New Heterocyclic Derivative to Stop Carbon Steel Corrosion

Article abstract of DOI:10.1515/zpch-2019-1399

The new compound 4-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothioamide (PY) was synthesized. Its anti-corrosion properties for C-steel in acid solution (1.0 M HCl) were evaluated utilize electrochemical tools. The synthesized compound was described using FT-IR and ¹H-NMR analyses. The purity of PY was affirmed by thin-layer chromatography (TLC). The outcome data proved that PY possess adequate anti-corrosion features for C-steel in corrosive solution. The polarization parameters mentioned that the PY is a mixed inhibitor. Inhibition performance obtained by polarization measurements (i.e. 91.5%) are consistent with the one obtained by EIS (i.e. 88.6%). Quantum chemical parameters for PY were studied to supply assist knowledge into the anti-corrosion properties of the new compound.

Full text of DOI:10.1515/zpch-2019-1399

Z. Phys. Chem. 2019; aop
M. A. Deyab*, A. S. Fouda and S. Abdel-Fattah
New Heterocyclic Derivative to Stop Carbon
Steel Corrosion
https://doi.org/10.1515/zpch-2019-1399
Received February 18, 2019; accepted April 5, 2019
Abstract: The new compound 4-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-
dihydro-1H-pyrazol-4-yl)hydrazono)-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-
carbothioamide (PY) was synthesized. Its anti-corrosion properties for C-steel in
acid solution (1.0 M HCl) were evaluated utilize electrochemical tools. The syn-
thesized compound was described using FT-IR and 1H-NMR analyses. The purity
of PY was affirmed by thin-layer chromatography (TLC). The outcome data proved
that PY possess adequate anti-corrosion features for C-steel in corrosive solution.
The polarization parameters mentioned that the PY is a mixed inhibitor. Inhibition
performance obtained by polarization measurements (i.e. 91.5%) are consistent
with the one obtained by EIS (i.e. 88.6%). Quantum chemical parameters for PY
were studied to supply assist knowledge into the anti-corrosion properties of the
new compound.
Keywords: acid solution; corrosion inhibitor; electrochemical; FT-IR; heterocycle.
1 Introduction
Carbon steel, the foremost broadly utilized designing metal, accounts for around
85% of the yearly steel generation around the world. The chemicals compounds
play a critical role to conserve the steel from the corrosion in acidic solutions.
Generally, the acid inhibitors are organic and inorganic molecules contain nitro-
gen, sulfur, and/or oxygen atoms [1–3]. The performance of corrosion inhibitors
depend on molecular construction of the inhibitors [4–9].
The nitrogen-heterocyclic inhibitors form complex or chelate compounds
with iron metal. In addition, the nitrogen atoms in heterocyclic compounds can be
*Corresponding author: M. A. Deyab, Egyptian Petroleum Research Institute (EPRI),
PO Box 11727, Nasr City, Cairo, Egypt, Tel.: +201006137150; Fax: +202 22747433,
e-mail: hamadadeiab@yahoo.com
A. S. Fouda: Department of Chemistry, Faculty of Science, El-Mansoura University, El-Mansoura,
Egypt
S. Abdel-Fattah: Egyptian Petroleum Research Institute (EPRI), PO Box 11727, Nasr City, Cairo,
Egypt
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simply protonated in acidic solutions to offer strong inhibitory behavior. The hete-
rocyclic inhibitors work by the adsorption and maintain the metal from corrosion
by film coverage. The hetero-atoms, such as phosphor, sulfur, nitrogen, oxygen or
those containing multiple bonds are considered as adsorption centers [10–12].
Overview of previous works showed that pyrazole derivatives are potent
corrosion inhibitors [13–16]. This reinforces our next work to synthesize other
new compounds with high efficiency and low toxicity. There is no literature
to date about the corrosion inhibitive effect of new prepared pyrazole azo dye
derivative (PY).
Here, we studied the inhibition properties of new prepared pyrazole azo dye
derivative (PY) for carbon steel corrosion in 1.0 M HCl solution. In this study
we used both experimental (i.e. electrochemical measurements) and theoretical
studies to verify the investigations.
2 Experimental
2.1 Electrode and electrolyte
The C-steel specimens (Origin: Egyptian steel company) with formula (wt %): C
(0.18), Si (0.08), Mn 0.35), P (0.17) and Fe (Rest) act as a working electrode. Its
dimension is 2.0 cm × 1.0 cm × 0.05 cm. The surface of electrodes were prepared
a corroding to ASTM G1 – 03(2017)e1.
The acidic electrolyte is 1.0 M HCl solution (Sigma-Aldrich).
2.2 Inhibitor (PY) synthesis
In glass flask, 2.03 g Antipyrine mixed with 3.0 mL HCl (37%), 2.0 mL distil-
lated water at 278 K. This mixture was diazotized with NaNO2 solution (0.7 g in
10 mL H2O). The produced mixture was added drop wise 3-methyl-1-thiocarbomol-
2-pyrazolin-5-one (0.01 M) in the presence of 15 mL pyridine (see Scheme 1).
The complete reaction was obtained after 2 h stirring at 278 K. The final com-
pound was obtained after filtration and washing with distilled H2O and re-
crystallization from ethanol. The yield of this process is 74% and melting point
of the prepared compound is 504 K. The purity of PY is confirmed by thin-layer
chromatography (TLC).
1
The inhibitor synthesized was recognized by H-NMR using a Bruker spec-
trometer at 300 MHz. The function groups for new compound was detected using
Thermo Scientific FT-IR spectrometer.
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New Heterocyclic Derivative to Stop Carbon Steel Corrosion
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Scheme 1: The synthetic procedure of pyrazole azo dye derivative (PY).
2.3 Electrochemical measurements
The performance of new corrosion inhibitor was determined using the electro-
chemical techniques (i.e. potentiodynamic polarization and EIS). Standard prac-
tice for electrochemical measurements including the cell and the methods were
conducted according to ASTM G3 – 14. The potentials of polarization experiments
were measured versus saturated (Hg/Hg2Cl2) (SCE). Three repeat experiments
were carried out for all measurements.
The Electrochemical researches were achieved via Potentiostat/Galvanostat
instrument (Gamry PCI4G750).
2.4 Quantum parameters
Quantum parameters were calculated to find the linkage between the inhibition
character of PY compound and its structure. In this regards we used VAMP module
(Materials Studio–Accelrys).
3 Result and discussion
3.1 The structure identity of PY
The IR spectrum (Figure 1) of PY exhibited absorption bands at 3337, 3265 and
3214 cm−1. These bands refer to the NH2 and NH groups [17]. The two absorp-
tion bands at 1653 and 1636 cm−1 refer to the two carbonyl groups. The band at
1602 cm−1 refer to the C=N group.
The 1H NMR spectrum (Figure 2) displayed signals at 2.19, 2.51 and 3.14 ppm
due to methyl protons of two pyrazole rings. The multiplet signals at 7.39–7.58 ppm
refer to the aromatic protons. The two signals at 8.00 and 10.35 ppm refer to the
NH2 and tatuomerized OH groups, respectively.
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M. A. Deyab et al.
Fig. 1: FTIR spectra of prepared PY compound.
Fig. 2: The 1H NMR spectrum of prepared PY compound.
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New Heterocyclic Derivative to Stop Carbon Steel Corrosion
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3.2 Electrochemical studies
The inhibition performance of PY for C-steel corrosion in acid electrolyte (1.0 M
HCl) was inspected using polarization method. Figure 3 shows the Tafel curves
(the potential range ±250 mV vs. OCP and scan rate = 0.5 mV s−1) for blank and
PY at 298 K.
Table 1 represents the polarization parameters, rest potential (Ecorr) and cor-
rosion current (Icorr) and Tafel slopes (βa, βc). The inhibition efficiency (Ep%) of
PY is calculated using equation 1 [18–20].
Icorr(0) − Icorr
Ep% =
× 100
(1)
Icorr(0)
here Icorr(o) represents the corrosion current for blank solution.
Fig. 3: Potentiodynamic polarization curves for carbon steel in 1.0 M HCl in absence and
presence of various concentrations of PY at 298 K.
Tab. 1: Polarization parameters and the corresponding corrosion inhibition eflciency for
carbon steel in 1.0 M HCl in the absence and presence of PY at 298 K.
C
inh (ppm)
I
corr (µA cm−2
)
−Ecorr (mV vs. SCE)
βa (mV/dec.)
βc (mV/dec.)
E
p (%)
0
160.5 ± 5
43.6 ± 3
510.92 ± 8
473.01 ± 6
464.28 ± 5
463.45 ± 5
463.01 ± 3
470.79 ± 4
82.20
74.60
72.70
71.80
73.10
59.80
137.80
139.50
136.70
130.30
133.60
182.70
0.00
100
150
200
250
300
72.81
77.06
80.53
83.20
91.50
36.82 ± 3
31.25 ± 3
26.96 ± 1
13.66 ± 1
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M. A. Deyab et al.
We concluded from above data that the corrosion rate of C-steel in 1.0 M HCl
decreased significantly with the addition of a variable dose of PY. The greatest effi-
ciency (91.5%) (See Table 1) has been obtained at 300 ppm of PY. The movements
of Ecorr in the case of inhibited solutions are less than 85 mV, indicating that the
PY is mixed type inhibitor with more control of anodic reaction [21–23].
The changes in the values of Tafel slopes (βa, βc) after adding PY are insignif-
icant. This confirms that the main mechanism of corrosion inhibition by PY is the
blocking the active sites over the metal surface [24–26].
EIS responses were conducted to support the potentiodynamic polarization.
The EIS spectra (i.e. Nyquist and Bode) for this system are shown in Figure 4.
Fig. 4: EIS spectra for carbon steel in 1.0 M HCl in absence and presence of various concentra-
tions of PY at 298 K.
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In this case the EIS experiments were conducted at OCP in the frequency zone 0.1
Hz-100 kHz. The experiments start after 1 h of electrode insertion. The supposed
equivalent circuit for this system is shown in Figure 5. It contains charge transfer
resistance (Rct), electrolyte resistance (Rsol) and dielectric capacitance (Q). These
parameters are registered in Table 2.
The inhibition effectiveness (ER%) of PY is estimated using equation 2 [27–29].
Rct − Rcto
ER% =
× 100
(2)
Rct
here Rcto represents the charge transfer resistance for blank solution.
The addition of PY to 1.0 M HCl produces the accretion in Rct values and the
reduction in Q values (see Figure 4). This confirms the inhibitory effective of PY.
Where, H2O molecules over the C-steel surface were exchanged by PY molecules,
causing the extension in the thickness of the electrical double layer [30–33]. The
“n” values fall in 0.9 and 0.8 range (Table 2) indicates that this case is not the
ideal capacitor [34–36]. It was noted also that there are no significant changes in
the “n” with and without PY molecules. It was noted that the ER% increased with
PY concentration (see Table 2). The efficiency of PY reached the maximum value
Fig. 5: The equivalent circuit the used to represent impedance data.
Tab. 2: EIS parameters and the corresponding corrosion inhibition eflciency for carbon steel in
1.0 M HCl in the absence and presence of PY at 298 K.
C
inh (ppm)
R
sol (O cm2)
R
ct (O cm2)
Q (µF cm−2
)
n
E
R (%)
0
1.81 ± 0.4
1.49 ± 0.4
2.65 ± 0.2
6.60 ± 0.2
3.87 ± 0.3
5.23 ± 0.5
74.75 ± 3
252.0 ± 3
268.9 ± 6
312.1 ± 7
347.2 ± 3
657.8 ± 4
81.40
65.24
68.82
75.03
68.45
77.71
0.90
0.88
0.88
0.88
0.88
0.82
0.00
100
150
200
250
300
70.30
72.20
76.00
80.00
88.60
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M. A. Deyab et al.
at 300 ppm. The inhibition efficiency of PY from EIS method complies with that
from polarization method.
3.3 Quantum studies
The optimized structure of PY molecule was given in Figure 6. Both HOMO and
LUMO regions (see Figure 7) are focused on sulfur, oxygen and nitrogen atoms
Fig. 6: The optimized structure of PY molecule.
a
b
Fig. 7: HOMO (a) and LUMO (b) distributions in PY molecule.
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Fig. 8: The electron density is distributed over the whole PY molecule.
where HOMO is localized on sulfur atom while LUMO is distributed over the oxy-
gen and nitrogen atoms. This indicates that the S, O and N atoms are the functional
parts in PY molecule. The high value of EHOMO (−8.912 V) means the susceptibil-
ity of the PY to supply electrons to unoccupied d-orbitals of Fe atom, forming a
coordinate bond [37–39]. The low value of ELUMO (−1.324 eV) means the suscepti-
bility of the PY molecule to accept electrons from filled Fe d-orbital [40]. The low
value of energy gap (∆E = 7.588 eV) suggests the high inhibition efficiency. The
electron density moves over the whole PY (Figure 8), suggests that adsorption of
PY on the steel surface occurs by flat-lying orientations [41–44].
3.4 Mechanism of action of pyrazole derivative
From the above results, we concluded that the main step in mechanism action
of PY to control the degradation of C-steel in 1.0 M HCl is the adsorption pro-
cess. The performance of pyrazole derivative depends mainly on the chemical
structure of the PY. The surface charge plays a great role beside the potential
of zero charge (pzc) of steel in acid solution in the inhibitor efficacy [45–50].
Generally, the surface of carbon steel is almost positively charged in acidic
solutions [51].
In this status, PY molecules could be adsorbed on the C-steel surface by the
interaction between π electrons in benzene ring or lone pair electrons of O, N
and S atoms and the unfilled d-orbital of Fe surface atoms [52–55]. Based on
this assumption, pyrazole derivative PY control C-steel dissolution by adsorb-
ing on the corroding sites of metal and isolate its exposure to the acid solution
(1.0 M HCl).
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M. A. Deyab et al.
4 Conclusions
4-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-3-
methyl-5-oxo-4,5-dihydro-1H-pyrazole-carbothioamide (PY) was prepared, and
its chemical structure was proven using spectroscopic techniques. The corrosion
of C-steel in 1.0 M HCl has been inhibited via pyrazole derivative PY. The inhibi-
tion performance was reached to 91.50% at 300 ppm concentration. According
to Ecorr, PY molecules affected both anodic and cathodic reactions. Quantum
calculations were utilized to support the experimental data and the adsorption
behavior of pyrazole derivative PY.
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