Egyptian Journal of Petroleum 28 (2019) 155–159

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Egyptian Journal of Petroleum

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Full Length Article

Mild steel corrosion inhibition by Parsley (Petroselium Sativum) extract

in acidic media q
Mokhtar Benarioua ⇑, Abdelkader Mihi, Nora Bouzeghaia, Mahieddine Naoun
Corrosion Laboratory, Mechanical Department, Faculty of Technology, Batna2 University, Algeria

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

Article history: The inhibition effect of Parsley (Petroselium Sativum) leaves extract (PSL) on mild steel in one molar HCl
Received 9 October 2018 solution was investigated by weight loss, potentiodynamic polarization, impedance spectroscopy and
Revised 25 December 2018 scanning electron microscopy. Steel corrosion rate decreased significantly in the presence of PSL. The cor-
Accepted 3 January 2019
rosion inhibition efficiency increased with the increase of PSL concentration up to 92.39% obtained at
Available online 16 January 2019
25 °C for a 5 gL
1 concentration. Polarization showed that PSL acts as a mixed type inhibitor. The adsorp-
tion of the extract on mild steel surface was spontaneous, physisorption type and according to the
Keywords:
Langmuir adsorption isotherm. Results obtained by different tests proved that the extract is an effective
Corrosion
Mild steel
green inhibitor for mild steel corrosion in acid solution.
Parsley Ó 2019 Egyptian Petroleum Research Institute. Published by Elsevier B.V. This is an open access article
Polarization under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Impedance spectroscopy

1. Introduction leaves [17], Adhatoda Vasica [18], Ilex paraguariensis [19], Brown
Onion [20], Gongronema latifolium [21], Grape Pomace [22],
Corrosion remains a serious problem when steel is used in most Tiliacora accuminata [23], Juniperus [24], Argania Spinosa [25].
industrial sectors. It costs billions of dollars each year, especially Parsley (Petroselium Sativum), is rich in antioxidant components
in industrial processes when metal is exposed to the acid solution, such as: alkaloids, flavonoids, flavones glycosides, carotenoids,
a very corrosive agent. These acids play an important role in proteins, amino acids etc. [26,27], but unfortunately, it has not
industry; in the refining of crude oil, acid pickling, industrial been sufficiently studied in the inhibition of metal corrosion as
cleaning, acid scaling, and in petrochemical processes. evidenced by the limited number of papers published in this field
In the last three decades, environment protection became a [28–30]. The purpose of this work is to contribute to the efforts
major concern. In the field of science, researches turned to made on this plant and further explore its inhibitory capacity
anything biodegradable and respectful of the environment. In the against corrosion of mild steel in hydrochloric acid. The
field of corrosion inhibitors, conventional and organic inhibitors investigation was carried out by different tests as weight loss,
have been ruled out because of their adverse effects on human potentiodynamic polarization, impedance spectroscopy and
health and the environment. scanning electron microscopy.
Researches increasingly focus on the development of safe
inhibitors by the use of plant extracts. This interest to plant 2. Materials and methods
extracts has been very encouraging, as evidenced by the density
of researches published in international journals, such as Justicia 2.1. Samples preparation
gendarussa [1], Nypa fruticans Wurmb [2], Garcinia Mangostana
[3], Leocarpus Gum Anogessus [4], Siparuna Guianensis [5], Working electrodes were prepared from steel specimens A60
Eggplant Peel [6], Piper guineensis [7], Potato Peel [8], Fig Leaves (E335) with the following chemical composition (% w/w); 0.48C,
[9], Psidium guajava [10], Garcinia Kola [11], Chamaerops humilis 0.218Si, 0.717 Mn, 0.018 Al, 0.147 Cu, 0.022 S and Fe balance. They
[12], Tiliacora accuminata [13], Cucumis Sativus (cucumber) [14], were cut from Ø14 mm bar into cylindrical rods. Weight loss
Setaria verticillata [15], Reutera lutea (Desf.) Maire [16], Henna specimens were enrobed in epoxy resin with 1.54 cm2 exposed
area, whereas for electrochemical tests, they were mounted in
Peer review under responsibility of Egyptian Petroleum Research Institute. sample holders with 1 cm2 exposed area. The specimens were
⇑ Corresponding author. abraded with 180, 400, 600 and 1000 grade emery paper, washed
E-mail address: Mokhtar.arioua@gmail.com (M. Benarioua). with double-distilled water, degreased with acetone, and dried.

https://doi.org/10.1016/j.ejpe.2019.01.001
1110-0621/Ó 2019 Egyptian Petroleum Research Institute. Published by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
156 M. Benarioua et al. / Egyptian Journal of Petroleum 28 (2019) 155–159

2.2. Plant extracts preparation 3. Results and discussion

Dried leaves of Petroselinum Sativum (Parsley) were ground 3.1. Weight loss measurements
and pulverized into a fine powder. 20 g were added to 500 ml of
1 M HCl. The mixture was shacked for two hours. The extract Corrosion rates (CR), inhibition efficiency (IE) and surface
was cooled, filtered and completed up to 500 ml using 1M HCl. This coverage (h) values obtained from gravimetric measurement in
was considered as the stock solution. The required concentrations 1 M HCl without and with different concentrations of the inhibitor
were prepared by diluting the stock solution. (1–5 gL
1) after 24 h immersion at 25 °C are listed in Table 1. As
shown in Fig. 1, the corrosion rate was reduced with the addition
of the extract and the inhibition efficiency increases as the
2.3. Solution preparation inhibitor concentration increase.

The corrosive media (1 M HCl) was prepared by dilution of

analytical grade HCl (37%) in double distilled water. The 3.2. Polarization curves
concentration range of the extract used was from 1 to 5 gL
1 and
the electrolyte volume was 200 ml. Fig. 2 presents the polarization curves of M-steel in 1 M HCl
without and with 1, 2, 3, 4 and 5 gL
1 of PSL at room temperature.
The corresponding parameters are summarized in Table 2.
2.4 wt. loss measurements From Table 2 we can see that the presence of the extract caused
a clear decrease in both anodic and cathodic current densities; this
Specimens were immersed 24 h in acid solutions at 25 °C in the may be due to the adsorption of organic compounds present in the
absence and presence of 1, 2, 3, 4 and 5 gL
1 of Petroselinum Sati- extract at the sample surface active sites, delaying both metallic
vum leaves extract (PSL). The specimens were removed, rinsed dissolution and hydrogen evolution and consequently slowing
with water and acetone, dried in warm air and stored in desicca- the corrosion process. Tafel slopes (ba’ bc) did not significantly
tors. Weight loss was determined with an analytical balance change with the addition of the extract, indicating that the anodic
(0.1 mg precision). The tests were repeated twice for each experi- and cathodic reactions are not affected by the inhibitor. Corrosion
ment. The inhibition efficiency IE (%) was calculated using Eq. (1) potential values shifted to positive potentials in the presence of PSL
extract, but did not change significantly with respect to the inhibi-
  tor concentrations; this indicates that the extract acted as a mixed-
W
IE ¼ 1
:100 ð1Þ type inhibitor with anodic dominance. The inhibition efficiency
Wo
increases with increasing concentrations and the maximum inhibi-
tion (95.28%) was obtained at 5 gL-1 concentration. This value is
where: W0 and Ware M-steel corrosion rates (mgcm
2h
1) in the
higher than those obtained by M. Abdallah et al. [29], Al-Sanani
absence (blank) and presence of the extract, respectively.
[30] and Hui Cang et al. [31].

2.5. Electrochemical procedure 3.3. Electrochemical impedance spectroscopy measurements (EIS)

The electrochemical tests were carried out with three-electrode The mild steel experimental impedance results in 1 M HCl with-
cells. A saturated calomel electrode (SCE) and a platinum electrode out and with 5 gL
1 of PSL are displayed in Nyquist (Fig. 3) and
were used as a reference and auxiliary electrodes, respectively. Bode (Fig. 4) plots. They show a single depressed half circle. This
In all experiments, the mild steel electrode was left (30 min) to indicates that the corrosion of mild steel in 1 M HCl acidic solution
reach a stable open-circuit potential. Polarization tests were was mainly controlled by a charge-transfer process. It is clear that
performed with 10 mVmin
1 scanning rate in the range ± 200 mV the extract changed the impedance response of mild steel. The
from the corrosion potential. The tests temperature was diameter of the capacitive loop in the presence of PSL is larger than
25 ± 2 °C. For each extract concentration, the tests were repeated the one in the blank solution. In order to determine the impedance
twice. The electrochemical measurements were performed using parameters from the experimental results, the data were fitted to
a computer-controlled Potentiostat (Solartron SI-1260) and data the electrical equivalent circuit (Fig. 5) using the Zview software.
were analyzed using gain phase analyzer electrochemical interface In the equivalent circuit, (Fig. 5), Rs is the uncompensated
(Solartron SI-1287). solution resistance, Rct refers to the charge-transfer resistance
The inhibition efficiency IE was calculated from the and CPE is the constant phase element (CPE).
potentiodynamic polarization curves and the electrochemical Constant-phase elements (CPE) are used extensively in equiva-
impedance diagrams, using Eqs. (2) and (3), respectively: lent electrical circuits for fitting of experimental impedance data.
  The CPE behavior is generally attributed to distributed surface
Icorr reactivity, surface inhomogeneity, roughness or fractal geometry,
IE ¼ 1
ð2Þ
Icorr; 0 electrode porosity, and to current and potential distributions asso-
ciated with electrode geometry [32].
  The impedance of constant phase element (ZCPE) is defined by
Rct; o
IE ¼ 1
ð3Þ Eq. (4) [33]
Rct
1
ZCPE ¼ ð4Þ
Q ðjxÞ
n
where: Icorr,0 is the corrosion current density without inhibitor
(blank) and Icorr. the corrosion current density with the inhibitor
(Tafel plots). where Q (O
1sncm
2) and n are independent of the frequency. The
And Rct,0 is the charge-transfer resistance without inhibitor factor n is the CPE power, its deviation from unity is an indication of
(blank) and Rct is the charge-transfer resistance with inhibitor deviation of Q from the ideal capacitance behavior. j is the imagi-
(Nyquist plots). nary unit (j2 =
1) and x is the angular frequency (x = 2pf ). The
 M. Benarioua et al. / Egyptian Journal of Petroleum 28 (2019) 155–159 157

Table 1
Corrosion rate of M-steel after 24 h immersion in 1 M HCl at different PSL concentrations.

Concentration (gL
1) 0 1 2 3 4 5

2
1
Corrosion rate (mgcm h ) 0.230 0.055 0.039 0.032 0.031 0.029
IE (%) 77.32 84.38 86.14 87.15 87.65
Surface coverage h 0.7732 0.8438 0.8614 0.8715 0.8765

where xmax is the angular frequency at which the imaginary com-

ponent of the impedance reaches its maximum values. The results
show that the value of charge transfer resistance (Rct) has signifi-
cantly increased after addition of the extract, suggesting the forma-
tion of a protective film on the electrode/solution interface and the
Cdl value decreased. The decrease in Cdl may be due to the adsorp-
tion of the extract compounds at the metal surface leading to the
formation of protecting layer [34].

3.4. Adsorption studies

Basic information on the interaction between the inhibitor and

mild steel surface is investigated by the adsorption isotherms. Inhi-
bition efficiency is directly proportional to the fraction of the sur-
g

face covered by the adsorbed molecules (h) where h ¼ 100 . The
change in C/h as a function of the extract concentration specifies
the adsorption isotherm that describes the system. The fit of the
obtained data to the Langmuir isotherm is illustrated by plotting
Fig. 1. Corrosion rate and inhibition efficiency for M-Steel in 1 M HCl solution for
(against concentration) according to Eq. (6).
24 h immersion at 25 °C without and with different concentrations of PSL.
C 1
¼Cþ ð6Þ
h K
where C is the inhibitor concentration, h is the occupied fraction of
the surface, and K is the adsorption constant. Fig. 6 shows linear
plots with a correlation coefficient of 0.9999 for gravimetric data
and 0.9987 for polarization data with slopes of 1.104 and 1.023
respectively.
The Kads and R2 values are listed in Table 4, where R2 is the
correlation coefficient, which is the degree of fit between the
experimental data and the isotherm equation. The plot showed
good linearity, with R2 values very close to unity, indicating that
the Langmuir model is suitable for describing the adsorption
process. It also indicates a strong adsorption of PSL on mild steel’s
surface [28].
The inhibitor molecules gained stability when their free
energies were reduced by their adsorption on the mild steel
surface, where they rearrange themselves or react with the ions
or molecules near the surface [35].
The adsorption free energy DG°ads were determined using Eq.
(7) [33].
Fig. 2. Mild steel polarization curves in 1 M HCl for different concentrations of PSL.
^  ads ¼
RTlnð55:5KadsÞ
DGA ð7Þ
where R is the universal gas constant, T is the absolute temperature,
impedance parameters obtained by fitting are compiled in Table 3. and the molar heat of adsorption of water is 55.5.
The double layer capacitance (Cdl) was calculated by Eq. (5) [33]. The free energy of adsorption, DGoads, the equilibrium constant,
Kads, coefficient of correlation, R2 and slopes were presented in
Cdl ¼ Q ðxmax Þn
1 ð5Þ Table 4. The DG°ads value gives information about the spontaneity

Table 2
Mild steel corrosion polarization parameters in acid solutions with and without different PSL concentrations.

Concentration(gL
1) Ecorr.(mV) icorr. (mAcm
2) Rp (O cm2) ba bc IE% Surface coverage h

0
488.6 0.1653 53.77 63.5 54.7 /
1
472.8 0.0211 418.17 51.7 55.7 87.23 0.8723
2
474.7 0.0188 440.45 47.8 52.3 88.62 0.8862
3
473.8 0.0153 529.81 47.0 51.3 90.74 0.9074
4
468.7 0.0110 839.42 49.0 54.2 93.34 0.9334
5
477.8 0.0078 1070 47.5 44.6 95.28 0.9528
158 M. Benarioua et al. / Egyptian Journal of Petroleum 28 (2019) 155–159

Fig. 3. Nyquist plots of M-Steel in 1 M HCl with (h) and without (Ο) 5 gL
1 PSL.

Fig. 6. Langmuir isotherm for PSL adsorption on mild steel surface.

Table 4
Langmuir adsorption isotherm parameters for adsorption of PSL on mild steel surface.

1
Fig. 4. Bode plots of M-Steel in 1 M HCl with (h) and without (Ο) 5 gL PSL.
Methods Slope Intercept R2 Kads DG0 (kJ/mol)
Weight loss 1.1041 0.1755 0.9999 5.698
14.272
Polarization 1.0231 0.1790 0.9987 5.5865
14.069

and type of adsorption. If DG°ads is between
20 and
40 kJmol
1,

the adsorption could proceed via (mixed adsorption) and if it is more
than
40 kJmol
1, the adsorption type would be chemisorptions
[36]. Chemisorption occurs via sharing or transfer of charge from
the inhibitor molecule to the mild steel surface to form a covalent
bond, while physisorption involves electrostatic attraction between
the charged mild steel surface and the charged inhibitor molecules
[37].Other researchers, such as Suleiman et al. [38] claimed that
any values around
20 kJmol
1 or less negative are consistent with
Fig. 5. Equivalent circuit model. electrostatic interaction (physisorption). For our case the DG°ads

Table 3
Mild steel impedance parameters for in1M HCl solution with and without 5 gL
1 of PSL.

Concentration (mgL
1) Rs (O) Rct (O.cm2) Qdl (X
1sncm
2) Chi-Squared n Cdl (mFcm
2) IE %
00 4.21 34.52 0.000170 0.00057 0.91 103.38
5 4.097 453.7 0.000161 0.00018 0.78 75.38 92.39
 M. Benarioua et al. / Egyptian Journal of Petroleum 28 (2019) 155–159 159

Fig. 7. SEM micrograph (3000) of M-steel immersed in 1 M HCl; polished (a) in the absence of PSL (b) and with 5 gL
1 of PSL (c).

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