The effect of an N-heterocyclic compound on corrosion inhibition of J55 steel in sweet corrosive medium

Article abstract of DOI:10.1039/c9nj00356h

The corrosion inhibition behavior of a naphthoxazinone derivative 1-phenyl-1,2-dihydronaphtho[1,2-e][1,3]oxazin-3-one (PNO) on J55 steel in 3.5 wt% NaCl solution saturated with carbon dioxide was evaluated using weight loss, electrochemical impedance spec

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The effect of N-heterocyclic compound on corrosion inhibition of J55 steel in
sweet corrosive medium
1
,2
3*
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Ambrish Singh , K. R. Ansari , M.A.Quraishi , Savas Kaya , Priyabrata Banerjee
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1School of Materials Science and Engineering, Southwest Petroleum University, Chengdu-
6
2
10500, Sichuan, China.
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest
Petroleum University, Chengdu, Sichuan 610500, China.
Centre of Research Excellence in Corrosion, Research Institute, King Fahd University of
Petroleum and Minerals, Dhahran 31261, Saudi Arabia
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Cumhuriyet University, Faculty of Science, Department of Chemistry, 58140, Sivas, Turkey
Surface Engineering & Tribology Group, CSIR-Central Mechanical Engineering Research Institute,
Mahatma Gandhi Avenue, Durgapur 713209, West Bengal, India.
Corresponding author
*
E-mail: kashif.ansari@kfupm.edu.sa; ka3787@gmail.com
Abstract
The corrosion inhibition behavior of naphthoxazinone derivative namely 1-Phenyl-1,2-dihydro-
naphtho[1,2-e][1,3]oxazin-3-one (PNO) on J55 steel in 3.5 wt.% NaCl solution saturated with
carbon dioxide was evaluated using weight loss, electrochemical impedance spectroscopy (EIS)
and potentiodynamic polarization. The surface morphology on metal sample was analyzed using
scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The adsorption of
PNO obeyed the Langmuir isotherm. The results of potentiodynamic polarization indicated that
the PNO molecule behaved as a mixed type inhibitor by reducing both the anodic and the
cathodic electrochemical reactions. The surface analysis showed that the metal surface is
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considerably smoother and with more uniform morphology in the presence of the inhibitor. The
DFT based quantum chemical calculations and molecular dynamic (MD) simulation supported
the experimentally obtained results.
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Keywords: Carbon dioxide; Corrosion; DFT; MD
1
. Introduction
In petroleum industry, carbon steels are commonly used for the manufacture of casing,
tubing, transportation etc. Although carbon steel has limited corrosion resistance, but because of
economic reasons they are given more preference than other materials [1]. In oil and gas industry
carbon dioxide, which is a naturally occurring or intentionally injected constituent in presence of
high chloride concentration is the most aggressive and frequent environment [2]. When carbon
dioxide corrosion dissolves in aqueous, medium it produces carbonic acid, which undergoes
interaction with carbon steel and causes its corrosion [3].
Organic compounds are the best and cost effective way to reduce the carbon dioxide
corrosion during oil and gas production. The effective corrosion inhibitor are the organic
compounds which contains heteroatoms like nitrogen, oxygen, phosphorous and sulphur, phenyl
rings, lone pair of electrons and π-bonds conjugation in their molecular framework [4-8]. The
adsorptions mechanism of inhibitors could be physical involving electrostatic interaction
between the protonated inhibitor molecule and charged metal surface [9, 10] or chemical bond
formation by transfer of electrons to the vacant metal d-orbitals or combination of both
pathways. However, an additional route of inhibitor adsorption onto the metal surface known as
back bonding, which is the ability of inhibitor molecules to accept the electrons from the filled
metal orbitals into their antibonding orbitals [11]. All these mechanisms lead to the formation of
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a protective inhibitor films and thereby resists the corrosive attack of the acid onto the metal
surface.
Review of literature reveals that various imidazoline derivative has been reported as
effective corrosion inhibitors due to their strong ability to adsorb onto the steel surface [12, 13].
Although, imidazolines in the form of cationic surfactants, can causes anodic dissolution by
creating a number of micro anodes and thus leads to localized corrosion [14]. In fact, pitting
corrosion is initiated in the pipelines [15].
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In present time, corrosion scientists are interested to find environment friendly inhibitors
[16]. Thus, Naphthoxazinone due to its antibacterial activity is categorized as green compound
[17]. We herein report the synthesis and detailed investigation on the application of
naphthoxazinone derivative for the corrosion inhibition study of J55 steel in 3.5% NaCl solution
saturated with carbon dioxide. The techniques used for the analysis of corrosion inhibition
includes weight loss and electrochemical. SEM and AFM analyzed the surface morphology of
N80 steel specimen. Furthermore, the experimental results were validated by theoretical study
i.e. density functional theory (DFT) and molecular dynamics (MD) simulation.
2
2
. Experimental procedures
.1. Inhibitor synthesis
The inhibitor was synthesized as per the literature procedure [18]. In a round bottom flask
β-Naphthol (2mmol), benzaldehyde (2 mmol), urea (2mmol), and I (0.1 g) were taken, stirred,
2
and heated on a hot plate at 80 C for 5 min. The obtained contents were cooled to room
temperature, then water was added, and finally the obtained solid precipitate was filtered and
washed repeatedly with water to get the corresponding naphthoxazinones. Pure compound was
obtained by recrystallization from ethanol. The molecular structure of the synthesized compound
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(
PNO) is given in Fig.1. The inhibitor was characterized by H NMR and C NMR spectra and
are given in supplementary file S1and S2.
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H
I2
O
N
O
OH
+
+
O
O
H N
NH2
Hot plate
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5
mins
Figure 1: Synthetic scheme and molecular structure inhibitor
.2. Analytical data
-Phenyl-1,2-dihydro-naphtho[1,2-e][1,3]oxazin-3-one: Mp: 230-232 C; H NMR (300
2
1
o
1
MHz, DMSO-d ): δ= 6.34 (s, 1H, CH), 7.21-8.04 (m, 11H, Ar-H), 7.80 (d, 1H, NH)
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3
C NMR (100 MHz, DMSO-d ): δ= 152.07, 145.05, 143.18, 141.12, 131.94, 130.97, 130.71,
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29.07, 128.78, 128.73, 128.41, 127.77, 126.93, 126.35, 125.85, 123.05, 115.76, 52.01
2.3. Materials and specimens
In the present work J55 steel is used and its chemical composition is as follows: C (0.31),
Mn (0.92), Si (0.19), P (0.01), Cr (0.2), S (0.008), and Fe in balance. The steel specimens used
for weight loss experiment were cut into rectangular shape with the size of 2.5×2.0×0.2 cm. For
electrochemical experiments rectangular rod was used, which was sealed with epoxy resin,
2
leaving an exposed face with an area of 1.0 cm . All the steel specimens were abraded with
silicon carbide papers of 400 to 1200 grits. The samples were degreased with acetone, washed
with ethanol, and finally dried in oven. An aggressive solution of 3.5 wt.% NaCl solution was
prepared with analytical grade sodium chloride and double distilled water.
2
.4. Weight loss measurements
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Three identical steel coupons were used for weigh loss experiments and these coupons
were weighted using an electric balance with precision of ±0.1 mg. The inhibitor concentration is
in the range of 50-500 mg/L. All the steel specimens were immersed into the aggressive
solutions containing different concentrations of PNO. The the test solutions were purged with
pure nitrogen gas for 1 h in order to remove the oxygen, after this carbon dioxide at the rate of 20
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ml min was introduced into the test solution throughout the experiment. The carbon dioxide
containing brine solutions with the steel coupons were sealed using silicone sealants and
incubated at 60 ± 1 °C for 72 h.
After the weight loss, the steel coupons were taken out, immersed in Clarke’s solution for
5 min in order to clean the corrosion products, washed under running water, degreased in
acetone, rinsed with ethanol, dried, and re-weighed accurately. The corrosion rate (ν ) of J55
corr
steel was calculated using the below equation:
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.7610 m
corr


At
(1)
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where νcorr is corrosion rate (mm/y), Δm is weight loss (g), ρ is steel coupon density (g/cm ), A is
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exposed area of steel coupons (cm ) and t is exposure duration (h).
2.5. Electrochemical Analysis
Autolab Potentiostat device was used for electrochemical analysis. A three-electrode
setup was attached to the potentiostat in which saturated calomel electrode (SCE) as reference
electrode, a graphite rod as auxiliary electrode, and J55 steel as the working electrode. At first,
working electrode was immersed in the test medium i.e. 3.5 % NaCl saturated with carbon
dioxide for 30 min at 303 K before each experiment to maintain the steady state corrosion
potential (Ecorr).
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The electrochemical impedance spectroscopy (EIS) was performed in the range of
frequency 100 kHz to 10 mHz at open circuit potential, by setting 10 mV as the AC sine wave
amplitude frequencies per decade. Calculation of inhibitions efficiencies were done as follows:
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
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100
Rct(i)
(2)
where R and R are the representative of resistance of charge transfer without and with the
ct
ct(i)
studied inhibitor respectively.
The potentiodynamic polarization study of the J55 steel without and with the inhibitor
was conducted in the range of -250 mV to +250 mV potential and the sweep rate used was 0.2
mV/s. The below mentioned equation was used for inhibition efficiency calculation:

icorr(i)
icorr




%  1
100


(3)
where, icorr and icorr(i) represents the values of corrosion current densities without and with
inhibitor, respectively.
2
.6. Computational details
2.6.1. Quantum chemical calculation
The molecular property of inhibitor molecule was explored using quantum chemical
calculations. In the present time density functional theory (DFT) is the popular computational
technique because it performed the calculation shorter time period with high accuracy. In the
present paper all quantum chemical calculations were performed using ORCA programme
package module version 2.7.0 [19]. The optimization of inhibitor molecule geometry was done
hybrid B3LYP functional level of DFT [20-24]. In this calculation, a triple-ζ quality basis sets,
TZV(P), along with one set of polarization functions on the O and N atoms have been employed
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[
25]. Whereas, slightly smaller polarized split-valence SV(P) basis sets were used for atoms like
carbon and hydrogen. Since, electrochemical corrosions take place in aqueous phase. So, it
becomes important to consider the effects of solvent molecules. Here, COSMO model was used
for incorporating solvent effect (water in present study) for all the calculations.
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.6.2. Molecular Dynamics simulation
The study of interaction between the inhibitor molecules and metal surface can be
explored by molecular dynamics (MD) simulation. In the present analysis, the interaction of Fe
(
110) surface and inhibitor molecules was studied by Material StudioTM software (version 6.1)
[26].
The preferential used of Fe (110) surface is based on the fact that it consists of packed
and high stabile/low energy lattice crystal plane as compared to other iron lattice plane [27].
The investigation of the interactions between the Fe (110) surface and the concerned molecule
have been performed in a modelled box (dimension: 39.85 × 39.85 × 76.46 Å) under periodic
boundary conditions. The number of layers of Fe atoms is to be selected in such a manner that
the depth of the surface is higher than the non-bond cut-off radius used in the calculation. Herein,
ten layers of Fe atoms have been chosen in order to maintain the surface depth and the related
cutoff radius. The constructed simulation box comprises of the iron slab (lower most layer),
solution slab (the middle layer) and the vacuum layer (upper most layer). The solution slab
contains 1 inhibitor molecule, 150 H O molecules. After constructing the simulation box, an
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initial geometry optimization has been performed in order to minimize the energy of the whole
system and dispose of unfavorable structures. All MD simulations were done at 298 K
temperature and maintained constant by the Andersen thermostat, a time step of 0.1 fs, NVT
(fixed atom number, system volume and temperature) ensemble and a simulation time of 2000 ps
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to reach simulation system under an equilibrium state. The energy minimization and MD
calculation processes were performed using Condensed-phase Optimized Molecular Potential for
Atomistic Simulation Studies (COMPASS) force field [28].
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. Results and discussion
.1. Weight loss experiment
.1.1. Concentration effect
The effect of inhibitor concentrations on the protection ability of metal surface is
represented in the form of concentration vs. inhibition efficiency plot (Fig. 2).
C. (mM)
Figure 2: Variation of inhibition efficiency (η %) with inhibitor concentration at 333 K
From figure, it is obvious that the inhibitory performance of inhibitor is going to increase
with increase in inhibitor concentration and attain a maximum value of 90 % at 500 mg/L. The
increase in inhibition efficiency is due to adsorption of inhibitor molecules onto the metal
surface. In the present study, the molecular structure of inhibitor contains π electrons in the
aromatic ring, non-bonding electrons on heteroatom’s like oxygen and nitrogen, which help the
inhibitor molecules to adsorb onto the J55 steel surface [29].
3
.1.2. Adsorption isotherm of inhibitor on J55 steel
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Many adsorption isotherms like Langmuir, Frumkin, Flory Huggins and Temkin were
investigated to find a good fitting with the experimental study. Out of these isotherms Langmuir
isotherm i.e. C /θ vs. the inhibitor concentration (C ) was found to be the best fit due to the
inh
inh
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slope and regression coefficient (R ) values approaching towards unity (Fig. 3).
[(C)] / mM
Figure 3: Langmuir Isotherm plots for adsorption of inhibitor
The Langmuir isotherm is given by the following formula [30,31]:
Cinh
1

 Cinh
Kads

(4)
where Cinh is PNO concentration (mM), θ and Kads represents the surface coverage and
equilibrium adsorption constant respectively. Supplementary file (S3-S5) contains the Frumkin,
Flory Huggins and Temkin isotherm plots. The Kads value was determined from the intercept of
the Langmuir plot and listed in Table 1.
Table 1
Parameter of Langmuir adsorption isotherm for the synthesized inhibitors
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Inhibitor
Slope Regression Coefficient
Kads
(10 M )
ΔG
ads
2
3
-1
(R )
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TMI
0.996
0.997
4.56
-34.45
The strength of PNO molecules adsorption on J55 steel is represented by the values of K . From
ads
the table it could be observed that the value of Kads is large, which suggests its strongest
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5
6
7
8
9
0
adsorption onto the metal surface [32, 33]. The standard free energy of adsorption i.e. ΔG0ads
could be correlated to Kads according to the below mention equation [34].
ο

G  2.303RT log(55.5K )
ads
ads
(5)
where, absolute temperature and universal gas constant are represented by T and R respectively,
5.5 is magnitude of water molecules concentration. Table 1 reveals that the ΔG0ads values are
5
negative, suggesting towards a spontaneous adsorption process [35]. Since, the value ΔG0 is
ads
between -40 kJ/mol to -20 kJ/ mol, which confirms that the adsorption of inhibitor molecules on
J55 steel surface is both physical and chemical [36-39].
3
.2. Electrochemical Analysis
3.2.1. Electrochemical Impedance spectroscopy (EIS)
The fitted EIS results were presented in Figs. 4a in the form of Nyquist plots for J55 steel
exposed to the 3.5 % solution of NaCl saturated with carbon dioxide at 308 K temperature with
and without PNO.
(
a)
2
Z (Ω cm )
re
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Figure 4a: Nyquist plots in absence and presence of different concentration of inhibitor
The Nyquist plot, from high to low frequency consists a depressed semicircle with a
small inductive loop at low frequency. The presence of capacitive semicircle in the Nuquist plots
is attributed towards the presence of double layer capacitance and charge transfer resistance
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
phenomenon. The adsorption of intermediate product (FeOH ) results in the appearance of
ads
inductive loop. The consecutive steps of the mechanism of intermediate formation can be written
as follows [40]:
+
-
Fe + H O →FeOH +H + e
2
ads
-
FeOH → FeOH+ + e
ads
+
2+
FeOH+ + H → Fe + H O
2
The equivalent circuit shown in Fig. 4b was used to simulate the capacitive and inductive process
occurring during corrosion inhibition.
(b)
Figure 4b: Equivalent circuit used
The fitted values of impedance parameters are tabulated in Table 2. The roughness and
inhomogeneities on the solid surfaces is responsible for the depressed semicircle in the
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1
1
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1
2
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2
2
2
2
2
2
2
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3
3
4
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4
4
4
4
4
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5
5
5
5
5
5
5
5
5
6
impedance spectra [41-43]. Thus, a constant phase element (CPE) was employed to describe the
double layer capacitance, which has a non-integer power dependence on the frequency [44]. As
can be observed from the figure that the diameter of the Nyquist plots are increasing with
increasing the PNO concentration, which is due to the increase in the corrosion resistance
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
property of metal surface because of adsorption of PNO moleculs. As per the table, the values of
0
R increases with the addition of PNO, while the values of Y , which represents the double layer
ct
0
capacitance decreases. The increase of R and decrease in Y is attributed to the adsorption and
ct
finally inhibitor film formation over the metal surface. Also, the values of inhibition efficiency
increases with increasing the inhibitor concentration, indicating that more metal surface is
covered with increasing inhibitor concentration.
Table 2
Electrochemical impedance parameters in absence and presence of different concentrations of
inhibitor at 308K
Cinh
Rs
(Ω)
Rct
(Ω cm2)
Y0
(μF/cm2)
n
L
RL
(Ω cm2)
η
(%)
-
1
(H cm2)
(mgL )
Blank
100
4.817 135.57
1.025 471.87
1.190 711.21
1.262 843.71
1.101 993.09
1.028 1297.38
512.7
0.601
0.728
0.801
0.821
0.853
0.891
8.04
4.01
--
208.12
175.34
123.86
90.89
51.63
77.61
61.63
116.26
297.14
31.54
65.82
45.82
85.12
178.28
71.2
80.9
83.9
86.3
89.5
2
3
4
5
3
00
00
00
00
62.52
.2.2. Potentiodynamic polarization
The corrosion kinetics of J55 steel immersed in 3.5% NaCl solution saturated with carbon
dioxide without and with different concentration of PNO at 308 K is shown in Fig. 5.
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2
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2
2
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0
1
2
3
4
5
6
7
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9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
E (mV vs. SCE)
Figure 5: Potentidynamic polarization curves in absence and presence of different
concentration of inhibitor
It could be observed from figure that the addition of PNO reduces both the anodic and
cathodic current densities. The obtained kinetic parameters like corrosion potential (Ecorr),
corrosion current density (i ), anodic and cathodic Tafel slope (β , β ) are tabulated in Table 3.
corr
a
c
Table 3
Electrochemical polarization parameters in absence and presence of different concentrations of
inhibitor at 308K
Inhibitor
Ecorr
mV/SCE)
icorr
(μA/cm )
104.4
βa
- βc
(mV/dec)
590
η
(%)
--
2
(
(mV/dec)
154
Blank
-703
-714
-734
-743
-776
-826
1
2
3
00
00
00
34
21
18
14
10
192
184
183
164
171
583
543
599
582
574
67.4
79.8
82.7
86.5
90.4
400
00
5
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5
5
6
The values of corrosion potentials (E ) shifts towards the cathodic direction with the
corr
addition of PNO and this shifts depends upon the concentration of PNO. The reduction of both
anodic and cathodic current density slows down the corrosion rate, along with the slight negative
shift in corrosion potential, indicating towards the mixed-type inhibitor inhibition action. From
Table 3, it is reveals that the value of inhibition efficiency increases with increase in PNO
concentration, which suggests that PNO, inhibits the corrosion of J55 steel. In addition, the
values of cathodic (β ) and anodic (β ) Tafel slopes were not considerably affected, thus
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
c
a
revealing that the mechanism of corrosion reactions are not changed with the addition of PNO.
In the anodic polarization curves there was an increase of corrosion current density
occurs as the polarization potential approach a relatively positive value. This was due to the
anodic desorption of inhibitor [45]. The increase of polarization potential accelerates metal
dissolution not only on the surface without adsorbed species but also with adsorbed inhibitive
species because they become unstable at a high polarization potential [46]. Thus, at positive
potential the equilibrium between adsorption-desorption process gets disturbed due to the slower
adsorption process than desorption one, which causes a reduction in the surface coverage and
finally enhance the metal dissolution.
3
3
.3. Surface analysis: SEM and AFM
.3.1. Scanning electron microscopy (SEM)
The morphological changes on the J55 steel surface without and with optimum
concentration of PNO were shown in Fig. 6(a, b). Fig. 6a represents that in absence of PNO the
surface was highly corroded. However, with the addition of PNO the morphology of J55 steel
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surface becomes smooth (Fig. 6b). This is due to the adsorption of PNO on the J55 steel surface.
These results are in good agreement with the weight loss and electrochemical measurement.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
3
3
3
3
3
4
4
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4
4
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5
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5
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(a)
(b)
Figure 6: SEM images (a) In absence of inhibitor (b) In presence of inhibitor
.3.2. Atomic force microscopy (AFM)
The AFM images in three-dimensional form for uninhibited and inhibited surface were
3
shown in Fig. 7(a, b). J55 steel surface was strongly damaged for uninhibited system, and
achieved an average roughness value to 700 nm (Fig. 7a). However, for inhibited system, the J55
steel surface appears to be smooth and homogeneous morphology with an average roughness
value of 20 nm (Fig. 7b) due to the adsorption of PNO on the J55 steel surface.
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3
3
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5
5
5
6
(a)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(b)
Figure 7: AFM images (a) In absence of inhibitor (b) In presence of inhibitor
3
.4. Quantum chemical calculations
3.4.1. Optimized geometrical structure
The optimized structure, HOMO and LUMO of the inhibitor molecule (PNO) are shown
in Fig. 8a-c.
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5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
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8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(a)
Figure 8a: Optimized geometry of inhibitor
(b)
(c)
Figure 8b, c: Frontier molecular orbital’s of inhibitor (b) HOMO (c) LUMO
The optimized parameters like bond lengths, bond angles and torsion angles are tabulated
in Table 4.
Table 4
Bond lengths (Å), bond angles (°) and torsion angles of the optimized forms of inhibitor in
aqueous phase
Geometrical parameters
Bond lengths
C1-C2
C2-C3
C3-C4
C4-C5
C5-C6
C6-C1
1.4250
1.4378
1.4230
1.3812
1.4170
1.3829
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
C2-C7
C7-C8
C8-C9
1.4350
1.3790
1.4161
1.3748
1.4258
1.5142
1.5323
1.4045
1.3982
1.4014
1.3990
1.4005
1.4029
1.4740
1.3477
1.3713
1.3934
1.2214
C9-C10
C10-C3
C7-C14
C14-C18
C18-C21
C21-C20
C20-C19
C19-C16
C16-C17
C17-C18
C14-N15
C12-N15
C12-O11
C8-O11
C12-O13
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Bond angles
C1-C2-C3
C2-C3-C4
C3-C4-C5
C4-C5-C6
C5-C6-C1
C6-C1-C2
C2-C7-C8
C7-C8-C9
C8-C9-C10
C9-C10-C3
C10-C3-C2
C3-C2-C7
C7-C14-C18
C18-C21-20
C21-C20-C19
C20-C19-C16
C19-C16-C17
C16-C17-C18
C17-C18-C21
C18-C21-C20
118.16
119.39
120.97
119.80
120.66
121.03
118.66
122.91
119.09
120.90
119.35
119.08
114.50
120.52
120.14
119.72
120.01
120.63
118.98
120.52
Torsion angles
C7-C14-C18-C21
N15-C14-C18-C17 99.84
45.32
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C7-C14-C18-C17
N15-C14-C18-C21 -77.81
C7-C14-C18-C21
C2-C7-C14-C18
C2-C7-C14-N15
-137.03
45.32
74.00
-161.61
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Table 4 reflects that the carbon-carbon (C-C) bond lengths in the benzene ring are in the
range of 1.398-1.402 Å. Thus, in benzene ring the bonds are shorter than C-C bond lengths as
compared to the normal C-C single bond length and also it is longer than the C=C double bond
length [47]. The obtained bond length in the present study reveals that there exists a -bonds
conjugation in the benzene ring. It is important to find out that the optimized structure of
inhibitor molecule possessed an ideal geometrical structure or not. So, it becomes important to
study the other bond lengths present in the inhibitor molecules.
In the heterocyclic ring, the bond length values of C14-N15 and C12-N15 are 1.474 and
1
.347 Å respectively. These bond lengths are close to C-N bond length reported in the literature
[48]. Furthermore, the obtained bond length of C-O (C12-O13) is 1.2063 Å, which is also
coming in the range of C-O double bond length as per the literature [49]. Therefore, finally it is
concluded that the geometrical structure of inhibitor molecule is ideal.
Inhibitor molecule must process planar structure in order to achieve stronger adsorption
on the iron surface. Therefore, it becomes important to analyze all the bond angles and torsion
angles of the inhibitor molecule. The values of the bond angles are given in Table 4. It can be
observed that the bond angle values for heterocyclic and phenyl rings are lying in the range of
°
°
°
1
14.50 -122.91 . The values of bond angles are very much close to 120 , revealing that benzene,
2
heterocycle rings atoms are sp hybridized, and thus they have planar orientation. Therefore,
inhibitor molecules possessed an ideal planar structure.
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1
1
1
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1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
It is important to analyze wither both the heterocyclic ring and phenyl ring participate in
adsorption on the iron surface or one participate in adsorption and other remains free. In order to
answer these questions, it becomes necessary to analyze the torsion angles values.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The values of torsion angles listed in the Table 4. It is observed from table that the values
torsion angles formed by the planes of atoms C7-C14-C18-C2, N15-C14-C18-C17, C7-C14-
C18-C17, N15-C14-C18-C21, C7-C14-C18-C21, C2-C7-C14-C18, C2-C7-C14-N15 are
°
°
°
°
°
°
4
5.32 ,99.84 , -137.03, -77.81 ,45.32 , 74.00 and -161.61 respectively. Here none of the torsion
angles lie nearby to either 0° or 180°. Thus, the deviation in the torsion angle confirmed that the
orientation of the heterocyclic ring and phenyl ring are non-planar to each other i.e. their position
exists in different plane position. This deviation in planarity reveals that only one participate in
adsorption process and other will do not. Review of literature suggests that adsorption of
heterocyclic ring is dominated as compared to phenyl ring because of the presence of
heteroatoms in their molecular framework.
The inhibitor adsorption onto the metal surface depends upon the position of the frontier
orbital energy level between the inhibitor molecules and the Fermi level of the iron metal [50].
The optimized geometry and frontier orbital energy of inhibitor are shown in Fig. 9.
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0
1
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9
0
1
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3
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9
0
1
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9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 9: Interaction of molecular orbital’s of inhibitor and iron
The frontier orbital energies of inhibitor molecules and the Fermi level of iron are shown
in Fig. 9. Figure 9 shows that the EHOMO energy level of inhibitor is at -6.160 eV, which is very
close to the iron Fermi level i.e., -5.177 eV. However, the ELUMO energy level of inhibitor is at -
1
.510 eV eV, which is far away from the iron Fermi level. Therefore, the electron transfer from
the HOMO energy level of inhibitor to the iron surface is possible. While, the energy gap
between the LUMO of inhibitor and iron Fermi level is quite large. Therefore, the electron
transfer from the iron surface to the LUMO orbital of the inhibitor molecule is difficult.
3
.4.2. Molecular dynamics simulation
In the modern time, the interaction between the inhibitor and metal surface can be
analyzed using molecular dynamics (MD) simulation. Literature survey supports in recent times
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the use of MD simulation in the corrosion inhibition study is well-recognized [51-53]. Thus, in
the present study MD simulation has been performed in order to explore the inhibitor-metal
interaction and to understand the mechanism of inhibitor molecules adsorption onto metal
surface.
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In MD simulation, initially inhibitor molecules were optimized by applying 'smart'
algorithm. In this first step is steepest decent path, followed by conjugate gradient path and lastly
completed with Newton's method [26]. When the total energy of inhibitor molecules approach at
the minimum energy level, then the inhibitor molecules atomic coordinates were adjusted using
COMPASS force field [54]. After completing this, a simulation box was constructed and within
this simulated box inhibitor and water molecules were incorporated. Figs. 10 and 11 represents
the minimum energy state of the inhibitor in the midway of simulation processes.
Figure 10: Temperature equilibrium curve obtained from molecular dynamics simulation for
inhibitor
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Figure 11: Energy fluctuation curves obtained from molecular dynamics simulation for inhibitor
The equilibrium configurations of adsorbed inhibitor molecule on the metal surface are
represented in Fig. 12. The close observation of Fig. 12 reveals a flat/parallel adsorption of
inhibitor molecule on the metal surface. This kind of parallel adsorption of inhibitor molecules
confirmed that it occupies maximum area of metal surface and provide stronger adsorption.
(a)
(b)
Figure 12: Side and top views of the final adsorption of inhibitor molecule on the Fe (110)
surface in solution (a) Side view (b) Top view
The values of interaction and binding energies is useful in determining the adsorption
potential ability of the inhibitor molecules onto the metal surface.
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Table 5
Selected energy parameters obtained from MD simulations for adsorption of inhibitors on Fe
110) surface
(
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Systems
Einteraction (kjoule/mol) Ebinding (kjoule/mol)
-606.855 606.855
Fe + PNO
Inspection of Table 5 reveals that the interaction and binding energies values are -
6
06.855 kJ/mol and 606.855 kJ/mol respectively. The negative value of interaction energy
suggests that inhibitor adsorption on metal surface (Fe110) is spontaneous. The values of
interaction and binding energies in the present case is higher than presents in the literature. This
confirmed the stronger adsorption of the studied inhibitor on the metal surface [55-57].
4
. Conclusions
1
. The corrosion inhibition performance of PNO increased with increase in concentration
and achieved maximum value of inhibition efficiency of 90.4 at 500 mg/L concentration
2
. he adsorption of PNO obeyed the Langmuir isotherm.
0
ads
3. The ΔG values showed spontaneous adsorption of PNO on the metal surface involving
both the physical and chemical interaction.
4
5
. In EIS, study charge transfer resistance values increases with increase in the
concentration of PNO.
. Potentiodynamic polarization studies suggests the mixed mode of PNO action.
6. The quantum chemical calculations showed the planar structure of PNO.
. MD study reveals that PNO can interact strongly with the metal surface.
7
Acknowledgment
Authors are thankful to the Sichuan 1000 Talent Fund and financial assistance provided by the
National Natural Science Foundation of China (No. 51274170).
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