ISSN 20702051, Protection of Metals and Physical Chemistry of Surfaces, 2015, Vol. 51, No. 5, pp. 918–927.

© Pleiades Publishing, Ltd., 2015.

PHYSICOCHEMICAL PROBLEMS
OF MATERIALS PROTECTION

Inhibition of Mild Steel Corrosion in Hydrochloric Acid Solution

by Fe and Cr Schiff base Complexes1
Mohammadreza Karbaschia, Mojtaba NasrEsfahanib, and Mahmoud Zendehdelb
a
Department of Materials, Najafabad Branch, Islamic Azad University, Najafabad, Iran
b
Department of Chemistry, Najafabad Branch, Islamic Azad University, Najafabad, Iran
email: mnasresfahani@iaun.ac.ir
Received January 27, 2015

Abstract—A comparative study of Fe and Cr complexes with a Schiff base ligand (1[(2hydroxy
ethyl)amino]2(5methoxysalicylideneamino)ethane) as inhibitors for mild steel corrosion in 0.5 M HCl
solution at 25°C was carried out. Electrochemical techniques were applied to study the metal corrosion
behavior of these inhibitors. EDX, SEM and ATRFTIR studies of the electrode surface confirmed existence
of a protective adsorbed film of the inhibitors on the electrode surface. The inhibition efficiency was increased
with the inhibitor concentration. The mechanism of adsorption is concluded that the adsorbed chloride ions
on the metal surface could be stabilized in their anionic form like a crabclaw.
DOI: 10.1134/S2070205115050135

1
1. INTRODUCTION
Mild steel is widely used in store tanks, petroleum
refineries, and so on. The main problem of using mild
steel is its dissolution in acidic media. Acid solutions
are widely used for removal of undesirable scale and
rust in many industrial processes [1].
Inhibitor is a keyword in the case of corrosion pre
vention by changing the chemistry of corrosive media.
Many industrial divisions such as acid cleaning bath,
water cooling system, various refinery units, pipelines,
chemical operations, steam generators, ballast tanks,
oil and gas production units are involved with inhibi
tors due to high corrosion rates in these parts [2].
The use of inhibitors is one of the most practical
methods for protection against corrosion especially in
acidic conditions [3, 4]. Acid solutions are generally
used in several industrial processes. Severe corrosion
problems arise due to the wide use of hydrochloric acid
for pickling, rescaling and cleaning processes of mild
steel surfaces [5]. Because of their aggressiveness, the
use of corrosion inhibitors is considered as the most
effective method for protection of many metals and
alloys against such acid attack [6, 7]. Compound con
taining functional groups with heteroatoms, (N, O, S)
which can donate one pair of electrons, are found to be
very effective as inhibitor against metal corrosion in
many environments. Many heterocyclic compounds
with polar groups and/or π electrons are used as inhib
itors in acidic solutions [8]. Organic molecules of this
type can adsorb on the metal surface and form a bond
between their heteroatoms and/or π molecular orbitals
and the metal surface, thereby reducing the corrosion
1 The article is published in the original.
rate [9–10]. Schiff base, an organic compound having
general formula R–C=N–R' where R and R' are aryl,
alkyl or cycloalkyl or heterocyclic groups formed by
the condensation of an amine and a carbonyl group, is
a potential inhibitor for different metallic surfaces.
Several Schiff bases had been reported as effective cor
rosion inhibitors for mild steel in HCl media [11–13].
The existing data show that these inhibitors act by
adsorption on the metal/solution interface. This phe
nomenon could take place via: i—electrostatic attrac
tion between the charged metal and the charged inhib
itor molecules, ii—dipoletype interaction between
unshared electron pairs in the inhibitor with the metal,
iii—π electron interaction with the metal, and iv—
combination of all of the above [14]. On the other
hand, some organic inhibitors could react with metal
ions resulting from corrosion process to form analo
gous complexes spontaneously that may decrease the
corrosion rate. However, studies about metal com
plexes as corrosion inhibitor for mild steel in acid solu
tion appeared in the literature are extremely limited
[15, 16].
Metal Schiff base complexes are widely used as cat
alyst of chemical reactions [17], biological [18], anti
fungal [19], anti tumor and anti HIV activities [20].
Very few works have been performed to study anticor
rosive behaviour of metal Schiff base complexes.
AbdelGaber et al. [21] proposed corrosion inhibition
through a bulky Co (III) Schiff base complex molecule
could cover more than one active site, where mild steel
was immersed in HCl solution. Some metal complexes
of Schiff base are suggested as an effective corrosion
inhibitor for Cu and mild steel [22, 23].

918
 INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION
The aim of the present investigation is to examine
the inhibitory action of two novel Schiff base com
plexes of Iron and Chromium with unique steric
molecular structure with two OH bonding tail,
absorbed at the interface of the metal and two hydro
phobic tail at the opposite side of the metal, namely:
Bis[N(2(2hydroxyethylamino)ethyl)5methox
ysalicylideneimine) For the corrosion of mild steel in
0.5 M HCl on the basis of weight loss, potentiody
namic polarization and impedance measurements.
2. EXPERIMENTAL
2.1. Synthesis of Schiffbase Metal Complexes
The Schiffbase Fe complex (SBIC) was synthe
sized by reaction of precursor compound N(2(2
hydroxyethylamino)ethyl) 5methoxysalicylidene
imine (L) with FeCl3 ⋅ 6H2O. The precursor com
pound L was synthesized by reaction of equimolar sal
icylaldehyde (0.84 mmol, 103 mg) and 2(2aminoet
hylamino)ethanol (1.2 mmol, 122 mg) in anhydrous
ethanol (5 ml). FeCl3 ⋅ 6H2O (0.12 mmol, 33 mg) in
anhydrous ethanol (5 ml) was added to previous solu
tion. After keeping the solution in air to evaporate
about half of the solvent, dark brown prisms of the
complex compound were formed. The crystals were
isolated, washed with ethanol three times and dried in
a vacuum desiccator using silica gel. The Schiffbase
Cr complex (SBCC) was synthesized in the same pro
cedure. All the chemicals chosen for our study were of
analytical grade and double distilled water was used
throughout the experiment. The chemical structure of
synthesized inhibitors (SBIC and SBCC) has shown in
Fig. 1.
2.2. Electrodes
Prior to all measurements, the mild steel speci
mens, having composition (in wt%) 0.099 C, 0.166 Si,
0.346 Mn, 0.131 Cr, 0.040 Mo and the remainder iron,
were abraded successively with fine grade emery
papers (600–1200 grade). The specimens were washed
thoroughly with double distilled water and finally
degreased with acetone and dried at room tempera
ture. For weight loss measurements, mild steel speci
mens dimensions 26 mm diameter and 2 mm thick
ness were used. For polarization and electrochemical
impedance studies, the metal was embedded in epoxy
resin, to expose a geometrical surface area of 1 cm2 to
the electrolyte. The aggressive solution 0.5 M HCl was
prepared by dilution of analytical grade HCl (37%)
with double distilled water and all experiments were
carried out in unstirred solutions.
2.3. Corrosion Tests
2.3.1 Weight loss measurements. Gravimetric cor
rosion measurements were carried out according to
the ASTM standard procedure described in [24]. In
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 5 2015
919
(a)
MeO N N OH
H
O
Fe O
NH N OMe
HO
(b)
MeO N N OH
H
O Cr O
NH N OMe
HO
Fig. 1. Chemical structures of Schiff base metal com
plexes, (a) SBIC and (b) SBCC.
brief, mild steel specimens in triplicate were immersed
for a period of 4 h in 50 mL HCl 0.5 M containing var
ious concentrations of studied inhibitors. After
immersion, the surface of the specimen was cleaned by
double distilled water followed by rinsing with ace
tone. The mass of the specimens before and after
immersion was determined using an analytical bal
anced accurate to 0.1 mg. In the present study, for the
specified experimental conditions, relative differences
between replicate experiments were found to be less
than 6% indicating good reproducibility. For further
data processing, the average of the three replicate val
ues was used. For each experiment, a freshly prepared
solution was used and the solution temperature was
controlled at a desired value thermostatically.
2.3.2 Electrochemical techniques. Electrochemical
impedance measurements (EIS) and potentiody
namic polarization studies were carried out using an
electrochemical unit (model PARstat 2273). A three
electrode setup was employed using a graphite of con
venient area as counter electrode and a SCE electrode
(Radiometer Copenhague) as reference electrode.
The working electrode mild steel (7.5 cm long stem)
with the exposed surface of 1.0 cm2 was immersed into
aggressive solutions with and without inhibitor and the
open circuit potential was measured after 30 min, (the
stable potential time). EIS measurements were per
formed at corrosion potentials, Ecorr, over a frequency
range of 100 kHz to 10 mHz with an AC signal ampli
tude perturbation of 10 mV peak to peak. Potentiody
namic polarization studies were performed with a scan
rate of 1 mVs–1 in the potential range from 250 mV
below the corrosion potential to 250 mV above the
corrosion potential. All potentials were recorded with
respect to SCE. All measurements were done at 25 ±
0.1°C. Impedance fitting was performed using Zview
software.
920 MOHAMMADREZA KARBASCHI et al.

Table 1. Weight loss results of mild steel corrosion in 0.5 M HCl with addition of various concentrations of inhibitor at 25°C
CrSchiff base complex (SBCC) FeSchiff bae complex (SBIC)
C/(mg/L) weight corrosion weight corrosion
θ IEw (%) θ IEw (%)
loss (mgr) rate (mpy) loss (gr) rate (mpy)
0 8.3 – – 75 8.3 – – 75
100 2.1 0.74 74 19 3.3 0.60 60 30
200 1.6 0.81 81 14.5 2.4 0.71 71 21.7

2.4. Surface Examination
and Analysis of Corrosion Products
2.4.1 Scanning electron microscope (SEM). The
morphology and inhibition effect of the surface of
mild steel in 0.5 m HCl solution in absence and pres
ence of 400 ppm of Schiff base complexes for 4 h was
also tested by SEM examinations.
2.4.2 UVreflectance spectral studies. Spectropho
tometer technique was employed in this study to inves
tigate the stability of the complexes under study. Spec
tra were achieved using UVvisible double beam ratio
recording, spectrophotometer JASCO model V670.
3. RESULTS AND DISCUSSION
3.1. Weight Loss Measurements
The weight loss method of monitoring corrosion
rate is useful because of its simple application and reli
ability [25]. Therefore, a series of weight loss measure
ments were carried out in the absence and presence of
various concentrations of the inhibitors. The behavior
of corrosion inhibition for mild steel by SBCC and
SBIC was investigated by the corrosion weight loss
measurements in 0.5 M HCl solution is shown in Table 1.
Weight loss, surface coverage (θ) and inhibition effi
ciency (IEW(%)) for different SBCC and SBIC con
centrations were reported. Inhibition efficiency with
200 ppm of inhibitor concentration for SBCC and
SBIC inhibitors at room temperature was obtained
respectively to 82 and 73%. By increscent of SBCC
and SBIC concentration, the surface coverage and
inhibition efficiency were improved. Corrosion rate in
different concentrations of the inhibitors are shown in
Table 1. Average corrosion rate of steel in 0.5 M HCl is
169 mpy but in present of 200 ppm of SBCC and SBIC
the corrosion rate slow down respectively to 29.8 and
46.8 mpy.
3.2. Polarization Measurements
Potentiodynamic polarization plots for mild steel
specimens in 0.5M HCl solution and at room temper
ature in the absence and presence of different concen
trations of SBIC and SBCC are shown in Fig. 2. The
results of polarization measurements are given in Table 2.

(a) (b)
1 3 1 1
1 1–4
2 4 2
–2 3 –2
3
4
4
Current density, i/Acm–2

–3 2 –3
Eb
Eb
–4 –4
1 – 0 ppm 1 – 0 ppm
2 – 100 ppm 2 – 100 ppm
–5 3 – 200 ppm –5 3 – 200 ppm
4 – 400 ppm 4 – 400 ppm

–6 –6
–0.8 –0.6 –0.4 –0.2 –0.8 –0.6 –0.4 –0.2
E (vs. SCE)/V

Fig. 2. Polarization curves of mild steel in 0.5 M HCl in the absence and presence of various concentrations of inhibitors; SBIC
(a), SBC (b).

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 INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION 921

Table 2. Kinetic parameters of mild steel in 0.5 M HCl at 25 ± 1°C containing different concentrations of SBIC and SBCC
–Ecorr Icorr βc βa
Inhibitor C (mg/L) θ IE (%) mpy
(mV SCE–1) (μAcm–2) (mV dec–1) (mV dec–1)
Blank 0 343 230 97 72.9 0 – 108
SBIC 100 306 79 97 78 0.65 65.5 36
200 302 37 98 78 0.83 83.9 17
400 294 33 94 69 0.85 85.6 15
SBCC 100 284 34 97 42 0.85 85.2 16
200 290 26 101 65 0.88 88.7 12
400 294 24 90 61 0.89 89.5 11

The respective kinetic parameters including corrosion inhibitor concentration reflect the formation of anodic
current density (icorr), corrosion potential (Ecorr), protective films on the electrode surface.
cathodic Tafel slope (βc) and anodic Tafel slope (βa)
are listed in Table 2. The degree of surface coverage (θ)
and the percentage of inhibition efficiency (IE%) were 3.4. Electrochemical Impedance Measurements
calculated using the following equations [26]: Impedance measurements of steel electrode at its
0
i corr– i corr open circuit potential after 0.5 h of immersion in
θ = 
0
. (1) 0.5 M HCl solution alone and in the presence of vari
i corr ous inhibitors concentrations were performed over the
IE% = θ × 100, (2)
0 (a)
where i corrand i corr are corrosion current densities in
90
the absence and presence of inhibitors, respectively. It
is illustrated from the data of Table 2 that the addition
of SBIC and SBCC decrease corrosion current den 80
sity. It can be clearly seen that the inhibition efficiency SBIC
of SBIC and SBCC increase with inhibitor concentra SBCC
IE, %

tions. Maximum Inhibition efficiencies of SBIC and 70

SBCC were obtained 85.4 and 86 respectively.
The response graphs for the both of two inhibitors
that related to results of electrochemical measure 60
ments such as inhibition efficiency and corrosion rate
vs. inhibitor concentration are shown in Fig. 3. With
increase of inhibitors concentration, the corrosion 50
rate (mpy) is shifted to lesser extent and surface occu 150 250 350 450
pied degrees (θ) enhanced to the positive amounts. Concentration, ppm
These behaviors show that SBIC and SBCC act as 120 (b)
good inhibitors for the corrosion of the mild steel in
0.5M HCl solution at room temperature as well as 100 SBIC
good coverage of the metal surface. Addition of SBIC
reduces the anodic dissolution without affecting active SBCC
80
cathodic current density in the polarization curves.
But the presence of SBCC results in a marked shift in
mpy

60
the cathodic branches and to a lesser extent in the
anodic branches of the polarization curves. Moreover,
in the presence of SBIC and SBCC the values of cor 40
rosion potential Ecorr are nearly constant; therefore,
SBIC could be classified as a mixedtype inhibitor 20
with predominant anodic effectiveness and SBCC
could be classified as a mixed type inhibitor with pre
dominant cathodic effectiveness. On the other hand, the 0 100 200 300 400
recorded polarization curves in the presence of inhibitors Concentration, ppm
are characterized by the presence of anodic breakdown
potential, Eb. The noble shift of Eb and the decrease of the Fig. 3. Plots of inhibition efficiency and mpy vs. concen
corresponding current densities with increasing the tration of inhibitor.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 5 2015

922 MOHAMMADREZA KARBASCHI et al.
ZCPE
(a)
–60
0 ppm
–50 randelz fit

–40 Rs
Zim/Ω cm2

–30
–20 Rct

–10 Fig. 5. Equivalent circuits used to fit the EIS data of steel
in 0.5 M HC1 + xM inhibitor.
0
10 process are also given in Fig. 4a. The intersection of
0 20 40 60 80 100 120 the capacitive loop with the real axis represents the
Zre/Ω cm2 ohmic resistance of the corrosion product films and
(b) the solution enclosed between the working electrode
–250 and the reference electrode, Rs [27, 28]. Rct represents
0 ppm
100 ppm
the chargetransfer resistance whose value is a mea
–200 sure of electron transfer across the surface and is
200 ppm
400 ppm inversely proportional to corrosion rate [29]. The con
–150 randelz fit
stant phase element, CPE, is introduced in the circuit
Zim/Ω cm2

instead of a pure double layer capacitor to give a more

–100 accurate fit [30]. The impedance of the CPE is
expressed as:
–50
1
Z CPE = n , (2)
0 Y 0 ( jω )
where Y0 is the magnitude of CPE, –1 ≤ n ≤ 1. The HF
50
0 100 200 300 400 500 loops have depressed semicircular appearance, 0.5 ≤ n ≤ 1,
Zre/Ω cm2 which is often referred to as frequency dispersion as a
(c) result of the nonhomogeneity or the roughness [32] of
–300 0 ppm
the solid surface. The HF capacitive loop, RctCPE,
100 ppm can be attributed to the chargetransfer reaction. The
–250 200 ppm presence of the LF inductive RLL loop may be attrib
400 ppm
–200 uted to the relaxation process obtained by adsorption
Zim/Ω cm2

randelz fit
–150
–100
–50
0 0.5 M HCl solution has been studied at the respective
50
0 100 200 300 400 500 600 700
Zre/Ω cm2
Fig. 4. Nyquist plot of the steel electrode in 0.5 M HC1
without (a) and with different concentrations of (b) SBIC
and (c) SBCC after immersing the electrode in the working
solutions for 1 h under open circuit conditions.
frequency range from 100 KHz to 10 MHz. The
recorded EIS spectrum for steel in 0.5 M HCl, Fig. 4a,
shows one depressed capacitive loop at higher fre
quency range (HF) followed by an inductive loop that
is observed in the lower frequency region (LF). The
equivalent circuit of Fig. 5, fits well our experimental
results, simulated points originated from the fitting
– +
specis like Cl ads. and H ads. on the electrode surface
[33]. It may also attribute to the redissolution of the
passivated surface at low frequencies [34].
The effect of addition of increasing concentrations
of the investigated compounds on the EIS of steel in
open circuit potentials; some of the obtained results
are shown in Figs. 4b and 4c. The electrochemical
parameters obtained from fitting the recorded EIS
data using equivalent circuit of Fig. 5 are listed in Table 3.
The inhibition efficiencies, IE%, of the tested inhibi
tors were calculated from the Rct values at different
concentrations using the following equation [35]:
–1 –1
R ct ( free ) – R ct ( inh )
–1
 × 100,
IE% =  (3)
R ct ( free )
where Rct(free) and Rct(inh) are the chargetransfer resis
tance values in the absence and presence of inhibitor,
respectively. Increasing the concentration of either
SBIC or SBCC increases the corresponding IE% val
ues till Cinh =400 ppm without passing through a max
imum, Figs. 4b and 4c and Table 3. We can note from

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 INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION 923

Table 3. Electrochemical impedance parameters for mild steel corrosion in 5.0 M HCl solution in the absence and presence
various concentrations of inhibitors
CPET
Inhibitor Cinh (ppm) CPEP fmax (μF cm–2) Rs (Ω) Rct (Ω) θ IE %
(μF cm–2)
Blank 0 140 0.93 13.9 140 1.62 110 – –
SBIC 100 90 0.91 5.17 69 0.071 455 0.75 75
200 83 0.90 5.18 51 2.74 599 0.81 81
400 68 0.90 5.18 48 2.52 630 0.83 83
SBCC 100 140 0.92 7.2 140 3.01 210 0.48 48
200 120 0.92 7.2 76 2.48 290 0.62 62
400 90 0.92 5.18 65 2.71 470 0.77 77

Figs. 4b and 4c that the characteristic frequencies of
the inductive loop diminish with increasing the mag
nitude of the electrode impedance whatever the inhib
itor concentration is. In the high impedance Nyquist
plots, the growing up inhibiting film delays the charge
transfer processes to lower frequencies. The high
impedance EIS curves were fitted to the one time con
stant equivalent circuit shown in Fig. 5 where the
induction loops shifted below the studied low fre
quency limit. The protection layer resistance and the
diffuse charge capacitance in it are not separated in
this approximation, rather they are conceived to be
included in the elements of the used circuits.
Inspection of the data reveals that its addition of
the inhibitors increases the capacitive loop diameter of
the Nyquist plots without affecting their characteristic
features. This means that the inhibition action of this
inhibitor is due to its adsorption on the metal surface
without altering the corrosion mechanism. In addi
tion, the double layer capacitances, Cdl, for a circuit
including a CPE were calculated from the following
equation [36, 37]:
n–1
C dl = Y 0 ( ω max ) , (4)
where ωmax = 2πfmax, fmax is the frequency at which the
imaginary component of the impedance is maximal.
The data of Table 3 show that the magnitude of Cdl
decreases with increasing Cinh. The decrease in Cdl
could be attributed to the adsorption of the inhibitors
forming protective adsorption layers [38]. The thick
ness of the protective layer (d) is related to Cdl accord
ing to the following equation [39]:
εε
C dl = 0 , (5)
d adsorption of inhibitor on the mild steel surface
where ε is the dielectric constant of the protective layer and
ε0 is the permittivity of free space (8.854 × 10–14 F cm–1).
3.5. Adsorption Isotherms
Adsorption isotherms provide information about
the interaction of the adsorbed molecules with the
electrode surface [40, 41]. The adsorption of an
organic adsorbate at metalsolution interface can be
presented as a substitution adsorption process between
the organic molecules in aqueous solution, (Org
(sol)), and the water molecules on metallic surface,
(H2O (ads)) [42]:
Org ( sol ) + xH 2 O ads ⇔ Org ( ads ) + H 2 O ( sol ) , (6)
where Org(sol) and Org(ads) are the organic specie dis
solved in the aqueous solution and adsorbed onto the
metallic surface, respectively, H2O(ads) is the water
molecule adsorbed on the metallic surface and x is the
size ratio representing the number of water molecules
replaced by one organic adsorbate. For the studied
inhibitors, it was found that the experimental data
obtained from polarization readings could be fitted by
Langmuir’s adsorption isotherm.
According to this isotherm, the surface coverage (θ) is
related to inhibitor concentration (C) by [43, 40]:
θ
 = K ads C. (7)
1–θ
Rearranging Eq. 7 gives:
C 1
 =   + C, (8)
θ K ads
where Kads is the equilibrium constant of the inhibitor
adsorption process, C is the inhibitor concentration
and θ is the surface coverage that was calculated by Eq. 1.
This model for Langmuir’s adsorption isotherm has
been used extensively in the literatures for various
metal/inhibitor/acid solution systems [41]. A fitted
straight line is obtained for the plot of C/θ versus C
with slopes close to 1 as seen in Fig. 6a and Fig. 6b.
The strong correlation (R2 > 0.99) suggests that the
obeyed this isotherm. This isotherm assumes that the
adsorbed molecules occupy only one site and there are
no interactions with other adsorbed species [41].
The Kads values can be calculated from the intercept
lines on the C/θaxis. This is related to the standard
0
free energy of adsorption ( ΔG ads ) with the following
equation [41]:

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 5 2015

924 MOHAMMADREZA KARBASCHI et al.

(a) exist between inhibitor and the charged metal surface

0.9 (i.e., physisorption). Those around –40 kJ/mol or more
y = 0.978x + 0.126
0.8 R2 = 0.990 negative are indicating of charge sharing or transfer
ring from organic specie to the metal surface to form a
0.7 coordinate type of metal bond (i.e., chemisorption)
C/θ (mM)

0
0.6 [41]. In some literatures, the values of ΔG ads are
0.5 reported less negative than –40 kJ/mol for physical
adsorption commonly interpreted as the formation of
0.4 an adsorptive film with an electrostatic character [41].
0
0.3 Regarding the present work, the calculated ΔG ads val
0.2 ues for SBIC and SBCC show that an electrostatic
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 interaction, i.e., physisorption, is presented between
C (mM) the inhibitors and charged metal surface. The higher
(b) 0
values of Kads and ΔG ads refer to higher adsorption and
0.9
y = 1.134x + 0.018 higher inhibiting effect. The higher inhibition effects
0.8 R2 = 0.999 of SBCC in comparison with the SBIC may be attrib
0.7 uted to the deposition of trivalent chromium on the
surface. In physisorption process, it can be assumed
0.6 that acid anions such as Cl– ions are specifically
C/θ (mM)

0.5 adsorbed on the metal surface, donating an excess

negative charge to the metal surface. In this way,
0.4 potential of zero charge (PZC) becomes less negative
0.3 which promotes the adsorption of inhibitors in cat
ionic form. This is also outlined by other researchers
0.2 [44]. On the other hand, the adsorbed chloride ions on
0.1 the metal surface could be stabilized in their anionic
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 form by hydrogen bonding of oxygen and nitrogen
C (mM) atoms in the tail of the complexes, like a crabclaw
(Fig. 7). This molecular selfassembling not only sta
Fig. 6. Langmuir adsorption isotherm (C/θ vs. C) of inhib bilized the corrosive chloride ions but also improve the
itors in 1M HCl at 25°C (a) SBIC and (b) SBCC. surface coverage by four mediumstrength hydrogen
bonding.
0
ΔG ads = RT ln ( 55.5K ads ), (9) Attenuated total reflection (ATR) is a sampling
technique used in conjunction with infrared spectros
where R is the gas constant and T is the absolute tem copy, which enables samples to be examined directly
perature. The constant value of 55.5 is the concentra in the solid state without further preparation [45].
tion of water in solution in mol/dm3. The values of Kads Corrosion inhibition of SBIC and SBCC on the metal
0
and ΔG ads for SBIC and SBCC are given in Table 4. steel is evaluated by ATRFTIR method. Figure 8
0 shows the FTIR reflection of the pure mild steel and
The negative sign of ΔG ads indicate that the inhibitors are mild steel sample in the HCl solution with and without
spontaneously adsorbed onto the metal surface [41]. corrosion inhibitors. The ATRFTIR curve of the mild
0
Generally, the magnitude of ΔG ads around –20 kJ/mol steel sample after 1 day aging in HCl solution shows
or less negative is assumed for electrostatic interactions the corrosion products stretching modes but the sam
ples, which are aged in present of SBIC and SBCC
show stretching modes of the Schiffbase complexes.
Table 4. Thermodynamic and equilibrium adsorption param The OH and NH bending FTIR peaks are appeared
eters for adsorption SBIC and SBCC on mild steel surface in in 1020 cm–1 to 1200 cm–1 wavenumbers. Also, O–H
0.5M HCl solutions stretching modes are appeared in 2800–3000 cm–1.
0 These modes are directly related to displacements of
Inhibitor Kads (L/mol) ΔG ads (kJ/mol) the hydrogen atoms in the crabclaw site, which are
bonded by hydrogen bonding with chloride ion.
Blank – –
Another important FTIR peak, which appears in
SBIC 10 × 103 –32.7 1400 cm–1, is related to C=N stretching of the imine
SBCC 50 × 103 –36.7 bonds.

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 INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION 925

(a)
Cl1
H3A H6A Mild Steel
O3 O6
Mild Steel in HCl

H2A H4A

Reflectance
N2 N4

Mild Steel in HCl + SBCC

3800 3400 3000 2600 2200 1800 1400 1000 600

Wavenumber, cm–1
(b)
Mild Steel

Fig. 7. Hydrogen bondings in the crabclaw site of the Mild Steel in HCl
complexs.

3.6. Stability Measurements of Schiff base Complexes Reflectance

Stability of SBIC and SBCC was measured in eth
anol and HCl solutions by UVVis technique. UVVis
absorption spectra of SBIC and SBCC in ethanol and
HCl solutions are shown in Fig. 9a and 9b respectively.
In HCl solution, the absorption spectra of SBIC and
SBCC did not change with ethanol solution, which
demonstrates the stability of both inhibitors in acidic
media. Maximum absorption picks of SBIC and
SBCC in ethanol solution are 355 and 285 nm and in
HCl solution at 350 and 287 nm, respectively. The
small difference between absorption picks is from sol
vent effects.
3.7. Surface Analysis
SEM and EDX analysis for the mild steel speci
mens after immersion in 0.5 M HCl solutions before
and after potentiodynamic tests, with and without
SBIC and SBCC, are shown in Fig. 8 and Table 5. The
morphology of specimen surface in Fig. 10b shows a
characteristic uniform corrosion of mild steel in
hydrochloric acid already documented [46, 47]. In the
corrosion product is found to contain chlorine ele
ment besides oxygen and iron, indicating hydrate
product of iron with hydrochloric acid. It suggested an
uncovered surface in acid and mild steel severely cor
Mild Steel in HCl + SBIC
3800 3400 3000 2600 2200 1800 1400 1000 600
Wavenumber, cm–1
Fig. 8. FTIR reflectance spectra of mild steel before and
after immersion in 0.5M HCl solution without inhibitors
and after immersion in 0.5M HCl solution containing
inhibitors, (a) SBIC and (b) SBCC for 24 h.
roded. The highly oxidized phase perhaps formed in air
when desiccated under no protection for the surface.
In the case of addition of SBIC to the acid solution
(see Fig. 10c), the morphology is more integrative
than that in blank. Some areas are still oxidized phases
but their oxygen content decrease when compared to
that in blank, and chloride hydrate was detected lower
than that in the blank. This indicated that there is an
adsorption layer formed and protect the specimen sur
face after immersion in the acid containing SBIC, so

Table 5. EDX results corresponding to Fig. 8 (normalized, in wt%)

Inhibitor Fe Cr O C Cl Total
Blank 81.81 – 11.92 3.81 2.46 100
SBIC 85.75 – 9.55 2.99 1.71 100
SBCC 88.82 1.08 6.80 2.77 0.93 100

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 5 2015

926 MOHAMMADREZA KARBASCHI et al.

(a)
1.2
SBIC in Ethanol
SBIC in acid
1.0

0.8
Absorbance

0.6 100 µm (b) 20 µm

(а)
0.4

0.2
0
250 350 450 550 650
Wavelength, nm
2.0 (c) 20 µm (d) 20 µm
(b) SBCC in Ethanol
SBCC in Acid
Fig. 10. SEM micrographs of mild steel after immersion in
1.5 0.5 M HCl (a) Blank; (b) 400 mg/L SBIC; (c) 400 mg/L
SBCC after potentiodynamic tests.
Absorbance

1.0
0.5
0 Chromium on their molecules structure) and the neg
250 350 450 550 650
Wavelength, nm
Fig. 9. UVvisible absorption spectra for synthesized com
plexes; SBIC(a), SBCC(b) in alcoholic and acidic solu
tions.
the oxidation and corrosion of mild steel is lightly in
comparison with that in blank.
As shown in Fig. 10d, after addition of SBCC in the
acid, the surface morphology of mild steel is smoother
than that in SBIC case, and some mechanically pol
ishing nicks can still be found. Chloride hydrate was
detected lower than that in SBIC case, and the oxida
tion degree is lower than that in SBIC reflected by the
oxygen content.
It can be concluded that, the inhibition ability is in
descent order as SBCC > SBIC from the evidence of
surface corrosion and oxidation degree after immer
sion in acid and drying in air. It is in good accordance
with the results obtained from potentiodynamic and
impedance measurement.
Comparing the EDX results (Table 5) one could
hypothesize the process of inhibition. The results
demonstrate formation of a layer on the sample
immersed in SBCC electrolyte composed of Cr 1.08%
atm. In other words, SBCC and SBIC form a layer on
the mild steel surface. A schematic interaction mech
anism of metal Schiff base complexes with mild steel
surface is displayed in Fig. 9. To consider the structure
of the investigated inhibitors, several potential source
of inhibitormetal interaction can be identified. First
the electrostatic force between the cationic molecules
(followed by protonation of its basic functionalities in
acidic media with excess positive charge of Iron and
ative charged of the metal surface (especially in acidic
media which may be brought about by specific adsorp
tion of chloride anions) leading the SBCC and SBIC
molecules coming toward the water interface of the
metal, then there are the free electron pair on OH den
tate capable of forming a coordinate bond with dtype
orbitals of the metal [48]. Further, the double bonds in
the molecules allow back donation of metal delec
trons to the π*orbitals. Thirdly, π electrons from the
aromatic rings may interact with metal surface.
4. CONCLUSION
Two novel synthesized Schiff base of iron and chro
mium complexes are found to inhibit the corrosion of
mild steel in 0.5 M HCl solution and the extent of
inhibition is concentration dependent. Inhibition effi
ciency increases with increasing inhibitor concentra
tion. The value of Gibbs free energy of adsorption
indicates that SBIC and SBCC is more physically
adsorbed onto the surface of the metal and the nega
0
tive values of ΔG ads show the spontaneity of the
adsorption. The results of potentiodynamic polariza
tion measurements point to SBIC and SBCC func
tioning as a mixed type (cathodic/anodic) inhibitors.
The adsorption characteristics of SBIC and SBCC
were approximated by Langmuir’s adsorption iso
therm.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 5 2015

 INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION
ACKNOWLEDGMENTS
This research has been supported financially by
Najafabad Branch, Islamic Azad University.
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