Portugaliae Electrochimica Acta 2014, 32(4), 271-280 PORTUGALIAE

ELECTROCHIMICA
DOI: 10.4152/pea.201404271 ACTA
ISSN 1647-1571

Corrosion Inhibition of Carbon Steel in Hydrochloric Acid

Solution by Mentha Pulegium Extract

A. Khadraoui,a,* A. Khelifa,a H. Boutoumi,a B. Mettai,b

Y. Karzazi,c,d B Hammouti c,*
a
Laboratoire de Génie chimique, Département de Génie des Procédés, Faculté de
Technologie, Université de Blida I, BP 270, Route de Soumaâ, 09000, Blida, Algérie
b
Centre de Recherche et Développement, BP 194, Bouchaoui, 16000, Alger, Algérie
c
LACE-URAC18, Faculty of Sciences, University Mohammed Premier,
B.P. 4808, 60046 Oujda, Morocco
d
National School of Engineering and Applied Sciences, University Mohammed Premier,
B.P. 3, 32003 Sidi Bouafif, ENSA Al Hoceima, Morocco

Received 15 June 2014; accepted 21 August 2014

Abstract
The inhibition effect of Mentha pulegium extract (MPE) on the acid corrosion of carbon
steel in 1 M HCl solution was investigated using weight loss, potentiodynamic
polarisation, and electrochemical impedance spectroscopy. The results show that the
Mentha pulegium extract is a good inhibitor, and that the inhibition efficiency depends
on the concentration of the plant extract. Efficiency is higher than 88 % for 33% Mentha
pulegium extract. Polarization measurements also show that Mentha pulegium extract is
a good mixed inhibitor. The remarkable inhibition efficiency of MPE was discussed in
terms of blocking of the electrode surface by adsorption of inhibitor molecules through
active centres. Mentha pulegium extract is adsorbed on the carbon steel surface
according to the Temkin adsorption model. The effect of temperature on the corrosion
behaviour of carbon steel in 1 M HCl with addition of 33% MPE was studied in the
temperature range 308-338 K. SEM also confirmed the adsorption of MPE on carbon
steel surface.

Keywords: Mentha pulegium; Green Inhibitor; Adsorption; SEM; Carbon steel.

Introduction
Natural products were previously used as corrosion inhibitors for different metals
in various environments [1, 2] and their optimum concentrations were reported.

*
Corresponding author. E-mail address: hammoutib@gmail.com; khadraoui.abdelkader@gmail.com
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The obtained data showed that plant extracts could serve as effective corrosion
inhibitors and they have become important because they are environmentally
acceptable, readily available and renewable sources for a wide range of needed
inhibitors. Plant extracts are viewed as an incredibly rich source of naturally
synthesized chemical compounds that can be extracted by simple procedures
with low cost. The extracts from the leaves, seeds, heartwood, bark, roots and
fruits of plants have been reported to inhibit metallic corrosion in acidic media
[3-5].
It has been established that the inhibitory actions of plant extracts are due to the
presence of some organic compounds such as saponin, tannin, alkaloid, steroids,
glycosides, and amino acids [6-10]. Most of these compounds have centers for π-
electrons and functional groups which provide electrons that facilitate the
adsorption of the inhibitor on the metal surface. Also, the presence of hetero
atoms such as N, P, O, and S enhances the adsorption (which is the initial
mechanism of inhibition) of the inhibitor on the metal surface [11-22].
In Algeria, collection of medicinal and aromatic plants to extract, after
distillation, essential oils for the manufacture of cosmetics, pharmaceuticals as
well as flavors for food products, is a virgin field. The distillation of plants is
sufficiently known, but remains largely untapped, despite the availability in
Algeria of large tracts of forests and fields, whose territory covers important
plant resources distributed on the coasts, plains, mountains, steppes, the Sahara
and around water points.
Mentha pulegium can be used as a corrosion inhibitor for carbon steel. It is a
native and perennial aromatic herb of the Mediterranean region, but it is widely
growing in many parts of the world in temperate and tropical countries; Mentha
pulegium is a species of flowering plant in the family Lamiaceae. The leaves
exhibit a very strong fragrance similar to spearmint. It is a traditional culinary
herb, folk remedy, and abortifacient. Mentha pulegium are sources of diverse
classes of natural compounds such as flavonoids, alkaloids, essential oils [23].
In the present work, the inhibitive action of Mentha pulegium extract (MPE) as a
cheap, eco-friendly and naturally occurring substance on the corrosion behavior
of carbon steel in 1 M HCl has been investigated through weight loss
measurements, potentiodynamic polarization and electrochemical impedance
spectroscopy (EIS) methods and surface analyses.

Experimental procedure
Plant collection and extraction
Mentha pulegium was collected during June 2009 in Ain-defla, north Algeria, at
280 m altitude. The aerial parts of the plant were air-dried in the laboratory at
room temperature. Stock solutions of the plant extract were prepared by
extracting weighed amounts of the powder of the dried leaves for 3 days in 1 M
HCl (Merck) at 298 K with continuous agitation. The solution was filtered and
stored.

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The filtrates from both acid extractions had a reddish-brown appearance. From
the stock solutions, inhibitor test solutions were prepared in the concentration
range 1–50 % (v/v).

Weight loss measurements

Coupons cut into (2 × 1.5 × 0.2) cm3 dimensions having composition (0.13% C,
0.32% Si, 0.64% Mn, 0.15% Cu, 0.012% S, 0.01% P, 0.038% Al, 0.081% Cr,
0.011% Mo, 0.083% Ni, 0.01% V and Fe balance) are used for weight loss
measurements. Prior to all measurements, the exposed area was mechanically
abraded with 280, 400, 600, 800, 1200 grades of emery papers. The specimens
are washed thoroughly with bidistilled water, degreased and dried with ethanol
before being weighed and immersed in 60 mL of the corrosive medium. The
immersion time for the weight loss measurements was 6 hours at 298 K.

Electrochemical tests
The electrochemical study was carried out using an EG&G potensiostat/
galvanostat (PAR 273A) piloted by CORR III software. This potentiostat is
connected to a cell, with three electrodes, thermostats with double wall. A
saturated calomel electrode (SCE) and a platinum electrode were used as
reference and auxiliary electrodes, respectively. The material used for
constructing the working electrode was the same used for gravimetric
measurements. The surface area exposed to the electrolyte is 0.64 cm2.
Potentiodynamic polarization curves were plotted at a polarization scan rate of
1 mV/s. Before all experiments, the potential was stabilized at free potential
during 30 min. The polarization curves are obtained from −750 mV to -
250mV at 298 K. The solution test has been done after de-aerated by bubbling
nitrogen. Gas bubbling is maintained prior and through the experiments. The
data in Tafel region have been processed for evaluation corrosion kinetic
parameters by plotting the polarization curves. The linear Tafel segments, in a
large domain of potential, of the cathodic curves were extrapolated to the
corresponding corrosion potentials to obtain the corrosion current values.
The electrochemical impedance spectroscopy (EIS) measurements are
carried out with the Analyzer of function of transfer model 5210, piloted by
Powersuite software. After the determination of the steady-state current at a
corrosion potential, sine wave voltage (10 mV) peak to peak, at frequencies
between 100 kHz and 10 mHz are superimposed on the rest potential.
Computer programs automatically controlled the measurements performed at
rest potentials after 30 min of exposure at 298 K. The impedance diagrams
are given in the Nyquist representation. Experiments are repeated three times
to ensure the reproducibility.

Results and discussion

Gravimetric measurements
The effect of the addition of Mentha pulegium extract (MPE) tested at different
concentrations on the corrosion of carbon steel in 1 M HCl solution was studied

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using weight-loss method at 298 K after 6 h of immersion period. Inhibition

efficiency E (%) is calculated as follows:
 Wcorr- W'corr 
E(%) =   100 (1)
 Wcorr 
where Wcorr and W'corr are the corrosion rate of carbon steel in 1 M HCl in
absence and presence of the inhibitor, respectively.
Table 1 gives values of the rate of corrosion (mg cm-2 h-1) and inhibition
efficiency (E %) for corrosion of carbon steel in 1 M HCl in the presence of
mentha pulegium extract as green inhibitor at different concentrations.

Table 1. Gravimetric results of the carbon steel corrosion with and without addition of
MPE after 6 h of immersion in 1 M HCl at 298 K.
System W (mg/cm2h) E (%)
Blank 0.1693 /
6.25% 0.1049 38.04
12.5% 0.0820 51.55
25% 0.0620 63.36
33% 0.0295 82.54

From Table 1, it’s clear that the corrosion rate of carbon steel in the blank is
higher in comparison with the blank containing MPE. The W decreased when the
concentration of inhibitors increased. The addition of 6.25% mentha pulegium
extract into the aggressive medium reduces the corrosion rate by 38 %, reaching
82.54 % with the addition of 33% of mentha pulegium extract. The inhibition
efficiency of mentha pulegium extracts increases as a function of their
concentration. This result suggests that an increase in extract concentration
increases the number of inhibitor molecules adsorbed onto the carbon steel
surface and reduces the surface area that is available for the direct acid attack on
the metal surface.

Figure 1. Potentiodynamic polarisation curves for carbon steel in 1 M HCl in the

presence of different concentrations of plant extract (MPE).

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Polarization curves
Potentiodynamic polarization curves of carbon steel in molar HCl in the absence
and presence of MPE at different concentrations at 298 K are presented in Fig. 1.
From this figure, it can be seen that with the increase of the extract
concentrations, both anodic and cathodic currents were inhibited. This result
shows that the addition of the Mentha pulegium inhibitor reduced anodic
dissolution and also retarded the hydrogen evolution reaction.
In addition, the parallel cathodic Tafel curves in Fig. 1 show that the hydrogen
evolution is activation controlled, and the reduction mechanism is not affected by
the presence of the plant extract [24].
Table 2 shows the fitting results of the polarization curves obtained. Other
electrochemical parameters and the inhibition efficiencies of the extract can be
determined from the corrosion current densities (icorr) with and without inhibitors,
which are also presented in Table 2.

Table 2. Electrochemical data for steel in 1 M HCl in the absence and presence of
different concentrations of Mentha pulegium extract, and the corresponding inhibition
efficiency.
Ecorr Icorr βc E
System 2
(mv/SCE) (µA/cm ) (mV/dec) (%)
Blank -504 422.3 115.4 -
6.25% -497 220.9 140.7 47.69
12.5% -499 208.1 141 50.72
25% -501 133.6 138 68.63
33% -500 49.22 144.5 88.34

In this case, the inhibition efficiency is defined as follows:

 I'  (2)
E% = 1 − corr 100
 I corr 

where Icorr and I’corr are current densities in absence and presence of MPE,
respectively. We noted that Icorr and I’corr were calculated from the intersection of
cathodic and anodic Tafel lines.
The inspection of results in Table 2 indicates that the inhibition efficiency of the
Mentha pulegium extract is 88%; the free corrosion potential determined after 30
mn of immersion does not change in the presence of the green inhibitor; thus, it
can be classified as a mixed-type inhibitor in 1 M HCl.

Electrochemical impedance spectroscopy measurements

EIS has been shown to be a powerful tool to study the corrosion processes of
metals in different environments and to characterize the inhibition ability of a
corrosion inhibitor, which is related to the charge transfer resistance (Rt). The
double-layer capacitance (Cdl) can also be used to determine the inhibition
ability. The inhibition performance of an organic or natural substance on a metal
surface depends not only on the chemical structure of the organic substance and
the nature of the metal, but also on the experimental conditions such as the
immersion time and the concentration of the adsorbent.

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The corrosion behavior of carbon steel, in acidic solution with and without
Mentha pulegium extract, is also investigated by electrochemical impedance
spectroscopy (EIS) measurements at 298 K (Fig. 2).

Figure 2. Nyquist plots of steel in 1 M HCl with and without different concentrations of
Mentha pulegium extract at 298 K.

The electrochemical impedance parameters derived from these investigations are

mentioned in Table 3.

Table 3. Impedance parameters for corrosion of carbon steel in 1 M HCl in the absence
and presence of different concentrations Mentha Pulegium extract at 298 K.
System Rt (Ω.cm2) E (%) fmax(Hz) Cdl (ŋF/cm2)

98.46
Blank 62.63 / 25.82
6.25% 116.8 46.37 45.39 30.03
26.55
12.5% 122.2 48.74 49.08
25% 207.7 69.84 100.81 7.60
33% 457.3 86.30 146.01 2.38

The inhibition efficiency got from the charge transfer resistance is calculated by:
 R − R°t 
E % =  t 100 (3)
 Rt 
where Rt and R0t are the charge transfer resistances in inhibited and uninhibited
solutions respectively.
The charge transfer resistance (Rt) values are calculated from the difference in
impedance at lower and higher frequencies, as suggested by Tsuru et al. [25].
As it can be seen from Fig. 2, impedance diagrams show a semi-circular
appearance, indicating that a charge transfer process mainly controls the
corrosion of carbon steel. From the impedance data, we notice an increase in the
charge transfer resistance and decrease of the double layer capacitance with
increasing the inhibitor concentration, indicating that Mentha pulegium extract
inhibits the corrosion rate of carbon steel by an adsorption mechanism.

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Therefore, the decrease in the Cdl value can be attributed to a decrease in the
local dielectric constant and/or an increase in the thickness of the electrical
double layer, suggesting that the inhibitor molecules act by adsorption at the
metal/solution interface as a consequence of the replacement of water molecules
by the inhibitor molecules [26].
A comparison may be made between the inhibition efficiency E (%) values
obtained by different methods (weight loss and electrochemical methods).We can
see that whatever the method used, no significant changes are observed in E (%)
values. We can then conclude that there is a good agreement with the three
methods used in this investigation at all tested concentrations and that the acid
extract of Mentha pulegium acts as green inhibitor for acid corrosion of carbon
steel.

Adsorption considerations
Adsorption isotherm is necessary in studying the mechanism of adsorption and
also the adsorption characteristics of the inhibitor.
In order to obtain the isotherm, coverage ө as a function of MPE concentration
must be obtained being Ө is the ratio E (%)/100. Several isotherms were tested,
such as Langmuir, Temkin, Frumkin, etc., to well fit experiments data.
Fig. 3 shows the variation of Ө against the logarithm of the Mentha pulegium
extract concentration. The data fit a straight line, with a slope nearly equal to
unity, indicating that these compounds adsorb according to Temkin adsorption
isotherm. The linear correlation coefficient is 0.993, close to unity.

Figure 3. Plots of Temkin adsorption isotherm of Mentha pulegium extract on the

carbon steel surface at 298 K.

The Temkin isotherm equation is:

Exp ( − 2 a.θ ) = K ads .C (4)

where C is the Mentha pulegium extract concentration and Kads the equilibrium
constant of the adsorption process.

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Effect of temperature
The effect of temperature on the corrosion parameters of carbon steel in free and
inhibited solutions of 1 M HCl was studied using weight loss measurements
during 1 hour in the temperature range 308–338 K; the corresponding results are
summarised in Table 4.

Table 4. Effect of temperature on the carbon steel corrosion in the presence and absence
of 33% of MPE at 1 h.
T (K) W0 (mg/cm2.h) W (mg/cm2.h) E (%)
308 0.3381 0.0626 81. 62
318 1.1464 0.2207 80.74
328 4.0315 0.6920 82.84
338 12.391 1.852 85.05

The data in Table 4 indicate that the acid attacks were inhibited by addition of
33% of Mentha pulegium extract. But the increase in corrosion rate is more
pronounced with the rise of temperature for the uninhibited acid solution. The
presence of the inhibitor leads to decrease of the corrosion rate. E% depends
upon the temperature and increases with it.

Activation energy calculations

The change of the corrosion rate in presence and absence of 33% of Mentha
pulegium extract was plotted against temperature for calculation of the activation
energy (Fig. 4).

Figure 4. Arrhenius plots of carbon steel in 1 M HCl with and without 33% MPE.

The apparent activation energies (Ea) for the corrosion process in absence and
presence of the inhibitor were evaluated from the Arrhenius equation:
Ea
W = A. exp(− ) (5)
R.T
The effects of MPE increase the energy of activation and reduce the surface
available for corrosion [27]. Addition of plant extracts at 33% in 1 M HCl
decreases the activation energy from 92.41 to 89.32 kJ mol-1. This diminution
may be attributed to the change in the mechanism of the corrosion process in the

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presence of adsorbed inhibitor molecules [28, 29]. The lower value of the
activation energy of the process in the inhibitor’s presence when compared to
that in its absence is attributed to its chemisorptions [30-32].

Scanning Electron Microscopy (SEM)

SEM images were recorded to investigate the changes occurred on the surface of
the carbon steel samples after 24 h immersion in 1 M HCl solution in the absence
and presence of the inhibitor. Fig. 5 (a) presents the micrograph obtained for a
carbon steel sample after exposure to blank solution, while Fig. 5 (b) presents the
surface morphology of carbon steel specimens immersed in 1 M HCl medium
containing 33% of Mentha pulegium extract.

Figure 5. SEM images of carbon steel surface after 24 h immersion in 1 M HCl

solutions in the absence (a) and presence (b) of 33% MPE.

As can be seen from Fig. 5 (a), carbon steel surface in the uninhibited solution is
severely damaged and rough due to an aggressive attack of the corroding
medium. Fig. 5 (b) reveals that the corrosion marks on the inhibited samples
decrease in presence of Mentha pulegium extract which also attests the inhibition
ability and adsorption of the inhibitor on the carbon steel surface. Moreover the
parallel lines on the carbon steel surface can be attributed to polishing scratches.

Conclusion
In this study, corrosion inhibition efficiency of Mentha pulegium extract (MPE),
in 1 M HCl medium was determined by weight loss, potentiodynamic
polarisation and electrochemical techniques. Results evidenced that this green
inhibitor showed excellent performance (more than 88% at 33%) as corrosion
inhibitor. It inhibits through adsorption process and was found to follow Timkin
adsorption isotherm.
Impedance studies revealed that the inhibitor reduced the corrosion rate by
increasing the resistance of the system. Potentiodynamic polarization studies
confirmed that the inhibitor acted through a mixed type of corrosion inhibition
mechanism.
From SEM images, it can be deducted that the carbon steel surface became
smoother in the presence of Mentha pulegium extract which had a positive effect
on the corrosion properties of carbon steel.

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