Experimental and molecular simulation of corrosion of steel in [BMIM]HSO4 ionic liquid

ZHANG Jinwei1 CHENG Hongye1 CHEN Lifang1 QI Zhiwen1

(1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, China 200237)

【Abstract】The corrosion behaviors of steel in [BMIM]HSO4 ionic liquid (IL) were investigated by immersion tests and molecular simulation. The corrosion rates of stainless steel 304 in IL were determined by mass loss measurement. The result indicates that the presence of H2O greatly enhances the corrosivity of IL. The distribution of HOMO and LUMO, Fukui indices and quantum chemical parameters on IL molecule were calculated. The results show that the imidazolium ring and hydrogen sulfate play the most important role in the interaction between IL and metal surface. The quantum chemical parameters of IL in aqueous solution significantly change. The chemical adsorption ability of IL becomes weak. The adsorption process and adsorption energy of IL on steel surface in water-free and aqueous environments were investigated by molecular dynamics simulation. The molecular simulation results are consistent well with corrosion results, which can provide a better understanding of the interaction between ionic liquid and metal surface at the molecular level.

【Keywords】 ionic liquids; corrosion; mass loss measurement; molecular simulation; quantum chemical calculation; molecular dynamics simulation;


【Funds】 National Natural Science Foundation of China (21406063, U1462123)

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(Translated by ZHANG PY)


    [1] WISHART J F. Energy applications of ionic liquids [J]. Energy & Environmental Science, 2009, 2 (9): 956–961.

    [2] MEINDERSMA G W, PODT A J, DE HAAN A B. Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures [J]. Fuel Processing Technology, 2005, 87 (1): 59–70.

    [3] KULKARNI P S, AFONSO C A. Deep desulfurization of diesel fuel using ionic liquids: current status and future challenges [J]. Green Chemistry, 2010, 12 (7): 1139–1149.

    [4] ZHAO D S, WANG J L, ZHOU E P. Oxidative desulfurization of diesel fuel using a Brønsted acid room temperature ionic liquid in the presence of H2O2 [J]. Green Chemistry, 2007, 9 (11): 1219–1222.

    [5] ZHANG W, XU K, ZHANG Q, et al. Oxidative desulfurization of dibenzothiophene catalyzed by ionic liquid [BMIm]HSO4 [J]. Industrial & Engineering Chemistry Research, 2010, 49 (22): 11760–11763.

    [6] SONG Z, ZHOU T, ZHANG J N, et al. Screening of ionic liquids for solvent-sensitive extraction-with deep desulfurization as an example [J]. Chemical Engineering Science, 2015, 129: 69–77.

    [7] SONG Z, ZHANG J J, ZENG Q, et al. Effect of cation alkyl chain length on liquid–liquid equilibria of {ionic liquids + thiophene + heptane}: COSMO-RS prediction and experimental verification [J]. Fluid Phase Equilibria, 2016, 425: 244–251.

    [8] GREAVES T L, DRUMMOND C J. Protic ionic liquids: properties and applications [J]. Chemical Reviews, 2008, 108 (1): 206–237.

    [9] UERDINGEN M, TREBER C, BALSER M, et al. Corrosion behaviour of ionic liquids [J]. Green Chem., 2005, 7 (5): 321–325.

    [10] MASHUGA M, OLASUNKANMI L, ADEKUNLE A, et al. Adsorption, thermodynamic and quantum chemical studies of 1-hexyl-3-methylimidazolium based ionic liquids as corrosion inhibitors for mild steel in HCl [J]. Materials, 2015, 8 (6): 3607–36032.

    [11] SHERIF E S, ABDO H, ABEDIN S. Corrosion inhibition of cast iron in arabian gulf seawater by two different ionic liquids [J]. Materials, 2015, 8 (7): 3883–3895.

    [12] QIANG Y J, GUO L, ZHANG S T, et al. Synergistic effect of tartaric acid with 2,6-diaminopyridine on the corrosion inhibition of mild steel in 0.5 mol·L1 HCl [J]. Scientific Reports, 2016, 6: 33305.

    [13] TANAK H, KÖYSAL Y, ÜNVER Y, et al. Experimental and DFT studies of ethyl N′-3- (1H-imidazol-1-yl)propylcarbamoyl benzohydrazonate monohydrate [J]. Structural Chemistry, 2009, 20 (3): 409–416.

    [14] ULLAH S, BUSTAM M A, SHARIFF A M, et al. Experimental and quantum study of corrosion of A36 mild steel towards 1-butyl-3-methylimidazolium tetrachloroferrate ionic liquid [J]. Applied Surface Science, 2016, 365: 76–83.

    [15] CAO J S, REN Q, CHEN F W, et al. Comparative study on the methods for predicting the reactive site of nucleophilic reaction [J]. Science China Chemistry, 2015, 58 (12): 1–8.

    [16] HU S Q, HU J C, GAO Y J, et al. Corrosion inhibition and adsorption of lauryl-imidazolines for Q235 steel [J]. CIESC Journal, 2011, 62 (1): 147–155 (in Chinese).

    [17] QIAN J H, PAN X N, ZHANG Q, et al. Synthesis of 2,5-diaryl-1,3,4-thiadiazole corrosion inhibitors and their performance [J]. CIESC Journal, 2015, 66 (7): 2737–2748 (in Chinese).

    [18] FAN C H, HUANG X M, HAN L H, et al. Novel colorimetric and fluorescent off-on enantiomers with high selectivity for Fe3+ imaging in living cells [J]. Sensors & Actuators B Chemical, 2015, 224: 592–599.

    [19] FAUVET P, BALBAUD F, ROBIN R. Corrosion mechanisms of austenitic stainless steels in nitric media used in reprocessing plants [J]. Journal of Nuclear Materials, 2008, 375 (1): 52–64.

    [20] SCHUTT T C, HEGDE G A, BHARADWAJ V S, et al. Impact of water-dilution on the biomass solvation properties of the ionic liquid 1-methyltriethoxy-3-ethylimidazolium acetate [J]. The Journal of Physical Chemistry B, 2017, 121 (4): 843–853.

    [21] KANNAN P, KARTHIKEYAN J, MURUGAN P, et al. Corrosion inhibition effect of novel methyl benzimidazolium ionic liquid for carbon steel in HCl medium [J]. Journal of Molecular Liquids, 2016, 221: 368–380.

    [22] OLASUNKANMI L, OBOT I B, KABANDA M M, et al. Some quinoxalin-6-yl derivatives as corrosion inhibitors for mild steel in hydrochloric acid: experimental and theoretical studies [J]. Journal of Physical Chemistry C, 2015, 119 (28): 16004–16019.

    [23] ZHENG X W, ZHANG S T, LI W P, et al. Experimental and theoretical studies of two imidazolium-based ionic liquids as inhibitors for mild steel in sulfuric acid solution [J]. Corrosion Science, 2015, 95: 168–179.

    [24] ASEGBELOYIN J, EJIKEME P, OLASUNKANMI L, et al. A novel schiff base of 3-acetyl-4-hydroxy-6-methyl- (2H)pyran-2-one and 2, 2′-(ethylenedioxy)diethylamine as potential corrosion inhibitor for mild steel in acidic medium [J]. Materials, 2015, 8 (6): 2918–2934.

    [25] ONA O B, DE CLERCQ O, ALCOBA D R, et al. Atom and bond Fukui functions and matrices: a Hirshfeld-I atoms-in-molecule approach [J]. Chemphyschem A European Journal of Chemical Physics & Physical Chemistry, 2016, 17 (18): 2881–2889.

    [26] UDHAYAKALA P, JAYANTHI A, RAJENDIRAN T V, et al. Quantum chemical studies on some thiadiazolines as corrosion inhibitors for mild steel in acidic medium [J]. Research on Chemical Intermediates, 2012, 39 (39): 895–906.

    [27] SULAIMAN K O, ONAWOLE A T. Quantum chemical evaluation of the corrosion inhibition of novel aromatic hydrazide derivatives on mild steel in hydrochloric acid [J]. Computational & Theoretical Chemistry, 2016, 1093: 73–80.

    [28] YILMAZ N, FITOZ A, ERGUNÜ, et al. A combined electrochemical and theoretical study into the effect of 2-((thiazole-2-ylimino)methyl)phenol as a corrosion inhibitor for mild steel in a highly acidic environment [J]. Corrosion Science, 2016, 111: 110–120.

    [29] DENG S D, LI X H, XIE X G. Hydroxymethyl urea and 1,3-bis(hydroxymethyl)urea as corrosion inhibitors for steel in HCl solution [J]. Corrosion Science, 2014, 80 (3): 276–289.

    [30] LIU X Q, XUE Y, TIAN Z Y, et al. Adsorption of CH4 on nitrogenand boron-containing carbon models of coal predicted by density-functional theory [J]. Applied Surface Science, 2013, 285 (19): 190–197.

    [31] WANG X L, WAN H, GUAN G F. Structure and interaction of ion-pairs of [EPy]Cl and [EPy]Br in gas and liquid phases [J]. Acta Phys. -Chim. Sin., 2008, 24 (11): 2077–2082 (in Chinese).

This Article


CN: 11-1946/TQ

Vol 69, No. 02, Pages 808-814

February 2018


Article Outline


  • Introduction
  • 1 Experimental methods
  • 2 Results and discussion
  • 3 Conclusions
  • Symbol description
  • References