Article

pubs.acs.org/IECR

Natural Products for Material Protection: Inhibition of Mild Steel

Corrosion by Date Palm Seed Extracts in Acidic Media
Saviour A. Umoren,* Zuhair M. Gasem, and Ime B. Obot
Centre of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261,
Kingdom of Saudi Arabia
*
S Supporting Information

ABSTRACT: The corrosion inhibition effect of date palm (Phoenix dactylifera) seed extracts for mild steel in 1 M HCl and 0.5
M H2SO4 solutions was investigated by weight loss and electrochemical methods. The inhibition efficiency increased with an
increase in the extract concentration and decreased with an increase in the temperature. Extract concentrations of 2.5 and 1.5 g
L−1 gave maximum inhibition efficiencies in 1 M HCl and 0.5 M H2SO4, respectively. The immersion time was also found to
influence the corrosion inhibition effect in both acidic media. Polarization curves indicate that the extract functions as a mixed
inhibitor, affecting both the anodic and cathodic partial reactions of the corrosion process. Adsorption of the extract onto a mild
steel surface followed the Langmuir adsorption isotherm. The mechanism of physical adsorption has been proposed based on the
trend of the inhibition efficiency with temperature. The date palm seed extract is a better corrosion inhibitor for mild steel in HCl
than in a H2SO4 solution.

1. INTRODUCTION reported the corrosion inhibition effect of Neolamarckia cadamba

Some aqueous fluids used to stimulate oil and gas wells, clean
surfaces, or pickle steel include formulations that contain HCl
used at up to 15% concentration.1 In addition, formulations of
chelating agents, such as ethylenediaminetetraacetic acid, organic
acids, concentrated solutions of sulfuric acid, and other mineral
acids, are also used. The major problem with hydrochloric acids
and any other acids used in these processes is the enhanced
corrosion rate of oil and gas well equipment during acid
treatment. In order to control the corrosion rate of oil and gas
well equipment during acid treatment, the acid must be inhibited.
Among the several methods of corrosion control and prevention,
the use of corrosion inhibitors is very popular in an acidic
medium. The majority of the well-known inhibitors are organic
compounds containing heteroatoms, such as oxygen, nitrogen, or
sulfur, and multiple bonds, which allow adsorption on the metal
surface.1 Unfortunately, many common corrosion inhibitors that
are still in use today are hazardous to health.2
As a result of more stringent environmental regulations that
have been implemented in recent years, production chemicals
used in the oil and gas production industry are required to have
an environmentally friendly profile. Production chemicals are
required to be nonbioaccumulative and biodegradable and have a
low toxicity level.3 Researches nowadays are directed toward the
development of environmentally compatible, nonpolluting
corrosion inhibitors. Plant extracts, viewed as an incredibly rich
source of naturally synthesized chemical compounds, can readily
satisfy this need. In addition to being inexpensive, they are
environmentally friendly, ecologically acceptable, renewable, and
readily available. They can also be extracted by simple procedures
with low cost.
In recent times, considerable effort has been devoted to
studying the corrosion inhibiting efficacy of some natural
products, particularly biomass extracts of plant origin for mild
steel in HCl and H2SO4 solutions. For instance, Raja et al. have
for mild steel in 1 M HCl.4 Also, Oguzie and co-workers have
reported the corrosion inhibition of mild steel in 1 M HCl and
0.5 M H2SO4 solutions by leave extracts of Piper guineense,5,6
Af ramomum melegueta,7 and Coffee senna8 and seed extracts of
Punica granatum.9 Schinopsis lorentzii extract has been reported as
a green corrosion inhibitor for low carbon steel in a 1 M HCl
solution.10 Also, the corrosion inhibition effects of extracts of
Artemesia pallens,11 bamboo leaf,12 Ginkgo leaves,13 garlic peel,14
Osmanthus f ragran leaves,15 Salvia off icinalis leaves,16 Oxandra
asbeckii,17 Argemone mexicana,18 Acalypha torta leaf,19 and
Caulerpa racemosa20 for steel in HCl and/or H2SO4 have been
reported in the literature.
The date palm (Phoenix dactylifera) is a monocotyledonous
woody perennial fruit species belonging to the Arecaceae family.21
It has long been one of the most important fruit crops in the arid
regions of the Arabian Peninsula, North Africa, and the Middle
East. Date palms produce many products that are useful to
humans. The primary product is the date fruit, which can be
eaten fresh, dried, or in various processed forms. The
anticorrosive effect of date palm fruit juice on 7075 type
aluminum alloy in a 3.5% NaCl solution22 as well as leaf extract
on steel, aluminum, copper, and brass in hydrochloric acid and
sodium hydroxide solutions23 has been reported.
Date palm seeds ground into paste has been reported to be
effective in treating ague.24 It is also used as feed for livestock or
strung as beads for decoration.21 The date palm seeds apart from
the above-mentioned purposes have no commercial value and
may be considered as waste products. Recently, the corrosion
inhibition effect of date palm seed extracts (DPSEs) for mild steel
Received: May 31, 2013
Revised: September 21, 2013
Accepted: September 27, 2013
Published: September 27, 2013

© 2013 American Chemical Society 14855 dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research
in a 2 M H2SO4 solution has been reported using weight loss and
hydrogen evolution methods.25 However, there is no published
report on the corrosion inhibition effect of DPSE for mild steel in
a HCl solution and electrochemical investigations highlighting
the influence of DPSE on the kinetics of anodic and cathodic
partial reactions of the corrosion process. The present study was
undertaken to evaluate the corrosion inhibition potential of
DPSE for mild steel in 1 M HCl and 0.5 M H2SO4 solutions using
weight loss, linear polarization, potentiodynamic polarization,
and electrochemical impedance spectroscopy (EIS) measure-
ments at 25 and 60 °C.
2. EXPERIMENTAL SECTION
2.1. Material Preparation. The concentrations of the blank
corrodent were 1 and 0.5 M prepared from AR-grade 37−38%
HCl (Merck) and 98% H2SO4 (Baker), respectively. All
preparations were made using doubly distilled water. The tested
extract was prepared by boiling 10 g of dried and ground date
palm seed in 1 L of 1 M HCl and 0.5 M H2SO4, respectively, for
10 min. The solutions were cooled, filtered using Whatman filter
paper No. 1, and adjusted to 1 L of volume to obtain a stock
solution (10 g L−1). Different concentrations of the extract (0.5−
2.5 g L−1) were prepared by diluting the stock solution with the
respective blank corrodent of 1 M HCl and 0.5 M H2SO4.
Mild steel specimens with the following chemical composition
(weight percentage) were used in the experiments: C, 0.15; Mn,
1.26; V, 0.017; Si, 0.035; S, 0.008; Cr, 0.036; Ni, 0.03; Al, 0.083;
Cu, 0.038; balance Fe. Test coupons for weight loss and
electrochemical measurements were cut into 3 cm × 3 cm × 0.25
cm dimensions. These coupons were abraded with silicon
carbide abrasive paper (from grade no. 320 to 800), rinsed with
distilled water, placed in an ultrasonic acetone bath for about 5
min to remove possible residue of polishing, rinsed with acetone,
dried in warm air, and then stored in moisture-free desiccators
prior to use.
2.2. Weight Loss Measurements. Weight loss measure-
ments were conducted in glass vessels containing 250 mL of a
test solution maintained at 25 and 60 °C with a thermostatted
water bath. Tests were performed under total immersion in
aerated and unstirred conditions in the absence and presence of
the inhibitor. In each experiment, triplicate samples of the
precleaned and weighed mild steel coupons were freely
suspended in different test solutions. The test coupons were
retrieved after 24 and 72 h of immersion, thoroughly cleaned
using the chemical method for cleaning rust products as
previously reported,26 and reweighed using a digital analytical
balance with a sensitivity of 0.1 mg. The weight loss was taken as
the difference between the weight at a given time and the initial
weight of the coupon. The standard deviation values among
parallel triplicate experiments were found to be smaller than 5%,
indicating good reproducibility.
From the weight loss values, corrosion rates in terms of
thickness loss (mm year−1) were computed using the equation
87600ΔW
C R (mm year −1) =
ρAT (1)
where CR is the corrosion rate, W is the average weight loss (mg),
ρ is the density of a mild steel specimen (g cm−3), A is the surface
area of the specimen (cm2), and T is the exposure time (h).
The inhibition efficiency (η %) of DPSEs was evaluated from
the following equation:
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C R (blank) − C R(inh)
η%= × 100
C R (blank) (2)
where CR(blank) and CR(inh) are the corrosion rates in the
absence and presence of the inhibitor, respectively, in 1 M HCl
and 0.5 M H2SO4 at the same temperature.
2.3. Electrochemical Measurements. All electrochemical
experiments were performed in a one-compartment cell with
three electrodes connected to Gamry Instrument potentiostat/
galvanostat/ZRA (Reference 3000) with a Gamry framework
system based on ESA410. Gamry applications include software
DC105 for corrosion, EIS300 for EIS measurements, and the
Echem Analyst 6.0 software package for data fitting. The mild steel
was the working electrode with an exposed surface area of 0.7855
cm2 in the corrosive environment; platinum wire was used as the
counter electrode and saturated calomel electrode (SCE) as the
reference electrode. All potentials were measured versus the SCE
reference electrode. Tafel curves were obtained by changing the
electrode potential automatically from −250 to +250 mV versus
the open-circuit potential (Ecorr) at a scan rate of 1 mV s−1. Linear
polarization resistance (LPR) experiments were done from −20
to +20 mV versus Ecorr at a scan rate of 0.125 mV s−1. EIS
measurements were carried out under potentiostatic conditions
in a frequency range from 100 kHz to 100 mHz, with an
amplitude of 10 mV peak-to-peak, using an alternating-current
(ac) signal at Ecorr. All experiments were measured after
immersion for 30 min in 1 M HCl and 0.5 M H2SO4 with and
without the addition of inhibitor.
2.4. Scanning Electron Microscopy (SEM) Surface
Morphology. Morphological studies of the mild steel electrode
surface were undertaken by SEM examinations of electrode
surfaces exposed to different test solutions using a JSM-5800 LV
scanning electron microscope. Mild steel specimens of
dimensions 3 × 3 × 0.25 cm3 were polished successively with
silicon carbide abraded paper of different grades (nos. 320−800)
and thereafter using cloth with 1 μm diamond paste to a near-
mirror finished surface. The precleaned coupons were immersed
for 12 h in the blank solutions 1 M HCl and 0.5 M H2SO4
without and with 1.5 g L−1 DPSE at 25 ± 1 °C, then washed with
distilled water, dried in warm air, and submitted for SEM surface
examination.
3. RESULTS AND DISCUSSION
3.1. Corrosion Rates and Inhibition Efficiency. The effect
of the addition of DPSE tested at different concentrations on the
corrosion of mild steel in 1 M HCl and 0.5 M H2SO4 solutions
was studied by weight loss measurements at 25 and 60 °C after 24
h of immersion. The results of the weight loss determinations of
mild steel in 1 M HCl and 0.5 M H2SO4 media without and with
the addition of different concentrations of DPSE are presented in
Figure 1. Figure 1 shows plots of the (a) corrosion rate and (b)
inhibition efficiency as a function of the concentration of the
extract at 25 and 60 °C for mild steel in 1 M HCl and 0.5 M
H2SO4. These results show that the tested extract inhibits the
corrosion of mild steel in 1 M HCl and 0.5 M H2SO4 at all
concentrations used in this study because there is a general
decrease in the corrosion rates of mild steel at the end of the
corrosion-monitoring process. Inspection of the plots shows
higher corrosion rates in 0.5 M H2SO4 and also reveals clearly
that DPSE inhibited the corrosion of mild steel in both acidic
environments with a pronounced effect observed in 1 M HCl.
The corrosion inhibiting effect increases with increasing DPSE
concentration, indicating a dependence of the inhibition process
dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research Article

centers of adsorption in their molecules. The adsorption of

DPSE constituents through these atoms onto the metal surface
creates a barrier for mass and charge transfer and thus isolates the
metal from further attack of the corrosive anions.
3.2. Effect of the Immersion Time. The corrosion behavior
of mild steel in 1 M HCl and 0.5 M H2SO4 in the absence and
presence of DPSE was studied at 24 and 72 h in order to
determine the influence of the immersion time on the corrosion
inhibition effect of DPSE using the weight loss method. The
results obtained are presented in Figure 2. Figure 2 shows plots of

Figure 1. Plots of the (a) corrosion rate and (b) inhibition efficiency
against the inhibitor concentration at different temperatures for mild
steel in 1 M HCl and 0.5 M H2SO4 from weight loss measurements.

on the amount of inhibiting species present in the corrosive

medium. Examination of the figures shows that corrosion rates
increased with an increase in the temperature in both the absence
and presence of DPSE in both acidic environments. Also the
inhibition efficiency is observed to decrease with an increase in
the temperature. The trend of the inhibition efficiency with the
DPSE concentration shown in Figure 1b for mild steel in 1 M
HCl revealed an increase in the inhibition efficiency with an
increase in the extract concentration, reaching maximum values
of 90.95% and 61.95% at 25 and 60 °C, respectively. In 0.5 M
H2SO4, however, a maximum inhibition efficiency of 86.25% was
obtained at an extraction concentration of 1.0 g L−1 at 25 °C and Figure 2. Plots of the (a) corrosion rate and (b) inhibition efficiency
42.14% at an extract concentration of 1.5 g L−1 at 60 °C. against the inhibitor concentration at different immersion times for mild
The inhibitive action of DPSE toward the corrosion of mild steel in 1 M HCl and 0.5 M H2SO4 from weight loss measurements.
steel in both HCl and H2SO4 can be attributed to adsorption of
the DPSE constituents onto the steel surface. Corrosion the (a) corrosion rate and (b) inhibition efficiency as a function
inhibition is initiated by displacement of the adsorbed water of the concentration of the extract at 24 and 72 h of immersion
molecules by the inhibitor species, leading to specific adsorption for mild steel in 1 M HCl and 0.5 M H2SO4. It is observed from
on the metal surface.27 Some of the important chemical the plot that the corrosion rate increased with an increase in the
constituents of date palm seed have been reported to include immersion time in both the absence and presence of a low
carbohydrate, alkaloids, and tannins.21 These constituents have concentration of DPSE (0.5 and 1.0 g L−1) in a HCl solution and
heteroatoms such as nitrogen and oxygen, which are regarded as a decrease in the corrosion rate with an increase in the immersion
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Industrial & Engineering Chemistry Research Article

time at high extract concentration. In a H2SO4 solution, the

corrosion rate is observed to increase with the immersion time in
both the absence and presence of DPSE within the range of
concentrations studied (except at 2.5 g L−1). Inspection of the
figure further reveals a slight decrease in the inhibition efficiency
with an increase in the immersion time from 24 to 72 h at low
extract concentration and an increase in the inhibition efficiency
with prolonged immersion as the extract concentration is
increased in a 1 M HCl solution. However, in a 0.5 M H2SO4
solution, a decrease in the inhibition efficiency with an increase in
the immersion time from 24 to 72 h is observed from the plots at
all DPSE concentrations with the exception of 2.5 g L−1 extract
concentration. The increase in the inhibition efficiency with
longer immersion time, as noted in the HCl solution, can be
attributed to the formation of a protective film, which is time-
dependent on the mild steel surface. It has been pointed out that
stable, two-dimensional layers of inhibitor molecules are formed
on metal surfaces after longer immersion time.28,29 On the other
hand, according to Outirite et al.,30 the decrease in the inhibition
efficiency with prolonged immersion time can be due to
instability of the protective layer as a result of desorption of
the constituents of the DPSE and/or diffusion process through
the interface protective layer.
3.3. Potentiodynamic Polarization Measurements.
Polarization measurements are suitable for monitoring the
progress and mechanisms of the anodic and cathodic partial
reactions as well as identifying the effect of an additive on either
partial reaction.6 Potentiodynamic polarization experiments
were undertaken to determine the effect of the anodic (Fe →
Fe2+ + 2e) and cathodic (2H+ + 2e → H2) partial reactions of the
corrosion process. Typical potentiodynamic polarization curves
for the mild steel specimens in 1 M HCl and 0.5 M H2SO4
without and with DPSE are shown in parts a and b of Figure 3,
respectively. The polarization curves reveal that the mild steel
specimen is seen to exhibit active dissolution with no distinctive
transition to passivation within the studied potential range in
both acidic environments. The plots also show that the anodic
and cathodic reactions in blank acid and upon the addition of Figure 3. Potentiodynamic polarization curves for mild steel in (a) 1 M
DPSE follow Tafel’s law. Hence, the linear Tafel segments of the HCl and (b) 0.5 M H2SO4 in the absence and presence of different
anodic and cathodic curves were extrapolated to corrosion concentrations of DPSE.
potential to obtain the corrosion current densities (icorr).
The corresponding electrochemical parameters, namely, Table 1. Potentiodynamic Polarization Parameters for Mild
corrosion current densities (icorr), the corrosion potential Steel in 1 M HCl and 0.5 M H2SO4 Solutions in the Absence
(Ecorr), the cathodic Tafel slope (βc), and the anodic Tafel and Presence of DPSE
slope (βa), derived from the polarization curves are presented in extract Ecorr
Table 1. Results in the table indicate that the corrosion current acidic concn (g (mV/ icorr (μA βc (mV βa (mV
density decreases markedly in the presence of DPSE compared medium L−1) SCE) cm−2) dec−1) dec−1) η%
to the blank solution and also decreases with an increase in the 1 M HCl −511.6 303.3 97.3 76.5
concentration of the extract. It is also observed that the presence HCl 0.5 −495.0 49.9 108.8 81.5 83.6
of DPSE does not shift Ecorr remarkably; therefore, DPSE could 1.0 −502.8 48.3 105.8 88.6 84.1
be regarded as a mixed-type inhibitor, and inhibition of mild steel 1.5 −500.4 40.7 103.2 85.9 86.6
corrosion by DPSE occurred by the geometric blocking effect 2.0 −497.7 36.5 109.2 77.8 87.9
mechanism.31 2.5 −499.6 32.5 104.7 79.0 89.3
The values of the corrosion current density in the absence 0.5 M −517.9 836.9 117.7 111.6
(iocorr) and presence (icorr) of inhibitor were used to estimate the H2SO4
H2SO4 0.5 −479.3 170.1 126.4 62.5 79.67
inhibition efficiency from polarization data as follows:
1.0 −488.8 116.7 119.9 69.9 86.1
⎛ i ⎞ 1.5 −479.0 106.6 124.3 62.9 87.3
η % = ⎜1 − corr ⎟ × 100 2.0 −480.7 119.3 130.1 65.9 85.8
⎝ i°corr ⎠ (3) 2.5 −471.8 175.8 137.6 52.2 78.9

The values obtained are listed in Table 1. From the table, it is

seen that the inhibition efficiency increases with an increase in at the highest concentration (2.5 g L−1) of the extract studied in 1
the concentration of DPSE, reaching a maximum value of 89.3% M HCl. However, in 0.5 M H2SO4, the inhibition efficiency
14858 dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research
increases with an increase in the concentration of the extract up
to 1.5 g L−1 and thereafter decreases with a further increase in the
concentration. Hence, a maximum inhibition efficiency of 87.3%
was obtained at an extract concentration of 1.5 g L−1. This result
clearly demonstrates that DPSE is a better corrosion inhibitor in
HCl than in H2SO4.
3.4. EIS Measurements. EIS experiments were undertaken
in order to understand the characteristics and kinetics of the
electrochemical processes on mild steel in 1 M HCl and 0.5 M
H2SO4 solutions and how they were modified by DPSE. Figure 4
Figure 4. Impedance plots for mild steel in 1 M HCl in the absence and
presence of different concentrations of DPSE exemplified as (a) Nyquist
and (b) Bode plots.
shows the impedance spectra represented in panels a and b as
Nyquist and Bode plots, respectively, in the absence and
presence of different concentrations of DPSE for mild steel
corrosion in 1 M HCl. Similar plots for mild steel corrosion in 0.5
M H2SO4 are depicted in parts a and b of Figure 5, respectively.
In an HCl solution, the complex impedance diagrams recorded at
Ecorr in the absence and presence of different concentrations of
DPSE have similar shape, indicating that almost no change in the
corrosion mechanism occurred as a result of DPSE addition. The
Nyquist plots show single semicircles for all systems over the
frequency range studied, corresponding to one time constant in
the Bode plots. The high-frequency intercept with the real axis in
14859
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Figure 5. Impedance plots for mild steel in 0.5 M H2SO4 in the absence
and presence of different concentrations of DPSE exemplified as (a)
Nyquist and (b) Bode plots.
the Nyquist plots is assigned to the solution resistance (Rs), and
the low-frequency intercept with the real axis is ascribed to the
charge-transfer resistance (Rct). However, in a H2SO4 solution,
the Nyquist plots in the presence of DPSE are characterized by a
large capacitive loop at high-to-medium frequency and an
inductive loop at low frequency. The capacitive loop at high
frequencies represents the phenomenon associated with the
double electric layer. It arises from the time constant of the
electrical double layer and charge transfer in the corrosion
process.32,33 The presence of an inductive loop may be attributed
to relaxation of adsorption species like Hads+ and SO42− on the
electrode surface, exhibiting a negative change in the surface
coverage with the potential on the surface of the metal.34,35
Inspection of Figures 4 and 5 reveals an increase in the size of the
semicircle in Nyquist plots in the presence of DPSE compared to
the blank solutions, which is an indication of the inhibition of the
corrosion process. Also, the sizes of the semicircles increase with
an increase in the concentration of DPSE particularly in an HCl
solution. In a H2SO4 environment, however, the sizes of the
semicircles increase with an increase in the concentration of
DPSE up to 1.5 g L−1 and thereafter decrease. It is observed that
the semicircles are not perfect but depressed with the center
under the real axis. This depressed form of the semicircles has
dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research Article

been attributed to a surface inhomogeneity of structural or layer capacitance (Cdl). The increase in Rct values in inhibited
interfacial origin such as those found in adsorption processes.36 systems, which corresponds to an increase in the diameter of the
The impedance spectra were analyzed by fitting to the Nyquist semicircle, confirms the corrosion inhibiting effect of the
equivalent circuit model shown in parts a and b of Figure 6 for DPSE. The observed decrease in the Cdl values, which normally
results from a decrease in the dielectric constant and/or an
increase in the double-layer thickness, can be attributed to
adsorption of the extract organic matter (with a lower dielectric
constant compared to the displaced adsorbed water molecules)
onto the metal/electrolyte interface, thereby protecting the
metal from corrosive attack.5 The decrease in Cdl is in accordance
with the Helmholtz model given by the following equation:39
εε0A
Cdl =
d (5)
where d is the thickness of the protective layer, ε is the dielectric
constant of the medium, ε0 is the vacuum permittivity, and A is
the effective area of the electrode. The double-layer capacitance,
Cdl, values were obtained at the frequency at which the imaginary
component of the impedance is a maximum from the equation40
1
Cdl =
2πfmax R ct (6)
The inhibition efficiency from the impedance data was
computed by comparing the values of the charge-transfer
Figure 6. Equivalent circuit diagrams used to fit impedance data in the
resistance in the absence and presence of DPSE as follows:
absence and presence of DPSE in (a) 1 M HCl and (b) 0.5 M H2SO4.
R ct − R ct°
mild steel corrosion in 1 M HCl and 0.5 M H2SO4, respectively. η%= × 100
R ct (7)
The circuit consists of the solution resistance Rs, the charge-
transfer resistance Rct, the constant phase element (CPE) for a where Rct° and Rct are the charge-transfer resistances in the
HCl corrosive medium, and in addition the inductive elements absence and presence of the inhibitor, respectively. The values of
RL and L for a H2SO4 corrosive medium. For the description of a inhibition efficiency given in Tables 2 and 3 for mild steel
frequency-independent phase shift between an applied ac corrosion in 1 M HCl and 0.5 M H2SO4, respectively, show that
potential and its current response, a CPE is used, which is the inhibition efficiency increases with an increase in the
defined in impedance representation as37 concentration of DPSE in 1 M HCl, while in 0.5 M H2SO4, the
inhibition efficiency increases with an increase in the
ZCPE = Y0−1(jω)−n (4) concentration of the extract up to 1.5 g L−1 and thereafter
where Y0 is the CPE constant, n is the CPE exponent, which can decreases with a further increase in the concentration.
be used as a guage of the heterogeneity or roughness of the LPR measurements give a virtual instantaneous measurement,
surface,38 j2 = −1 is an imaginary number, and ω is the angular enabling the corrosion rate and performance of the inhibitors to
frequency in rad s−1. Depending on n, CPE can represent be monitored with time. The most important electrochemical
resistance (ZCPE = R, n = 0), capacitance (ZCPE = C, n = 1), parameter derived from LPR measurements is the polarization
Warburg impedance (ZCPE = W, n = 0.5), or inductance (ZCPE = resistance (Rp), which is defined as the slope of the potential−
L, n = −1). The values of the electrochemical parameters derived current density (E vs i) curve at the corrosion potential, Ecorr. The
from Nyquist plots for mild steel corrosion in 1 M HCl and 0.5 M polarization resistance values without and with different
H2SO4 in the absence and presence of different concentrations of concentrations of DPSE for mild steel corrosion in 1 M HCl
DPSE are listed in Tables 2 and 3, respectively. The results and 0.5 M H2SO4 as well as corrosion inhibition efficiency
presented in the tables reveal that the DPSE increased the obtained by the LPR method are given in Table 4. The inhibition
magnitude of Rct, with a corresponding decrease in the double efficiency from the LPR data was estimated by comparing the
values of the polarization resistance in the absence and presence
Table 2. EIS Parameters for Mild Steel in a 1 M HCl Solution of DPSE as follows:
in the Presence of DPSE Rp
η%=1− × 100
extract Y0 (Ω sn R p° (8)
concn Rs (Ω cm−2) × Rct (Ω Cdl (μF α2 ×
(g L−1) cm2) 10−6 n cm2) cm2) 10−4 η% where Rp° and Rp are the polarization resistances in the absence
1M 3.249 139.7 0.90 54.72 122.7 0.78 and presence of inhibitor (DPSE), respectively. The results
HCl obtained show that the polarization resistance increased upon
0.5 1.884 75.2 0.89 312.4 3.9 2.34 82.48 introduction of DPSE into the corrosive media. Also, the
1.0 3.607 67.8 0.88 325.2 3.6 2.60 83.17 polarization resistance increases with an increase in the
1.5 3.587 66.4 0.89 369.9 2.7 2.67 85.21 concentration of DPSE in an HCl medium. In a H2SO4 medium,
2.0 4.694 65.9 0.89 387.5 2.5 0.92 85.88 the polarization resistance increases with an increase in the DPSE
2.5 3.707 66.3 0.89 414.0 2.2 1.08 86.78 concentration up to 1.5 g L−1 and thereafter decreases. The
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Table 3. EIS Parameters for Mild Steel in a 0.5 M H2SO4 Solution in the Presence of DPSE
extract concn (g L−1) Rs (Ω cm2) Y0 (Ω sn cm−2) × 10−6 n Rct (Ω cm2) L (Ω cm2) RL (Ω cm2) Cdl (μF cm2) α2 × 10−4 η%
0.5 M H2SO4 3.84 165.2 0.89 28.2 257.3 1.08
0.5 5.62 131.4 0.91 117.6 875.4 1199 27.2 1.99 76.0
1.0 6.32 112.3 0.87 147.3 71.1 2107 17.1 2.06 80.9
1.5 5.74 99.9 0.87 177.5 2021.0 3220 11.8 2.68 84.1
2.0 5.99 101.2 0.87 164.8 1401.0 2875 13.6 2.73 82.9
2.5 5.39 146.2 0.88 113.0 431.2 2519 29.3 3.35 75.1

Table 4. Comparison of the Inhibition Efficiencies from the Three Electrochemical Techniques
EIS PDP LPR
acidic medium extract concn (g L−1) Rct (Ω cm−2) η% icorr (μA cm−2) η% Rp (Ω cm−2) η%
1 M HCl 54.72 303.3 44.41
HCl 0.5 312.4 82.5 49.9 83.6 249.1 82.2
1.0 325.2 83.2 48.3 84.1 281.8 84.2
1.5 369.9 85.2 40.7 86.6 360.0 87.7
2.0 387.5 85.9 36.5 87.9 354 87. 5
2.5 414.0 86.8 32.5 89.3 414.4 89.4
0.5 M H2SO4 28.2 836.9 32.54
H2SO4 0.5 117.6 76.0 170.1 79.67 107.7 69.8
1.0 147.3 80.9 116.7 86.1 154.8 78.9
1.5 177.5 84.1 106.6 87.3 168.1 80.6
2.0 164.8 82.9 119.3 85.8 158.2 79.4
2.5 113.0 75.1 175.8 78.9 94.4 65.7

increase in the Rp values in inhibited systems also confirms the
corrosion inhibiting effect of the DPSE. Table 5 shows
comparative values of the corrosion inhibition efficiency of
DPSE with other plant-based extracts for mild steel in acidic
media at ambient temperature. The results in the table show that
the values of the inhibition efficiency obtained from DPSE
compare favorably with other plant extracts reported in the
literature.
A comparison of some corrosion parameters and inhibition
efficiencies obtained from the three electrochemical methods
(EIS, PDP, and LPR) used in the present study are given in Table
4. From the table, it can be observed that the values of the
parameters obtained from the three techniques are in good
agreement. The corrosion inhibition efficiencies followed the
same trend. DPSE is observed to be a better corrosion inhibitor
in HCl than in H2SO4. Comparative studies of corrosion
inhibition of organic species in chloride (HCl)- and sulfate
(H2SO4)-containing solutions have shown that the inhibiting
effect of organic species in HCl is much higher than that in
H2SO4 acid solutions.41−43 It has been suggested that chloride
ions, being less hydrated than sulfate ions, have a stronger
tendency to adsorb than do sulfate ions on the metal by creating
an excess negative charge toward the solution phase, which favors
synergistic adsorption on the metal surface.43 This may be the
reason for an increased protective effect in the chloride-
containing solution.
3.5. Adsorption Isotherms. The general consensus in
corrosion inhibition literature is that the primary step in the
action of inhibitors in acidic solutions is believed to be adsorption
onto the metal surface. This involves the assumption that the
corrosion reactions are prevented from occurring over the area of
the metal surface covered by adsorbed inhibitor species, whereas
these corrosion reactions occurred normally on the inhibitor-free
area.44 To clarify the nature of the adsorption, the degree of
surface coverage (θ) is very important and its value for the
different concentrations of DPSE at the two temperatures
14861
studied was computed from the weight loss measurements as η %
= θ × 100 (assuming a direct relationship between the surface
coverage and inhibition efficiency) and then fitted theoretically
to different adsorption isotherms. The value of the correlation
coefficient (R2) was used to determine the best-fit isotherm. The
best result was obtained with a Langmuir adsorption isotherm
model. Figure 7 shows the plot of C/θ against C. Linear plots
were obtained that show that adsorption of the constituents of
DPSE onto a mild steel surface follows the Langmuir adsorption
isotherm. The Langmuir adsorption isotherm is characterized by
C 1
= +C
θ K ads (9)
where θ is the surface coverage, C is the concentration, and Kads is
the equilibrium constant of the adsorption process and is related
the standard Gibbs free energy of adsorption by the equation
1 ⎛ −ΔGads° ⎞
K ads = exp⎜ ⎟
55.5 ⎝ RT ⎠ (10)
where 55.5 is the concentration of water expressed in mol dm−3,
R is the molar gas constant, and T is the absolute temperature.
Adsorption parameters derived from the plots are listed in the
Supporting Information (Table S1). The results in the table
indicate that Kads, whose values indicate the binding power of the
inhibitor to the metal surface,45 is seen to decrease with
increasing temperature. Such behavior can be interpreted on the
basis that increases in the temperature result in desorption of
some adsorbed constituents of the extracts on the metal surface
and are consistent with the proposed physisorption mechanism.
The values of the free energy of adsorption, which lie between
−9.0 and −18.72 kJ mol−1 (in both environments), indicate that
the extracts function by physically adsorbing on the metal
surface. Generally, values of the free energy of adsorption up to
−20 kJ mol−1 are consistent with electrostatic interaction
between charged molecules and a charged metal (which indicates
dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research Article

Table 5. Comparison of the Corrosion Inhibition Efficiency of

DPSE with Other Plant-Based Extracts for Mild Steel in Acidic
Media at Ambient Temperature
inhibition
plant acidic immersion efficiency
extract medium max concn time (h) (%) ref
−1 a
date palm 1 M HCl 2.5 g L 24 90.95 present
seed study
−1 a
0.5 M 1.0 g L 86.50
H2SO4
garlic peel 1 M HCl 1000 24 96.0a 18
mg L−1
A. 1 M HCl 600 mg L−1 5 92.53a 22
mexicana
S. lorentzii 1 M HCl 2000 ppm 66.0b, 63.0c 14
Ginkgo 1 M HCl 100 mg L−1 6 94.8a 17
leaves
0.5 M 82.0a
H2SO4
A. torta 1 M HCl 1000 ppm 89a 23
N. 1 M HCl 5 mg L−1 0.5 88.0b, 84.0c 8
cadamba
P. guineense 1 M HCl 900 mg L−1 24 96.5a 9
0.5 M 97.0a
H2SO4
A. 1 M HCl 800 mg L−1 3 96.1a 11
melegueta
a
0.5 M 55.0
H2SO4
C. senna 1 M HCl 1000 3 76.6a 12
mg L−1
0.5 M 82.4a
H2SO4
P. 1 M HCl 400 mg L−1 24 92.0a 13
granatum
−1 a
0.5 M 600 mg L 95.0
H2SO4
A. pallens 1.0 M 400 mg L−1 24 98a 15
HCl
bamboo M HCl 200 mg L−1 6 89.0a 16
leaf
0.5 M 79.4a
H2SO4
O. f ragran 1.0 M 0.34 g L−1 1 94.1b, 95.3c 19 Figure 7. Langmuir adsorption isotherm for DPSE on mild steel in (a) 1
HCl M HCl and (b) 0.5 M H2SO4 at 25 and 60 °C.
S. 1.0 M 2.0 g L−1 1 96.6a 20
of f icinalis HCl 3.6. Effect of the Temperature. In order to evaluate the
O. asbeckii 1.0 M 100 mg L−1 3 87b, 92c 21 effect of the temperature on the corrosion inhibition effect of
HCl
C. 1.0 M 100 ppm 2 83a 24 DPSE, the weight loss experiments were undertaken at 25 and 60
racemosa HCl °C for 24 h immersion time. The results obtained, as illustrated in
a
Values from the weight loss method. bValues from the potentiody- Figure 1 for mild steel dissolution in 1 M HCl and 0.5 M H2SO4,
namic polarization method. cValues from the EIS method. respectively, show that corrosion rates increase with an increase
in the temperature in the absence and presence of the extract as
well as a decrease in the inhibition efficiency with increasing
temperature in both acidic environments. Some authors have
physical adsorption), while those more negative than −40 kJ opined that an increase in the temperature will enhance the rate
mol−1 involve charge sharing or transfer from the inhibitor of H+ diffusion to the metal surface as well as ionic mobility.46 At
molecules to the metal surface to form a coordinate type of bond lower temperatures, the adsorbed hydrogen atoms block the
(which indicates chemsisorption). The data in Supporting cathodic area, while an increase in the solution temperature
Information (Table S1) also show considerable deviation of causes desorption of hydrogen. Such hydrogen desorption leads
the slope from unity for mild steel corrosion in 0.5 M H2SO4, to an increase in the cathodic area and consequently increases the
indicating that the isotherm may not be strictly applied. The corrosion rate. A decrease in the inhibition efficiency with
deviation may be explained on the basis of the interaction among increasing temperature is often attributed to physisorption of
the adsorbed species on the surface of the metal. The differences inhibitor species on the corroding metal surface.7,47 The
in the corrosion behavior for mild steel in 1 M HCl and 0.5 M physisorption process is hindered by the enhanced rates of
H2SO4 in the presence of DPSE confirm the vast variety of hydrogen gas evolution at higher temperatures, which increas-
corrosion systems and the specificity of action of most acid ingly agitates the interface and also promotes dispersal of the
inhibitors. adsorbed inhibitor.7 Accordingly, an increase in the temperature
14862 dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research
Figure 8. SEM images for exposed mild steel in (a) a 1 M HCl solution, (b) 1 M HCl containing 1.5 g L−1 DPSE, (c) a 0.5 M H2SO4 solution. and (d) 0.5
M H2SO4 containing 1.5 g L−1 DPSE at 25 °C for 12 h.
is accompanied by desorption of those constituents of DPSE that
are attached to the metal surface via physical adsorption, leading
to reduced surface coverage and, hence, lower inhibition
efficiency.
The activation parameters for the corrosion process were
calculated from an Arrhenius-type plot according to the
following equation:
CR 2 Ea ⎛ 1 1⎞
log = ⎜ − ⎟
CR1 2.303R ⎝ T1 T2 ⎠ (11)
where CR1 and CR2 are the corrosion rates at temperatures T1
and T2, respectively, and R is the molar gas constant.
An estimate of the heat of adsorption was obtained from the
trend of the surface coverage with the temperature as follows:48
⎡ ⎛ θ ⎞ ⎛ θ ⎞⎤⎛ TT ⎞
Q ads = 2.303R ⎢log⎜ 2
⎟ − log⎜ 1 ⎟⎥⎜ 1 2 ⎟
⎣⎢ ⎝ 1 − θ2 ⎠ ⎝ 1 − θ1 ⎠⎦⎥⎝ T2 − T1 ⎠
kJ mol−1 (12)
where θ1 and θ2 are the degrees of surface coverage at
temperatures T1 and T2, respectively.
The calculated values for both parameters are given in
Supporting Information (Table S2). Inspection of the data shows
that the activation energy is higher in the presence of extracts
compared to the blank solutions. A similar observation has been
reported for the corrosion inhibition effect of steel in 0.2 M HCl
using date palm leaves and henna extracts.23 This result, in
addition to the observed decrease in the inhibition efficiency with
an increase in the temperature, suggests that DPSE did not alter
the mechanism of the corrosion process.49 Rather, corrosion
inhibition occurred primarily through a geometric blocking effect
of the inhibitor on the mild steel surface, reducing access of the
aggressive corrosive media. The negative Qads values indicate that
the degree of surface coverage decreased with increasing
14863
Article
temperature, supporting the earlier proposed physisorption
mechanism for DPSE.
3.7. Surface Morphology. The surface morphologies of
exposed mild steel to 1 M HCl and 0.5 M H2SO4 solutions in the
absence and presence of 1.5 g L−1 DPSE after 12 h of immersion
at 25 °C were examined using SEM. The results shown in Figure
8a,c reveal that the mild steel specimens underwent active
dissolution, as indicated by the roughness of the surface in the
absence of DPSE in both acidic environments, as expected due to
corrosive attack of the acidic solutions. The attack was uniform
with no evidence of selective corrosion (localized attack). In the
presence of DPSE (parts b and d of Figure 8 in 1 M HCl and 0.5
M H2SO4, respectively), the rough surface is seen to decrease,
indicating an inhibiting effect of DPSE on the surface of mild
steel due to the formation of protective layers that create a barrier
for charge and mass transfer, and there is slight evidence of
adsorbate presence on the metal surface.
4. CONCLUSIONS
The following conclusions can be drawn from the work.
1. DPSE is found to inhibit the corrosion of mild steel in 1 M
HCl and 0.5 M H2SO4 solutions. The inhibition effect is
concentration-dependent. The extract concentrations of 2.5 and
1.5 g L−1 gave maximum inhibition efficiency in 1 M HCl and 0.5
M H2SO4, respectively.
2. The corrosion inhibition effect was also found to be
influenced by the immersion time. An increase in the inhibition
efficiency with prolonged immersion as the extract concentration
is increased in 1 M HCl was observed, while in a 0.5 M H2SO4
solution, a decrease in the inhibition efficiency with an increase in
the immersion time was observed with an increase in the extract
concentration up to 2.0 g L−1.
3. DPSE offers better corrosion protection for mild steel in 1 M
HCl than in 0.5 M H2SO4.
dx.doi.org/10.1021/ie401737u | Ind. Eng. Chem. Res. 2013, 52, 14855−14865
Industrial & Engineering Chemistry Research
4. Corrosion inhibition is afforded by virtue of adsorption of
DPSE components onto the mild steel surface, which can be
approximated by the Langmuir adsorption isotherm.
5. The results of potentiodynamic polarization measurements
indicate that DPSE behaved as a mixed inhibitor, affecting both
cathodic hydrogen evolution and anodic mild steel dissolution
reactions.
6. Impedance spectra show a high-frequency capacitive loop
related to the charge-transfer process of the metal corrosion and
double-layer behavior.
7. The phenomenon of physical adsorption is proposed from
the trend of a decrease in the inhibition efficiency with an
increase in the temperature, which is corroborated by the values
of the kinetic parameters obtained from the experimental data.
■
*
ASSOCIATED CONTENT
S Supporting Information
Parameters obtained from the Langmuir adsorption isotherm
and activation (Ea and Qads) data. This material is available free of
charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: umoren@kfupm.edu.sa. Phone: +966 3 860 7902. Fax:
+966 3 860 3996.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge King Fahd University of
Petroleum and Minerals (KFUPM) for providing the facilities for
the research.
■
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