Current Applied Physics 11 (2011) 382e392

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Current Applied Physics

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Anti-corrosive properties of xanthone on mild steel corrosion in sulphuric acid:

Experimental and theoretical investigations
I.B. Obot a, *, N.O. Obi-Egbedi b
a
Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017, Uyo, Akwa Ibom State, Nigeria
b
Department of Chemistry, University of Ibadan, Ibadan, Nigeria

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

Article history: The anti-corrosive effect of xanthone (XAN) on the corrosion of mild steel in 0.5 M H2SO4 has been
Received 8 May 2010 studied by gravimetric and UVevisible spectrophotometric methods at 303e333 K. Results obtained
Received in revised form revealed that XAN performed excellently as a corrosion inhibitor for mild steel in sulphuric acid solution.
23 July 2010
Inhibition efficiency increases with increase in concentration of XAN but decreases with rise in
Accepted 6 August 2010
Available online 13 August 2010
temperature which is suggestive of physical adsorption mechanism although chemisorption may also
play a part. DubinineRadushkevich adsorption isotherm model was found to adequately describe the
adsorption of XAN onto the mild steel surface. Kinetic parameters of activation and thermodynamic
Keywords:
Xanthone
parameters using the statistical model were calculated and discussed. The corrosion process in 0.5 M
Mild steel corrosion inhibitors H2SO4 in the absence and presence of XAN follows first-order kinetics. The UVevisible absorption spectra
Density functional theory (DFT) of the solution containing the inhibitor after the immersion of mild steel specimen indicate the
Sulphuric acid formation of a XANeFe complex. Quantum chemical calculations have been performed using DFT and
several quantum chemical indices were calculated and correlated with the inhibitive effect.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction
Mild steel is widely applied as constructional material in many
chemical and petrochemical industries due to its excellent
mechanical properties and low cost [1]. The main problem of mild
steel is its dissolution in acidic solutions. The use of inhibitors is one
of the most practical methods for the protection of mild steel
against corrosion especially in acidic media. The inhibitors are
effective even in very small concentrations. The application of
inhibitors has led to a lower iron dissolution rate and a considerable
prolongation of the life time of mild steel [2].
Most well known acid inhibitors are organic compounds con-
taining nitrogen, sulphur, and oxygen atoms. It is generally
accepted that organic molecules inhibit corrosion by adsorption on
metal surface. Furthermore, the adsorption depends on the elec-
tronic structure of inhibiting molecules, steric factor, aromaticity
and electron density at donor site, presence of functional group
such as eC]O, eN]N, ReOH, etc., molecular area, molecular
weight of the molecule, temperature and electrochemical potential
at the metal/solution interface [3e13].
* Corresponding author. Tel.: þ234 8067476065.
E-mail address: proffoime@yahoo.com (I.B. Obot).
For many years in the steel industry, the use of inorganic salts or
their blends such as chromate, nitrite, phosphonates, silicates, zinc
salts, cadmium salts, arsenic salts and other cations have been found
effective as inhibitors of metal corrosion as cited by Abboud et al.
[14], but a major disadvantage is their toxicity and their use may
cause reversible (temporary) or irreversible (permanent) damage to
organ system, namely kidneys or liver, or to disturb a biochemical
process or to disturb an enzyme system at some site in the body [15].
Thus, the investigation of more environmentally acceptable corro-
sion inhibitors is of great practical interest. Recently, we have
reported on the use of quinoxaline derivatives [16e18], antifungal
drugs [19], and ketoconazole [20] as eco-friendly, cheap and non-
toxic inhibitors for mild steel in sulphuric acid solution.
Xanthone is an organic compound with the molecular formula
C13H8O2 (Fig. 1). It is off-white in appearance. It has a melting of
174
C. Xanthone also has a boiling point of 351
C. In 1938,
xanthone was introduced as an insecticide and is currently find
uses as ovicide for codling moth eggs and as a larvicide [21]. The
chemical structure of xanthone forms the central core of a variety of
naturally occurring compounds such as mangostin, which are
sometimes collectively referred to as xanthones [21]. This makes
the investigation of their inhibiting properties significant in the
context of the current priority to produce eco-friendly and cheap
inhibitors. The compound contains a carbonyl group, oxygen atom

1567-1739/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2010.08.007
 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392
Fig. 1. Molecular structure of xanthone (XAN).
and aromatic rings with several p bonds which could possibly serve
as active sites for the adsorption process. Furthermore, the mole-
cule has a large molecular mass (196.19 g/mol) and likely to effec-
tively cover more surface area (due to adsorption) of the mild steel
In continuation of our studies on eco-friendly inhibitors, we
report for the first time the use of xanthone as acid corrosion
inhibitor for mild steel surface in sulphuric acid solution using
gravimetric method. The effect of temperature on corrosion and
inhibition processes is thoroughly assessed and discussed. Ther-
modynamic parameters, UVevis spectroscopy together with
quantum chemical study using density functional theory were
further employed to provide additional insight into the mechanism
of inhibitory action.
2. Materials and methods
2.1. Material
Test was 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. The metal specimens were
prepared, degreased and cleaned as previously described [16,17]
2.2. Inhibitor
Xanthone (XAN) was purchased from SIGMA-ALDRICH and used
as inhibitor. Stock solution was made in 10:1 water:methanol
mixture to ensure solubility [2]. This stock solution was used for all
experimental purposes. Fig. 1 shows the molecular structure of
XAN. It is evident that XAN is a heterocyclic compound containing
oxygen atoms, which could easily be protonated in acidic solution,
and several p-electrons exist in this molecule.
2.3. Solutions
The aggressive solutions, 0.5 M H2SO4 were prepared by dilution
of analytical grade 98% H2SO4 with distilled water. The concentra-
tion range of XAN was 2  106e10  106 M.
2.4. Gravimetric measurements
The gravimetric method (weight loss) is probably the most
widely used method of inhibition assessment [16e18,22e25]. The
simplicity and reliability of the measurement offered by the weight
loss method is such that the technique forms the baseline method
of measurement in many corrosion monitoring programmes [26].
Weight loss measurements were conducted under total immersion
using 250 mL capacity beakers containing 200 mL test solution at
303e333 K maintained in a thermostated 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 interval
progressively for 10 h, washed thoroughly in 20% NaOH solution
383
containing 200 g/L of zinc dust [16] with bristle brush, rinsed
severally in deionized water, cleaned, dried in acetone, and re-
weighed. 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. 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 5%, indicating good reproducibility.
The corrosion rate (r) in g cm2 h1 was calculated from the
following equation [27]:
DW
r¼ (1)
St
where W is the average weight loss of three mild steel sheets, S 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 follows [28]:


r1 r2
%I ¼  100 (2)
r
Where r1 and r2 are the corrosion rates of the mild steel coupons in
the absence and presence of inhibitor, respectively.
2.5. Spectrophotometric measurements
UVevisible absorption spectrophotometric method was carried
out on the prepared mild steel samples after immersion in 0.5 M
H2SO4 with and without addition of 10  106 M of xanthone at
303 K for 3 days. All the spectra measurements were carried out
using a Perkin-Elmer UVevisible Lambda 2 spectrophotometer.
2.6. 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 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 Spartan’06V112 program package [29] in order to determine
whether they correspond to a maximum or a minimum in the
potential energy curve. The theoretical parameters were calculated
for molecules in aqueous phase in the neutral and protonated form
for comparison. It is well known that the phenomenon of electro-
chemical corrosion occurs in liquid phase. As a result, it was
necessary to include the effect of a solvent in the computational
calculations. In the Spartan ’06V112 program, SCRF methods (Self-
consistent reaction field) were used to perform calculations in
solution. These methods model the solvent 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 measurements
Weight loss of mild steel, in g cm2 h1, was determined at
various time intervals in the absence and presence of different
concentrations of xanthone. Fig. 2 shows the weight lossetime
curves obtained for mild steel in 0.5 M H2SO4 in the absence and
presence of different concentrations of XAN at 303 K. The figure
shows that the presence of inhibitor falls significantly below that of
384 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392

1.4

1.2 Blank 2 x 10 ^-6 M

4 x 10^-6 M 6 x 10 ^-6 M
1

Weight loss (g cm-2) 8 x 10 ^-6 M 10 x 10^ -6 M

0.8

0.6

0.4

0.2

0
2 4 6 8 10
Time (h)

Fig. 2. Variation of weight loss against time for mild steel corrosion in 0.5 M H2SO4 in the presence of different concentrations of XAN at 303 K.

free acid. Similar curves were obtained for 313e333 K (not shown).
The calculated values of corrosion rates (r) and inhibition efficiency
(%I) obtained from weight loss measurements for different
concentrations of xanthone in 0.5 M H2SO4 after 10 h immersion at
303e333 K are listed in Table 1. It is evident from this table 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 93.12%. This may be due to
the adsorption of xanthone onto the mild steel surface through
non-bonding electron pairs of oxygen atoms as well as the p-
electrons of the aromatic rings. The high inhibitive performance of
xanthone suggests a higher bonding ability of the inhibitor to the
mild steel surface. Similar observation has been reported [2].
The influence of temperature on percentage inhibition effi-
ciency was studied by conducting weight loss measurements at
303e333 K containing different concentrations of XAN (Table 1).
Fig. 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 decrease in inhibition efficiency with increase in
temperature may be probably due to increased rate of desorption of
XAN from the mild steel surface at higher temperature [30].
3.2. Effect of temperature
The effect of temperature is another tool that has been used to
explain the mechanism of corrosion inhibition [14]. The relationship
between the corrosion rate (r) of mild steel in acidic media and
temperature (T) is often expressed by the Arrhenius equation [27]:
Ea
log r ¼ log A  (3)
2:303RT
where r is the corrosion rate Ea is the apparent activation energy, R is
the molar gas constant (8.314 J K1 mol1), T is the absolute temper-
ature, and A is the frequency factor. The plot of log r against 1/T for
mild steel corrosion in 0.5 M H2SO4 in the absence and presence of
different concentrations of XAN is presented in Fig. 4. All parameters
are given in Table 2. In the present study, it could be seen that the
activation energy was higher in the presence of XAN when compared
with the blank. Furthermore, with increasing concentration of XAN,
the activation energy increased. The increase in activation energies in
the presence of inhibitor is attributed to an appreciable decrease
in the adsorption process of the inhibitor on the metal surface with
increase in temperature; and corresponding increase in the reaction
rate because of the greater area of the metal exposed to acid [14]. A
decrease in inhibition efficiency with rise in temperature, with
analogous increase in corrosion activation energy in the presence of
inhibitor compared to its absence, is a good evidence for phys-
isorption mechanism of XAN on the steel surface [4,14,20].
Experimental corrosion rate values obtained from weight loss
measurements for mild in 0.5 M H2SO4 in the absence and presence
of XAN was used to further gain insight on the change of enthalpy
(DH*) and entropy (DS*) of activation for the formation of the acti-
vation complex in the transition state using transition equation [28]:
! !


RT D S* DH*
r¼ exp exp (4)
Nh R RT
where r is the corrosion rate, h is the Plank’s constant (6.626176  1034 J s),
N is the Avogadro’s number (6.02252  1023 mol1), R is the universal

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 XAN at 303e333 K.

System/concentration Corrosion rate  103(g cm2 h1) Inhibition efficiency (%I)

303 K 313 K 323 K 333 K 303 K 313 K 323 K 333 K

Blank 1.89 2.85 4.98 8.25 e e e e
2  106 M 1.39 2.45 4.42 7.77 26.46 14.04 11.25 5.82
4  106 M 1.09 1.88 3.84 7.53 42.33 34.04 22.89 8.73
6  106 M 0.89 1.56 3.68 7.02 52.91 45.26 26.11 14.91
8  106 M 0.49 1.19 3.14 6.34 74.08 58.25 36.95 23.15
10  106 M 0.13 0.78 2.18 4.50 93.12 72.63 56.23 45.46
 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392 385

100
10 x 10 ^-6 M
90
8 x 10 ^-6 M
80
6 x 10 ^-6 M

Inhibition efficiency (%I)

70 4 x 10 ^-6 M
60 2 x 10 ^-6 M

50

40

30

20

10

0
303 313 323 333
Temperature (K)

Fig. 3. Variation of inhibition efficiency of XAN with temperature.

gas constant and T is the absolute temperature. Fig. 5 shows the
plot of log r/T versus 1/T for mild steel corrosion in 0.5 M H2SO4 in
the absence and presence of different concentrations of XAN.
Straight lines were obtained with slope of (DH*/2.303R) and an
intercept of [log (R/Nh) þ (DS*/2.303R)] from which the values of
DH* and DS* respectively were computed and listed also in Table 2.
The positive signs of DH* reflect the endothermic nature of the mild
steel dissolution process [31]. Large and negative values of (DS*)
imply that the activated complex in the rate determining step
represents an association rather than a dissociation step, meaning
that a decrease in disordering takes place on going from reactants
to the activated complex [32]. Furthermore, the DH* for the
inhibited system increases with increase in the concentration of
XAN whereas DS* showed no appreciable changes in the presence
of different concentrations of XAN as compared to the blank (Table
2). Therefore, the decrease in corrosion rate is mostly decided by
higher values of Ea and DH* since both parameters increases with
concentration and as a result, the corrosion rate of the mild steel is
reduced. The results obtained are in agreement with Eq. (3) and (4)
which indicate that higher Ea and DH* lead to lower corrosion rate.
3.3. Adsorption isotherm
It is widely acknowledged that adsorption isotherms provide
insights into the mechanism of corrosion inhibition. Thus, experi-
mental results obtained in this study were fitted into Dubi-
nineRadushkevich isotherm model (D-RIM). This model was
conceived by Dubinin and his co-worker for studies on subcritical
vapours in micropore solids where the adsorption process follows
a pore filling mechanism onto energetically non-uniform surface
[33]. The D-RIM isotherm equation is excellent for interpreting
organic compounds sorption equilibria (in gas phase condition) in
porous solids. D-RIM equation is rarely applied onto liquid phase
adsorption due to the complexities associated with other factors

Blank
-0.5
2 x 10 ^-6 M R² = 0.958
4 x 10^-6 M
-1 R² = 0.996
6 x 10 ^-6 M
R² = 0.997
8 x 10 ^-6 M R² = 0.999
-1.5
Log ρ (gcm -2 h-1) x 10 -3

10 x 10 ^-6 M
R² = 0.996
-2
R² = 0.994

-2.5

-3

-3.5

-4

-4.5
3 3.09 3.19 3.3
1000/ T(K-1)

Fig. 4. Arrhenius plot for mild steel corrosion in 0.5 M H2SO4 in the absence and presence of different concentrations of xanthone (XAN).
386 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392

Table 2 between ln q and s2 for the obtained data at 303 K. The regression
Activation parameters of the dissolution of mild steel in 0.5 M H2SO4 in the absence between ln q and s2 has been done and the correlation coefficient
and presence of different concentrations of XAN.
(R2) was good (0.986), showing the adsorption of XAN onto mild
C (M) Ea(kJ mol1) DH*(kJ mol1) DS*(J mol1 K1) steel surface obeys DubinineRadushkevich (D-RIM) adsorption
Blank 4.14 17.58 299.52 isotherm. The adsorption parameters for D-RIM isotherm are
2  106 4.76 19.76 298.34 a ¼ 0.30 mol2 kJ1 and E ¼ 2.33 kJ/mol respectively. The numerical
4  106 5.39 22.42 297.60
value of E supports the physical adsorption mechanism of XAN on
6  106 5.86 23.44 297.10
8  106 7.18 27.87 293.50 mild steel surface.
10  106 9.68 36.42 288.53

3.4. Thermodynamic consideration using the statistical model

such as pH and ionic equilibria inherent in these systems [33].
Additionally, the soluteesolvent interactions often render the bulk
solution non-ideal. D-RIM has been very useful in distinguishing
between physical and chemical adsorption for the removal of some
pollutants from aqueous solutions by adsorption on various
adsorbents [34]. It has recently been applied in corrosion inhibition
studies [35]. It can be expressed as:
ln q ¼ ln qmax  as2
where q is the degree of surface coverage, qmax is the maximum
surface coverage and s (Polanyi potential) can be correlated as:


1
s ¼ RTln 1 þ
Cinh
The constant a gives the mean adsorption energy, E, which is the
transfer energy of 1 mole of adsorbate from infinity (bulk solution)
to the surface of the adsorbent:
Basic information on the interaction between inhibitor and mild
steel surface can be provided by the thermodynamic parameters for
the inhibiting process. The different types of adsorption expres-
sions are determined by the different adsorption behavior of an
organic inhibitor on mild steel surface. The inhibition process of an
organic compound onto a metal surface can be explained by the
formation of metaleinhibitor reaction complex. The mechanism
involving two adsorbed intermediates has been proposed in order
(5) to account for the retardation of Fe anodic dissolution in the
presence of an inhibitor [36]:
Fe þ H2O 4 Fe$H2Oads (8)
(6)
Fe$H2Oads þ Y 4 FeOHads þ Hþ þ Y (9)
Fe$H2Oads þ Y 4 FeYads þ H2O (10)

1
E ¼ pffiffiffiffiffiffi (7) FeOHads / FeOHads þ e (rds) (11)
2a
The magnitude of E gives information about the type of adsorption.
FeYads 4 FeYþads þ e (12)
If this value is less than 8 kJ/mol, adsorption type can be explained
by physical mechanism whereas value of E equal to or greater than
8 kJ/mol signifies chemisorption [28]. Fig. 6 shows the relationship FeOHads þ FeYþads 4 FeYads þ FeOHþ (13)

Fig. 5. Transition state plot for mild steel corrosion in 0.5 M H2SO4 in the absence and presence of different concentrations of xanthone (XAN).
 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392 387

medium. The complex-forming process can be regarded as the

Fig. 6. The relationship between ln q and s2 at 303 K.
course of distribution of donor particles to the system. So it is
justifiable to extend the model of variable number of particles in
statistical physics for the inhibiting process.
According to statistical physics [37], the probability of distri-
bution for such kind of systems of variable number of particles is
given by:


im  3i
6ði; 3Þ ¼ Aexp (16)
q
where A is the normalizing coefficient, m the chemical potential
which depends upon the temperature and concentration of the
donor particles, i the number of donor particles distributed in each
system, q the distribution modulus, 3i the energy of the system
containing i donor particles, being assumed approximately equal
for the systems containing the same number i of donor particles,
and 3i ¼ 0 at i ¼ 0.
The normalizing condition is:

X
n
FeOHþ þ Hþ 4 Fe2þ þ H2O (14) 6ði; 3Þ ¼ 1 (17)
i¼o
where ‘rds’ denotes the rate determining step and Y represents
the inhibitor species. or
Considering the inhomogeneous nature of metallic surfaces (
)
X
n
im  3i
resulting from the existence of lattice defects and dislocations, A 1þ exp ¼ 1 (18)
a corroding metal surface is generally characterized by multiple i¼1
q
adsorption sites having definite activation energies and heat of
The average number of donor particles accepted by each system is:
adsorption. Inhibitor molecules may thus be adsorbed more readily

at surface sites having suitable adsorption enthalpies. According to X
n X
n
im  3i
n ¼ i6ði; 3Þ ¼ iAexp (19)
the detailed mechanism above, displacement of some adsorbed i¼1 i¼1
q
water molecules on the metal surface by inhibitor species to yield
the adsorbed intermediate FeYads (Eq. (10)), which reduces the Eliminating A from Eqs. (18) and (19), we obtain:
amount of species FeOHads available for the rate determining step Pn
and consequently retards Fe anodic dissolution. i ¼ 1 iexpððim  3i =ÞqÞ
n ¼ P (20)
Thus, the adsorption of an inhibitor species, I, on a metal surface, 1 þ ni¼ 1 expððim  3i =ÞqÞ
M, can be represented by a simplified equation:
For inhibiting process, the M (I)ads formation reaction corresponds
M þ I4MðIÞads (15) to the distribution with i ¼ 0 or 1. The condition for which i ¼ 0 is
taken to correspond to a state of complete corrosion (surface
Let M of the above reaction be the system in the ensemble and coverage h ¼ 0 and protection efficiency %I ¼ 0), i ¼ 1 to a state of
the solvent containing inhibitor molecules as donor particles be the complete inhibition (surface coverage h ¼ 1 and protection

Fig. 7. Application of the statistical model to the corrosion protection behavior of xanthone.
388 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392

Table 3 However, physisorption was the major contributor while chemi-

Some parameters from statistical model for mild steel in 0.5 M H2SO4. sorption only slightly contributed to the adsorption mechanism
Temperature (K) R2 q DGoads (kJ mol1) judging from the decrease of %I with increase in temperature and
303 0.948 1.24  10 3
31.22 the higher values of Ea obtained in the presence of inhibitor when
313 0.970 1.56  103 31.21 compared to its absence.
323 0.960 2.04  103 30.75 The enthalpy of adsorption can also be calculated from the
333 0.973 1.87  103 30.57
GibbseHelmholtz equation [43]:
 
vðDGoads =TÞ DHo
¼  2ads (23)
efficiency %I ¼ 100). The actual corrosion inhibition process is vT p T
a random distribution between i ¼ 0 and 1. So the corresponding
actual protection efficiency (%I) is a data between 0 and 100, and Eq. (23) can be arranged to give the following equation:
the actual surface coverage h is equal to the statistical average value
DGoads DHads
o
for such a (0, 1) distribution, then for inhibiting process, Eq. (20) is ¼ þk (24)
reduced to: T T
The variation of DGoads/T with 1/T gives a straight line with a slope
1 which is equal to DHoads (Fig. 8). It can be seen from the figure that
n ¼ h ¼ (21)
1 þ expðð3  mÞ=qÞ DGoads/T decreases with 1/T in a linear fashion. The obtained value of
Here 0 < n < 1. Considering h is related to the concentration of DHoads was 38.00 kJ mol1.
donor particles and 3 to the thermodynamic equilibrium constant The enthalpy and entropy for the adsorption of XAN on mild
of the complex-forming reaction, which is correlated to the change steel were also deduced from the thermodynamic basic equation
of free energy of adsorption DGoads, thus the following equation can [31]:
be derived from Eq. (21) [38]:
DGoads ¼ DHads
o
 T DSoads (25)


1h DGoads RTln C where DHoads and DSoads are the enthalpy and entropy changes of
ln ¼  (22)
h q q adsorption process, respectively. A plot of DGoads versus T was linear
(Fig. 9) with the slope equal to DSoads and intercept of DHoads. The
where C is the concentration of inhibitor particles.
enthalpy of adsorption DHoads, and the entropy of adsorption DSoads,
The curve fitting of data in Table 1 to the statistical model at
obtained are 38.56 kJ mol1 and 24.00 J mol1 K1 respectively.
303e333 K is presented in Fig. 7. Good correlation coefficient
The negative sign of DHoads indicates that the adsorption of XAN
(R2 > 0.94) was obtained. q and DGoads can be calculated from the
molecules is an exothermic process. In an exothermic process,
slope and intercept of Eq. (22). All the calculated parameters are
physisorption is distinguished from chemisorption by considering
given in Table 3. The negative values of DGoads indicate spontaneous
the absolute value of DHoads. For physisorption process, the enthalpy
adsorption of XAN onto the mild steel surface [39] and strong
of adsorption is lower than 40 kJ mol1 while that for chemisorp-
interactions between inhibitor molecules and the metal surface
tion approaches 100 kJ mol1 [43]. In the present study, the abso-
[40]. Generally, values of DGoads up to 20 kJ mol1 are consistent
lute value of enthalpy of adsorption obtained is typical of
with physisorption, while those around 40 kJ mol1 or higher are
physisorption. Values of DHoads obtained by the two methods are in
associated with chemisorption as a result of the sharing or transfer
good agreement.
of electrons from organic molecules to the metal surface to form
The entropy of adsorption obtained from Eq. (25) was negative
a coordinate bond [41]. The calculated values of DGoads are greater
because inhibitor molecule freely moving in the bulk solution
than 20 kJ mol1 but less than 40 kJ mol1, indicating that the
(inhibitor molecule were chaotic), were adsorbed in an orderly
adsorption of mechanism of XAN on mild steel in 0.5 M H2SO4
fashion onto the mild steel, resulting in a decrease in entropy [30].
solution at the studied temperatures may be a combination of both
physisorption and chemisorption (comprehensive adsorption) [42].

-30.2

-0.09
-30.4

-0.092

R² = 0.993 -30.6
-0.094 R² = 0.903
ΔG o ads (k J mol -1)
ΔGo ads / T(kJ mol -1 K -1)

-0.096 -30.8

-0.098
-31
-0.1

-31.2
-0.102

-0.104 -31.4
2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35 303 313 323 333

1000/T (K-1) Temperature (K)

Fig. 8. The relationship between DGoads/T and 1/T. Fig. 9. The relationship between DGoads and T.
 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392 389

R² = 0.973 R² = 0.924

-1
R² = 0.950 R² = 0.924

R² = 0.885 R² = 0.884
-2

-3
ln Wt

-4
10 x 10 ^-6 M
8 x 10 ^-6 M
-5
6 x 10 ^-6 M
4 x 10^-6 M
-6 2 x 10 ^-6 M
Blank

-7
2 4 6 8 10

Time (h)

Fig. 10. The plot of ln Wt against t for mild steel corrosion in 0.5 M H2SO4 with and without XAN.

Moreover, from thermodynamic principles, since the adsorption
was an exothermic process, it must be accompanied by a decrease
in entropy [44].
3.5. Kinetics of mild steel corrosion in H2SO4 with and without
xanthone
By far best result was obtained for first-order kinetics. The plot
of ln Wt against t which was linear (Fig. 10) with good correlation
coefficients (R2 > 0.9) confirms first-order kinetics for the corrosion
of mild steel in 0.5 M H2SO4 in the absence and presence of XAN.
The anodic dissolution of iron in acidic media and the corresponding
cathodic reaction has been reported to proceed as follows [27]:

The kinetics of the mild steel corrosion in the absence and
presence of different concentrations of XAN in 0.5 M H2SO4 was
studied at 30
C by fitting the corrosion data into different rate laws.
Correlation coefficients R2 were used to determine the best rate law
for the corrosion process. The rate laws considered were [45]:
Zero-order : Wt ¼ kt
First order : ln Wt ¼ kt þ ln Wo
Second order : 1=Wt ¼ kt þ 1=Wo
where Wo is the initial weight of mild steel, Wt is the weight loss of
mild steel at time t and k is the rate constant.
Fe / Fe2þ þ 2e (29)
2Hþ þ 2e / 2Hads / H2 (30)
Fig. 10 reflects the reaction order with respect to iron. This result
(26) suggests that the adsorption of XAN molecules do not influence the
anodic reaction. As seen in Fig. 10, similar plot was obtained when
(27) ln Wt was plotted against t for mild steel in 0.5 M H2SO4 without
(Blank) and with inhibitor. XAN by being adsorbed probably hinders
the adsorption of Hþ on the surface of the mild steel thereby slowing
(28)
down the cathodic reaction, i.e. the rate determining steps in strong
acids [46], and consequently slowing down the removal of Fe ions
from the reaction sites on the surface; the anodic reaction [47].

2.5

10 x 10E-6 M Fe + inhibitor
2
Absorbance

1.5

b a
0.5

0
0 100 200 300 400 500 600
wavelength (nm)

Fig. 11. UVevisible spectra of the solution containing 0.5 M H2SO4 (10  106 M) XAN (a) before (blue) and (b) after 3 days of mild steel immersion (red) (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.).
390 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392

Fig. 12. Optimized structure of xanthone (XAN) (ball and stick model).

Fig. 14. The lowest unoccupied molecular orbital (LUMO) density of xanthone (XAN)
3.6. UVevisible spectroscopy using DFT at the B3LYP/6-31G (d) basis set level.

In order to confirm the possibility of the formation of XANeFe

complex, UVevisible absorption spectra obtained from 0.5 M to describe the structural nature of the inhibitor on the corrosion
H2SO4 solution containing 10  106 M XAN before and after 3 days process [49]. Furthermore, DFT is considered a very useful tech-
of mild steel immersion are shown in Fig. 11. Abboud et al. [48] has nique to probe the inhibitor/surface interaction as well as to
reported that change in position of the absorbance maximum and analyze the experimental data. Thus in the present investigation,
change in the value of absorbance indicate the formation of quantum chemical calculation using DFT was employed to explain
a complex between two species in solution. the experimental results obtained in this study and to further give
The electronic absorption spectra of XAN before the steel immer- insight into the inhibition action of XAN on the mild steel surface.
sion display a main visible band at 380 nm. This band may be assigned Figs. 12e15 show the optimized geometry, the HOMO density
to pep* transition involving the whole electronic structure system of distribution, the LUMO density distribution and the Mulliken
the compound with a considerable charge transfer character [14].
After 3 days of steel immersion (Fig.11), it is clearly seen that the band
maximum underwent a blue shift, suggesting the interaction
between XAN and Fe2þ ions in the solution [48]. Furthermore, there is
an increase in the absorbance of this band. It is clear that there was no
significant difference in the shape of the spectra before and after the
immersion of XAN showing a possibility of weak interaction between
XAN and mild steel (physisorption). These experimental findings give
a strong evidence for the possibility of the formation of a complex
between Fe2þ cation and XAN in 0.5 M H2SO4.

3.7. Theoretical study

Recently, the density functional theory (DFT) has been used to

analyze the characteristics of the inhibitor/surface mechanism and

Fig. 13. The highest occupied molecular orbital (HOMO) density of xanthone (XAN) Fig. 15. Mulliken charges population analysis of xanthone (XAN) using DFT at the
using DFT at the B3LYP/6-31G (d) basis set level. B3LYP/6-31G (d) basis set level (a) neutral form (b) protonated form.
 I.B. Obot, N.O. Obi-Egbedi / Current Applied Physics 11 (2011) 382e392
Table 4
Some molecular properties of xanthone calculated using DFT at the B3LYP/6-31G (d)
basis set in aqueous phase both in neutral and protonated form.
Molecular parameters XAN (neutral) XAN (protonated at O2)
Heat of formation (au) 650.68 651.06
Dipole moment (D) 2.91 3.08
EHOMO (eV) 6.28 10.37
ELUMO (eV) 1.78 6.68
DE (eV) 4.50 3.69
Volume (A3) 199.98 201.97
Area (
A2) 209.09 212.47
Point group C2v C2v
Average polarizability (au) 117.18 129.48
charge population analysis plots for XAN molecule obtained with
DFT at B3LYP/6-31G (d) level of theory.
From Figs. 13 and 14, it could be seen that XAN have similar
HOMO and LUMO distributions, which were all located on the
entire xanthone moiety. This is due to the presence of oxygen atoms
together with several p-electrons on the entire molecule. Thus, the
unoccupied d orbitals of Fe atom can accept electrons from inhib-
itor molecule to form coordinate bond. Also the inhibitor molecule
can accept electrons from Fe atom with its anti-bonding orbitals to
form back-donating bond.
The use of Mulliken population analysis to estimate the adsorption
centers of inhibitors has been widely reported and it is mostly used for
the calculation of the charge distribution over the whole skeleton of
the molecule [50e52]. There is a general consensus by several authors
that the more negatively charged heteroatom is, the more is its ability
to adsorb on the metal surface through a donoreacceptor type reac-
tion [4,16e18,20]. The Mulliken charge distributions of XAN in the
neutral and protonated forms are shown in Fig. 15(a) and (b)
respectively. The figures shows that the two oxygen atoms have high
charge densities implying that the most probable reactive site for the
adsorption of iron is located on the oxygen atoms.
The calculated molecular properties for XAN are presented in
Table 4. Higher values of EHOMO are likely to indicate a tendency of the
molecule to donate electrons to appropriate acceptor molecules with
low energy or empty electron orbital. It is evident from Table 4 that
XAN has the highest EHOMO in the neutral form and a lower EHOMO in
the protonated form. This means that the electron donating ability of
XAN is weaker in the protonated form. This confirms the experi-
mental results that interaction between XAN and mild steel is elec-
trostatic in nature (physisorption). The negative coefficient of EHOMO
also confirms the physisorption mechanism [20]. This theoretical
result is in agreement with the values of Ea, DHoads and DGoads obtained
experimentally. The energy of the LUMO is directly related to the
electron affinity and characterizes the susceptibility of the molecule
towards attack by neuclophiles. The lower the values of ELUMO are, the
stronger the electron accepting abilities of molecules. It is clear from
Table 4 that the protonated form of XAN exhibits the lowest EHOMO,
making the protonated form the most likely form for the interaction
of mild steel with xanthone molecule. Low values of the energy gap
(DE) will provide good inhibition efficiencies, because the excitation
energy to remove an electron from the last occupied orbital will be
low [52]. A molecule with a low energy gap is more polarizable and is
generally associated with a high chemical reactivity. The calculation
in Table 4 shows that XAN in the protonated form has the smallest
energy gap value indicating that it is in this form that xanthone can
easily adsorb on the metal surface causing higher protection. Similar
report has been documented [53]. According to literature, there is
a lack of agreement on the correlation between dipole moment and
inhibition mechanism [52,53]. However, the dipole moment of XAN
is higher in the protonated form than in the neutral form. The high
value of dipole moment probably increases the adsorption between
chemical compound and metal surface [30].
391
Inhibitive effect of organic inhibitors increases as the molecular
area and area of the molecules increases due to the increase of the
contact area between molecules and surface [53]. It is seen from
Table 4 that XAN in the protonated form has a higher molecular
area and volume than in the neutral form, which is also propor-
tional to the average polarizability value leading to increase in both
its adsorptive properties on the metal surface and inhibition
efficiency.
4. Conclusions
The following conclusions may be drawn from the study:
1. Xanthone (XAN) acts as an excellent inhibitor for the corrosion
of mild steel in 0.5 M H2SO4. Inhibition efficiency values
increase with the inhibitor concentration but decrease with
rise in temperature suggesting physical adsorption mechanism.
2. The adsorption of XAN on steel surface was found to accord
with DubinineRadushkevich adsorption isotherm model. The
adsorption process is spontaneous, exothermic and accompa-
nied with a decrease in entropy of the system from thermo-
dynamic point of view.
3. A first-order kinetics relationship with respect to the mild steel
was obtained with and without XAN from the kinetic treatment
of the data.
4. UVevisible spectrophotometric studies clearly reveal the
formation of FeeXAN complex which may be responsible for
the observed inhibition.
5. Data obtained from quantum chemical calculations using DFT
at the B3LYP/6-31G (d) level of theory were correlated to the
inhibitive effect of xanthone. Both experimental and theoret-
ical calculations are in excellent agreement.
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