ARTICLE

pubs.acs.org/IECR

Anticorrosion Potential of 2-Mesityl-1H-imidazo[4,5-f][1,10]-

phenanthroline on Mild Steel in Sulfuric Acid Solution:
Experimental and Theoretical Study
I. B. Obot,*,† N. O. Obi-Egbedi,‡ and A. O. Eseola§
†
Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017, Uyo, Akwa Ibom State, Nigeria
‡
Department of Chemistry, University of Ibadan, Ibadan, Nigeria
§
Chemical Sciences Department, Redeemer’s University, Redemption City, Km. 46 Lagos - Ibadan Expressway, Nigeria
bS Supporting Information
ABSTRACT: A new phenanthroline derivative, 2-mesityl-1H-imidazo[4,5-f][1,10]phenanthroline (MEIP), was synthesized and
characterized by elemental analysis, FT-IR, 1HNMR, and 13CNMR spectra. MEIP was evaluated as corrosion inhibitor for carbon
steel in 0.5 M H2SO4 solution using gravimetric and UV-visible spectrophotometric methods at 303-333 K. Results obtained
show that MEIP is a good inhibitor for mild steel in H2SO4 solution. The inhibition efficiency was found to increase with increase in
MEIP concentration but decreased with temperature, which is suggestive of physical adsorption mechanism. Activation parameters
and Gibbs free energy for the adsorption process using Statistical Physics were calculated and discussed. The UV-visible absorption
spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a MEIP-Fe
complex. The calculations of global reactivity indices of MEIP such as the localization of frontier molecular orbitals, EHOMO, ELUMO,
energy gap (ΔE), dipole moment (D), hardness (η), softness (σ), the fractions of electrons transferred (ΔN), electrophilicity index
(ω), total energy change (ΔET), and Mulliken charge distributions together with local reactivity by means of Fukui indices were
used to explain the electron transfer mechanism between the MEIP molecules and the steel surface. The quantum chemical
calculations were performed at the density functional theory (DFT) level using B3LYP functional with the 6-31G (d) basis set for all
atoms using Spartan’06 V112 program package.

1. INTRODUCTION forming coordinate covalent bond during such chemical adsorp-

Mild steel is a common constructional material for many
industrial units because of its excellent mechanical properties.
They are used widely in industries as reaction vessels, pipelines
for petroleum industries, machinery, storage tanks, and chemical
batteries.1 It is a well-known fact that acids are used in many
industrial operations such as pickling, cleaning, descaling and oil
well acidizing, etc. Because of their aggressiveness, inhibitors are
used to reduce the rate of dissolution of metals, and it constitutes
one of the most economical ways to preserve industrial facilities.2
Molecular design has become a very useful tool for the syn-
thesis of corrosion inhibitors that not only allows one to control
the corrosion rate but at the same time also fulfills environmental
protection standards. In this regard, the treatment of mild steel
corrosion in an acidic environment through organic compounds
of low toxicity which do not contain heavy metals and organic
phosphates has resulted in considerable savings to the oil and gas
industry.3 Most of the efficient inhibitors used in industry are
organic compounds which mainly contain oxygen, sulfur, nitro-
gen atoms, and multiple bonds in the molecule through which
they are adsorbed on metal surface.4 Moreover, many N-hetero-
cyclic compounds have been used as effective inhibitors for the
corrosion of metals and alloys in aqueous media.5-10 It has been
reported that many organic inhibitors usually promote the for-
mation of a chelate on the metal surface, which includes the
transfer of electrons from the organic compounds to metal
tion process.11 In this way, the metal acts as an electrophile,
whereas the nucleophile centers of inhibitor molecule are nor-
mally heteroatoms with free electron pairs which are readily avai-
lable for sharing, to form a bond.
Phenanthroline derivatives are of interest due to their potential
activity against cancer, bacterial, virial, and antifungal infections.
Recently, Roy et al.12 has reported on the use of phenanthroline
derivatives with improved selectivity as DNA-targeting anticancer
or antimicrobial drugs. Imidazo[4,5-f][1,10]phenanthrolines are
versitile ligands because they can form stable complexes with
varioud d-block transition metals.13 Metal complexes of phenan-
throline derivative (example, Mn(II) complex of 2H-5-hydroxy-
1,2,5-oxadiazo[3,4-f][1,10]phenanthroline) has been reported to
show antitumor activity.14 The choice of 2-(6-methylpyridin-2-yl)-
1H-imidazo[4,5-f][1,10]phenanthroline (MEIP) for the present
investigation was based on the following considerations: (i) it can
be synthesized easily from relatively cheap materials; (ii) it con-
tains two heterocyclic moiety in one compound i.e. imidazole and
phenanthroline rings with several π-electrons and aromatic systems
containing four N atoms, which can induce greater adsorption of
Received: October 6, 2010
Accepted: December 28, 2010
Revised: December 28, 2010
Published: January 18, 2011

r 2011 American Chemical Society 2098 dx.doi.org/10.1021/ie102034c | Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

the inhibitor molecule onto the surface of mild steel compared Scheme 1
with compounds containing only imidazole ring already used as
corrosion inhibitor in industry;15 (iii) the compound has a higher
molecular weight (311.34 g mol-1) than most N-heterocyclic
compounds already studied as corrosion inhibitors such as piper-
azine derivatives.16 Moreover, there is no report in the literature on
the use of 2-mesityl-1H-imidazo[4,5-f][1,10]phenanthroline as
corrosion inhibitor for mild steel in sulfuric acid.
Quantum chemical calculations have been widely used to study
reaction mechanism. They have also proved to be a very important
tool for studying corrosion inhibition mechanism.16-18 In recent
times, Density Functional Theory (DFT) has become an attractive
theoretical method because it gives exact basic vital parameters for
even huge complex molecules at low cost.19-21 Furthermore, by
using sophisticated computational tools, we can understand
reactivity behavior of hard and soft acid-base (HSAB) theory
that provide a systematic way for the analysis of the inhibitor/
surface interaction.22 Thus, the DFT has become a main source of
connecting some traditional empirical concepts with quantum
mechanics. Therefore, DFT is a very powerful technique to probe
the inhibitor/surface interaction and to analyze experimental data.
In continuation of our quest for developing corrosion inhibitors
with high effectiveness and efficiency, the present paper explores the
use of 2-mesityl-1H-imidazo[4,5-f][1,10]phenanthroline (MEIP)
as corrosion inhibitor for mild steel surface in sulfuric acid solution
using gravimetric method and UV-visible spectrophotometric
methods. The effect of temperature is assessed in order to propose
a suitable mechanism for the inhibitory action of MEIP on the mild
steel surface. Quantum chemical calculations have been performed
using DFT, and several quantum chemical indices were calculated
and correlated with the inhibitive effect of MEIP.

2. EXPERIMENTAL SECTION
2.1. General Considerations. All starting materials were
obtained commercially as reagent grade and used without further
purification. Phenanthroline-5,6-dione was synthesized according
to literature procedure.23 All air or moisture sensitive manipulations
were carried out under an atmosphere of nitrogen using standard
Schlenk techniques. All purifications were done on silica gel column
to exclude impurities, and TLC glass slides were routinely em-
ployed to monitor extents of reactions as well as the progess of
silica gel column chromatography.
2.2. Synthesis of 2-Mesityl-1H-imidazo[4,5-f][1,10]phena-
nthroline. The inhibitor (MEIP) was synthesized as reported
in the literature.23 1,10-Phenanthroline-5,6-dione (0.50 g, 2.37
mmol), mesitaldehyde (0.35 g, 2.37 mmol), ammonium acetate
(3.65 g, 47.40 mmol), and glacial acetic acid (10 mL) were heated
under reflux condition for 2 h followed by cooling, dilution in
20 mL of distilled water, and neutralization with concentrated
aqueous ammonia solution. The crude product was filtered off as
yellow precipitate which was recrystallized from ethanol to obtain
2-mesityl-1H-imidazo[4,5-f][1,10]phenanthroline (Scheme 1) as
microcrystals (0.75 g, Yield: 93%).
Analytical Data for Inhibitor. Yield: (0.75 g, 93%). Mp. >300 °C.
Selected IR peaks (KBr disk, cm-1): v 3272 vs, 3061s, 1610 m,
1542s, 1454s, 741s, 1H NMR (400 MHz, TMS, CDCl3); δ 8.85
(d, 4H); 7.46(br, s, 2H); 6.65(s, 2H); 2.19(s, 3H); 1.93(s, 6H).
13
CNMR (TMS, CDCl3). δ 151.24, 147.69, 143.87, 139.12,
137.83, 130.54, 127.97, 127.56, 123.03, 121.15, 119.90. Anal. Calc.
for C22H18N4: C, 70.57; H, 5.92; N, 14.96%. Found: C, 70.74; H,
5.74; N, 14.59%.
2099
2.3. Instrumentation. C, H, and N analyses were carried out
on a Flash EA 1112 microanalyzer. 1HNMR and 13CNMR
spectra were obtained with a Bruker ARX-400 MHz spectrom-
eter using CDCl3 as the solvent and TMS as an internal
standard. Fourier transformation infrared (FT-IR) spectra were
recorded in KBr pellets using Shimadzu 8740 FT-IR spectrom-
eter as KBr discs in the range of 4000-400 cm-1. The melt-
ing point was determined on a digital melting point instrument
(Electrothermal model 9200).
2.4. Material. Tests were performed on a freshly prepared
sheet of mild steel of the following composition (wt %): 0.13% C,
0.18% Si, 0.39% Mn, 0.40% P, 0.04% S, 0.025% Cu, and bal Fe.
Specimens used in the weight loss experiment were mechanically
cut into 5.0 cm
4.0 cm
0.8 cm dimensions, then abraded with
SiC abrasive papers 320, 400, and 600 grit respectively, washed in
absolute ethanol and acetone, dried in room temperature, and
stored in a moisture free desiccator before their use in corrosion
studies.24
2.5. Solutions. The aggressive solutions, 0.5 M H2SO4 were
prepared by dilution of analytical grade 98% H2SO4 with distilled
water. Stock solution of MEIP was made in a 10:1 water:methanol
mixture to ensure solubility.25 This stock solution was used for all
experimental purposes. The concentration range of MEIP pre-
pared and used in this study was 2 μM-10 μM.
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research
2.6. Gravimetric Measurements. The gravimetric method
(weight loss) is probably the most widely used method of inhi-
bition assessment.26 The simplicity and reliability of the mea-
surement offered by the weight loss method is such that the
technique forms the baseline method of measurement in many
corrosion monitoring programs.27 Several authors have reported
on comparable agreement between weight loss technique and
other well established techniques of corrosion monitoring such
as polarization technique,28 electrochemical impedance spectro-
scopy,29 gasometric,30 thermometric,31 and atomic absorption
spectroscopy.32 Recently, weight loss method together with po-
tentiodynamic polarization and electrochimical impedance spec-
troscopy were used to evaluate the corrosion inhibitive effect of
cigarette butt on N80 steel at 90 °C in hydrochloric acid solu-
tion.33 Results obtained for the three independent methods were
in good agreement. Recently, there are several reports in interna-
tional reputable journals on the use of weight loss alone in cor-
rosion inhibition studies.24-27 The weight loss method in com-
bination with quantum chemical studies has been found to be
adequate in elucidating the mechanism of inhibition.5-8,18,20,22
Thus, weight loss measurements were conducted under total
immersion using 250 mL capacity beakers containing 200 mL of
test solution at 303-333 K maintained in a thermostatted water
bath. The mild steel coupons were weighed and suspended in
the beaker with the help of rod and hook. The coupons were
retrieved at 2 h intervals progressively for 10 h, washed thor-
oughly in 20% NaOH solution containing 200 g/L of zinc dust25
with bristle brush, rinsed severally in deionized water, cleaned,
dried in acetone, and reweighed. The weight loss, in grams, was
taken as the difference in the weight of the mild steel coupons
before and after immersion in different test solutions determined
using LP 120 digital balance with sensitivity of (0.1 mg. Then
the tests were repeated at different temperatures. In order to get
good reproducibility, experiments were carried out in triplicate.
In this present study, the standard deviation values among parallel
triplicate experiments were found to be smaller than (2%, indi-
cating good reproducibility.
The corrosion rate (F) in mg cm-2 h-1 was calculated from
the following equation34
ΔW
F ¼ ð1Þ
At
where W is the average weight loss of three mild steel sheets, A is
the total area of one mild steel specimen, and t is the immersion
time (10 h) . With the calculated corrosion rate, the inhibition
efficiency (%I) was calculated as follows24
 
F1 - F2
%I ¼ x100 ð2Þ
F1
where F1 and F2 are the corrosion rates of the mild steel coupons
in the absence and presence of inhibitor, respectively.
2.7. Spectrophotometric Measurements. UV-visible ab-
sorption spectrophotometric method was carried out on the
prepared mild steel samples after immersion in 0.5 M H2SO4
with and without addition of 10 μM of MEIP at 303 K for 3 days.
All the spectra measurements were carried out using a Perkin-
Elmer UV-visible Lambda 2 spectrophotometer.
2.8. Computational Details. B3LYP, a version of the DFT
method that uses Becke’s three parameter functional (B3) and
includes a mixture of HF with DFT exchange terms associated
with the gradient corrected correlation functional of Lee, Yang
2100
ARTICLE
and Parr (LYP), was used in this paper to carry out quantum
calculations. Then, full geometry optimization together with the
vibrational analysis of the optimized structures of the inhibitor
was carried out at the (B3LYP/6-31G (d) level of theory using
the Spartan’06 V112 program package35 in order to determine
whether they correspond to a maximum or a minimum in the
potential energy curve. The quantum chemical parameters were
calculated for molecules in neutral as well as in the protonated
form for comparison. It is well-known that the phenomenon of
electrochemical corrosion occurs in liquid phase. As a result, it
was necessary to include the effect of a solvent in the computa-
tional calculations. In the Spartan ’06 V112 program, SCRF
methods (Self-consistent reaction field) were used to perform
calculations in aqueous solution. These methods model the sol-
vent as a continuum of uniform dielectric constant, and the solute
is placed in the cavity within it.
3. RESULTS AND DISCUSSION
3.1. Weight Loss, Corrosion Rate, and Inhibition Effi-
ciency. The mechanism of inhibition and the effect of inhibitor
in aggressive acidic environment in the presence of mild steel
requires some knowledge of interaction between the protective
compound and the metal surface. According to the mechanism
for the dissolution of iron in acidic sulfate solution initially pro-
posed by Bockris et al.36 and reported also by us,8 iron electro-
dissolution in acidic sulfate solution depends primarily on the
adsorbed intermediate as follows
Fe þ H2 O T FeOHads þ Hþ þ e- ð3Þ
FeOHads f FeOHþ þ e- ðrate determining stepÞ ð4Þ
FeOHþ þ Hþ T Fe2þ þ H2 O ð5Þ
The cathodic hydrogen evolution follows the steps
Fe þ Hþ T ðFeHþ Þads ð6Þ
ðFeHþ Þads þ e- T ðFeHÞads ð7Þ
ðFeHads Þ þ Hþ þ e- f Fe þ H2 ð8Þ
The following mechanism involving two adsorbed intermedi-
ates to account for the retardation of Fe anodic dissolution in the
presence of an inhibitor has been reported37
Fe þ H2 O T FeH2 Oads ð9Þ
FeH2 Oads þ M T FeOH -ads þ Hþ þ M ð10Þ
FeH2 Oads þ M T FeMads þ H2 O ð11Þ
FeOH - ads f FeOHads þ eðrate determining stepÞ ð12Þ
FeMads T FeMþ ads þ e ð13Þ
FeOHads þ FeMþ ads T FeMads þ FeOHþ ð14Þ
FeOHþ þ Hþ T Fe2þ þ H2 O ð15Þ
where M represents the inhibitor species.
According to the detailed mechanism above, displacement of
some adsorbed water molecules on the metal surface by inhibitor
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

Figure 1. Variation of weight loss against time for mild steel corrosion in 0.5 M H2SO4 in the presence of different concentrations of MEIP at 303 K.

Table 1. Calculated Values of Corrosion Rate and Inhibition Efficiency for Mild Steel Corrosion for Mild Steel in 0.5 M H2SO4 in
the Absence and Presence of MEIP at 303-333 K

corrosion rate (mg cm-2 h-1) inhibition efficiency (%I)

system/concentration 303 K 313 K 323 K 333 K 303 K 313 K 323 K 333 K

blank 1.19 1.54 4.00 4.89 - - - -

2 μM 0.57 0.80 2.68 3.36 52 48 33 31
4 μM 0.48 0.76 2.36 2.98 60 51 41 39
6 μM 0.37 0.62 1.92 2.44 69 61 52 50
8 μM 0.29 0.48 1.24 2.03 75 70 69 58
10 μM 0.15 0.27 0.80 1.51 87 83 80 69

Figure 2. The relationship between corrosion rate and temperature for different concentrations of MEIP.
species to yield the adsorbed intermediate FeMads (eq 11) re- Figure 1 shows a representative plot of weight loss against time
duces the amount of the species FeOH-ads available for the rate for mild steel in 0.5 M H2SO4 solution containing no inhibitor
determining steps and consequently retards Fe anodic dissolution. (blank) and in the presence of different concentrations of MEIP
2101 dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

Table 2. Some Parameters from Statistical Model for Mild

Steel in 0.5 M H2SO4 in the Presence of MEIP
temperature (K) R2 θ ΔGoads (kJ mol-1)

303 0.969 2.45
103 -32.70

313 0.967 2.71
103 -33.11
323 0.982 2.11
103 -33.19
333 0.996 2.86
103 -33.49

Table 3. Activation Parameters of the Dissolution of Mild

Steel in 0.5 M H2SO4 in the Absence and Presence of Different
Concentrations of MEIP
concentration Ea (kJ mol-1) ΔH*(kJ mol-1) ΔS*(J mol-1K-1)

blank 43.31 203.34 285.52

2 μM 54.26 225.36 339.13
Figure 3. Variation of inhibition efficiency of MEIP with temperature.
4 μM 55.25 229.57 349.08
6 μM 56.69 232.95 345.83
8 μM 57.73 2.37.84 353.19
10 μM 65.71 270.16 450.95

atoms as well as the π-electrons of the aromatic rings. Moreover,

Figure 4. Application of the statistical model to the corrosion protec-
tion behavior of MEIP.
at 303 K. Similar plots were obtained for other temperatures
(313-333 K) (not shown). From the plot, it is evident that the
weight loss of mild steel in the different test solutions increases
with time. The nonuniformity and nonlinearity of the curves of the
weight loss plot may be attributed to the presence of mill scale on the
mild steel surface. It may also suggest that the mild steel corrosion by
H2SO4 is a heterogeneous process involving several steps. Similar
observation has been reported recently.38 A further inspection of the
plots reveal that the weight loss of mild steel was reduced in the
presence of MEIP compared to the free acid solution, an indication
of inhibiting effect of acid corrosion of mild steel.
The calculated values of corrosion rates (F) and inhibition
efficiency (%I) obtained from weight loss measurements for dif-
ferent concentrations of MEIP in 0.5 M H2SO4 after 10 h immersion
at 303-333 K are listed in Table 1. It is evident from this table and
Figure 2 that the corrosion rate decreased with increasing inhibitor
concentration but increased with rise in temperature. Table 1 also
shows that inhibition efficiency (%I) increased with increasing
inhibitor concentration, reaching a maximum of 87.0%. This may
be due to the adsorption of MEIP molecules onto the mild steel
surface through nonbonding electron pairs of the four nitrogen
2102
the high molecular weight of MEIP ensures effective surface
coverage of the inhibitor on the steel surface. This isolates the
steel from the agressive acid solution thus inhibiting its dissolution.
Similar observation has been documented.39 Figure 3 shows the
variation of percentage inhibition efficiency with temperature. It is
clear from the figure that percentage inhibition efficiency increases
with concentration but decreases with temperature. The increase
in percentage inhibition efficiency of MEIP with concentration
may be due to the adsorption of its molecules onto the mild steel
surface. The decrease in inhibition efficiency with increase in
temperature may be probably due to decreasing strength of
adsorption (shifting the adsorption-desorption equilibrium to-
ward desorption) and roughening of the electrode surface which
results from enhanced corrosion.10
3.2. Thermodynamic Consideration Using the Statistical
Model. According to statistical physics, the change of free energy
of adsorption ΔGoads can be calculated from eq 10 as follows40
 
1-η ΔGoads RTln C
ln ¼ - ð16Þ
η θ θ
where C is the concentration of inhibitor particles.
The curve fitting of data in Table 1 to the statistical model at
303-333 K is presented in Figure 4. Good correlation coefficient
(R2 > 0.96) was obtained. θ and ΔGoads can be calculated from the
slope and intercept of eq (16). All the calculated parameters are
given in Table 2. The negative values of ΔGoads demonstrates that
the inhibitor is spontaneously adsorbed onto the metal surface.
Generally, values of ΔGoads up to -20 kJ mol-1 are consistent with
physisorption, while those around -40 kJ mol-1 or higher are
associated with chemisorption as a result of the sharing or transfer
of electrons from organic molecules to the metal surface to form a
coordinate bond.24 In the present study, the calculated values of
ΔGoads obtained for MEIP are more than -20 kJ mol-1 but less
than -40 kJ mol-1 (Tables 3), indicating that the adsorption of
mechanism of MEIP on mild steel in 0.5 M H2SO4 solution at the
studied temperatures may be a combination of both physisorption
and chemisorption (comprehensive adsorption).41
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

Figure 5. The variation of ΔGoads/T with 1/T.

Figure 6. The variation of ΔGoads with temperature.

The enthalpy of adsorption can also be calculated from the where ΔHoads and ΔSoads are the enthalpy and entropy changes of
Gibbs-Helmholtz equation42 adsorption process, respectively. A plot of ΔGoads versus T was
  linear (Figure 6) with the slope equal to -ΔSoads and intercept of
∂ðΔGoads =TÞ ΔH o ΔHoads. The enthalpy of adsorption ΔHoads and the entropy of
¼ - 2ads ð17Þ
∂T p T adsorption ΔSoads obtained are -58.66 kJ mol-1 and 92.00 J mol-1
K-1, respectively. The enthalpy of adsorption ΔHoads from the two
Equation 17 can be arranged to give the following equation approaches is in agreement.
ΔGoads ΔHads
o It has been reported that when the process of adsorption is
¼ þk ð18Þ exothermic (i.e negative values for ΔHoads), physisorption can be
T T
distinguished from chemisorption according to the absolute
The variation of ΔGoads/T with 1/T gives a straight line with a value of ΔHoads. For physisorption processes, this magnitude is
slope which is equal to ΔHoads (Figure5). It can be seen from the usually lower than 40 kJ mol-1 while that for chemisorption ap-
figure that ΔGoads/T decreases with 1/T in a linear fashion. The proaches 100 kJ mol-1.43 In this work, the negative sign of ΔHoads is
obtained value of ΔHoads was -58.00 kJ mol-1. an indication that the adsorption of MEIP on steel surface is
The enthalpy and entropy for the adsorption of MEIP on mild exothermic while its absolute value (around -50 kJ mol-1) sug-
steel were also deduced from the thermodynamic basic equation19 gests that the adsorption of MEIP is not merely physical or chemical
but a combination of physisorption and chemisorption exists between
ΔGoads ¼ ΔHads
o
- TΔSoads ð19Þ the inhibitor and the metal surface (comprehensive adsorption).42,43
2103 dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research
Figure 7. Arrhenius plot for mild steel corrosion in 0.5 M H2SO4 in the absence and presence of different concentrations of MEIP.
The positive sign of ΔSoads arises from substitutional process,
which can be attributed to the increase in the solvent entropy
and more positive water desorption entropy. This leads to
an increase in disorder due to the fact that more water mole-
cules can be desorbed from the metal surface by one inhibitor
molecule.44
3.3. Effect of Temperature. Temperature has a great effect
on the rate of metal electrochemical corrosion. In case of corro-
sion in a neutral solution (oxygen depolarization) the increase in
temperature has a favorable effect on the overpotential of oxygen
depolarization and the rate of oxygen diffusion, but it leads to
a decrease of oxygen solubility. In case of corrosion in acidic
medium (hydrogen depolarization), the corrosion rate increases
exponentially with temperature increase because the hydrogen
evolution overpotential decreases.38 The relationship between
the corrosion rate (F) of mild steel in acidic media and tempera-
ture (T) is often expressed by the Arrhenius equation43
Ea
log F ¼ log A - ð20Þ
2:303RT
where F is the corrosion rate, Ea is the apparent activation energy,
R is the molar gas constant (8.314 J K-1 mol-1), T is the absolute
temperature, and A is the frequency factor. The plot of log F
against 1/T for mild steel corrosion in 0.5 M H2SO4 in the
absence and presence of different concentrations of MEIP is
presented in Figure 7. All parameters were given in Table 3. Ea
values in the table are higher for inhibited solutions than the
unhibited one, indicating a strong inhibitive action of the
additives by increasing the energy barrier for the corrosion pro-
cess, emphasizing the electrostatic character of the inhibitor’s ad-
sorption on the mild steel surface (physisorption).34 It is logical
to assume that in this case the electrostatic cation adsorption is
responsible for the good protective properties of this compound.
However, the adsorption phenomenon of an organic molecule
is not considered only as a physical or as chemical adsorption
phenomenon but a wide spectrum of conditions, ranging from
2104
ARTICLE
the dominance of chemisorption or electrostatic effects may arise
due to the complex nature of the corrosion inhibiting process.42
Experimental corrosion rate values obtained from weight loss
measurements for mild in 0.5 M H2SO4 in the absence and
presence of MEIP was used to further gain insight on the change
of enthalpy (ΔH*) and entropy (ΔS*) of activation for the
formation of the activation complex in the transition state using
transition equation45
     
RT ΔS - ΔH 
F ¼ exp exp ð21Þ
Nh R RT
where F is the corrosion rate, h is the Plank’s constant (6.626176

10-34 Js), N is Avogadro’s number (6.02252
1023 mol-1), R
is the universal gas constant, and T is the absolute temperature.
Figure 8 shows the plot of log F/T versus 1/T for mild steel
corrosion in 0.5 M H2SO4 in the absence and presence of dif-
ferent concentrations of MEIP. Straight lines were obtained with
slope of (ΔH*/2.303R) and an intercept of [log (R/Nh) þ
(ΔS*/ 2.303R)] from which the values of ΔH* and ΔS* respec-
tively were computed and listed also in Table 3. The positive
values of ΔH* both in the absence and presence of MEIP reflect
the endothermic nature of steel dissolution process. Results in
Table 3 further indicate that the activation enthalpies increases
with increase in the concentration of MEIP, which vary in the
same manner as the activation energies, supporting the proposed
inhibition mechanism. The entropy of activation ΔS* was also
positive in the absence and presence of MEIP, implying that the
rate-determining step for the activated complex is dissociation step
rather than association. In other words, the adsorption process is
accompanied by an increase in entropy, which is the driving force
for the adsorption of inhibitor onto the mild steel surface.38
3.4. UV-Visible Spectroscopy. A substantial support for the
formation of metal complex is often obtained by UV-visible
spectroscopic investigation. Since there is often a certain quantity
of metal cation in the solution that is first dissolved from the
metal surface, such procedures were conducted in the present
work to confirm the possibility of the formation of [MEIP-Fe2þ]
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

Figure 8. Transition state plot for mild steel corrosion in 0.5 M H2SO4 in the absence and presence of different concentrations of MEIP.

Figure 9. UV-visible spectra of the solution containing 0.5 M H2SO4 (10 μM) MEIP before (blue) and after 3 days of mild steel immersion (red).

complexes as described in literature.46-48 Furthermore, Abboud
et al.47 has reported that change in position of the absorbance
maximum and change in the value of absorbance indicate the
formation of a complex between two species in solution. In order
to confirm the possibility of the formation of MEIP-Fe complex,
UV-visible absorption spectra obtained from 0.5 M H2SO4
solution containing 10 μM MEIP before and after 3 days of mild
steel immersion is shown in Figure 9. The electronic absorption
spectra of MEIP before the steel immersion display two bands in
the visible region (550 and 680 nm). The absorption bands at
this longer wavelengths are as a result of the presence of aromatic
systems in MEIP which are highly conjugated. These bands may
also be assigned to π-π* transition involving the whole electro-
nic structure system of the compound with a considerable charge
transfer character.34 After 3 days of steel immersion (Figure 10),
it is evident that there is an increase in the absorbance of this
band. However, there was no significant difference in the shape of
2105
the spectra before and after the immersion of MEIP showing
a possibility of weak interaction between MEIP and mild steel
(physisorption). These experimental findings give strong evi-
dence for the possibility of the formation of a complex between
Fe2þ cation and MEIP in H2SO4.
3.5. Quantum Chemical Studies Using Density Functional
Theory (DFT). There is no doubt that the recent progress in
DFT has provided a very useful tool for understanding molecular
properties and for describing the behavior of atoms in molecules.
DFT methods have become very popular in the past decade due
to their accuracy and less computational time. The mechanism of the
inhibition action can be elucidated with the help of quantum chemi-
cal calculation which is widely reported in the literature.21,22,24,25
However, further studies using electrochemical methods like
polarization and impedance spectroscopy coupled with some
surface analytical and spectroscopic techniques like SEM,
FT-IR, EDAX, and AFM will soon be carried out on the
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

Figure 11. The highest occupied molecular orbital (HOMO) density of

Figure 10. Optimized structure of MEIP (ball and stick model): (a) MEIP using DFT at the B3LYP/6-31G (d) basis set level: (a) neutral
neutral molecule and (b) protonated at N4. molecule and (b) protonated molecule.

parameters were calculated in the neutral as well as in the

Table 4. Some Molecular Properties of MEIP Calculated
protonated form of MEIP in the aqueous phase.
Using DFT at the B3LYP/6-31G (d) Basis Set in Aqueous
Frontier orbital theory is useful in predicting adsorption
Phase
centers of the inhibitor molecules responsible for the interaction
quantum chemical properties neutral form protonated form with surface metal atoms. Terms involving the frontier molecular
orbitals (MO) could provide dominative contribution, because
total energy (au) -1068.25 -1068.63 of the inverse dependence of stabilization energy on orbital
EHOMO (eV) -5.72 -9.50 energy difference.49 EHOMO is often associated with the electron
ELUMO (eV) -1.32 -5.86 donating ability of a molecule; high values of EHOMO are likely to
ΔE (eV) 4.40 3.64 indicate the tendency of the molecule to donate electrons to
dipole moment (D) 5.64 3.89 appropriate acceptor molecules with lower energy MO. ELUMO,
ionization potential (I) (eV) 5.72 9.50 on the other hand, indicates the ability of the molecule to accept
electron affinity (A) (eV) 1.32 5.86 electrons.50 The binding ability of the inhibitor to the metal
electronegativity (χ) 3.02 7.68 surface increases with increasing HOMO and decreasing LUMO
hardness (η) 2.20 1.82 energy values. Thus, the lower the value of ELUMO, the most
probable it is that the molecule would accept electrons. More-
softness (σ) 0.45 0.55
over, the gap between the HOMO and LUMO energy levels of
fraction of electrons transferred (ΔN) 0.90 -0.186
the molecule is an important parameter that determines the
neucleophilicity (ω) 2.07 16.20 reactivity of the inhibitor molecule toward the adsorption on the
metallic surface. As ΔE decreases (most especially for the
inhibitor to further characterize the mechanism of inhibition cationic species), the reactivity of the molecule increases leading
action. to increase in the inhibition efficiency of the molecule.49
Figures 10-13 show the optimized geometry, the HOMO From Figures 11 and 12, it could be seen that MEIP have
density distribution, the LUMO density distribution, and the different HOMO and LUMO distributions in the neutral and in
Mulliken charge population analysis plots for MEIP molecule the protonated forms. The HOMO densities were concentrated
obtained with DFT at the B3LYP/6-31G (d) level of theory in on both the phenanthroline and the imidazole rings in the neutral
both the neutral and protonated form in aqueous phase. The form, while the protonated form has the HOMO mainly in the
theoretical parameters which provide information about the reac- phenanthroline ring. For the LUMO distributions, the reverse is
tive behavior of MEIP are presented in Table 4. These theoretical the case. Thus, unoccupied d orbitals of an Fe atom can accept
2106 dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research
Figure 12. The lowest unoccupied molecular orbital (LUMO) density
of MEIP using DFT at the B3LYP/6-31G (d) basis set level: (a) neutral
molecule and (b) protonated molecule.
electrons from inhibitor molecule mainly in the neutral form to
form a coordinate bond. Also the inhibitor molecule can accept
electrons from an Fe atom with its antibonding orbitals to form
back-donating bond mainly in the protonated form. These
donation and back-donation processes strengthen the adsorption
of MEIP onto the mild steel surface.22
Figure 13 shows the Mulliken atomic charges calculated for
MEIP. It has been reported that the more negative the atomic
charges of the adsorbed center, the more easily the atom donates
its electron to the unoccupied orbital of the metal.51 It is clear
from Figure 13, that all the nitrogen atoms as well as some
carbons atoms carries negative charge centers which could offer
electrons to the mild steel surface to form a coordinate bond. It
should be noted that there are more negative charge centers in
the neutral form of MEIP than in the protonated form. The
nitrogen atoms (N1, N2, N3, and N4) are the probable reactive
sites for the adsorption of iron. Thus, the neutral form of MEIP
donates more negative charge to the d-orbitals of Fe than the
protonated form. The protonation of the inhibitor molecule took
place at N4 because of the following reasons: (1) It does not
possess any attached proton like the N3, which although has the
highest negative charge cannot form another bond again (has
three bonds already); (2) It has the next higher negative charge
and so protonation was most favorable on this nitrogen and it
gives the least total energy after protonation.
It is evident from Table 4 that MEIP has the highest EHOMO in
the neutral form and a lower EHOMO in the protonated form.
This means that the electron donating ability of MEIP is weaker
in the protonated form. It is clear from Table 4 that the
2107
ARTICLE
Figure 13. Mulliken charges population analysis of MEIP using DFT at
the B3LYP/6-31G (d) basis set level: (a) neutral molecule and (b)
protonated molecule.
protonated form of MEIP exhibits the lowest ELUMO, making
the protonated form the most likely form for the interaction of
mild steel with MEIP molecule. The calculations in Table 4
further show that MEIP in the protonated form (MEIPHþ) has
the smallest ΔE value (3.64 eV) indicating that MEIPHþ is the
most reactive inhibitor that can easily adsorb on the metal surface
causing higher protection. This agrees with the experimental
results that MEIP could have better inhibitive performance on
mild steel surface in the protonated form i.e. through electrostatic
interaction between the cation form of MEIP and the vacant
d-orbital of mild steel (physisorption). Moreover, the adsorption
of MEIP on the steel surface using the neutral form also plays a
part in the overall inhibiting process. This also agrees well with
the value of ΔGoads and ΔHoads obtained experimentally. The
dipole moment, which is defined as the first derivative of the
energy with respect to an applied electric field, is mainly used to
study the intermolecular interactions involving the van der Waals
type dipole-dipole forces etc., because the larger the dipole
moment the stronger will be the intermolecular attraction.38
There is lack of agreement in the literature on the correlation
between dipole moment and inhibition efficiency.52 In this study,
it could be noted that the protonated compound exhibit lower
value of dipole moment than the neutral form of MEIP.
Absolute hardness, η, and softness, σ, are important properties
to measure the molecular stability and reactivity. A hard molecule
has a large energy gap and a soft molecule has a small energy
gap. Soft molecules are more reactive than hard ones because
they could easily offer electrons to an acceptor. For the simplest
transfer of electrons, adsorption could occur at the part of the
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research
Table 5. Calculated Mulliken Atomic Charges, Fukui Func-
tions, and Philicity Indices for Heteroatoms of MEIP Using
DFT at the B3LYP/6-31G (d) Basis Set
atom qN qNþ1 qN-1 fþ
k f-
k
N1 -0.483 -0.469 -0.535 0.014 0.052
N2 -0.489 -0.475 -0.528 0.014 0.039
N3 -0.555 -0.574 -0.571 -0.019 0.016
N4 -0.732 -0.760 -0.733 -0.028 0.001
molecule where σ has the highest value and η the lowest value.19
The result from Table 4 shows that MEIP in the protonated form
has the lowest energy gap, lowest hardness, and the highest
softness; this agrees with the experimental results that MEIP
could have better inhibitive performance on mild steel surface in
the protonated form i.e. through electrostatic interaction be-
tween the cation form of MEIP and the vacant d-orbital of mild
steel (physisorption). Futhermore, the calculations show that the
neutral form of MEIP have positive ΔN value which becomes
negative value upon protonation. In all cases, the value of ΔN <
3.6, agrees with the study initially proposed by Lukovit and
reported elsewhere that inhibition efficiency increased with
increasing electron donating ability at the metal surface.53 Thus
in the present study MEIP in both the neutral and protonated
forms were donor of electrons and the mild steel surface was the
acceptor of electrons. The electrophilicity index, ω, which
measures the electrophilic power of a molecule was calculated
for both neutral and protonated forms of MEIP. It has been
reported that the higher the value of ω, the higher the capacity of
the molecule to accept electrons.38 In this study, the protonated
form of MEIP has the highest value of ω and by extension the
highest capacity to accept electrons from the metal. This process
increases the adsorption capacity of MEIP on the steel surface. In
a corroding system, it is important to note that the inhibitor acts
as a Lewis base while the metal acts as a Lewis acid.
The calculations from Table 4 indicate that η > 0 and ΔET < 0
in both neutral and protonated form of MEIP. This result implies
that the charge transfer to MEIP molecule followed by back-
donation from the molecule is energetically favorable. Similar
observation has been reported.20 However, it is important to
note that ΔET values obtained does not predict that a back-
donation process is going to occur; it only establishes that if both
processes occur (charge transfer to the molecule and back-
donation from the molecule), the energy change is directly
proportional to the hardness of the molecule. The calculated
Fukui indices for the charged species (Nþ1 and N-1) as well as
the neutral specie (N) are presented in Table 5. For simplicity,
only the charges and Fukui functions over the Nitrogen (N)
atoms is presented. For a finite system such as an inhibitor
molecule, when the molecule is accepting electrons one has fþ k,
the index for nucleophilic attack; when the molecule is donating
electrons, one has f- k , the index for electrophilic attack. It is
possible to observe from Table 5 that Nitrogen atoms (N1, N2)
are the most susceptible sites for electrophilic attacks. These sites
present the highest values of f-k which are 0.052 for N1 and 0.039
for N2, respectively. In the same vein, N1 and N2 are the most
susceptible sites for nucleophilic attacks. These sites have the
highest values of fþk which are 0.014 for N1 and 0.014 for N2,
respectively. Similar conclusions have been reported by Liu et al.,54
on the molecular modeling study on inhibition performance of
imidazolines for mild steel in CO2 corrosion.
2108
ARTICLE
4. CONCLUSIONS
The following conclusions may be drawn from the study:
1. 2-Mesityl-1H-imidazo[4,5-f][1,10]phenanthroline (MEIP)
acts as an inhibitor for the corrosion of mild steel in 0.5 M
H2SO4. Inhibition efficiency values increase with the inhib-
itor concentration but decrease with rise in temperature
suggesting physical adsorption mechanism.
2. The Gibbs free energy for the adsorption process calculated
using Statistical Physics is negative indicating that the
process is spontaneous.
3. UV-visible spectrophotometric studies clearly reveal the
formation of Fe-MEIP complex which may be responsible
for the observed inhibition.
4. Data obtained from quantum chemical calculations using
DFT at the B3LYP/6-31G (d,p) level of theory were
correlated to the inhibitive effect of MEIP. Both experi-
mental and theoretical calculations are in agreement.
’ ASSOCIATED CONTENT
bS Supporting Information. Derivation of thermodynamic
parameters using statistical model and some global and local
reactivity parameters based on the density functional theory.
This material is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Phone: þ234 8067476065. E-mail: proffoime@yahoo.com.
’ ACKNOWLEDGMENT
The authors wish to acknowledge the Department of Chem-
istry, University of Uyo, Nigeria, for providing the facilities for
the work. One of the authors Dr. A. O. Eseola is also acknowl-
edged for providing the newly synthesized inhibitor used in this
research.
’ REFERENCES
(1) Zhang, J.; Liu, J.; Yu, W.; Yan, Y.; You, L.; Liu, L. Molecular
modelling of the inhibition mechanism of 1-(2-aminoethyl)-2-alkyl-
imidazole. Corros. Sci. 2010, 52, 2059–2065.
(2) Liu, J.; Yu, W.; Zhang, J.; Hu, S.; You, L.; Qjao, G. Molecular
modelling study on inhibition performance of imidazolines for mild steel
in CO2 corrosion. Appl. Surf. Sci. 2010, 256, 4729–4733.
(3) Hosseini, S. M. A.; Azimi, A. The inhibition of mild steel
corrosion in acidic medium by 1-methyl-3-pyridin-2-yl-thiourea. Corros.
Sci. 2009, 51, 728–732.
(4) Gomez, B.; Likhhanova, N. V.; Dominguez-Aguilar, M. A.;
Martinez-Palou, R.; Vela, A.; Gazquez, J. L. Quantum chemical study
of the inhibitive properties of 2-pyridyl-azoles. J. Phys. Chem. B 2006,
110, 8928–8934.
(5) Obot, I. B.; Obi-Egbedi, N. O. Acenaphtho [1,2-b] quinoxaline
as a novel corrosion inhibitor for mild steel in 0.5 M H2SO4. Corros. Sci.
2010, 52, 923–926.
(6) Obot, I. B.; Obi-Egbedi, N. O. Indeno-1-one [2,3-b]quinoxaline
as an effective inhibitor for the corrosion of mild steel in 0.5 M H2SO4.
Mater. Chem. Phys. 2010, 122, 325–328.
(7) Obot, I. B.; Obi-Egbedi, N. O. 2,3-Diphenylbenzoquinoxaline: A
new corrosion inhibitor for mild steel in sulphuric acid. Corros. Sci. 2010,
52, 282–285.
(8) Obot, I. B.; Obi-Egbedi, N. O. Adsorption properties and inhi-
bition of mild steel corrosion in sulphuric acid solution by ketoconazole:
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research
Experimental and theoretical invesrigation. Corros. Sci. 2010, 52, 198–
204.
(9) Yan, Y.; Li, W.; Cai, L.; Baorong, H. Electrochemical and
quantum chemical study of purines as corrosion inhibitors for mild steel
in 1 M HCl solution. Electrochim. Acta 2008, 53, 5953–5960.
(10) Abd El Rehim, S. S.; Sayyah, S. M.; El-Deed, M. M.; Kamal,
S. M.; Azooz, R. E. Poly(o-phenylenediamine) as an inhibitor for
mild steel corrosion in HCl solution. Mater. Chem. Phys. 2010, 123,
20–27.
(11) Fang, J.; Li, J. Quantum chemistry study on the relationship
between molecular structure and corrosion inhibition efficiency of
amides. J. Mol. Struct. (Theochem) 2002, 593, 179–185.
(12) Roy, S.; Hagen, K. D.; Maheswari, P. U.; Lutz, M.; Spek, A. L.;
Reedijk, J.; Van Wezel, G. P. Phenanthroline derivatives with improved
selectivity as DNA-targeting anti-cancer or antimicrobial drugs. Chem-
MedChem 2008, 3, 1427–1434.
(13) Cardinaels, T.; Ramaekers, J.; Nockemann, P.; Driesen, K.; Van
Hecke, K.; Van Meervelt, L.; Lei, S.; De Feyter, S.; Guillon, D.; Donnio,
B.; Binnemans, K. Imidazo[4,5-f][1,10] phenanthrolines: Versatile
ligands for the design of metallomesogens. Chem. Mater. 2008, 20,
1278–1291.
(14) Zu, Z.; Liu, H.; Xiao, S.; Yang, M.; Bu, X. Synthesis, crystal
structure, antitumor activity and DNA-binding study of Mn(II) complex
of 2H-5-hydroxy-1,2,5-oxadiazo[3,4-f][1,10] phenanthroline. J. Inorg.
Biochem. 2002, 90, 79–84.
(15) Rodriguez-Valdez, L. M.; Villamisar, W; Casales, M.; Gonzalez-
Rodriguez, J. G.; Martinez-Villafane, A.; Martinez, L.; Glossman-Mitnik,
D. Computational simulations of the molecular structure and corrosion
properties of amidoethyl, aminoethyl and hydroxyethyl imidazolines
inhibitors. Corros. Sci. 2006, 48, 4053–4064.
(16) Bereket, G.; Ogretir, C.; Ozsahin, C. Quantum chemical studies
on the inhibition efficiencies of some piperazine derivatives for the
corrosion of steel in acidic medium. J. Mol. Struct. (Theochem) 2003, 663,
39–46.
(17) Khaled, K. F.; Babic-Samardzija, K.; Harkerman, N. Theoretical
study of the structural effects of polymethylene amines on corrosion
inhibition of iron in acid solutions. Electrochim. Acta 2005, 50, 2515–
2520.
(18) Obot, I. B.; Obi-Egbedi, N. O. Fluconazole as an inhibitor for
aluminium corrosion in 0.1 M HCl. Colloids Surf., A 2008, 330, 207–212.
(19) Masoud, M. S.; Awad, M. K.; Shaker, M. A.; El-Tahawy,
M. M. T. The role of structural chemistry in the inhibitive performance
of some aminopyrimidines on the corrosion of steel. Corros. Sci. 2010,
52, 2387–2396.
(20) Ebenso, E. E.; Arslan, T.; Kandemirli, F.; Caner, N.; Love, I.
Quantum chemical studies of some rhodanine azosulpha drugs as
corrosion inhibitors for mild steel in acidic medium. Int. J. Quantum
Chem. 2010, 110, 1003–1018.
(21) Laarej, K.; Bouachrine, M.; Radi, S.; Kertit, S.; Hammouti, B.
Quantum chemical studies on the inhibiting effect of bipyrazoles on steel
corrosion in HCl. E-J. Chem. 2010, 7 (2), 419–424.
(22) Arslan, T.; Kandemirli, F.; Ebenso, E. E.; Love, I.; Alemu, H.
Quantum chemical studies on the corrosion inhibition of some sulpho-
namides on mild steel in acidic medium. Corros. Sci. 2009, 51, 35–47.
(23) Eseola, A. O. Photoluminescent and catalytic properties of
azole-substituted pyridine and phenol ligands and their NiII and ZnII
complexes. Ph.D. Thesis, University of Ibadan, Ibadan, 2010, 222p.
(24) Obot, I. B.; Obi-Egbedi, N. O. Anticorrosive properties of
xanthone on mild steel corrosion in sulphuric acid: Experimental and
theoretical investigations. Curr. Appl. Phys. 2010, doi: 10.1016/j.
cap.2010.08.007.
(25) Obi-Egbedi, N. O.; Obot, I. B. Adsorption behavior and
corrosion inhibitive potential of xanthene on mild steel/sulphuric acid
interface. Arab. J. Chem. 2010, doi: 10.1016/j.arabjc.2010.08.004.
(26) Khadom, A. A.; Yaro, A. S.; Kadum, A. H. Corrosion inhibition
by naphthylamine and phenylenediamine for the corrosion of copper-
nickel alloy in hydrochloric acid. J. Taiwan Inst. Chem. Eng. 2010, 41,
122–125.
2109
ARTICLE
(27) Rahim, A. A.; Kassim, J. Recent development of vegetal tannins
in corrosion protection of iron and steel. Recent Pat. Mater. Sci. 2008, 1,
223–231.
(28) Shukla, S. K.; Singh, A. K.; Ahamad, I.; Quraishi, M. A.
Streptomycin: A commercially available drug as corrosion inhibitor for
mild steel in hydrochloric acid solution. Matt. Lett. 2009, 63, 819–822.
(29) Shukla, S. K.; Quraishi, M. A. Cefotaxime sodium: A new and
efficient corrosion inhibitor for mild steel in hydrochloric acid solution.
Corros. Sci. 2009, 51, 1007–1011.
(30) Umoren, S. A.; Obot, I. B. Polyvinylpyrollidone and polyacry-
lamide as corrosion inhibitors for mild steel in acidic medium. Surf. Rev.
Lett. 2008, 15 (3), 277–286.
(31) Umoren, S. A.; Obot, I. B.; Ebenso, E. E.; Obi-Egbedi, N. O.
The inhibition of aluminium corrosion in hydrochloric acid solution by
exudate gum from Raphia hookeri. Desalination 2009, 247, 561–572.
(32) Abboud, Y.; Abourriche, A.; Saffaj, T; Berrada, M.; Charrouf,
M.; Bennamara, A.; Hannache, H. A novel azo dye, 8-quinolinol-5-
azoantipyrine as corrosion inhibitor for mild steel in acidic media.
Desalination 2009, 247, 175–189.
(33) Zhao, J.; Zhang, N.; Qu, C.; Wu, X.; Zhang, J.; Zhang, X.
Cigarette and their application in corrosion inhibition for N80 steel at
90 °C in hydrochloric acid solution. Ind. Eng. Chem. Res. 2010, 49 (8),
3986–3991.
(34) Umoren, S. A.; Solomon, M. M.; Udousoro, I. I.; Udoh, A. P.
Synergistic and antagonistic effects between halide ions and carboxy-
methyl cellulose for the corrosion inhibition of mild steel in sulphuric
acid solution. Cellulose 2010, doi: 10.1007/s10570-010-9409-7.
(35) Spartan,06; Wavefunction, Inc.: Irvine, CA, Shao, Y.; Molnar,
L. F.; Jung, Y.; Kussmann, J.; Ochsenfeld, C.; Brown, S. T.; Gilbert,
A. T. B.; Slipehenko, L. V.; Levehenko, S. V.; O’Neill, D. P.; DiStasio,
R. A., Jr.; Lochan, R. C.; Wang, T.; Beran, G. J. O.; Besley, N. A.; Herbert,
J. M.; Lin, C. Y.; Van Voorhis, T.; Chien, S. H.; Sodt, A.; Steele, R. P.;
Rassolov, V. A.; Maslen, P. E.; Korambath, P. P.; Adamson, R. D.; Austin,
B.; Baker, J.; Byrd, E. F. C.; Dachsel, H.; Doerksen, R. J.; Dreuw, A.;
Dunietz, B. D.; Dutoi, A. D.; Furlani, T. R.; Gwaltney, S. R.; Heyden, A.;
Hirata, S.; Hsu, C. P.; Kedziora, G.; Khalliulin, R. Z.; .Klunzinger, P.;
Lee, A. M.; Lee, M. S.; Liang, W. Z.; Lotan, I.; Nair, N.; Peters, B.;
Proynov, E. I.; Pieniazek, P. A.; Rhee, Y. M.; Ritchie, J.; Rosta, E.; Sherrill,
C. D.; Simmonett, A. C.; Subotnik, J. E.; Woodcock, H. L., III; Zhang,
W.; Bell, A. T.; Chakraborty, A. K.; Chipman, D. M.; Keil, F. J.; Warshel,
A.; Hehre, W. J.; Schaefer, H. F.; Kong, J.; Krylov, A. I.; Gill, P. M. W.;
Head-Gordon, M. Phys. Chem. Chem. Phys. 2006, 8, 3172-3181.
(36) Bockris, J. O. M.; Drazic, D.; Despic, A. R. The electrode
kinetics of the deposition and dissolution of iron. Electrochim. Acta 1961,
4, 325–361.
(37) Omar, B.; Mokhtar, O. Inhibition of cold rolled steel in
sulphuric acid solution by 2-mercapto-1-methylimidazole: Time and
temperature effects treatments. Arab. J. Chem. 2010, doi: 10.1016/j.
arabjc.2010.07.016.
(38) Obi-Egbedi, N. O.; Obot, I. B. Inhibitive properties, thermo-
dynamics and quantum chemical studies of alloxazine on mild steel
corrosion in H2SO4. Corros. Sci. 2010, doi: 10.1016/j.corsci.2010.09.020.
(39) Singh, A. K.; Quraishi, M. A. Investigation of adsorption of
isoniazid derivatives at mild steel/hydrochloric acid interface: Electro-
chemical and weight loss methods. Mater. Chem. Phys. doi: 10.1016/j.
matchemphys.2010.05.035.
(40) Wang, H.; Fan, H.; Zheng, J. Corrosion inhibition of mild steel
in hydrochloric acid solution by a mercapto-triazole compound. Mater.
Chem. Phys. 2002, 77, 655–661.
(41) Ahamad, I.; Prasad, R.; Quraishi, M. A. Adsorption and inhibitive
properties of some new Mannich bases of Isatin derivatives on corrosion
of mild steel in acidic media. Corros. Sci. 2010, 52, 1472–1481.
(42) Singh, A. K.; Quraishi, M. A. Effect of cefazolin on the corrosion
of mild steel in HCl solution. Corros. Sci. 2010, 52, 152–160.
(43) Noor, E. A.; Al-Moubaraki, A. H. Thermodynamic study of
metal corrosion and inhibitor adsorption processes in mild steel/1-
methyl-4[40 (-X)-styrlpyridinium iodides/hydrochloric acid systems.
Mater. Chem. Phys. 2008, 110, 145–154.
dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110
Industrial & Engineering Chemistry Research ARTICLE

(44) Benabdellah, M.; Tounsi, A.; Khaled, K. F.; Hammouti, B.

Thermodynamic, chemical and electrochemical investigations of 2-mer-
capto benzimidazole as corrosion inhibitor for mild steel in hydrochloric
acid solutions. Arab. J. Chem. 2010, doi: 10.1016/j.arabjc.2010.06.010.
(45) Herrag, L.; Hammouti, B.; Elkadiri, S.; Aouniti, A.; Jama, C.;
Vezin, H.; Bentiss, F. Adsorption properties and inhibition of mild steel
corrosion in hydrochloric solution by some newly synthesized diamine
derivatives: Experimental and theoretical investigations. Corros. Sci.
2010, doi: 10.1016/j.corsci.2010.05.024.
(46) Abdallah, M.; El-Naggar, M. M. Cuþ2 cation þ 3,5-dimethyl-
pyrazole mixture as a corrosion inhibitor for carbon steel in sulfuric acid
solution. Mater. Chem. Phys. 2001, 71, 291–298.
(47) Abboud, Y.; Abourriche, A.; Saffaj, T.; Berrada, M.; Charrouf,
M.; Bennamara., Al; Himidi, N.; Hannache, H. 2,3-Quinoxalinedione as
a novel corrosion inhibitor for mild steel in 1 M HCl. Mater. Chem. Phys.
2007, 105, 1–5.
(48) Goel, R.; Siddiqi, W. A.; Ahmed, B.; Khan, M. S.; Chaubey,
V. M. Synthesis, characterization and corrosion inhibition efficiency
of N-C2{(2E)-2-[4-(dimethylamino)benzylidene]hydrazinyl}2-oxo
ethylbenzamide on mild steel. Desalination 2010, doi: 10.1016/
j.desal.2010.06.033.
(49) Ahamad, I.; Prasad, R.; Quraishi, M. A. Experimental and
quantum chemical characterization of the adsorption of some Schiff
base compounds of phthaloyl thiocarbohydrazide on the mild steel in
acid solutions. Mater. Chem. Phys. 2010, doi: 10.1016/j.matchem-
phys.2010.08.051.
(50) Bouklah, M.; Harek, H.; Touzani, R.; Hammouti, B.; Harek, Y.
DFT and quantum chemical investigation of molecular properties of
substituted pyrrolidinones. Arab. J. Chem. 2010, doi: 10.1016/j.
arabjc.2010.08.008.
(51) Xia, S.; Qiu, M.; Yu, L.; Liu, F.; Zhao, H. Molecular dynamics
and density functional theory study on relationship between structure of
imidazoline derivatives and inhibition performance. Corros. Sci. 2008, 50,
2021–2029.
(52) Sahin, M.; Gece, G.; Karci, F.; Bilgic, S. Experimental and
theoretical study of the effect of some heterocyclic compounds on the
corrosion of low carbon steel in 3.5% NaCl medium. J. Appl. Electrochem.
2008, 38, 809–815.
(53) Ahamad, I.; Prasad, R.; Quraishi, M. A. Inhibition of mild steel
corrosion in acid solution by pheniramine drug: Experimental and
theoretical study. Corros. Sci. 2010, doi: 10.1016/j.corsci.2010.05.022.
(54) Liu, J.; Yu, W.; Zhang, J.; Hu, S.; You, L.; Qiao, G. Molecular
modelling study on inhibition performance of imidazolines for mild steel
in CO2 corrosion. Appl. Surf. Sci. 2010, 256, 4729–4733.

2110 dx.doi.org/10.1021/ie102034c |Ind. Eng. Chem. Res. 2011, 50, 2098–2110