Int. J. Electrochem. Sci., 13 (2018) 8198 – 8221, doi: 10.20964/2018.08.

79

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

Effect of Mentha Piperita essential oil on mild steel corrosion in

hydrochloric acid
Z. Bensouda1, M. Driouch1, M. Sfaira1, A. Farah2, M. Ebn Touhami3, B. Hammouti4,
K.M. Emran5,*
1
Laboratoire d’Ingénierie des Matériaux, de Modélisation et d’Environnement. Université Sidi
Mohamed Ben Abdellah USMBA, Faculté des Sciences BP 1796-30000 Fès-Atlas, Morocco.
2
Laboratoire de Chimie Organique Appliquée. Université Sidi Mohamed Ben Abdellah USMBA,
Faculté des Sciences et Techniques. Route Immouzer Fès, Morocco.
3
Laboratoire d’Ingénierie des Matériaux et Environnement : Modélisation et Application,
Faculté des Sciences, Université Ibn Tofaïl, BP. 133-14000, Kénitra, Morocco.
4
Laboratory of Applied Chemistry & Environment, Faculty of Science, Mohammed Premier
University - B.P. 4808, 60046 Oujda - Morocco.
5
Department of Chemistry, College of Science, Taibah University, Al-Madinah Al-Monawarah, PO
Box4050, Saudi Arabia
*
E-mail: kabdalsamad@taibahu.edu.sa; bensouda@yahoo.com

Received: 29 April 2018 / Accepted: 19 June 2018 / Published: 5 July 2018

The Mentha Piperita essential oil (MPEO) rich in anthraquinone,1-(p-fluorophen) as major compound
(42.8 %) has been investigated as corrosion inhibitor for mild steel in 1 M HCl. weight loss, polarization
curves (Tafel, Stern & Geary as well as Stern methods) and electrochemical impedance spectroscopy
measurements were used to evaluate the inhibition performance of MPEO. The results obtained from
different techniques were in best accord. The inhibiting efficiency, reaching circa 87 % at 0.7 g L-1 of
MPEO, was found to increase with rise of inhibitor concentration, whereas the increase of temperature
was in favour of its slow decrease. The adsorption data fitted well to Langmuir isotherm model and
involved both physisorption. Scanning electron microscopic results testified the formation of a protective
film onto the mild steel in the presence of MPEO.

Keywords: Mentha Piperita; Anthraquinone; Acid Corrosion; Inhibition; Adsorption isotherms.

1. INTRODUCTION

Corrosion is a natural phenomenon widely defined as degradation of metal surfaces in contact

with an aggressive environment. The direct and indirect consequences of corrosion are quite many and
are considered as a major problematic in industry, constructions and civil services. Mild steel appears to
Int. J. Electrochem. Sci., Vol. 13, 2018 8199

be extensively used for structural applications because of its low cost. However, its susceptibility to be
rusting in humid air and high dissolution rate in acidic solutions, are the major inconvenient for its use
on larger scale without protection.
Hydrochloric acid is generally used in industries for cleaning, descaling and pickling of steel
structures, such as reactors, agitators, pumps, drain, etc., which are subject of considerable metal
dissolution. To slow down the aggressiveness of this acid, the use of inhibitors is the most practical
protection method against corrosion process. Considerable synthetic compounds have been tested and
are still being to evaluate their corrosion inhibition potential [1–5].
Though many synthetic molecules presented good potential against corrosion, the greater part of
them is extremely toxicant to both human and environment. The safety and environmental issues of
corrosion inhibitors, arisen in industries, have always been a global concern. The toxicity may manifest
either during the synthesis of the molecules or during its application [6,7]. Consequently, as a result of
environmental concern, for these synthetic compounds, researches into the practice of eco-friendly
compounds, as green corrosion inhibitors, for mild steel have intensified to substitute toxic chemicals
currently in use. Indeed, in the most recent decade, several studies have been completed on corrosion
inhibition by using plant extract [8,9], purified compounds [10,11] and essential oils [12–21]. All of
them have been announced as good inhibitors for different metals and alloys in different acidic media.
This study aims at the investigation of the effect of Mentha Piperita essential oil, denoted
hereafter MPEO, on mild steel corrosion inhibition in molar hydrochloric solution. The extraction of
MPEO is done by hydrodistillation using a Clevenger-type apparatus and identification of MPEO
components is given by spectral analysis of gas chromatography coupled to mass spectrometry (GC–
MS). The corrosion performance is conducted by coupling weight loss, electrochemical associated with
scanning electron microscopy techniques. The adsorption and inhibition efficiency of MPEO inhibitor
are investigated and the thermodynamic along with kinetic parameters in the absence and presence of
MPEO are calculated and discussed.

2. EXPERIMENTAL

2.1 Plant material

Samples of Mentha x Piperita L. came from a land in the region of Kelâat Gouna (located in
southern of Morocco, in the Souss-Massa-Draa and the province of Tinghir). The sample collection was
done in the summer, during the flowering period of the plant. Only the aerial parts (leaves, flowers,
stems) were collected.

2.2 Preparation

The extraction of Mentha Piperita was conducted by hydrodistillation in a Clevenger-type

apparatus in the Laboratory of Green extraction of the Ex-National Institute of Medicinal and Aromatic
Plants-Taounate in Morocco. The distillation was carried out by boiling for 2 h. The essential oil yield
Int. J. Electrochem. Sci., Vol. 13, 2018 8200

was expressed in mL/100 g of dry matter. For the treated samples, the average yield of essential oil
obtained was of 1.15 %.
The oil was dried over anhydrous Na2SO4. The MPEO was subjected to GC-MS (type
QP2010Shimadzou) analysis using Trace GC/Polaris Q (GC-MS, ThermoElectron). The column was a
VB-5 (5 % phenyl and 95 % dimethylpolysiloxan) with film thickness of 0.25 μm, a length of 30 m, and
an internal diameter of 0.25 μm used with helium gas as mobile phase. The temperature was kept at 50
°C for 5 min and programmed to 250 °C for 3 min at rate of 4 °C min−1 and programmed to 300 °C at a
rate of 25 °C min−1. The injector temperature was set at 250 °C. Slip flow was adjusted at 50 mL min -1
and MS was occupied at 70 eV.

2.3 Weight loss, potentiodynamic polarization and EIS measurements

Prior to all measurements, the mild steel samples (0.21% C, 0.38% Si, 0.09% P, 0.01% Al,
0.05% Mn, 0.05% S and 99.21% Fe) were mechanically polished on wet SiC paper successively from
80 to 1500 grade. The specimens were washed thoroughly with double distilled water, defatted by
ethanol and finally dried with acetone at hot air before being immersed in the acidic medium.
The corrosive medium of 1 M HCl was prepared by dilution of analytical grade 37% HCl with
double distilled water. The test solutions were freshly prepared before each experiment by adding
MPEO, at different concentrations, directly into1 M HCl solution.
Weight loss tests have been done out in double-walled glass cell coupled with a thermostat-
cooling condenser. The solution capacity was 50 mL. The apparent surface part of mild steel samples
used was of circa 6 cm 2. The immersion time for the weight loss tests was 6 hours at room temperature
of 308 K in air without bubbling. After the corrosion test, the samples were carefully washed in bi -
distilled water, dried and then weighted.
The electrochemical study was performed with a Bio-Logic-Science Instruments ® potentiostat
piloted with Ec-Lab® software. This potentiostat was coupled to a three-electrode cell with a
thermostatted double wall. The mild steel used for the working electrode was identical to the one
employed for weight loss tests. The surface area in contact of mild steel was of 1 cm2. A platinum
electrode and a sutured calomel electrode (SCE) were used as auxiliary and reference electrodes,
respectively.
Potentiodynamic polarization curves were plotted from -900 to -100 mV at 308 K at a
polarization scan rate of 1 mVs -1. Before all experiments, the potential was stabilized at the open
circuit potential during a hold time immersion of 30 min.
The electrochemical impedance spectroscopy (EIS) measurements were realized using a
transfer function analyser, with a small amplitude a.c. signal (10 mV rms) over a frequency region
from 100 kHz to 10 mHz at 308 K with 10 points per decade. Computer program automatically
controlled the measurements realized at rest potentials after 30 min of immersion at the corrosion
potential, Ecorr . The EIS spectra were given both in the Nyquist and Bode representations. The
impedance data were analysed and fitted, in terms of a suitable electrical circuit, with the simulation
Ec-Lab (Bio-Logic) software.
Int. J. Electrochem. Sci., Vol. 13, 2018 8201

2.4 Surface analysis

The surface morphology of the samples, exposed to the acid solutions, was followed by a
scanning electron microscope (SEM) model FEI Quanta 200 equipped with EDAX probe microanalysis
of surface. The SEM analysis was complete after 24 h immersion at 308 K, for representative
specimens in uninhibited and inhibited solutions.

3. RESULTS AND DISCUSSION

3.1 Characterization and chemical composition of MPEO

Fig. 1 exemplifies the gas chromatography-mass spectral analysis of the sample which was
dissolved in hexane.

Figure 1. CG-MS MPEO Spectre.

The obtained components were of twenty compounds identified in the MPEO. The obtained
constituent percentages of MPEO are summarized in Table 1. The total identified was of 99.55 %.

Table 1. Chemical composition of MPEO.

Constituent % Constituent %
Anthraquinone, 1-(p-fluorophenyl) 42.03 Naphthalene 1.28
Methenolone 26.38 Aristolene 1.17
Selina-3,7(11)-diene 4.75 Menthol 1.12
Longifolene 4.29 Carvyl acetate 1.04
Isoledene 2.96 Carveol acetate 0.98
γ-Terpinene 2.80 δ-Cadinene 0.86
Calamenene 2.17 α-Bulnesene 0.81
Jasmone 2.04 Camphene 0.80
Isocaryophillene 1.72 Cubenol 0.42
Epi-bicyclosesquiphellandrene 1.59 tau.-Muurolol 0.34
Int. J. Electrochem. Sci., Vol. 13, 2018 8202

MPEO was well dissolved in hydrochloric acid solutions and the chemical structures of the
most abundant compounds are given in Fig. 2.

Anthraquinone, 1-(p-fluorophenyl):C20H11FO242.03% Methenolone: C20H30O226.38%

Selina-3,7(11)-diene:C15H244.75 % Longifolene: C15H244.29%

Figure 2. Chemical structures of the major components of MPEO.

3.2 Weight loss and SEM studies

The weight loss method is known to be the most widely applied technique for monitoring inhibition
efficiency. The corrosion rate in the absence and presence of MPEO is determined via the following Equation
1:
m
Wcorr  (1)
S t
where m is the average weight loss of the mild steel specimens, S is the total area of the mild steel
specimen and t is the immersion time. The percentage inhibition efficiency (WL % ) is calculated using
Equation 2:
 W0  Winh

WL %     100 (2)
 W0 
where W0 and Winh are the weight loss values in the absence and presence of MPEO.
Fig. 3 shows both the evolution of weight loss and the corresponding inhibiting efficiency against
MPEO concentration. It is evident that there is a tremendous decrease in the mild steel corrosion rate with the
addition of MPEO and hence the corrosion rate is concentration dependent. In turn, the inhibiting efficiencies
increases with rising inhibitor concentration to reach a maximum value of 86.41 % at 0.7 g L−1 of MPEO.
Further increase in MPEO concentration does not cause any significant change in the performance of MPEO.
Int. J. Electrochem. Sci., Vol. 13, 2018 8203

90
-2 -1
1.0 Weight loss, Wcorr / mg cm h
Inhibiting Efficiency, WL%

-1
Weight loss, Wcorr / mg cm h
80

Inhibiting Efficiency, WL%

0.8

-2
0.6 70

0.4
60

0.2

50
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
-1
Concentration, Cinh / g L

Figure 3. Corrosion rate and inhibiting efficiency of mild steel exposed for 6 h in 1M HCl at different
concentrations of MPEO at 308 K.

Figure 4. SEM micrographs of the mild steel surface: (a) Metallic surface after being polished, (b)
Metallic surface after 24h immersion in 1 M HCl and (c) Metallic surface after 24 h immersion
in 1 M HCl with 0.7 g L-1 of MPEO
Int. J. Electrochem. Sci., Vol. 13, 2018 8204

These results indicate that MPEO seems to be a good corrosion inhibitor for mild steel in molar
hydrochloric acid medium. The corrosion inhibition property of MPEO is probably due to the inhibitive action
of some MPEO components having the ability to be adsorbed onto the mild steel surface and can be considered
as effective inhibitors. Indeed, the fact that the major components of MPEO contain lone pairs from
heteroatom ketones, Fluor and  -orbitals (═), these can block the active sites and therefore reducing the
corrosion rate. Besides, the inhibitive nature of MPEO may also be imputed to a synergistic intermolecular
effect of different active constituents present in this essential oil although minor compounds (Table 1).
The scanning electron microscopy (SEM) micrographs (Fig.4a-c) of the surfaces of mild steel strips
were recorded. Fig.4a exemplifies the polished steel surface before exposure to the corrosive solution and
clearly visible parallel features appear linked to abrading scratches. Fig.4b-c show the SEM micrographs of
mild steel surface before and after immersion in molar hydrochloric acid, during 24 hours, with and without
MPEO inhibitor in order to see the changes that can occur during the corrosion process. The result of the high-
resolution SEM micrograph (50 µm) shows that the metal surface is strongly damaged in the absence of
MPEO due to a rapid corrosion attack (Fig. 4b). However, a relatively smoother and less corroded morphology
of mild steel surface can be observed with 0.7 g L-1 of MPEO (Fig. 4c) for which the best inhibiting efficiency
is registered. Consequently, MPEO inhibits the mild steel corrosion in 1 M HCl.

3.3 Potentiodynamic polarization study

1000

10
-2
Current density, i / mA cm

0,1
Blank
-1
0.4 g L
-1
0.5 g L
-1
1E-3 0.6 g L
-1
0.7 g L

1E-5
-1,0 -0,8 -0,6 -0,4 -0,2 0,0
Potential, E / VSCE

Figure 5. Polarization curves of mild steel in 1 M HCl at different concentrations of MPEO at 308 K.

Most widely corrosion phenomena are of electrochemical type and comprise of reactions on
surface corroding metal. Formerly, electrochemical methods can be utilized to evaluate corrosion rates
and to characterize corrosion mechanisms. The effect of MPEO concentration on the potentiodynamic
anodic and cathodic polarization curves of mild steel is then also studied in 1 M HCl solution.
Fig. 5 illustrates the potentiodynamic polarization curves for mild steel, in acidic solution, in the
absence and presence of restricted and representative concentrations of MPEO. The anodic and cathodic
Int. J. Electrochem. Sci., Vol. 13, 2018 8205

current densities of mild steel in the presence of MPEO have been significantly reduced with respect to
that of blank. This decrease is slightly marked with rise of MPEO concentration. Furthermore, a small
change in the corrosion potential is registered towards more positive potentials when MPEO is added in
1 M HCl solution.
The anodic branches show a decrease in current densities when compared to the uninhibited
acidic solution. This reduction is almost identical for all explored concentrations of MPEO since the
corrosion potential until -0.35 VSCE. However, beyond this potential, curves stand out from each other.
It is likewise important that the anodic Tafel slopes can easily be identified from these curves as opposed
to several published studies which report the appearance of a potential said desorption potential or
potential of molecules rearrangement forming an inhibitor film [2,3,12,22].
The cathodic part represent rise to parallel Tafel lines suggesting that the hydrogen evolution is
activation controlled. Thus, hydrogen discharge, at the mild steel interface, takes place mainly through
a charge transfer mechanism [23,24]. Accordingly, the inhibition process perhaps caused by a simple
blocking surface effect, namely the reduction of reaction area on the corroding surface [25]. Thereby, a
higher coverage of the essential oil film on the electrode surface can be expected and more pronounced
at higher inhibitor concentrations [26].
Consequences of the Tafel fit are ascertained whenever a marker is moved. The default positions
of the markers are ± 85 mV and ± 200 mV around Ecorr ; i.e., the explored potential domain, to deduct
the electrochemical parameters, is situated beyond ± 85 mV when compared to Ecorr and in a potential
window of ± 115 mV conditioned by a good linearity of the corresponding curves. The software deduces
the open circuit potentials, Ecorr from the linear regressions intersection, the corrosion current density
values, icorr and the Tafel slopes,  c and  a .The inhibiting efficiency is calculated by using corrosion
current densities as given in Equation 3:
i i 
 Tafel %   corr corr / inh   100 (3)
 icorr 
where icorr / inh and icorr are the corrosion current density values with and without inhibitor,
respectively, determined by extrapolation of cathodic and anodic Tafel lines to the corrosion potentials
using software (Ec-Lab, Bio-Logic).
The examination of the electrochemical parameters given in Table 2 reveals that the corrosion
current densities icorr decreases considerably with rise of MPEO concentration. Correspondingly, the
inhibition efficiency  Tafel % increases to reach its maximum value of 85 % at 0.7 g L-1 of MPEO. This
behavior suggests that the MPEO adsorption protective film formed onto the mild steel surface tends to
be more and more complete and stable with increasing of MPEO concentration. The presence of MPEO
causes a slight shift of corrosion potential when compared to that in the absence of inhibitor. In our
study, Ecorr of mild steel shifts anodically in the range of 7-15 mV compared to the uninhibited solution.
From reports in the literature, it has been revealed that if the displacement of Ecorr is more than 85 mV
the inhibitor can be considered as a cathodic or anodic type inhibitor whereas when the displacement of
Ecorr is less than 85 mV, the inhibitor can be considered as mixed type [27]. Consequently, the obtained
results indicate that MPEO acts as mixed-type inhibitor.
Int. J. Electrochem. Sci., Vol. 13, 2018 8206

Table 2. Electrochemical data evaluated from Tafel and Stern & Geary methods for mild steel in 1 M
HCl without and with MPEO at 308 K.

Tafel data LPR data

Cinh  Ecorr icorr  c a  Tafel Rp  S&G
g L-1 mVSCE µA cm2 mV dec-1 mV dec -1
% Ωcm2 %
Blank 479 623 168 176 - 59.4 -
0.4 468 128 192 156 79.33 284 79.08
0.5 472 105 200 119 83.09 309 80.77
0.6 469 97 182 146 84.33 362 83.59
0.7 464 91 192 132 85.37 382 84.45

Further, the values of the cathodic Tafel slopes  c , in the presence of the inhibitor, significantly
not change with the MPEO addition, which implies that its influence on the cathodic reaction does not
modify the mechanism of hydrogen evolution discharge [28]. Nevertheless, the values of the slopes of
the anodic Tafel lines,  a , change significantly with the addition of MPEO suggesting that the inhibitor
is first adsorbed onto the electrode surface and hindered by simply blocking the anodic reaction sites,
and thereby affect the anodic reaction mechanism [29].
The Linear Polarization Resistance (LPR) extraction, with ± 20mV in the vicinity of Ecorr , is
carried out in order to exclude the influence of the surface changes which may occur during polarization
at higher over potentials in the case of potentiodynamic polarization method. The corresponding
polarization resistance R p values of mild steel in 1 M HCl, in the absence and presence of different
concentrations of MPEO, are also given in Table 2. R p is determined from the slope of the potential
versus current lines. Stern &Geary (S&G) [30] formulated the following Equation 4 for corrosion current
calculation:
C
icorr  (4)
Rp
where the constant C is:
a  c
C (5)
2.303  (  a   c )
It is remarked that R p increases with increasing the inhibitor concentration. This, in turn slows
down the icorr values. The inhibition efficiency  S&G % is calculated as follows:
 R p / inh  R p 
 S &G %     100

(6)
 R p / inh 
where R p and R p / inh are the polarisation resistance values without and with MPEO, respectively.
From Table 2,  S&G % increased with inhibitor concentration reaching a maximum value of 84.45
% at 0.7 g L-1 for MPEO. This is in logically good agreement with the values of inhibitor efficiency got
from Tafel extrapolation along with those obtained from weight loss measurements.
Meanwhile, as a third method, derived from steady-state polarization curves, it is likewise so
interesting to search for corrosion kinetic parameters from a fitting by the Stern equation. To do as
Int. J. Electrochem. Sci., Vol. 13, 2018 8207

such, the global current density values, i , is considered as the summation of two contributions,
cathodic and anodic current density, ic and ia respectively. Thus, it can be derived from Equation 7:

i  ia  ic  icorr  e ba  ( E  Ecorr )  e bc  ( E  Ecorr )  (7)
-1
where bc and ba are the Tafel constants of cathodic and anodic reactions (V ), respectively.
These constants are linked to the Tafel slopes  (Vdec-1), in usual logarithmic scale, by the following
Equation 8:
ln 10
 (8)
b
However, for this calculation, the potential window is limited in the vicinity of corrosion
potential, Ecorr ±100 mV [31]. A significant systematic divergence is sometimes registered for both
cathodic and anodic domains.
Fig. 6 shows the results of regressions calculation for the cathodic and anodic branches for mild
steel electrode in 1 M HCl at different concentrations of MPEO. A better trend between the experimental
and the calculated polarization data is acquired as is indicated in Fig. 6.

1
-2
Current density, i / A cm

0,1

Blank
-1
0.4 g L
0,01 -1
0.5 g L
-1
0.6 g L
-1
0.7 g L
1E-3 fitting data

-0,60 -0,55 -0,50 -0,45 -0,40 -0,35

Potential, E / VSCE

Figure 6. Comparison of experimental (scatter) and fitting (line) data using a nonlinear fitting with Stern
Equation for mild steel electrode at different concentrations of MPEO.

To yield quantitative approach, icorr , and Ecorr are evaluated from the experimental results using
a defined function ‘’Non-linear least squares curve fit’’ of graphic software (Origin, Origin-Lab). Hence,
the electrochemical parameters, obtained from the Stern extrapolation method, such as Ecorr , icorr ,  a ,  c
, R 2 , and  2 , are reported in Table 3. The fit accuracy  2 equation used in this method is defined as
follows in Equation 9 [32]:
1 N
2   (imes ,i  ical ,i )
2
(9)
N i 1
Int. J. Electrochem. Sci., Vol. 13, 2018 8208

where N is the freedom degrees, im es designates the measured data whereas ical corresponds to
model data calculated from Stern Equation 7. The corresponding inhibiting efficiency is calculated by
using corrosion current densities as formulated in Equation 10:
i i 
 Stern %   corr corr / inh   100 (10)
 i corr 
 Stern % seems to be similar to that of  Tafel % . The difference between them is situated in the
potential domains from which the overall electrochemical parameters are extracted.

Table 3. Electrochemical data evaluated from Stern method for mild steel in 1 M HCl solution at different
concentrations of MPEO at 308 K.

Cinh - Ecorr icorr  c a R2 103  2  Stern

g L-1 mVSCE µA cm 2 mV dec-1 mV dec -1
%
Blank 479±0.52 640±2.4 163±11 167±12 0.999 0.61 -
0.4 468±0.18 138±9.0 192±6 177±5 0.999 0.52 78.45
0.5 472±0.18 102±3.3 196±5 120±4 0.999 0.85 83.97
0.6 469±0.27 92±5.6 175±7 139±6 0.999 0.43 85.48
0.7 464±0.23 88±2.7 189±6 121±5 0.999 0.18 86.22

The statistic chi square value  2 relates a measurement of how expectations compare to
experimental values. It is observed that a good accuracy of the fitting is obtained, as evidence by an
order of 10-3 for all the experimental data. On the other hand, the determination coefficient R 2 is a
statistical measure of how close the experimental data are when compared to the fitted regression line.
It is also known that R 2 , or the factor of multiple determinations for multiple regressions, is always
between 0 and 1. In general, the elevated the value of R 2 , the better model fits the experimental data.
From Table 3, an excellent fit is observed with R 2 up to 0.999, which indicates that the experimental
results are well described by the Stern model.
Fig. 6 clearly shows that the addition of MPEO in 1 M HCl solution reduces both the anodic mild
steel dissolution and the cathodic hydrogen evolution reactions. The reduction described by the Stern
method is in agreement with that of the Tafel method (Fig. 5). In reality, the fact that the corrosion
potentials are very neighbour justifies the validity of the branches comparison. Moreover, the overall
electrochemical parameters, summarized in Table 3, and derived from the Stern method, at all MPEO
concentrations, are in very good agreement with those obtained from Tafel method. Thus, the inhibiting
efficiencies follow the same trend with a maximum value of 86 % at 0.7 g L-1 of MPEO.

3.4 EIS measurements

A better comprehension of the mechanism taking place at the mild steel interface is often attained
through impedance measurements. EIS is performed under potentiostatic conditions at Ecorr and 308 K in
the blank and inhibited solution containing different concentrations of MPEO. Before each measurement, the
Int. J. Electrochem. Sci., Vol. 13, 2018 8209

electrode is left at the open circuit conditions during half an hour as observed for the steady-state experiments.
The electrode system does not evolve significantly during EIS measurements.
Nyquist (Z’, -Z”) and Bode log (f)-log (|Z|) and log (f)–Phase diagrams of the mild steel electrode
obtained in 1 M HCl solution in the absence and presence of various concentrations of MPEO, are shown in
Fig.7 a-c. The insert diagram in Fig.7a is the one of the uninhibited medium.

Blank
40
Data Fitting

300 Blank
-Immaginary Part,- Z"/ cm²

30 HCl 1M -1
0.4 g L
-1
0.5 g L
20 10 Hz
-Immaginary Part, - Z" / cm²

a
100 Hz
-1
250 10
1 Hz
0.5 g L
-1
0.7 g L
0.1 Hz
1000 Hz
0.01 Hz
0

Fitting data
0 10 20 30 40 50 60 70
Real Part,Z'/ cm²

200
10 Hz

150
1 Hz
100 Hz
100

50 1 Hz
0.1 Hz

0.01 Hz 0.01 Hz
0
0 100 200 300 400 500
Real Part, Z' / cm²

3,0
b c Blank
0.4 g L
-1

-1
70

2,5 0.5 g L
-1 60
0.5 g L
-1
0.7 g L
Fitting data
50
2,0

40
2

Phase angle / Degree

log Z /  cm

1,5
30

20
1,0

10
0,5
0

0,0 -10
-2 -1 0 1 2 3 4 5

log f / Hz

Figure 7. Z’, -Z” (a) log(f), log (|Z|) (b) and log (f), Phase (c) diagrams of mild steel in 1M HCl at
different concentrations of MPEO at 308 K. The insert is the one in uninhibited medium.

A depressed semicircle, in the Nyquist representation, is registered, and only one-time constant
appears in log (f)–log (|Z|) plot, as often obtained in acidic media [33–35]. The presence of MPEO, in 1 M
HCl, does not affect the appearance of both the Nyquist and the Bode plots, which suggests a similar
corrosion mechanism in the presence of MPEO. The difference from theoretical results is generally attributed
Int. J. Electrochem. Sci., Vol. 13, 2018 8210

to Cole-Cole [36,37] and/or Cole-Davidson [38] representations inherent to frequency dispersion and
commonly attributed to the generation of microscopic roughness at the electrode surface during the corrosion
process [39,40]. The existence of single semicircle relates the presence of single charge-transfer process,
which is unaffected by the presence of MPEO.
The various impedance results such as Rs , Rt , C dl ,  , n , A and  ' 2 are depicted in Table 4. The
 ' 2 given in Equation 11 used in this method, is defined as follows [32]:
Z meas (i )  Z mod el ( f i , param)
2
n
'  
2
2
(11)
i 1 Di
where Z m easi  is the measured impedance at the fi frequency, Z model  f i , param is function of
the chosen model and param is the model parameter ( Rs , Rt , A ). Di is the normal deviation. Estimates
of the margins of error calculated for some parameters are also reported in Table 4. The electrolyte
resistance Rs determined between working and reference electrodes can be obtained from the abscissa axis
intercept of the semicircle at f →  , Rs ≈ 3 Ω cm2 in all studied solutions. Whereas, the charge transfer
resistance Rt is calculated from the subtraction in impedance at lower and higher frequencies, i.e. the
diameter of the semicircle and the double layer capacitance C dl is determined by a transfer function with
the constant phase element CPE. Indeed, CPE is used to substitute the double layer capacitance for a
more accurate fit and is calculated as follows, Equation 12:
Z CPE  A1 ( j   )  n (12)
In the same Table 4 are shown also the calculated C dl , using the Hsu and Mansfield formula
(Equation 13) reported by Hamdani . [41]:
 
1
Cdl  A  Rt1n n (13)
where A is a proportional factor (µF sn-1), j is an imaginary number with j 2 = -1, n is an
exponent related to the phase shift which can be used as a measure of surface irregularity and ω is the
angular frequency in rad s-1. max  2    f max , where f max is the frequency at which the imaginary
component of the impedance is maximal (  Z max
''
). In first approximation, C dl and the frequency f max are
found as represented in Equation14:
1
f (Z max
''
) where   Rt  C dl (14)
2   
The impedance diagrams analysis led to research an equivalent circuit which may translate the
metal/solution interface behavior, compatible with the shape of the diagrams. According to a classical
method, the impedance spectra of Fig. 7 will be interpreted in terms of a simple modified Randles circuit,
with one relaxation time constant  , as given in Fig.8 with a CPE in parallel to Rt , the all are in series
with another resistor corresponding to the electrolyte solution resistance Rs .

Figure 8. The equivalent circuit used for fitting the impedance spectra.
Int. J. Electrochem. Sci., Vol. 13, 2018 8211

The quality of fitting to the equivalent circuit is judged by chi square value  2 [42]. The
corresponding values (0.0376–0.697), reported in Table 4, testify the good quality fitting with the
proposed circuit.
It may be assumed, as an approximation, that either ( Rt )−1 [43] or C dl [44] parameters are directly
related to the corrosion rate icorr . The inhibiting efficiency  EIS % got from the charge transfer resistance is
calculated as follows, Equation15:
R  Rt 
 EIS %   t / inh   100 (15)
 Rt / inh 
where Rt and Rt / inh are the charge-transfer resistance values without and with inhibitor,
respectively.

Table 4. EIS data of mild steel in 1M HCl containing different concentrations of MPEO at 308 K.

Cinh Rs Rt C dl  A n   '2  EIS

g L-1 Ω cm2 Ω cm2 µF cm-2 ms µF sn-1 %
Blank 1±0.22 61±0.36 113 6 268±22.10-3 0.826 -0.62 0.0376 -

0.4 2±0.21 290±0.37 50 14 100±1.10-3 0.838 -0.72 0.0697 78.91

0.5 2±0.20 362±0.37 48 17 87±1.10-3 0.852 -0.75 0.0460 82.98
0.6 3±0.20 397±0.37 45 18 86±1.10-3 0.841 -0.74 0.0548 84.59
0.7 3±0.20 433±0.37 44 19 80±1.10-3 0.849 -0.75 0.0493 85.87

The analysis of Table 4 reveals that addition of increasing concentration of MPEO increases Rt and
decreases C dl , and consequently enhances  EIS % till reaching its maximum value at 0.7 g L-1. It is to be
noted that the diameter of the capacitive loop of the Nyquist plots increases with rise of MPEO concentration
without affecting their characteristic features. This behaviour means that the inhibition action of MPEO is
related to its adsorption on the metal surface without altering the corrosion mechanism. Furthermore, the
magnitude of C dl decreases with increasing MPEO concentrations. This situation can be interpreted as a
result of increase in the surface coverage by MPEO, to the soft surface of mild steel or other poorly
conductive products such as oxides and hydroxides, which led to an increase in the inhibiting efficiency
[45].
The addition of MPEO in 1 M HCl increases slightly the relaxation time constant  value with an
opposite trend of C dl (cf. Table 4). Indeed, in uninhibited and at 0.7 g L-1 of MPEO, the interface  parameter
increases from 6 to 19 ms while the C dl value decreases from 113 to 44 µF cm-2, signifying that the charge
and discharge rates to the mild steel/solution interface is greatly decreased. This indication shows that there
is conformity between the amount of charge that can be stored (i.e., C dl ) and the discharge velocity at the
interface [29]. It is worth mentioning that the value of the relaxation time constant  remains almost constant
despite the slight increase of circa 4 ms in inhibited media at different concentrations. This finding justifies
the choice of the circuit represented in Fig. 8. The thickness of the protective film  is linked to C dl by the
following Equation16:
Int. J. Electrochem. Sci., Vol. 13, 2018 8212

  0
 S (16)
C dl
where  ,  0 , and S stand for the vacuum dielectric constant (  0 = 8.854 10-14 F cm-2), the relative
dielectric constant, and the surface area, respectively. The decrease in C dl , which can result from an increase
in the thickness of the electrical double layer and/or a decrease in local dielectric constant, suggests that
MPEO functions by adsorption on the mild steel at the metal/solution interface.
The slopes  of the plots log(|Z|)-log(f) (Fig. 7b), which correspond to the medium-frequency part,
are calculated and the obtained data are also reported in Table 4. In theory, the value of  should be equal
to -1 for an ideal capacitor. However, the experimental  values range from -0.62 to -0.75, which might be
explained by the non-ideal structure of the metal/solution interface [5].
The n value seems to be related with the non-uniform distribution of current as a result of
roughness and possible oxide surface defects. When n = 1, CPE represents a perfect capacitor. A true
capacitive behavior is rarely obtained that is why CPE is usually used for data fitting instead of a perfect
capacitor. The present study shows that n < 1, in both uninhibited and inhibited media, confirming the surface
heterogeneity despite the adsorption of MPEO on the most active adsorption sites of the mild steel surface.
As reported in the literature, the slight decrease of n is an indicator of the surface inhomogeneity as a
result of the inhibitor’s adsorption [41]. An opposite trend is registered in our case which suggests an
enhance of homogeneity when MPEO is adsorbed.

3.5 Comparison of the overall results

90
Inhibiting Efficiency, %

85

80

75

0,7 70
Con 0,6 EIS
cen Ste
trat 5 rn
ion 0, S&
G
,C Tafe
inh / g 0,4 l
L -1 Gra
vim
th od
Me
etri
c

Figure 9. Comparison of the inhibition efficiency  % values obtained by weight loss, potentiodynamic
polarisation (Tafel, Stern & Geary and Stern) and EIS methods.
Int. J. Electrochem. Sci., Vol. 13, 2018 8213

A comparison may be made between inhibition efficiency  % values acquired from the different
undertaken weight loss, potentiodynamic polarisation curves (Tafel, Stern &Geary, Stern) and EIS
techniques. Fig. 9 shows a histogram of all results which can identify the gaps when comparing the
obtained  % values. One can see that whatever the method used, no significant changes are observed
in  % values and the same trend is conserved with rise of MPEO concentration when the best inhibiting
efficiency always stand for 0.7 g L-1 of MPEO. The coincidence between Tafel, Stern & Geary, and
Stern methods can suggest that no significant surface changes occur during the polarization
measurements at ± 200 mV versus Ecorr . The values of  % obtained by means of the polarization and
EIS experiments are somewhat higher than in the weight loss study but the trends persist the same. These
distinctions are most likely due to a more prominent to the variant contact time in the corrosive solution
which are 6 h and 1 h for weight loss and electrochemical techniques, respectively. It would then be able
to be inferred that there is a best correlation with the five methods apply in this examination at all studded
concentrations and that MPEO is an effective corrosion inhibitor for mild steel in 1 M HCl.

3.6 Effect of temperature

It is worthwhile considered to investigate the temperature effect as it can modify the interaction
among the metal electrode and the acidic medium in the presence and absence of MPEO. Table 5
illustrates the impact of temperature on metallic dissolution using weight loss measurements in the
temperature range from 308 to 348 K.
It is observed that the weight loss is circa 13 and 15 times greater, at 348 K when compared to
308 K, in uninhibited and inhibited media, respectively. However, it is worth to recall that the presence
of MPEO slows down the average corrosion rate, at all the studied temperatures, by 7 times by
comparison to the free medium. In contrast, the inhibitive efficiency seems to be little sensitive to the
effect of temperature.

Table 5. Weight loss results of the mild steel corrosion with and without addition of 0.7 g L −1 of MPEO
studied at different temperatures and after 2 h of immersion period.

Temperature Corrosion rate Wcorr WL

K mg cm-2 h-1 %
Blank MPEO
308 0.9736 0.1323 86.41
318 2.1325 0.2944 86.19
328 4.3174 0.6410 85.15
338 8.3047 1.2399 85.06
348 12.8556 1.9809 84.59
The activation energies of mild steel dissolution process in free and inhibited media are
calculated using Arrhenius Equation 17:
Int. J. Electrochem. Sci., Vol. 13, 2018 8214

 Ea

Wcorr  F e RT
(17)where F
is a frequency factor, E a is the apparent activation corrosion energy, R is the gas constant and T the
absolute temperature. Plotting ln Wcorr versus 1 / T gives straight lines as revealed from Fig. 10.

Blank
2 -1
0.7 g L of MPEO
-1
ln Wcorr / mg cm h

1
-2

-1

-2

2,9 3,0 3,1 3,2 3,3

-1
Temperature, 1000/T (K )

Figure 10. Arrhenius plots of mild steel in 1 M HCl with and without 0.7 g L-1 of MPEO.

-3

Blank
-1
-4 0.7 g L of MPEO
-1
ln (Wcorr /T ) mg cm h K
-1
-2

-5

-6

-7

-8
2,9 3,0 3,1 3,2 3,3
-1
Temperature, 1000/T (K )

Figure 11. Variation of ln Wcorr / T  vs. 1 / T in 1 M HCl with and without 0.7 g L−1 of MPEO.

The kinetic parameters are evaluated from the effect of temperature by using an alternative
formulation of Arrhenius relationship also called transition Equation 18 [46]:
S *  H *
RT R
Wcorr  e e RT (18)
Nh
where N is the Avogadro’s number, h is the Plank’s constant. S * and H * the entropy and
enthalpy of activation, respectively.
Int. J. Electrochem. Sci., Vol. 13, 2018 8215

Figure 11 shows the plots of ln Wcorr / T  against 1 / T for MPEO and straight lines are obtained
with a slope of (  H * / R ) and an intercept of ln R / N h  S * / R from which the values of H * and
S * are calculated, respectively.
Table 6 collects the values of activation parameters ( E a , H * and S * ) for mild steel dissolution
in the corrosive media with and without addition of 0.7 g L−1 of MPEO. In general, if an inhibitor causes
a rise in E a value when compared to the uninhibited solution, this could be frequently explicated as a
suggestion for the formation of an adsorptive film by physisorption mechanism [47,48]. While, a
decrease in E a value when compared to the uninhibited solution is often interpreted as an indication of
chemisorption [49]. Furthermore, Popova [50] has also discussed the evolution not only of E a but also
those of pre-exponential factor and inhibiting efficiency to get information on the adsorption mode. In
fact, physisorption is accepted, although the inhibiting efficiency decreases with rise of temperature and
the E a is higher than that in inhibitor’s free as well the pre-exponential factor which becomes greater in
the presence of inhibitor.

Table 6. The values of activation parameters F , E a , H * , S * for mild steel in 1M HCl in the absence
and presence of 0.7 g L-1 of MPEO.

Kinetic parameter Blank MPEO

F / mg cm-2 h-1 7.8089× 109 3.3416× 109
E a / kJ mol-1 58 61
H * / kJ mol-1 55 58
S * / J K-1 mol-1 -64 -71
E a - H * / kJ mol-1 3 3

In the present study, the obtained apparent activation energy values are 58 and 61 kJ mol-1 for
blank, and at 0.7 g L-1 of MPEO, respectively. This indicates that the presence of MPEO inhibitor in
aggressive solution apparently does not considerably affect the E a value of the metal dissolution.
Comparable results have been described by Hammouti when using Lavender oil, and Pennyroyal mint
oil in acidic solutions [20,51]. The frequency factor F decreases by circa two times while WL %
decreases very slightly and remains higher close to 86 % though temperature rising which go together
with a slow increase of E a by 3 kJ mol-1. These finding testify that physisorption constitutes the most
probable type of adsorption of MPEO onto mild steel surface. This electrostatic or physical adsorption
can be understood because of the acidic medium nature in which by protonation of the MPEO
components (having heteroatom), the molecules become positively charged and can interact with
previously adsorbed chloride anions Cl- at the positively charged surface [41].
Besides, Table 6 reveals that the positive value of activated enthalpy H * means that the process
is an endothermic process and it needs more energy to achieve the activated state or equilibrium state
[52,53]. It is to be noted that E a and H * values vary similarly allowing to confirm the well-known
thermodynamic Equation 19 between E a and H * as exposed in Table 6 [54]:
Int. J. Electrochem. Sci., Vol. 13, 2018 8216

H *  Ea  R  T  (19)
Concerning the entropy of activation S * , it is clear that the entropy S * increases negatively
in the presence of MPEO than that in the blank one. This reflects the formation of an ordered stable layer
of MPEO onto the mild steel surface electrode [55]. The decrease of S * in inhibited medium implies
that the activation of MPEO in the rate-determining step represents dissociation rather than an
association step, meaning a decrease in disordering taking place on moving from reactants to activated
complex [56]. This finding is in agreement with those of other co-workers [57,58].

3.7. Adsorption isotherm

The adsorption isotherm provides insights into the mechanism of corrosion inhibition. So, the
determination of relation among corrosion inhibition and adsorption is of great importance. The
adsorption of inhibitor molecules at the electrode/solution interface takes place through the substitution
of water molecules according to Equation 20:
Org ( sol )  xH 2 O( ads )  Org ( ads )  xH 2 O( sol ) (20)
where Org (sol ) and Org (ads ) are organic molecules in the solution and adsorbed on mild steel
surface, respectively.

Table 7. The different linearized isotherm models undertaken in the present study.

Isotherm Linearized form Equation

C inh 1
Langmuir   C inh (22)
 K ads
  
El-Awady log    y log K ads  y log C inh (23)
1   

Flory-Huggins log( )  log x K ads  x log(1   ) (24)
C inh
1 
Langmuir-Freundlich log( Cinh )   log K ads  log( ) (25)
m 1
1 1
Temkin   ln K ads  ln C inh (26)
2 a 2a
Dubinin-Radushkevich ln   ln  max  P   2 (27)
Freundlich ln   ln K ads  z ln Cinh (28)
1 
Frumkin ln C inh     ln K ads  2d (29)
  

The surface coverage  values are followed from weight loss, dc polarization methods (Tafel,
Stern & Geary, Stern), and EIS measurements at various concentrations of MPEO at 308 K according to
Equation 21.
Int. J. Electrochem. Sci., Vol. 13, 2018 8217

%
 (21)
100
Several adsorption isotherms are assessed and reported in Table 7. The adsorption models
including Langmuir, El-Awady, Flory-Huggins, Freundlich, Dubinin-Radushkevich, Langmuir-
Freundlich, Temkin and Frumkin isotherms are applied to fit the surface coverage values at different
concentrations of MPEO. On the basis of isotherms criteria [59–61],  is related to the inhibitor
concentration Cinh via Equations 22-29 given in Table 7:
where 1/ y gives the number of H2O molecules removed by one inhibitor molecule. x is a size
parameter and constitute a measure of the number of adsorbed water molecules replaced by a given
inhibitor molecule. z is the constant describing the nature of mild steel/medium (MPEO) interface,
where 0  z  1. m is the heterogeneity parameter (0 <m< 1) is the heterogeneity parameter which
characterizes the distribution of adsorption energy at different sites on a non-ideal surface.  max is the
maximum surface coverage and  is the polany potential and can be estimated from the following
Equation 30:
1
  R T (1  ) (30)
C inh
The constant  max and P (mol2 kJ-2) are estimated from the intercept and slope of the plot,
respectively. And E , which is the transfer energy of one mole of adsorbate from infinity (bulk solution)
to the surface of the adsorbent given by Equation 31:
1
E (31)
2P
a and d represent interactions factors among adsorbed molecules (these interaction parameters
may be negative or positive: a or d  0 indicates repulsion force, a or d  0 shows the lateral attraction
between adsorbed organic molecules. K ads , expressed in L g-1, is the adsorption coefficient or adsorption
equilibrium constant which is related to the standard Gibbs free energy of adsorption,  r Gads
0
, in kJ mol-
1
, according to Equation 32 [62]:
  r G 0 ads
1
K ads  e RT
(32)
C H 2O
where R is the universal gas constant, T the thermodynamic temperature and the concentration
of water in the solution is 1000 g L-1.
The straight lines are traced using the least squares method. The experimental data (points) and
fitting data (lines) for the best isotherm model are plotted in Figure 12.
To select the isotherm that good fit to experimental results, R 2 was utilized. The best fitting was
calculated with the value of R 2 reaches to 0.999 and the fitted line gives a slope very close to unity,
which suggests that the experimental results can obtain by Langmuir isotherm. This isotherm postulates
that the energy of adsorption is independent of θ and it is no interaction among the adsorbed compounds
contained in MPEO. Moreover, Langmuir isotherm accepts that the mild steel surface contains a fixed
number of adsorption sites, and each holds one adsorbed species [21].
Int. J. Electrochem. Sci., Vol. 13, 2018 8218

0.8 Langmuir

-1
0.7

Cinh/  g L
Gravimetric
Tafel
Stern & Geary
0.6
Stern
EIS

0.5

0.4 0.5 0.6 0.7

-1
Inhibitor Concentration, Cinh/ g L

Figure 12. Langmuir isotherm model of MPEO onto the mild steel obtained from five undertaken
methods.

Table 8. Parameters values issued from linearized Langmuir adsorption isotherm model for the
adsorption of MPEO onto the mild steel surface in 1 M HCl at 308 K.

Isotherm Method R2 Slope K ads  r Gads

0

Weight loss 0.997 0.933 6 -22

Tafel 0.999 1.056 12 -24
S&G 0.999 1.067 12 -24
Stern 0.996 1.012 10 -23
EIS 0.999 1.031 10 -23

Finally,  r Gads
0
is calculated from Equation 32 despite the controversies met in the literature
[20,63] because the component(s) of the essential oil components remain(s) unknown. In contrary, other
researchers [17–19] calculate this variable and discussed it on the basis of  r Gads
0
values around ‒20 kJ
mol-1 or less negative are related to an electrostatic interaction between charged mild steel surface and
charged essential oil molecules; that is physisorption. whereas, those of ‒40 kJ mol-1 or more negative
apply charge sharing or transfer from MPEO molecules to the electrode surface to form a coordinate
type bond; i.e., chemisorption [64]. Thus, it remains not easy to discriminate either chemisorption or
physisorption simply based on these criteria, particularly when charged species are adsorbed. The
opportunity of Coulomb interactions between adsorbed anions and specifically adsorbed cations can
increase the Gibbs energy even if no chemical bond appears [66]. Once again, referring to the whole
results and on the basis of the obtained  r Gads
0
, it seems difficult to be able to pronounce in a categorical
way on both mechanisms.
Int. J. Electrochem. Sci., Vol. 13, 2018 8219

4. CONCLUSION

The corrosion inhibition of mild steel in molar hydrochloric medium by Mentha Piperita
essential oil (MPEO) was studied using common weight loss, electrochemical and SEM techniques.
According to experimental results, it could be concluded that:
1. MPEO constitutes an effective corrosion inhibitor for the mild steel in 1 M HCl. The
inhibiting efficiency is concentration dependent reaching value up to 87% at 0.7 g L−1.
2. The high-resolution scanning electron microscopy micrograph indicates that the surface
morphology shown in the presence of MPEO is significantly different and more regular than that
obtained in free inhibitor medium.
3. The potentiodynamic polarization curves are three times explored with Tafel, Stern &
Geary, Stern methods and show that MPEO acts as mixed type inhibitor. No significant surface change
can be registered in the potential window ranged from - 200 mV to + 200 mV vs. the corrosion potential.
4. EIS measurements studies reveal that the MPEO reduced the corrosion rate by increasing
the resistance of the system, and all the diagrams are interpreted in terms of an appropriate equivalent
circuit.
5. The overall results derived from weight loss, (Tafel, Stern & Geary, Stern) polarizations,
and EIS measurements are in fairly good agreement.
6. The adsorption of MPEO molecules obeys to Langmuir adsorption isotherm model.

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