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Journal of Environmental Chemical Engineering 3 (2015) 286–296

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering


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

Watermelon waste products as green corrosion inhibitors for mild steel


in HCl solution
N.A. Odewunmi * , S.A. Umoren, Z.M. Gasem
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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

Article history: Three agro-waste products namely; watermelon rind extract (WMRE), watermelon seed extract (WMSE)
Received 19 June 2014 and watermelon peel extract (WMPE) were investigated for their corrosion inhibition potentials for mild
Accepted 19 October 2014 steel in HCl solution using electrochemical techniques at 25  C. All the extracts inhibited acid-induced
Available online 22 October 2014
corrosion of mild steel in the order WMSE > WMRE > WMPE. Corrosion inhibition effect was found to be
dependent on extracts’ concentrations. Inhibitive action of the extracts could be attributed to adsorption
Keywords: of the extracts’ components on mild steel surface by physisorption mechanism according to Langmuir
Watermelon
adsorption isotherm model and functions as mixed-typed inhibitors as revealed by potentiodynamic
Waste products
Mild steel
polarization studies.
Corrosion inhibition ã 2014 Elsevier Ltd. All rights reserved.
Acid corrosion

Introduction corrosion inhibition are scanty. For instance Noor [27] studied the
effect of aqueous extract of Fenugreek leaf (AEFL) and seed (AEFS)
The importance of mild steel cannot be under estimated in the on the corrosion of mild steel in HCl and H2SO4 solutions. Results
constructions and chemical industries based on their cost obtained showed that the seed extract was more potent than the
effectiveness and tremendous mechanical properties. Despite leaf extract in mitigating mild steel corrosion. This was attributed
the availability of mild steel, its poor corrosion resistance in acidic to the high concentration of the phytochemical constituents in the
media has been a major challenge to its application [1–3]. seed than in the leaf part of the plant. Similarly, Okafor et al. [28]
However, the use of corrosion inhibitors had been reported to reported on the inhibitive action of leaves (LV), seeds (SD) and a
be an efficient way of controlling its corrosion processes [4,5]. combination of leaves and seeds (LVSD) extracts of Phyllanthus
Most of the inhibitors used in the industries compose of amarus on mild steel corrosion in HCl and H2SO4 solutions by
some compounds that are toxic and have been presently facing hydrogen evolution and gravimetric methods. Inhibition efficien-
a lot of criticisms due to their threat to human and their cies were found to follow the trend LV > LVSD > SD. Corrosion
environments. Consequently, the use of natural products as inhibition of mild steel in 1 M H2SO4 by leaves and stem extracts of
corrosion inhibitors is in the fore front in the current trend of Sida acuta at different temperatures has been reported [29]. The
corrosion inhibition studies. The advocacy on the use of natural leaves extract was found to be a better inhibitor than the stem
products as corrosion inhibitors stemmed from the facts that extract.
they are cheap, renewable, readily available, ecologically There are few reports in the literature on the use of watermelon
acceptable and environmentally friendly. More so can be parts for corrosion protection. For example, the protection of zinc
obtained by simple extraction procedures. Corrosion inhibition in natural seawater by watermelon peel (WMP) [30] and mild steel
of metals and alloys using plant extracts as green inhibitors has by watermelon leaf [31] based on weight loss corrosion monitoring
been reported by many researchers [6–26]. technique have been reported. Previous reports had no informa-
Reports in the literature on the use of plant extracts as corrosion tion on the kinetics of the anodic and cathodic reactions of the
inhibitors are focused largely on single plant part (leaves, stems, corrosion phenomenon and how these were modified by the
barks, roots, fruits etc.). However, comparative studies on addition of the extracts of the watermelon waste products. Earlier,
utilization of extracts of various parts of a particular plant for we have reported on the corrosion inhibition effect of watermelon
rind extract (WMRE) for mild steel in HCl and H2SO4 solutions
using electrochemical techniques [32]. In an attempt to extend the
* [19_TD$IF]Corresponding author. Tel.: +966 13 860 7895; fax: +966 13 860 [20_TD$IF]3996. investigation to other watermelon waste products, the present
E-mail address: adewalen@kfupm.edu.sa (N.A. Odewunmi). paper reports on the corrosion inhibition effect of WMPE and

http://dx.doi.org/10.1016/j.jece.2014.10.014
2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.
[(Fig._2)TD$IG]
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 287
[(Fig._1)TD$IG]

Fig. 1. Chemical structure of L-citrulline.

WMSE and compares with that of WMRE for mild steel in 1 M HCl
as a corrosive medium at 25  C. UV–vis spectroscopy and
Attenuated Total Reflectance Fourier Transform Infrared
(ATR-FTIR) spectroscopy techniques were also employed to gain
insight into the possible corrosion inhibition mechanism.

Experimental

Materials preparation

The test solution was 1 M HCl prepared from A-R grade 37% HCl
(Sigma–Aldrich). Watermelon (Citrullus lanatus) was purchased in
the local market. The rind, seed and peel were separated from the
edible pulp, cut into pieces, sun dried and ground into powdery
form. Extracts of WMR, WMS and WMP were prepared by
weighing about 5.00 g portion of each watermelon parts in 1 L
of 1 M HCl, heat to boiling and allowed to boil for 10 min. The
solutions were cooled and then filtered with a sintered glass
Buchner funnel no. 36060 to obtain the stock solution. The
difference between the initial weight of the powdered materials
and the weight of the residue gave the amount of materials
extracted into the solution. Different concentrations of the extracts
(0.10–2.00 g/L) were prepared from the stock solution by dilution
with the corrodent (1 M HCl). All solutions were prepared with
double distilled water.
The mild steel chemical composition (weight %) used in the
experiment is: 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 and Fe (balance). The mild steel
was made into coupons of 3 cm  3 cm  0.25 cm dimension,
abraded with silicon carbide abrasive papers of different grades
(# 120–800), and rinsed with distilled water. The residue particles
from the grinding process were removed by sonication in ethanol
bath for 10 min, rinsed with ethanol and dried in warm air, and
then stored in the desiccator prior to use for corrosion measure-
ments.

Electrochemical measurements

A single compartment electrochemical cell designed for


varieties of flat samples for electrochemical test at room
temperature was used to perform the electrochemical measure-
ments. It consists of a three electrode systems; working electrode
(mild steel) with exposed area of 0.7855 cm2, saturated calomel
electrode (SCE) as the reference electrode and graphite rod as the
auxiliary/counter electrode. Gamry Potentiostat/Galvanostat/ZRA
(Reference 3000) instrument integrated with Gamry framework
that composed of ESA410 was used as electrochemical work
station. The work station is embedded with various Gamry
softwares including DC105 for the linear polarization resistance
(LPR) and potentiodynamic polarization (PDP) measurements and
EIS300 for the electrochemical impedance spectroscopy (EIS) Fig. 2. OCP curves for mild steel in 1 M HCl in the presence and absence of different
concentration of extracts; (a) WMRE (b) WMSE and (c) WMPE.
measurements. Electrochem 6.0 software was used for data
analysis.
PDP measurements were made from the cathodic potential of
250 mV to anodic potential of +250 mV with respect to the open
circuit potential (Ecorr) at a sweep rate of 1 mV/s. Polarization an alternative (ac) amplitude of 5 mV r.m.s. (7.07 mV peak-to-peak)
resistance (Rp) was obtained from LPR at a scan rate of 0.125 mV/s signal at Ecorr. The electrochemical measurements were performed
polarized between 20 mV and +20 mV against Ecorr. EIS measure- after the Ecorr attained stable potential at the end of 1800 s without
ment frequencies range was between 100 kHz and 100 mHz with and with WMSE, WMRE and WMPE.
288 N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296

SEM surface morphology efficiency (E) was calculated from the values of corrosion current
density in the absence (Icorr ) and presence (Icorr) of the inhibitors
The mild steel coupon (3 cm  3 cm  0.25 cm) surfaces were using Eq. (1) and the value obtained are listed in Table 1.
ground with silicon carbide paper of different grades (# 120–800)
Icorr  Icorr
and polished to near mirror surface finished with a cloth sprayed E¼  100 (1)
Icorr 
with 1 mm diamond paste. The well surface treated mild steel was
rinsed with double distilled water, sonicated with ethanol bath for
10 min to remove polished residues and then placed in a desiccator.
The coupons were completely immersed in 1 M HCl without and [(Fig._3)TD$IG]
with 2.0 g/L of WMSE, WMRE and WMPE in a glass vessel at 25  C.
They were retrieved after 24 h of exposure, rinsed with distilled
water, dried in warm air and stored in desiccator before submission
for SEM surface examination. The surfaces of the mild steel
samples were examined with a Joel JSM-6610 LV scanning electron
microscope.

UV–vis and ATR-FTIR spectroscopy

UV–vis absorption studies were performed for 1 M HCl solution


in the absence and presence of 2.0 g/L WMRE, WMSE and WMPE
before and after mild steel immersion for 24 h at 25  C. The spectra
were obtained using Jasco UV-670 UV–vis spectrophotometer.
Solid residues obtained from 100 mL stock solutions of WMRE,
WMSE and WMPE by evaporation to dryness at 60  C on Stuart
scientific magnetic stirrer hot plate (UK) were used for the
ATR-FTIR analysis by Fourier transform infrared (Nicolet 6700
FT-IR, Thermo Scientific) spectrophotometer. The FTIR spectrum
ranged from 4000 to 500 cm1 at a resolution of 4 cm1.

Results and discussion

PDP measurements

Prior to all electrochemical measurements, the mild steel


specimens were immersed in 1 M HCl with and without WMRE,
WMSE and WMPE for 1800 s to attain a stable open circuit
potential (OCP). The potential–time curves are presented in
Fig. 2a–c for WMRE, WMSE and WMPE respectively. It could be
observed from the plots that attainment of stable potentials after
1800 s was achieved. The corrosion potentials (Ecorr) are observed
to shift toward positive values on the introduction of the extracts
into the corrosive medium in comparison to the blank solution. The
shifting of the potentials toward a noble direction was also found to
be dependent on the extracts’ concentration that is, shifting more
toward more positive values with increasing concentration. This
could be attributed to the formation of protective film on the
surface of the mild steel electrode as a result of adsorption of the
components of the extracts on the surface.
The curves generated from the PDP measurements for mild
steel dissolution in 1 M HCl in the absence and presence of various
concentrations of WMRE, WMSE and WMPE are shown in Fig. 3.
The curves revealed well-defined anodic and cathodic polarization
Tafel regions. It is observed that the corrosion potentials (Ecorr) for
the mild steel in the presence of WMRE (Fig. 3a), WMSE (Fig. 3b)
and WMPE (Fig. 3c) are slightly shifted toward the negative
potentials compared with the mild steel in 1 M HCl. Both anodic
and cathodic current densities were reduced in the presence of
WMRE, WMSE and WMPE which suggests a mixed-type inhibitor
behavior [33]. Anodic Tafel slopes (ba) and cathodic Tafel slopes
(bc) obtained from the extrapolation of the linear Tafel regions of
the PDP curves for all the extracts investigated are given in Table 1
along with other electrochemical parameters such as corrosion
rate (CR), corrosion current density (Icorr) and corrosion potential
(Ecorr). The Icorr values are found to decrease as the concentration of
the extracts increased except between the 0.50 and 1.00 g/L of Fig. 3. PDP curves for mild steel in 1 M HCl in the presence and absence of different
WMPE where the Icorr values are almost the same. The inhibition concentration of extracts; (a) WMRE (b) WMSE and (c) WMPE.
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 289

Table 1
PDP data of mild steel in 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and WMPE.

Extracts Concentration (g/L) Ecorr (mV/SCE) Icorr (mA/cm2) ba (mV/dec) bc (mV/dec) CR (mpy) E (%)
Blank 1 M HCl 487.60 226.00 97.05 125.00 131.50 –

WMRE 0.10 503.60 106.70 114.30 109.70 62.07 52.79


0.50 508.50 68.01 121.60 115.10 39.56 69.91
1.00 509.80 63.77 135.70 121.50 37.10 71.78
2.00 504.40 45.51 120.30 109.00 26.47 79.86

WMSE 0.10 514.00 81.82 137.90 124.40 47.57 63.80


0.50 517.20 62.61 125.40 116.70 36.42 72.30
1.00 520.80 38.85 123.50 116.10 22.60 82.81
2.00 510.50 36.90 111.70 121.30 21.46 83.67

WMPE 0.10 506.30 67.02 102.90 109.30 38.99 70.35


0.50 519.90 69.52 127.60 130.70 40.44 69.24
1.00 513.00 68.92 114.80 121.90 40.09 69.51
2.00 517.20 62.33 127.50 131.50 36.26 72.42

From Table 1, it is observed that inhibition efficiency Bode modulus plots which also increases as the concentration of
increased with increasing concentration of the three watermel- the extracts increases. The adsorption of some components such as
on waste products extract studied. Also, the order of corrosion tannins, flavonoids, polyphenols, saponnins and citrulline on the
inhibition efficiency for the highest concentration (2.0 g/L) of mild steel surface could be responsible for the corrosion inhibition
the extracts studied is WMSE (83.67%) > WMRE effects of the extracts. It has been reported that watermelon rind
(79.36%) > WMPE (72.42%). and seed contain majorly citrulline in addition to tannins,
flavonoids, polyphenols, saponins [38,39]. The adsorptions of
EIS measurements these compounds through the aromatic ring and the heteroatoms
(N, O) onto the mild steel surface could prevent the attack of
The kinetics of the electrochemical processes and capacitive corrosive ions in the solution by creating a barrier for mass and
behaviors at 1 M HCl/steel interface in the presence and absence charge transfer. Corrosion inhibition efficiency (E) from the
of WMRE, WMSE and WMPE were characterized with EIS impedance spectroscopy measurements were estimated by
measurements. Figs. 4–6 show the (a) Nyquist, (b) Bodes’ comparing the charge transfer resistance with (Rct) and without
modulus and (c) phase angle plots for WMRE, WMSE and (Rct ) WMRE, WMSE and WMPE using the expression given in
WMPE respectively. The shape of the impedance plot remains Eq. (2):
the same in spite of addition of different concentrations of
Rct  Rct 
WMRE, WMSE and WMPE which indicates similar corrosion E¼  100 (2)
Rct
mechanism of the mild steel in HCl medium in the absence and
presence of the extracts. Also the diameter of the semi-circle in
the Nyquist plots increases as the concentration of the extracts The double layer capacitance Cdl, values (Table 2) obtained at
increased. The Bode phase angle plots of all the extracts show the maximum frequency (fmax) of the imaginary component of the
just one relaxation process which correspond to one semi-circle impedance using Eq. (3) was observed to decrease with the
capacitive loop in the Nyquist plots over the range of the introduction of the extract into the acidic medium. This can be
studied frequencies. This behavior is attributed to a time attributed to the displacement of water molecules by the adsorbed
constant in an electrochemical system [34]. It is also observed species of the extracts onto the mild steel surface, as a result lead to
in the phase angle plots that the phase angle maxima of all the decrease in the dielectric constant due to the increase in double
extracts’ concentrations as well as the blank solution are less layer thickness [40], thereby protect the surface of the mild steel
than 90 . The semi-circles of the Nyquist plots are depressed from acid attack.
with the center under the real axis. Many reasons including
1
surface roughness, inhomogeneity in the dielectric material and C dl ¼ : (3)
2pf max Rct
so on have been attributed to such impedance behavior of the
interface as revealed by the Nyquist and Bode phase angle plots
[35]. A constant phase element (CPE) should be introduced to The reduction in the Cdl value as the double layer thickness
replace a true capacitor in the equivalent circuit to account for increases can also be linked to the Helmholtz model (Eq. (4)).
these effects in order to estimate the impedance parameters
ee0 A
[36,37]. The enumerated characteristics of the EIS plots for mild C dl ¼ (4)
d
steel electrode in 1 M HCl with and without WMRE, WMSE and
WMPE, lead to the consideration of the equivalent circuit where the dielectric constant of the medium is e, vacuum
shown in Fig. 7 to fit the EIS experimental data to generate the permittivity is e0,A is the exposed area of the electrode and d is
impedance parameters of interest listed in Table 2. the thickness of the protective layer. The corrosion inhibition
The intercept of the semi-circle in the low and high frequency efficiency of 83.35%, 85.96% and 79.52% are obtainable for
region on the real impedance axis were assigned to the charge WMRE, WMSE and WMPE respectively which follow the trend
transfer resistance (Rct) and solution resistance (Rs) respectively. (WMSE > WMRE > WMPE) obtained in the PDP results.
The corrosion inhibition effectiveness of WMRE, WMSE and WMPE The same order of corrosion inhibition efficiency was observed
can also be interpreted in the real impedance values axis of the in the LPR experiment where the polarization resistance (Rp) using
290 N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296
[(Fig._4)TD$IG] [(Fig._5)TD$IG]

Fig. 4. Impedance plots for mild steel in 1 M HCl in the presence and absence of Fig. 5. Impedance plots for mild steel in 1 M HCl in the presence and absence of
different concentrations of WMRE; (a) Nyquist, (b) Bode modulus and (c) Bode different concentrations of WMSE; (a) Nyquist, (b) Bode modulus and (c) Bode
phase angle. phase angle.

Eq. (5) was utilized to estimate the data shown in Table 3. where Rp and Rp  represent the polarization resistance in the
presence and absence of WMRE, WMSE and WMPE respectively.
Rp  Rp 
E¼  100 (5) The Rp increases as the concentration of the extracts increases in
Rp
the same way as the other electrochemical measurements
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 291
[(Fig._6)TD$IG]
observed trend is not clear, the differences in the phytochemical
composition and the amount of the materials extracted into the
solution may not be ruled out.

Adsorption isotherm

Assuming direct relationship between surface coverage (u ) and


inhibition efficiency (E) as u = E/100, the degree of surface coverage
(u) values estimated from the EIS data were used to determine the
adsorption isotherm model by which the adsorption of WMRE,
WMSE and WMPE on the mild steel surface followed. Langmuir
adsorption isotherm characterized by Eq. (6) was found to be the
best fit from all the tested isotherms. The value of correlation
coefficient (R2) was used as a gauge to determine the best fit
adsorption isotherm.
C inh 1
¼ þ C inh (6)
u K ads
where (Cinh) is the extract concentration, u is the degree of
surface coverage and Kads is the equilibrium constant of
adsorption–desorption process. Fig. 8 shows the Langmuir
isotherm plot as (Cinh) against Cinh/u. Good straight lines graphs
were obtained. The correlation coefficients (R2) of 0.9983,
0.9988 and 0.9973 for WMRE, WMSE and WMPE respectively
and other adsorption parameters derived from the Langmuir
isotherm plot are listed in Table 5.
Langmuir isotherm postulates monolayer adsorption of adsor-
bate (inhibitor) on the adsorbent (metal surface) and does not
account for interactions between the adsorbed species. The
deviation of the slopes (Table 5) from unity shows that there is
interaction between adsorbed species on the metal surface. This is
not surprising given the fact that plant extracts are comprised of
many organic compounds that may adsorbed differently on the
metal surface. Such adsorbed species may interact by mutual
repulsion or attraction. It is also possible that some components of
the extracts can be adsorbed on the anodic and cathodic sites
resulting in deviation from unit gradient.
The equilibrium constant for the adsorption–desorption
process (Kads) shown in Table 5 was estimated from the intercept
of the Langmuir isotherm plot and used to compute the standard

Gibbs free energy (DGads ) of the adsorption process based on the
relationship given in Eq. (7):
DGads ¼ RTlnð55:5  K ads Þ (7)
where R is the molar gas constant, T is the absolute temperature
and 55.5 is the concentration of water expressed in mol/dm3. It can

be seen in Table 5 that the DGads values of WMRE, WMSE and
WMPE are all negative which indicates the stability and
spontaneity of the adsorption process. These values which are

[(Fig._7)TD$IG]

Fig. 6. Impedance plots for mild steel in 1 M HCl in the presence and absence of
different concentrations of WMPE; (a) Nyquist, (b) Bode modulus and (c) Bode
phase angle.

(EIS and PDP). Table 4 highlights the comparison of the efficiencies


of the extracts from the three electrochemical techniques. The data
in the table revealed the order of corrosion inhibition effect of the
extracts to be WMSE > WMRE > WMPE. Although the reason for the Fig. 7. Equivalent circuit for the EIS data fittings.
292 N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296

Table 2
EIS data of mild steel in 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and WMPE.

Extracts Concentration (g/L) Rs (V/cm2) Rct (V/cm2) Yo (mV Sn/cm2) Ceff (mF/cm2) Cdl (mF/cm2) n u E (%) x2  104
Blank 1 M HCl 4.13 73.14 154.60 58.32 87.19 0.90 – – 0.24

WMRE 0.10 5.02 179.70 89.43 28.30 55.85 0.89 0.59 59.30 10.51
0.50 5.06 253.20 94.14 26.60 50.85 0.87 0.71 71.11 5.74
1.00 6.63 339.90 78.92 17.00 47.10 0.86 0.78 78.48 9.66
2.00 4.23 439.20 94.89 23.80 57.28 0.87 0.83 83.35 3.54

WMSE 0.10 6.17 272.50 96.98 19.00 47.10 0.85 0.73 73.16 8.65
0.50 4.08 306.90 99.00 17.10 52.20 0.84 0.76 76.17 3.84
1.00 5.88 433.20 79.66 11.50 37.00 0.83 0.83 83.12 6.33
2.00 9.15 520.80 78.30 11.30 38.40 0.83 0.86 85.96 2.78

WMPE 0.10 3.94 201.10 133.90 31.35 63.80 0.86 0.64 63.63 2.84
0.50 13.37 289.60 81.45 13.55 44.30 0.84 0.75 74.74 6.84
1.00 4.50 273.90 102.80 20.33 46.80 0.85 0.73 73.30 6.60
2.00 14.49 357.10 79.59 15.04 44.80 0.85 0.80 79.52 6.75

Table 3 UV–vis and ATR-FTIR spectroscopy


LPR data of mild steel in 1 M HCl in the absence and presence of different
concentrations of WMRE, WMSE and WMPE.
Iron (Fe) is a major component of mild steel and the mechanism
Extracts Concentration (g/L) Rp (V/cm2) E (%) of corrosion inhibition of mild steel can be studied by the
Blank 1 M HCl 75.95 – complexation reaction of Fe ions and the active corrosion
inhibiting species. UV–vis spectra (Fig. 9) confirmed the presence
WMRE 0.10 156.90 51.70 of Fe ions with an absorption peak around 340 nm in 1 M HCl
0.50 287.00 73.54
solution after 24 h immersion of mild steel sample without the
1.00 363.70 79.12
2.00 403.00 81.15 extracts. However, it was observed that the peak disappeared in
the presence of WMRE, WMSE and WMPE (Fig. 9a–c). The
WMSE 0.10 270.60 71.93 disappearance of the peak indicated that Fe ions in the solution
0.50 297.20 74.44 are not detectable. The protective film formed on the surface of
1.00 432.00 82.42
2.00 545.70 86.08
mild steel might tremendously reduce the amount of Fe ions
passed into solution, probably due to the formation of a complex
WMPE 0.10 260.90 70.89 reaction product with the extracts species that function as
0.50 301.90 74.84 corrosion inhibitor.
1.00 296.70 74.47
ATR-FTIR analysis was utilized to confirm the presence of some
2.00 344.40 77.95
functional groups of the active corrosion inhibitor components
such as citrulline present in WMRE, WMSE and WMPE. The spectra
of these extracts are presented in Fig. 10. A broad peak at about
3400 cm1 which could be assigned to a carboxylic acid O—H
all less than 20 kJ/mol are consistent with physisorption of the stretch was observed in all the extracts with a less intensity in the
components of the extracts on the mild steel surface arising from WMRE. Two weak to medium peaks around 2800 cm1 and a small
electrostatic interaction between charged molecules and a charged sharp peak at about 1680 cm1 were also observed in all the
metal surface [41,42]. extracts which is assigned to amine (secondary and primary) N—H

Table 4
Comparison of inhibition efficiency of the electrochemical techniques data of mild steel 1 M HCl in the absence and presence of different concentrations of WMRE, WMSE and
WMPE.

Extracts PDP EIS LPR

Extract concentration Icorr E(%) Rct E(%) Rp E(%)


(mA/cm2) (V/cm2) (V/cm2)
1 226.00 – 73.14 – 75.95 –

WMRE 0.10 106.70 52.79 179.70 59.30 156.90 51.70


0.50 68.01 69.91 253.20 71.11 287.00 73.54
1.00 63.77 71.78 339.90 78.48 363.70 79.12
2.00 45.51 79.86 439.20 83.35 403.00 81.15

WMSE 0.10 81.82 63.80 272.50 73.16 270.60 71.93


0.50 62.61 72.30 306.90 76.17 297.20 74.44
1.00 38.85 82.81 433.20 83.12 432.00 82.42
2.00 36.90 83.67 520.80 85.96 545.70 86.08

WMPE 0.10 67.02 70.35 201.10 63.63 260.90 70.89


0.50 69.52 69.24 289.60 74.74 301.90 74.84
1.00 68.92 69.51 273.90 73.30 296.70 74.47
2.00 62.33 72.42 357.10 79.52 344.40 77.95
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 293

[(Fig._8)TD$IG] [(Fig._9)TD$IG]

Fig. 8. Langmuir adsorption isotherms for the WMRE, WMSE and WMPE in 1 M
HCl on mild steel.

stretch and amide C¼O stretch respectively. However, a very sharp


peak that can be linked to carboxylic acid and/or ketonic C¼O
stretch was only observed at about 1710 cm1 in WMRE alone. The
presence two medium peaks which could have interfered with
carboxylic acid and/or ketonic C¼O stretch around 1710 cm1 in
WMSE and WMPE could be suspected to be an aromatic C¼C
bending that is expected from the fatty acid oil components from
the WMSE and the chlorophyll contents of the WMPE. They can
also be responsible for hydrocarbons ¼C—H bend around 1000–
650 cm1 and various C—H bending, scissoring and methyl rock
that can be found around 1400–700 cm1 in the WMSE and WMPE
spectra. The ATR-FTIR spectra show that the three watermelon
waste product extracts contain oxygen and nitrogen atoms in
functional groups (O—H, N—H, C—O etc.) that are present in L-
citrulline, hydrocarbons and aromatic rings from other compo-
nents of the extracts. The adsorption of the compounds of the
extracts on the mild steel surface through these heteroatoms
generally regarded as adsorption centers is responsible for the
observed corrosion inhibition effect.

Surface morphology

The highest studied concentration (2.0 g/L) of the WMRE,


WMSE and WMPE at a temperature of 25  C was used for the
surface morphology of mild steel. The SEM image of polished mild
steel without exposure to 1 M HCl in the absence and presence of
extracts is presented in Fig. 11a while Fig. 11b shows the SEM image
of mild steel exposed to 1 M HCl devoid of the extracts. A severe
damage surface can be observed in Fig. 11b due to the attack of HCl
on its surface. The attack could be seen to be relatively general
without pits formation (absence of localized attack). However, a

Fig. 9. UV–vis absorption spectra of solutions of extracts without mild steel, mild
Table 5
steel in 1 M HCl and mild steel 1 M HCl with 2.0 g/L concentration of extracts; (a)
Langmuir adsorption isotherms for WMRE, WMSE and WMPE in 1 M HCl on mild
WMRE (b) WMSE and (c) WMPE.
steel.

Extract Slope R2 Kads DG ads (kJ/mol)


protected surface as a result of corrosion inhibition effect of the
WMRE 1.1637 0.9983 11.23 16.88
extracts can be observed in Fig. 11c–e for WMRE, WMSE and WMPE
WMSE 1.1425 0.9988 19.04 18.26
WMPE 1.2424 0.9973 17.17 17.99
respectively with a slight evidence of adsorbate presence on the
mild steel surface.
294 N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296
[(Fig._10)TD$IG]
Mechanism of inhibition

The ATR-FTIR results of the three watermelon waste product


extracts reveal the presence of heteroatoms of N and O that may
come from L-citrulline (Fig. 1), hydrocarbons and aromatic rings
from other phytoconstituents of the extracts. The adsorption of
inhibitor molecules present in the extracts blocks the surface of the
mild steel against charge and mass transfer and thereby hindering
corrosion. Two modes of adsorption are generally considered. The
neutral molecules of the extracts’ components may be adsorbed on
the metal surface through chemisorption mechanism involving
the sharing of electrons between O or N atom and Fe and the
displacement of water molecules from the metal surface. The
components of the extract inhibitor molecules could as well adsorb
on the metal surface by pi electrons of the fused benzene rings and
vacant D-orbital of iron. On the other hand, the protonated
components of the extracts inhibitor molecules may be physically
adsorbed by electrostatic interactions between the cations and
already adsorbed chloride ions. This is probably the mode of
adsorption of the extracts components on the mild steel surface
Fig. 10. ATR-FTIR spectra of crude WMRE, WMSE and WMPE.

[(Fig._1)TD$IG]

Fig. 11. SEM images of unexposed and exposed mild steel in 1 M HCl in the presence and absence of extracts for 24 h at room temperature. (a) Unexposed mild steel, (b) 1 M
HCl, (c) 1 M HCl with 2.0 g/L WMRE (d) 1 M HCl with 2.0 g/L WMSE and (e) 1 M HCl with 2.0 g/L WMPE.
N.A. Odewunmi et al. / Journal of Environmental Chemical Engineering 3 (2015) 286–296 295

given that the thermodynamics parameters point to physisorption Acknowledgement


of the extracts on mild steel surface.
Some authors have proposed the following mechanism for the The support of the Center of Research Excellence in Corrosion
corrosion of iron and steel in HCl solution [43,44]: (Core-c), Research Institute, King Fahd University of Petroleum and
Based on the proposed mechanism, the anodic reaction which is Minerals supports is gratefully acknowledged.
the metal dissolution follows:
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