Corrosion Science 90 (2015) 284–295

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Halogen-substituted imidazoline derivatives as corrosion inhibitors for

mild steel in hydrochloric acid solution
Kegui Zhang a, Bin Xu a, Wenzhong Yang a,⇑, Xiaoshuang Yin a, Ying Liu a, Yizhong Chen b
a
School of Science, Nanjing Tech University, Nanjing 210009, PR China
b
School of Environmental and Safety Engineering, Jiangsu Polytechnic University, Changzhou 213164, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Two novel imidazoline derivatives, 2-(2-trifluoromethyl-4,5-dihydro-imidazol-1-yl)-ethylamine (1-IM)

Received 17 July 2014 and 2-(2-trichloromethyl-4,5-dihydro-imidazol-1-yl)-ethylamine (2-IM), have been investigated as cor-
Accepted 21 October 2014 rosion inhibitors for mild steel in 0.5 M HCl solution by weight loss, potentiodynamic polarization and
Available online 30 October 2014
electrochemical impedance spectroscopy (EIS) tests. The surface morphology of sample was presented
through scanning electron microscope (SEM) and the inhibition mechanism was elucidated by measuring
Keywords: the potential of zero charge (Epzc) at the solid/liquid interface. Results of theoretical calculation
A. Mild steel
confirm that the chloride-substituted compound shows better inhibitive performance than the fluoride-
B. Weight loss
B. SEM
substituted one.
C. Acid corrosion Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction inhibition performance [23]. In order to study the adsorption con-

Mild steel has been widely used in industry as a material for
reaction vessels, tunnels, etc. [1]. Acid solutions, especially hydro-
chloric acid, are usually employed for acid picking, acid cleaning,
acid descaling and oil well acidizing, which may result in the cor-
rosion of iron [2,3]. Mild steel damaged by aggressive media causes
serious losses on the economy and potential problems in industrial
equipment safety [4]. An effective method to protect metal from
corrosion is the use of inhibitors. Currently, the corrosion behav-
iour of material and the adsorption mechanism of organic inhibi-
tors are hot subjects [5–7]. Many compounds which contain
hetero-atoms and multiple bonds are known as efficient corrosion
inhibitors [8–11]. Heterocyclic compounds usually act as effective
inhibitors for the corrosion of metal, such as benzaldehydes [12],
furans [13], isoxazolidines [14], triazoles [15], pyridines [16],
thiadiazole [17], oxadiazoles [18] and imidazolines [19–22].
Particularly, imidazoline is popular for its high efficiency and low
toxicity. Nowadays, most research about imidazoline inhibitors
focuses on common electron-rich groups, e.g. S, N atoms and mul-
tiple bonds. However, it has not been investigated that whether
halogen atoms which contain more lone pair of electrons can
enhance the inhibition properties of compounds.
Quantum chemical calculations have been employed to explore
the relationship between the molecular structures and the
⇑ Corresponding author. Tel./fax: +86 25 83172359.
E-mail address: njutkeguizhang@163.com (K. Zhang).
figurations of inhibitors on metal surface, molecular dynamics
(MD) method was utilized to study the interaction of phase inter-
faces. MD simulations can supply visualized views into the adsorp-
tion systems with superior properties and clarify the adsorption
mechanism at a molecular level [24].
1-IM and 2-IM (Fig. 1) are halogen-substituted imidazoline
compounds. This study is aimed to evaluate the inhibiting effect
of the two compounds on the corrosion of mild steel in 0.5 M
HCl solution via weight loss tests, electrochemical experiments,
SEM and computational methods. Moreover, Epzc has been
conducted to elucidate the inhibition mechanism.
2. Experimental details
2.1. Materials and sample preparation
Two imidazoline derivatives, 1-IM and 2-IM have been synthe-
sized in laboratory according to the improved path in Fig. 2 [25].
Herein, a brief synthesis process of 1-IM was provided. Firstly,
50 mL methylbenzene and 10 mL trifluoroacetic acid were placed
in a 250 mL three-neck round-bottom flask and the mixture was
heated to 160 °C. 30 mL diethylenetriamine was slowly added to
the mixture. The reaction flask was equipped with a condenser
to collect water and methylbenzene. The mixture solution was stir-
red for 4 h with reflux at 160 °C. After the first-step dehydration,
the colourless solution turned yellow. The temperature was

http://dx.doi.org/10.1016/j.corsci.2014.10.032
0010-938X/Ó 2014 Elsevier Ltd. All rights reserved.
 K. Zhang et al. / Corrosion Science 90 (2015) 284–295
increased to 200 °C for the second-step dehydration which lasted
4 h. Afterwards, ethanol was added to the crude residues to extract
the target production (3  50 ml). Finally, 1-IM was obtained by
removing ethanol in vacuum. The structures of molecules were
confirmed by 1H NMR, 13C NMR and FT-IR spectroscopic methods
and the purity of compounds was guaranteed by the identification
of atoms (C and H) and melting point.
1-IM: 1H NMR (DMSO-d6, 300 MHz), d, J: 3.34, 6.0 Hz (t, 2H,
AC@NACH2A), 3.30, 10 Hz (t, 2H, ACH2ANA), 2.78, 15 Hz (t, 2H,
ACH2ACAN), 2.71 3 Hz (t, 2H, AC@NACACH2ANA), 7.6 (s, 2H,
ANH2). FT-IR (KBr) m: 3357, 1652, 1558, 1488, 1319, 1118, 819,
591 cm1. 13C NMR (DMSO-d6, 300 MHz) d: 164.7 (C@N), 124.8
(CF3), 54.1 (CANH2), 44.8 (NACring), 40.2 (CACANH2), 39.4
(CringAN@). Melting point: 167.5–168.2 °C.
2-IM: 1H NMR (DMSO-d6, 300 MHz), d: 3.34 10 Hz (t, 2H,
AC@NACH2A), 3.32 6 Hz (t, 2H, ACH2ANA), 2.76 3 Hz (t, 2H,
ACH2ACANA), 2.70 6 Hz (t, 2H, AC@NACACH2ANA), 7.3 (s, 2H,
ANH2). FT-IR (KBr) m: 3359, 1662, 1560, 1477, 1330, 1122, 831,
651 cm1. 13C NMR (DMSO-d6, 300 MHz) d: 160.7 (C@N), 94.6
(CCl3), 55.9 (CANH2), 45.2 (NACring), 39.6 (CACANH2), 38.5
(CringAN@). Melting point: 186.1–186.5 °C.
The aggressive solutions of 0.5 M HCl were prepared by the
dilution of an analytical grade HCl (37 wt.%) with deionized water.
The concentrations of imidazoline derivative inhibitors in the work
were set as 0.1, 0.5, 1, 1.5, 2 mM, and the blank solution was also
prepared for comparison. Mild steel coupons (0.17 wt.% C,
0.37 wt.% Mn, 0.20 wt.% Si, 0.03 wt.% S, 0.01 wt.% P and balance
Fe) were cut into 5.00 cm  2.50 cm  0.20 cm for weight loss
tests. For the sake of electrochemical experiments, the cylindrical
steel specimens were placed into epoxy resin with an exposed area
of 0.5 cm2 to the acid solution. Prior to use, the steel specimens
were cleaned with ultrapure water and ethanol, and dried in room
temperature.
2.2. Weight loss experiments
Weight loss measurements were conducted by placing the cell
in a thermostat-cooling water bath. The volume of 0.5 M HCl solu-
tion was 500 mL, in which steel samples were immersed for 8 h in
the presence and absence of inhibitors at different temperatures
(30, 40, 50, 60 and 70 °C). Once the corrosion tests finished, the
specimens were washed with ultrapure water and ethanol, dried
and then weighed.
Fig. 1. Chemical structures of two imidazoline derivatives.
285
2.3. Electrochemical measurements
Electrochemical measurements were executed with a ZAHNER
IM6ex electrochemical workstation, controlled by ZAHNER THALES
software. The electrochemical tests were performed by using a
standard three-electrode cell system. A saturated calomel elec-
trode (SCE) coupled to a Luggin capillary were used as a reference
electrode, along with a platinum mesh as a counter electrode. The
cylindrical mild steel acted as a working electrode (WE) and the
surface was treated carefully as described above.
Electrochemical experiments were performed in 0.5 M HCl
solution at 30 °C with and without different concentrations of
inhibitors. For all electrochemical tests, WE was requested to reach
a stable open-circuit potential (OCP) through 1 h of immersion in
the electrolyte. A steady open-circuit potential, standing for the
stable state of the electrode, guarantees that the response to
the electrical excitation is only determined by the condition of
the solid/liquid interface without the impact of electrode quality
or other unfavorable factors. With a scan rate of 1 mV/s, the poten-
tiodynamic polarization curves were performed in the potential
range from 700 mV to 300 mV (vs. SCE) at a steady open-circuit
potential. Impedance spectra from 0.01 Hz to 100 kHz were
obtained by superimposing a sinusoidal alternating current (AC)
signal of small amplitude, 5 mV (peak to peak). All electrochemical
measurements were conducted in naturally aerated acid media
under non-stirred conditions, and the cell temperatures were
controlled by a thermostatic water bath. In order to obtain mean
values of weight loss and electrochemical parameters, all the
measurements were repeated three times under the same
condition. Relative deviations and error bar of measured values
were provided in the study. The relative difference, uncertainty
of the test results, was found to be lower than 8%, and that
demonstrated the acceptable reproducibility of experiments.
2.4. Measurements of the potential of zero charge
With an AC excitation of 5 mV, the double layer capacitance
(Cdl) values of WE were recorded against the potential after 1 h
of immersion in 0.5 M HCl solution with and without 1 mM
inhibitors at 30 °C.
2.5. Scanning electron microscope
SEM was used to observe the surface morphologies of coupons
after 24 h of immersion in 0.5 M HCl in the absence and presence of
1 mM 1-IM or 2-IM at 70 °C. SEM figures were obtained via using a
TM 3000 scanning electron microscope under the condition of
vacuum and 15.0 kV EHT.
2.6. Computational methods
Using Material Studio 5.5 software, molecular dynamics (MD)
simulations were employed to study the adsorption behaviour of
inhibitor molecules. With the Fe (1 1 0) crystal chosen for the
matrix of simulation study, MD calculation of the simulative inter-
action between the inhibitor molecule and the metal surface was
performed in a stereoscopic simulation box (19.86 Å  19.86 Å 
38.10 Å). After being cleaved from Fe crystal, the Fe (1 1 0) plane
was optimized to the minimal energy condition and enlarged to
get an appropriate supercell. A vacuum space with a thickness of
30 Å was built above the Fe (1 1 0) plane. Next, the imidazoline
molecule was also built and optimized. Coordinates of the Fe atoms
were fixed while the atoms of inhibitor molecule were permitted
to relax during the geometry optimization. Finally, the interac-
tional interface system between the Fe (1 1 0) crystal and the inhib-
itor molecule was built by layer builder, and the dynamic
286 K. Zhang et al. / Corrosion Science 90 (2015) 284–295

Fig. 2. Reaction pathway of 1-IM and 2-IM.

behaviour of inhibitors close to the Fe (1 1 0) surface was then sim-
ulated by PCFF force field.
With a time step of 0.1 fs and simulation time of 50 ps, MD
simulation was conducted at 298 K under isothermal-isochoric
conditions. The interaction energy between the target molecule
and the Fe (1 1 0) plane was calculated as follows:
Einteraction ¼ Etotal  ðEsurface þ Einhibitor Þ
where Etotal is the total energy of Fe crystal together with the
imidazoline molecule, Esurface and Einhibitor are the energy of the Fe
crystal and the free inhibitor molecule, respectively. The binding
energy equals the negative value of the interaction energy,
Ebinding = Einteraction.
Quantum chemical calculations were performed to obtain theo-
retical data based on DMol3 module in Materials Studio software.
With a fine choice of convergence accuracy and a basis set of
double zeta plus polarization (DNP), the GGA/BLYP method was
applied to calculate the electron densities of imidazoline
molecules. Frequency analysis was involved to ensure that the
calculated structure is the minimum point on potential energy
surface (without imaginary frequency).
3. Results and discussion
3.1. Weight loss experiments
The results of weight loss tests for the corrosion of mild steel in
0.5 M HCl with and without different inhibitor concentrations at
various temperatures were presented in Table 1. The inhibition
efficiency (g) is calculated by the following equation:
concentrations, suggesting the stronger adsorption layer of inhibitor
molecules on the metal surface. 1-IM shows good inhibiting ability
at relatively low solution temperature, e.g., the inhibition efficiency
of 1 mM 1-IM at 30 °C is 91%. As the temperature increases, the cor-
rosion rate of iron is exacerbated and the inhibiting performance of
1-IM becomes poor. Table 1 shows the inhibition efficiency of 1 mM
2-IM is always greater than 92% from 30 °C to 70 °C. In order to bet-
ð1Þ
ter compare the anticorrosion property of inhibitors, the relation
between the temperature and the efficiency of inhibitors at 1 mM
is shown in Fig. 3. It can be observed that 2-IM possesses better inhi-
bition effectiveness than 1-IM even though their efficiency is close at
30 °C. In spite of the increasing temperatures, 2-IM keeps efficient
compared with 1-IM whose inhibition performance fades evidently.
However, we can notice that 2 mM 1-IM is efficient at high temper-
atures. For instance, the inhibition percentage of 2 mM 1-IM at 70 °C
is 96%, much greater than that of 1.5 mM 1-IM (69%).
3.2. Open circuit potential (OCP) curves
The relationship between open circuit potential and immersion
time for mild steel in 0.5 M HCl in the absence and presence of
1 mM 1-IM or 2-IM at 30 °C is expressed by Fig. 4. At preliminary
20 min, OCP shifts to the positive quickly, which indicates the
imbalanced corrosion process. We can observe that the change in
OCP of the blank solution is the rapidest among these three cases
(blank, 1-IM, 2-IM). This information may reveal that the dissolu-
tion action of mild steel is delayed by halogen-substituted inhibi-
tors. When the immersion time is over 30 min, OCP keeps stable
enough. So 1 h is chosen as immersion time for electrochemical
measurements.

W0  W
g¼  100% ð2Þ 3.3. Potentiodynamic polarization measurements
W0
where W0 and W represent the corrosion rates of steel The potentiodynamic polarization curves for mild steel in
specimens without and with inhibitors, respectively. The inhibition 0.5 M HCl in the absence and presence of inhibitors are shown
efficiency of 1-IM and 2-IM increases with the increasing inhibitor in Fig. 5. The addition of imidazoline derivatives causes a

Table 1
Weight loss results of mild steel in 0.5 M HCl with and without various concentrations of imidazoline inhibitors at different temperatures, with an immersion time of 8 h.

Conc. (mM) T = 30 °C 40 °C 50 °C 60 °C 70 °C
2 1
m (mg cm h ) g (%) m g m g m g m g
1-IM
Blank 0.666 ± 0.017 1.724 ± 0.022 – 3.175 ± 0.024 – 6.221 ± 0.092 – 11.06 ± 0.087 –
0.1 0.187 ± 0.011 72 0.860 ± 0.074 50 1.760 ± 0.014 44 3.956 ± 0.043 36 8.096 ± 0.096 27
0.5 0.030 ± 0.003 84 0.400 ± 0.028 77 0.965 ± 0.025 70 2.851 ± 0.024 54 5.630 ± 0.034 49
1 0.108 ± 0.005 91 0.184 ± 0.009 89 0.348 ± 0.011 89 2.002 ± 0.023 68 4.651 ± 0.067 58
1.5 0.047 ± 0.005 93 0.162 ± 0.002 91 0.169 ± 0.006 95 0.853 ± 0.013 86 3.478 ± 0.021 69
2 0.036 ± 0.004 95 0.151 ± 0.007 94 0.160 ± 0.005 95 0.288 ± 0.010 95 0.421 ± 0.011 96
2-IM
0.1 0.061 ± 0.004 91 0.085 ± 0.003 95 0.183 ± 0.004 94 1.888 ± 0.009 70 2.651 ± 0.005 76
0.5 0.043 ± 0.003 94 0.084 ± 0.006 95 0.175 ± 0.011 94 0.699 ± 0.015 89 1.177 ± 0.012 89
1 0.043 ± 0.002 94 0.082 ± 0.002 95 0.160 ± 0.005 95 0.315 ± 0..007 95 0.559 ± 0,013 95
1.5 0.043 ± 0.001 94 0.044 ± 0.001 97 0.066 ± 0.009 98 0.246 ± 0.004 96 0.248 ± 0.018 98
2 0.040 ± 0.003 95 0.044 ± 0.001 97 0.062 ± 0.004 98 0.205 ± 0.008 97 0.225 ± 0.006 98
 K. Zhang et al. / Corrosion Science 90 (2015) 284–295
Fig. 3. Inhibition efficiency of 1-IM and 2-IM at 1 mM for mild steel in 0.5 M HCl as
a function of temperature, with an immersion time of 8 h.
Fig. 4. OCP-time curves for mild steel in 0.5 M HCl without and with 1 mM
inhibitors at 30 °C.
decrease in corrosion rates, which accounts for the displacements
of both anodic and cathodic Tafel curves toward lower current
densities by a broad range. This phenomenon indicates anodic
metal dissolution and cathodic hydrogen evolution reactions are
Fig. 5. Potentiodynamic polarization curves for mild steel after 1 h of immersion in 0.5 M HCl in the absence and presence of different concentrations of inhibitors at 30 °C:
(a) 1-IM, (b) 2-IM.
287
suppressed via the coverage of inhibitor molecules on the metal
surface. Meanwhile, the suppressions of these processes are more
pronounced with the increase in inhibitor concentrations. The
shift amplitude of 2-IM is greater than that of 1-IM, suggesting
2-IM is more effective on corrosion inhibition. The shape of
cathodic Tafel curves in the inhibited solution hardly changes
with respect to that in the blank solution, i.e., the mechanism
of cathodic reaction is unaffected by inhibitors [26–28]. On the
other hand, the deformed anodic curves show that iron dissolu-
tion reaction is deeply affected. Polarization curve parameters
such as corrosion potential (Ecorr), cathodic and anodic Tafel
slopes (bc and ba), as well as corrosion current density (Icorr) are
provided in Table 2 where the inhibition efficiency (g) of imidaz-
oline compounds obtained via Eq. (3) is also listed.
I0corr  Icorr
g¼  100% ð3Þ
I0corr
where I0corr and Icorr represent the corrosion current density values
for the mild steel in the absence and presence of imidazoline inhib-
itors, respectively. An inhibitor can be defined as cathodic or anodic
type if the displacement in corrosion potential is more than 85 mV
compared with that of the blank solution [29]. In the presence of
1-IM and 2-IM, the shifts of corrosion potential are all less than
30 mV (vs. SCE), indicating that the two compounds are mixed-type
inhibitors. The parallel cathodic Tafel curves and the almost con-
stant cathodic Tafel slopes in Table 2 suggest cathodic process,
the hydrogen production reaction, is activation-controlled, and that
the addition of inhibitors does not influence the mechanism of this
process [30]. In other words, the two compounds hinder the reduc-
tion of hydrogen ions by covering the active reaction sites on mild
steel surface with protective barrier. However, the value of the ano-
dic Tafel slopes from Table 2 presents obvious change in the pres-
ence of inhibitors with respect to the blank case, suggesting 1-IM
and 2-IM can impact the kinetics process of the anodic reaction.
According to the structures of compounds shown in Fig. 1, halogen,
N atoms and double bond possess a number of lone pair of electrons
and may conduce to the formation of Fe (II)–IM complex compound,
which thus affect the dissolution process of Fe [31]. In addition,
data of Table 2 shows corrosion current density decreases with
increasing concentrations of inhibitors. This detail reveals the
protective layer of inhibitor molecules may become stronger and
thicker, attributed to the increasing coverage of compound
molecules on metal surface.
288 K. Zhang et al. / Corrosion Science 90 (2015) 284–295

Table 2
Electrochemical parameters calculated from polarization measurements after 1 h of immersion in 0.5 M HCl solution in the absence and presence of various inhibitor
concentrations at 30 oC.

Inhibitor Conc. (mM) Ecorr (mV vs. SCE) Icorr (mA cm2) ba (mV dec1) bc (mV dec1) g (%)
1-IM Blank 493.6 ± 1.4 0.912 ± 0.022 125 ± 4 108 ± 5 –
0.1 497.9 ± 2.1 0.463 ± 0.013 108 ± 1 105 ± 3 49
0.5 504.1 ± 0.9 0.385 ± 0.011 95 ± 1 108 ± 2 53
1 513.2 ± 1.7 0.237 ± 0.009 79 ± 2 101 ± 3 58
1.5 516.4 ± 1.6 0.195 ± 0.005 72 ± 3 98 ± 5 79
2 518.5 ± 2.3 0.175 ± 0.011 89 ± 1 107 ± 3 81
2-IM 0.1 490.2 ± 1.1 0.187 ± 0.004 106 ± 4 100 ± 1 79
0.5 488.4 ± 1.4 0.142 ± 0.003 96 ± 1 97 ± 2 84
1 494.7 ± 2.2 0.102 ± 0.005 105 ± 2 103 ± 2 89
1.5 489.1 ± 1.8 0.093 ± 0.002 90 ± 2 106 ± 3 90
2 507.2 ± 1.3 0.089 ± 0.002 87 ± 3 99 ± 3 90

3.4. Electrochemical impedance spectroscopy
Corrosion behaviour of mild steel samples in 0.5 M HCl solution
without and with different concentrations of 1-IM and 2-IM was
evaluated by EIS at 30 °C after 1 h of immersion. The Nyquist plots
of WE in acid solutions in the absence and presence of inhibitors
are shown in Fig. 6. The depressed semicircles in impedance spec-
tra indicate a non-ideal electrochemical behaviour at the solid/
liquid interface [32]. The addition of inhibitors does not change
the type of the shape, i.e., those compounds control the activity
of the corrosion reaction rather than inflect its nature. The
depressed capacitive loops in Fig. 6 suggest the only time constant
related to the charge transfer process [33,34]. It is well known that
the irregular loops are caused by a phenomenon called ‘‘dispersion
effect’’ which is usually correlative with the heterogeneities of
metal surface [35]. As evident from Fig. 6, the diameters of the
capacitive loop in the inhibited solution is greater than that in
the blank solution, which suggests the corrosion process is
restrained by inhibitors.
Bode and phase angle curves for mild steel in 0.5 M HCl with
and without inhibitors are displayed in Fig. 7. Inhibition ability of
imidazoline compounds can be observed from impedance values
at the low frequency and the increasing absolute impedance value
indicates the higher inhibition efficiency (Fig. 7a and c). According
to shifting trend of phase angle plots, raising the concentration of
inhibitors conduces to more negative values of the phase angle,
which indicates the better inhibitive behaviour of compounds with
higher concentrations. Fig. 7b and d shows there is only a phase
peak in the studied frequency range, suggesting the sole time con-
stant connected with the formation of double layer capacitance at
solid/liquid interface. Based on the above results, the impedance
data is fitted via the equivalent circuit (Fig. 8) composed of solution
resistance (Rs), charge transfer resistance (Rct), constant phase ele-
ment (CPE) and inductance (L), an assistant element with small
value to improve the accuracy of fit. Various impedance data with
a deviation less than 8% can be obtained via LR(QR) model. The
impedance function of the CPE is represented by the expression
[36]:
n
Z CPE ¼ Y 1
0 ðjxÞ ð4Þ
where Y0 is a proportional factor, n, a deviation parameter
(1 6 n 6 1), means a phase shift depending on its whole number
value. For n = 0, CPE represents a pure resistance, for n = +1 a pure
capacitance and for n = 1 a pure inductance. Related impedance
data obtained from the equivalent circuit is listed in Table 3.
The double layer capacitance (Cdl) and inhibition efficiency (g) are
calculated as the following formulae:
n1
C dl ¼ Y 0 ðjx00m Þ ð5Þ
Rct  R0ct
g¼  100% ð6Þ
Rct
where x00m is the angular frequency, Rct and R0ct are charge transfer
resistance values in the presence and absence of inhibitors, respec-
tively. The values of Cdl are expressed by the Helmholtz model [37]:
e0 e
C dl ¼ S ð7Þ
d
where d is the thickness of the double layer capacitance, S is the
electrode surface area, e0 and e are the dielectric constant of vacuum

Fig. 6. Nyquist plots for mild steel immersed in 0.5 M HCl for 1 h without and with various concentrations of inhibitors at 30 °C: (a) 1-IM, (b) 2-IM.
 K. Zhang et al. / Corrosion Science 90 (2015) 284–295 289

Fig. 7. The Bode and phase angle plots for mild steel in 0.5 M HCl in the absence and presence of different concentrations of inhibitors at 30 °C, along with an immersion time
of 1 h: (a and b) 1-IM, (c and d) 2-IM.

the metal surface. At the same concentration of inhibitors, the val-

ues of Rct answer for the order of 2-IM > 1-IM and the values of Cdl
follow the order of 2-IM < 1-IM. Those rankings result in the inhibi-
tion efficiency order: 2-IM > 1-IM. The above experimental results
reveal 2-IM is more effective than 1-IM on corrosion inhibition in
acid solution, i.e., Cl atoms may play a more important role in anti-
corrosion performance compared with F atoms.
Fig. 8. LR(QR) model used to fit the data of EIS experiment.

3.5. Adsorption isotherm

and solution, respectively. The results of Table 3 show the Rct values
increase with increasing inhibitor concentrations and that the trend
is opposite for Cdl. The decrease in Cdl suggests a fading in the local
dielectric constant or an enhancement in the thickness of the capac-
itor, attributed to the adsorption of more imidazoline molecules on
Important information about the interaction between the imi-
dazoline inhibitors and metal surface is provided by the adsorption
isotherm. In this study the surface coverage (h) for inhibitors in
0.5 M HCl solution is obtained by using the following equation:

Table 3
Electrochemical impedance results for mild steel immersed in 0.5 M HCl for 1 h in the absence and presence of different concentrations of inhibitors at 30 °C.

Inhibitor Conc. (mM) Rs (X cm2) Rct (X cm2) Cdl (lF cm2) L (lH cm2) g (%)
1-IM Blank 0.26 ± 0.02 14.6 ± 1.1 780 ± 2 0.47 ± 0.02 –
0.1 1.05 ± 0.04 28.5 ± 2.2 651 ± 3 0.12 ± 0.01 48.8
0.5 1.60 ± 0.06 35.7 ± 1.7 623 ± 6 0.23 ± 0.01 59.1
1 0.85 ± 0.05 38.1 ± 3.2 545 ± 1 0.53 ± 0.02 61.7
1.5 0.31 ± 0.02 43.3 ± 1.5 498 ± 2 0.42 ± 0.03 66.3
2 0.40 ± 0.03 56.5 ± 3.1 298 ± 5 0.35 ± 0.01 74.2
2-IM 0.1 0.16 ± 0.01 53.7 ± 2.8 556 ± 3 0.27 ± 0.01 72.7
0.5 0.40 ± 0.02 94.9 ± 1.2 432 ± 2 0.26 ± 0.02 84.5
1 0.86 ± 0.05 117.4 ± 4.8 367 ± 1 0.11 ± 0.01 87.5
1.5 1.04 ± 0.03 127.1 ± 2.3 287 ± 3 0.17 ± 0.01 88.5
2 1.64 ± 0.02 174.4 ± 2.9 175 ± 2 0.34 ± 0.03 91.6
290 K. Zhang et al. / Corrosion Science 90 (2015) 284–295

g Table 4
h¼ ð8Þ
100 Thermodynamic and equilibrium adsorption data of inhibitors on mild steel surface in
0.5 M hydrochloric acid solution.
where g is the inhibition efficiency from weight loss measure-
ments. Some isotherm models have been tested for the two inhib- System Kads (L mol1) DG0ads (kJ mol1) Ea (kJ mol1)

itors, such as Langmuir, Temkin and Frumkin isotherm. As shown HCl – – 59.85
in Fig. 9 and Table 4, the results reveal that the plots of C/h versus HCl + 1-IM 1.69  104 34.65 85.20
C present straight lines with the slopes and the linear correlation HCl + 2-IM 1.36  105 39.67 62.13

coefficients close to 1. Therefore, the adsorption of the inhibitors

on the mild steel surface is well fitted to the Langmuir adsorption
isotherm: where CR is the corrosion rate from Table 1, Ea is the apparent acti-
vation energy, R is the ideal gas constant, T is the temperature, and k
C 1
¼ þC ð9Þ is the Arrhenius pre-exponential factor. Plots of log CR vs.1000/T
h K ads
shown in Fig. 10 give straight lines, indicating the good accuracy
where C and Kads are the inhibitor concentration and the equilib- of fit. Results from Table 1 depict corrosion rates increase with
rium constant, respectively. The standard free energy of adsorption the increasing temperature in inhibited and blank solutions. It can
(DG0ads ) is determined by Kads according to the following expression be noticed that the dissolution rate of metal is obviously slowed
[38]: down by 2-IM with respect to 1-IM, i.e., the protective layer of
2-IM is stabler at relatively high temperatures than that of 1-IM.
DG0ads ¼ RT lnð55:5K ads Þ ð10Þ
Table 4 shows that values of Ea in the blank solution without and
1 1 3 with 1-IM or 2-IM are 58.95, 85.20 and 62.13 kJ/mol, respectively.
where R (J mol K ) is the ideal gas constant, 55.5 (mol dm ) is
the molar concentration of water in solution and T (K) is the ther-
modynamic temperature. Employing the above equation, values of 3.7. Surface analysis
DG0ads for 1-IM and 2-IM were 34.65  kJ/mol and –39.67 kJ/mol,
 
respectively. The high values of DG0ads  suggest the strong interac- Surface analyses for the corrosion of mild steel coupons in 0.5 M
tion between imidazoline  molecules
 and the mild steel surface HCl solution with and without inhibitors were carried out by SEM.
 
[39]. The difference in DG0ads  indicates the adsorptive behaviour Fig. 11 represents the morphologies of metal specimens immersed
of the two compounds is affected
 by the halogen groups. 2-IM pos- for 24 h in 0.5 M HCl solutions without and with 1 mM 1-IM or 2-
 
sesses greater value of DG0ads  than 1-IM, i.e., Cl atoms may enhance
the adsorption property of the molecule and hence improve the
inhibition efficiency.
3.6. Effect of temperature
Usually, the impact of temperature on the corrosion behaviour
of metal is highly complicated because many changes take place
on the solid/liquid interface, such as rapid dissolution of metal
and the adsorbed inhibitor film. In order to calculate the activation
parameters and explore the inhibition mechanism, weight loss
measurements have been performed in 0.5 M HCl with and with-
out 1 mM imidazoline inhibitors in the temperature range of 30–
70 °C. According to corresponding data shown in Table 1, some
activation parameters of the corrosion process can be obtained
by the Arrhenius equation [40]:
Ea
log C R ¼ þk
2:303RT
Fig. 9. Langmuir isotherm plots for the adsorption of inhibitors on mild steel
surface in 0.5 M HCl at 30 °C.
IM at 70 °C. The rude surface of iron (Fig. 11a) shows that the steel
sample is seriously damaged by the aggressive solution. With
respect to the blank case, the surface of the sample with the addi-
tion of 1-IM (Fig. 11b) or 2-IM (Fig. 11c) is less rough, which is due
to the protective film of adsorptive imidazoline molecules. Evi-
dently, 2-IM is more effective than 1-IM on corrosion inhibition
since the mild steel gets better protection from the former, such
as smoother surface and clearer grain of polishing.
3.8. Computational methods
MD simulations were used to investigate the adsorption behav-
iour of imidazoline molecules on the Fe (1 1 0) surface. The values
of Etotal, Esurface and Einhibitor were calculated and presented in
Table 5 when both temperature and energy of the system contain-
ing Fe (1 1 0) surface and the studied molecules reached equilib-
rium. Fig. 12 depicts imidazoline molecules are absorbed above
ð11Þ
the surface of iron in different configurations. As can be seen from
Fig. 10. Arrhenius plots for the corrosion rate of mild steel versus the temperature
in 0.5 M HCl, 0.5 M HCl + 1 mM 1-IM and 0.5 M HCl + 1 mM 2-IM.
 K. Zhang et al. / Corrosion Science 90 (2015) 284–295
Fig. 11. SEM photos of mild steel samples after 24 h of immersion in 0.5 M HCl at 70 °C: (a) blank, (b) 1 mM 1-IM, (c) 1 mM 2-IM.
Fig. 12a and c, the amidogen and halogen groups are close to the
metal surface owing to the coordinate bond that heteroatoms with
lone pair of electrons donate the charge to the unoccupied
d-orbital of iron, indicating that those atoms play an important role
in the formation of protective layer.
Fig. 12a shows that the imidazoline ring of adsorbed 1-IM mol-
ecule stands vertically above the metal surface. As for 2-IM shown
in Fig. 12d, the heterocyclic ring covers the interface in relatively
planar form, and that conduces to the sharing of charge between
imidazoline ring and iron, i.e., 2-IM can reduce the exposed area
of the iron surface more efficiently. This phenomenon reveals Cl
atoms affect the charge contribution and the adsorption form of
imidazoline ring, which may be due to the weaker induction effect
of the chloride-substituted group. The binding energy indicates the
stability of adsorptive system and the more positive value suggests
the higher inhibition efficiency [24,41]. The binding energy for
1-IM and 2-IM, shown in Table 5, is 214.6 and 217.3 kJ mol1,
respectively. Therefore, it can be concluded that the adsorption
system of 2-IM is more stable and yields better inhibition perfor-
mance. Investigating the adsorption configurations of 1-IM and
2-IM can explain the difference in the inhibiting ability of the
two compounds.
Quantum chemical calculations were conducted to further
study the relation between the molecular structures of the novel
imidazoline derivatives and their electron density distributions.
Fig. 13 shows the optimized geometrical configurations and the
frontier molecule orbital density distributions of target molecules.
The quantum chemical parameters of 1-IM and 2-IM are listed in
Table 5. It is accepted that the reactivity of the molecule for cor-
rosion inhibition depends on the molecular orbital distribution.
The energy of the highest occupied molecular orbital (EHOMO) is
often regarded as the electron donating ability of the molecule
and the energy of the lowest unoccupied molecular orbital
(ELUMO) suggests the ability of the inhibitor to accept electrons.
According to Fig. 13, the two imidazoline molecules have differ-
ent frontier orbital density distributions. As for 1-IM (Fig. 13a),
the highest occupied molecular orbital (HOMO) is mainly associ-
ated with imidazoline ring and N atom which are the active sites
for the electrophilic attack by metallic cations. Besides, the lowest
Table 5
Results of computational methods for 1-IM and 2-IM via molecular dynamics simulation and quantum chemical calculation.
Compound Einteraction (kJ mol1) Ebinding (kJ mol1) EHOMO (eV)
1-IM 214.6 214.6 5.12
2IM 217.3 217.3 4.93
291
unoccupied molecular orbital (LUMO) is almost distributed
through the whole molecule (Fig. 13b) which can act as a good
electron acceptor. As expected, the obvious character of 2-IM is
that the chloride-substituted region becomes a part of HOMO
(Fig. 13c), suggesting the ability of Cl atom to donate electrons.
Usually, the higher EHOMO value indicates the inhibitor molecule
donate electrons to the empty d-orbital of the metal more easily.
On the contrary, the lower ELUMO value implies the easier transfer
of electrons from the superficial metal to the inhibitor. Results
from Table 5 show 2-IM has higher EHOMO and lower ELUMO values
than 1-IM. Frontier orbital theory illustrates that the adsorption
process of the inhibitor is affected by the energy difference (DE)
between EHOMO and ELUMO [42]. Thereby, the smaller energy gap
(DE) enhances the ability of inhibitor molecules to donate and
accept electrons. DE values for 1-IM and 2-IM are 3.94 and
1.64 eV, respectively.
Furthermore, the dipole moment (l) with greater values con-
tributes to better corrosion inhibition [43]. Values of l from Table 5
follow the order of 2-IM > 1-IM, which may result from the weaker
polarity of CACl bond. In order to better investigate the relation-
ship between inhibition efficiency and parameters of the molecular
orbital, the fraction of electron transferred from the inhibitor mol-
ecule to the iron surface is calculated. Based on Lukovits theorem,
EHOMO and ELUMO of the inhibitor molecule are related to the ioni-
zation potential (I) and the electron affinity (A) [44]. The ionization
potential and the electron affinity are defined as I = EHOMO and
A = ELUMO, respectively. The absolute electronegativity (v) and
the global hardness (c) of the inhibitor molecule are defined as fol-
lows [45]:
IþA
v¼ ð12Þ
2
IA
c¼ ð13Þ
2
Therefore, the fraction of electrons transferred from the inhibi-
tor to the metal surface, DN, is given by:
vFe  vinh
DN ¼ ð14Þ
2ðcFe þ cinh Þ
ELUMO (eV) DE (eV) l (Debye) DN
1.18 3.94 7.543 0.977
3.29 1.64 7.972 1.762
292 K. Zhang et al. / Corrosion Science 90 (2015) 284–295

Fig. 12. Equilibrium adsorption configurations of 1-IM (a and b) and 2-IM (c and d) molecules on Fe (1 1 0) surface in vacuum obtained by molecular dynamic simulations.
Left: side view, right: top view.

Fig. 13. Frontier molecule orbital density distributions of the two molecules, 1-IM: HOMO (a), LUMO (b); 2-IM: HOMO (c), LUMO (d).
 K. Zhang et al. / Corrosion Science 90 (2015) 284–295 293

Fig. 14. Plots of Cdl versus applied electrode potential in 0.5 M HCl solution at 30 °C: blank (a), 1 mM l-IM (b) and 1 mM 2-IM (c).

The value of DN, shown in Table 5, is calculated by quoting the indicate that excess positive charge exists on the metal
theoretical values of vFe (7 eV mol1) and cFe (0 eV mol1). Gener- surface before and after the addition of the inhibitor in 0.5 M HCl
ally, the higher value of DN implies better inhibition effectiveness, solution.
attributed to electron donation in the case of DN less than 3.6 [45]. The interaction between adsorbed inhibitor and metal surface
We can notice that 2-IM has a greater value of DN (7.972 D) than in the acid solution can be defined as follows: (i) electron-sharing
1-IM (7.543 D). The above results of EHOMO, ELUMO, DE, l and DN between the inhibitor molecule (unpaired or p electrons) and the
confirm the inference that Cl atoms impact the charge distribution vacant d orbitals of the metal (chemisorption); (ii) electrostatic
of 2-IM and thus improve the inhibitory effect. interaction between the charged inhibitor and Fe surface (physi-
sorption); (iii) mixed type (both chemisorptions and physisorp-
3.9. Mechanism of adsorption and inhibition tion). Due to the acquired results of experiments and theoretical
calculation, a credible inference of the adsorption process is
Organic inhibitors possess inhibiting ability by the formation of expressed by Fig. 15 in which 2-IM is set as an example. Firstly,
protective film on the metal surface and the adsorption behaviour hydrated chloride ions are specifically adsorbed onto the
is mainly determined by the electrostatic interaction between the electropositive metal surface to bring excess negative charges from
mild steel and the inhibitor. The surface charge of the metal can be the solution, enhancing the adsorption of cations. As a result of
examined by comparing the open circuit potential (Eocp) with Epzc. electrostatic interaction, the protonated imidazoline molecules
After 1 h of immersion in 0.5 M HCl solution without and with are attracted toward the solid/liquid interface to form a protective
1 mM inhibitors, we was characterized by the plots of Cdl in film, preventing the metal from touching the aggressive medium
Fig. 14. The surface charge of iron in the aggressive medium can
be explored according to the equation:
Table 6
EC ¼ Eocp  Epzc ð15Þ Values of Eocp, Epzc and EC for mild steel in blank and inhibited solutions at 30 °C,
along with an immersion time of 1 h.
where EC is the ‘‘rational’’ corrosion potential [46,47]. As seen from
Fig. 14, the lowest points of the curves can be regarded as the Epzc of Medium Epzc (mV vs. SCE) Eocp EC (mV vs. SCE)
(mV vs. SCE)
the electrode when Cdl reaches its minimum value. Furthermore,
the decrease of Cdl for 1-IM and 2-IM reveals the protective barrier 0.5 M HCl 551 507 44
0.5 M HCl + 1 mM 1-IM 550 508 42
of inhibitors compared with the blank. As shown in Table 6, the 0.5 M HCl + 1 mM 2-IM 549 510 39
positive values of EC in the blank and inhibitor-containing solutions
294 K. Zhang et al. / Corrosion Science 90 (2015) 284–295
Fig. 15. Schematic illustration of the adsorption mechanism of 2-IM on mild steel
surface in HCl solution.
[48]. In addition to the physisorption form, the inhibitors may
cover the metal surface by the chemisorption process at the same
time, which may be proved by analyzing the details of MD
simulations and quantum chemical calculations. In conclusion,
the adsorption behaviour of the two compounds is mixed-type,
involving physical and chemical interactions.
4. Conclusions
New halogen-substituted imidazoline compounds (1-IM and
2-IM) have been synthesized and studied as corrosion inhibitors
for mild steel in 0.5 M HCl solution. The main conclusions are as
follows:
(1) 1-IM and 2-IM act as good inhibitors for the corrosion of
mild steel in 0.5 M HCl solution and the efficiency increases
with the increasing compound concentration.
(2) When the temperature increases, the inhibitive effect of
1-IM decreases while that of 2-IM does not significantly
change.
(3) The adsorption behaviour of each inhibitor on the mild sur-
face obeys the Langmuir adsorption isotherm.
(4) The results of Epzc indicate that the surface of mild steel is
positively charged before and after the addition of inhibitors.
(5) The evaluation of corrosion inhibition of halogen-substi-
tuted imidazoline indicates that the chloride substituted
inhibitor functions more effectively than the fluoride
version.
Acknowledgement
The authors are greatly thankful to Petrochemical Wastewater
as Resources and Industrialization of Zero-discharge Key Technol-
ogy in Key Watersheds (2013ZX07210001) for financial support.
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