Electrochemical and Quantum Chemical Studies on Corrosion Inhibition Performance of 2,2'-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] on Mild Steel Corrosion in 1M HCl Solution

Danaee, Iman; RameshKumar, S.; RashvandAvei, M.; Vijayan, M.

doi:10.1590/1980-5373-MR-2018-0610

Iman Danaee ^**e-mail: danaee@put.ac.ir

Petroleum University of Technology, Abadan Faculty of Petroleum Engineering, Abadan, Iran

https://orcid.org/0000-0002-1108-8955

S. RameshKumar

Sri Vasavi College, Department of Chemistry, Erode, Tamilnadu-638 316, India.

M. RashvandAvei

K. N. Toosi University of Technology, Department of chemistry, Tehran, Iran

M. Vijayan

Central Electrochemical Research Institute, Centre for Conducting Polymers, Electrochemical Materials Science Division, Karikudi, 630006, India

*e-mail: danaee@put.ac.ir

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Figure 1
Chemical structure of Oxethazaine drug, (2,2'-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethyl phenethyl)-N-methylacetamide].

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Figure 2
The Nyquist plots for MS electrode obtained in 1 M HCl solutions in the absence and presence of (2,2'-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methyl acetamide] at various concentrations.

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Figure 3
Equivalent circuit for the mild steel surface/corrosive media interface with CPE.

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Figure 4
Tafel plots for mild steel in 1.0M HCl solution in the absence and presence of the inhibitor at various concentrations.

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Figure 5
Typical Arrhenius plots for corrosion of mild steel in 1 M HCl solutions in the absence (■) and presence (♦) of inhibitor (200 mg/L) at various temperatures.

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Figure 6
The plot of differential capacitance vs. applied electrode potential in 1 M HCl solution (o) and 1 M HCl containing 200 mg/L of the inhibitor solution (□).

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Figure 7
SEM monographs of mild steel specimen immersed in 1 M HCl solutions in the absence (a) and presence (b) of inhibitor.

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Figure 8
Different perspective of DFT optimized structure of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] obtained at the B3LYP/6-31G(d,p).

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Figure 9
HOMO and LUMO populations of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] obtained at different levels.

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Figure 10
(Left) molecular orbitals LUMO, HOMO, HOMO-1 and HOMO-2 of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] obtained at the B3LYP/6-31G(d,p) level and their energies. (Right) the electron density of corresponding orbitals for the studied compound.

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Figure 11
Iso-surface representation of electrostatic potential of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] as a system based on the independent single-point calculation for corresponding N+1, N and N-1 electron systems, top to bottom respectively, at the B3LYP/6-31G(d,p) level.

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Figure 12
Electrostatic properties of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] at the B3LYP/6-31G(d,p) level: Mulliken charge population and the side view of the dipoles are displayed on the top while the middle and bottom panels show the contour and iso-surface representation of electrostatic potential, respectively.

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Figure 13
(A) Correlation of experimental and theoretical inhibition efficiencies of 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] using the B3LYP/6-31G(d,p) method. (B) Plot of IE_exp% and IE_Theor% versus 2,2’-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] concentrations.

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Table 1
Inhibition efficiency from weight loss measurement for mild steel in 1M HCl solutions in the presence and absence of inhibitor.

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Table 2
Impedance parameter values for the corrosion of mild steel in 1N HCl and 1N H₂SO₄ solutions in the presence and absence of inhibitor.

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Table 3
Tafel polarization curves for mild steel in 1N HCl and 1N H₂SO₄ solutions in the presence and absence of inhibitor.

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Table 4
Excess charge on MS electrode in 1N HCl and 1N H₂SO₄ solutions in the presence and absence of inhibitor.

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Table 5
Selected Bond Lengths (in angstroms) and Bond Angles (in degrees) of the oxetacaine with B3LYP/6-31G(d,p).

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Table 6
Some quantum chemical parameters for oxetacaine obtained at (A) B3LYP/6-31G(d,p), (B) B3LYP/3-21G, (C) HF/6-31G(d,p) and (D) HF/3-21G.

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Table 7
The Mulliken population analysis of the condensed Fukui functions and local softness parameters on the selected atoms of oxetacaine.

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Inhibitor Concentration / ppm	Corrosion rate / mpy	Inhibition efficiency (IE %)
Blank	168	-
20	19.08	88.64
40	17.19	89.77
60	15.29	90.90
100	11.46	93.18
200	7.64	95.45

Concentration / ppm	R_p / Ωcm²	Y₀ (× 10^-6) / Ω^-1cm^-2	n	C_dl / µFcm^-2	IE %
Blank	14.8	304	0.902	116.5	-
20	135.8	92.4	0.911	38.2	89.1
40	151.1	78.5	0.913	31.2	90.2
60	172.1	64.3	0.929	25.4	91.4
100	255.2	31.4	0.978	19.7	94.2
200	422.9	27.7	0.963	10.4	96.5

Concentration / ppm	E_corr / mV	I_corr / μA cm^-2	β_c / mV	β_a / mV	Corrosion rate / mpy	IE %
Blank	-429	1.88×10³	127	68	858.27	-
20	-448	2.09×10²	228	103	95.41	89
40	-451	1.88×10²	219	109	85.83	90
60	-452	1.69×10²	286	140	77.15	91
100	-452	1.32×10²	292	179	60.26	93
200	-454	7.50×10¹	331	151	34.24	96

Medium	E_ocp (mV)	PZC (mV)	Excess Charge
1M HCl	-429	-500	+
1M HCl + 200 ppm of inhibitor	-454	-620	+

	Oxetacaine
Bong lengths
C1-C2	1.51891
C1-C8	1.57368
C8-C9	1.54404
C8-C10	1.54313
C8-N1	1.52506
N1-C12	1.37926
N1-C11	1.47386
C12-O1	1.25651
C12-C13	1.54886
C13-N2	1.45299
N2-C14	1.46445
C14-C15	1.53759
C15-O2	1.46285
N2-C16	1.44272
C16-C17	1.55497
C17-O3	1.25633
C17-N3	1.38034
N3-C18	1.47461
N3-C19	1.53139
C19-C20	1.54441
C19-C21	1.54391
C19-C22	1.57095
C22-C23	1.51985
Avg. of (C-C)_Ar	1.40184
Bond angles
C9-C8-C10	110.95813
C20-C19-C21	111.28902
C1-C8-N1	107.38026
C22-C19-N3	108.53638
N1-C12-C13	118.77695
N3-C17-C16	118.79765
C13-N2-C16	119.63392
C1-C8-N1-C12	161.48218
C8-N1-C12-C13	-168.54489
N1-C12-C13-N2	139.89526
C12-C13-N2-C16	-108.15446
C13-N2-C16-C17	76.44796
N2-C16-C17-N3	164.04930
C16-C17-N3-C19	-176.78487
C17-N3-C19-C22	172.19852
N2-C14-C15-O2	-179.98150

quantum chemical properties	A	B	C	D
total energy (eV)	-40305.741	-40096.458	-40041.844	-39836.299
E_LUMO (eV)	-0.116	-0.077	3.831	3.885
E_HOMO (eV)	-5.009	-4.797	-8.693	-8.530
∆E (eV)	4.893	4.720	12.523	12.415
dipole moment (D)	5.827	5.729	5.259	5.881
ionization potential (I/eV)	5.009	4.797	8.693	8.530
electron affinity (A/eV)	0.116	0.077	-3.831	-3.885
hardness (η/ev)	2.446	2.360	6.262	6.207
softness (S/eV)	0.204	0.212	0.080	0.081
electronegativity (χ)	2.563	2.437	2.431	2.322
fraction of electrons transferred (∆N)	0.907	0.967	0.365	0.377
electrophilicity (ω)	1.342	1.258	0.472	0.434
∆E_T	-0.612	-0.590	-1.565	-1.552
molar volume (cm³ mol^-1)	316.023	388.615	353.746	397.661

Selected atoms	Mullikene charge	$f_{k}^{+}$	$f_{k}^{-}$	$f_{k}^{o}$	$S^{+} (e V)$	$S^{-} (e V)$	$S^{o} (e V)$	$\frac{S^{+}}{S^{-}}$	$\frac{S^{-}}{S^{+}}$
C1	-0.328	-0.001	-0.005	-0.003	0.000	-0.001	-0.001	0.290	3.445
C2	0.104	-0.006	-0.001	-0.004	-0.001	0.000	-0.001	5.059	0.198
C3	-0.151	0.019	0.001	0.010	0.004	0.000	0.002	23.742	0.042
C4	-0.128	0.034	0.004	0.019	0.007	0.001	0.004	8.516	0.117
C5	-0.122	0.001	0.007	0.004	0.000	0.001	0.001	0.076	13.238
C6	-0.128	0.017	0.004	0.010	0.003	0.001	0.002	4.551	0.220
C7	-0.152	0.035	0.001	0.018	0.007	0.000	0.004	26.153	0.038
C8	0.192	-0.005	-0.023	-0.014	-0.001	-0.005	-0.003	0.215	4.646
C9	-0.425	-0.002	-0.003	-0.002	0.000	-0.001	0.000	0.810	1.235
C10	-0.402	-0.003	0.000	-0.002	-0.001	0.000	0.000	24.857	0.040
C11	-0.249	-0.009	-0.016	-0.013	-0.002	-0.003	-0.003	0.533	1.877
C12	0.589	0.003	0.010	0.007	0.001	0.002	0.001	0.262	3.811
C13	-0.147	-0.004	-0.050	-0.027	-0.001	-0.010	-0.006	0.076	13.073
C14	-0.081	-0.007	-0.064	-0.036	-0.001	-0.013	-0.007	0.113	8.833
C15	-0.040	0.002	-0.007	-0.002	0.000	-0.001	0.000	-0.326	-3.070
C16	-0.188	-0.007	-0.043	-0.025	-0.001	-0.009	-0.005	0.170	5.896
C17	0.553	0.017	0.012	0.015	0.004	0.002	0.003	1.445	0.692
C18	-0.247	-0.012	-0.014	-0.013	-0.002	-0.003	-0.003	0.845	1.184
C19	0.196	-0.011	-0.017	-0.014	-0.002	-0.003	-0.003	0.642	1.558
C20	-0.415	-0.002	-0.002	-0.002	0.000	0.000	0.000	0.738	1.355
C21	-0.405	-0.004	-0.001	-0.002	-0.001	0.000	0.000	6.457	0.155
C22	-0.336	-0.007	-0.006	-0.006	-0.001	-0.001	-0.001	1.217	0.822
C23	0.104	0.023	-0.002	0.011	0.005	0.000	0.002	-13.928	-0.072
C24	-0.151	0.008	0.000	0.004	0.002	0.000	0.001	29.694	0.034
C25	-0.128	0.014	0.003	0.008	0.003	0.001	0.002	4.832	0.207
C26	-0.122	0.039	0.006	0.023	0.008	0.001	0.005	6.510	0.154
C27	-0.128	0.002	0.003	0.003	0.000	0.001	0.001	0.808	1.237
C28	-0.150	0.021	0.000	0.011	0.004	0.000	0.002	98.626	0.010
N1	-0.546	-0.003	0.012	0.005	-0.001	0.003	0.001	-0.201	-4.969
N2	-0.477	-0.002	0.111	0.055	0.000	0.023	0.011	-0.016	-60.921
N3	-0.553	0.000	0.008	0.004	0.000	0.002	0.001	0.031	32.623
O1	-0.504	0.014	0.054	0.034	0.003	0.011	0.007	0.250	4.002
O2	-0.619	0.010	0.056	0.033	0.002	0.012	0.007	0.169	5.915
O3	-0.486	0.012	0.023	0.017	0.002	0.005	0.004	0.500	1.998

I E_{T h e o r} = \frac{\begin{array}{l} (3.91 E_{H O M O} - 8.22 E_{L U M O} + 4.31 Δ E + \\ 2.06 Δ N + 4.51 μ - 0.10 V + 1.45) C_{i} \end{array}}{\begin{array}{l} 1 + (3.91 E_{H O M O} - 8.22 E_{L U M O} + 4.31 Δ E + \\ 2.06 Δ N + 4.51 μ - 0.10 V + 1.45) C_{i} \end{array}} \times 100

I E_{T h e o r} = \frac{\begin{array}{l} (1.05 E_{H O M O} + 1.00 E_{L U M O} + 0.95 Δ E + \\ 0.99 Δ N + 0.94 μ - 0.02 V + 0.99) C_{i} \end{array}}{\begin{array}{l} 1 + (1.05 E_{H O M O} + 1.00 E_{L U M O} + 0.95 Δ E + \\ 0.99 Δ N + 0.94 μ - 0.02 V + 0.99) C_{i} \end{array}} \times 100

I E_{T h e o r} = \frac{\begin{array}{l} (1.06 E_{H O M O} + 0.97 E_{L U M O} + 0.92 Δ E + \\ 1.00 Δ N + 0.96 μ - 0.03 V + 0.99) C_{i} \end{array}}{\begin{array}{l} 1 + (1.06 E_{H O M O} + 0.97 E_{L U M O} + 0.92 Δ E + \\ 1.00 Δ N + 0.96 μ - 0.03 V + 0.99) C_{i} \end{array}} \times 100

I E_{T h e o r} = \frac{\begin{array}{l} (1.06 E_{H O M O} + 0.97 E_{L U M O} + 0.91 Δ E + \\ 1.00 Δ N + 0.96 μ - 0.03 V + 0.99) C_{i} \end{array}}{\begin{array}{l} 1 + (1.06 E_{H O M O} + 0.97 E_{L U M O} + 0.91 Δ E + \\ 1.00 Δ N + 0.96 μ - 0.03 V + 0.99) C_{i} \end{array}} \times 100

[1] *e-mail: danaee@put.ac.ir

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Electrochemical and Quantum Chemical Studies on Corrosion Inhibition Performance of 2,2'-(2-Hydroxyethylimino)bis[N-(alphaalpha-dimethylphenethyl)-N-methylacetamide] on Mild Steel Corrosion in 1M HCl Solution

Abstract