent effect is applied to elucidate the relationship between the inhibitor molecular structure and inhibition efficiency. The difference in inhibition performance between neutral
inhibitor molecule and protonated inhibitor molecule is further
investigated. It is expected to get general information on the adsorption and inhibition effect of pyrimidine derivatives on steel
in HCl solution.

2 Experimental
2.1 Materials and inhibitors
Weight loss and electrochemical tests were performed on
cold rolled steel with the following composition: 0.05% C,
0.02% Si, 0.28% Mn, 0.023% P, 0.019% S, and the remainder
Fe. Two pyrimidine derivatives of 2- hydroxypyrimidine (HP,
C4H4N2O) and 2- mercaptopyrimidine (MP, C4H4N2S) were obtained from Shanghai Chemical Reagent Company of China.
Fig.1 shows the molecular structures of HP and MP, and they
are of good solubility in water. The aggressive solution of 1.0
mol L 1 HCl solution was prepared by dilution of AR grade
37% HCl with distilled water. The concentration range of inhibitor is 1.010.0 mmolL1.
2.2 Weight loss measurements
The CRS rectangular coupons of 2.5 cm 2.0 cm 0.04 cm
were abraded by a series of emery paper (grade 320-500-800)
and then washed with distilled water, degreased with acetone,
and finally dried at room temperature. After weighing using
digital balance with sensitivity of 0.1 mg, the specimens were
immersed in glass beakers containing 250 mL 1.0 molL1 HCl
solution without and with different concentrations of inhibitor
using glass hooks and rods. The temperature was controlled at
(25.00.1) C using a water thermostat bath. All the aggressive
acid solutions were open to air without bubbling. After immersion for 6 h, the specimens were taken out, washed with bristle
brush under running water to remove the corrosion product,
dried with a hot air stream, and re-weighed accurately. In order
to get good reproducibility, experiments were carried out in

Fig.1

Chemical molecular structures of two

pyrimidine derivatives

(a) 2-hydroxypyrimidine (HP); (b) 2-mercaptopyrimidine (MP)

No.10

LI Xiang-Hong et al.: Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid

triplicate. The average mass loss of three parallel CRS sheets

was obtained, and then the inhibition efficiency (w) was calculated.1
2.3 Electrochemical measurements
Electrochemical experiments were carried out in the conventional three-electrode system with a platinum counter electrode
(CE) and a saturated calomel electrode (SCE) coupled to a fine
Luggin capillary as the reference electrode. In order to minimize Ohmic contribution, the Luggin capillary was placed
close to the working electrode (WE) which was in the form of
a square CRS embedded in polyvinyl chloride (PVC) holder using epoxy resin so that the flat surface was the only surface in
the electrode. The working surface area was 1.0 cm 1.0 cm,
and prepared as described above (Section 2.2). The electrode
was immersed in test solution at open circuit potential (OCP)
for 2 h to be sufficient to attain a stable state before measurement. All electrochemical measurements were carried out at
25 C using PARSTAT 2273 advanced electrochemical system
(Princeton Applied Research).
The potential of potentiodynamic polarization curves was increased at 0.5 mVs 1 and started from a potential of 250 mV
to +250 mV (versus OCP). Inhibition efficiency (p) was calculated through the corrosion current density (icorr) values.1 Electrochemical impedance spectroscopy (EIS) was carried out at
OCP over a frequency range of 10 mHz 100 kHz using a 10
mV root mean square (RMS) voltage excitation. The number
of points per decade is 30. Inhibition efficiency (R) was estimated using the charge transfer resistance (Rt) values.1
2.4 Quantum chemical calculations
Quantum chemical calculations were performed with DMol3
numerical based DFT in Materials Studio 4.1 software from
Accelrys Inc.16 Geometrical optimizations and frequency calculations were carried out with the generalized gradient approximation (GGA) functional of Becke exchange plus Lee-YangParr correlation (BLYP)17 in conjunction with double numerical
plus d-functions (DND) basis set.18 Fine convergence criteria
and global orbital cutoffs were employed on basis set definitions. Considering the solvent effects, all the geometries were
re-optimized at the BLYP/DND level by using COSMO (conductor- like screening model)19 and defining water as the solvent. Through the frequency analysis, it is found that all optimized species have no imaginary frequencies.

3 Results and discussion

3.1 Effect of pyrimidine derivatives on inhibition
efficiency
Fig.2 shows the relationship between inhibition efficiency
(w) values obtained from weight loss method and the concentrations of HP and MP in 1.0 molL 1 HCl solution at 25 C.
Apparently, w increases with the increase of the inhibitor concentration. This behavior is due to the fact that the adsorption
coverage of inhibitor on steel surface increases with the inhibitor concentration. For both pyrimidine compounds, when the

2223

Fig.2 Relationship between inhibition efficiency (w) and

concentration of inhibitor (c) in 1.0 molL1 HCl solution at 25 C
weight loss method, immersion time: 6 h

concentration reaches about 5.0 mmol L 1, w reaches certain

value and changes slightly with a further increase in the inhibitor concentration. At 10.0 mmolL1, the maximum w is 87.2%
for HP and 95.4% for MP, which indicates that two studied pyrimidine compounds act as good corrosion inhibitors for CRS
in 1.0 molL 1 HCl solution. Inhibition efficiency follows the
order of MP>HP. It is evident that the difference in inhibition
efficiency of HP and MP was related to the presence of OH
and SH on the pyrimidine ring.
3.2 Adsorption isotherm and adsorption free energy
(G0)
Fundamental information on the adsorption of inhibitor on
metal surface can be obtained by the adsorption isotherm.
Several isotherms such as Frumkin, Langmuir, Temkin,
Freundlich, Bockris-Swinkels, and Flory-Huggins isotherms
are employed to fit the experimental data. It is found that the
adsorption of the studied inhibitors on steel surface obeys
Langmuir adsorption isotherm equation:11
c = 1 +c
(1)
K
where c is the concentration of inhibitor, K the adsorption equilibrium constant, and is the surface coverage and calculated
by the ration w.
The straight lines of c/ against c for two inhibitors are
shown in Fig.3, and the corresponding linear regression parameters are listed in Table 1. Both straight lines have very good
linear fit with the linear regression coefficients (r) up to 0.99
and the slopes also very close to 1.0, which suggests that the
adsorption of the pyrimidine inhibitors on steel surface obeys
Langmuir adsorption isotherm. Also, the adsorptive equilibrium constant (K) follows the order: MP>HP.
Generally, large value of K means the more stability of adsorptive inhibitor on metal surface, and then the better inhibition performance of a given inhibitor. This is in good agreement with the values of w obtained from Fig.2.
The adsorption equilibrium constant K is related to the standard adsorption free energy G0 according to the following
equation:20
0
K = 1 exp -G
(2)
55.5
RT

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Acta Phys. -Chim. Sin. 2013

Fig.3 Langmuir isotherm adsorption modes of HP and MP

on the CRS surface in 1.0 molL1 HCl solution at 25 C
from weight loss measurement
Table 1 Parameters of the straight lines of c/c and adsorption
free energy (G0) in 1.0 molL1 HCl solution at 25 C
Inhibitor

Slope

K/(Lmol1)

G0/(kJmol1)

HP

0.9999

1.04

9.1910

26.9

MP

0.9997

0.97

1.22103

27.6

weight loss method, immersion time: 6 h; r: linear correlation coefficient

where R is the gas constant (8.314 JK 1 mol 1), T is the absolute temperature (K), and the value 55.5 is the concentration of
water in solution in mol L 1.20 The G0 values are calculated
and also given in Table 1. Generally, values of G0 up to 20 kJ
mol 1 are consistent with the electrostatic interaction between
the charged molecules and the charged metal (physisorption)
while those more negative than 40 kJmol 1 involve sharing
or transfer of electrons from the inhibitor molecules to the metal surface to form a co-ordinate type of bond (chemisorption).21
In the present study, the value of G0 is found to be within the
range from 40 to 20 kJmol 1; probably means that the adsorption of each pyrimidine inhibitor on steel surface contains
both physical adsorption and chemical adsorption. It may be assumed that adsorption occurs firstly through the physical forces, and then the removal of water molecules from the surface is
accompanied by chemical interaction between the metal surface and inhibitor.22
3.3 Effect of temperature
Temperature is an important kinetic factor that influences
the corrosion rate of metal and modifies the adsorption of inhibitor on electrode surface. In order to study the effect of temperature on the corrosion inhibition, experiments were conducted at 25 to 50 C at an interval of 5 C. Effect of temperature
on inhibition efficiency (w) of 10.0 mmol L 1 inhibitor is
shown in Fig.4. Clearly, inhibition efficiency of either HP or
MP fluctuates slightly with the experimental temperature. At
50 C, w is 83.2% for HP and 95.3% for MP, which reflects
that the adsorption film of pyrimidine inhibitor is more stable
even at higher temperature.
According to Arrhenius equation, the natural logarithm of
the corrosion rate (lnv) is a linear function with 1/T:11
-E
(3)
ln v = a + ln A
RT

Fig.4

Relationship between inhibition efficiency (w) and

temperature in 1.0 molL1 HCl solution
weight loss method, immersion time: 6 h

where Ea and A represent apparent activation energy and preexponential factor, respectively. The corrosion rate (v) was calculated from the following equation:
v= W
(4)
St
where W is the average mass loss of three parallel CRS sheets
(g), S is the total area of one CRS specimen (m2), and t is the
immersion time.
The linear regressions between ln v and 1/T were calculated,
and the parameters are given in Table 2. Fig.5 shows the Arrhenius straight lines of lnv vs 1/T for the blank and different inhibitors. All the linear regression coefficients (r) are very close
to 1, which indicates that the corrosion of steel functioning
with temperature follows Arrhenius equation.
Kinetic parameter of apparent activation energy (Ea) is important to study the inhibitive mechanism. Compared with uninhibited solution, the increase of Ea in inhibited solution may
be interpreted as the physical adsorption.22 In visa, a drop in Ea
Table 2

Parameters of the straight lines of lnv1/T in

1.0 molL1 HCl solution

Inhibitor

Ea/(kJmol1)

A/(gm2h1)

0.9972

60.4

2.841011

HP

0.9971

70.8

2.231012

MP

0.9811

64.1

6.181010

Fig.5 Arrhenius plots related to the corrosion rate of CRS for

various inhibitors in 1.0 molL1 HCl solution

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LI Xiang-Hong et al.: Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid

with respect to the uninhibited solution probably indicates chemisorption.23 However, the criteria of Ea can not be taken as decisive due to competitive adsorption with water whose removal
from the surface requires also some activation energy.24 According to Solmaz et al.,25 the adsorption phenomenon of an organic molecule is not considered as a mere physical or mere chemical adsorption phenomenon. In addition, Moretti et al.26 proposed that the adsorption criteria of chemisorption or physisorption could be decided by other adsorption parameters. According to the adsorption parameter of G0 mentioned above in
Section 3.2, the adsorption of oxime inhibitor would involve
both physical and chemical processes. Thus, in the present
study, the value of Ea in the presence of each inhibitor is higher
than that in the uninhibited HCl solution, which does not necessarily mean that the adsorption of inhibitor is mere the physical
adsorption.27 In a word, both physical adsorption and chemical
adsorption would be considered simultaneously for the adsorption of either HP or MP.
According to Eq.(3), it can be seen that the lower A and the
higher Ea lead to the lower corrosion rate (v) and exhibit inhibition performance. After adding HP to the acid media, the value
of A is higher than that in uninhibited solution. Accordingly,
the decrease in corrosion rate after adding inhibitor to acid media is mostly caused by the increase of Ea. On the other hand,
in the presence of MP, the decrease in corrosion rate is mostly
caused by the combination of the increase of Ea and the increase of A. In a word, the effect of A on the corrosion rate
needed to be considered, especially for MP inhibitor.
3.4 Effect of immersion time
The immersion time is another important parameter in assessing the stability of inhibitive behavior, so it is necessary to
evaluate the inhibition efficiency for a long immersion time. In
the present study, effect of immersion time (1156 h) on corrosion inhibition of 10.0 mmolL1 HP and 10.0 mmolL1 MP in
1.0 mol L 1 HCl solution at 25 C was investigated using
weight loss method. Dependence inhibition efficiency (w) on
the immersion time (t) is shown in Fig.6. For both HP and MP,
inhibition efficiency is higher than 60% when the immersion
time is only 1 h, which indicates that the adsorption rate of pyrimidine inhibitor adsorbing on the steel surface is relatively
high. Also, the changed rule of w for two inhibitors is similar.
w firstly increases with immersion time from 1 to 6 h, and
then fluctuates slightly (<4% ) with prolonging time to 156 h.
The reasons could be attributed to the adsorptive film of inhibitor that rests upon the immersion time. The adsorptive film
reaches more compact and uniform along with prolonging immersion time (1 6 h), and then the adsorptive film becomes
the relative saturated state within 6156 h.
3.5 Effect of acid concentration
In order to study the effect of acid concentration on the corrosion of steel in the presence of 10.0 mmolL 1 inhibitor, dependence of inhibition efficiency (w) on the concentration of
HCl solution (1.05.0 molL1) at 25 C is shown in Fig.7 (im-

2225

Fig.6 Relationship between inhibition efficiency (w) and

immersion time (t) in 1.0 molL1 HCl solution at 25 C
weight loss method

mersion time is 6 h). For either HP or MP inhibitor, w decreases almost linearly with the HCl concentration. In 5.0 molL 1
HCl solution, w values are reduced to 55.6% and 60.4% for
HP and MP, respectively. At same acid concentration solution,
inhibition performance still follows the order: MP>HP.
It is found that the corrosion rate (v) against the molar concentration of acid (C) obeys the kinetic expression reported by
Mathur and Vasudevan:29
lnv=lnk+BC
(5)
where k is the rate constant, and B is the reaction constant. The
straight lines of lnv versus C are shown in Fig.8, and the corresponding kinetic parameters are listed in Table 3.
The rate constant of k means the corrosion ability of acid for
metal.29 Inspection of Table 3 reveals that in the presence of pyrimidine derivatives, there is a drop of k to more extent, which
indicates that the steel corrosion is retarded by the inhibitors of
HP and MP. Furthermore, the value of k for MP is lower than
that for HP, which confirms that the inhibition performance of
MP is more superior to that of HP. According to Eq.(5), B is
the slope of the line lnvC, thus B reflects the changed extent
of v with the acid concentration.29 It is observed that the value
of B in the presence of inhibitor is larger than that of blank
HCl solution, which suggests that the changed extent of corrosion rate with acid concentration in inhibited acid is larger than

Fig.7

Relationship between inhibition efficiency (w) and

acid concentration (C) at 25 C
weight loss method, immersion time: 6 h

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Acta Phys. -Chim. Sin. 2013

Fig.8

Straight lines of lnv versus C at 25 C

immersion time: 6 h

Table 3

Parameters of the linear regression between lnv and C

for the corrosion of steel in HCl solution
k/(gm2h1)

B/(gm2h1Lmol1)

0.9945

0.46

0.73

0.9944

0.15

0.91

Inhibitor

0.9974

HP
MP

4.59

0.39

that in uninhibited acid. In addition, the value of B for MP is

higher than that for HP, which indicates that the changed degree of corrosion rate with acid concentration for MP is greater
than that for HP.
3.6 Potentiodynamic polarization curves
Potentiodynamic polarization curves of CRS in 1.0 molL 1
HCl solution in the presence of different concentrations of HP
and MP at 25 C are shown in Fig.9. Obviously, the presence
of each pyrimidine compound causes a remarkable decrease in
the corrosion rate, i.e., shifts both anodic and cathodic curves
to lower current densities. In other words, both cathodic and anodic reactions of CRS electrode are drastically inhibited, which
indicates that the pyrimidine compounds act as mixed-type inhibitors.
The potentiodynamic polarization parameters including corrosion current densities (icorr), corrosion potential (Ecorr), cathodic Tafel slope (bc), anodic Tafel slope (ba), and inhibition efficiency (p) are listed in Table 4. It can be seen from Table 4
that icorr decreases sharply with the increase of the concentration of each pyrimidine inhibitor. In the presence of the inhibitor concentration of 10.0 mmolL 1, the corrosion current density decreases from 319.4 Acm 2 to 31.6 and 11.5 Acm 2
in the case of HP and MP, respectively. Correspondingly, p increases with the inhibitor concentration, due to the increase in
the blocked fraction of the electrode surface by adsorption. At
10.0 mmol L 1 inhibitor concentration, inhibition efficiency
(p) reaches up to a maximum of 90.1% for HP and 96.4% for
MP, which again confirms that both pyrimidine derivatives are
good inhibitors for steel in 1.0 molL1 HCl solution, and p follows the order: MP>HP. Compared with the corrosion potential
(Ecorr) in 1.0 molL 1 HCl solution without inhibitor, Ecorr in the
presence of HP or MP does not change, which indicates that all
studied pyrimidine derivatives act as mixed-type inhibitors. 30

Fig.9 Potentiodynamic polarization curves for CRS in

1.0 molL1 HCl solution without and with different
concentrations of inhibitors at 25 C
Immersion time is 2 h. (A) HP; (B) MP

Table 4 Potentiodynamic polarization parameters for the

corrosion of CRS in 1.0 molL1 HCl solution containing
different concentrations of HP and MP at 25 C
Inhibitor

Ecorr

icorr

bc

ba

(mmolL1) mV (vs SCE) (Acm2) (mVdec1) (mVdec1)

p
%

0.0

440

319.4

101

51

HP

1.0

435

144.0

118

61

54.9

MP

5.0

444

53.6

119

60

83.2

10.0

426

31.6

126

61

90.1

1.0

431

116.9

105

57

63.4

5.0

434

26.9

111

55

91.6

10.0

432

11.5

113

58

96.4

immersion time: 2 h

Furthermore, in the presence of each inhibitor, the slight

change of Tafel slopes of bc and ba indicates that the mechanism of steel does not change. According to Cao,30 the inhibition is caused by geometric blocking effect. Namely, the inhibition effect comes from the reduction of the reaction area on the
surface of the corroding metal.
3.7 Electrochemical impedance spectroscopy (EIS)
Fig.10 represents the Nyquist diagrams for CRS in 1.0 mol
L 1 HCl solution in the presence of HP and MP at 25 C. As
can be seen from the figures, all the impedance spectra exhibit
one single capacitive loop, which indicates that the corrosion
of steel is mainly controlled by the charge transfer process, and
usually related to the charge transfer of the corrosion process

No.10

LI Xiang-Hong et al.: Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid

Fig.10

2227

Nyquist plots of the corrosion of CRS in 1.0 molL1 HCl solution without and with different concentrations of inhibitors at 25 C
Immersion time is 2 h. The points represent experimental data and continuous line in figure corresponds to the EIS diagram fitted using the
equivalent electric circuit. (A) HP; (B) MP

and double layer behavior.31 In addition, the shape is maintained throughout all tested inhibitor concentrations compared
with that of blank solution, indicating that there is almost no
change in the corrosion mechanism which occurs due to the inhibitor addition.32
The diameter of the capacitive loop in the presence of inhibitor is larger than that in the absence of inhibitor (blank solution) and increases with the inhibitor concentration. This suggests that the impedance of inhibited substrate increases with
the inhibitor concentration. Further inspection of Fig.10 reveals that there is a little difference between HP and MP at low
inhibitor concentration (1.0 mmolL1), while there is large difference at high inhibitor concentration (10.0 mmolL 1). Such
behavior may be considered the suggestion that physisorption
at lower concentration and chemisorption at higher concentration for a given inhibitor.
Noticeably, these capacitive loops are not perfect semicircles that can be attributed to the frequency dispersion effect as
a result of the roughness and inhomogeneousness of the electrode surface.33 Accordingly, the EIS data are simulated by the
equivalent circuit shown in Fig.10B. Rs and Rt are the solution
resistance and charge transfer resistance, respectively. CPE is
constant phase element to replace a double layer capacitance
(Cdl) for more accurate fit. The solid lines in Fig.10 correspond
to the fitted plots for EIS experiment data using this electric circuit, which indicates that the experimental data can be fitted using this equivalent circuit.
Table 5
Inhibitor

The CPE is composed of a component Qdl and a coefficient a

which quantifies different physical phenomena like surface inhomogeneousness resulting from surface roughness, inhibitor
adsorption, porous layer formation, etc. The double layer capacitance (Cdl) can be simulated via CPE, and calculated from
the following equation:34
Cdl=Qdl(2fmax)a1
(6)
where fmax represents the frequency at which the imaginary value reaches a maximum on the Nyquist plot. The electrochemical parameters of Rs, Rt, CPE, a, Cdl, and R are listed in Table
5. The chi-squared (2) is used to evaluate the precision of the
fitted data.35 Table 5 shows that 2 value is low, which confirms
that the fitted data and the experimental data are in good agreement. It is observed that Rs is very small, which confirms that
the IR drop could be neglect. Rt value increases prominently
while Cdl reduces with the concentration of inhibitor. A large
charge transfer resistance is associated with a slower corroding
system. At any given inhibitor concentration, Rt(HP) <Rt(MP),
which confirms that MP shows better inhibitive performance
between two pyrimidine compounds. According to Cao,30 the single capacitive loop again indicates that the adsorption mode of
each pyrimidine inhibitor is geometric blocking effect.
Through the light of the tendency to form a stronger coordination bond, S atom shows more stable coordination ability than
O atom, which results in that it could be more easily for MP to
chemisorb on steel than HP.
The decrease in Cdl in comparing with that in blank solution

EIS parameters for the corrosion of CRS in 1.0 molL1 HCl solution containing HP or MP at 25 C

c/(mmolL1)

Rt/(cm2)

Rt/(cm2)
30.4

CPE/(1sacm2)

Cdl/(Fcm2)

1022

R/%

413.4

0.924

368

1.11

0.0

0.77

HP

1.0

0.84

67.0

245.0

0.917

187

1.36

54.6

5.0

1.08

206.6

170.5

0.923

95

1.28

85.3

10.0

0.72

273.3

148.5

0.847

71

2.30

88.9

1.0

0.67

75.0

214.9

0.908

174

1.22

59.5

5.0

0.86

278.9

124.6

0.922

68

1.17

89.1

10.0

0.71

448.7

94.2

0.892

47

1.55

93.2

MP

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Acta Phys. -Chim. Sin. 2013

(without inhibitor), 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
function by adsorption at the metal/solution interface.36 R increases with the concentration of inhibitor, and follows the order: R(MP) >R(HP). The R values at 10.0 mmol L 1 are
88.9% and 93.2% for HP and MP, respectively. These results
again confirm that all pyrimidine derivatives exhibit good inhibitive performance for CRS in HCl solution.
Inhibition efficiencies obtained from weight loss (w), potentiodynamic polarization curves (p), and EIS (R) are in good
reasonably agreement.
3.8 Quantum chemical calculations
In order to investigate the adsorption mode through light on
the pyrimidine molecular structure, quantum chemical calculations were carried out. It is well known that the N-heterocyclic
compound could be protonated in the acid solution. According
to some quantum chemical studies about protonated N-heterocyclic inhibitor in HCl solution,37 the proton affinity is clearly
favored toward the hetero N atom of N-heterocyclic ring.
Fig.11 shows the optimized molecular structures of two neutral
and their protonated pyrimidine derivatives. Through quantum
chemical calculations, the protonated affiliation energy (PA)
values of HP and MP are 1088.8 and 1091.5 kJmol 1, respectively. This result indicates that two studied pyrimidine derivatives are easily protonated. From Fig.11, the pyrimidine ring
and substitution group (OH, SH) are in one plane. It is
well known that inhibitor can form coordination bonds between the unshared electron pair of O, N, or S atom and the unoccupied d orbit of Fe. The larger negative charge of the atom,
the better is the action as an electronic donor. Mulliken charges
of the atoms are listed in Table 6. By careful examination of

Fig.11
Table 6
Atom

the values of Mulliken charges, the larger negative atoms are

found in N1, N3, O7, and S7, which are active adsorptive centers that could donate the lone electron pairs to the unfilled orbits of Fe. When pyrimidine compounds are protonated, the
Mulliken charge of N5 becomes more negative than N3, while
the Mulliken charge of O7 or S7 increases. This result implies
that if the inhibitor is protonated, N5 exhibits more active than
N3, while the adsorptive ability of O7 or S7 would decrease.
Fukui function is necessary in understanding the local site
selectivity. The Fukui function ( f (r)) is defined as:38
(r)
(7)
f (r) =

N
V (r)

The nucleophic attack Fukui function ( f (r)+) and electophilic

attack Fukui function ( f (r)-) can be calculated as:39
f (r)+ = qi (N + 1) - qi (N)
(8)
f (r) = qi (N) - qi (N - 1)
(9)
where qi(N +1), qi(N), qi(N 1) are charge values of atom i for
cation, neutral, and anion, respectively. The values of f (r)+
and f (r)- are also listed in Table 6. Generally, high values of
f (r)+ and f (r)- mean the high capacity of the atom to gain
and lost electron, respectively. For the nucleophic attack, the
most reactive site is C2 and C6 for all neutral and protonated
molecules, which can accept electrons from metal surface to
form back-donating bond. The difference of f (r)+ index of reactivity between HP, and MP is small. But when compounds
are protonated, f (r)+ values follow the order of p-HP>HP; pMP>MP. This result implies that the nucleophic attack activity
of protonated molecule decreases. On the other hand, the values of f (r)- indicate that it will happen on the N3 for HP, O7
for p-HP and S7 for MP and p-MP, which can denote electrons
to metal surface to form coordinate bond. The atom of S7 has

Optimized molecular structures of the neutral and protonated pyrimidine derivatives

Quantum chemical parameters of Mulliken charge, f (r)+ and f (r)- for neutral and protonated pyrimidine molecules
Mulliken charge

f (r)+

f (r)-

HP

MP

p-HP

p-MP

HP

MP

p-HP

p-MP

HP

MP

p-HP

p-MP

C1

0.208

0.222

0.173

0.196

0.023

0.018

0.028

0.024

0.053

0.085

0.141

0.082

C2

0.013

0.040

0.026

0.004

0.174

0.176

0.188

0.186

0.065

0.036

0.062

0.035

N3

0.381

0.344

0.318

0.290

0.128

0.120

0.102

0.081

0.203

0.067

0.106

0.073

C4

0.556

0.356

0.690

0.479

0.057

0.026

0.069

0.041

0.114

0.020

0.077

0.027

N5

0.396

0.342

0.452

0.411

0.123

0.116

0.077

0.079

0.183

0.065

0.051

0.038

C6

0.014

0.039

0.077

0.057

0.174

0.175

0.179

0.162

0.062

0.036

0.105

0.051

O7

0.606

0.543

0.041

0.055

0.041

0.165

S7

0.347

0.196

0.103

0.137

0.476

0.459

No.10

LI Xiang-Hong et al.: Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid

the largest f (r)- value among N3, O7, and S7 atoms, which
indicates that the adsorptive ability of S atom is higher than N
atom. Accordingly, the better inhibition efficiency of MP is related to the higher adsorptive ability of S atom of SH.
The dipole moment () is widely used to represent the polarity of the molecule, and related to the inhibitive ability. The
large value of dipole moment probably increases the inhibitor
adsorption through electronic force.40 In Table 7, the of HP is
larger than that of MP. On the contrary, the inhibition efficiency follows the order: MP>HP. These results indicate that the
better inhibitive performance of MP might not be arisen form
intermolecular electrostatic force. Table 7 shows that the protonated molecules of p-HP and p-MP have larger dipole moment values than corresponding neutral molecules of HP and
MP. Thus, p-HP and p-MP could be easily adsorbed via physical adsorption compared with HP and MP. It is well known that
the charge of the metal surface can be determined from the value of EcorrEq=0 (Ecorr: corrosion potential, Eq=0: zero charge potential).41 The Eq=0 of iron is 530 mV (vs SCE) in HCl solution,42
and the value of Ecorr obtained in 1.0 molL 1 HCl solution is
440 mV (vs SCE). Thus, the steel surface charges positive
charge in HCl solution because of Ecorr Eq=0>0. Since the acid
anion of Cl could be specifically adsorbed, it creates excess
negatives charge towards the solution and favors more adsorption of the cations, p-HP or p-MP may adsorb on the negatively
charged metal surface. In other words, there may be a synergism between anion (Cl) and protonated inhibitor.
Besides the above mentioned quantum chemical parameters,
the global reactivity of a molecule depends on molecular distributions. HOMO is often associated with the capacity of a molecule to donate electrons, whereas LUMO represents the ability
of the molecule to accept electrons. The electric/orbital density
distributions of HOMO and LUMO for the studied inhibitors
(neutral and protonated molecules) are shown in Fig.12, respectively. It is found that that the electron density of the frontier
orbital is well proportioned. For four molecules, the electron
densities of both HOMO and LUMO are localized principally
on the pyrimidine ring, which indicates that the pyrimidine
ring could be both the acceptor of the electron and the donor of
the electron. That is, there is electron transferring in the interaction between the pyrimidine ring and metal surface. The adsorption of inhibitor on steel may be in a manner in which the
plane of the pyrimidine ring is parallel to the metal surface. It
should be noted that HOMO density is absent on O7 atom for
HP, whereas present on S7 for MP. The result indicates that the
Table 7 Quantum chemical parameters of , EHOMO, ELUMO, E,
and N for neutral and protonated pyrimidine molecules
Molecule

1030/(Cm)

EHOMO/eV

ELUMO/eV

E/eV

HP

3.8495

6.215

2.241

3.974

0.698

MP

3.5148

5.943

2.334

3.609

0.793

p-HP

5.9086

4.613

3.624

3.989

0.346

p-MP

4.7736

6.097

3.691

3.216

0.529

Fig.12

2229

Frontier molecule orbital density distributions

of pyrimidine compounds
(left) HOMO; (right) LUMO

substituted S7 atom on pyrimidine ring of MP is an additional

adsorption centre in comparison with the substituted O7 atom
of HP. Accordingly, the efficiency of MP is higher than that of
HP. The LUMO density is absent on either O7 of HP or S7 of
MP; however, LUMO density is located on either O7 of p-HP
or S7 of p-MP. Thus, it is reasonable to deduce that the protonated molecule exhibits better adsorptive ability than neutral
molecule.
The values of energy of the highest occupied molecular orbital (EHOMO), energy of the lowest unoccupied molecular orbital (ELUMO), and the separation energy (ELUMO EHOMO, E) are also
presented in Table 7. High value of EHOMO indicates a tendency
of the molecule to donate electrons to act with acceptor molecules with low-energy, empty molecular orbital.3 Similarly, the
ELUMO represents the ability of the molecule to accept electrons,
and the lower value of ELUMO suggests the molecule accepts
electrons more probable.3 From Table 7, EHOMO obeys the order:
MP>HP, while ELUMO obeys the order: MP<HP. When compound is protonated, the order is still same. Obviously, the two
sequences are in completely accordance with the order of inhibition efficiency. This may explain that the better inhibition efficiency of MP molecule than HP is due to both lower ELUMO
and higher EHOMO. Both EHOMO and ELUMO values of protonated
molecules decrease compared with those of neutral molecules,

2230

Vol.29

Acta Phys. -Chim. Sin. 2013

Therefore, it could be deduced that the protonated molecule

strengthens accepting electrons from metal surface while weakens donating electrons to Fe atom.
The separation energy (energy gap) E (ELUMO EHOMO) is an
important parameter as a function of reactivity of the inhibitor
molecule towards the adsorption on metallic surface. As E decreases, the reactivity of the molecule increases in visa, which
facilitates adsorption and enhances the efficiency of inhibitor.3
Inspection of the data in Table 7 shows that the E value follows the order of MP<HP and p-MP<p-HP, which confirms
that MP (or p- MP) facilitates its adsorption on the metal surface so that it has higher inhibition efficiency. Furthermore, E
value of protonated molecule is lower than neutral molecule,
which again confirms that the protonated molecule exhibits better inhibitive performance than neutral molecule.
The energies of HOMO and LUMO of the inhibitor molecule are related to the ionization potential (I ) and the electron
affinity (Y), respectively, by the following relations: 45
I=EHOMO
(10)
Y=ELUMO
(11)
Then absolute electronegativity () and global hardness ()
of the inhibitor molecule are approximated as follows:44
(12)
= I+Y
2
= I-Y
(13)
2
The fraction of electrons transferred from the inhibitor to
metallic surface (N) is calculated depending on the quantum
chemical method:45
-
(14)
N = Fe inh
2( Fe + inh)
For Fe, the theoretical values of Fe and Fe are 7 and 0 eV, respectively.46 The values of N are also listed in Table 7. According to some studies,46 values of N exhibit inhibitive performance resulted from electrons donations. If N<3.6, the inhibition efficiency increases with the increase in electron-donation ability to the metal surface.47 It can be seen from Table 7
that N follows the order of MP>HP and p-MP>p-HP, which is
in good agreement with the order of inhibition efficiency of
these inhibitors. When the compounds are protonated, N follows the order of p-HP>HP and p-MP<MP, which again implies
that the ability of donating electrons decreases for protonated
molecule.

sorption and chemical adsorption.

(3) Both HP and MP are arranged as mixed- type inhibitors
in 1.0 molL1 HCl solution. EIS spectra exhibit one capacitive
loop, and the presence of each inhibitor enhances Rt while reduces Cdl.
(4) The large protonated affiliation energy (PA) values confirm that two studied pyrimidine derivatives are easily protonated. The chemical molecules of HP, MP, p-HP, and p-MP are in
one plane. The larger negative Mulliken charges are found in
N1, N3, O7, and S7, which are adsorptive centers. The nucleophic attack active atoms are C2 and C6 atoms. The electrophilic attack active atoms are N3 for HP, O7 for p-HP, S7 for
MP and p-MP.
(5) The electron densities of both HOMO and LUMO are localized principally on the pyrimidine ring. The pyrimidine ring
could be both the acceptor of the electron and the donor of the
electron. The better inhibition efficiency of MP than HP could
be explained with the quantum parameters of ELUMO, EHOMO, E,
and N.
(6) The protonated molecules of p- HP and p- MP could be
easily adsorbed via physical adsorption; there may be a synergism between anion (Cl ) and protonated inhibitor. Comparing
with neutral molecule, the protonated molecule exhibits better
inhibitive performance. The protonated molecule strengthens
accepting electrons while weakens donating electrons.
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