Corrosion Science 49 (2007) 1143–1161

www.elsevier.com/locate/corsci

Corrosion inhibition of mild steel by plant extract

in dilute HCl medium
L.R. Chauhan, G. Gunasekaran *

Naval Materials Research Laboratory, Shil Badlapur Road, Addl. Ambernath (E) Dist. Thane 421 506, MH, India

Received 2 November 2005; accepted 21 August 2006

Available online 16 October 2006

Abstract

The inhibition effect of Zenthoxylum alatum plant extract on the corrosion of mild steel in 5% and
15% aqueous hydrochloric acid solution has been investigated by weight loss and electrochemical
impedance spectroscopy (EIS). The corrosion inhibition efficiency increases on increasing plant
extract concentration till 2400 ppm. The effect of temperature on the corrosion behaviour of mild
steel in 5% and 15% HCl with addition of plant extract was studied in the temperature range 50–
80 C. Surface analysis (SEM, XPS and FT-IR) was also carried out to establish the corrosion inhi-
bitive property of this plant extract in HCl solution. Plant extract is able to reduce the corrosion of
steel more effectively in 5% HCl than in 15% HCl. The adsorption of this plant extract on the mild
steel surface obeys the Langmuir adsorption isotherm.
 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Mild steel; B. EIS; B. IR spectroscopy; B. Polarization; C. Acid inhibition

1. Introduction

Acid solutions are generally used for the removal of undesirable scale and rust in several
industrial processes. Hydrochloric and sulphuric acids are widely used in the pickling
processes of metals. Use of inhibitors is one of the most practical methods for protec-
tion against corrosion especially in acid solutions to prevent metal dissolution and acid

*
Corresponding author. Tel.: +91 251 2620602; fax: +91 251 2620604.
E-mail address: gunanmrl@rediffmail.com (G. Gunasekaran).

0010-938X/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.08.012
1144 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

consumption [1]. The use of organic compounds containing oxygen, sulphur and nitrogen
to reduce corrosion attack on steel has been studied in some details [2–5]. Sulphur and
nitrogen containing compounds are more effective as corrosion inhibitor in sulphuric acid
[6] and hydrochloric acid [7].
The existing data show that most organic inhibitors get adsorbed on the metal surface
by displacing water molecules and form a compact barrier film [8]. Availability of lone
pairs and p electrons in inhibitor molecules facilitate electron transfer from the inhibitor
to the metal, forming a coordinate covalent bond [9]. The strength of the chemisorption
bond depends on the electron density on the donor atom of the functional group and also
the polarisability of the group.
Extracts of naturally occurring products contain mixtures of compounds and are bio-
degradable in nature. These compounds having nitrogen and sulfur as constituent atoms
were studied as corrosion inhibitor in HCl medium [10,11]. Ec Hosary et al. [12] studied
the corrosion inhibition of Al and Zn in 2 N HCl using naturally occurring Hibiscus sub-
dariffa (Karkode) extract. Zucchi and Omar [13] studied the dissolution of mild steel in 1 N
and 2 N HCl using plant extracts of Papaya, Poinciana pulcherrima, Cassia occidentalis
and Datura stramonium seeds. Other extracts of natural products studied as corrosion
inhibitors for mild steel is tobacco, black pepper and soya been [10].
Alkaloids have nitrogen as one of their main constituent atoms. Many plants are
known to produce various types of alkaloids [10,11]. Alkaloids such as papaverine, strych-
nine, quinine and nicotine were also studied as corrosion inhibitors in acid medium [14].
Zenthoxylum alatum, a dicot family plant is generally found at an altitude of around
5000–6000 feet above sea level. In India these plants are mostly found in Himalayan region
and has medicinal value. Our earlier studies showed that this plant extract has good cor-
rosion inhibition properties in phosphoric acid medium [15]. However, they have never
been studied in HCl solutions for the purpose of corrosion inhibition. To explore this pos-
sibility, an attempt has been made to ascertain their corrosion inhibition properties.
In the present work inhibiting properties of alcoholic extract of Zenthoxylum alatum in
5% HCl and 15% HCl were studied using weight loss method, and electrochemical imped-
ance method. Inhibited metallic surface are examined using SEM, XPS and FT-IR.

2. Experimental

2.1. Preparation of plant extract

Dried Zenthoxylum alatum (350 g) plant fruits were soaked in 900 ml of reagent grade
methanol for 24 h and refluxed for 5 h. The methanolic solution was filtered and concen-
trated to 500 ml. This extract was used to study the corrosion inhibition properties.
To know the mass of plant extract, it was dried at 60 C (removal of methanol) under
vacuum. From the weight of the vacuum dried liquid, plant extract was found to contain
80 mg/ml of plant compounds (80,000 ppm).

2.2. Preparation of specimens

Mild steel coupons having percent composition of 0.54 Mn, 0.05 Si, 0.01 S, 0.01 P, 0.16
C and remaining Fe were used. The specimens were polished successively using 1/0 to 6/0
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1145

emery papers, degreased with trichloroethylene and washed with distilled water before
experiment.

2.3. Electrolyte

The solutions used were made of AR grade hydrochloric acid. Appropriate concentra-
tions of acids were prepared by using triple distilled water. The molar concentration of 5%
and 15% HCl are 1.61 and 4.84 mol dm3. The concentration range of inhibitor (plant
extract) employed was varied from 100 to 2800 ppm and the electrolyte used was 200 ml.

2.4. Weight loss method

Weight loss of rectangular steel specimens of size 1 · 5 · 2 cm in triplicate immersed in

200 ml of electrolyte with and without the addition of different concentrations of plant
extract was determined after 4 h at 30 C or 1 h in the temperature range 50–80 C. The
percentage inhibition efficiency (IE) was calculated from,
W1W2
IE ð%Þ ¼  100
W1
where W1 and W2 are weight losses of steel in uninhibited and inhibited solutions.

2.5. Electrochemical measurements

A three electrode cell assembly consisting of a mild steel coupon of the size 1 · 1 cm2
embedded in specimen holder as working electrode (WE), a large area Platinum mesh
of negligible impedance as counter electrode (CE) and a saturated calomel electrode as
reference electrode (RE) containing 200 ml of electrolyte was used for electrochemical
measurements. The temperature of the electrolyte was maintained at 30, 50, 60, 70 and
80 C.

2.6. Potentiodynamic polarization

The polarization curves were recorded by using computer controlled Gamry electro-
chemical system. The potential increased with the speed of 30 mV min1. Experiments
were carried out from 200 to 700 mV potential ranges. Before recording the polariza-
tion curves, the WE was maintained at its corrosion potential for 10 min until a steady
state was obtained.

2.7. Electrochemical impedance spectroscopy (EIS)

EIS experiments were conducted using computer controlled Gamry electrochemical

system. EIS 300 software was used for collecting and evaluating the experimental data.
Our investigation measured the response of the electrochemical system to a.c. excitation
with a frequency ranging from 50,000 to 0.1 Hz and peak-to-peak a.c. amplitude of
10 mV. Various equivalent circuit models were fitted to the impedance data using a
non-linear optimization computed programme. The percentage inhibition efficiency (IE)
was calculated from,
1146 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

R2  R1
IE ð%Þ ¼  100
R2
where R1 and R2 are charge transfer resistance of steel in uninhibited and inhibited
solutions.

2.8. Surface analysis

The test coupons of the size 1 · 1 cm2 were exposed in 100 ml of 5% HCl having
2800 ppm plant extract for 1 h at 30 C and washed with distilled water. After washing,
specimens were dried in a critical point drying apparatus (M/S Balzers, Switzerland)
and were examined for their structural and topographical features using Scanning electron
microscope (SEM) and Electron spectroscopy for chemical analysis (ESCA). For FT-IR
studies (KBr pellet method), the surface of the dried specimens were scratched with a knife
and the resultant powder was used. In case of FT-IR studies of plant extract, vacuum
dried plant extract liquid was used.

3. Results and discussion

3.1. Analysis of plant extract

Gas chromatography (GC)–mass spectroscopy (MS) analysis of dried plant extract

showed that the plant extract contains 11 different compounds (Table 1). MS analysis
of these compounds showed the presence of plant acids or its esters (75%) and possible
derivatives of terpineol, isoxazolidine (6.96%) and imidazolinedione (6.44%). CHN ana-
lysis of plant extract showed presence of carbon (48.24%), hydrogen (5.56%), nitrogen
(16.5%), sulfur (1.58%), metals (5.5%) and oxygen (rest).

3.2. Weight loss measurements: effect of plant extract concentration and temperature

Fig. 1 shows the corrosion rate and inhibition efficiency of mild steel exposed to 5%
HCl at 30, 60 and 80 C in the absence and presence of plant extract. It is evident from
these results that inhibition efficiency of mild steel increases on addition of plant extract

Table 1
Gas chromatography (GC)–mass spectroscopy (MS) and CHN analysis of vacuum dried plant extract
Sr. no. Retention time of Amount (%) Possible compound (by MS)
compounds (min)
1 2.16 10.32 Methyl ester of plant acid
2 2.68 64.51 Methyl ester of plant acid
3 6.64 2.96 Derivatives of isoxazolidine
4 8.43 2.23 Unsaturated plant acid
5 8.54 8.68 Derivatives of terpineol
6 9.52 0.74 Derivatives of terpineol
7 9.95 1.61 Derivatives of isoxazolidine
8 10.2 0.90 Derivatives of isoxazolidine
9 11.18 1.49 Derivatives of isoxazolidine
10 12.95 2.96 Derivatives of imidazolinedione
11 13.30 3.48 Derivatives of imidazolinedione
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1147

120 100
30oC
100 60oC

Corrosion rate (mg m s )

-1
80oC

Inhibition efficiency ( %)
75

-2
80

60 50

40
25
20

0 0
0 500 1000 1500 2000 2500 3000
Plant extract concentration ( ppm)

Fig. 1. Corrosion rate and inhibition efficiency plots of mild steel immersed in 5% HCl with and without plant
extract at 30, 60 and 80 C.

up to 2400 ppm at 30 C. However beyond this concentration, decrease in corrosion inhi-
bition efficiency was noticed. As the temperature increases, the corrosion rate increases
and the inhibition efficiency decreases. At 80 C maximum inhibition efficiency of 89%
was obtained in 5% HCl solution containing 2800 ppm plant extract. It shows that this
plant extract is capable enough to reduce corrosion rate of mild steel in the temperature
range 30–80 C in 5% HCl solution. Comparing this result with the literature available,
this plant extract (Zenthoxylum alatum) is better (maximum 96% corrosion inhibition effi-
ciency for mild steel in 5% HCl (1.6 M) with 2400 ppm of plant extract at 30 C) than plant
extracts of tobacco, black pepper, castor seed and soya bean [10].
Fig. 2 shows the corrosion rate and inhibition efficiency of mild steel exposed to 15%
HCl at 30, 60 and 80 C in the absence and presence of plant extract. As the temperature
increases, the corrosion rate increases and the overall inhibition efficiency decreases. Cor-
rosion inhibition efficiency for mild steel in 15% HCl medium containing 2800 ppm plant
extract at 60 and 80 C are 75% and 45%. It shows that this plant extract inhibits mild steel
corrosion in the temperature range 30–60 C in 15% HCl medium.

3.3. Potentiodynamic polarization

Potentiodynamic polarization curves for the mild steel in 5% HCl containing different
concentrations of plant extract are shown in Fig. 3. The respective kinetic parameters are
given in Table 2. The addition of plant extract does not change the values of corrosion
potential (Ecorr) and anodic Tafel slope (ba). Corrosion current of mild steel decreases
on increasing the concentration of plant extract till 2400 ppm. Increase in cathodic Tafel
slope (bc) on increasing the plant extract concentration indicates that this plant extract
inhibits corrosion by inhibiting cathodic reaction.

3.4. Electrochemical impedance spectroscopy

The corrosion of mild steel in 5% HCl solution in the presence of plant extract was
investigated by EIS at 30 C after an exposure period of 10 min. Nyquist plots for mild
1148 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

100

30oC
200 60oC
75
Corrosion rate ( mg m s ) 80oC
-1

Inhibition efficiency ( %)
-2

50

100

25

0 0
0 500 1000 1500 2000 2500 3000
Plant extract concentration ( ppm)

Fig. 2. Corrosion rate and inhibition efficiency plots of mild steel immersed in 15% HCl with and without plant
extract at 30, 60 and 80 C.

-300
Potential (mV vs SCE)

-400

- 0 ppm
-500 - 400 ppm
- 800 ppm
- 1600 ppm
-600 - 2400 ppm
- 2800 ppm

-5 -4 -3 -2 -1
Log current density (A cm-2)

Fig. 3. Potentiodynamic polarization plots of mild steel immersed in 5% HCl with and without plant extract
(PE).

steel obtained at the interface in the absence and presence of plant extract at different con-
centrations is given in Fig. 4. The impedance diagram obtained with 5% HCl shows only
one capacitive loop. The same trend (one capacitive loop) was also noticed for mild steel
immersed in 5% HCl containing plant extract (100–2400 ppm). The diameter of Nyquist
plots increases on increasing the plant extract concentration. This suggested that the
formed inhibitive film was strengthened by addition of plant extract.
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1149

Table 2
Kinetic parameters derived from potentiodynamic polarization plots of mild steel immersed in 5% HCl medium
containing plant extract at 30 C
Concentration (ppm) Ecorr (mV/SCE) Icorr (mA cm2) bc (mV dec1) ba (mV dec1)
0 432 9.47 89 64
400 432 3.06 88 66
800 430 0.69 122 70
1600 430 0.32 196 66
2400 430 0.10 210 76
2800 430 0.32 189 69

0 ppm
10 Hz 100 ppm
400 ppm
200 800 ppm
1600 ppm
2000 ppm
2400 ppm
-Imag (Ohm)

2800 ppm

100 1 Hz
100 Hz

0.1 Hz
0
0 100 200 300 400 500 600 700
Real (Ohm)

Fig. 4. Nyquist plots (EIS) of mild steel immersed in 5% HCl with and without plant extract at 30 C.

The above impedance diagram (Nyquist) contains a depressed semicircle with the center
under the real axis, such behaviour characteristic for solid electrodes and often referred to
frequency dispersion have been attributed to roughness and inhomogeneities of solid sur-
face [12]. In these cases, the parallel network polarization resistance and double layer
capacitance (Rp  Cdl) is usually a poor approximation especially for system where an effi-
cient inhibitor is used. For the description of a frequency independent phase shift between
an applied alternating potential and its current response a constant phase element (CPE) is
used.
The CPE is defined by the mathematical expression [16–21]
1=ZðCPEÞ ¼ Y ðCPEÞ ¼ AðjxÞa
where Z(CPE), impedance of CPE; Y(CPE), admittance of CPE; A, a proportional factor;
j, (1)1/2; x, angular frequency; a, surface irregularity. The CPE, which is considered a
surface irregularity of the electrode, causes a greater depression in the of Nyquist semicir-
cle diagram [16], where the metal solution interface acts as a capacitor with irregular sur-
face. If the electrode surface is homogeneous and plane, the exponential value (a) becomes
equal to 1 and the metal solution interface acts as a capacitor with regular surface, i.e.
when a = 1, A = capacitance.
1150 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

80

100 Hz
60

10 Hz
-Imag (Ohm)

40

1 Hz
20
0.1 Hz

0
0 50 100 150 200 250
Real (Ohm)

Fig. 5. Simulation of experimental data with one time constant CPE model.

Since most of the spectra show only one semicircle, they were fitted using one time con-
stant equivalent model (Randle’s model) with constant phase element (CPE) and charge
transfer resistance (Rt). Simulation of Nyquist plots with above model showed excellent
agreement with experimental data (Fig. 5). The main parameters deduced from the anal-
ysis of Nyquist diagram for 5% HCl medium containing various concentrations of plant
extract are given in Table 3. The lower adl value for 5% HCl medium indicates surface
inhomogeneity resulting from surface metal roughening due to corrosion. The values of
adl lies between 0.68 and 0.78. Addition of plant extract increases adl value indicating
reduction of surface inhomogeneity due to the chemisorption of plant extract molecules.
Capacitance (Adl) values decreases on increasing the plant extract concentration indicates
reduction of charges accumulated in the double layer due to formation of chemisorbed
plant extract layer [15]. The charge transfer resistance of double layer (Rt) increases on
increasing the plant extract concentration indicating that increase in concentration of
plant extract decreases corrosion rate i.e., increases corrosion inhibition. The corrosion
inhibition efficiencies calculated using these values are comparable with the same

Table 3
Kinetic parameters derived from Nyquist plots of mild steel immersed in 5% HCl medium containing plant
extract at 30 C
Plant extract concentration Charge transfer resistance Adl adl Inhibition efficiency
(ppm) (Rt) (X) (lF cm2) (%)
0 34 308 0.68 –
100 93 305 0.69 63
400 250 272 0.69 86
800 338 249 0.69 90
1200 355 194 0.71 90
1600 525 112 0.72 94
2000 555 97 0.76 94
2400 636 91 0.78 95
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1151

calculated using weight loss data. The maximum of corrosion inhibition efficiency of 95%
was noticed for 2400 ppm plant extract.
EIS experiments were also conducted for mild steel immersed in 5% HCl with and with-
out plant extract at temperature range 50–80 C. The respective plots were analysed using
one time constant model with CPE and the respective charge transfer resistance (Rt) values
were plotted and shown in Fig. 6a. The Rt increases on increasing the plant extract con-
centration at 30 C. The maximum Rt values were achieved for 2000 ppm of plant extract
concentration at temperature range 50–80 C. As the temperature increases, the Rt
decreases. The respective corrosion inhibition efficiency data calculated using Rt values
are given in Fig. 6b. Corrosion inhibition efficiency decreases on increasing the tempera-
ture. It also shows that inhibition efficiency increases on increasing the plant extract con-
centration. The corrosion inhibition efficiency for 2000 ppm plant extract was 81% at
80 C. The above results show that this plant extracts acts as inhibitor in the temperature
range 30–80 C.
Fig. 7 shows Nyquist plots of mild steel immersed in 15% HCl with and without plant
extract at 30 C. The impedance diagram obtained with 15% HCl shows only one capac-
itive loop with a low frequency dispersion (Inductive arc). This inductive loop is generally
attributed to anodic adsorbed intermediates controlling the anodic process [22–24]. In 15%
HCl, with the presence of various concentrations of plant extract studied, the impedance
diagram shows capacitive behaviour. The diameter of Nyquist plots increases on increas-
ing the plant extract concentration. This suggested that addition of this plant extracts
strengthens the corrosion inhibitive film in 15% HCl medium.
Using Randle’s one time constant model with CPE instead of capacitance, Nyquist
plots for 15% HCl medium containing various concentrations of plant extract were ana-
lysed and the data were presented in Table 4. The lower adl value for 15% HCl medium
indicates surface inhomogeneity resulting from surface metal roughening. The values of
adl lies between 0.67 and 0.74. Addition of 100 ppm of plant extract increases adl value
from 0.67 to 0.72 indicating reduction of surface inhomogeneity due to the chemisorption

a 600
30oC b100
50oC
Polarization resistance (Ohm)

500 60oC
70oC
Inhibition efficiency (%)

400 80oC 80

300

30oC
200 60 50oC
60oC
70oC
100
80oC

0 40
0 500 1000 1500 2000 0 500 1000 1500 2000
Plant extract concentration (ppm) Plant extract concentration / ppm

Fig. 6. Charge transfer resistance (Rt) (a) and inhibition efficiency (b) of mild steel immersed in 5% HCl with and
without plant extract at 30, 50, 60, 70 and 80 C.
1152 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

100
0 ppm
10 Hz 100 ppm
400 ppm
75 800 ppm
1600 ppm
-Imag (Ohm)
100 2000 ppm
Hz 2400 ppm
2800 ppm
50

1 Hz

25
0.1 Hz

0
0 100 200 300
Real (Ohm)

Fig. 7. Nyquist plots of mild steel immersed in 15% HCl with and without plant extract at 30 C.

Table 4
Kinetic parameters derived from Nyquist plots of mild steel immersed in 15% HCl medium containing plant
extract at 30 C
Plant extract Charge transfer Adl (lF cm2) adl Inhibition efficiency
concentration (ppm) resistance (Rt) (X) (%)
0 28 277 0.67 –
100 58 211 0.72 52
400 72 201 0.72 61
800 122 201 0.73 77
1200 214 197 0.73 87
1600 244 128 0.73 89
2000 267 131 0.74 90
2400 297 104 0.74 91

of plant extract molecules. Further addition of plant extract changes adl value to small
extent (from 0.72 to 0.74) indicating that addition of more than 100 ppm of plant extract
has little effect on reduction of surface inhomogeneity. However the addition of plant
extract decreases the capacitance (Adl) and increases Rt indicating reduction of corrosion
rate by the plant extract. The corrosion inhibition efficiencies calculated using these values
are comparable with the same calculated using weight loss data. The maximum corrosion
inhibition efficiency of 91% was noticed for 2400 ppm plant extract.
Polarization resistance values of mild steel immersed in 15% HCl at various tempera-
tures is plotted against plant extract concentration shown in Fig. 8a. Rt values increases
on increasing the plant extract concentration. The respective corrosion inhibition effi-
ciency data calculated using Rt values are given in Fig. 8b. Corrosion inhibition efficiency
decreases on increasing the temperature. It also shows that inhibition efficiency increases
on increasing the plant extract concentration. The corrosion inhibition efficiencies for
2000 ppm plant extract were 88%, 77% and 68% at 60, 70 and 80 C. The above results
shows that this plant extracts acts as inhibitor in the temperature range 30–60 C.
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1153

a b 100
Polarisation resistance (Ohm)

300
30oC

Inhibition efficiency (%)

50oC 80
60oC
70oC
200 80oC
60

100 30oC
40 50oC
60oC
70oC
80oC
0 20
0 500 1000 1500 2000 2500 0 1000 2000
Plant extract concentration (ppm) Plant extract concentration (ppm)

Fig. 8. Charge transfer resistance (Rt) of mild steel immersed in 15% HCl with and without plant extract at 30, 50,
60, 70 and 80 C.

3.5. Surface analysis of mild steel surface exposed to plant extract

Scanning electron micrographs (SEM) of mild steel surface immersed in 5% HCl

(blank) and 5% HCl containing 2400 ppm plant extract are shown in Fig. 9. A rough sur-
face was noticed for mild steel immersed in 5% HCl solution. In case of mild steel
immersed in 5% HCl with 2400 ppm plant extract, a smooth surface was noticed and it
is easily comparable with the polished surface. This shows that this plant extract inhibits
corrosion of mild steel in 5% HCl solution.
The Electron spectroscopy for chemical analysis (ESCA) measurements was performed
to obtain information on the surface coverage of the inhibitor. Fig. 10 shows ESCA of
Fe2p3/2, O1s, N1s, C1s and S2p for the mild steel specimen after immersion for one hour
in 5% HCl solution containing 2800 ppm plant extract. The Fe2p3/2 spectrum has peak at
706.76 eV. This peak is attributable to metallic iron which is reported to appear at
706.9 ± 0.10 [25]. A broad peak was observed in the O1s spectrum at about 530–
536 eV. Using a non-linear least squares algorithm with a Shirley base line and a Gauss-
ian–Lorentzian combination, these spectra could be deconvoluted into two components
labeled as 1 and 2. The binding energies of these components along with their intensities
are given in Table 5. The O1s spectra show the strong presence of C–O/S–O (532.6 eV)
and C@O/S@O groups (534 eV). The peak that originates from plant extract is included
in these two peaks because in general the O1s peaks of organic compounds have been
reported to appear at this energy position [26]. Peak for N1s electron at 399.55 eV indi-
cates presence of imines. The respective C1s spectra could be deconvoluted into three
components labeled as 1, 2 and 3. It shows that the peaks at 285 eV, 287 eV and
288.6 eV are mainly due to the C–C, C–O and C@O bonds. The peaks at 166 eV is
due to 2P electron of sulphur atom (C–SO2–C). The above XPS spectrum shows that
the inhibitive film formed on the mild steel surface contains mixtures of compounds hav-
ing C, O, N and S atoms. This confirms that the formed corrosion inhibitive layer con-
tains plant extracts.
1154 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

Fig. 9. SEM graphs of mild steel: (a) polished surface (b) mild steel immersed in 5% HCl and (c) mild steel
immersed in 5% HCl with 2800 ppm of plant extract.
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1155

Fe 2p O 1s
Intensity (CPS)

Intensity (CPS)
723 717 711 705 699 537 535 533 531
Binding energy (eV) Binding energy (eV)

N 1s Intensity (CPS) C 1s
Intensity (CPS)

401 399 397 291 288 285 282

Binding energy ( eV) Binding energy (eV)

S 2p
Intensity (CPS)

168 166 164

Binding energy (eV)

Fig. 10. X-ray photoelectron spectrum of mild steel immersed in 5% HCl solution with 2400 ppm of plant extract.

The above evidences were further confirmed by FT-IR spectra of plant extract and mild
steel surface immersed in 5% HCl with 2400 ppm plant extract (Fig. 11). The respective
FT-IR peaks of plant extract and mild steel immersed in 5% HCl with 2400 ppm plant
extract are given in Table 6. The peaks at 3350, 2927 and 2857 cm1 can be assigned to
1156 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

Table 5
Binding energies and relative intensities of various atoms from X-ray photoelectron spectrum of mild steel
immersed in 5% HCl with 2400 ppm of plant extract at 30 C
Electron Species Binding energy (eV) Relative intensity (CPS) Mass concentration (%)
Fe2p3/2 1 706.8 100 13.11
O1s1/2 1 532.6 44.9 29.58
2 534.0 55.1
N1s1/2 1 399.6 100 4.61
C1s1/2 1 285.9 46.1 50.90
2 287.1 41.6
3 288.6 12.3
S2p3/2 1 166.2 100 1.80

680
Transmittance (%)

712
B
1260
1171

1034
1738

1527
1587

1440

793

663
A
1375
1448
1664
1636

1248
1712
2857

1073
1031
3350

2927

3500 3000 2500 2000 1500 1000 500

Wavelength (cm-1)

Fig. 11. FT-IR spectra of samples: (A) mild steel immersed in 5% HCl solution with 2400 ppm of plant extract,
(B) plant extract.

Table 6
Peaks from FT-IR spectra of samples: (A) mild steel immersed in 5% HCl solution with 2400 ppm of plant
extract, (B) plant extract and their identification
Peaks from FT-IR spectra Possible groups Reference
MS in plant extract Plant extract
3350 3360 O–H/N–H [27,28]
2922 2927 Aliphatic C–H [27,28]
2857 2858 Aromatic C–H [27,28]
– 1738 C@O [29]
1712 – C@O complexed with metal cation [30]
1664 1664 R2C@N, [29]
1636 1636 C@C, [29]
1580 1587 Aromatic substituted C@N [29]
1522 1527 Aromatic ring (C@C). [29]
1448 1440 C–C [29]
1248 1260 C–SO2–C [29]
– 1171 C–O [29]
1073 – C–O [29]
1031 1034 OH [29]
793, 663 – c-Fe2O3 [31]
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1157

the presence of a superficial adsorbed water, stretching mode of an O–H and/or N–H and
aliphatic and aromatic C–H groups (from plant extract) [27,28]. The peaks at 1712, 1664,
1636, 1587 and 1527 cm1 corresponds to C@O, R2C@N, C@C, Aromatic substituted
C@N and aromatic ring (C@C). Peaks for C–SO2–C, OH are noticed at 1260 and
1034 cm1 [29]. This shows that this plant extract contains mixtures of compounds.
Almost all peaks observed for plant extract is also noticed for mild steel immersed in
5% HCl containing 2400 ppm of plant extract. The peak shift from 1738 to 1712 cm1
shows formation of Iron–plant extract complex or salt [30]. The band at 450–700 cm1
probably originates mainly from c-Fe2O3 (680 cm1 [31]).

3.6. Adsorption isotherms analysis

The nature of corrosion inhibition has been deduced in terms of the adsorption char-
acteristics of the inhibitor [32]. The metal surface in aqueous solution is always covered
with adsorbed water dipoles. Therefore, the adsorption of inhibitor molecules from aque-
ous solution is a quasi substitution process [33,34]. A correlation between h and the con-
centration (C) of inhibitor in the electrolyte can be represented by the Langmuir
adsorption isotherm.
C/h = 1/K + C where, K is constant of adsorption. The relation between C/h and C at
30, 50 and 80 C for mild steel in 5% HCl with various concentration of plant extract is
shown in Fig. 12. The plots at each temperature were found to yield a straight line with
slopes measured were close to 0.7. As can be seen by the good fit, this plant extract as
inhibitor found to obey Langmuir adsorption isotherm. The same trend was noticed for
mild steel immersed in 15% HCl with varying concentration of plant extract at all temper-
atures (Fig. 13). This confirms that this inhibitor (plant extract) also obeys Langmuir
adsorption isotherm at 15% HCl medium.

30oC
3 60oC
80oC

2
C/θ

0
0 1 2 3
Plant extract concentration (g litre-1)

Fig. 12. Langmuir adsorption plots for mild steel immersed in 5% HCl with and without plant extract at 30, 60
and 80 C.
1158 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

6
30oC
60oC
80oC
C/ θ 4

0
0 1 2 3
Plant extract concentration (g liter-1)

Fig. 13. Langmuir adsorption plots for mild steel immersed in 15% HCl with and without plant extract at 30, 60
and 80 C.

3.7. Activation energy calculations

The change of the corrosion rate in presence and absence of plant extract containing 5%
and 15% HCl was plotted against temperature for calculation of activation energy (Figs.
14 and 15) and the respective activation energy data [4] are given in Table 7. The effect of
chemically stable surface active inhibitors increase the energy of activation and to the dim-
inution of the surface available for corrosion [35]. Addition of plant extracts up to
2400 ppm in 5% HCl increases the activation energy from 48 to 80 kJ mol1. However,
addition of more than 2400 ppm plant extract decreases the activation energy. In 15%
HCl medium, activation energy increases on increasing the plant extract concentration.
The maximum activation energy of 69.5 kJ mol1 was noticed for 2800 ppm plant extract.
The results show that addition of plant extract in 5% and 15% HCl medium decreases

3
Log (Corrosion rate) (mg m-2 s-1)

0 ppm
0 100 ppm
400 ppm
800 ppm
1600 ppm
-1
2000 ppm
2400 ppm
2800 ppm
-2
28 29 30 31 32 33 34
10000/T (K-1)

Fig. 14. Variations of Ln (corrosion rate) with 1/T in 5% HCl with and without plant extract.
 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161 1159

2.5

Log (Corrosion rate) ( mg m-2 s-1)

2

1.5

0 ppm
1 100 ppm
400 ppm
800 ppm
1600 ppm
2000 ppm
0.5
2400 ppm
2800 ppm

0
28 29 30 31 32 33 34
10000/T ( K-1)

Fig. 15. Variations of Ln (corrosion rate) with 1/T in 15% HCl with and without plant extract.

Table 7
Calculated values of activation energy (Ea) for the corrosion of mild steel in 5 and 15% HCl with and without
plant extract
Concentration of plant Activation energy (Ea)a for 5% HCl Activation energy (Ea)a for 15% HCl
extract (ppm) solution (kJ mol1) solution (kJ mol1)
0 48.06 43.07
400 49.99 46.63
800 50.41 48.19
1200 53.8 50.99
1600 55.1 53.51
2000 59.33 56.19
2400 79.93 62.89
2800 69.76 69.47
a
Error ± 1.5%.

metal dissolution. This hindrance to dissolution is due to the formation of the Fe–plant
extract layer.
Weight loss method, electrochemical experiments (Potentiodynamic polarization and
EIS) and surface analytical experiments (ESCA and FT-IR), show that plant extract
inhibit corrosion of mild steel in HCl medium. GC–MS analysis of plant extract showed
presence of derivatives of plant acids, terpineol, isoxazolidine and imidazolinedione. Fur-
ther analysis of individual compounds by Mass spectroscopy showed that the plant acid
and terpineol does not contain either nitrogen or sulphur groups. So these compounds
are not effective as corrosion inhibitors for mild steel in acid medium [6,7]. However the
derivatives of isoxazolidine and imidazolinedione are known to contain nitrogen groups
and are responsible for the corrosion inhibition properties of this plant extract. Presence
of N1s peak in ESCA spectrum and FT-IR peaks at 1664 and 1587 cm1 corresponds to
1160 L.R. Chauhan, G. Gunasekaran / Corrosion Science 49 (2007) 1143–1161

R2C@N and aromatic substituted C@N on mild steel immersed in HCl containing plant
extract confirms the presence of derivatives of isoxazolidine and imidazolinedione in the
corrosion inhibitive layer.
Our earlier results [15] showed that the inhibitive film formation on mild steel in phos-
phoric acid medium containing plant extract was due to the formation of iron oxides, iron
phosphate and iron–plant extract complex. However in case of HCl medium containing
plant extracts, the inhibitive film formation is due to iron oxides and iron–plant extract
complex.

4. Conclusions

1. GC–MS analysis of plant extract shows that this plant extract contains plant acids or its
esters (75%) and derivatives of terpineol, isoxazolidine (6.96%) and imidazolinedione
(6.44%).
2. The inhibition efficiency of mild steel in 5% and 15% HCl medium increases on increas-
ing the concentration of plant extract. These plant extracts act as inhibitor in 5% HCl
medium up to 80 C. The performance of this extract as corrosion inhibitor is better
than plant extracts of tobacco, black pepper, castor seed, soya bean, etc.
3. A.C. impedance plots of mild steel in 5% and 15% HCl medium containing plant
extracts shows that charge transfer resistance increases with increase of plant extract
concentration.
4. XPS and FT-IR show that the compounds present in plant extract forms corrosion
inhibitive layer by reacting with iron ions present on the mild steel surface.
5. Adsorption of inhibitor molecules (plant extract) on the mild steel surface is found to
obey the Langmuir adsorption isotherm.
6. Addition of plant extract increases activation energy for metal dissolution reaction indi-
cating that this plant extracts hinders metal dissolution in 5% and 15% HCl medium.

Acknowledgements

The authors are grateful to Dr. J. Narayana Das, Director, NMRL and Dr. J. Rang-
arajan for their invaluable guidance and support.

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