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(Wuli Huaxue Xuebao)

1254

Acta Phys. Chim. Sin., 2009, 25(7)


1254-1258

[Article]

July
www.whxb.pku.edu.cn

Limonene as Green Inhibitor for Steel Corrosion in


Hydrochloric Acid Solutions
CHAIEB E.

BOUYANZER A.

HAMMOUTI B.

(Laboratoire de Chimie Applique et Environnement, Facult des Sciences

BERRABAH M.

60 000 Oujda, Morocco)

Abstract:
The inhibition of steel corrosion in hydrochloric acid solutions by limonene, which was extracted from
citrus and orange fruit, was studied using measurements of mass loss, electrochemical polarisation and electrochemical
impedance spectroscopy (EIS) methods. Naturally, the substance reduced the rate of corrosion. The linearity of the cathodic
curves for all concentrations indicated that the law of Tafel was followed. The effectiveness of inhibition increased
with the increase in concentration of limonene and this exceeded 72% at 0.220 gL -1. The inhibition efficiency is
temperature independent in the temperature range of 298-328 K. Adsorption of the substance on the surface of steel
obeys the Frumkin isotherm model.
Key Words:

Corrosion; Inhibition; Limonene; Acid;

Inhibitors are generally required to secure metals against acid


attack. Their inhibitive properties arise from their ability to adsorb onto the electrode surface. The relation between the adsorption inhibition mechanism and variation in the electronic structure of the inhibitor has been widely studied[1-5]. The most important fields of application of inhibitors are acid pickling, industrial acid cleaning, acid descaling and oil well acidizing.
Organic compounds are either synthesized or extracted from
aromatic herbs, spices and medicinal plants. Unfortunately, most
of these synthetic chemical compounds are very expensive and
hazardous to living creatures and environments. The current preoccupation of the researchers is to find nontoxic inhibitors.
Nevertheless, an important disadvantage of these compounds is
their toxicity and most of them are not biodegradable heterocyclics. Trends in environmental protection and ecological policies for the use of chemicals have changed the traditional approach of corrosion inhibition science. Currently, research is focused on producing and testing environmentally friendly corrosion inhibitors. A feasible solution to this problem is the use of
corrosion inhibitors derived from amino acids; these compounds
constitute an important potential class of natural substances
called green inhibitors[6-8].
Literature showed a growing trend in the use of natural products known as nontoxic compounds for corrosion inhibitors. We
cited natural honey[9], opuntia extract [10], nypa fructicans wurmb [11],
ginger [12], henna [13], azadirachta indica [14], thyme [15], jojoba oil [16],
Artemisia oil[17], rosemary oil[18], eugenol[19], bgugaine[20] and pulegone[21], which have been found to be very efficient corrosion inhibitors for metal in aggressive media.

Adsorption
In this optic, survey literature shows that limonene has a number of medical applications. Limonene is a very versatile chemical which can be used in a wide variety of applications like anti
tumour, antiinflammatory activities[22-24]. It is extremely safe and
more effective than typical cleaning solutions. These properties
incite us to test limonene in the corrosion protection field.
The objective of this paper is to study the effect of limonene
on the corrosion of steel in 1 molL -1 HCl solution by gravimetric, electrochemical polarisation and EIS methods. The effect of
temperature is also studied.

1 Experimental
Steel (0.21% C, 0.38% Si, 0.09% P, 0.01% Al, 0.05% Mn, 0.05%
S) is used. The aggressive solution (1 molL -1 HCl) is prepared
by dilution of analytical grade 37% HCl with double distilled
water.
Limonene is extracted in the following way: to adapt a cooling agent to water with a balloon of one litre in which we put the
higher part of the bark of 10 cut oranges in small pieces
(weighed beforehand) and 300 mL of water and some stones
pounces (or crushed brick). The balloon is quickly heated and then
one continues the heating in a very soft way. The distillate is
collected in a testtube graduated. We elutriate in a funnel separating and then the limonene phase is collected after separating
the aqueous phase.
Limonene is an uncoloured liquid at the ambient temperature.
The plane structural formula for limonene is shown in Fig.1.
Mass loss is measured on sheets of steel of apparent surface

Received: January 23, 2009; Revised: April 1, 2009; Published on Web: April 21, 2009.

Corresponding author. Email: hammoutib@gmail.com; Tel: +212536500602; Fax: +212536500603.


The project was supported by the University of Oujda, Morocco.

Editorial office of Acta PhysicoChimica Sinica

No.7

CHAIEB E. et al.
Limonene as Green Inhibitor for Steel Corrosion in Hydrochloric Acid Solutions

1255

R= Rt-R t 100%
(3)
Rt
0
where, R t and Rt are the uninhibited and inhibited charge transfer resistance, respectively,
0

2 Results and discussion

Fig.1

Chemical structure of limonene

area of 5 cm . These sheets are abraded successively with fine emery paper until 1200 grade. The sheets are then rinsed with distilled water, degreased and dried before being weighed and immersed in 100 mL corrosive medium. The immersion time for
the mass loss is 6 h at room temperature (298 K) and 1 h at the
other temperatures in air without bubbling in a double walled
glass cell equipped with a thermostatcooling condenser.
The inhibition efficiency for the mass loss method (EM) is
calculated as follows:
0
corr
100%
(1)
EM= W corr-W
W 0corr
0
where, Wcorr and W corr
are the corrosion rates of steel with and
without inhibitor, respectively.
Electrochemical measurements are carried out in a conventional three-electrode cylindrical glass cell. The working electrode, a disc cut from steel, has a geometric area of 1 cm2 . A
saturated calomel electrode (SCE) and platinum electrode are
used as reference and auxiliary electrodes, respectively. The
temperature is thermostatically controlled at 298 K. The polarisation curves are recorded with a potentiostat type EG&G 273,
at a scan rate of 30 mVmin -1 . The steel electrode is pre
polarised at -800 mV for 10 min and thereafter the curves are
recorded to more noble potentials. The test solution is deaerated
for 30 min in the cell with pure nitrogen. Gas bubbling is maintained throughout the experiments.
Electrochemical impedance spectroscopy (EIS) was carried
out with a Tacussel electrochemical system which included a
digital potentiostat model Voltalab PGZ 100 computer at Ecorr
(corrosion potential) after immersion in solution without bubbling, and the circular surface of steel exposing of 1 cm2 to the
solution was used as work electrode (WE). After the determination of steadystate current at a given potential, sine wave volt
age (10 mV) peak to peak, at frequencies between 100 kHz and
10 mHz was superimposed on the rest potential. Computer programs automatically controlled the measurements performed at
the rest potentials after 30 min of exposure. The impedance diagrams are given in the Nyquist representation.
In the case of polarisation method the relation determines the
inhibition efficiency ():
0
corr
100%
(2)
= I corr-I
I 0corr
0
where, I corr
and Icorr are the uninhibited and inhibited corrosion
current densities, respectively, determined by extrapolation of
cathodic Tafel lines to corrosion potential.
2

0
Table 1 lists the corrosion rates in 1 molL-1 HCl (Wcorr
) and at
various concentrations of the tested compound (Wcorr) determined
during 6 h of immersion at 298 K and the corresponding inhibition efficiency (EM).
It is clear that the addition of limonene reduces the corrosion
rate in HCl solution. The inhibitory effect increases with the increase of limonene concentration to reach a maximum of 72% at
0.220 gL -1 for limonene. We may conclude that limonene is a
good inhibitor of steel corrosion in 1 molL-1 HCl solution.
Fig.2 shows the cathodic polarisation curves of steel in 1 mol
L-1 HCl in the absence and presence of limonene at various concentrations. The corrosion potential (Ecorr), corrosion current density (Icorr), cathodic Tafel slope (bc) deduced from Fig.2 and the calculated efficiency () are listed in Table 2.
It is clear that the addition of the natural substance decreases
the corrosion current density. The cathodic portions rise to Tafel
lines indicating that the hydrogen evolution reaction is activation
controlled. The parallel Tafel line obtained reveals that the addition of the natural substance to the corrosive solution does not
modify the mechanism of the reduction process.
The calculated inhibition efficiency () increases with the
increase in concentration of limonene to attain a maximum value

Table 1

Steel mass loss data and inhibitor efficiency of


limonene at 298 K for 6 h

Climonene/(gL-1) 104climonene /(molL-1)

Wcorr/(mgcm-2h-1)

EM(%)

0.000

0.00

0.674

0.0088

0.65

0.638

0.022

1.63

0.601

11

0.044

3.26

0.321

52

0.066

4.89

0.269

60

0.088

6.52

0.212

69

0.132

9.78

0.202

70

0.220

16.3

0.188

72

Fig.2 Polarisation curves of steel in 1 molL-1 HCl with


various contents of limonene at 298 K

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Table 2 Polarisation parameters for the corrosion of steel in


1 molL-1 HCl with different concentrations of limonene at 298 K
Climonene/(gL-1)

Ecorr /mV (vs SCE)

Icorr/(Acm-2)

0.000

-439

520

196

0.022

-440

376

194

28

0.044

-446

280

197

46

0.066

-437

232

195

55

0.088

-431

168

192

67

0.132

-434

160

192

69

0.220

-424

136

188

74

bc/(mVdec-1) (%)

of 74% at 0.220 gL-1.


On the other hand, the anodic curves obtained in Fig.2 reveal
that limonene brings down the anodic current density without
causing any appreciable change in free corrosion potentials determined after 1 h of immersion, suggesting that limonene is a
mixed type inhibitor.
We notice that the presence of limonene acts on the anodic
curves by a decrease of the current density. Then the decrease in
corrosion rate may be explained by the inhibitory action on both
cathodic and anodic sites of the steel surface. The natural substance of limonene is then a good inhibitor and acts as a mixed
inhibitor.
The impedance diagrams obtained after 30 min of immersion
of the electrode in the absence and presence of limonene at various contents at 298 K are shown in Fig.3. The impedance parameters, such as charge transfer resistance (Rt), maximum frequency (fmax ) and double layer capacitance (Cdl ), are derived
from these investigations and listed in Table 3.
As we notice, the impedance diagrams (Fig.3) show perfect
semicircles indicating a charge transfer process mainly controlling the corrosion of steel. The charge transfer resistance (Rt)
values are calculated from the difference in impedance at lower
and higher frequencies. The double layer capacitance (Cdl) and the
frequency at which the imaginary component of the impedance
is maximal (-Zmax) are found as represented in equation:
Cdl=fmaxRt/2
(4)
The inhibition efficiency got from the chargetransfer resistance (ERt) is calculated by:

Table 3

Nyquist diagrams for steel with or without limonene


after 30 min of immersion

EIS parameters of steel in 1 molL-1 HCl at


different concentrations of limonene
Cdl /(Fcm-2)

ERt(%)

0.00

136

16.0

74.0

1.63

226

9.4

72.3

40

6.52

384

5.9

69.5

65

9.78

429

5.8

63.0

68

16.3

482

5.6

58.0

72

104climonene /(molL-1) Rt /(cm2)

fmax /Hz

t
100%
(5)
ERt= R -R
R0t
where, Rt and R 0t are the chargetransfer resistance values with
and without inhibitor, respectively. In fact, the presence of limonene
enhances the value of Rt in acidic solution. Values of double layer capacitance are also brought down to the maximum extent in
the presence of inhibitor. The decrease in Cdl is due to the adsorption of this compound on the metal surface leading to the
formation of film from acidic solution [11]. We also note that the
value of Rt increases with the increase in concentration of the inhibitor and this indicates an increase in the corrosion inhibition
efficiency.
Gravimetric measurements were carried out at various temperatures of 298-328 K in the presence (W) and the absence (W0) of
inhibitor for a period of 1 h at a maximal concentration (0.220
gL -1) and the corresponding results are given in Table 4.
Table 4 indicates that the corrosion rate increases both in
blank and inhibited acid with the rise of temperature. But the inhibition efficiency of the natural substance is almost constant
with the rise of temperature.
Fig.4 shows Arrhenius plots of the corrosion rate for the solution with or without inhibitor. The relation can determine the apparent activation energies:
Wcorr=Aexp(-Ea /RT)
0
Wcorr
=Aexp(-E0a /RT)
(5)
where, Ea and E 0a are the apparent activation energies with and
without inhibitor, respectively. A is the preexponential factor
and R is the gas constant. The activation energies calculated
from the Arrhenius plots in uninhibited and inhibited solution
are 65.6 and 65.8 kJmol-1, respectively.
The presence of inhibitor does not modify the values of apparent activation energy, and seeing that the efficiency is independent of temperature, this is often interpreted as an indication of
the formation of an adsorption film of a physical (electrostatic)
character[4].
The variation of surface coverage against the inhibitor concentration c indicates the nature of adsorption. Several adsorption isotherms are commonly used to characterize inhibitor per0
t

Table 4

Fig.3

Vol.25

Acta Phys. Chim. Sin., 2009

Effect of temperature on the corrosion rate of


steel at 1 h at 0.220 gL-1 of limonene

T/K

W0/(mgcm-2h-1)

W/(mgcm-2h-1)

ERt(%)

298

0.612

0.235

61

308

2.223

0.776

65

318

3.469

1.318

62

328

7.825

3.130

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No.7

CHAIEB E. et al.
Limonene as Green Inhibitor for Steel Corrosion in Hydrochloric Acid Solutions

1257

Fig.6 Proposed adsorption model of limonene


is the covered surface and 1- is the uncovered surface.

Fig.4 Arrhenius plots of the corrosion rate for the solution


with or without inhibitor limonene

formance. The Langmuir isotherm (c/ vs c) assumes that there is


no interaction between adsorbed molecules on the surface. The
Frumkin adsorption isotherm ( vs c) assumes that there is some
interaction between the adsorbates, and the Temkin adsorption
isotherm ( vs lgc) represents the effect of multiple layer coverage[25].
Adsorption isotherms are very important to understand the
mechanism of inhibitioncorrosion reactions. The most frequently used isotherms are Langmuir, Frumkin and Temkin [26-28]. In
this study, the Frumkin adsorption isotherms best explain the experimental results for limonene at 298 K:
exp(-2a)=K c
ads
1-
Gads
Kads= 1 exp (6)
RT
55.5

where, c is the additive concentration, and the parameter a is a


heterogeneous factor that gives the variation of adsorption energy with coverage, Kads is the equilibrium constant of the adsorption reaction and Gads is the standard free energy of adsorption.
Isotherms produced from these inhibitor studies were not direct measurements of adsorption, i.e., they were derived from the
EIS data. The Frumkin adsorption isotherm exhibited the best fit
of as a function of the inhibitor concentration (Fig.5).
The values obtained are: a=-1.26, Kads=13913.5 Lmol -1 and
Gads=-6.46 kJmol -1. The value of Gads is negative indicating
that limonene is spontaneously adsorbed on the metal surface [29].

Values of Gads >-40 kJmol -1 are generally interpreted by the


physical adsorption which is the result of electroactive forces between inhibiting double bonds of limonene and the electrically
charged surface of the metal. Values of Gads -40 kJmol -1 is
regarded as chemisorption phenomenon [30]. The value of Gads
obtained suggests that limonene acts by physical adsorption.
More information may be obtained by the calculation of the
indices as EHOMO (the highest occupied molecular orbital energy),
ELUMO ( the lowest unoccupied molecular orbital energy) and
band gap E= ELUMO-EHOMO of the limonene molecule [31]. EHOMO
is associated to the electron donating ability of the molecule and
then high values of EHOMO indicate a tendency of the molecule to
donate electrons to appropriate acceptor molecules with low energy empty molecular orbital. Literature shows that less negative
EHOMO, higher ELUMO and smaller E=ELUMO-EHOMO are reflected in
stronger adsorption bond [32]. In this case, the values obtained of
EHOMO (-9.229 eV), ELUMO (1.191 eV) and E (10.420 eV) indicate the efficiency obtained[33].
Moreover the non modification of the mechanism of the reduction process may be explained by the existing of free surface
of steel on which the hydrogen reduction is done as shown in
Fig.6.

3 Conclusions
The principal finding of present work can be summarised as
follows:
(1) Steady state electrochemical measurements show that the
limonene acts as a mixed inhibitor for the corrosion of steel in 1
molL -1 HCl solution without modifying the mechanism of hydrogen evolution reaction.
(2) The inhibition efficiency of the limonene attains a maximum value at 0.220 gL-1.
(3) The inhibition efficiency of the natural substance is temperature independent.
(4) The adsorption of molecule of limonene on the steel surface in molar hydrochloric acid obeys to Frumkin adsorption
isotherm model.
(5) EIS results are in good agreement with those of the stationary ones.
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