Arabian Journal of Chemistry (2016) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Inhibitory effect of Gentiana olivieri extracts on the

corrosion of mild steel in 0.5 M HCl:
Electrochemical and phytochemical evaluation
Evrim Baran a,*, Ahmet Cakir a, Birgül Yazici b

a
Department of Chemistry, Faculty of Science and Literature, Kilis 7 Aralık University, 79000 Kilis, Turkey
b
Department of Chemistry, Faculty of Science and Literature, Çukurova University, 01000 Adana, Turkey

Received 26 March 2016; accepted 11 June 2016

KEYWORDS Abstract Natural inhibitors including plant extracts and their pure metabolites have become
Gentiana olivieri; important as environmentally acceptable, low-cost, readily available and renewable source for a
Mild steel; wide range of corrosion inhibitors. In the current study, the inhibitory effect of the methanol extract
EIS; of Gentiana olivieri and its fractions on the corrosion of mild steel in a 0.5 M HCl solution were
Acid inhibition; investigated using potentiodynamic polarization and electrochemical impedance spectroscopy
SEM/EDX (EIS). The chemical compositions of the methanol extract and its fractions were identified by
high-performance liquid chromatography (HPLC). EIS results showed maximum inhibition effi-
ciency (93.7%) at an inhibitor concentration of 800 mg/L. Polarization curves indicated that the
plant extract and its fractions are mixed-type inhibitors. Surface analyses (SEM/EDX) were carried
out to establish the corrosion-inhibitive properties of the samples. Thermodynamic parameters
(Ea, DH°, DS°, DG°) were also examined.
Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Mild steel is an abundant and efficient building material. However, it is

* Corresponding author at: Kilis 7 Aralık University, Science and
Letters Faculty, Chemistry Department, 79000 Kilis, Turkey. Fax:
+90 348 822 23 51.
E-mail address: evrimbaran@kilis.edu.tr (E. Baran).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
difficult to protect mild steel exposed to harsh environments against
corrosion (Li et al., 2009). The use of corrosion inhibitors is one of
the most practical and economical methods for diminishing corrosion
rates and the protection of metal surfaces against corrosion (Palou
et al., 2014). Although many inorganic, organic and polymeric com-
pounds have performed well as corrosion inhibitors for different met-
als and alloys, it has been reported that many of these inhibitors are
toxic to aquatic and animal life (Palou et al., 2014; Garai et al.,
2012). Natural inhibitors are often nontoxic or at least have lower tox-
icities to species in the environment compared with the synthetic
organic inhibitors (Lebrini et al., 2011). Therefore, many researchers

http://dx.doi.org/10.1016/j.arabjc.2016.06.008
1878-5352 Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
2 E. Baran et al.
have focused on the study of ‘‘green’’ or ‘‘eco-friendly’’ corrosion inhi-
bitors synthesized or isolated from various aromatic herbs, spices and
medicinal plants (Ansari and Quraishi, 2014). The corrosion inhibitory
effects of the extracts and their pure components of various plants,
such as Phaseolus vulgaris L. (Abdel-Gaber et al., 2006), henna
(Ostovari et al., 2009), Aloe vera (Abiola and James, 2010), Jasminum
nudiflorum Lindl (Deng and Li, 2012a), Salvia officinalis (Soltani et al.,
2012), bamboo (Li et al., 2012), Ficus hispida (Muthukrishnan et al.,
2015), Aniba rosaeodora (Chevalier et al., 2014), Mansoa alliacea
(Suedile et al., 2014), Ginkgo species (Deng and Li, 2012b), on carbon
steel, cold rolled steel, stainless steel and zinc metals have been
reported, with the very promising efficiency. The inhibition perfor-
mances of plant extracts are closely related to their chemical composi-
tions, which take the form of tannins, alkaloids, carbohydrates,
phenolics, and proteins, to name a few. These metabolites usually bear
polar functional groups containing nitrogen, sulphur, or oxygen
atoms, as well as moieties consisting of triple or conjugated double
bonds or aromatic rings, which are the major adsorption centres.
The adsorption of molecules on metal surfaces depends on a range
of functional group properties, including steric factors and electron
density (Liao et al., 2011).
Gentiana olivieri Griseb. (Afat), belonging to the Gentianaceae
family (Deliorman Orhan et al., 2003), is widely used as a bitter tonic,
stomachic, appetizer, antipyretic, anticonvulsant, antidiabetic, anti-
hepatotoxic, antinociceptive, anti-inflammatory, antiulcerogenic, seda-
tive, antioxidant, antidepressant, and antianemic (Khan et al., 2014).
The plant is known to possess a number of bitter secoiridoids glyco-
sides, flavonoids (isoorientin and its derivatives), alkaloids, xhan-
thones, triterpenoid acids and fats (Singh et al., 2012). Recently,
among the species of the Gentianaceae family, G. olivieri have been
a focus of interest due to the identification of phytochemicals such
as amarogentin and sweroside as new potential drugs (Khan et al.,
2014; Singh et al., 2012; Peng et al., 2005; Wang et al., 2007). Accord-
ing to a literature survey, there have been no reports on the corrosion
inhibition effects of G. olivieri or its individual constituents on metals
such as mild steel, aluminium, iron, zinc and nickel in acidic or alkaline
solutions. Therefore, the aim of this study was to evaluate the inhibi-
tion efficiency of the methanol extract of the aerial parts of G. olivieri
and the ethyl acetate, n-butanol and water fractions of the methanol
extract on the corrosion of mild steel in 0.5 M HCl. High-
performance liquid chromatography (HPLC) and FT-IR spectrometry
were applied to identify the components in the methanol extract of
G. olivieri and its separated fractions. Investigations of the corrosion
parameters were performed by electrochemical polarization measure-
ments and electrochemical impedance spectroscopy (EIS) at different
concentrations (200, 400, 600 and 800 mg/L) of the extract and its frac-
tions at different temperatures (293, 303, 313, and 323 K). The surface
charge of the mild steel in inhibited solutions, the adsorption isotherms
and thermodynamic parameters were determined to clarify the poten-
tial inhibition mechanism. Scanning electron microscopy (SEM) and
energy dispersive X-ray spectroscopy (EDX) analyses were also carried
out to establish the corrosion inhibitory properties of the samples in
0.5 M HCl solution.
2. Experimental
2.1. Preparation of methanol extract and its fractions of G.
olivieri
The aerial parts of G. olivieri were collected at the flowering
stage from the Gaziantep region of Turkey in June 2014, and
dried. The dried and powdered plant samples (250 g) were
extracted with methanol (99.9%) (5
1 L) at room tempera-
ture. The extract was filtered and concentrated using a rotary
evaporator under reduced pressure and temperature, yielding
a dark brown extract (53.11 g). The concentrated extract
Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
(40 g) was then dissolved in distilled water at 60 °C and was
filtered to remove lipophilic substances and chlorophyll. After-
wards, this solution was extracted with ethyl acetate and
n-butanol. The organic solvents were removed under reduced
pressure using a rotary evaporator. Hence, the methanol
(MeOH) extract was fractioned into three fractions, ethyl acet-
ate fraction (EtOAc Fr., 5.20 g), n-butanol fraction (n-BuOH
Fr., 14.97 g) and water Fr. (19.83 g) (Aydin et al., 2014).
2.2. Characterization of methanol extract and its fractions of
G. olivieri
The FT-IR spectra of the MeOH extract of G. olivieri and its
EtOAc-, n-BuOH- and water-soluble fractions were recorded
within the wavelength ranging between 4000 and 400 cm1
using a FT-IR spectrometer (Thermoscientific Nicolet iS10).
Chemical composition analyses of the extract and its fractions
were performed using a high-performance liquid chromato-
graphic system (Shimadzu class LC) consisting of a FCV-10
ACVP pump, a DGU-20A5 degasser, a thermostated CTO-
10VP column oven compartment and a SPD-20A prominence
UV/VIS detector. A reverse-phase Kromasil 100-5C18
(150 mm
4.6 mm, 5 lm) column was used. HPLC analyses
were performed at a column temperature of 30 ± 1 °C, with
a mobile phase of water: acetonitrile: acetic acid (79:20:1,
v/v), an injection volume of 20 ll, and a flow rate of 1.0 ml/
min (Sezik et al., 2005; Toker et al., 2011). The UV absorbance
of the eluent was measured at 244 nm.
2.3. Isolation procedures and characterization
In order to isolate the metabolites responsible for the inhibi-
tory effect of the extract and its fractions, the n-BuOH Fr.
(14.97 g) was fractioned on silica gel (250 g, 70–230 mesh)
using different EtOAc-EtOH solutions (9:1, 8:2, 7:3, 6:4, 4:6,
2:8, and 0:10) as the eluents. In the end of this process, five
major fractions (coded as A, B, C and D) were obtained in
the following amounts: 0.46, 8.87, 1.88 and 3.18 g, respectively.
Fraction B was submitted silica gel CC (100 g, 230–400 mesh)
and eluted with CH2Cl2-EtOH (7:3). The fraction was allowed
the isolation of two compounds coded as 1 (3.90 g) and 2
(200 mg) (Fig. 1). To isolate another major component, C
Fr. (1.88 g) was eluted with CHCl3-EtOH (6:4) on silica gel
(60 g) yielding compound 3 (70 mg). Compound 3 was crystal-
lized over methanol. The 1H NMR and 13C NMR spectra of
the isolated compounds were recorded on a Bruker 400
Avance III spectrometer (1H: 400 MHz, 13C NMR:
100 MHz). Dimethyl sulfoxide (DMSO)-d6 was used as sol-
vent, and tetramethylsilane (TMS) was used the internal stan-
dard for NMR analyses. The spectral data of the characterized
compounds are given below (Peng et al., 2005; Wang et al.,
2007, 2013; Jianga et al., 2011; Aydin et al., 2014).
Compound 1 (gentiopicroside): 1H NMR: (d values,
DMSO-d6): 5.00 (m, H-3), 5.64 (m, H-4), 3.30 (m, H-5), 5.59
(d, J = 3.14 Hz, H-6), 7.42 (d, J = 1.25 Hz, H-8), 5.72 (ddd,
J1 = 17.37 Hz, J2 = 10.10 Hz, J3 = 6.77 Hz, H-9), 5.22 (m,
H-C10), 4.48 (J = 7.92 Hz, H-10 ), 3.01 (dd, J1 = 9.07 Hz,
J2 = 5.37 Hz, 5.49 Hz, H-C20 ), 3.15 (m, H-30 ), 2.94 (m, H-40 ),
3.15 (m, H-50 ), 3.68 (Ha, dd, J1 = 11.29 Hz, J2 = 7.04 Hz,
H-60 ), 3.42 (Hb, dd, J1 = 12.85 Hz, J2 = 6.42 Hz, H-C60 ).
13
C NMR ((DMSO)-d6): 162.7 (C-1), 69.1 (C-3), 116.2 (C-4),
Corrosion of mild steel in 0.5 M HCl 3

O 5'
8 OH
6'
8a OH 4'
O 1 O OH 8 1
6' HO 7 9 O 2
6 4' 6'' 1' 3' OH
5
O 4'' O 2'
3 4a O 5' OH HO 5'' 6
4 OH HO 2'' 10
4 3
9 1'
2'
OH 3' 3'' OH1'' 5
10 OH O

Gentiopicroside (1) Isoorientin (2)

6' HO
5' O 1'
HO
O OH
2' 1
2
HO 4' 3'
OH O OH
3
5
4
HO OH
6

Sucrose (3)

Figure 1 The chemical structures of the gentiopicroside (1), isoorientin (2), and sucrose (3).

124.9 (C-4a), 44.3 (C-5), 96.3(C-6), 148.7 (C-8), 103.2 (C-8a),
133.9 (C-9), 117.9 (C-10), 98.7 (C-10 ), 69.0 (C-20 ), 76.5 (C-30 ),
72.7 (C-40 ), 77.3 (C-50 ), 61.0 (C-60 ).
Compound 2 (isoorientin): 1H NMR: (d values, DMSO-d6):
6.67 (s, H-3), 6.67 (s, H-8), 7.47 (br. s, H-20 ), 6.96 (d,
J = 8.25 Hz, H-50 ), 7.42 (dd, J1 = 7.40 Hz, J2 = 1.29 Hz, H-
60 ), 4.60 (d, J = 9.77 Hz, H-C-100 ). 13C NMR ((DMSO)-d6):
163.6 (C-2), 102.7 (C-3), 181.8 (C-4), 160.6 (C-5), 108.8
(C-6), 163.6 (C-7), 93.6 (C-8), 156.1 (C-9), 103.2 (C-10),
121.3 (C-10 ), 113.3 (C-20 ), 145.9 (C-30 ), 149.8 (C-40 ), 116.2 (C-
50 ), 118.9 (C-60 ), 72.5 (C-100 ), 70.1(C-200 ), 79.0 (C-300 ).
Compound 3 (sucrose): 1H NMR: (d values, DMSO-d6):
5.18 (d, J = 8.29 Hz, H-1), 3.88 (t, J = 8.13 Hz H-30 ), 3.77
(m, H-40 ), 3.65 (m, H-5), 3.56 (m, H-50 ), 3.48 (m, H-3), 3.39
(m, H-10 ), 3.18 (m, H-2), 3.14 (m, H-4). 13C NMR ((DMSO)-
d6): 104.0 (C-20 ), 91.7 (C-1), 82.5 (C-50 ), 76.9 (C-30 ), 74.2 (C-
40 ), 72.8 (C-3), 72.7 (C-5), 71.6 (C-2), 69.8 (C-4), 62.1 (C-60 ),
62.0 (C-10 ), 69.0 (C-20 ), 60.4 (C-6).
2.4. Electrodes and electrolytes
The mild steel (MS) sample used in the inhibitory assays had
the following chemical composition: 0.173 wt.% C, 0.046 wt.
% Si, 0.435 wt.% Mn, 0.026 wt.% P and 99.32 wt.% Fe.
The electrodes were prepared by embedding mild steel rods
in epoxy resin. The surface area of the mild steel exposed to
the test solution was 0.785 cm2. Before the measurements,
the surface of mild steel was mechanically abraded using differ-
ent grades of sand papers up to the 1200 grade, and then pol-
ished mechanically with 1 lm Al2O3 paste until a mirror bright
surface was obtained. Then, the electrode was cleaned with dis-
tilled water using an ultrasonic bath and quickly immersed into
the test solution. The corrosion tests were performed in a
0.5 M HCl solution in the absence and presence of 200, 400,
600 and 800 mg/L concentrations of the MeOH extract and
its EtOAc-, n-BuOH- and water-soluble fractions. Also, the
electrochemical tests were carried out at different temperatures
(293, 303, 313, 323 K) without stirring. The temperatures of
the solutions were controlled thermostatically.
2.5. Electrochemical measurements
The electrochemical measurements were carried out using a
CHI 604E A.C. electrochemical analyser with computer con-
trol. For these tests, an electrochemical cell with a three-
electrode configuration was used. A platinum sheet (with
2 cm2 total surface area) and an Ag/AgCl (3 M KCl) system
were used as the auxiliary and the reference electrodes, respec-
tively. All potential values were referred to the Ag/AgCl (3 M
KCl) electrode. EIS and potentiodynamic polarization mea-
surements were carried out establishing a steady-state open cir-
cuit potential (OCP), after which the mild steel electrodes were
immersed into the corrosive solutions for 1 h, in a 0.5 M HCl
solution with and without 200, 400, 600 and 800 mg/L concen-
trations of the MeOH extract and its fractions at different tem-
peratures (293, 303, 313, and 323 K). Potentiodynamic
polarization curves were obtained from 0.8 V (Ag/AgCl) to
0.2 V (Ag/AgCl) at a sweep rate of 1 mV s1. To obtain cor-
rosion current densities (Icorr), the linear Tafel segments of
cathodic curves were extrapolated to corrosion potential. EIS
experiments were carried out in a frequency range from
100 kHz to 102 Hz at OCP with 5 mV amplitude. For the
measurement of the potential of zero charge (PZC), electro-
chemical impedance spectra were recorded by scanning fre-
quencies from 105 Hz to 102 Hz at an AC amplitude of
5 mV, and by applying different potentials. The double layer
capacitance values obtained were plotted against the applied
potentials to determine the PZC.
2.6. Surface characterization
Mild steel surfaces exposed for 24 h to immersion in 0.5 M
HCl and inhibited solutions (MeOH extract of G. olivieri and
its EtOAc, n-BuOH and water fractions) were examined by a
Zeiss/Supra 55 Scanning Electron Microscope (SEM) and by
energy dispersive X-ray spectroscopy (EDX) under high vac-
uum at an accelerating voltage of 15.00 kV and with 5 K X
magnification. The average percentages of the elements on

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
4 E. Baran et al.

Figure 2 HPLC chromatograms of the MeOH extract of G. olivieri and its fractions.

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl 5

et al., 1998; Wang et al., 2007). Their chemical structures were

Table 1 The chemical composition of G. olivieri MeOH
confirmed by comparison with previous published spectro-
extract and its fractions obtained from the HPLC results.
scopic data (Peng et al., 2005; Wang et al., 2007, 2013;
Components Rt MeOH Water n-BuOH EtOAc Jianga et al., 2011; Aydin et al., 2014). The NMR data of
extract Fr. (%) Fr. (%) Fr. (%) the gentiopicroside, isoorientin and sucrose are shown in Sup-
(%) plementary material.
Gentiopicroside 3.42 56.10 37.18 54.18 41.52
Isoorientin 3.77 4.13 0.10 9.75 3.56 3.1.1. HPLC and Fourier transform infrared (FT-IR)
Sucrose 1.86 19.48 28.19 13.16 1.95 spectroscopy of the MeOH extract and its EtOAc, n-BuOH and
Total identified – 79.71 65.47 77.09 47.03 water fractions
(%)
According to HPLC analyses (Fig. 2), the extract and its frac-
tions contain approximately 7–10 major peaks, along with a
few small peaks belonging to minor constituents. HPLC anal-
the mild steel surface were determined by an EDX detector ysis showed that the extract and its fractions contained a major
coupled to the SEM. compound, gentiopicroside (1), with a retention time of
3.42 min. Gentiopicroside (1) is characteristic compound of
the Gentiana species, and constituted to 56.10%, 41.52%,
3. Results and discussion
54.18% and 37.18% of the MeOH extract, the EtOAc-
soluble fraction, the n-BuOH-soluble fraction and the water-
3.1. Chemical composition of the extract and its fractions
soluble fraction, respectively (Table 1). Sucrose was found to
be the second major component of the MeOH extract
The chemical structures of compounds 1, 2 and 3 isolated from (19.48%), the water fraction (28.19%) and the n-BuOH frac-
the n-BuOH soluble fraction of the MeOH extract of G. olivieri tion (13.16%). Isoorientin (2) was detected at low levels in
were characterized by IR, 1H NMR, 13C NMR, DEPT, the MeOH extract, constituting only 4.13% of total extract
HMQC and 1H,1H-COSY spectroscopic methods, and these (Table 1).
compounds were assigned as gentiopicroside, isoorientin and FT-IR was used to identify the functional groups of the
sucrose, respectively (Fig. 1). Gentiopicroside and isoorientin components in the extract and its fractions. The absorbance
are characteristic metabolites of the Gentiana genus (Ko bands observed the FT-IR spectra of the extract and its

Figure 3 FT-IR spectrums of the MeOH extract of G. olivieri (a) and its fractions (EtOAc Fr. (b), n-BuOH Fr. (c), and water Fr. (d)).

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
6 E. Baran et al.

-0.45 fractions (Fig. 3) are in accordance with the chemical struc-

0.5 M HCl tures of the components (gentiopicroside (1) isoorientin (2)
MeOH ext.
-0.46 and sucrose (3)). In the IR spectra, the absorption bands
n-BuOH Fr.
EtOAc Fr.
belonging to the OAH stretching vibration, a-b unsaturated
OCP / V vs Ag/AgCl

-0.47 carbonyl groups, CAH stretching vibrations, C‚C vibrations

Water Fr.
and CAOAC bonds vibrations were observed at the around
-0.48 3100–3500 cm1, 1705 cm1, 2900–3000 cm1,
1 1
1400–1600 cm and 1050 cm , respectively. As can been seen
-0.49
in Table 1, the amounts of gentiopicroside and isoorientin were
found as high amount in the MeOH extract, and its EtOAc
-0.50
and n-BuOH fractions. However, their amounts were detected
at low amount in the water fraction. These results are in accor-
-0.51
dance with the absorbance bands in the FT-IR spectra of water
fraction. In this spectrum, intensity of C‚O absorption band
-0.52
0 500 1000 1500 2000 2500 3000 3500 4000 was low, whereas OAH vibration band was observed to be
Time / s high as compared with the other spectra.

Figure 4 The change of open circuit potential as a function of
exposure time in 0.5 M HCl solution and containing 800 mg/L of
MeOH extract of G. olivieri and its fractions.
3.2. Electrochemical tests
3.2.1. Open circuit potential (OCP) curves
In the absence and presence of 800 mg/L concentration, which
exhibited the highest inhibition effect based on the EIS results

Figure 5 Polarization curves for mild steel in 0.5 M HCl without and with different concentrations of MeOH extract of G. olivieri and its
fractions (immersion time is 1 h).

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl
of the MeOH extract of G. olivieri and its fractions, the change
of open circuit potential of the mild steel in 0.5 M HCl with
time is depicted in Fig. 4. It can be seen from the curves in
the presence of the inhibitor solutions, OCP values obtained
for MeOH extract and its fractions shift towards the positive
potential. However, the MeOH extract has more positive
OCP than that of n-BuOH, water and EtOAc fractions. HPLC
results show that the MeOH extract contains the relatively
high amount of the major compound, gentiopicroside (1) when
compared with other fractions (Table 1). Therefore, the inhibi-
tion effect of the extracts and its fraction can be attributed to
gentiopicroside (1) adsorbing on the metal surface (Yıldız,
2015). As seen from OCP-time curves, the OCP values become
almost constant after 2000 s. So, 1 h is chosen as immersion
time for the electrochemical measurement.
3.2.2. Potentiodynamic polarization curves
The potentiodynamic polarization curves obtained for the mild
steel in 0.5 M HCl with and without various concentrations
(800, 600, 400 and 200 mg/L) of the MeOH extract and its
fractions at 293 K are shown in Fig. 5. The values of icorr, Ecorr
and cathodic Tafel slopes (bc) obtained by the extrapolation of
linear Tafel segments of cathodic curve and inhibition effi-
ciency (g) calculated using Eq. (1) are listed in Table 2.
 
i 0  icorr
g ¼ corr
100 ð1Þ
icorr0
where icorr0 and icorr are the corrosion current density values in
the absence and presence of the MeOH extract of G. olivieri
and its fractions, respectively. At all inhibitor concentrations,
the values of corrosion current density (icorr) were reduced,
compared with the value of inhibitor free. The corrosion cur-
rent density values of the MeOH extract and n-BuOH fractions
decreased with increasing the concentration of the inhibitor.
But, the icorr values calculated for EtOAc and water fractions
do not change regularly with varying of inhibitor concentra-
tion and the inhibitors showed better efficiency even at low
concentration values. This may explain the relatively low
amount of gentiopicroside (1) in the EtOAc and water frac-
tions (Table 1). As seen in Fig. 5, the current densities of the
anodic and cathodic branches decreased in the presence of
the G. olivieri methanol extract and its fractions which suggest
that the inhibitory molecules constitute a protective layer on
the metal surface (Zheng et al., 2014). The parallel cathodic
curves in the presence of various concentrations of the MeOH
extract and its fractions and the almost constant cathodic Tafel
slopes (bc) indicate that the presence of the inhibitory mole-
cules does not change the mechanism of hydrogen evolution
and the hydrogen evolution reaction is activation controlled
(Su et al., 2014; Biswas et al., 2015). In the presence of the
MeOH extract and its fractions, the values of corrosion poten-
tial (Ecorr) shifted to positive values (9–30 mV) as compared to
the blank. If the displacement in corrosion potential is less
than 85 mV with respect to corrosion potential (Ecorr) at the
blank, an inhibitor can be classified as mixed-type inhibitor
(Zhang et al., 2015; Verma et al., 2015; Rajeswari et al.,
2014; Umoren et al., 2010). Thus, the MeOH extract and its
fractions can be classified as mixed-type inhibitors.
The effect of temperature on the corrosion of mild steel in
0.5 M HCl in the absence and presence of 800 mg/L MeOH
extract and its fractions were investigated at different temper-
Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
7
atures (293, 303, 313 and 323 K) (Supplementary material).
The electrochemical parameters obtained from potentiody-
namic polarization plots are given in Table 3. In the presence
of the MeOH extract and its fractions, the values of inhibitor
efficiency were nearly constant in the studied temperature
range and the values of current density increase with increasing
temperature due to increase in the desorption rate of the
adsorbed molecules on the metal surface, that previously
blocked active sites against attacks by acid (Zhang et al.,
2009; Li et al., 2014; Daoud et al., 2014). To determine the
activation energy (Ea) of corrosion and the inhibition mecha-
nism in the absence and presence of the extract and its frac-
tions, the following Arrhenius equation was used:
 
Ea
icorr ¼ A exp ð2Þ
RT
In Eq. (2), icorr is the corrosion current density obtained
from the polarization curves, A is the Arrhenius pre-
exponential factor, T is the absolute temperature, and R is
the universal gas constant. The values of Ea calculated from
the slopes of line graphs in Fig. 6 are presented in Table 3.
As seen from the Table 3, while the Ea values do not show
remarkable change in the presence of MeOH extract and n-
BuOH fraction, the activation energy is slightly increased in
the presence of EtOAc fraction and decreased in the presence
of water fraction, compared to that in the inhibitor free. These
results indicate that the inhibitors do not lead to effective
change in the corrosion mechanism of steel in HCl environ-
ment (Sığırcık et al., 2015). Considering the Ea values and
the changes in g (%) with rise in temperature, the results sug-
gest that the strong physical adsorption or weak chemical
bonding occurs between the molecules of inhibitor and the
mild steel surface (Garai et al., 2012; Soltani et al., 2014).
3.2.3. Electrochemical impedance spectroscopy (EIS)
The Nyquist and bode plots for the mild steel in 0.5 M HCl
solutions in the absence and presence of different concentra-
tions of the MeOH extract and its fractions after 1 h are shown
in Fig. 7. As can be seen, the Nyquist plots of the mild steel
exhibit single capacitive semi-circles indicating a corrosion
process mainly controlled by charge transfer (Li et al., 2012;
Rosliza et al., 2008). The increase in the diameter of the capac-
itive semicircles with increasing concentrations of the MeOH
extract and its fractions during 1 h of immersion time points
to the formation of a strong protective film on the surface of
the mild steel (Li et al., 2014). When compared with the
0.5 M HCl solution, the shape of the EIS curves obtained from
solutions containing the MeOH extract and its fractions were
maintained. These results demonstrate that the corrosion
mechanism was not changed by the addition of inhibitors
(Deng and Li, 2012a,b; Rosliza et al., 2008). The Nyquist plots
deviating from a perfect semicircle can be attributed to fre-
quency dispersion and inhomogeneities of metal surface,
resulting in non-uniform charge loading between the metal
and OHP (outer Helmholtz plane) (Ansari and Quraishi,
2014; Soltani et al., 2014). Therefore, a constant phase element
CPE was employed instead of a pure double layer capacitor in
the equivalent circuit model (Fig. 8) to achieve a better fit in
the analysis of the EIS results. Rs and Rct in the equivalent cir-
cuit represent the solution resistance and charge transfer resis-
tance, respectively. The CPE is defined by the following
8 E. Baran et al.

Table 2 Electrochemical parameters obtained from potentiodynamic polarization plots of the mild steel immersed in 0.5 M HCl with
different concentrations of the MeOH extract and its fractions (immersion time is 1 h).
C Ecorr icorr bc g
(mg/L) (V vs. Ag/AgCl) (mA cm2) (mV dec1) (%)
0.5 M HCl – 0.524 0.302 105.4 –
MeOH ext. of G. olivieri 200 0.510 0.048 103.3 84.11
400 0.505 0.038 106.4 87.42
600 0.499 0.028 98.6 90.73
800 0.511 0.030 99.5 90.07
EtOAc Fr. 200 0.515 0.055 111.7 81.79
400 0.502 0.030 100.6 90.07
600 0.522 0.042 99.2 86.09
800 0.512 0.031 97.2 89.74
n-BuOH Fr. 200 0.512 0.052 111.2 82.78
400 0.511 0.048 109.7 84.11
600 0.511 0.042 107.2 86.09
800 0.519 0.033 112.6 89.07
Water Fr. 200 0.483 0.036 104.0 88.08
400 0.494 0.033 109.0 89.07
600 0.504 0.038 104.1 87.42
800 0.504 0.040 102.1 86.75

Table 3 Activation and polarization parameters for the steel immersed in 0.5 M HCl containing 800 mg/L of MeOH extract and its
fractions at 20–50 °C (immersion time is 1 h).
T Ecorr icorr bc g Ea
(°C) (V vs. Ag/AgCl) (mA cm2) (mV dec1) (%) (kJ mol1)
0.5 M HCl 20 0.524 0.302 105.4 – 42.59
30 0.505 0.510 109.9 –
40 0.500 0.892 121.1 –
50 0.498 1.522 131.7 –
MeOH ext. of G. olivieri 20 0.511 0.030 99.5 90.07 41.52
30 0.497 0.040 103.7 92.25
40 0.486 0.064 114.8 92.82
50 0.514 0.150 113.7 90.14
EtOAc Fr. 20 0.512 0.031 97.2 89.74 48.99
30 0.505 0.050 110.1 90.19
40 0.499 0.079 120.0 91.12
50 0.505 0.214 130.1 85.94
n-BuOH Fr. 20 0.519 0.033 112.6 89.07 40.69
30 0.503 0.053 113.2 89.58
40 0.497 0.076 118.1 91.53
50 0.488 0.165 114.3 89.13
Water Fr. 20 0.504 0.040 102.1 86.75 32.08
30 0.497 0.062 112.4 87.84
40 0.492 0.095 117.6 89.38
50 0.486 0.135 120.9 91.14

mathematical expression (Muthukrishnan et al., 2015; Torres surface irregularity resulting from surface roughness, inhibitor
et al., 2014): adsorption and porous layer formation (Deng and Li, 2012b).
1 The double layer capacitance (Cdl) was calculated from the fol-
ZCPE ¼ ð3Þ lowing equation, using parameters (Y0, n) of the CPE and the
Y0 ðjxÞn
frequency (fmax) at which the imaginary impedance reaches a
The CPE consists of two parameters, namely the admit- maximum value (Torres et al., 2014; Mehdipour et al., 2015):
tance magnitude (Y0) and the exponent (n) (Mehdipour
et al., 2015). The exponential parameter n is used to estimate Cdl ¼ Y0 ð2pfmax Þn1 ð4Þ

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl
-6.4
-6.8
-7.2
-7.6
-2
-8.0
ln icor / A cm
-8.4
-8.8
-9.2
-9.6
-10.0
-10.4
-10.8
0.00305 0.00310 0.00315 0.00320 0.00325
-1
1/T (K )
Figure 6 Arrhenius plots for mild steel corrosion rate in 0.5 M
HCl in the absence and presence of 800 mg/L of MeOH extract of
G. olivieri and its fractions.
The electrochemical parameters Rct, Y0, n and Cdl were
obtained by fitting of experimental data with the ZView soft-
ware package. The inhibition efficiency (g, Table 4) was calcu-
lated utilizing the following equation:
 
RctðinhÞ  Rct
g¼
100 ð5Þ
RctðinhÞ
As seen in the Table 4, charge transfer resistance (Rct)
increased with increasing concentrations of the MeOH extract
and its fractions. The greatest inhibitive effect was observed at
800 mg/L of the MeOH extract, the EtOAc fraction, the n-
BuOH fraction and the water fraction, giving Rct values of
1200 Ω cm2, 1159 Ω cm2, 1481 Ω cm2, and 1277 Ω cm2, respec-
tively. This is because the total amount of adsorption and the
coverage of inhibitor on the steel surface increase with increas-
ing inhibitor concentration (Li et al., 2014). The increase in the
charge resistance leads to an increase in inhibition efficiency.
The inhibition efficiency values of the fractions of the MeOH
extract were 93.7, 91.9 and 92.6 for 800 mg/L concentrations
of the n-BuOH, EtOAc and water fractions, respectively.
According to these results, there were no significant differences
in the inhibition effects provided by the MeOH extract or its
fractions. There were several investigations on corrosion inhi-
bitors of some plant extracts in various acidic media and their
optimum concentrations. For instance, the alkaloid extract
from Oxandra asbecki plant (OAPE) has been studied as a pos-
sible source of green inhibitor for the corrosion of C38 steel in
1 M HCl and the maximum inhibition efficiency of 92% is
achieved at 100 ppm OAPE (Lebrini et al., 2011). Use of some
plant extracts such as Chamomile, Halfabar, Black cumin and
Kidney bean plants for the corrosion of steel in 1 M H2SO4
resulted in 90.2%, 87.1%, 87.2% and 83.5% of inhibition effi-
ciency at the optimum plant concentrations of 7.56, 2.52, 1.14
and 2.4 g/L, respectively (Abdel-Gaber et al., 2006). The high-
est inhibition efficiency exhibited by the Pennisetum purpureum
extract for mild steel in 1 M HCl solution was reported to be
above 95% (Alaneme et al., in press). Alcohol and water
extracts of the leaves of Pimenta dioica (PD) were reported
as non-toxic corrosion inhibitor for mild steel in acidic med-
ium and the maximum of 98% and 97% percentage inhibition
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tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
9
0.5 M HCl efficiency has been exhibited by PD-water and alcoholic
MeOH ext. extract in 0.5 M HCl, respectively (Anupama et al., 2015).
n-BuOH Fr. These data and our results for the corrosion of mild steel in
EtOAc Fr.
Water Fr.
0.5 M HCl in the presence of the G. olivieri extract and its frac-
tions suggest that the plant extracts could serve as effective
corrosion inhibitors. The excellent inhibition effects of the
extract and its fractions can be attributed to its components,
including gentiopicroside (1) and isoorientin (2) (Table 1). As
seen from the Table 1, the extract and its fractions have similar
qualitative and quantitative chemical compositions and they
all contained gentiopicroside (1) as the major component.
The double layer capacitance (Cdl) decreased with increas-
ing concentrations of the MeOH extract and its EtOAc,
n-BuOH and water fractions. At an inhibitor concentration
0.00330 0.00335 0.00340 0.00345
of 800 mg/L, Cdl declined from 223.69 (inhibitor-free medium)
to 45.87 (MeOH), 38.16 (EtOAc), 39.07 (n-BuOH), and 30.97
(water) lF cm2. The Cdl value according to the Helmholtz
model is expressed in the following equation (Li et al., 2012;
Mehdipour et al., 2015; Bothi Raja et al., 2013):
e  e0
Cdl ¼ A ð6Þ
d
In Eq. (6), e0 is the permittivity of air, e is the local dielectric
constant, d is the thickness of the film and A is the surface area
of the electrode. Accordingly, Cdl values lower than found in
the absence of the inhibitors can be associated with a decrease
in the dielectric constant and/or increase in the electrical dou-
ble layer thickness due to displacement of ions and water mole-
cules originally adsorbed on the surface by inhibitor molecules
(Umoren et al., 2010). Increasing values of n, defined as a mea-
sure of the surface heterogeneity, compared with an inhibitor-
free medium, may be explained by the formation of a more
uniform surface as a result of adsorbed inhibitors (Abiola
and James, 2010; Umoren et al., 2010; Bothi Raja et al.,
2013). According to the data presented in Table 4, lower n val-
ues were found in environments containing the MeOH extract
and its fractions as compared to inhibitor-free 0.5 M HCl solu-
tions. These n values showed irregular trends with the increase
in inhibitor concentrations. This situation may be the result of
the random dispersion of organic molecules physically
adsorbed on the metal surface. In agreement with our results,
irregular trends in n values have been recorded in many studies
(Umoren et al., 2010; Khaleda, 2010).
EIS experiments were also carried out for the mild steel
immersed in 0.5 M HCl containing 800 mg/L of the MeOH
extract and its fractions at 20–50 °C (Fig. 9). EIS parameters
were calculated using the equivalent circuit model (Fig. 8).
The inhibition efficiencies of 800 mg/L concentrations of the
MeOH extract and its fractions at 20–50 °C on mild steel in
0.5 M HCl are given in Table 5. The decrease in the charge
transfer resistances (Rct) at high temperatures indicates an
increase in the corrosion rates of mild steel. The increasing rate
of metal dissolution and the shift of the adsorption/desorption
equilibrium towards inhibitor desorption led to a decrease in
the degree of the surface coverage (Lebrini et al., 2011;
Umoren et al., 2010). The values of n lie between 0.88 and
0.82, and the inhibition efficiency ranges between 86.4% and
93.7% in 0.5 M HCl solutions containing 800 mg/L of the
samples, indicating the formation of protective layers at the
electrode surfaces. These results confirm that the MeOH
extract and its fractions remain effective across all analysed
temperatures.
10 E. Baran et al.

Figure 7 Nyquist and bode plots of the mild steel in 0.5 M HCl without and with different concentrations of MeOH extract of G. olivieri
and its fractions at 20 °C (immersion time is 1 h).

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tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl 11

adsorbed on the mild steel surface. As a general rule, values

Figure 8 The equivalent circuit model.
3.2.4. Adsorption isotherms and thermodynamic
characterization
Adsorption isotherms are a very useful for understanding the
interactions between inhibitor molecules and steel surfaces.
As such, Langmuir, Freundlich and Temkin adsorption iso-
therms were tested in hopes of describing the adsorption beha-
viour of the MeOH extract and its fractions on mild steel in
0.5 M HCl. Through the use of the correlation coefficient
(R2), the results were found to be best fit by a Langmuir
adsorption isotherm (Fig. 10):
Cinh 1 (Li et al., 2010; Xu et al., 2014; Donahue and Nobe, 1965).
¼ þ Cinh
h Kads
In Eq. (7), Cinh is the concentration (mg/L) of the inhibitor,
Kads (L/mg) is the adsorptive equilibrium constant, and h is the
surface coverage calculated by using the g/100 ratio obtained
from the EIS measurements at different inhibitor concentra-
tions. The linear curves of Langmuir isotherm model for all
the samples are illustrated in Fig. 10. The adsorptive equilib-
rium constants (Kads) were determined from the intercepts of
the straight lines and Kads was also related to the standard
adsorption free energy (DG°) using a following equation
(Daoud et al., 2014).
DG0 ¼ RT lnðCw Kads Þ
In Eq. (8), R is the gas constant, T is the temperature, and
Cw is the concentration of water (1.0
106 mg/L), as the
molecular masses of the extract components are not known
(Li et al., 2010). In the current study, the high Kads values
obtained for the MeOH extract and its fractions (Table 6)
showed that the metabolites in all the samples strongly
of DG0 less than 20 kJ mol1 indicate physical adsorption,
which results from electrostatic interactions between the
charged inhibitor molecules and the charged metal, while those
more negative than 40 kJ mol–1 indicate sharing or transfer
of electrons from inhibitor molecules to the metal surface in
the formation of co-ordinate bonds (chemisorption) (Soltani
et al., 2014; Ozcan et al., 2008). The values of DG° obtained
for the samples are between 25.27 and 26.79 kJ/mol, indicating
that the interaction between the inhibitor molecules and the
surface of the mild steel involves both physisorption and
chemisorption (El-Shamy et al., 2015; Xu et al., 2014). Com-
bined with the results from values of Ea, therefore, it may be
said that firstly, the formation of an adsorptive film with elec-
trostatic character occurs due to the adsorbed water molecules
on the surface of mild steel, and then the removal of water
molecules from the surface is accompanied by chemical inter-
action between the metal surface and inhibitor molecules
ð7Þ
The other thermodynamic parameters, standard adsorption
enthalpy (DH°) and entropy (DS°), were calculated by the fol-
lowing equations:
   
h DH0
¼ A  C exp  ð9Þ
1h 2303RT
DH0  DG0
DS0 ¼ ð10Þ
T
All of the calculated thermodynamic parameters are pre-
sented in Table 6. As shown in Table 6, the negative values
of DH0 imply that the adsorption of the inhibitor molecules
ð8Þ on the mild steel surface is exothermic processes. The positive
sign of DS0 values can be explained by a quasi-substitution
process between the organic inhibitor(s) in the aqueous phase
(Org(sol)) and water molecules at the electrode surface (H2O
(ads)) (Li et al., 2009; Soltani et al., 2014). In this situation,
the adsorption of organic inhibitors is enabled by desorption
of water molecules from the surface. Thus, while the

Table 4 EIS parameters and inhibition efficiency for mild steel in 0.5 M HCl in the absence and presence of different concentrations
of MeOH extract and its fractions.
C Rct Y0 n Cdl g
(mg/L) (Ω cm2) (sn X1 cm2) (lF cm2) (%)
0.5 M HCl – 94.0 4.08  104 0.84 223.69 –
MeOH extract 200 627.3 1.07  104 0.85 66.40 85.0
400 722.8 1.02  104 0.83 59.40 87.0
600 915.3 1.07  104 0.81 60.64 89.7
800 1200.0 7.40  105 0.84 45.87 92.2
EtOAc Fr. 200 846.4 7.22  105 0.84 42.09 88.9
400 897.1 7.09  105 0.85 44.00 89.5
600 1119.0 6.35  105 0.85 39.41 91.6
800 1159.0 5.77  105 0.87 38.16 91.9
n-BuOH Fr. 200 889.9 6.53  105 0.85 39.37 89.4
400 1037.0 7.93  105 0.85 50.65 90.9
600 1169.0 6.84  105 0.85 43.69 92.0
800 1481.0 5.78  105 0.86 39.07 93.7
Water Fr. 200 663.6 8.78  105 0.86 54.76 85.8
400 876.5 6.99  105 0.86 44.78 89.3
600 955.2 5.18  105 0.86 32.31 90.2
800 1277.0 4.99  105 0.85 30.97 92.6

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tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
12 E. Baran et al.

Figure 9 Nyquist and bode plots of the mild steel in 0.5 M HCl and 800 mg/L MeOH extract of G. olivieri and its fractions at 20–50 °C
(immersion time is 1 h).

adsorption process for the inhibitor is believed to be associated
with a decrease in entropy of the solute, the opposite is true for
the solvent. Therefore, the gain in entropy is attributed to the
increase in solvent entropy (Zhang et al., 2015). The positive
values of DS0 imply that entropy is the driving force for the
adsorption of the molecules in the MeOH extract and its frac-
tions on the mild steel surface. Based on the thermodynamic
results, the calculated DG° and DH° values show that adsorp-
tion mechanism is not completely physical or chemical and a
combination of physisorption and chemisorption exists
between the inhibitor molecules and metal surface.
3.2.5. Determination of surface charge of the metal
The results discussed thus far indicate that the adsorption of
the extract and its fractions on the mild steel surface are dom-
inated by electrostatic interactions (physical adsorption).
Adsorption of organic inhibitors on the metal surfaces is pri-
marily associated with the surface charge of metal, chemical
structure of inhibitor, the inhibitor’s dipole moment or charge,
the chemical composition of the solution, the nature of metal
surface and the pH (Amin et al., 2007; Xu et al., 2013). EIS
measurements carried out at the different potentials were uti-
lized to determine the surface charge of metal (Epzc). To obtain

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tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl 13

Fig. 9 (continued)

Table 5 EIS parameters and inhibition efficiency for mild steel in 0.5 M HCl in the absence and presence of 800 mg/L concentrations
of MeOH extract and its fractions at different temperatures (immersion time is 1 h).
Temperature (°C) Rct Y0 n Cdl g
(Ω cm2) (sn X1 cm2) (lF cm2) (%)
0.5 M HCl 20 94.0 4.08  104 0.84 223.69 –
30 59.0 5.48  104 0.84 291.37 –
40 36.8 4.90  104 0.84 230.43 –
50 24.2 4.23  104 0.88 229.40 –
MeOH extract 20 1200.0 7.40  105 0.84 45.87 92.2
30 831.5 7.96  105 0.83 44.87 92.9
40 392.7 7.73  105 0.83 38.24 90.6
50 211.5 9.13  105 0.81 35.94 88.6
EtOAc Fr. 20 1159.0 5.77  105 0.87 38.16 91.9
30 933.2 4.52  105 0.87 28.44 93.7
40 502.7 6.11  105 0.86 35.16 92.7
50 246.1 7.37  105 0.88 42.83 90.2
n-BuOH Fr. 20 1481.0 5.78  105 0.86 39.07 93.7
30 771.0 7.90  105 0.85 47.64 92.4
40 480.9 6.09  105 0.87 35.55 92.3
50 220.4 8.26  105 0.86 42.68 89.0
Water Fr. 20 1277.0 4.99  105 0.85 30.97 92.6
30 614.5 8.37  105 0.84 47.32 90.4
40 384.6 8.70  105 0.83 43.04 90.4
50 177.6 9.03  105 0.82 37.33 86.4

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tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
14 E. Baran et al.

2 senting 56.10%, 41.52%, 54.18% and 37.18%, respectively,

900 MeOH ext. of G. olivieri: R =0.9993
2 of total extract and its fractions. These compounds, as well
n-BuOH Fr.: R =0.9997
800 2
EtOAc Fr.: R =0.9999
as others, in the extract and its fractions may exist in the pro-
2
Water Fr.: R =0.9996
tonated form in 0.5 M HCl. The protonated molecule can be
700 absorbed at cathodic sites in competition with hydrogen ions,
Cinh/θ (mg /L)

and thereby reduce the rate of hydrogen evolution (Döner

600 et al., 2013; Solmaz et al., 2008b; Hamani et al., 2014). The
effects of the extract and its fractions on the hydrogen evolu-
500
tion reaction were expressly displayed by the polarization mea-
400
surements. Gentiopicroside (1) and other phenolic
constituents, such as isoorientin (2) and sweroside, contain
300 one or two benzene rings and a,b-unsaturated carbonyl car-
bons. The presence of these groups and the delocalization in
200 the molecules biosynthesized by G. olivieri may contribute to
200 300 400 500 600 700 800
the electrostatic interactions between mild steel surfaces and
Cinh (mg /L)
the inhibitor molecules. Hence, the inhibitory effects of the
extract and its fractions can be attributed to the generation
Figure 10 Langmuir adsorption plots for mild steel in 0.5 M
of a protective adsorbed film on the steel surface, acting as a
HCl containing different concentrations of MeOH extract of G.
barrier against corrosion of the mild steel.
olivieri and its fractions.
3.3. Scanning Electron Microscope (SEM) and EDX

Table 6 The thermodynamic parameters of adsorption of

The SEM analysis results of the mild steel after 24 h of immer-
MeOH extract and its fractions on the mild steel surface at
sion are presented in Fig. 12. Rough, pitted surface formations
20 °C.
and corrosion products were observed (Fig. 12a), resulting
from excessive metal dissolution in the aggressive solution.
Kads DG° DH° DS° However, the SEM images (Fig. 12(b–d)) of the mild steel cor-
(L/g) (kJ mol1) (kJ mol1) (J mol1 K1) roded in solutions containing 800 mg/L of the extract and its
MeOH extract 31.91 25.27 21.25 13.73 fractions displayed smooth surfaces due to the formation of
EtOAc Fr. 45.23 26.12 19.47 22.70 a protective film on the metal surface. Through examination
n-BuOH Fr. 59.38 26.79 14.39 42.27 of the SEM images of the steel treated in the presence of the
Water Fr. 39.84 25.81 15.96 33.62 extract and its fractions, it was clear that the MeOH extract
and its n-BuOH fraction, containing a large amount of gen-
tiopicroside (1), gave a material without obvious corrosion
more information about the electrostatic adsorption mecha-
defects, pits and cracks on the mild steel surface. The SEM
nism, plots of the calculated charge transfer resistances (Rct)
images of material treated in the presence of the EtOAc and
versus applied potential were obtained (Fig. 11). The maxima
water fractions of the extract showed more irregularities.
of the parabola curves are termed the PZC of the electrode.
In the current study, EDX spectra were used to determine
The surface charge of the mild steel at open-circuit potential
the elements present on the mild steel surface after 24 h of
(OCP) was acquired using the following equation:
immersion in the blank and inhibitor-containing solutions.
Er ¼ Eocp  Epzc ð11Þ The elemental compositions obtained through EDX are dis-
played in Fig. 12. The EDX data obtained from mild steel
In Eq. (11), Er is the Antropov’s ‘‘rational’’ corrosion
immersed in the 0.5 M HCl solution showed that the electrode
potential (Mallaiya et al., 2011; Döner et al., 2013; Solmaz
surface consisted of excess oxygen due to the formation of iron
et al., 2008a).
oxides in the corrosion process. Chlorine is additionally pre-
The potentials (Epzc) corresponding to the maximum values
sent. Furthermore, the lower percentage of iron present on
of Rct, were 0.457, 0.452, 0.445, 0.452 V (vs. Ag/AgCl)
the mild steel surface exposed to 0.5 M HCl indicated severe
for 0.5 M HCl solutions containing 800 mg/L concentrations
corrosion damage. However, the oxygen percentages were sig-
of the MeOH extract, the n-BuOH fraction, the EtOAc-
nificantly reduced by the presence of the extract and its n-
soluble fraction, and water-soluble fraction, respectively. The
BuOH fraction, and there was no Cl detected on the surface
negative Er (10, 10, 20, and 20 mV for the extract and
of the material treated in the presence of the extract or its n-
its n-BuOH, EtOAc and water fractions, respectively) indi-
BuOH fraction. These findings suggested that the high effi-
cated that the surfaces of electrodes in the experimental condi-
ciency of the extract and its n-BuOH fraction can be attributed
tions were negatively charged.
to high contents of gentiopicroside (1) and isoorientin (2), as
According to these results, molecules in the extract and its
compared to the other fractions. In accord with these findings,
fractions that act as inhibitors can be directly absorbed by elec-
SEM and EDX confirmed that gentiopicroside (1), isoorientin
trostatic forces onto the metal surface. Both the extract and its
(2) and/or other metabolites contribute to the formation of a
fractions contain large amounts of secoiridoids and phenolic
protective film on the mild steel. When compared with the
compounds (Singh et al., 2012). As seen from the Table 1,
other fractions, the corrosion protection provided by the water
HPLC analyses show that the methanol extract, the EtOAc-
fraction, containing high proportion of sucrose, decreased
soluble fraction, the n-BuOH-soluble fraction, and the water-
after 24 h
soluble fraction contained mainly gentiopicroside (1), repre-

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
Corrosion of mild steel in 0.5 M HCl 15

Epzc

Eocp
Epzc

Eocp
Epzc

1400 Eocp

1200

1000 Epzc
2
Rct / Ω cm

800
Eocp

600

400

200

0
-0.65 -0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30 -0.25 -0.20
E / V vs Ag/AgCl

Figure 11 The plot of Rp vs. applied potential in 0.5 M HCl in the absence and presence of 800 mg/L of MeOH extract of G. olivieri and
its fractions (MeOH extract: , n-BuOH Fr.: , EtOAc Fr.: , water Fr.: ).

(a)0.5M HCl (b) MeOH extract

EDX Fe C O Cl EDX Fe C O Cl
wt. % 80.91 2.89 15.97 0.22 wt. % 97.19 1.90 0.90 -

(c)n- BuOH Fr. (d) EtOAc Fr. (e) Water Fr.

EDX Fe C O Cl EDX Fe C O Cl EDX Fe C O Cl

wt. % 98.76 1.07 0.17 - wt. % 95.87 2.26 1.77 0.12 wt. % 95.45 2.02 2.23 0.30

Figure 12 Surface morphology and EDX results of mild steel in 0.5 M HCl in the absence and presence of 800 mg/L of MeOH extract of
G. olivieri and its fractions.

4. Conclusions are mixed-type inhibitors. Both the thermodynamic parameters and

In the present study, EIS results show that the MeOH extract of G. oli-
vieri and its fractions are effective inhibitors of the corrosion of mild
steel. The highest inhibition efficiency calculated from the EIS results
was obtained for the n-BuOH-soluble fraction (93.7% at 20 °C). The
adsorption of the G. olivieri extract and its fractions on the mild steel
surface were found to obey the Langmuir model isotherm. Anodic and
cathodic polarization curves indicated that the extract and its fractions
the PZC results demonstrated that the adsorption mechanism is not
completely physical or chemical and a combination of chemisorption
and predominantly physisorption exists between the inhibitor mole-
cules and metal surface. The thermodynamic parameters show that
the SEM and EDX studies also showed that the EtOAc and water frac-
tions partially lose their inhibitory effect after an immersion time of
24 h, which is not the case for the MeOH extract and its n-BuOH frac-
tion. According to these results, the MeOH extract and its n-BuOH

Please cite this article in press as: Baran, E. et al., Inhibitory effect of Gentiana olivieri extracts on the corrosion of mild steel in 0.5 M HCl: Electrochemical and phy-
tochemical evaluation. Arabian Journal of Chemistry (2016), http://dx.doi.org/10.1016/j.arabjc.2016.06.008
16
fraction, containing the high amounts of gentiopicroside (1) and isoori-
entin (2), can be used as effective inhibitors against the corrosion of
mild steel.
Acknowledgements
The authors are greatly thankful to Çukurova University and
Kilis 7 Aralık University research fund. The authors also
thank to The Scientific and Technical Research Council of
Turkey (TUBITAK).
Appendix A. Supplementary material
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.arabjc.
2016.06.008.
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