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Experimental and quantum chemical evaluation of Schiff bases of isatin

as a new and green corrosion inhibitors for mild steel in 20% H2 SO4
K.R. Ansari, M.A. Quraishi∗
Department of Chemistry, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005, India

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

Article history: The corrosion inhibition property of Schiff bases of isatin namely 3-(4-(3-phenylallylideneamino)
Received 1 September 2014 phenylimino)indolin-2-one (PI) and 3-(4-(4-methoxybenzylideneamino)phenylimino)indolin-2-one (MI) has
Revised 16 February 2015
studied in 20% H2 SO4 for mild steel using gravimetric, electrochemical impedance spectroscopy (EIS), po-
Accepted 15 March 2015
tentiodynamic polarization (Tafel), scanning electron microscopy (SEM) techniques and quantum chemical
Available online xxx
calculation. Inhibitors adsorption takes place by obeying Langmuir adsorption isotherm. Potentiodynamic
Keywords: polarization measurements showed that inhibitors acted as a mixed type but cathodically dominant.
Adsorption © 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Corrosion
Polarization
H2 SO4

1. Introduction calculation, scanning electron microscopy (SEM) and quantum chem-

In the chemical industries huge amount of H2 SO4 is being used
for removal of undesired scales and rust which are present on the
metal surface. But during this process detoriation of metals occurs.
In order to reduce the metal destruction inhibitors are added. The
addition of corrosion inhibitors effectively protects the metal against
acid attack. Many studies in this regard using organic inhibitors have
been reported [1–5].
Now a day’s research is going for the development of such corro-
sion inhibitors which are non-toxic toward the environment and also
not affect the health [6]. Isatin ring is a prominent structural motif
found in several pharmaceutically active compounds and it is eco-
friendly also. Keeping these points in mind, two isatin derivatives
namely 3-(4-(3-phenylallylideneamino)phenylimino)indolin-2-one
(PI) and 3-(4-(4-methoxybenzylideneamino)phenylimino)indolin-2-
one (MI) are synthesized and used as corrosion inhibitor for mild
steel in 20% H2 SO4 . Previous records showed that very little atten-
tion has been given for the development of corrosion inhibitor in 20%
H2 SO4 [7].
The studied inhibitor is first time used as a corrosion inhibitor
on mild steel in 20% H2 SO4 . The inhibitive activity of inhibitor is ex-
amined successively via gravimetric measurement, electrochemical
impedance spectroscopy (EIS), Tafel polarization, Langmuir isotherm
∗
Corresponding author. Tel.: +91 9307025126; fax: +91 542 2368428.
E-mail address: maquraishi@rediffmail.com, maquraishi.apc@itbhu.ac.in (M.A.
Quraishi).
ical calculation.
2. Materials and methods
2.1. General
The inhibitor was synthesized according to the procedure given
elsewhere [8] and is shown in Fig. 1. The structure, abbreviations,
analytical data are given in Table 1. The inhibitor was recrystallized
from ethanol. The mild steel strips having composition of 0.12 wt.% C,
0.37 wt.% Mn, 0.20 wt.% Si, 0.03 wt.% S, 0.01 wt.% P and remaining Fe.
Mild steel with an area of 30.1 cm2 and 1 cm2 were used for gravimet-
ric and electrochemical studies respectively. The surface of the mild
steel specimens was abraded with emery papers (grade 600–1200),
which was then washed in deionized water, degreased ultrasonically
in, separately, ethanol and acetone and then dried at room temper-
ature. The test solution (20% H2 SO4 ) was prepared by diluting 98%
analytical grade H2 SO4 with double distilled water.
2.2. Gravimetric measurement
Gravimetric measurement was done according to ASTM method
[9]. The mild steel strips were immersed in 100 mL (20%) H2 SO4 in ab-
sence and presence of inhibitors. After immersion for 6 h at 308–328 K,
mild steel strips were taken out, washed, dried, and then weighed ac-
curately. The value of corrosion rate CR (mg/cm2 /h), surface coverage
(θ ) and inhibition efficiency (η %) were calculated from the following

http://dx.doi.org/10.1016/j.jtice.2015.03.013
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.03.013
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a personal computer with EIS software Gamry Instruments Inc., USA.

The electrochemical experiments were analyzed by electrochemical
software Echem Analyst 5.0 software package. These electrochemi-
cal measurements i.e. potentiodynamic polarization and impedance
measurements were carried out at 308 K.

2.4. Surface analysis

In order to find out the surface morphology of the mild steel spec-
imens in absence and presence of inhibitors, mild steel specimens
were exposed to 20% H2 SO4 solution in the absence and presence
of optimum concentration (200 mg/L) of inhibitor for 6 h at 308 K.
SEM was investigated by using Ziess Evo 50 XVP instrument at an
accelerating voltage of 1500 kV and 5000 × magnification.

2.5. Quantum chemical calculations

Fig. 1. Scheme for synthesis of inhibitors.
eqs. [10]:
W 6-31G (d, p) basis sets. Various quantum chemical parameters like
CR =
At
CR − CR(i)
θ=
CR
CR − CR(i)
η% = × 100
CR
where W is the weight loss, A is the total area, t is immersion time,
CR and CR(i) are corrosion rates (mg/cm2 /h) of mild steel strip in the
absence and presence of inhibitors respectively.
2.3. Electrochemical measurements
The electrochemical measurements were carried out using a con-
ventional three-electrode cell assembly at 308 K in which mild steel
strips, platinum foil and saturated calomel (SCE) were used as the
working, counter and reference electrodes respectively. Prior to the
measurement working electrode was immersed in the test solution
(20%) H2 SO4 in absence and presence of inhibitor for 30 min until a
steady potential was reached.
In order to find the potentiodynamic polarization curves the elec-
trode potential was changed from −250 to +250 mV vs. SCE at OCP at a
sweep rate of 1 mV/s. Impedance measurements were carried out us-
ing AC signals of amplitude 10 mV peak to peak at the open circuit po-
tential in the frequency range 100 kHz to 0.01 Hz. All impedance data
were fitted to appropriate circuits using the computer program Echem
Analyst 5.0. All electrochemical measurements were carried out us-
ing a Gamry Potentiostat/Galvanostat (Model G-300) connected with
In the present work, quantum chemical calculations were carried
out by using density function theory (DFT) method, with the Gaussian-
03 program [11]. The exchange-correlation was treated using hybrid,
B3LYP functional. Optimization of molecule was done by using the
(1) EHOMO , ELUMO , ELUMO–HOMO , the dipole moment (μ) and Mulliken
charges on heteroatoms were discussed both in neutral and aqueous
phases.
(2)
3. Results and discussion
(3)
3.1. Gravimetric measurements
3.1.1. Effect of inhibitor concentration
The effect of inhibitor concentrations is shown in Fig. 2a. It can
be easily observed from Fig. 2a that the inhibition efficiency (η %)
increased with increase in inhibitor concentration. Very good η % was
obtained (98.48% and 91.55%) at optimum concentration (200 mg/L)
for PI and MI respectively.
3.1.2. Effect of temperature
The gravimetric measurements were performed in the tempera-
ture range between 308 and 328 K in 20% H2 SO4 at optimum concen-
tration (200 mg/L) of inhibitors and is shown in Fig. 2a. The examina-
tion of Fig. 2a reveals that as the temperature increases the decrease
in inhibition efficiency occurs [12].
Arrhenius equation was used for the calculation of the energy of
activation for the corrosion process [13].
 
−Ea
CR = A exp (4)
RT
where Ea represents apparent activation energy, R is the gas constant,
A is the pre-exponential factor. Arrhenius plots of log (CR ) and 1/T for

Table 1
Molecular structure and analytical data of inhibitors.

Inhibitor Structure Analytical data

3-(4-(3-Phenylallylideneamino) M.P. 308 °C

phenylimino)indolin-2 one(PI) IR:3160,3095,1702,1590,1490

3-(4-(4-Methoxybenzylideneamino) M.P. 320 °C

phenylimino)indolin-2-one (MI) IR:3154,3082,1690,1650,1567,1271

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
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η (%)
η (%)

(a) (b)

C (mg/L) T (K)
log CR / mg cm-2 h-1

[(C/θ).10-4 ] / M

(c) (d)

[(1/T). 103] / K-1 [(C).10-4 ] / M

Fig. 2. (a) Variation of inhibition efficiency (η %) with inhibitor concentration at 308 K. (b) Variation of inhibition efficiency (η %) with solution temperature (308–338 K) at optimum
concentration of inhibitors. (c) Arrhenius plots of the corrosion rate (CR ) of mild steel in 20% H2 SO4 in absence and presence of optimum concentration of inhibitors. (d) Langmuir’s
isotherm plots for adsorption of inhibitors on mild steel surface in 20% H2 SO4 .

the corrosion rate of mild steel in 20% H2 SO4 are shown in Fig. 2c. The
values of Ea for mild steel in absence and presence of inhibitors were
calculated by linear regression between log (CR ) and 1/T. The value
of Ea is higher in presence of inhibitor (111.04 kJ/mol for PI, 101.79
kJ/mol for MI) than that in its absence (32.91 kJ/mol). The increase in
the values of Ea in presence of inhibitors revealed that inhibitors are
adsorbed on the mild steel surface and create more energy barrier for
the corrosion reaction.
3.2. Adsorption considerations
Adsorption isotherm provides useful insights into the mechanism
of corrosion inhibition. To find out the adsorption of the studied in-
hibitors on mild steel surface different adsorption isotherms were
tested. But out of these only Langmuir adsorption isotherm was
found to be best fit (Fig. 2d) and it can be given by the following
eq. [14]:
C/θ = 1/Kads + C
where θ is the surface coverage, C is the inhibitor concentration, Kads
is the equilibrium constant of adsorption process.
By using the intercepts of the straight lines Kads can be calculated
and its correlation with the standard free energy of adsorption (Goads )
can be given by the following eq. [15]
Goads = −RT ln(55.5Kads )
where R is the gas constant and T is the absolute temperature. The
value of 55.5 is the concentration of water in solution in mol/L. The
correlation coefficient value (R2 = 0.997) is approaching to 1, which
Table 2
Thermodynamic parameters for the adsorption of inhibitors on mild steel
at optimum concentration (200 mg/L) of inhibitors in 20% H2 SO4 at 308 K.
Inhibitor Kads (104 M−1 ) Goads (kJ/mol)
PI 2.99 −36.68
MI 1.40 −34.74
supports the best fitting of Langmuir adsorption isotherm (Fig. 2d)
[16]. The values of Kads and Goads are given in Table 2. Previ-
ously many authors said that when the values ofGoads goes up to
−20 kJ/mol are consistent with the electrostatic interaction between
the charged molecules and the charged metal (physical adsorption)
while those more negative than −40 kJ/mol involve the sharing or
transfer of electrons from the inhibitor molecules to the metal sur-
face to form a co-ordinate type of bond (chemisorption) [17,18]. In
the present study, the value of Goads is higher than −40 kJ/mol but
(5) lower than −20 kJ/mol which reveals that both the inhibitors were
adsorbed on the mild steel surface by a co-operation phenomenon
between chemisorption and physisorption [19].
3.3. Electrochemical measurements
3.3.1. Electrochemical impedance spectroscopy
(6)
The corrosion behavior of mild steel in 20% H2 SO4 solution in the
absence and presence of inhibitors at 308 K was investigated by the
electrochemical impedance spectroscopy. Nyquist plots of mild steel
were given in Fig. 3(a). Inception of Fig. 3(a) suggests that a single

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
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-Z im (Ω cm2)

(a)
(b)
Zre (Ω cm2)
log |Z| (Ωcm2)

α°

(c)

log f (Hz)
Fig. 3. (a) Nyquist plots for mild steel in 20% H2 SO4 in absence and presence of optimum concentration of inhibitors at 308 K. (b) Equivalent circuit model used to fit the EIS data.
(c) Bode (log f vs. log |Z|) and phase angle (log f vs. α °) plots of impendence spectra for mild steel in 20% H2 SO4 in absence and presence of optimum concentration of inhibitors at
308 K.

depressed semicircle is observed, which reveals that the charge trans- Table 3
Electrochemical impedance parameters for mild steel in 20% H2 SO4 solution in the
fer process is occurring at electrode/solution interface [20]. These
absence and presence of optimum (200 mg/L) concentration of inhibitors at 308 K.
impedance diagrams are not perfect semicircle, which indicate to-
ward the frequency dispersion due to the roughness and inhomo- Cinh (mg/L) Rs () Rct (/cm2 ) n Y0 (μF/cm2 ) Cdl (μF/cm2 ) η (%)
geneousness of the mild steel surface [20-22]. Also the impedance Blank 0.636 7.423 0.748 1730 524.49 –
response in absence and presence of inhibitors is quite different i.e. PI 1.011 535.48 0.850 78.2 43.22 98.6
bigger in presence of inhibitors than in its absence. MI 2.093 108.30 0.840 117.9 52.31 93.1
In order to extract the results from Nyquist plots, an equivalent
circuit was used (Fig. 3(b)) which consists of solution resistance (Rs ),
a charge transfer resistance (Rct ) and a constant phase element (CPE).
Constant phase element is used in place of capacitor in electrochem- and Cdl decreased (Table 2) [25]. This decrease in the Cdl values occurs
ical process in order to deal with the non-ideal capacitance response due to the decrease in local dielectric constant and/or an increase in
[20,21,23]. Rs , Rct , CPE and CPE exponent (n) values in 20% H2 SO4 in the thickness of the electrical double layer, which reveals that the
absence and presence of optimum concentration (200 mg/L) of both action of inhibitors molecules at the metal/solution interface occurs
inhibitors at 308 K are listed in Table 3. by adsorption [24].
The inhibition efficiencies from Rct were calculated by using the In the Bode plots log |Z| and phase angle (α °) are plotted against
following eq. [24]: log f as shown in Fig. 3(c). At intermediate frequencies, log |Z| vs.
  log f with slopes of the Bode impedance magnitude at intermediate
Rct
η% = 1− × 100 (7) frequencies (−S) and maximum phase angle values (α °) are listed in
Rct(i) Table 4. In case of an ideal capacitive behavior, slopes of the Bode
where Rct and Rct(i) are the charge transfer resistance in absence and impedance magnitude at intermediate frequencies (−S) and max-
presence of inhibitor. In presence of inhibitors Rct values increased imum phase angle values (α °) are −1 and −90° respectively. The

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
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Table 4
The slopes of the Bode impedance magnitude plots at intermediate fre-
quencies (S) and the maximum phase angles (α °) for mild steel in 1 M HCl
solution at optimum (200 mg/L) concentrations of inhibitors at 308 K.

Cinh (mg/L) −S −α °

Blank 0.660 22.60

E (mV vs. SCE)

PI 0.828 72.40
MI 0.761 61.28

observation of Table 4 reveals that slopes of Bode impedance mag-

nitude (−S) and maximum phase angle values shifting toward −1
and −90° in presence of inhibitors. This deviation in slopes of
Bode impedance magnitude (−S) and the phase angles (α °) oc-
curs because of the non-ideal capacitive behavior at intermediate
frequencies.

3.3.2. Potentiodynamic polarization

log i (A/cm2)
Tafel polarization curves of mild steel in 20% H2 SO4 in the absence
Fig. 4. Tafel curves for mild steel in 20% H2 SO4 in absence and presence of optimum and presence of optimum (200 mg/L) concentrations of inhibitors at
concentration of inhibitors at 308 K.

Fig. 5. SEM micrographs of mild steel surfaces: (a) uninhibited 20% H2 SO4 , (b) PI, (c) MI.

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
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308 K are shown in Fig. 4. The inspection of Fig. 4 reveals that the Table 5
Electrochemical polarization parameters for mild steel in 20% H2 SO4 solution in the
corrosion potentials (Ecorr ) shifts toward more negative direction in
absence and presence of optimum (200 mg/L) concentrations of inhibitors at 308 K.
the presence of inhibitors and cathodic curves are shifted to lower
current density region compared to that of the blank solution, which Inhibitor Ecorr (mV/SCE) Icorr (μA/cm2 ) β a (mV/dec) −β c (mV/dec) η (%)
results in Icorr values to decrease. This phenomenon clearly indicates Blank −472 3252 56 181.0 –
that both the inhibitors are cathodic type. But also the anodic curves PI −482 43 54.8 150.5 98.6
are shifted toward the lower current densities. So, a conclusion can MI −473 249 51.7 106.8 92.3
be drawn that inhibitors can retard both the anodic mild steel dis-
solution and cathodic hydrogen evolution reactions simultaneously.
Thus overall inhibitors acting as a mixed type, but pre-dominating the mild steel surface was strongly damaged due to the metal dis-
the cathodic reaction [19]. solution in aggressive solution and large number of cracks with high
Inhibition efficiency (η %) can be calculated using Eq. (7) [26]: depth were distributed all over the surface. In presence of inhibitors
  (Fig. 5(c and d)) the damage of mild steel surface has diminished and
Icorr(i)
η% = 1− × 100 (8) it looks relatively smoother than in its absence. This may be occur-
Icorr
ring due to the adsorption of inhibitor molecules which intern forms a
where Icorr and Icorr(i) are the uninhibited and inhibited corrosion protective film over the mild steel and reduces the corrosion process.
current densities, respectively.
Tafel parameters such as corrosion potential (Ecorr ), cathodic Tafel
3.5. Quantum chemical calculations
slopes (β c ), anodic Tafel slopes (β a ) and corrosion current density
(Icorr ) can be obtained by extrapolating the Tafel curves and are given
3.5.1. Neutral form of inhibitors
in Table 5. It is apparent from Table 5 that, there is a significant
The electronic parameters such as EHOMO , ELUMO , E, dipole mo-
decrease in the Icorr values after the addition of inhibitors, which
ment (μ) and Mulliken charges on hetero-atoms are listed in Table 6.
reveals the formation of a protective film of inhibitors on the mild
The optimized structure, EHOMO and ELUMO are shown in Figs. 6(A)
steel surface.
and 7. In general EHOMO and ELUMO are the electronic parameters
which indicate the tendency of the molecule to donate and accept
3.4. Surface characterization: SEM the electrons i.e. higher the EHOMO value greater is the ability of the
molecule to donate the electrons and lower the ELUMO value greater
SEM micrographs of mild steel after immersing in 20% H2 SO4 in is the ability of the molecule to accept the electrons [27]. The obser-
the absence and presence of optimum concentration (200 mg/L) of vation of Table 6 reveals that EHOMO value of PI is large than MI and
inhibitors at 308 K for 6 h are shown in Fig. 5(a–c). Fig. 5(a) is the SEM ELUMO value of PI is small than MI. This indicates higher adsorption
micrograph in absence of inhibitors. It can be clearly observed that of PI, which intern gives its higher inhibition efficiency. The other

a b

(A)

a
b
(B)
Fig. 6. (A) Optimized structures of neutral inhibitors: (a) PI, (b) MI. (B) Optimized structures of protonated inhibitors: (a) PI, (b) MI.

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
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Table 6
Calculated quantum chemical parameters of the neutral inhibitors.

Inhibitors Mulliken charges of heteroatoms Dipole (μ) (D) EHOMO (eV) ELUMO (eV) E (eV)
N7 N10 N18 O11 O26

PI −1.230 −0.789 −0.846 −0.613 – 3.460 −5.622 −3.453 2.169

MI −1.232 −0.788 −0.874 −0.615 −0.758 5.297 −6.269 −2.063 4.206

Table 7
Calculated quantum chemical parameters of the protonated inhibitors.

Inhibitors Mulliken charges of heteroatoms Dipole (μ) (D) EHOMO (eV) ELUMO (eV) E (eV)
N7 N10 N18 O11 O26

PI −1.080 −0.784 −0.311 −0.868 – 14.013 −3.717 0.021 3.738

MI −1.081 −0.780 −0.308 −0.896 −0.747 14.557 −2.320 0.088 2.408

important electronic parameter is energy gap (E), which indicates
the reactivity of molecule toward metal surface. The smaller the value
of E greater will be the reactivity of the molecule, which favors the
adsorption of the molecule [27]. As the E gap is small, the energy
to remove an electron from last occupied molecular orbital will be
less and thus stronger will be the adsorption of the molecule over
the metal surface. Table 6 shows that the value of E in PI is small
as compared to MI, which favors the easy transfer of electrons from
the EHOMO to ELUMO and provide stronger adsorption of PI than MI on
mild steel surface. Also due to the presence of conjugation in case of
PI favors its adsorption more strongly as compared to MI, which has
an electron donor OCH3 group. Thus, the order of inhibition efficiency
is PI > MI.
There is a lack of agreement in the literature on the correlation
between the dipole moment and inhibition efficiency [28-31]. Fig. 7
reveals that HOMO of PI and MI have large electron density over the
benzene ring, O atoms, N atoms and C=C bond. So, it is quite easy to
say that these are the suitable positions for adsorption, especially in
case of O and N, which are having lone pairs of electrons. In general, it
is said that to become a good corrosion inhibitor, organic compounds
not only have the ability to donate the electrons to unoccupied or-
bitals but also have tendency to accept electrons in their antibonding
orbitals [32]. After observing Fig. 7, it is understandable that PI and
MI could also accept the d-orbital electrons of iron by LUMO on the
benzene ring and N atoms. Consequently, this electron acceptance
could help to form more stable bond between inhibitor molecule and
iron surface. The calculated values of the Mulliken charges on N and
O atoms are given in Table 6 and the negative charge on these atoms
indicates that these are the prominent sites for the adsorption. Thus
overall it can be said that the order of inhibition efficiency is PI > MI.

HOMO LUMO
a

b
LUMO
HOMO
Fig. 7. The frontier molecular orbital density distributions of neutral inhibitors: (a) PI, (b) MI.

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
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HOMO a LUMO

b LUMO
HOMO
Fig. 8. The frontier molecular orbital density distributions of protonated inhibitors: (a) PI, (b) MI.

3.5.2. Protonated form of inhibitors
The presence of nitrogen and oxygen as heteroatoms in the in-
hibitor molecules provides high tendency toward protonation in
aqueous acidic medium. So, it becomes important to investigate the
protonated forms of these inhibitor molecules. The optimized struc-
tures of the investigated neutral inhibitor molecules contain more
than one active center for protonation. So, the site where protona-
tion occurs will be the one which has highest negative charge [33,34].
The electronic parameters of protonated inhibitor molecules such
as EHOMO , ELUMO , E, dipole moment (μ) and Mulliken charges on
hetero-atoms are listed in Table 7. And also the optimized struc-
ture, EHOMO and ELUMO are shown in Figs. 6(B) and 8. Observation of
Fig. 8 reveals that HOMO of PI and MI have electron density over
the benzene ring, O atoms, N atoms and C=C bond. Thus these are
the sites over the inhibitor molecules for adsorption. Also the LUMO
of PI and MI have electron density over the benzene ring and this
is the site which accepts electrons from the fielded metal orbitals.
It is confirmed from Table 7 that protonation produces remarkable
changes in all the calculated quantum chemical parameters. The val-
ues of EHOMO and ࢞E are not in accordance with the experimental
findings.
Comparison of quantum chemical calculations for neutral and pro-
tonated inhibitors indicates that there is a clear correlation between
most of the quantum chemical parameters in the neutral form but
not in the protonated form (Tables 6 and 7). For instance, it is only
ELUMO in the protonated form that correlate well with experimentally
determined inhibition efficiency. But the dipole moment in both the
neutral and protonated inhibitor follows the trend: MI > PI, which
is opposite to that of experimentally observed order. So, it is clear
from the discussion so far that there is a complete lack of correlation
between some quantum chemical parameters with the experimen-
tal inhibition efficiency in either the neutral or protonated inhibitor
molecules, which is an indication that none of them can describe the
adsorption mechanism of the inhibitors on the steel surface standing
alone. This is because of the complex nature of the corrosion inhibition
system and has further confirmed by the experimental findings that
both physical and chemical adsorption mechanisms involved in the
corrosion inhibition of mild steel in the presence of these inhibitors.

Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
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Fig. 9. Schematic adsorption and inhibition mechanism of inhibitors molecule on mild steel in 20% H2 SO4 .
Also the EHOMO value in both the inhibitors is higher for the proto-
nated molecules than that for the neutral molecules, this reveals that
the protonated one has greater tendency to donate electrons than the
neutral one and so it will bind strongly to the mild steel surface. It is
therefore reasonable to say that the protonated species of inhibitors
are more likely to interact with the mild steel surface as compared
to the neutral species. This also confirms the experimental evidence
that both physical and chemical mechanisms are involved in the ad-
sorption process.
4. Mechanism of inhibition
The mechanism of inhibition can be explained on the basis of ad-
sorption of inhibitors molecules on the mild steel surface (Fig. 9). In
H2 SO4 medium inhibitors may either exist as a protonated (cation)
or neutral species and these two species are in equilibrium with each
other. Also mild steel is positively charged in H2 SO4 with respect to
the potential of zero charge (PZC) [27]. So, three processes may involve
during adsorption: (i) cationic form of inhibitors undergoes electro-
static interaction with the SO4 2− ions which are initially adsorbed,
(ii) unshared electron pairs presenting on hetero-atoms interact with
the vacant d-orbital of iron atoms, (iii) retro-donation between the
π -electrons of aromatic ring presenting in the inhibitor and vacant
d-orbital of iron atoms presenting on the mild steel.
5. Conclusion
1. PI and MI are effective corrosion inhibitors for mild steel in 20%
H2 SO4 .
2. Data obtained from gravimetric and electrochemical measure-
ments are strongly comparable.
3. SEM micrograph shows the formation of protective film of PI and
MI over the mild steel surface.
4. Both PI and MI are acting as a mixed type but predominantly
cathodic.
5. Both PI and MI obeys Langmuir’s adsorption isotherm.
Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.03.013
[m5G;April 16, 2015;20:20]
9
Acknowledgment
K.R. Ansari thanks to Ministry of Human Resource and Develop-
ment (MHRD), New Delhi, India for the financial assistance.
References
[1] Prabhu RA, Venkatesha TV, Shanbhag AV, Kulkarni GM, Kalkhambkar RG. Inhibi-
tion effects of some Schiff’s bases on the corrosion of mild steel in hydrochloric
acid solution. Corros Sci 2008;50:3356–62.
[2] Singh AK, Shukla SK, Quraishi MA, Ebenso EE. Investigation of adsorption
characteristics of N,N -[(methylimino)dimethylidyne]di-2,4-xylidine as corro-
sion inhibitor at mild steel/sulphuric acid interface. J Taiwan Inst Chem Eng
2012;43:463–72.
[3] Muthirulan P, Kannan N, Meenakshisundaram M. Synthesis and corrosion
protection properties of poly(o-phenylenediamine) nanofibers. J Adv Res
2013;4:385–92.
[4] Li X, Deng S, Xie X. Experimental and theoretical study on corrosion inhibi-
tion of o-phenanthroline for aluminum in HCl solution. J Taiwan Inst Chem Eng
2014;45:1865–75.
[5] Kumar CBP, Mohana KN. Corrosion inhibition efficiency and adsorption charac-
teristics of some Schiff bases at mild steel/hydrochloric acid interface. J Taiwan
Inst Chem Eng 2014;45:1031–42.
[6] Fouda AS, Elewady GY, Shalabi K, Habbouba S. Gibberellic acid as green corro-
sion inhibitor for carbon steel in hydrochloric acid solutions. J Mater Environ Sci
2014;5:767–78.
[7] Khan S, Quraishi MA. Synergistic effect of potassium iodide on inhibitive perfor-
mance of thiadiazoles during corrosion of mild steel in 20% sulfuric acid. AJSE
2010;35:71–82.
[8] Prakash CR, Raja S, Saravanan G, Kumar PD, Selvam TP. Synthesis and evaluation
of antioxidant activities of some novel isatin derivatives and analogs. Asian J Res
Pharm Sci 2011;1:140–3.
[9] ASTM. G 31-72. Philadelphia, PA: American Society for Testing and Materials;
1990.
[10] Rosenfeld, I.L. (1981) Corrosion inhibitors. New York: McGraw-Hill.
[11] Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al.
Gaussian 03, Revision E.01. Wallingford CT: Gaussian Inc.; 2007.
[12] Ansari KR, Yadav DK, Ebenso EE, Quraishi MA. Novel and effective pyridyl sub-
stituted 1,2,4-triazole as corrosion inhibitor for mild steel in acid solution. Int J
Electrochem Sci 2012;7:4780–99.
[13] Tao Z, Zhang S, Li W, Hou B. Corrosion inhibition of mild steel in acidic solution
by some oxo-triazole derivatives. Corros Sci 2009;51:2588–95.
[14] Oguzie EE, Iheabunike ZO, Oguzie KL, Ogukwe CE, Chidiebere MA, Enenebeaku CK,
et al. Corrosion inhibiting effect of Aframomum melegueta extracts and adsorption
characteristics of the active constituents on mild steel in acidic media. J Disper
Sci Technol 2013;34:516–27.
JID: JTICE
ARTICLE IN PRESS
10 K.R. Ansari, M.A. Quraishi / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–10
[15] Parveen MM. Adsorption and corrosion inhibition behavior of l-cystine and syn-
ergistic surfactants additives on mild steel in 0.1 M H2 SO4 . J Disper Sci Technol
2013;35:29–37.
[16] Tabei ASE, Hegazy MA. Application of the synthesized novel 3,6,9,12,15,18,21-
heptaoxatricosane-1,23-diyl bis(4-((4-(dimethylamino)benzylidene)amino)
benzoate) as a corrosion inhibitor for carbon steel in acidic media. J Disper Sci
Technol 2014;35:1289–99.
[17] Badawy WA, Ismail KM, Fathi AM. Corrosion control of Cu–Ni alloys in neutral
chloride solutions by amino acids. Electrochim Acta 2006;51:4182–9.
[18] Bentiss F, Lebrini M, Lagrenée M. Thermodynamic characterization of metal dis-
solution and inhibitor adsorption processes in mild steel/2,5-bis(n-thienyl)-1,3,4-
thiadiazoles/hydrochloric acid system. Corros Sci 2005;47:2915–31.
[19] Ansari KR, Quraishi MA, Singh A. Schiff’s base of pyridyl substituted triazoles as
new and effective corrosion inhibitors for mild steel in hydrochloric acid solution.
Corros Sci 2014;79:5–15.
[20] Lebrini M, Lagrenée M, Vezin H, Traisnel M, Bentiss F. Experimental and theoretical
study for corrosion inhibition of mild steel in normal hydrochloric acid solution
by some new macrocyclic polyether compounds. Corros Sci 2007;49:2254–69.
[21] Qu Q, Hao Z, Li L, Bai W, Ding Z. Synthesis and evaluation of tris-hydroxymethyl-(2-
hydroxybenzylidenamino)-methane as a corrosion inhibitor for cold rolled steel
in hydrochloric acid. Corros Sci 2009;51:569–74.
[22] Mistry BM, Jauhari S. Synthesis and evaluation of some quinoline Schiff bases
as a corrosion inhibitor for mild steel in 1 N HCl. J Disper Sci Technol
2013;34:1758–68.
[23] Ansari KR, Quraishi MA. Effect of three component (aniline–formaldehyde and
piperazine) polymer on mild steel corrosion in hydrochloric acid medium.
JAAUBAS (2014). doi:10.1016/j.jaubas.2014.04.001.
[24] Ansari KR, Quraishi MA. Bis-Schiff bases of isatin as new and environmentally
benign corrosion inhibitor for mild steel. J Ind Eng Chem 2014;20:2819–29.
Please cite this article as: K.R. Ansari, M.A. Quraishi, Experimental and quantum chemical evaluation of Schiff bases of isatin as
a new and green corrosion inhibitors for mild steel in 20% H2 SO4 , Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.03.013
[m5G;April 16, 2015;20:20]
[25] Umoren S, Gasem Z. Influence of molecular weight on mild steel corrosion inhibi-
tion effect by polyvinyl alcohol in hydrochloric acid solution. J Disper Sci Technol
2014;35:1181–90.
[26] Ghasemi O, Ghadimi MR, Ghasemi V. Adsorption and inhibition effect of ben-
zaldehyde Schiff bases on mild steel corrosion in 1 M HCl medium. J Disper Sci
Technol 2014;35:1143–54.
[27] Gece G. The use of quantum chemical methods in corrosion inhibitor studies.
Corros Sci 2008;50:2981–92.
[28] Gao G, Liang C. Electrochemical and DFT studies of β -amino-alcohols as corrosion
inhibitors for brass. Electrochim Acta 2007;52:4554–9.
[29] Khalil N. Quantum chemical approach of corrosion inhibition. Electrochim Acta
2003;48:2635–40.
[30] Valdez LMR, Villafane AM, Mitnik DG. Computational simulation of the molec-
ular structure and properties of heterocyclic organic compounds with possible
corrosion inhibition properties. J Mol Struct (Theochem) 2005;713:65–70.
[31] Stoyanova A, Petkova G, Peyerimhoff SD. Correlation between the molecular struc-
ture and the corrosion inhibiting effect of some pyrophthalone compounds. Chem
Phys 2002;279:1–6.
[32] Herrag L, Hammouti B, Elkadiri S, Aouniti A, Jama C, Vezin H, et al. Adsorption
properties and inhibition of mild steel corrosion in hydrochloric solution by some
newly synthesized diamine derivatives: experimental and theoretical investiga-
tions. Corros Sci 2010;52:3042–351.
[33] Ebenso EE, Kabanda MM, Arslan T, Saracoglu M, Kandemirli F, Murulana LC, et al.
Quantum chemical investigations on quinoline derivatives as effective corrosion
inhibitors for mild steel in acidic medium. Int J Electrochem Sci 2012;7:5643–76.
[34] Kabanda MM, Murulana LC, Ozcan M, Karadag F, Dehri I, Obot IB, et al. Quan-
tum chemical studies on the corrosion inhibition of mild steel by some triazoles
and benzimidazole derivatives in acidic medium. Int J Electrochem Sci
2012;7:5035–56.