Understanding Corrosion Inhibition of Mild Steel in Acid Medium by Some Furan Derivatives: A Comprehensive

Journal of The Electrochemical Society, 157 3 C116-C124 2010
C116
0013-4651/2010/1573/C116/9/$28.00 The Electrochemical Society
Understanding Corrosion Inhibition of Mild Steel in Acid

Medium by Some Furan Derivatives: A Comprehensive
Overview
K. F. Khaledz
Electrochemistry Research Laboratory, Chemistry Department, Faculty of Education, Ain Shams
University, Roxy, Cairo 11566, Egypt and Materials and Corrosion Laboratory, Chemistry Department,
Faculty of Science, Taif University, Taif, Al-Haweiah, 888, Kingdom of Saudi Arabia
The inhibition performance of some furan derivatives, namely, methyl 2-furoate, ethyl 2-furoate, and amyl 2-furoate on mild steel
in normal hydrochloric acid medium 1 M HCl at 25C, was studied by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy EIS, and electrochemical frequency modulation measurements EFM. Furan derivatives inhibit the
acidic corrosion even at very low concentrations, reaching a value of inhibition efficiency up to 93% at a concentration of 20 mM.
The results obtained from the different corrosion evaluation techniques are in good agreement. Polarization curves indicate that the
studied furan derivatives are mixed-type inhibitors. Data obtained from EIS measurements were analyzed to model the corrosion
inhibition process through an appropriate equivalent circuit model. A constant phase element has been used. The adsorption of
furan derivatives on the steel surface in 1 M HCl solution was found to obey Langmuirs adsorption isotherm with a negative
. Molecular dynamics simulations were carried out to establish the inhibition

value of the free energy of adsorption Gads
mechanism.
2010 The Electrochemical Society. DOI: 10.1149/1.3274915 All rights reserved.
Manuscript submitted July 24, 2009; revised manuscript received October 26, 2009. Published January 12, 2010.
Corrosion inhibition of mild steel is a matter of theoretical as

well as practical importance.1 Acids are widely used in industries
such as pickling, cleaning, descaling, etc. Because of their aggressiveness, inhibitors are used to reduce the rate of dissolution of
metals. Compounds containing nitrogen, sulfur, and oxygen have
been reported as inhibitors.2-4 The most efficient organic inhibitors
are organic compounds having -bonds in their structures. The efficiency of an organic compound to act as an inhibitor is mainly
dependent on its ability to get adsorbed on the metal surface which
requires replacement of water molecule at a corroding interface as
Orgsol + nH2Oads Orgads + nH2Osol
An experimental inquiry into the kinetics of mild steel dissolution

and corrosion inhibition has been carried out with a view to clarify
certain debatable aspects about the mechanism of corrosion inhibition. Previous work in our laboratory has led us to a chemisorption
step as a possible mechanism of inhibition which accounts for the
persistence, specificity, and structural effects of the inhibitors.5,6 It
has been shown that systematic and orderly changes in the molecular structure of the organic compounds can be correlated to inhibition efficiency IE.7-9 This correlation is based on certain physicochemical properties of the inhibitor molecule such as functional
groups, steric factors, aromaticity, electron density at the donor atoms, and orbital character of the donating electrons.10-12
Because adsorption is the key to the explanation of inhibition
mechanism by organic molecules, the primary phenomenon of adsorption is as important as the subsequent phenomenon of inhibition.
The relationship between adsorption and inhibition has been inadequately explained in the literature.13-15 One reason for this is the
meagerness of available experimental techniques for in situ measurement of adsorption at electrodes. Evaluation of adsorption from
corrosion current measurements is indirect and with so many assumptions as to make the conclusions questionable. Donahue et al.
proposed adsorption involving surface complex formation between
the inhibitor and one of the intermediates in the anodic dissolution
of mild steel.16
Although heterocyclic compounds have been evaluated and used
extensively as corrosion inhibitors of mild steel, furan and its derivatives have not been given sufficient attention for such applications. Vaidyanathan and Hackerman14 tested such furan derivatives
as furfurylamine, furoic acid tetrahydrofurfurylamine, and tetrahy-
E-mail: khaledrice2003@yahoo.com
drofurfuryl alcohol for their inhibitive action on anodic dissolution,

cathodic partial processes, and corrosion currents. They found that
inhibitive efficiency of these compounds could be explained on the
basis of structure-dependent electron donor properties. Mitra17
tested furan, furfuryl amine, and furfuryl alcohol and correlated their
IEs with some quantum chemical values, namely, the energy of the
highest occupied molecular orbital and the lowest free molecular
orbital.
This study aims to use some furan derivatives as possible corrosion inhibitors for mild steel in 1 M HCl solutions. Measurements
were conducted using several corrosion monitoring techniques, such
as weight loss, potentiodynamic polarization, and electrochemical
impedance spectroscopy EIS. Electrochemical frequency modulation EFM, which is a recent nondestructive corrosion measurement
technique that can directly give values of corrosion current without
prior knowledge of Tafel constants, is also presented here with the
aim to make an accurate determination of the corrosion rate. It is
also the purpose of this paper to elucidate the adsorption behavior of
some furan derivatives at the mild steel surface using molecular
dynamics simulations.
The present work also involves an extensive investigation of
many furan derivatives, which have been chosen to evaluate the
effects of systematic changes in the molecular structure and the
polar function of the compound. This is achieved by changing the
substituent with respect to the oxygen polar function. Also, an attempt is made to discuss the inhibitive action of the tested compounds according to the interface and interphase modes of inhibition.
Experimental
The structures of the furan compounds studied are presented below
All the investigated compounds were obtained from Aldrich Chemical Co.; they were put in 1.0 M HCl Fisher Scientific without
pretreatment at concentrations of 5, 10, 15, and 20 mM.
All electrochemical measurements were performed in a typical
three-compartment glass cell that consisted of the mild steel rod
C = 0.14 wt %, S = 0.05 wt %, Si = 0.01 wt %, Mn = 0.9 wt %,
Downloaded 18 Mar 2010 to 202.170.57.251. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp
30 min
60 min
120 min
240 min
60
-Z"/ cm2
and Fe = balance, its surface area was 0.28 cm2 as a working electrode WE prepared using emery papers of different grit sizes up to
4/0 grit, polished with Al2O3 0.5 m particle size, the platinum
mesh as a counter electrode, and a saturated calomel electrode
SCE as the reference electrode. Solutions were prepared from bidistilled water. The electrode potential was allowed to stabilize for
60 min before starting the measurements. All experiments were conducted at 25C. The electrolyte solution was made from analytical
reagent grade HCl.
The electrodes were arranged in such a way that a onedimensional potential field existed over the WE surface in solution.
To get an impression about the process that occurred at the iron/acid
interface, Tafel curves were obtained by changing the electrode potential automatically from 250 to + 250 mVSCE vs open-circuit
potential with a scan rate of 1 mV/s. Also, EIS measurements were
carried out in a frequency range of 10040 mHz with an amplitude
of 10 mV peak to peak using ac signals at open-circuit potential.
EFM was carried out using frequencies of 2 and 5 Hz. The base
frequency was 1 Hz, so the waveform repeats after 1 s. The higher
frequency must be at least two times the lower one. The higher
frequency must also be sufficiently slow that the charging of the
double layer does not contribute to the current response. Often,
10 Hz is a reasonable limit. In this study, we use a perturbation
signal with an amplitude of 10 mV for both perturbation frequencies
of 2 and 5 Hz. The choice for the frequencies of 2 and 5 Hz was
based on three arguments.18 First, the harmonics and intermodulation frequencies should not influence each other. Second, the frequency should be as low as possible to avoid influence of the capacitive behavior of the electrochemical double layer. Third, the
frequency should be as large as possible to reduce time needed to
perform a measurement. While these arguments do not allow the
selection of perfect frequencies, the chosen frequencies were considered as reasonable compromise.
Measurements were performed with a Gamry potentiostat/
galvanostat/ZRA. This includes a Gamry framework system based
on the ESA400, Gamry applications that include DC105 for dc corrosion measurements, EIS300 for EIS measurements, and EFM140
to calculate the corrosion current and the Tafel constants along with
a computer for collecting the data. Echem Analyst 4.0 software was
used for plotting, graphing, and fitting data.
Gravimetric experiments were carried out in a double glass cell
equipped with a thermostated cooling condenser. The solution volume was 100 mL. The iron specimens used have a rectangular form
length = 2 cm, width = 1 cm, and thickness = 0.06 cm with an
exposed surface area of 4.36 cm2. The duration of tests was 6 h at
25 1C. Duplicate experiments were performed in each case, and
the two values obtained are very similar so the mean value of the
weight loss is reported. The weight loss allowed the calculation of
the mean corrosion rate in g cm2 h1.
C117
40
20
10
20
30
40
50
60
Z'/ cm
Figure 1. Impedance spectra recorded at different times of immersion of the

mild steel WE in 1 M HCl.
60 min exposure. Rp is determined from the real part of the complex

plane impedance diagram Nyquist plot because it is defined by
2
Rp = lim Zre
0
where Zre is the real part of the Nyquist plots, is the frequency in
radians, and Zre is the real part of faradaic impedance.22 Therefore,
at tending to 0, the imaginary part of the impedance Zimg 0,
while the real one Zre Rp + Rs, where Rs is the ohmic resistance
of the solution and the electrical leads. The fitted results derived
using the corresponding equivalent circuit, which is described later,
are presented in Table I.
Inspection of Fig. 1 and 2 shows that the initial dissolution of the
WE depends to a great extent on the electrodes preliminary treatment. At the beginning of the experiment, the dissolution process is
the greatest on the sharp edges of the WE, then the corrosion rate
decreases with time due to the formation of the corrosion products
and the depletion of the sharp edges that were found in the beginning. When all of these processes have taken place, the dissolution
rate is predominantly determined by the metals nature and the experimental conditions.23 Then the preliminary treatments effect
should not essentially affect the process any longer. The polarization
resistance decreases as the time of immersion increases after 1 h
Fig. 2. The corrosion products, which result from the dissolution of
70
Computational Details
60
Rp / cm2
The Discover molecular dynamics module in Materials Studio

4.3 software from Accelrys Inc.19 allows selecting a thermodynamic
ensemble and the associated parameters, defining simulation time
and temperature and pressuring and initiating a dynamics calculation. The molecular dynamics simulation procedures have been described in detail elsewhere.20,21
30 min.
60 min.
120 min.
240 min.
50
40
Results and Discussion

EIS measurements. Effect of exposure time in 1 M HCl solution. The effect of the exposure time of a mild steel WE in 1 M
HCl on the EIS spectra was studied. The results obtained provided
the determination of the WE exposure time. EIS was recorded after
exposures of 30, 60, 120, and 240 min. The results are presented in
Fig. 1. It is seen that the diameter of the impedance semicircle
depends on the duration of the WE exposure in the acid solution.
Figure 2 illustrates the variation in the polarization resistance Rp
with the exposure time t. It passes through a maximum at about
30
20
50
100
150
200
250
300
Time / min.
Figure 2. Dependence of polarization resistance Rp on the immersion time in

1 M HCl.
C118
300
Table I. Fitted parameters for iron in 1 M HCl after different

immersion times at 25C derived using equivalent circuit in Fig.
5a.
Immersion
time
min
250
Blank
5 mM ETF
10 mM ETF
15 mM ETF
20 mM ETF
30
60
120
240
Rs
cm2
CPE/Y 0
F cm2
25
60
30
22
0.40
0.35
0.39
0.52
600
580
630
700
0.82
0.84
0.85
0.81
-Z"/ cm2
200
Rp
cm2
150
100
50
0
mild steel in HCl, start to form on the electrode surface as soon as

the electrode immersed in the corrosive media. Their amount is insignificant, and besides, they have no protective properties. However, they could affect to a certain extent the impedance investigations at longer exposure time of the WE. Thus it was found
experimentally that 1 h exposure under the conditions stated above
was the compromise duration in view of minimization of the effect
of the electrodes preliminary treatment and of the corrosion products.
Effect of concentrations of furan derivatives. The effect of the
concentration of the studied furan derivatives was studied from
5 to 20 mM in 1 M HCl solutions at 25C 1. Organic compounds are known to yield unreliable and irreproducible results for
concentrations higher than 20 mM.24,25 For the same reasons, the
present work tests the compounds only up to a concentration of
20 mM, employing concentration intervals of 5 mM. Several factors
determine the appropriate inhibitor concentration in corrosion inhibition studies. Solubility of the inhibitor in the corrosive medium is
one of the key factors in determining the optimum concentrations.
No significant increase in the IE is obtained for the studied inhibitors above 20 mM. In the presence of methyl 2-furoate MEF and
ethyl 2-furoate ETF in the whole concentration range, the electro300
Blank
5 mM MEF
10 mM MEF
15 mM MEF
20 mM MEF
250
-Z"/ cm2
200
150
50
100
150
50
0
0
50
100
150
200
250
300
Z'/ cm2
Figure 3. Measured and simulated complex plane impedance plots of mild

steel corrosion in 1 M HCl solutions at Ecorr in the absence and presence of
MEF at 25C.
250
300
350

ETF at 25C.
chemical impedance spectra in Nyquist plots are characterized by

one semicircle, which its center lies under the real axis Fig. 3 and
4. The quantitative analysis of the electrochemical impedance spectra was studied based on a physical model of the corrosion process
with hydrogen depolarization and with charge-transfer controlling
step. The simplest model includes the polarization resistance Rp in
parallel to the constant phase element CPE connected with the
solution resistance Rs. The solid electrode is inhomogeneous both on
a microscopic and a macroscopic scale, and corrosion is a uniform
process with fluctuating active and inactive domains where anodic
and cathodic reactions take place at the corroding surface. The size
and distribution of these domains depend on the degree of surface
inhomogeneities.
Inhomogeneities may also arise from adsorption phenomena and
formation of porous and nonporous layers by passivation on
coating.26-28 For this reason the frequency distributed CPE was used
instead of the capacitance of the double layer Cdl at the mild steel/
solution interface. More generally, the CPE behavior could be
treated as a space fractality, i.e., as manifestation of a selfsimilarity in the frequency domain.29 The CPE impedance is given
by26,27,30,31
ZCPE =
100
200
Z'/ cm2
1
inA
where A is a proportionality coefficient and n has the meaning of the

phase shift, which value can be considered as a measure of the
surface inhomogeneity.26,30,32,33 The transfer function is thus represented by an equivalent circuit, having only one time constant Fig.
5a. Parallel to the double layer capacitance modeled by a CPE is
the polarization resistance Rp, Rs being the electrolyte resistance.
The fitted parameter values are presented in Tables II and III, while
the calculated curves, using this parameter set, are presented in Fig.
3 and 4 as solid lines.
Figure 5. Color online Equivalent circuits used to model impedance data in

1 M HCl solutions.
C119
Table II. Fitted parameters for iron in 1 M HCl in the absence and presence of various concentrations of MEF at 25C derived using equivalent
circuit in Fig. 5a.
MEF
Conc
Rp
cm2
Rs
cm2
CPE/Y 0
F cm2
IEi
%
Blank
60
0.35
580
0.84
5 mM
10 mM
15 mM
20 mM
93
114
157
261
0.6
0.65
0.63
0.7
30
28
27
22
0.76
0.78
0.81
0.83
35.48
47.36
61.78
77.01
In amyl 2-furoate AMF, an additional time constant becomes

visible, very well expressed in the Nyquist presentation Fig. 6. In
this case, it is possible to separate the processes of the double layer
charging and of the adsorption pseudocapacitance. It is clear that for
AMF, the structural model of Fig. 5a is inadequate and a two-timeconstant model Fig. 5b is used to describe the electrochemical
impedance spectra. The fitted parameters are presented in Table IV
and the calculated curves are presented in Fig. 6 as solid lines. This
model is valid for all concentrations of AMF. It can be seen that the
values of Rp are highly increased when the description is changed
from the one-constant model to the two-constant one. The values of
polarization resistance in AMF are composed of two components:
the charge-transfer resistance and the inhibitor film resistance Rf.
ing that the addition of furan derivatives reduces the anodic dissolution and also retards the cathodic hydrogen evolution reaction.
From Tafel curves in Fig. 7-9, it is clear that both anodic metal
dissolution and cathodic reduction reactions were inhibited when the
furan derivatives were added to the acid solution and this inhibition
was more pronounced with increasing inhibitor concentration. The
cathodic polarization curves give rise to parallel Tafel lines with the
nearly constant cathodic Tafel slopes c, indicating that the addition of inhibitor to the aggressive solution does not modify the proton reduction mechanism and this reaction is activation controlled.36
The inhibitor is first adsorbed onto iron surface and then impedes by
merely blocking the active sites of iron surface. In this way, the
surface area available for H+ ions is decreased, while the actual
reaction mechanism remains unaffected.36
Tafel polarization measurements. Polarization measurements

have been carried out to gain knowledge concerning the kinetics of
the anodic and cathodic reactions. Polarization curves of the mild
steel in 1 M HCl solutions without and with addition of different
concentrations of furan derivatives are shown in Figs. 7-9. The anodic and cathodic current-potential curves are extrapolated up to
their intersection at a point where corrosion current density jcorr
and corrosion potential Ecorr are obtained.34 The values of associated electrochemical parameters, i.e., corrosion potential Ecorr, corrosion current density jcorr, cathodic Tafel slopes c, anodic
Tafel solpes a, and percentage IE IEp % values, were calculated from polarization curves and listed in Table V. The IE IEp
% was calculated from corrosion current density measurements
according to the relation given below
IEp % =
0
jcorr
jcorr
0
jcorr
100
EFM. Figure 10 shows a plot of current density

jfrequency f that was obtained by fast Fourier transform from
the experimental current jtime t data determined with EFM on
iron after 1 h immersion in 1 M HCl solutions. The data in Fig. 10
were analyzed assuming that the cathodic reaction was under activation control. The EFM data were calculated for the studied system
and presented in Table VI. The electrochemical parameters presented in Table VI include corrosion current density jcorr, Tafel
slopes a,c, and causality factors CF-2 and CF-3, which act as
an internal check for the validity of EFM data. Inspections of these
data conclude that the values of causality factors obtained under
different experimental conditions are approximately equal to the theoretical values of 2 and 3, indicating that the measured data are of
high quality.37-40
As can be seen from Table VI, the corrosion current densities
decrease by increasing the concentrations of furan derivatives.
The IEs EEFM % calculated from Eq. 5 increase by increasing
furan derivative concentrations
0
and jcorr are uninhibited and inhibited corrosion current
where jcorr
densities, respectively. They are determined by extrapolation of
Tafel lines to the respective corrosion potentials. It is shown from
Figs. 7-9 that increasing the furan derivative concentrations reduces
both the cathodic and the anodic currents, and there is no definite
trend in the shift of Ecorr values. These results indicate that all furan
derivatives act as mixed-type inhibitors.35
Based on the marked decrease in the cathodic and anodic current
densities upon introducing the inhibitor in the aggressive solution,
furan derivatives can be considered as a mixed-type inhibitor, mean-
IEEFM % =
0
jcorr
jcorr
0
jcorr
100
0
where jcorr
and jcorr are the corrosion current densities in the absence
and presence of furan derivatives, respectively. As can be seen from
Table VI, as the inhibitor concentration increases, the inhibition increases up to 86% with the addition of 20 mM from AFM inhibitor.
Table III. Fitted parameters for iron in 1.0 M HCl in the absence and presence of various concentrations of ETF at 25C derived using
equivalent circuit in Fig. 5a.
ETF
Conc
Rp
cm2
Rs
cm2
CPE/Y 0
F cm2
IEi
%
Blank
60
0.35
580
0.84
5 mM
10 mM
15 mM
20 mM
106
134
194
286
1.2
1.5
2.3
1.9
10
8
6
2
0.83
0.81
0.79
0.80
43.39
55.22
69.07
79.02
C120
-0.3
600
Blank
5 mM AMF
10 mM AMF
15 mM AMF
20 mM AMF
-Z"/ cm2
400
300
Blank
5 mM MEF
10 mM MEF
15 mM MEF
20 mM MEF
-0.4
E / VSCE
500
200
-0.5
-0.6
100
0
-0.7
100
200
300
400
Z'/ cm
500
600
700
1e-7
1e-5
1e-4
1e-3
1e-2
1e-1
j / A cm-2

AMF at 25C.
Weight loss measurements. Table VII shows the values of IE

and corrosion rate Wcorr obtained from weight loss measurements
at different concentrations of furan derivatives at 25C. From the
weight loss values, the IEw % of each concentration were calculated using the following equations41
1e-6
w0 w
IEw % =
100
w0
where w0 and w are the corrosion rates in the absence and presence
of inhibitors, respectively. It has been found that IE of all of these
compounds increases by increasing their concentrations. The maximum IE for each compound was achieved at 20 mM and a further
increase in concentration did not cause any appreciable change in
the performance of the inhibitors data not included.
In Fig. 11 comparison figures, the corrosion rates obtained with
four different techniques including potentiodynamic polarization
curve, EIS, EFM, and weight loss are compared. In general, the
corrosion rates determined with the EFM technique are much higher
than the values determined with other techniques, exhibiting low
corrosion rates.42 The results from EFM, EIS, and polarization curve
are integral averages of the data in the experimental period of 1 h.
As electrochemical techniques, the EFM technique gives a higher
corrosion rate than analysis of the potentiodynamic polarization
curve, EIS, and weight loss measurements because the entire frequency range of the EFM measurement cannot be low enough to be
in the dc limit region of the impedance spectrum. The corrosion
rates obtained with the electrochemical techniques are both lower
than that with weight loss method. The results obtained with the four
techniques are at the same order of magnitude and show the same
trend, which is acceptable. The corrosion rates determined with the
EFM technique for the mild steel/HCl system are reasonable and
Figure 7. Anodic and cathodic Tafel polarization curves for mild steel in the
absence and presence of various concentrations of MEF in 1 M HCl at 25C.
significant. Meanwhile, the EFM technique proves that it can be

implemented to measure corrosion rates in a simple, inexpensive
way.
Adsorption isotherm. The corrosion inhibition process is based
on the adsorption of the furan derivative molecules on the metal
surface. It is essential to know the mode of adsorption and the adsorption isotherm that fits the experimental results.
The most frequently used adsorption isotherms are Langmuir,
Temkin, and Frumkin with the general formula
7
f,xexp 2a = KC
where is the surface coverage, x is the number of water molecules

replaced by one inhibitor molecule, a is the lateral interaction between adsorbed molecules, K is the adsorption equilibrium constant,
and C is the inhibitor concentration.
Plots of the data for each isotherm showed that all of the investigated compounds agreed with the Langmuir isotherm Fig. 12 that
is given by43
C 1
=
+C
K
To calculate the surface coverage , it was assumed that the IE is

due mainly to the blocking effect of the adsorbed species and hence
IE % = 100.44
In this work, the surface coverage was calculated from the
relation IEEFM % = 100 using the IE calculated from the EFM
technique.
The value of K is related to the standard free energy of adsorption Gads by the following equation45
Table IV. Fitted parameters for iron in 1 M HCl in the absence and presence of various concentrations of AMF at 25C derived using equivalent
circuit in Fig. 5b.
Rp
cm2
AMF
5 mM
10 mM
15 mM
20 mM
Rct
cm2
Rf
cm2
Cf
F cm2
Rs
cm2
CPE/Y 0
F cm2
IEi
%
138
175
371
520
17
33
45
93
900 106
1.2 103
1.5 103
1.7 103
2.1
2.3
2.5
3.5
30
20
15
10
0.81
0.83
0.79
0.82
61.29
71.15
85.57
90.21

-0.3
Blank
5 mM ETF
10 mM ETF
15 mM ETF
20 mM ETF
E / VSCE
-0.4
-0.5
-0.6
-0.7
1e-7
1e-6
1e-5
1e-4
1e-3
1e-2
1e-1
j / A cm-2
absence and presence of various concentrations of ETF in 1 M HCl at 25C.
Gads
= RT ln55.5Kads
where R is the gas constant and T is the absolute temperature. The

value of 55.5 is the molar concentration of water in solution expressed in mol l1.
-0.3
Blank
5 mM AMF
10 mM AMF
15 mM AMF
20 mM AMF
E / VSCE
-0.4
-0.6
-0.7
1e-8
1e-7
1e-6
The values of adsorption constant, slope, and linear correlation

coefficient R2 can be obtained from the regressions between C/
and C, and the results are listed in Table VIII. The result shows that
all the linear correlation coefficients and all the slopes are close to 1
and confirm that the adsorption of furan derivatives in 1 M HCl
follows the Langmuir adsorption isotherm. The thermodynamic parameters for adsorption process obtained from Langmuir adsorption
isotherms for the studied furan derivatives are given in Table VIII.
The negative values of Gads 21.1, 21.6, and 23.2 for MEF,
ETF, and AMF, respectively and the higher values of K reveal the
spontaneity of the adsorption process and they are characteristic of
strong interaction and stability of the adsorbed layer with the steel
surface. The absolute value of the standard free energy of adsorption
Gads of the investigated furan derivatives follows the order
AMF ETF MEF.
Generally, the energy values of 20 kJ mol1 or less negative are
associated with an electrostatic interaction between charged molecules and charged metal surface physisorption; those of
40 kJ mol1 or more negative involve charge sharing or transfer
from the inhibitor molecules to the metal surface to form a coordinate covalent bond chemisorption.46 The calculated Gads value,
being closer to 20 kJ mol1, between the threshold values for
physical adsorption and chemical adsorption indicates that adsorption of furan derivatives on the steel surface involves the two types
of interaction.47
There are many limitations on the application of Langmuir adsorption isotherm for the analysis of inhibition phenomena and related data. Some of these limitations are discussed below.
Simple adsorption is applicable only under the following conditions.
1. The surface of the metal is homogeneous.
2. The adsorbate is specifically adsorbed, and each adsorbed
species occupies only a single site of the surface.
3. There is no surface diffusion of the adsorbed compound.
4. The standard free energy of adsorption is independent of the
degree of coverage.
-0.5
1e-9
C121
1e-5
1e-4
1e-3
1e-2
1e-1
j / A cm-2
absence and presence of various concentrations of AMF in 1 M HCl at 25C.
The Langmuir adsorption isotherm is somewhat idealized notwithstanding the fact that the adsorption may be highly selective
with electrode reaction and may be potential-dependent, and the
adsorbates may be competitive with water molecules. Adsorption
isotherms are nonetheless useful if the uninhibited corrosion current
is, in fact, proportional to the total number of sites that can possibly
Table V. Electrochemical parameters calculated from polarization measurements on the mild steel electrode in 1 M HCl solutions without and
with various concentrations of the three furan derivatives at 25C.
Inhib.
M
a
mV dec1
c
mV dec1
Blank
83.1
158.5
MEF
5 mM
10 mM
15 mM
20 mM
101.6
101.5
99.9
109.8
ETF
5 mM
10 mM
15 mM
20 mM
AMF
5 mM
10 mM
15 mM
20 mM
Inhibitor
jcorr
A cm2
Ecorr
mVSCE
IEp
%
768
498
147.3
217
180.1
165.5
539
437
315
207.0
533
506
535
549
29.82
43.09
58.98
73.04
105.3
108.4
99.5
103.4
150.7
154.3
139.5
150.2
499
393
301.0
194
531
541
545
544
35.03
48.83
60.81
74.74
92.4
100.6
97.2
79.5
134.5
159.9
133.1
122.1
370.0
270.0
185.0
108
541
544
552
538
51.82
64.84
75.91
85.94
C122
Figure 10. Color online Intermodulation spectrum for mild steel in 1 M HCl in the absence and presence of various concentrations of furan derivatives at
25C.
adsorb inhibition. This, however, is not necessarily so, as it is known

that a substantial corrosion rate is often observed at the saturation
coverage of the inhibitor.
In this paper, such discussions cannot be supported with detailed
experimental data, which would be beyond the scope of this work.
Such analysis would involve a detailed study employing transient
experiments, in addition to the present dc and ac study. Moreover, it
could require some spectroscopic measurements, X-ray analysis, or
a combination of these techniques. Thus, it should be stressed at this
stage that the following discussion is mainly qualitative and, to a
significant degree, speculative.
The tested furan derivatives showed a good capacity to inhibit
the corrosion of mild steel for the tested range of the concentration.
They inhibited the corrosion reactions of the substrate active sites by
covering them with one or more of the interface adsorbing modes
mentioned previously to form a protective layer of these molecules.
The coverage of inhibitor particles may come out by adsorption
chemisorption, with electron donating or sharing of the polar function of the inhibitors, rather than van der Waals forces physisorption, which are known to be reversible and do not yield an effective
interface inhibition.
It is believed that even if a complexation takes place between
these compounds and the corrosion products or intermediates, it will
be with weak formation forces and hardly affecting bonding forces,

holding the surface atoms in the metal lattice and thus, the possibility of catalyzed reactions is very limited.
Understanding the adsorption phenomena is of key importance in
corrosion problems. Monte Carlo simulations help in finding the
most stable adsorption sites on metal surfaces through finding the
low energy adsorption sites on both periodic and nonperiodic substrates or to investigate the preferential adsorption of mixtures of
adsorbate components.
Adsorption energy as well as several outputs and descriptors calculated by the Monte Carlo simulation are presented in Table IX.
The parameters presented in Table IX include total energy, in
kJ mol1, of the substrateadsorbate configuration. The total energy
is defined as the sum of the energies of the adsorbate components,
the rigid adsorption energy, and the deformation energy. In this
study, the substrate energy iron surface is taken as zero. In addition, the adsorption energy, in kJ mol1, reports the energy released
or required when the relaxed adsorbate components furan derivatives are adsorbed on the substrate. The adsorption energy is defined as the sum of the rigid adsorption energy and the deformation
energy for the adsorbate components. The rigid adsorption energy
reports the energy, in kJ mol1, released or required when the un-
C123
Table VI. Electrochemical parameters calculated from EFM measurements on mild steel electrode in 1 M HCl solutions without and with
various concentrations of the three furan derivatives at 25C.
Concentration
M
jcorr
A cm2
a
mV dec1
c
mV dec1
CF-2
mV dec1
CF-3
mV dec1
IEEFM
%
Blank
734.89
83
126
1.99
2.89
MEF
5 mM
10 mM
15 mM
20 mM
488.11
394.89
303.87
231.94
91
93
109
101
131
127
136
141
1.89
1.99
2.01
1.97
2.96
2.89
2.96
3.01
33.58
46.26
58.65
68.44
ETF
5 mM
10 mM
15 mM
20 mM
447.00
350.11
266.44
190.76
110
115
111
112
151
139
153
148
1.96
2.02
1.98
1.89
2.99
2.96
2.89
2.88
39.17
52.36
63.74
74.04
AMF
5 mM
10 mM
15 mM
20 mM
331.76
235.61
170.28
99.82
90
93
98
101
133
142
146
152
1.76
1.85
1.98
1.89
2.95
2.94
2.29
3.00
54.85
67.94
76.83
86.42
Concentration
M
Corrosion rate
mg cm2 h1
IEw
%
Blank
4.95
MEF
5 mM
10 mM
15 mM
20 mM
2.98
2.517
1.81
0.93
39.79
49.15
63.43
81.21
ETF
5 mM
10 mM
15 mM
20 mM
2.70
2.00
1.22
0.76
45.45
59.59
75.35
84.64
5 mM
10 mM
15 mM
20 mM
1.33
1.03
0.58
0.33
73.13
79.19
88.28
93.33
Inhibitor
AMF
80
Inhibition Efficiency / %
Table VII. Corrosion rate (in g cm2 h1) and IE values obtained
from weight loss measurements for mild steel in 1 M HCl solutions without and with various concentrations of furan derivatives at 25C.
100
EFM
EIS
Polarization
Weight loss
60
40
20
MEF
ETF
AMF
Furan Derivatives
Figure 11. Comparison of IE obtained in the presence of 20 mM of the furan

derivatives by using EFM, EIS, Tafel polarization, and weight loss measurements at 25C.
0.035
0.030
MEF
ETF
AMF
0.025
C/ (M)
relaxed adsorbate components i.e., before the geometry optimization step are adsorbed on the substrate. The deformation energy
reports the energy, in kJ mol1, released when the adsorbed adsorbate components are relaxed on the substrate surface. Table I also
shows dEads /dNi, which reports the energy, in kJ mol1, of
substrateadsorbate configurations where one of the adsorbate components has been removed.
As can be seen from Table IX, AMF gives the maximum adsorption energy in a negative value found during the simulation process.
0.020
0.015
Table VIII. Thermodynamic parameters for the adsorption of

furan derivatives in 1 M HCl on the mild steel at 25C.
Inhibitor
Slope
K
M1
R2
Gads
kJ mol1
MEF
ETF
AMF
0.939
0.943
0.937
90.19
113.53
203.92
0.979
0.989
0.999
21.1
21.6
23.2
0.010
0.005
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
0.022
C (M)
Figure 12. Langmuir adsorption plots for mild steel in 1 M HCl in various
concentrations of furan derivatives at 25C.
C124
Table IX. Outputs and descriptors calculated by the Monte Carlo simulation for adsorption of furan derivatives on iron (100).
Inhibitor
MEF
ETF
AMF
Total energy
kJ mol1
Adsorption energy
kJ mol1
Rigid
adsorption
energy
kJ mol1
176.3
192.51
210.32
26.32
28.63
32.15
25.12
27.83
31.52
High values of adsorption energy obtained in AMF molecules explain its highest IE. From the molecular structure of iron, it is evident that the unoccupied d-orbital exhibits a tendency to obtain the
electron. The furan derivative, which is discussed in the present
work, has many lone-pair electrons containing atoms on oxygen
atoms, making it possible to provide electrons to the unoccupied
orbitals of iron, to form a stable coordination type of bond. Therefore, the studied molecules are likely to adsorb on the iron surface to
form stable adlayers and protect iron from corrosion.
Conclusions
The IEs of the three inhibitors obtained from weight loss, potentiodynamic polarization, and impedance methods well agree with
those obtained from the EFM technique.
Potentiodynamic polarization studies have shown that furan derivatives act as mixed-type inhibitors, and their inhibition mechanism is adsorption. Data obtained from EIS measurements were analyzed to model the corrosion inhibition process through appropriate
equivalent circuit model; a CPE has been used.
The adsorption of furan derivatives on the steel surface in 1 M
HCl solution was found to obey Langmuirs adsorption isotherm
with a negative value of the free energy of adsorption Gads

.
Monte Carlo simulation technique incorporating molecular mechanics and molecular dynamics can be used to simulate the adsorption of furan derivatives on the iron 110 surface in 1 M HCl.
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Understanding Corrosion Inhibition of Mild Steel in Acid Medium by Some Furan Derivatives: A Comprehensive

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Journal of The Electrochemical Society, 157 3 C116-C124 2010

0013-4651/2010/1573/C116/9/$28.00 The Electrochemical Society