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Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx

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Journal of Industrial and Engineering Chemistry


journal homepage: www.elsevier.com/locate/jiec

Utilization of watermelon rind extract as a green corrosion inhibitor


for mild steel in acidic media
N.A. Odewunmi *, S.A. Umoren, Z.M. Gasem
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, 31261, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Article history: Electrochemical techniques were used to investigate the efficacy of watermelon rind extract (WMRE) as
Received 17 December 2013 corrosion inhibitor for mild steel in HCl and H2SO4 solutions. The inhibition efficiency increased as the
Accepted 17 February 2014 concentration of the extract increases. Potentiodynamic polarization results indicate that WMRE act as a
Available online xxx
mixed-type inhibitor. The values of effective capacitance obtained by utilizing the impedance
parameters in both acidic media are in the range of double layer capacitance. Corrosion inhibition effect
Keywords: of WMRE can be attributed to the adsorption of constituents of WMRE onto the mild steel surface which
Watermelon
can be approximated by Temkin adsorption isotherm model.
Acid corrosion
Corrosion inhibition
ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Mild steel reserved.
Biomaterials

1. Introduction anti-nutrients namely saponin, alkaloids, hydrogen cyanide,


tannins, phytate, phenol, oxalate and flavonoids in fresh and dried
Mild steels are frequently used for a wide range of applications watermelon peel (WMP), watermelon pulp (WMPu) and water-
in construction industry due to their very good mechanical melon rind (WMR). In addition, WMR being an agricultural waste
properties and low cost compared with many metallic materials. product has been reported to be a natural source of citrulline, a
The poor corrosion resistance of mild steel in acid [1–3] is a major non-essential amino acid [31]. The chemical structure of citrulline
constraint in its applications. The use of inhibitors in controlling its (major component of WMRE) is shown in Fig. 1. These compounds
corrosion processes has proven to be efficient and most practicable contain heteroatoms (N, O) and aromatic ring which are regarded
[4,5]. However, most of the compounds that constitute these as centers of adsorption hence the extracts obtained from
inhibitors are toxic to human and its environments. The toxicity of watermelon waste products could function as a potential corrosion
these organic and inorganic inhibitors has paved way to explore inhibitor. There are few reports on the use of watermelon parts as
the use of non-toxic natural products inhibitors [6–9] that are corrosion inhibitor for metals in some corrosive environments. For
environmentally friendly. The use of extracts of some plants to instance watermelon peel extract (WMPE) and watermelon leaf
inhibit the corrosion of steel in acid media has been reported in the have been used for corrosion protection of zinc in natural sea water
literature [10–27]. [32]. However, there is no report to the best of our knowledge on
Watermelon is vine-like flowering plant which belongs to the the use of watermelon rind as corrosion inhibitor for any metal in
family of Cucurbitaceae with varieties of seeded and seedless any corrosive environment. Therefore our main objective in the
species. It is widely grown due to its large edible fruits that contain present work is to utilize extract of WMR as a corrosion inhibitor
a hard green rind and a watering reddish, yellowish or pink pulp. It for mild steel in acidic media (HCl and H2SO4) using electrochemi-
is an essential agricultural product utilized in the production of cal impedance spectroscopy (EIS), potentiodynamic polarization
many food products such as fruit cocktails, juices and nectars (PDP) and linear polarization (LPR) methods.
[28,29]. The most useful part of the watermelon in the food
industry is its pulp. Watermelon, Citrullus lanatus has been
2. Experimental
reported by Johnson et al. [30] to contain valuable amount of
2.1. Materials preparation

* Corresponding author. Tel.: +966 13 860 7895; fax: +966 13 860 3996. 1 M HCl and 0.5 M H2SO4 solutions as corrosive media were
E-mail address: adewalen@kfupm.edu.sa (N.A. Odewunmi). prepared with A-R grade 37% HCl (Sigma–Aldrich) and 98% H2SO4

http://dx.doi.org/10.1016/j.jiec.2014.02.030
1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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paste to near mirror surface finish. The same procedure for removing
the residue of polishing by sonication in ethanol bath was employed.
The cleaned mild steel specimens were immersed in both 1 M HCl
and 0.5 M H2SO4 without and with 2.0 g/L WMRE. The coupons were
retrieved after 24 h, rinsed with distilled water, dried and submitted
for SEM examination.

Fig. 1. Chemical structure of citrulline. 4. Results and discussion

4.1. Open circuit potential


(Baker), respectively, and double distilled water. Extract of the
WMR was prepared by weighing 5 g of dried grounded WMR in 1 L
The variation of open circuit potential (Eocp) with time for mild
of 1 M HCl and 0.5 M H2SO4 and boiled for 10 min. The solutions
steel in 1 M HCl and 0.5 M H2SO4 without and with addition of
were cooled and later filtered with sintered glass Buchner funnel
different concentrations of WMRE is shown in Fig. 2. It could be
No. 36060 to obtain 5 g/L stock solution. Different concentrations
observed from the figure that a stable OCP values were attained
of the extract (0.1–2.0 g/L) were prepared from the stock solution
after 1800 s immersion both in the absence and presence of the
by dilution with the respective corrodents (1 M HCl and 0.5 M
inhibitor. It is also observed that on introduction of WMRE into the
H2SO4).
corrosive medium, the potentials shift to noble values than those
The chemical composition (weight %) of the mild steel sample
observed in the blank acid solution. The positive shift of corrosion
used in the experiment is: C, 0.15; Mn, 1.26; V, 0.017; Si, 0.035; S,
potential was found to be concentration dependent. This suggests a
0.008; Cr, 0.036; Ni, 0.03; Al, 0.083; Cu, 0.038 and Fe (balance). The
possible influence of the extracts on both anodic and cathodic
mild steel was cut into coupons of 3 cm  3 cm  0.25 cm
polarization.
dimension, abraded with silicon carbide abrasive papers of
different grades (# 120–800), and rinsed with distilled water.
4.2. Electrochemical impedance spectroscopy (EIS) measurements
The residues of polished particles were removed by sonication in
ethanol bath for 10 min. The cleaned mild steel specimens were
EIS measurements were taken to characterize the kinetics of the
kept in the desiccator prior to use for corrosion test using
electrochemical processes and the capacitive behavior of WMRE on
electrochemical measurements.
mild steel. Figs. 3 and 4 show the Nyquist and Bode (modulus and
phase angle) plots of WMRE in 1 M HCl and 0.5 M H2SO4 without
2.2. Electrochemical measurements
and with different concentrations of WMRE respectively. The
Nyquist plots in both media exhibited a semi-circle (one shoulder)
The electrochemical measurements were performed in a single
and a single relaxation process (one time constant) over the range
compartment electrochemical cell designed for mounting varieties
of the studied frequencies as shown by the Bode phase angle plots.
of flat samples for electrochemical test at 25 8C with three
The number of distinguishable maxima or related shoulder is an
electrodes system. Gamry potentiostat/galvanostat/ZRA (Refer-
indication of number of relaxation (time constant) taking place in
ence 3000) embedded with Gamry framework system composed of
electrochemical system as reported by Beverskog et al. [33]. Also,
ESA410. Gamry software applications include EIS300 for the
Figs. 3c and 4c revealed a phase angle maxima smaller than 908. It
electrochemical impedance spectroscopy (EIS) measurements,
is observed from the plots (Figs. 3a and 4a) that the semi circles are
DC105 for the potentiodynamic polarization (PDP) and linear
not perfect but depressed with the centers under the real axis.
polarization (LPR) measurements and Echem Analyst 6.0 for data
Some reasons advanced to explain this behavior include the
fittings. The exposed area of the working electrode (mild steel) to
surface roughness, frequency dispersion of time constants as a
the corrosive acidic medium was 0.7855 cm2; graphite rod and the
result of local inhomogeneity in the dielectric material, relaxation
saturated calomel electrode (SCE) were used as the counter and
and porosity in mass transport effects [34]. To account for these
reference electrodes, respectively.
effects, a constant phase element (CPE) must be introduced to the
Tafel curves were obtained from the potentiodynamic polari-
equivalent circuit to estimate the EIS experimental results [35,36].
zation measurements between the potential range of +250 mV and
Fig. 5 shows the equivalent circuit used to accurately fit the
250 mV against the open circuit potential (Ecorr) at scan rate of
experimental data obtained from EIS measurements for mild steel
1 mV s1. A scan rate of 0.125 mV s1 was used to generate a linear
in (a) 1 M HCl and (b) 0.5 M H2SO4 in the absence and presence of
polarization resistance (LPR) at +20 mV and 20 mV against the
WMRE. The circuit comprised of the CPE in parallel with the charge
Ecorr. EIS measurements were done at frequencies of 100 kHz to
transfer resistance (Rct) and solution resistance (Rs) in HCl medium
100 mHz with an alternative (ac) amplitude of 5 mV r.m.s.
and additional inductive elements (L and RL) in H2SO4 medium.
(7.07 mV peak-to-peak) signal from the Ecorr. The open circuit
In HCl solution, there is no change in the corrosion mechanism
potential (Ecorr) was allowed to attain a stable state which was
in spite of the addition of different concentrations of WMRE as the
achieved after 1800 s before the electrochemical measurements
shape of the impedance plots largely remain the same as shown in
were carried out both in the absence and presence of the inhibitor
Fig. 3, however, the diameter of the semi-circle (Fig. 3a) and the
(WMRE).
real impedance value (Fig. 3a and b) increased as the extract
concentration increases from 0.1 g/L up to 1.5 g/L and a lower
3. Morphological studies diameter as the concentration was raised to 2.0 g/L. The solution
resistance (Rs) and the Rct are assigned as the high and low
A JSM-5800 LV scanning electron microscope (SEM) was used to frequencies intercept on the real impedance axis, respectively.
examine the surface morphology of the mild steel specimen with However, for mild steel corrosion in 0.5 M H2SO4 the impedance is
and without WMRE in the acidic media (1 M HCl and 0.5 M H2SO4) characterized by a large capacitance loop at high-medium
after 24 h exposure. Prior to the exposure in different test solutions, frequency region and an induction loop at the low frequency
the mild steel coupons of dimensions 3 cm  3 cm  0.25 cm were (LF) in the presence of WMRE (Fig. 4a). The high frequency
ground with silicon carbide abraded papers of different grades capacitive loop could be attributed to double layer capacitance in
(# 120–800) followed by polishing with a cloth using 1 mm diamond parallel with the Rct but the phenomenon of the LF inductive loop

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Fig. 2. OCP plots for mild steel in (a) 1 M HCl and (b) 0.5 M H2SO4 in the absence and presence of different concentration of WMRE.

have been reported by several authors in the literature and indicated that WMR majorly contain citrulline (Fig. 1) in addition
recently by Umoren et al. [37] to be probably originated from the to alkaloids, saponnins, tannins, flavonoids and polyphenols. The
adsorption relaxation of intermediates such as H+ads and SO42–. The adsorption of these compounds through heteroatoms (N, O) and
inductive loop could also be as a result of the re-dissolution of the aromatic ring onto the mild steel surface create barrier for mass
passivated surface at the LF region [38]. The electrochemical and charge transfer thus isolating the metal from attack of the
parameters and inhibition efficiency from the impedance mea- corrosive ions present in the solution.
surements for mild steel in HCl and H2SO4 in the absence and The inhibition efficiency (Eimp) for the impedance data was
presence of WMRE are listed in Tables 1 and 2, respectively. The estimated by comparing the charge transfer resistances (Rct) in the
results in the table show that inhibition efficiency increased with absence and presence of WMRE as follows.
increase in concentration of the extract reaching the maximum
Rct  R ct
values of 83.35% and 77.34% at extract concentration of 1.5 g/L and Eim p ¼  100 (1)
Rct
2.0 g/L in HCl and H2SO4, respectively. The corrosion inhibition
effect could be attributed to the adsorption of some components of where Rct and R8ct are the charge transfer resistance values in the
the extract onto the mild steel surface. Literature reports [30,31] presence and absence of WMRE, respectively.

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Fig. 4. EIS plots for mild steel in 0.5 M H2SO4 in the absence and presence of different
Fig. 3. EIS plots for mild steel in 1 M HCl in the absence and presence of different concentration of WMRE exemplified as: (a) Nyquist, (b) bode modulus and (c) bode
concentration of WMRE exemplified as: (a) Nyquist, (b) bode modulus and (c) bode phase angle plots.
phase angle plots.

The transfer function with a simple Faradiac reaction without independent of frequency and characterized by a phase angle
diffusion in terms of CPE had been expressed to show the maxima smaller than 908 [39].
proportionality factor (Y) as it deviated from the ideal capacitance In a surface time constant distribution when n < 1, Brug et al.
by n < 1. The cause of CPE behavior in a blocking electrode is [40] formula have been developed using numerical simulation for

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CPE 4.3. Potentiodynamic polarization (PDP) measurements


(a)
PDP curves for mild steel samples in the presence and absence
of WMRE in 1 M HCl and 0.5 M H2SO4 are shown in Fig. 6a and b,
respectively. The anodic and cathodic polarization curves for the
Rs WMRE in HCl medium exhibited a well-defined Tafel regions
(Fig. 6a) while the anodic region of the H2SO4 are not distinct
(Fig. 6b). This behavior is attributed to the formation of non-
Rct passive film from the corrosion product or the impurities in the
mild steel [2]. The electrochemical parameters such as corrosion
potential (Ecorr), corrosion rate (Crate), corrosion current density
(b) CPE (Icorr), anodic Tafel slopes (ba) and cathodic Tafel slopes (bc)
extrapolated from the curves in both media are given in Table 3.
Results in the table for both media indicate that the Icorr decreases
in the presence of WMRE when compared with blank acid
solutions. Further inspection of the table revealed that Icorr
Rct
Rs decreased as the concentration of WMRE increased up to 1.5 g/L
and thereafter, slightly increased as the concentration was
increased to 2.0 g/L. It could also be observed from the table that
RL there is no significant change in the Ecorr values in the presence
L
and absence of the extract. This shows that the inhibition of mild
Fig. 5. Equivalent circuit for the EIS data fittings: (a) WMRE in 1 M HCl and (b) steel corrosion by WMRE occurred by the geometric blocking
WMRE in 0.5 M H2SO4. effect mechanism [44] hence WMRE can be regarded as a mixed-
type inhibitor. The inhibition efficiency (Epdp) estimated from the
values of corrosion current density (Icorr) in the presence and in
the influence of geometry induced current distribution [41] to the absence (I8corr) of the inhibitor using Eq. (7) are listed in
Eq. (2) and proven to be a more accurate way to determine effective Table 3.
capacitance (Ceff) in a CPE behavior impedance. 
Icorr  Icorr
E pd p ¼   100 (7)
ð1nÞ=n Icorr
C e f f ¼ Y 1=n Rs (2)
It is seen in the table that inhibition efficiency increases with
The values of effective capacitance obtained by utilizing the increase in concentration of WMRE in both acid media reaching
impedance parameters (Rs and Yo) in both acidic media are in the maximum values of 80.71 and 79.90% at the extract concentration
range of double layer capacitance. The double layer capacitance Cdl, of 1.5 g/L and 2.0 g/L in HCl and H2SO4, respectively. The results are
values (Tables 1 and 2) obtained at the maximum frequency (fmax) in close agreement with the ones obtained from EIS measurements.
of the imaginary component of the impedance was observed to
decrease with the introduction of the extract into the acidic media. 4.4. Linear polarization resistance (LPR) measurements
The decrease in Cdl resulted from the increase in double layer
thickness that will lead to decrease in dielectric constant as a result Fig. 7 shows linear polarization resistance plots for mild steel in
of adsorption of extract (organic matter) on to the surface of the the absence and presence of different concentrations of WMRE in
mild steel by displacing the adsorbed water molecule [42], thereby (a) 1 M HCl and (b) 0.5 M H2SO4 solutions. The slope of the
protected it from acid attack. This behavior is in conformity with potential (E) versus current density (i) curve measured at the
the mathematical expression of Helmholtz model [43] that relates corrosion potential (Ecorr) was used to estimate the polarization
the dielectric constant of the medium (e), vacuum permittivity (e0), resistance (Rp) values obtained from the LPR measurement. The
exposed area (A) and the thickness of the protective layer (d). inhibition efficiency (Elpr) estimated by comparing the Rp values

Table 1
EIS data of mild steel in 1 M HCl in the absence and presence of different concentrations of WMRE.

WMRE (g/L) Rs (V cm2) Rct (V cm2) Yo (mV Sn cm2) Ceff (mF cm2) Cdl (mF cm2) n u Eimp (%) x2  104
1 M HCl 4.13 73.14 154.60 68.30 87.19 0.90 – – 0.24
0.10 5.02 179.70 89.43 38.00 55.85 0.89 0.59 59.30 10.51
0.50 5.06 253.20 94.14 40.30 50.85 0.87 0.71 71.11 5.74
1.00 6.63 339.90 78.92 34.10 47.10 0.86 0.78 78.48 9.66
1.50 3.56 439.30 97.50 40.30 57.26 0.87 0.83 83.35 5.00
2.00 4.23 439.20 94.89 39.90 57.28 0.87 0.83 83.35 3.54

Table 2
EIS data of mild steel in 0.5 M H2SO4 in the absence and presence of different concentrations of WMRE.

WMRE (g/L) Rs (V cm2) Rct (V cm2) L (V m2) RL (V cm2) Yo (mV Sn cm2) Ceff (mF cm2) Cdl (mF cm2) n u Eimp (%) x2  104
0.5 M H2SO4 4.67 50.91 – – 148.80 66.10 98.60 0.92 – – 1.41
0.10 5.23 67.61 4.94 604.10 148.90 67.80 74.14 0.89 0.25 24.70 1.78
0.50 5.34 135.70 1707.0 1870.0 116.80 51.50 58.99 0.88 0.62 62.48 2.04
1.00 4.98 137.80 560.60 1482 145.30 65.10 72.84 0.87 0.63 63.05 1.76
1.50 4.86 195.30 4229.0 0.049 119.20 52.10 81.98 0.89 0.74 73.93 1.97
2.00 4.93 224.70 1810.0 3530 113.40 49.40 57.06 0.88 0.77 77.34 2.53

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the extract increases in the H2SO4 medium. However, the Rp values


increases up to 1.5 g/L in the HCl medium and thereafter decreases
to confirm its optimum concentration in the medium.
Comparison of the inhibition efficiencies from EIS, PDP and LPR
techniques shown in Fig. 8 show that 1.5 g/L of the inhibitor
(WMRE) was the optimum concentration in all the electrochemical
methods. The values obtained from all the techniques were in close
agreement in both the HCl and H2SO4 environments.
Results obtained in the present work shows that WMRE is a
better corrosion inhibitor in HCl than H2SO4 solution. Reports in
the literature on the comparative studies of corrosion inhibition of
organic species in HCl and H2SO4 solutions indicate that the
inhibiting effect of organic species in HCl is much higher than that
in H2SO4 acid solutions [45–48]. This observation has been
attributed to the influence of chloride and sulphate anions. It
has been suggested that chloride ions being less hydrated than
sulphate ions has a stronger tendency to adsorb on the metal
surface than do sulphate ions thereby creating an excess negative
charge toward the solution phase, which favors synergistic
adsorption of the organic species on the metal surface [46]. This
may be the reason for an increased protective effect in the HCl
solution.

4.5. Adsorption isotherm

The EIS experimental data was utilized to obtain useful


information on the nature of adsorption of WMRE on the mild
steel surface via adsorption isotherms. Langmuir isotherm which is
derived for a monolayer adsorption without the consideration of
interactions between the adsorbed species was first considered.
Fig. 9 (a) shows the plot of the ratio of surface coverage (u) and
extracts concentration (Cinh) against the WMRE concentration. A
straight line graphs were obtained with a correlation coefficient
(R2) of 0.9987 and 0.9925 in HCl and H2SO4, respectively, but the
slopes were greater than unity. The deviation of the slopes from
unity indicates that there are interactions between the adsorbed
species in both media. Langmuir isotherm is characterized by:

Fig. 6. PDP curves for mild steel in 1 M HCl in the absence and presence of different C inh 1
concentration of WMRE: (a) 1 M HCl and (b) 0.5 M H2SO4. ¼ þ C inh (9)
u K ads

obtained in the presence and absence of WMRE using Eq. (8) is where u is the surface coverage, Cinh is the concentration and Kads is
given in Table 4. the equilibrium constant of the adsorption process. Kads is also
related to the standard Gibbs energy (DG8ads) of adsorption by the
R p  R p equation:
El pr ¼  100 (8)
Rp
DGads ¼ RT lnð55:5  KÞ (10)
where Rp and R8p represent the polarization resistance in the
presence and absence of WMRE, respectively. It can be observed where R is the molar gas constant, T is the absolute temperature in
from the table that the Rp values increases as the concentration of Kelvin and 55.5 as the concentration of water in mol dm3.

Table 3
PDP data of mild steel in 1 M HCl and 0.5 M H2SO4 in the absence and presence of different concentrations of WMRE.

Medium WMRE (g/L) Ecorr (mV/SCE) Icorr (mA cm2) ba (mV dec1) bc (mV dec1) Crate (mpy) Epdp (%)

HCl 1 M HCl 487.60 226.00 97.05 125.00 131.50 –


0.1 503.60 106.70 114.30 109.70 62.07 52.79
0.5 508.50 68.01 121.60 115.10 39.56 69.91
1.0 509.80 63.77 135.70 121.50 37.10 71.78
1.5 498.20 43.59 128.70 108.20 25.36 80.71
2.0 504.40 45.51 120.30 109.00 26.47 79.86

H2SO4 0.5 M H2SO4 491.60 360.60 77.93 134.50 209.80 –


0.1 489.10 347.90 77.91 145.80 202.40 3.52
0.5 484.20 142.00 63.41 129.50 82.58 60.62
1.0 477.90 98.35 55.54 126.60 57.21 72.73
1.5 467.00 88.08 48.54 128.60 51.24 75.57
2.0 473.30 72.51 53.39 123.10 42.18 79.90

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(a) 90
EIS
80

Inhibition efficiency (%)


PDP
70
LPR
60

50

40

30

20

10

0
0.10 0.50 1.00 1.50 2.00
Extract Concentration (g/L)

(b) 90

80 EIS

Inhibition Efficiency (%)


70 PDP
60 LPR
50

40

30

20

10

0
0.10 0.50 1.00 1.50 2.00
Extract Concentration (g/L)

Fig. 8. Bar chart for the comparison of the inhibition efficiencies for the three
electrochemical techniques: (a) 1 M HCl and (b) 0.5 M H2SO4.

where ‘‘a’’ is the lateral interaction term and K is the adsorption–


Fig. 7. LPR plots for mild steel in (a) 1 M HCl and (b) 0.5 M H2SO4 in the absence and desorption equilibrium constant. A linear plot with R2 of 0.9872
presence of different concentration of WMRE.
and 0.9545 for mild steel in 1 M HCl and 0.5 M H2SO4 in the
presence of WMRE were obtained from the Temkin plot (u vs ln C)
Temkin adsorption isotherm model was tested to account for as shown in Fig. 9(b). The adsorption parameters such as Kads, DGads
the observed interactions between the adsorbed species from and ‘‘a’’ values derived from Temkin isotherm plot are presented in
Langmuir isotherm model. It is given by the equation: Table 5. The larger the value of K, the better the inhibitor efficiency
[2]. The higher values of K in HCl medium indicate stronger
1 1 adsorption of WMRE in HCl than H2SO4 solution. The existence of
u¼ ln K þ ln C inh (11)
2a 2a lateral forces of attraction between the adsorbent molecule in the
adsorption layer was revealed by the positive values of ‘‘a’’ [49].
Table 4
Also, the spontaneity and the stability of the adsorption process are
LPR data of mild steel in 1 M HCl and 0.5 M H2SO4 in the absence and presence of
different concentrations of WMRE. deduced from the negative values of DG8ads. The values of DGads in
both media lies between 10.69 and 15.92 kJ mol1, which
Medium WMRE (g/L) Rp (V cm2) Elpr (%)
indicates that the WMRE is physically adsorbed on the mild steel
HCl 1 M HCl 75.95 – surface. Generally, the values of DG8ads of up to 20 kJ mol1 are
0.1 156.90 51.70 consistent with electrostatic interaction between charged inhibi-
0.5 287.00 73.54
tor molecules and the mild steel surface (physical adsorption) and
1.0 363.70 79.12
1.5 428.20 82.26 those more than 40 kJ mol1 involves charge sharing or transfer
2.0 403.00 81.15 from the inhibitor molecule to mild steel surface to form a
H2SO4 0.5 M H2SO4 58.16 –
coordinate bond (chemisorption) [50,51].
0.1 69.75 16.62
0.5 144.40 59.72 4.6. Morphological study
1.0 144.50 59.75
1.5 182.80 68.18
The surface analysis of the mild steel was done after exposure to
2.0 219.20 73.47
1 M HCl and 0.5 M H2SO4 solutions in the absence and presence of

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(a) 3.00 Table 5


Adsorption isotherms for WMRE in 1 M HCl and 0.5 M H2SO4 on mild steel.

2.50 Isotherms Medium Slope R2 Kads DG8ads a

Langmuir HCl 1.1564 0.9987 11.22 15.92 –


2.00 H2SO4 1.1633 0.9925 3.41 12.97 –

Temkin HCl – 0.9872 2.23 11.92 5.92


1.50
H2SO4 – 0.9545 1.36 10.69 2.92
C/

HCl
1.00
H2SO4

0.50
2.0 g/L concentration of WMRE for 24 h at 25 8C. The results
indicated that the surface of the mild steel were severely damaged
0.00
0.00 0.50 1.00 1.50 2.00 2.50
as shown in Fig. 10a andb due to the roughness of the surface as
reveal by SEM when the mild steel was immersed in HCl and
C (g/L) H2SO4, respectively, without WMRE. The corrosion was relatively
uniform with no evidence of localized attack. However, in the
0.90
(b) presence of WMRE, the SEM images revealed a reduced surface
0.80 roughness compared with the acidic media. The corrosion
0.70 inhibition effects observed in Fig. 10c and d in the presence of
WMRE in HCl and H2SO4, respectively, on the mild steel was due to
0.60
the formation of a protective film.
0.50

0.40 5. Conclusions
HCl
0.30 H2SO4
Based on the experimental results, the following conclusions
0.20
can be drawn from the study:
0.10

0.00 (1) WMRE inhibits corrosion of mild steel in 1 M HCl and 0.5 M
-2.50 -2.00 -1.50 -1.00 -0.50 0.00 0.50 1.00 H2SO4 solution at 25 8C. The corrosion inhibition was found to
be concentration dependent with an optimum concentration of
In C
1.5 g/L in 1 M HCl medium.
Fig. 9. Adsorption isotherms for WMRE in 1 M HCl and 0.5 M H2SO4 on mild steel: (2) WMRE was found to be more effective toward corrosion
(a) Langmuir isotherm and (b) Temkin isotherm. protection in the 1 M HCl medium than in 0.5 M H2SO4.

Fig. 10. SEM images of mild steel exposed in 1 M HCl and 0.5 M H2SO4 in the absence and presence of WMRE for 24 h at room temperature: (a) 1 M HCl, (b) 0.5 M H2SO4, (c)
1 M HCl with 2.0 g/L WMRE and (d) 0.5 M H2SO4 with 2.0 g/L WMRE.

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(3) The values of effective capacitance obtained by utilizing the Rs [20] J.R. Vimala, S. Raja, Research Journal of Chemistry and Environment 17 (2013)
84–91.
and Yo for both acidic media are between 20 and 70 mF cm2 [21] G. Chen, M. Zhang, M. Pang, X.Q. Hou, H. Su, J. Zhang, Research on Chemical
which are in the range of double layer capacitance. Intermediates 39 (2013) 3545–3552.
(4) PDP results indicate a mixed inhibitor effect of WMRE affecting [22] N.L. Patel, S. Jauhariand, G.N. Mehta, S.S. Al-Deyab, I. Warad, B. Hammouti,
International Journal of Electrochemical Science 8 (2013) 2635–2655.
both the anodic dissolution of mild steel and cathodic hydrogen [23] I.B. Obot, Z.M. Gasem, S.A. Umoren, International Journal of Electrochemical
evolution. Science 9 (2014) 510–522.
(5) WMRE was found to be physically adsorbed on the mild steel [24] I.E. Uwah, P.C. Okafor, V.E. Ebiekpe, Arabian Journal of Chemistry 6 (2013) 285–
293.
surface in both acid media following Temkin adsorption [25] P.C. Okafor, M.E. Ikpi, U.I. Ekanem, E. Ebenso, International Journal of Electro-
isotherm model. chemical Science 8 (2013) 12278–12286.
[26] E. Chebouat, B. Dadamoussa, N. Gherraf, M. Gouamid, M. Allaoui, A. Cheriti, A.
Khiari, International Journal of Electrochemical Science 8 (2013) 12147–12153.
Acknowledgments [27] C.O. Akalezi, C.K. Enenebaku, E.E. Oguzie, Journal of Materials and Environmental
Science 4 (2013) 217–226.
[28] J. Ahmed, Indian Food Packer 50 (1996) 15–20.
The support of the Center of Research Excellence in Corrosion, [29] S.S. Hour, E.M. Ahmed, R.D. Carter, Journal of Food Science 45 (1980) 718–719.
King Fahd University of Petroleum and Minerals is gratefully [30] J. Johnson, E. Iwang, J. Hemen, M. Odey, E. Efiong, O. Eteng, Annals of Biological
Research 3 (2012) 5145–5150.
acknowledged. [31] A.M. Rimando, P.M. Perkins-Veazie, Journal of Chromatography A 1078 (2005)
196–200.
[32] A. Petchiammal, P. Deepa Rani, S. Selvaraj, K. Kalirajan, Research Journal of
References Chemical Sciences 2231 (2012) 606X.
[33] B. Beverskog, M. Bojinov, A. Englund, P. Kinnunen, T. Laitinen, K. Mäkelä, T. Saario,
[1] W. Guo, S. Chen, Y. Feng, C. Yang, Journal of Physical Chemistry C 111 (2007) P. Sirkiä, Corrosion Science 44 (2002) 1901–1921.
3109–3115. [34] R.M. Carranza, M.G. Alvarez, Corrosion Science 38 (1996) 909–925.
[2] M.A. Amin, M.M. Ibrahim, Corrosion Science 53 (2011) 873–885. [35] L.A.S. Ries, M. Da Cunha Belo, M.G.S. Ferreira, I.L. Muller, Corrosion Science 50
[3] S. Banerjee, V. Srivastava, M.M. Singh, Corrosion Science 59 (2012) 35–41. (2008) 968–977.
[4] P.G. Cao, J.L. Yao, J.W. Zheng, R.A. Gu, Z.Q. Tian, Langmuir 18 (2002) 100–104. [36] T.K. Rout, Corrosion Science 49 (2007) 794–817.
[5] N. Hackerman, Langmuir 3 (1987) 922–924. [37] S.A. Umoren, Z.M. Gasem, I.B. Obot, Industrial and Engineering Chemistry Re-
[6] I. Radojčić, K. Berković, S. Kovač, J. Vorkapić-Furač, Corrosion Science 50 (2008) search 52 (2013) 14855–14865.
1498–1504. [38] E.M. Sherif, S.M. Park, Electrochimica Acta 51 (2006) 1313–1321.
[7] A.Y. El-Etre, Corrosion Science 40 (1998) 1845–1850. [39] B. Hirschorn, M.E. Orazem, B. Tribollet, V. Vivier, I. Frateur, M. Musiani, Electro-
[8] E.E. Oguzie, Corrosion Science 50 (2008) 2993–2998. chimica Acta 55 (2010) 6218–6227.
[9] O.K. Abiola, J.O.E. Otaigbe, O.J. Kio, Corrosion Science 51 (2009) 1879–1881. [40] G.J. Brug, A.L.G. Van Den Eeden, M. Sluyters-Rehbach, J.H. Sluyters, Journal of
[10] S. Leelavathi, R. Rajalakshmi, Journal of Materials and Environmental Science 4 Electroanalytical Chemistry 176 (1984) 275–295.
(2013) 625–638. [41] V.M.W. Huang, V. Vivier, M.E. Orazem, N. Pébère, B. Tribollet, Journal of the
[11] P.B. Raja, M. Fadaeinasab, A.K. Qureshi, A.A. Rahim, H. Osman, M. Litaudon, K. Electrochemical Society 154 (2007) C81–C88.
Awang, Industrial and Engineering Chemistry Research 52 (2013) 10582–10593. [42] E.E. Oguzie, K.L. Oguzie, C.O. Akalezi, I.O. Udeze, J.N. Ogbulie, V.O. Njoku, ACS
[12] P.R. Vijayalakshmi, R. Rajalakshmi, Inhibition of mild steel corrosion using Sustainable Chemistry and Engineering 1 (2013) 214–225.
aqueous extract of Cocos nucifera L. Peduncle in acidic solutions and their [43] K.F. Khaled, M.M. Al-Qahtani, Materials Chemistry and Physics 113 (2009) 150–
adsorption characteristics, 2013. 158.
[13] Ramananda M. Singh, Journal of Materials and Environmental Science 4 (2013) [44] X. Li, S. Deng, H. Fu, G. Mu, Corrosion Science 51 (2009) 620–634.
117–126. [45] T. Vasudevan, S. Muralidharan, S. Alwarappan, S.V.K. Iyer, Corrosion Science 37
[14] A. Singh, A. Kumar, T. Pramanik, Oriental Journal of Chemistry 29 (2013) 277–283. (1995) 1235–1244.
[15] A.I. Ikeuba, P.C. Okafor, U.J. Ekpe, E.E. Ebenso, International Journal of Electro- [46] E.A. Noor, International Journal of Electrochemical Science 2 (2007) 996–1017.
chemical Science 8 (2013) 7455–7467. [47] L. Elkadi, B. Mernari, M. Traisnel, F. Bentiss, M. Lagrenée, Corrosion Science 42
[16] O. Benali, H. Benmehdi, O. Hasnaoui, C. Selles, R. Salghi, Journal of Materials and (2000) 703–719.
Environmental Science 4 (2013) 127–138. [48] M.A. Quraishi, D. Jamal, Materials Chemistry and Physics 78 (2003) 608–613.
[17] A.S. Yaro, A.A. Khadom, R.K. Wael, Alexandria Engineering Journal 52 (2013) 129– [49] J.O.M. Bockris, S.U.M. Khan, Surface Electrochemistry: A Molecular Level
135. Approach (1993).
[18] L. Afia, R. Salghi, A. Zarrouk, H. Zarrok, E.H. Bazzi, B. Hammouti, M. Zougagh, [50] R.A. Alberty, R.J. Silbey, Physical Chemistry (1997).
Transactions of the Indian Institute of Metals 66 (2013) 43–49. [51] F.W. Schapink, M. Oudeman, K.W. Leu, J.N. Helle, Transactions of the Faraday
[19] K.S. Beenakumari, Journal of Industrial Pollution Control 29 (2013) 213–218. Society 56 (1960) 415–423.

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