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University of Bahrain
ORIGINAL ARTICLE
Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005, India
Received 23 February 2015; revised 20 April 2015; accepted 25 April 2015
KEYWORDS
Mild steel;
Corrosion;
EIS;
Tafel polarization;
SEM/EDX
Abstract The inuence of three Bis (indolyl) methanes (BIMs) namely, 3,30 -((4-nitrophenyl) methylene) bis (1H-indole) (BIM-1), 3,30 -(phenyl methylene) bis (1H-indole) (BIM-2) and 4-((1H-indol-2yl)(1H-indol-3-yl) methyl) phenol (BIM-3) on the mild steel corrosion in 1 M HCl was studied by
weight loss, electrochemical, scanning electron microscopy (SEM), and dispersive X-ray spectroscopy (EDX) methods. Results showed that BIM-3 shows maximum inhibition efciency of
98.06% at 200 mg L1 concentration. Polarization study revealed that the BIMs act as mixed type
inhibitors. Adsorption of BIMs on the mild steel surface obeyed the Langmuir adsorption isotherm.
The weight loss and electrochemical results were well supported by SEM and EDX studies.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Bahrain. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
Organic compounds particularly, N-heterocyclic have been
reported as effective corrosion inhibitors for mild steel against
corrosion during several industrial processes (Solmaz, 2014;
Musa et al., 2012; Mahdavian and Ashhari, 2010; Ozkir
et al., 2012). Ultrasound irradiation has immerged as a powerful technique for the synthesis of various heterocyclic compounds of industrial and biological interest (Goharshad
et al., 2009) due to their shorter reaction time, simple operating
* Corresponding author. Tel.: +91 9307025126; fax: +91 542
2368428.
E-mail addresses: maquraishi.apc@itbhu.ac.in, maquraishi@
rediffmail.com (M.A. Quraishi).
Peer review under responsibility of University of Bahrain.
http://dx.doi.org/10.1016/j.jaubas.2015.04.003
1815-3852 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Bahrain.
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: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
C. Verma et al.
g%
h
CR CRi
100
CR
CR CRi
CR
Alum (10%)
+
R
Solvenr free, US
R
H
Scheme 1
NH
Figure 1 Variation of inhibition efciency with BIMs concentration of mild steel immersed in 1 M HCl obtained by weight loss
measurement.
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
308
318
328
338
BIM-1
BIM-2
BIM-3
7.60
11.0
14.3
18.6
0.46
1.23
2.03
3.30
0.30
1.10
1.80
2.76
0.13
0.83
1.56
2.46
2.1
To investigate the effect of temperature on inhibition performance of BIMs, the weight loss experiments were also performed at different temperatures (308338 K). The values of
the CR at different studied temperatures are listed in Table 1.
It is apparent from results that the value of the CR increases
on increasing temperature for inhibited as well as uninhibited
solutions. This increased values of CR is attributed to desorption of the adsorb BIMs molecules from mild steel surface at
elevated temperatures, resulting in enhanced CR (Barmatov
et al., 2015).
The temperature dependency of corrosion rate can be best
represented by the Arrhenius and transition state equations
(Deng et al., 2011):
log CR
CR
Ea
log k
2:303RT
RT
DS
DH
exp
exp
Nh
R
RT
1.8
-2
-1
2.4
log CR(mg cm h )
1.5
1.2
0.9
Blank
BIM-1
BIM-2
BIM-3
0.6
0.3
2..95
3..00
3..05
3.10
3.15
3.20
3.25
Inhibitor
Ea (kJ mol1)
DS* (J/mol K)
Blank
BIM-1
BIM-2
BIM-3
28.48
62.72
65.83
73.93
26.04
54.06
54.53
72.43
148.9
147.12
127.5
68.2
[(1//T)103]K-1
(a)
1.8
1.6
log (/1-)
1.4
BIM-1
BIM-2
BIM-3
1.2
1.0
0.8
0.6
0.4
-3.9 -3.8 -3.7 -3.6 -3.5 -3.4 -3.3 -3.2
(b)
Figure 2 Arrhenius plots for mild steel in 1 M HCl in the
absence and presence of different concentrations of BIMs.
log C(inh)
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
C. Verma et al.
Table 3 The values of Kads and DGads for mild steel in the absence and presence of optimum concentration of BIMs in 1 M HCl at
different studied temperatures.
Kads (104 M1)
Inhibitor
BIM-1
BIM-2
BIM-3
308
318
328
338
308
318
328
338
18.43
20.98
25.85
5.37
5.87
6.35
3.54
3.89
4.65
2.37
2.46
2.85
35.75
35.98
36.42
34.39
34.13
35.52
33.53
33.23
34.43
33.38
33.35
33.47
Ecorr
(V/SCE)
icorr
(lA/cm)
ba
(mV/dec)
bc
(mV/dec)
g%
Blank
BIM-1
BIM-2
BIM-3
445
466
463
527
1150
95.8
94.1
63.51
70.5
66.8
61.3
80.9
114.6
151.0
138.4
127.9
91.66
91.82
94.47
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
Cinh
Kads
h
where, C(inh) is the inhibitor concentration and Kads is the equilibrium constant for the adsorptiondesorption process. The
values of Kads were calculated at different studied temperatures
from the intercept of the Langmuir plot shown in Fig. 3 and
The value 55.5 in above equation represents the concentration of water in acid solution in mol L1. Generally, a higher
value of Kads associated with higher tendency to adsorb on
mild steel surface. In our present study the Kads value of different BIMs follows the order: BIM-3 > BIM-2 > BIM-1 which
is in accordance with the order of the g%. In our present
Table 5 Electrochemical impedance parameters obtained from EIS measurements for mild steel in 1 M HCl in the absence and
presence of optimum concentration of BIMs.
Inhibitor
Rs (X cm2)
Rct (X cm2)
g%
Goodness of t
Blank
BIM-1
BIM-2
BIM-3
1.12
0.73
1.11
1.05
9.58
161.8
199.9
264.4
106.21
36.68
29.99
24.80
0.827
0.827
0.848
0.854
94.07
95.20
97.44
3.735 103
1.332 103
674.1 106
858.9 106
Figure 6 SEM micrographs of mild steel surfaces in the absence (a) and presence of optimum concentration of BIM-1 (b), BIM-2 (c) and
BIM-3 (d).
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
C. Verma et al.
i0corr iicorr
100
i0corr
8
3.3.2. EDX analysis
The EDX spectra in the absence and the presence of the optimum concentration of the BIMs after 3 h immersion are
shown in Fig. 7. The EDX spectrum without BIMs gives signals only for carbon (C) and Fe as shown in Fig. 7a.
However, the EDX spectra of mild steel in the presence of
BIMs (Fig. 7bd) showed characteristics signal for N and O
along with C and Fe. The presence of N and O in the EDX
spectra suggests that BIMs inhibit mild steel corrosion by
adsorbing on the mild steel surface. Moreover, intensity of N
and O increases in the order: BIM-3 > BIM-2 > BIM-1
Yxn1
sinnp=2
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003
Please cite this article in press as: Verma, C. et al., A thermodynamical, electrochemical and surface investigation of Bis (indolyl) methanes as Green corrosion inhibitors for mild steel in 1 M hydrochloric acid solution. Journal of the Association of Arab Universities for Basic and Applied Sciences (2015), http://dx.doi.org/
10.1016/j.jaubas.2015.04.003