Accepted Manuscript

Controlling of mild-steel corrosion in acidic solution using

environmentally friendly ionic liquid inhibitors: Effect of alkyl
chain

Fadhel A. Azeez, Osama A. Al-Rashed, Ahmed Abdel Nazeer

PII: S0167-7322(17)36039-7
DOI: doi:10.1016/j.molliq.2018.05.093
Reference: MOLLIQ 9148
To appear in: Journal of Molecular Liquids
Received date: 17 December 2017
Revised date: 19 May 2018
Accepted date: 21 May 2018

Please cite this article as: Fadhel A. Azeez, Osama A. Al-Rashed, Ahmed Abdel Nazeer
, Controlling of mild-steel corrosion in acidic solution using environmentally friendly
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was captured as affiliation for all authors. Please check if appropriate. Molliq(2017),
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 ACCEPTED MANUSCRIPT

Controlling of Mild-Steel Corrosion in Acidic Solution using

Environmentally Friendly ionic liquid Inhibitors: Effect of alkyl chain

Fadhel A. Azeez a,*, Osama A. Al-Rashed a, Ahmed Abdel Nazeer a, b

a
Chemical Engineering Department, College of Engineering and Petroleum, Kuwait University, P.O.
Box 5969, Safat 13060, Kuwait.
b
Electrochemistry and Corrosion Lab., National Research Centre, Dokki, Cairo-12622, Egypt

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Abstract

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In this study three environmentally friendly ionic liquids (ILs) namely: 1-
Methyl-3-propylimidazolium iodide (MPIMI), 1-Butyl-3-methylimidazolium iodide
(BMIMI) and 1-Hexyl-3-methylimidazolium iodide (HMIMI) were examined as
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inhibitors for suppressing mild-steel corrosion in 1 M HCl solution. PDP, EFM and
EIS techniques were used to study the inhibition action on the metal surface. PDP
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study revealed that these ILs acted as mixed-type inhibitors due to their adsorption on
the steel surface following Langmuir adsorption isotherm. The negative values
obtained for Gibbs free energy supported the spontaneous physical adsorption of these
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inhibitors. Pronounced elevation in the inhibition efficiency was achieved with

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increasing the concentration of the ILs with maximum inhibitions of 93.1%, 87.8%
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and 80.4% using 5 x 10-3M for HMIMI, BMIMI and MPIMI, respectively. To
confirm the electrochemical results, the surface morphology of mild-steel was
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examined using AFM, SEM, and FT-IR analysis. The results confirmed the
significance of the alkyl-chain length and the iodide anion present in the ILs on the
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inhibition mechanism. The results obtained from the different electrochemical and
imaging techniques supported each other and strongly suggested that these eco-
friendly compounds can be important for several industrial applications.

Key words: Mild steel, ionic liquids, corrosion inhibition, HCl, EIS, SEM/AFM.

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Introduction
Due tᴏ its excellent mechanical properties and moderate cost, mild-steel is one of the
major construction materials used in different industries such as petroleum,
desalination plants, food production, pharmaceutical, chemical and electrochemical
industries [1-3]. However, it is susceptible to corrosion in different environments
especially when exposed to acidic solutions. HCl solution is commonly used for acid
cleaning, decaling, pickling and different applications; but due to its destructive effect

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it can cause severe corrosion to the components of the system [4-6]. Using corrosion
inhibitors is considered as an efficient economical and practical approach for metallic

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surfaces protection from corrosion. It is well-known that the inhibition of corrosion is
commonly related to the formation of an organic film over the metallic surface. In

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order to achieve a good corrosion inhibition, it is important to understand the
mechanism of the inhibitor growth on the metallic surface. The inhibitor adsorption
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mode depends on its chemical structure as well as its physical properties [7, 8]. For
example, the presence of oxygen, sulfur and nitrogen atoms in the organic compounds
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facilitate their adsorption on the metallic surface and make it more effective in
industry [9-12].
Although different organic materials have been used for corrosion inhibition, the
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factors for selecting the appropriate inhibitor for a specific application is governed by
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different criteria. These include adhering to environmental regulations and finding

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eco-friendly solutions to overcome the hazards associated with common inhibitors

currently used to protect human health and the environment [13]. Consequently,
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researchers focused their efforts towards the development of environmentally-friendly

corrosion inhibitors with high efficiencies [14]. Different researchers reported the use
of environmentally safe drugs and plant extracts for inhibiting mild-steel corrosion
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which depends on their adsorption mechanism ᴏn steel surface [15-23].

In the last decade, ILs have been used in different applications like fuel cells,
corrosion inhibitors, catalytic processes, batteries and chemical synthesis. ILs are
considered to be environmentally friendly solvents, which have characteristic high
stability, negligible vapor pressure and no toxicity [24].
Recently, ILs have attracted a great deal of attention as potential corrosion inhibitors
for different important alloys in various media as they shows pronounced inhibition
efficiency [25, 26]. Among these compounds, imidazolium ionic liquids containing

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carbon chain of different lengths have been proposed as good candidates for
suppressing corrosion due to the presence of an aromatic ring acts as the bonding site
between the metallic surface and the ionic liquid [27-30]. On the other hand, the
carbon chain tail leads to the formation of a hydrophobic film which helps in
protecting the metallic surfaces by forming a proper coverage. For instance, Shi et al.
[31] studied the effect of the alkyl chain length connecting with imidazolium ring of
novel ILs on corrosion inhibition performance in acidic solution. They concluded that

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the inhibition efficiency was increased with increasing the carbon chain length of the
alkyl group. The inhibition performance of 1-ethyl-3-methylimidazolium chloride
(EMIm Cl), 1-butyl-3-methylimidazolium chloride (BMIm Cl) and 1-hexyl- 3-

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methylimidazolium chloride (HMIm Cl) for mild steel corrosion in hydrochloric acid

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solution was investigated by Yousefi et al [28], the authors reported that the inhibition
efficiency increased with increasing the alkyl chain length. In other work, quantum
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and experimental studies about imidazolium ILs presented that the length of the alkyl
chain showed pronounced effect on the inhibition efficiency [32, 33]. Furthermore,
Alkylimidazolium ILs with 4, 6 and 8 carbons in the chain showed good corrosion
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inhibition for copper and aluminum and the ILs with the largest chain length is the
best one in the acidic environments [34, 35].
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This work aims to assess corrosion inhibition effect of three environmentally friendly
ionic liquids on mild-steel. The choice of these ILs is based on their easily produced,
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environmentally safe, easily soluble in water, and the presence of iodide atoms as
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active centers. Additionally, the roles of iodide anion as well as the effect of alkyl
chain length in these compounds on corrosion inhibition using different
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electrochemical and surface characteristic techniques have been thoroughly

investigated. Quantum chemical calculations have been used to predict the
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anticorrosive capability of the examined ILs.

2. Experimental
In this study the experiments were carried out using mild-steel with
compositions (weight %): C (0.15), Mn (0.56), P (0.22), S (0.14), Si (0.36), V (0.05),
Ni (0.04) and the balance is Fe. The studied corrosive media was HCl prepared by
diluting the analytical grade 32% HCl from MERCK CHEMICALS with distilled
water with pH of about 0 for 1M HCl. The inhibitor concentrations: from 5x10-5M to

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5x10-3M were prepared with pH range from 1 to 2. The mild-steel samples were
abraded with emery papers of grades 600, 800, 1200 and 2000, degreased with
acetone, washed thoroughly with doubly-distilled water, and finally dried.

The names, molecular formulae, structures and molecular weights of the

examined compounds are:

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Cᴏmp. Structures Names M. FW. and M. Wt.

1-Hexyl-3-

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HMIMI methylimidazolium C10H19IN2
iodide
Mol.Wt. 294.18

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1-Butyl-3- C8H15IN2
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BMIMI methylimidazolium
iodide Mol.Wt. 266.12
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1-Methyl-3- C7H13IN2
MPIMI propylimidazolium
iodide Mol.Wt. 252.1
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Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and

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Electrochemical frequency modulation (EFM) tests were performed in a three

electrode cell consisting of platinum foil 1 cm2, saturated calomel electrode, and mild-
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steel sheet (1cm x 1cm) as counter electrode, reference electrode and working
electrode, respectively. Mild-steel sample was dipped in the studied media for 20
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minute before scanning till achieving steady-state. All potentiodynamic tests were
carried out with 2273 PARSTAT electrochemical workstation instrument. Tests were
done in 1M HCl solution alone and with the tested ILs by applying potentials from -
250 mV to +250 mV from OCP with 0.5 mV s-1 scan rate. EFM was performed using
Gamry 3000 instrument and the data was evaluated using Echem analyst program. 10
mV potential perturbation signals were applied with 2 and 5 Hz sine waves. EIS
experiments were performed at 25 ±1 oC and the data were measured at OCP after
dipping the steel sample for 30 minutes in the studied media. The tests were carried
out at frequency from 100 kHz to 0.2 Hz while the AC signal was 5 mV peak to peak.

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The surface morphology of the studied samples was examined using SEM model
(JSM-6300 JEOL). AFM analysis was carried out using a model VEECO-Nano scope
IV multiple AFM/SPM. FT-IR measurements were recorded at 400-4000 cm-1 and a
resolution of 4.0 cm-1 and the FT-IR spectroscopy of the samples was taken by
attenuated total reflectance (ATR)-extended part using FT-IR spectrometer model
2000 Perkin-Elmer, (USA).
For quantum chemical calculation, EHOMO, ELUMO and ΔE calculations were

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performed using DMol3 module in Materials Studio version 6.0. These calculations
employed an ab initio, gradient-corrected functional (GGA) method with a double
numeric plus polarization (DNP) basis set and a Becke One Parameter (BOP)

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functional. It is well-known that the phenomena of electrochemical corrosion appear

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in aqueous phase. DMol3 includes certain COSMO controls, which allow for the
treatment of solvation effects.
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3. Results and discussion
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3.1. Potentiodynamic polarization technique

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The polarization technique was used to study the inhibiting effect of MPIMI,
BMIMI and HMIMI ILs on mild-steel alloy dissolution in 1.0 M HCl as presented in
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Figure 1. The measurements were conducted after immersing the studied electrode for
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20 min in the aerated test solution till reaching the steady-state at 0.5 mVs−1 scan rate.
Inspection ᴏf Figure 1 revealed that the presence of the ILs inhibitors caused
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pronounced shift in the anodic metal dissolution curves to lower current values
indicating their inhibition action. Moreover, a markedly decrease in the cathodic
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polarization curves to lesser values can be related to suppression of hydrogen gas

evolution reaction of mild-steel corrosion. This behavior was ascribed to adsorption of
the studied ILs molecules covering the active centers present ᴏn the steel surface [36].
From Figure 1, the different electrochemical parameters of: Ecorr, jcorr, the anodic and
cathodic Tafel slopes (βa and βc), and efficiency of inhibition (η%) were calculated and
tabulated in Table 1. From this Table it is observed that the current of corrosion was
pronouncedly decreased in the presence of the ILs compared to the bare solution (1M
HCl). Moreover, the current values were dropped with increasing the investigated ILs
concentrations. It was also clear that the addition of the studied compounds caused a

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slight shift in the Ecorr to less than 85 mV and in Tafel slopes. Taken all of the above
into consideration, these compounds could be treated as inhibitors for mild-steel
corrosion of mixed-type which affect the anodic and cathodic reactions by the
blocking mechanism [37, 38].
The inhibition efficiencies and the coverage degrees of surface (θ) of the
studied inhibitors were measured from the polarization curves using the following
equation [39]:
ηpp % = θ x 100 = [(jcorr - jˋcorr) / jcorr] ×100

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(1)
where jcorr and jˋcorr are the corrosiᴏn currents (µA cm-2) without and with inhibitors,
respectively.

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From the corrosion inhibition efficiencies determined using equation (1), it is evident

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that HMIMI features the maximum inhibition efficiency of 93.1% in presence of 5 x
10-3 M HMIMI while 87.8% and 80.4% were obtained in the presence of BMIMI and
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MPIMI, respectively using the same optimum concentration. The investigated ILs
showed the following order according to their inhibition efficiency: HMIMI > BMIMI
> MPIMI.
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To confirm the important role of iodide ions in the investigated ionic liquids,
Zhang and Hua [27], studied the inhibition of mild steel in 1 M HCl using 1-butyl-3-
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methylimidazolium chlorides; they obtained inhibition of 81.1% in presence of 5 x 10-

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3
M while in our study we obtained 87.8% using BMIMI which contains bromide
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instead of chloride which confirm the role iodide in inhibition compared with chloride
ions. Moreover, Yousefi et al [28], obtained inhibition efficiency of 75%, 73%, 79%
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and 84% using 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium

chloride, 1-butyl-3-methylimidazolium chloride and 1-hexyl-3-methylimidazolium
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chloride, respectively. These results also lower than our results using the same
compounds using iodide instead of chloride or bromide. Ashassi-Sorkhabi and
Es’haghi [40], investigated 1-butyl-3-methylimidazolium bromide [BMIM]Br
inhibition on mild steel corrosion in 1 M HCl and recorded 72% inhibition efficiency
using 4x10-3 M of [BMIM]Br which also lower than our results using BMIMI
confirming the protecting role of iodide.

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Figure 1 Polarization graphs for mild-steel in presence of 1M HCl alone (blank) and
with various concentrations of HMIMI, BMIMI and MPIMI ionic liquids at 25oC.

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Table 1 Electrochemical data calculated from PDP for mild-steel alloy in 1 M HCl in
the absence and presence of various concentrations of MPIMI, BMIMI and HMIMI
ionic liquids at 25oC.

jcorr., -Ecorr., -βc, βa, Corrosiᴏn

Cᴏnc., M  ηpp % rate (CR)
µA cm-2 mV mV dec.-1 mV dec.-1 mm/year

Blank 4776.0 461 283 198 -- -- 2186.0

5 x 10-5 2011.9 466 203 140 0.579 57.9 723.2

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1 x 10-4 1381.3 476 194 122 0.711 71.1 304.6

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HMIMI 5 x 10-4 710.4 477 197 131 0.851 85.1 209.2

1 x 10-3 413.5 471 171 75 0.913 91.3 107.6

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5 x 10-3 330.2 479 NU 162 71 0.931 93.1 62.6

5 x 10-5 2820.4 480 199 164 0.409 40.9 427.1

1 x 10-4 2091.3 481 201 156 0.562 56.2 316.7

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BMIMI 5 x 10-4 1633.4 483 186 141 0.658 65.8 247.3

1 x 10-3 914.7 489 192 151 0.808 80.8 138.5

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5 x 10-3 581.6 491 183 142 0.878 87.8 88.1

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5 x 10-5 3517.8 473 207 159 0.263 26.3 532.7

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1 x 10-4 2818.2 474 202 148 0.409 40.9 426.7

PMIMI 5 x 10-4 2015.6 475 196 152 0.578 57.8 305.2

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1 x 10-3 1460.7 481 201 156 0.694 69.4 221.2

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5 x 10-3 936.7 481 191 141 0.804 80.4 141.8

3.2. The adsorption isotherm

The adsorption isotherm was studied to gain important insight on the mode of
action among the investigated ILs and the active sites present on the metallic surface
[41]. There are different factors influencing the adsorption mode such as: the metal
nature and its charge, the inhibitors chemical structure and the electrolyte type. The

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(θ) of mild-steel surface by the studied inhibitors was estimated from the inhibition
efficiency data (η% /100).
The values of θ at temperature of 25 oC were used to establish the suitable isotherm of
the ILs adsorption. Different isotherms were examined and the best fit achieved for
the Langmuir adsorption isotherm as follow [42]:
C/ θ = 1/Kads + C (2)
Kads = (1/55.5) exp (-ΔGºads/RT) (3)
where C is the inhibitor conc., Kads is the adsorption equilibrium constant, and ΔG°ads

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is the standard free energy of adsorption. The value of 55.5 is the molar concentration
of water.

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Figure 2 depicts the relation of C/θ vs. C for the studied ILs at 25 oC showing straight

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lines with slopes very near to unity and linear correlation coefficients between
0.99993 and 0.99942 which clearly showed good agreement between the Langmuir
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isotherm and the experimental data. This suggested that the adsorption of the
investigated ILs on the mild-steel alloy surface follows the Langmuir adsᴏrption
isotherm.
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Also, the calculated values of Kads for HMIMI, BMIMI and MPIMI were 26627, 9039
and 5499 M-1 at 25 oC, respectively. The high Kads values in case of HMIMI implied
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its strong adsorption ability on steel surface. Furthermore, the negative values of
∆G˚ads are presented in Table 2 confirm a spontaneous adsorption of the studied ILs
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on mild-steel surface which clarifies its high corrosion inhibition efficiency.

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Moreover, the values of ∆G°ads ranged from -33.4 to -35.2 kJ mol-1 which were less
negative than -40 kJ mol-1, which confirmed the physical adsorption of the studied
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inhibitors on the alloy surface via electrostatic interaction among the charged
molecules and the charged surface of metals [43].
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Figure 2 Langmuir isotherm for MPIMI, BMIMI and HMIMI adsorption on mild-
steel in 1 M HCl at 25oC.
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Table 2 Equilibrium constant (K), free energy of adsᴏrption (ΔGads) of MPIMI,

BMIMI and HMIMI compounds fᴏr corrosion of mild-steel in 1 M HCl at 25oC.
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Langmuir isotherm
Compound
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K -ΔGads
R2
(M-1) (kJ mol-1(
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35.2
HMIMI 0.99993 26627

BMIMI 0.99944 9039 33.6

MPIMI 0.99942 5499 33.4

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3.3 EIS measurements

To confirm the results achieved from PDP, further investigation was

carried out using EIS technique to provide a deeper insight regarding the corrosion
protection mechanism of the studied electrochemical system in this study.
Nyquist plots for bare mild-steel in 1.0 M HCl solution alone and with different
concentrations of the investigated ILs (HMIMI, BMIMI and MPIMI) are presented in
Figure 3 a-c. From Figure 3, it is clear that the EIS data showed a depressed

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semicircle charge transfer which can be assigned to the double-layer capacitance and
time constant of charge-transfer [44-46]. Additionally, the profile of impedance

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spectra has not changed in the presence of the ILs. This strongly suggested similar
mechanism of corrosion. Moreover, the impedance values pronouncedly increased in

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the presence of the ILs compared to the pure HCl solution and increased more with
increasing the ILs concentrations suggesting the development of a protection layer on
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the steel surface and subsequently a decrease in the rate of corrosion.
To characterize the mild-steel corrosiᴏn in 1.0 M HCl solution, an equivalent
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circuit was suggested with only one time constant (Figure 4). The circuit contained
the following elements: solution resistance (Rs), charge transfer resistance Rct, and
double-layer capacitance Cdl. Additionally, the capacitive element was replaced by
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constant phase element (CPE) to provide a correct fit [47], where the resulted
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capacitive loop is depressed-semicircle instead of regular one.

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Table 3 implies the values of Cdl and Rct recorded for mild-steel in 1 M HCl solution
alone and with different concentrations of the investigated ILs at 25oC. It was
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observed that the Rct values increased with increasing the ILs concentration, while the
Cdl decreased which confirmed the adsorption of the investigated ILs on the electrode
surface [48]. Moreover, the HMIMI showed the highest resistance followed by
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BMIMI and finally MPIMI.

To calculate the inhibition efficiency, the Rct values were used according to the
following equation:
ηEIS % = [(Rct(inh) – Rct) / Rct(inh)] X 100 (4)
where Rct and Rct(inh) are the charge transfer resistances recorded in uninhibited and
inhibited solutions, respectively. As depicted in Table 3 the inhibition efficiency
values increased with increasing the inhibitors concentration with maximum
inhibitions of 93.6, 88.1 and 83.9% in presence of 5x10-3 M for HMIMI, BMIMI and

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MPIMI, respectively. The results obtained confirmed that the investigated ILs have
created a pronounced coverage of the steel surface which strongly suppressed the rate
of corrosion and provided a protective shield. The inhibition action of the ILs for
metallic surfaces depended on both: the adsorption mechanism and the type of the
charged head group [49]. For ILs of the same head group, the higher chain length, the
higher inhibition efficiency [28]. In this study, the HMIMI had the highest chain
length, and as was expected it showed the best inhibition efficiency for mild-steel in

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HCl solution followed by BMIMI and PMIMI. Increasing the adsorption at the metal
surface related to increasing the chain length and hence the molecular size. In
conclusion, it is noticeable that the inhibition efficiencies achieved from PDP and EIS

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are supported on each other.

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Figure 3 Nyquest plots for mild-steel in presence of 1.0 M HCl alone and containing
various concentrations of HMIMI, BMIMI and MPIMI ionic liquids at 25oC.

Figure 4 The circuit used for fitting the data.

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Table 3 Data attained by EIS technique for the corrosion of mild-steel alloy in 1 M
HCl uninhibited and inhibited with various concentrations of MPIMI, BMIMI and
HMIMI ionic liquids at 25oC. χ2 is the goodness of the fit.

Rs Rct Cdl χ2
Conc., M n  ηEIS %
Ω cm2 Ω cm2 µFcm−2

Blank 1.52 23.3 0.833 102.3 -- -- 0.00024

5 x 10-5 1.43 56.4 0.846 68.3 0.587 58.7 0.00035

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1 x 10-4 1.22 92.2 0.865 57.1 0.747 74.7 0.00046

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HMIMI 5 x 10-4 1.31 156.9 0.849 47.6 0.851 85.1 0.00032

1 x 10-3

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1.17 307.1 0.873 38.1 0.924 92.4 0.00038

5 x 10-3 1.25 364.9 0.843 34.7 0.936 93.6 0.00027

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5 x 10-5 1.13 42.6 0.834 77.4 0.453 45.3 0.00045

1 x 10-4 1.26 57.1 0.855 66.7 0.592 59.2 0.00042

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5 x 10-4 1.37 91.3 0.841 58.5 0.745 74.5 0.00029

BMIMI
1 x 10-3 1.31 132.5 0.862 49.1 0.824 82.4 0.00031
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5 x 10-3 1.12 196.2 0.877 44.8 0.881 88.1 0.00037

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5 x 10-5 1.44 32.9 0.864 85.6 0.292 29.2 0.00030

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1 x 10-4 1.36 56.8 0.856 68.1 0.589 58.9 0.00022

5 x 10-4
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MPIMI 1.08 79.6 0.846 61.2 0.707 70.7 0.00039

1 x 10-3 1.17 103.1 0.872 51.6 0.774 77.4 0.00014

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5 x 10-3 1.29 144.3 0.855 47.8 0.839 83.9 0.00026

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3.4 EFM technique

EFM is a powerful and nondestructive technique employed in corrosion studies

which can directly measure the corrosion current using a small polarizing signal [50].
EFM provides a spectrum of current responses as a function of frequency. The input
frequency perturbation employed has the ratio 2:5. The choice frequency must cause
minimal capacitance at the metal–electrolyte interface. The details of the theory and
recent application of EFM technique in corrosion was previously discussed [51].

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Figure 5 shows the intermodulation figures recorded from EFM measurements
for the corrosion of mild-steel alloy in 1.0 M HCl alone and with 5x10-3 M of the

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studied ILs (HMIMI, BMIMI and MPIMI). The data using the different

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concentrations was obtained to study the effect of inhibitor concentration (data not
shown). From these figures the different electrochemical parameters (jcorr, βa, βc, CF-2
and CF-3) were measured using the largest peaks and given in Table 4.
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Form this Table, it can be noticed that the addition of the investigated ILs to the
HCl solution resulted in a decrease in the corrosion current, and this decrease was
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more manifest by increasing the inhibitors concentration confirming that these

compounds inhibit the corrosion process by adsorption mechanism. One of the
important parameters to confirm the validity of the EFM measurements is the
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causality factor (CF) [52]. The values of CF obtained at various concentrations of the
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investigated ILs were almost equal to the theoretical values (2 and 3) confirming the
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consistency of the measured data [53]. In agreement with PDP results, lower
corrosion current density values were calculated in presence of the investigated ILs
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compared with the bare mild-steel.

The efficiency of inhibition (ηEFM%) was calculated from the next equation:
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ηEFM% = [(jocorr - jcorr) / jocorr] x 100 (5)

where jocorr and jcorr are the corrosiᴏn current densities in the absence and presence of
the studied inhibitors, respectively.
From the measured inhibition data, it was clear that the inhibition efficiency increases
by increasing the inhibitor concentration and HMIMI featured the highest inhibition
efficiency followed by BMIMI and then MPIMI at constant concentration. Generally,
the EFM results are in good agreement with the results obtained from the PDP and
EIS techniques.

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Figure 5 EFM plots for mild-steel in presence of 1.0 M HCl alone (blank) and
containing the optimum concentration of HMIMI, BMIMI and MPIMI ionic liquids at
25oC.

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Table 4 Data obtained by EFM technique for mild-steel alloy in 1.0 M HCl
uninhibited and inhibited with various concentrations of MPIMI, BMIMI and HMIMI
ionic liquids at 25 oC.

Conc.,
Comp. jcorr βc βa
CF-2 CF-3 θ ηEFM %
M µAcm-2 mVdec−1 mVdec−1

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3693 112 94 1.94 2.87 - -
Blank
5 x 10-5 1514 129 107 1.89 2.85 0.59 59.0

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1 x 10-4 1094 134 142 1.95 2.96 0.704 70.4

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HMIMI 5 x 10-4 566 128 111 1.830 3.04 0.847 84.7

1 x 10-3 372 151 123 1.92 3.17 0.899 89.9

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5 x 10-3 262 117 116 1.83 3.13 0.929 92.9

5 x 10-5
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2095 121 101 1.93 2.98 0.433 43.3

1 x 10-4 1557 120 105 1.86 2.93 0.578 57.8

BMIMI 5 x 10-4 1235 125 109 1.95 2.95 0.666 66.6

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1 x 10-3 701 119 114 1.83 2.86 0.81 81.0

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5 x 10-3 522 127 121 1.94 2.89 0.859 85.9

5 x 10-5 2759 132 106 1.88 2.92 0.253 25.3

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1 x 10-4 2132 147 123 1.92 3.05 0.423 42.3

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PMIMI 5 x 10-4 1614 152 124 1.89 3.01 0.563 56.3

1 x 10-3 1058 122 112 1.94 2.92 0.714 71.4

5 x 10-3 766 141 119 1.87 2.90 0.793 79.3

3.5 SEM and AFM surface analysis

To verify the protective film formation of the ILs on mild-steel surface, SEM
micrographs were recorded for the steel surface after dipping it in 1M HCl solution

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for 24 hours without and with 5x10-3 M of HMIMI, BMIMI and MPIMI, as shown in
Figure 6. Comparing the obtained micrographs, it was clear that the bare mild-steel
surface in the acidic solution without the ILs (Figure 6 a) was severely defected,
rough and corroded due to its low resistance towards the aggressive media. In
contrast, in the presence of the ILs, improved resistance of the metallic surface
towards corrosion and resulted in the formation of smooth steel surfaces as shown in
Figures 6 b, c, d. In conclusion, the presence of the investigated ILs led to achieving

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high efficiency due to the development of a protective film on the metallic surface
which looks to be nearly not affected by corrosiᴏn.
One of the powerful tools for exploring the morphology of metallic surfaces at the

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nano- and microscale is atomic force microscopy (AFM) technique. Figure 7 shows

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the three-dimensional (3D) AFM graphs for the metallic steel surface after dipping in
1 M HCl solution without and with the optimum concentration of HMIMI, BMIMI
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and MPIMI. From the Figure, it was evident that the AFM graphs of steel surface
immersed in HCl showed a rough, scratched and porous structure due to the
aggressive attack by the acidic media. On the other hand, the steel surface exposed to
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1 M HCl solution containing the ILs was relatively smoother compared with the
acidic solution alone, which obviously revealed that the important role of the
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investigated compounds in decreasing the corrosion rate of mild-steel surface.

Moreover, it was demonstrated that the protection efficiency in case of HMIMI was
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higher than BMIMI and MPIMI which was supported by the electrochemical results.
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(a)
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(b)

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(c)

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(d)
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(e)
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Figure 6 SEM images of the polished mild-steel (a), in 1M HCl alone (b) and
containing 5x10-3 M of HMIMI (c), BMIMI (d) and MPIMI (e) ionic liquids at 25 oC
for 24 hr.

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(a)

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(b)

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(c)
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(d)
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Figure 7 AFM 3D images of mild-steel in 1M HCl alone (a) and containing 5x10-3 M
of HMIMI (b), BMIMI (c) and MPIMI (d) ionic liquids at 25 oC for 24 hr.

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3.6 FT-IR studies

As the electrochemical measurements and the surface studies discussed above showed
that the investigated ILs formed a protective film on the steel surface by adsorption, it
is of great importance to confirm the formation of these protective layers by using
infrared spectroscopy.
Figure 8 shows FT-IR absorption spectra of mild-steel samples after immersion in 1M
HCl solution in presence of 5 x 10-3 M of the studied ILs. From the figure in presence

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of BMIMI, absorption peaks at 2958 and 2872 cm-1 can be ascribed to C–H stretching
vibration methyl group in the side chain [54]. The peak located at 2930 cm-1

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corresponds to C–H stretching vibration in the –CH2 group. The absorption peaks at
1613, 1571 and 1169 cm-1 are ascribed to the C=C stretching, C=N stretching and C–

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H bending vibration in the imidazole ring, respectively. The peak at 820 cm-1 is
assigned to C-N stretching vibration. For the broad peak at 3461 cm-1 it is due to the
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formation of quaternary amine salt with iodine. For HMIMI and MPIMI, the same
peaks were obtained with small changes in range of about 2 cm-1. These results
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confirmed the adsorption of the studied ILs on the steel surface and hence there
inhibition action.
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Figure 8 FT-IR absorption spectra of mild-steel in 1M HCl solution containing 5 x

10-3M of HMIMI, BMIMI and MPIMI.

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3.7 Quantum chemical calculation

To investigate the relation between the molecular structures of studied ILs and their
inhibition action, Quantum chemical calculations were performed. Different quantum
chemical parameters were calculated, such as highest occupied molecular orbital
energy (EHOMO) and lowest unoccupied molecular orbital energy (ELUMO) which help
to determine the way the molecule interacts with other species.
Table 5 summarizes the quantum chemical parameters (EHOMO, ELUMO and gap energy

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(ΔE)) which have been calculated and correlated with experimental results. The high
value of EHOMO is related to the ability of a molecule to donate electrons to an

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appropriate acceptor molecule with low energy vacant molecular orbital [55]. From
Table 5, the energy of HOMO is as follow: HMIMI > BMIMI > MPIMI. Increasing

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the EHOMO value facilitates the adsorption and hence the inhibition by inducing the
transport process through the adsorbed layer [56]. Furthermore, the energy of LUMO
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represents the ability of the molecules to accept electrons. Accordingly, the
probability of the molecules to accept electrons increased with decreasing the value of
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ELUMO. In addition, decreasing the energy band gap value (ΔE = ELUMO - EHOMO)
offers better inhibition efficiency due to decreasing the energy required to remove an
electron from the last occupied orbital. Consequently, HMIMI showed the lowest
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band gap followed by BMIMI and then MPIMI. In conclusion, the less negative
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EHOMO and the smaller ΔE values of HMIMI reflect the pronounced inhibition
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efficiency compared with BMIMI and MPIMI. These results are in good agreement
with the inhibition efficiencies values obtained from, PDP, EFM and EIS techniques.
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IL Structure HOMO LUMO

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MPIMI

BMIMI

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HMIMI

Figure 9. Frontier orbitals isᴏsurfaces of the ILs MPIMI, BMIMI and HMIMI. Blue
and yellow isᴏsurfaces of the HOMO and LUMO denote pᴏsitive and negative
wavefunctiᴏn phases, respectively.

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Table 5. The calculated quantum chemical parameters of the ILs MPIMI, BMIMI and
HMIMI.

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MPIMI BMIMI HMIMI

EHOMO, eV -6.321 -6.254 -6.026

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ELUMO, eV 0.320 -0.144 -0.674
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ΔE, eV 6.641 6.110 5.352

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3.8 Corrosion inhibition mechanism

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It is important to find an interpretation for the corrosiᴏn mechanism of mild-steel in

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the acidic media (HCl) without and with the investigated ILs. Generally, the corrosion
of metals and alloys undergoes two known processes; (1) anodic dissolution of metal
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and (2) cathodic reactions which involve the evolution of hydrogen or reduction of
oxygen gases [57]. Based on the above results and discussion, the suggested
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mechanism of corrosion in this work will be designed according to the following.

In absence of the inhibitors, it is well established that the steel surface is positively
charged in acidic media and the presence of the chloride ions of the acid enhances the
metal dissolution. In presence of organic compounds as inhibitors, its functional
groups, structures, the corrosive media and the nature of the metal all will affect the
inhibition action. For mild-steel corrosion inhibition it is mostly ascribed to the
adsorption of the studied ILs at the interface between metal surface and the solution.
All of the investigated inhibitors are ILs with iodide as anion and alkyl imidazole as
cation. The presence of iodide ions in their molecular structure played an important

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role in interacting with the metal surface which promoted the formation of the
protective layer. Iodide has the largest atomic radius compared to the other halides,
additionally, it is derived from a strong acid which assist in its adsorption on the
metallic surface and facilitate the formation of bridges between the organic cations of
the ILs and the metal atoms. Furthermore, nitrogen atoms of imidazole can donate
lone pairs of electrons to the surface of mild-steel which forms a coordinate bond
which can help in the corrosion inhibition. Meanwhile, the presence of the electron

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donating group (I) on the imidazolium base IL increases the electron density on the
nitrogen of the –C=N– group, resulting in high inhibition efficiency. Finally, the π-
electrons of the aromatic rings of imidazole can interact with the vacant d-orbital of

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the metal to protect it from dissolution.

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The quantum chemical calculations confirmed that HMIMI was the best corrosion
inhibitor compared with BMIMI or MPIMI due to its lowest band gab and highest
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EHOMO.
For comparing the studied inhibitors, it is clear that the inhibition effect occurs by
covering the metallic surface with the aromatic ring and the alkyl chains present in the
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ILs. Longer alkyl chain will facilitate the formation of more compact films at the
interface between the steel and the solution resulting in high surface coverage and
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better corrosion inhibition. For this reason, HMIMI, is considered the best corrosion
inhibitor compared to BMIMI which is better than MPIMI due to the presence of
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hexyl, butyl and propyl groups, respectively.

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4. Conclusion
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HMIMI, BMIMI and MPIMI are ILs investigated in this study have shown a
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pronounced corrosion inhibition behavior for the mild-steel in acidic solution (1 M

HCl) at 25 ºC. The results obtained from PDP, EIS and EFM measurements
confirmed that the studied ILs were suitable for using as inhibitor for mild steel in
HCl solution. The maximum protection efficiency of 93.1 % was achieved by using
5x10-3 M of HMIMI. Increasing the alkyl chain length on the imidazolium cations
increases the protection of mild-steel from corrosion in the acidic media. The surface
analysis results confirmed the protection of steel surface in presence of the studied ILs
from uniform corrosion. SEM, AFM and FT-IR of the metal surface analysis
indicated that the inhibition mechanism arises from the adsorption of the ILs on the

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steel surface and the inhibition process obeyed Langmuir adsorption isotherm. The
calculated quantum chemical parameters support the improved inhibiting performance
of HMIMI compared with BMIMI or MPIMI. The investigated ILs have proven to be
effective as corrosion inhibitors and can be widely adopted for several industrial
applications.

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Acknowledgements
The authors acknowledge the support of Kuwait University Research Administration

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and the general facilities projects No. GE03/08. Furthermore, Nanoscopy Science
Centre is highly appreciated.

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Highlights

► Three ILs studied as effective corrosion inhibitors for Mild steel in HCl solution.

► SEM/AFM and FTIR confirmed the steel protection which is attributed to ILs
adsorption on its surface.

► Role of iodide anion and the length of alkyl-chain of ILs in the inhibition were
studied.

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► The maximum protection efficiency achieved was 93.1% obtained using HMIMI.

► The adsorption of ILs on steel surface followed Langmuir adsorption isotherm.

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