Corrosion Inhibition of 3-Butyl-5,5-dimethyhydantoin Imidazole Ammonium Salt on Q235 Steel in HCl Solution†

doi:10.7503/cjcu20170557

Abstract

Abstract:

The corrosion inhibition performance and adsorption behavior of 3-butyl-5,5-dimethyhydantoin imidazole ammonium(BDMHI) for Q235 steel in HCl solution was investigated by mass loss method, polarization curve, electrochemical impedance spectroscopy(EIS), scanning electron microscopy(SEM), and contact angle measurements. The results show that inhibition efficiency increases with the increase of mass concentration of BDMHI and decreases with the increase of temperature; the highest inhibition efficiency is 91.62%; inhibition efficiency is above 80% at a BDMHI mass concentration of 1.0 g/L in the temperature range of 25—35 ℃. The adsorption properties of BDMHI were estimated using the standard adsorption Gibbs free energy change(Δ $G ads 0$ ) and enthalpy change (Δ $H ads 0$ ), respectively. The results reveal that the adsorption processes are exothermal and belong to a mix-type adsorption with physical adsorption and chemical adsorption, following Langmuir adsorption isotherm. The relationship between the molecular structure of BDMHI and the inhibition efficiency was investigated using quantum chemical calculations.

Key words: Imidazole ammonium salt, Corrosion inhibition, Adsorption, Quantum chemistry

CLC Number:

O646

TrendMD:

GUO Rui,LI Yunpeng,TU Ruixiang,SONG Bo,GUO Yu. Corrosion Inhibition of 3-Butyl-5,5-dimethyhydantoin Imidazole Ammonium Salt on Q235 Steel in HCl Solution^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 1018.

Figures/Tables 16

Fig.1 Molecular structure of compound BDMHI

Fig.2 Relationship between inhibition efficiency and mass concentration of BDMHI at different temperatures

Fig.3 Relationship between inhibition efficiency of BDMHI(a) and v(b) and corrosion time, respectively

Fig.4 Polarization curves of Q235 steel in 6% HCl solution in the absence(A) and in the presence(B) of 1.0 g/L BDMHI at 25—55 ℃

Table 1 Polarization parameters of Q235 steel in 6% HCl solution in the absence and presence of 1.0 g/L BDMHI at different temperatures*

Temperature/℃	Solution	E_corr/mV	j_corr/(μA·cm^-2)	b_a/(mV·dec^-1)	b_c/(mV·dec^-1)	η_ie(%)
25	Blank	-442.5	265.26	116.81	64.41
	BDMHI	-419.9	23.18	111.12	74.23	91.3
35	Blank	-449.5	343.24	105.49	72.05
	BDMHI	-424.5	39.61	117.71	79.69	88.4
45	Blank	-449.6	411.25	116.28	104.67
	BDMHI	-442.0	78.09	100.35	78.30	81.0
55	Blank	-450.3	502.37	101.40	85.38
	BDMHI	-449.7	112.90	103.52	68.84	77.5

Fig.5 Nyquist plots of Q235 steel in 6% HCl solution in the absence(A) and in the presence(B) of 1.0 g/L BDMHI at different temperatures

Table 2 Simulative electrochemical parameters for Q235 steel in 6% HCl solution in the absence and in the presence of 1.0 g/L BDMHI at different temperatures*

Temperature/℃	Solution	R_s/(Ω·cm²)	R_ct/(Ω·cm²)	n	C_dl/(μF·cm^-2)	η_ie(%)
25	Blank	0.4866	30.2	0.9433	216.0
	BDMHI	0.5674	326.8	0.8703	168.9	90.76
35	Blank	0.5475	19.4	0.9352	215.8
	BDMHI	0.5310	163.5	0.8886	169.0	88.13
45	Blank	0.5357	13.9	0.9351	214.5
	BDMHI	0.5171	74.8	0.8615	178.1	81.42
55	Blank	0.4602	8.7	0.9338	217.4	-
	BDMHI	0.4160	39.2	0.8832	186.2	77.81

Fig.6 SEM images for Q235 steel after 24 h immersion at 25 ℃ in 6% HCl solution in the absence(A) and in the presence(B) of 1.0 g/L BDMHI

Fig.7 Contact angles for Q235 steel after 24 h immersion at 25 ℃ in 6% HCl solution in the absence(A) and presence of 0.2 g/L(B), 0.6 g/L(C) and 1.0 g/L(D) BDMHI

Table 3 Contact angles and surface energy for Q235 steel after 24 h immersion at 25 ℃ in 6% HCl solution in the absence and in the presence of BDMHI

ρ(BDMHI)/(g·L^-1)	CA/(°)	γ_s/(mJ·m^-2)	ρ(BDMHI)/(g·L^-1)	CA/(°)	γ_s/(mJ·m^-2)
0	32.8	62.87	0.6	96.7	24.79
0.2	61.3	46.44	1.0	112.0	16.94

Fig.8 Langmuir adsorption isotherm fitting for BDMHI at Q235 steel surface

Table 4 Thermodynamic parameters of adsorption of BDMHI on Q235 steel surface at different temperatures

Temperature/K	Slope	R²	K/mol^-1	$Δ G ads 0$ /(kJ·mol^-1)	$Δ H ads 0$ /(kJ·mol^-1)	$Δ S ads 0$ /(J·mol^-1·K^-1)
298	1.00400	0.99953	3.642	-30.283	-42.66	-41.53
308	0.99648	0.99911	2.090	-29.879	-42.66	-41.50
318	0.98819	0.99903	1.377	-29.741	-42.66	-40.63
328	0.86603	0.99955	0.725	-28.926	-42.66	-41.87

Table 4 Thermodynamic parameters of adsorption of BDMHI on Q235 steel surface at different temperatures

Temperature/K	Slope	R²	K/mol^-1	$Δ G ads 0$ /(kJ·mol^-1)	$Δ H ads 0$ /(kJ·mol^-1)	$Δ S ads 0$ /(J·mol^-1·K^-1)
298	1.00400	0.99953	3.642	-30.283	-42.66	-41.53
308	0.99648	0.99911	2.090	-29.879	-42.66	-41.50
318	0.98819	0.99903	1.377	-29.741	-42.66	-40.63
328	0.86603	0.99955	0.725	-28.926	-42.66	-41.87

Fig.10 Optimized molecular structures of BDMHI(A) and BDMHI+(B) by GGA/BLYP

Fig.11 Frontier molecule orbital density distribution of BDMHI+ [HOMO(A) and LUMO(B)]

Table 5 Frontier orbital energies of BDMHI+ and Fe*

Molecule	E_HOMO/eV	E_LUMO/eV	ΔE/eV	ΔE₁/eV	ΔE₂/eV
BDMHI⁺	-7.849	-5.871	1.978	1.939	7.599
Fe	-7.810	-0.250

Table 6 Fukui index values for BDMHI+

Atom		Atom
C13	0.010	C1	-0.006
C15	-0.012	C3	0.049
N10	-0.007	C5	0.057
N12	0.005	C7	-0.008
O17	0.233	N2	0.056
O18	0.197	N4	0.028

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