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Article history: Ketoconazole (KCZ) has been evaluated as a corrosion inhibitor for mild steel in aerated 0.1 M H2SO4 by
Received 15 March 2009 gravimetric method. The effect of KCZ on the corrosion rate was determined at various temperatures and
Accepted 2 September 2009 concentrations. The inhibition efficiency increases with increase in inhibitor concentration but decrease
Available online 11 September 2009
with rise in temperature. Adsorption followed the Langmuir isotherm with negative values of DG0ads , sug-
gesting a stable and a spontaneous inhibition process. Quantum chemical approach was further used to
Keywords: calculate some electronic properties of the molecule in order to ascertain any correlation between the
Ketoconazole
inhibitive effect and molecular structure of ketoconazole.
Mild steel
Corrosion inhibition
Ó 2009 Elsevier Ltd. All rights reserved.
Quantum chemistry
Sulphuric acid
0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.09.002
I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204 199
0.08 0.06
1 x 10 -4 1 x 10 -4
8 x 10^-5
0.07 8 x 10^-5
6 x 10^-5
4 x 10^-5 0.05 6 x 10^-5
4 x 10^-5
Weight loss (g /cm2)
0.06 2 x 10^-5
Blank ^ 2 x 10^-5
Blank ^
0.04
0.03
0.03
0.02 0.02
0.01
0.01
0
1 2 3 4 5 6 7
Time (days) 0
1 2 3 4 5 6 7
0.08
Time (days)
1 x 10 -4
0.07 8 x 10^-5 Fig. 2b. Plot of weight loss against time (average) for ketoconazole at 30 °C.
6 x 10^-5
4 x 10^-5
0.06 2 x 10^-5
Blank ^ Fe þ H2 O ¡ Fe H2 Oads ð5aÞ
Weight loss (g /cm2)
2 x 10^-5
0.035 Blank ^ molecules on the metal surface by inhibitor species to yield the ad-
0.03 sorbed intermediate FeYads (Eq. (5c)) reduces the amount of the
species FeOH ads available for the rate-determining steps and conse-
0.025
quently retards Fe anodic dissolution.
0.02
Further inspection of Table 2 clearly shows that the presence of
0.015 KCZ in the solution inhibits the mild steel corrosion and the extent
0.01 of protection efficiency increases with increasing inhibitor concen-
0.005 tration. In contrast, the inhibition efficiency decreases with
increasing temperature. The variation of inhibition efficiency with
0
temperature is a very important tool oftentimes used to deduce the
1 2 3 4 5 6 7
mode of adsorption of inhibitors [23]. For a chemical adsorption
Time (days)
mechanism, the inhibition efficiency increases with increase in
Fig. 2a. Plot of weight loss against time for mild steel corrosion in 0.1 M H2SO4 for temperature while an increase in inhibition efficiency with de-
triplicate determination of ketoconazole prepared under identical conditions at crease in temperature is suggestive of a physical adsorption mech-
30 °C. anism as obtained in this study. Similar observations have been
documented by us [7,31]. Furthermore, the low values of the inhi-
bition efficiency obtained in the present study (Table 2) may be
The increase in corrosion rate with temperature is reasonable and due to the low adsorption and less interference by SO2 4 ion on
is in agreement with that earlier reported by Ebenso [21] that a the mild steel surface as compared to other anion like Cl which
doubling in reaction rate is expected with a 10 °C rise in have a smaller degree of hydration and is expected to be more ad-
temperature. sorbed on the metal surface thus increasing the inhibition effi-
According to the Bockris mechanism outlined earlier, Fe electro- ciency. Similar observations have been documented by El Azhar
dissolution in acidic sulphate solutions depends primarily on the et al. [24] on the study of the inhibitive effect of 2,5-bis (n-pyri-
adsorbed intermediate FeOHads. Ashassi-Sorkhabi and Nabavi-Amri dyl)-1,3-thiadiazoles (n-PTH) on the corrosion of mild steel in
[22] proposed the following mechanism involving two adsorbed 1 M HCl and 0.5 M H2SO4. There is an ongoing research in our lab-
intermediates to account for the retardation of Fe anodic dissolu- oratory to improve the efficiency of ketoconazole using some metal
tion in the presence of an inhibitor: cations and anions.
I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204 201
Table 2
Corrosion parameters for mild steel in 0.1 M H2SO4 in the absence and presence of different concentrations of ketoconazole at 30 and 50 °C.
surface. Large values of K ads imply more efficient adsorption and corrosion field [41]. The studies of Vosta and Eliasek [42] and Chak-
hence better inhibition efficiency while low values imply weak rabarti [43] can be respected as the first theoretical studies on cor-
adsorption and hence low inhibition efficiency as obtained in this rosion inhibitors in the literature.
study [34]. Semi-empirical calculations to evaluate the efficiency of some
imidazole derivatives as acidic corrosion inhibitors for steel have
3.3. Effects of temperature been performed by Bereket et al. [44] using AM1, PM3, MNDO
and MINDO/3 methods. Charges on nitrogen atoms, total energy,
Temperature has a great effect on the rate of metal electro- ionization potential, EHOMO, ELUMO, DE (ELUMO EHOMO) and dipole
chemical corrosion. In case of corrosion in a neutral solution (oxy- moment (D) were calculated and correlated with experimental re-
gen depolarization) the increase in temperature has a favourable sults. A satisfactory agreement was found between theoretical and
effect on the overpotential of oxygen depolarization and the rate experimental data. Similar studies on these compounds have been
of oxygen diffusion but it leads to a decrease of oxygen solubility. carried out by Ogretir et al. [45,46] in order to probe the inhibition
In case of corrosion in an acidic medium (hydrogen depolariza- mechanism of corrosion via metal–ligand interaction using semi-
tion), the corrosion rate increases exponentially with temperature empirical methods. According to their conclusion, semi-empirical
increase because the hydrogen evolution overpotential decreases calculations can be used to elucidate the mechanism of inhibition.
[35]. An experimental dependence of an integrated Arrhenius-type Recently we have reported on the inhibition of acid corrosion of Al
equation is observed between the corrosion rate and temperature in HCl using fluconazole and 2,3-diaminonaphthalene using both
[36]: experimental and semi-empirical quantum studies at the AM1 le-
vel of theory [7,31]. Results obtained using this level of theory
q2 Ea 1 1
log ¼ ð10Þ was satisfactory.
q1 2:303R T 1 T 2 Table 5 shows some of the key quantum chemical parameters
where q2 and q1 are the corrosion rates at temperature T1 and computed using AM1 method. These are mainly the energies of
T2, respectively, and R the molar gas constant. An estimate of heat the highest occupied (EHOMO) and lowest unoccupied (ELUMO)
of adsorption was obtained from the trend of surface coverage with molecular orbitals, energy of the gap, DE (ELUMO EHOMO) and di-
temperature as follows [37]: pole moment (D). These quantum chemical parameters were ob-
tained after geometric optimization with respect to all nuclear
h2 h1 T 1X T 2 1
coordinates.
Q ads ¼ 2:303R log log x kJ=mol
1 h2 1 h1 T2 T1 Frontier orbital theory is useful in predicting adsorption centres
ð11Þ of the inhibitor molecules responsible for the interaction with sur-
face metal atoms [47]. Moreover, the gap between the LUMO and
where h1 and h2 are the degrees of surface coverage at temperatures T1
HOMO energy levels of the molecules was another important fac-
and T2, The calculated values for both parameters are given in Table 4.
tor that should be considered. It has been reported that excellent
Some studies [7,15,31,38] showed that compared with the acti-
corrosion inhibitors are usually those organic compounds who
vation energy, Ea in the absence of inhibitors, higher values of Ea
are not only offer electrons to unoccupied orbital of the metal,
were found in the presence of inhibitors. Other studies [36,37]
but also accept free electrons from the metal [48]. It is also well
showed that in the presence of inhibitor the activation energy Ea
documented in literature that the higher the HOMO energy of
was lower than that in the absence of inhibitor. In the present study,
the inhibitor, the greater its ability of offering electrons to unoccu-
however, it could be found that the values of Ea in the presence of dif-
pied d-orbital of the metal, and the higher the corrosion inhibition
ferent concentrations of KCZ were higher than that in its absence.
efficiency. In addition, the lower the LUMO energy, the easier the
This is often interpreted as an indication of the formation of an
acceptance of electrons from metal surface, as the LUMO–HOMO
adsorptive film of a physical electrostatic character [39]. Thus, the
energy gap decreased and the efficiency of inhibitor improved.
adsorbed KCZ molecules create a physical barrier to charge and mass
Quantum chemical parameters listed in Table 4 reveal that KCZ
transfer [40]. The negative Q ads values also signify that the degree of
has high HOMO and low LUMO with high energy gap. Similar
surface coverage decreased with rise in temperature. The reason for
observations have been reported by Khaled [41] on the adsorption
this, as suggested by Oguzie [19], may be that the attainment of
and inhibitive properties of a new synthesized guanidine deriva-
physical adsorption equilibrium is usually rapid and the process
tive on corrosion of copper in 0.5 M H2SO4.
readily reversible whereas in chemisorptions, the occurrence of
According to Pearson [49], when two systems Fe and inhibitors
chemical reactions at the metal surface makes the process relatively
are brought together electrons will flow from lower v (inhibitor) to
slow and not readily reversible. Thus, enthalpy changes for chemi-
higher v (Fe) until the chemical potentials become equal. As a first
sorptions are usually higher than for physisorption.
approximation, the fraction of electron transferred, DN, is given by:
3.4. Quantum chemical calculations vFe vinb
DN ¼ ð12Þ
2ðgFe þ ginh Þ
Computational methods have a potential application towards
the design and development of organic corrosion inhibitors in Table 5
Quantum chemical parameters for KCZ.
where vFe and vinh denote the absolute electro-negativity of Fe and could interact with the lowest unoccupied molecular orbital
the inhibitor molecule, respectively; gFe and ginh denote the abso- (LUMO) of the latter. Similar interaction has been reported
lute hardness of Fe and the inhibitor molecule, respectively. From [57,24,58].
Eq. (4), the Fe is the lewis acid according to HSAB (Hard and Soft
Acid and Base) theory [50]. The difference in electro-negativity 4. Conclusions
drives the electron transfer, and the sum of the hardness parame-
ters acts as a resistance [49]. These quantities are related to electron 1. Results obtained from the experimental data shows that keto-
affinity (A) and ionization potential (I) which are useful in their abil- conazole acts as inhibitor for the corrosion of mild steel in
ity to help predict chemical behaviour [51]. 0.1 M H2SO4.
IþA 2. Inhibition efficiency increases with increase in the concentra-
v¼ ð13Þ tion of the studied inhibitor but decreases with rise in
2
IA temperature.
g¼ ð14Þ 3. The adsorption of KCZ on mild steel surface from 0.1 M H2SO4
2
obeys the Langmuir adsorption isotherm.
I and A are related in turn to EHOMO and ELUMO as follows: 4. Phenomenon of physical adsorption is proposed from the values
of (Ea, Q ads , DG0ads ) obtained.
I ¼ EHOMO ð15Þ
5. The adsorption of KCZ onto mild steel surface was a spontane-
A ¼ ELUMO ð16Þ ous process.
Values of v and g were calculated by using the values of I and A ob- 6. Quantum chemical calculations show that apart from KCZ mol-
tained from quantum chemical calculations. Using a theoretical v ecules adsorbing as cationic species on the mild steel surface, it
value of 7 eV/mol according to pearsons electro-negativity scale can also adsorbed as molecular species using oxygen, nitrogen
[49] and a global hardness g value of 0 eV/mol for Fe by assuming and the p electrons of the aromatic ring as its active centres.
that for a metallic bulk I = A [52], DN, which is the fraction of elec- 7. The relationship between the inhibition efficiency of KCZ on
trons transferred from inhibitor to the mild steel surface was calcu- mild steel in 0.1 M H2SO4 and the EHOMO, EHOMO ELUMO, and
lated (Table 5). Values of DN showed inhibition effect resulted from DN of KCZ were calculated by AM1 method and discussed.
electrons donation. According to Lukovits [53], if DN <3.6, the inhi-
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