Journal of Molecular Liquids 233 (2017) 403–414

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Review

Ionic liquids as green and sustainable corrosion inhibitors for metals and
alloys: An overview
Chandrabhan Verma a, Eno E. Ebenso b, M.A. Quraishi a,⁎
a
Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005, India
b
Department of Chemistry, Material Science Innovation & Modelling (MaSIM) Research Focus Area, Faculty of Agriculture, Science and Technology, North-West University (Mafikeng Campus),
Private Bag X2046, Mmabatho 2735, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Development of green and sustainable technologies for the corrosion prevention is highly desirable due to in-
Received 16 January 2017 creasing ecological awareness and strict environmental regulations. In the last decade, metallic corrosion inhibi-
Received in revised form 16 February 2017 tion using ionic liquids has attracted considerable attention due to their interesting properties such as low
Available online 2 March 2017
volatility, non-inflammability, non-toxic nature, high thermal and chemical stability and their ability to adsorb
on the metallic surface. The review covers on ionic liquids as “green corrosion inhibitors” for different metals
Keywords:
Ionic liquids
and alloys such as mild steel, aluminum, copper, zinc, and magnesium in several electrolytic media. The ionic liq-
Corrosion uids are promising, noble, green and sustainable candidates to replace the traditional volatile corrosion inhibitors
Adsorption and can be effectively adsorb on metallic surface. Several ionic liquids have been used successfully as corrosion
Green corrosion inhibitors inhibitors for mild steel; however their use as corrosion inhibitors for non-ferrous metals is scares. Present review
Designer solvents also describes the mechanism adsorption behavior of ionic liquids on metallic surface in common electrolytic
Ferrous and non-ferrous metals media using quantum chemical calculations.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.1. Corrosion and its economic impact. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.2. Causes of corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.3. Corrosion prevention methods and corrosion inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.4. Ionic liquids as green corrosion inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.4.1. Properties and applications of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
1.4.2. Classification of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
1.5. Comparison between organic inhibitors and ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
2. Ionic liquids as corrosion inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
2.1. Ionic liquids as corrosion inhibitors for mild steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
2.2. Ionic liquids as corrosion inhibitors for aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
2.3. Ionic liquids as corrosion inhibitors for copper and zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
2.4. Ionic liquids as corrosion inhibitors for magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
3. Ionic liquids as corrosion inhibitors: DFT study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
4. Mechanism of corrosion inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
5. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412

⁎ Corresponding author.
E-mail address: maquraishi.apc@itbhu.ac.in (M.A. Quraishi).

http://dx.doi.org/10.1016/j.molliq.2017.02.111
0167-7322/© 2017 Elsevier B.V. All rights reserved.
404 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414
1. Introduction
1.1. Corrosion and its economic impact
Corrosion is an irreversible and spontaneous deterioration of metal
or alloy through chemical or electrochemical reaction with the environ-
ment [1]. In general, deterioration of metallic materials by physical
causes is termed as erosion, galling or wear but corrosion is limited to
destructive attack of metals only [1,2]. Several non-metallic materials
may undergo deterioration by chemical reaction with the environment
such as plastic may swell or even crack, granite may erode, wood may
split and Portland may leach away, the term corrosion is limited to de-
structive chemical and/or electrochemical attack metals. Corrosion
causes enormous wastes of metallic materials which leads to enormous
economic losses all over the world. Therefore, corrosion has drawn con-
siderable academic and industrial attention [1–4]. Corrosion is a global
problem, adversely affecting the growth of both developed as well as
developing countries. According to highly cited study carried out by
the National Association of Corrosion Engineers (NACE), in 1998, the
total annual direct cost (estimated) of corrosion in U.S. was US $276 bil-
lion, equating approximately around 3.1% Gross Domestic Product
(GDP; NACE 2002) [5]. In 2011, the total cost of corrosion in U.S. became
more than US $2.2 trillion. As for as the corrosion cost in India is concern,
it was around Rs. 2 lakhs crores (US $45 billion) as proposed by 1st
Global Corrosion Summit held in New Delhi, India in 2011 [6]. However,
these estimated data are outdated and recently closer investigation of
the NACE on the cost of corrosion is available according to which the an-
nual global cost of corrosion is approximately US $2.5 trillion, equating
3.4% of the global GDP [7,8]. In India, the annual corrosion cost is more
than US $100-billion, while in South Africa, the direct corrosion cost is
estimated to be around R130-billion (i.e. about US $ 9.6 billion) [7,8].
This cost of corrosion can be reduced from 15 (US $ 375 billion) to
35% (US $ 875 billion) by properly applying the existing methods of cor-
rosion prevention.
1.2. Causes of corrosion
Pure metals are chemically unstable and undergo chemical and/or
electrochemical reactions with their environments to form more stable
corrosion products. The chemical reactivity of pure metals is related
with their natural tendency of oxidation (except gold, silver and plati-
num), as they have tendency to return their natural state by chemical
reactions with the constituents of environment [9,10]. Since corrosion
is a spontaneous process, relative rate of corrosion among a given series
of metals is related to the change in standard Gibb's free energy (ΔG°). A
more negative value of ΔG° related with higher spontaneity of reaction
i.e. higher corrosion rate [9,10]. Metals and alloys when exposed to en-
vironment particularly in acid solution during several industrial pro-
cesses like acid pickling, acid descaling etc. corroded in order to form
stable corrosion products [11]. Therefore, these processes required
some additive known as corrosion inhibitors that from protective cover-
ing over the metallic surface and isolates metals from the environment
and thereby inhibitors from corrosive degradation [11,12]. The corro-
sion products such as rust and scale can also act as corrosion inhibitors
as they can accumulate on the surface and act as physical protective bar-
rier. The natural tendency of metallic corrosion can be affected by sever-
al factors, however, the relative rate of corrosion of any particular metal
is depend upon the Pilling – Bedworth ratio which is defined as Md/nmD,
where m and d are the atomic weight and density of the metal, respec-
tively and M and D are the molecular weight and density of scale (corro-
sion product) accumulated on the metallic surface, and n denotes the
number of metallic atoms in the molecular formula of corrosion product
(rust or scale); for example for Fe2O3 and Al2O3, n = 2 [13]. The magni-
tude of Pilling – Bedworth ratio can be used to explain where the surface
film will be protective or not. The volume of corrosion product will be
small than the volume of metal from which it is forms for Md/nmD b 1,
in this situation it is expected that surface film of corrosion product con-
tains pores and cracks that would be relatively non-protective. On the
other hand, volume of corrosion product will be larger than the volume
of metal for Md/nmD N 1, in that situation it is expected that surface
film of corrosion product is relatively more compressed and compact
that would be relatively more protective.
1.3. Corrosion prevention methods and corrosion inhibitors
There are several methods of corrosion protection have been devel-
oped among which use of synthetic corrosion inhibitors is one of the
best methods due to their cost effectiveness and ease of application in
industry [14]. The flow diagram of the available corrosion protection
measures is shown in Fig. 1. The passivating inhibitors are also known
as anodic inhibitors because they general inhibit the metallic corrosion
by forming the surface oxide (passive) film and causes the large anodic
shift corrosion potential (Ecorr) [15]. The passivating inhibitors can be
further classified into oxidizing anions that passivate the metallic sur-
face in the absence of oxygen such as chromate, nitrite and nitrate and
non-oxidizing anions that can passivate the metallic surface only in
the presence of oxygen such as phosphate, tungstate and molybdate.
The cathodic inhibitors either decrease the rate of cathodic reactions
or precipitate on the cathodic areas to increase the surface impedance
that decrease the diffusion of reducible species to these areas [15,16].
The cathodic inhibitors act by three different mechanisms namely, ca-
thodic poisons, cathodic precipitates and oxygen scavengers. Generally,
arsenic and antimony make the association of hydrogen more difficult
and act as cathodic poisons, calcium, zinc and magnesium precipitates
in their oxide forms and act as cathodic precipitates and sodium sulfite
and hydrazine react with surrounding oxygen and act as oxygen scav-
engers [17–20].
Organic compounds are also known as filming inhibitors; generally
inhibit metallic corrosion by forming the protective surface film that
separates the metal form the surrounding (corrosive) environments.
Most of the well known organic inhibitors are heterocyclic compounds
containing polar functional groups such as\\NO2,\\OH,\\OCH3,\\CH3,
\\NH2,\\COOC2H5,\\CONH2,\\COOH, etc. [21]. These polar functional
groups and conjugated π-electrons of multiple bonds (double and tri-
ple) act as adsorption centers during metal-inhibitor interactions. This
type of adsorption results into blocking of anodic and cathodic reactions
indirectly. The adsorption of these inhibitors is affected by several fac-
tors such as nature and magnitude of charge present on metal, nature
of electrolyte, electronic structure of inhibitor molecules, nature of sub-
stituents, solution temperature, exposure time etc. [21,22].
1.4. Ionic liquids as green corrosion inhibitors
“Green chemistry” which is also called as sustainable chemistry is
relatively new and rapidly growing area of chemistry and chemical en-
gineering which involves designing of products and processes that re-
duce the use and production of toxic substances [23]. Recently,
worldwide growing ecological awareness and strict environmental pro-
tocols do not permit the synthesis and utilization of hazardous tradi-
tional volatile corrosion inhibitors. Therefore, there is vital need for
improvement in the synthetic and engineering chemistry either by en-
vironmental friendly starting materials or proper designing for
synthesis using non-classical energy sources such as ultrasound and mi-
crowave heating. In this regard use of multicomponent reactions
(MCRs) in combination with ultrasonic (sonochemical) and microwave
irradiation is one of the best alternative synthetic strategies toward
“green synthesis”. Recently scientists are trying to develop plant ex-
tracts and drugs as green corrosion inhibitors due to their natural and/
or biological origins and non-toxic nature [24]. However, extraction
and purification of plant extracts is very tedious, laborious, and ex-
tremely expensive as well as time consuming process. Moreover, such
type of extraction requires relatively large amount of organic solvents
 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414 405

Fig. 1. Available methods of metallic corrosion protection.

that may adversely affect the environment and living beings. In addi-
tion, sometime extraction of plant materials required high temperature
that can decompose the active constituents and thereby may decrease
the relative inhibition efficiency. Similarly, use of drugs as corrosion in-
hibitors is also limited due to their multi steps synthesis and extremely
expensive nature [25]. Therefore, there is need to develop “green inhib-
itors” by proper designing of the synthesis that can be achieved either
by using cheap and environmental friendly starting materials or by syn-
thesizing them from one step MCR reactions, and solid support
synthesis in combination with more energy efficient non-conventional
microwave and ultrasound heating methods.
Toward, “green chemistry”, utilization of ionic liquids has immersed
as new strategy due to their several fascinating properties such as lower
melting point (lower that 100 °C), high polarity, low toxicity, lower
vapor pressure, very high thermal and chemical stability, less hazardous
influence on environment and living being [26]. Recently, the use of
ionic liquids for specific applications is increasing significantly particu-
larly in the field of fundamental chemical and chemical engineering

Fig. 2. Applications of ionic liquids.

406 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414
researches such as catalysis, solvents for chemical transformations, syn-
thesis of nanomaterials, extraction and separation, and energy conver-
sion [26,27]. By definition, ionic liquids are materials that mainly
composed of ions with melting point below than 100 °C. The properties
of ionic liquids can be modifying according to the need by proper selec-
tion of cations and anions, which is the greatest advantage for designing
ionic liquids of specific properties [28]. Due to this reason ionic liquids
are also known as “designer chemicals” that have potential to consume
as solvent or catalysis for various chemical transformations [26–28]. It is
recall that unlike to conventional organic volatile chemicals that is not
only pollutes the environment but also adversely affects the public
health, ionic liquids are “green and sustainable” solvents having negligi-
ble volatility, non-inflammability, non-toxic, and high thermal and
chemical stability. These chemicals are characterized by extremely low
vapor pressure which is greatest advantage of ionic liquids. According,
a recently published review article, a search using CAS Sci Finder and
Scopus with the keyword “ionic liquids” yielded 727 and 694 review ar-
ticles, respectively [27b]. The rapid utilization of ionic liquids in almost
all fields of chemistry and chemical engineering is attributed due their
above mentioned fascinating properties which enable them as “green
and sustainable chemicals” having tendency to dissolve wide range of
inorganic and organic compounds. The ionic liquids follow the princi-
pals of “green chemistry” proposed by Paul Anastas and John Warner
[29,30].
1.4.1. Properties and applications of ionic liquids
The ionic liquids have several fascinating properties such as low vol-
atility (low vapor pressure), very high stability over wide range of pH
and temperature, capability to dissolve a wide range of organic and in-
organic compounds, capability to solubilize gases like H2, CO, CO2 etc.,
dependency of solubility on the nature of cations and anions, accelera-
tion of reaction rate for chemical transformation under microwave
heating, long time stability without decomposition and their high selec-
tivity [31,32]. These fascinating properties of ionic liquids make them
good candidature to replace conventional organic volatile solvents
with non-conventional ionic liquids that have been employed in variety
of chemical transformations such as solvents for synthesis of
nanomaterials and nanostructure, biochemical transformations, nucleo-
philic substitution reactions, electrodeposition of metals and semicon-
ductors and solvent extraction, separation of petrochemical relevance
mobile phase converter in HPLC, catalyst in various chemical and bio-
chemical transformations, dye sensitizer for solar cells, oil shale process-
ing, etc. (Fig. 2) [31,32].
1.4.2. Classification of ionic liquids
The ionic liquids can be classified into several categories on various
bases. Hajipour and Refiee [33] have classified the ionic liquids into
eleven classes namely, neutral ionic liquids, acid ionic liquids, basic
ionic liquids, ionic liquids with amphoteric anions, functionalized ionic
liquids, protic ionic liquids, chiral ionic liquids, supported ionic liquids,
bio-ionic liquids, poly-ionic liquids, and energetic ionic liquids and
also have described common feature and properties of these ionic liq-
uids. However, Suresh and Sandhu [32d,33] classified ionic liquids into
only two classes namely, cationic and anionic ionic liquids. They were
further subdivided anionic ionic liquids into several subclasses namely,
borates, dicyanamide (DCN), halide, bis(trifluoromethylsulfonyl)imide
(NTF), nonaflate (NON), phosphate, sulfate, sulfonate, thiocyanate
(SCN), tricyanomethide (TCC) based anionic liquids. Some common
classes of ionic liquids with examples and their salient features are de-
scribed in Table 1.
1.5. Comparison between organic inhibitors and ionic liquids
Over past two decades corrosion inhibition using ionic liquids (ILs)
has experienced an outstanding growth and there are abundant exam-
ples on corrosion inhibitions are available that have been effectively
carried out in different corrosive media. Although, traditional volatile
compounds have been most extensively used as corrosion inhibitors
in several industries, however, most of them are toxic to living being
and environment [34–36]. In view of this, ionic liquids (ILs) have been
used extensively in recent years. Ionic liquids have several advanta-
geous physiochemical properties including non-toxic, high conductivi-
ty, non-flammability, as well as high thermal and chemical stability
[23–33]. One of the most significant characteristics of ionic liquids is
their environmental friendly and non-hazardous nature due to their
non-negligible vapor pressure. Unlike to traditional volatile corrosion
inhibitors, due to their extremely low vapor pressure these compounds
will not evaporate and will not contaminate the surrounding environ-
ment [37,38]. Additionally, sometimes the use of organic inhibitors par-
ticularly polymeric and high molecular weighted organic compounds is
limited due to their extremely low solubility in the polar corrosive
media [39–42]. However, ionic liquids are highly soluble in the polar
corrosive environments due to their ionic nature [43]. Further, there is
limitless prospect of suitably modifying the structure of the anion and
cation of any given ionic liquids delivers an unlimited amount of poten-
tial derivatives having numerous physiochemical properties, while this
type of modification is not possible with volatile corrosion inhibitors. In
summary, the use of ionic liquids as corrosion inhibitors is preferred as
compared to traditional volatile (toxic) corrosion inhibitors due to their
several advantageous physiochemical properties including their high
solubility, non-toxic, high conductivity, non-flammability, less volatility
as well as high chemical stability and more importantly due to their
“green and sustainable” nature.
2. Ionic liquids as corrosion inhibitors
Several fascinating properties of the ionic liquids make them ideal
candidates to replace the tradition corrosion inhibitors that have several
adverse effects on environment and living beings. Recently, a large
number of works have been reported describing the use of ionic liquids
as corrosion inhibitors.
2.1. Ionic liquids as corrosion inhibitors for mild steel
The high mechanical strength and low cost make the iron and its al-
loys one of the best construction materials for several industries [44].
However, these materials are highly reactive and undergo corrosive
degradation during various industrial processes like acid cleaning, acid
descaling, acid etching, and acid pickling processes that require use of
additives in order to increase the lifespan of metal/alloy has used [45].
The use of organic compounds containing heterocyclic rings and polar
fictional groups such as amino, hydroxyl, methyl, methoxy, nitro, nitrile
etc. as additive is one of the most important alterative to protect metals
and alloys from these unsolicited reactions [44a,45]. These compounds
become effective by adsorbing over the metallic surface in which the
heteroatoms of polar functional groups and π- electrons of double and
triple bonds act as adsorption centers [44–46]. However, the use of
these highly volatile traditional toxic corrosion inhibitors is limited
due to increasing ecological awareness and strict environmental regula-
tions. In this regards consumption of “ionic liquids” as corrosion inhibi-
tors has become an important green alternative methods of corrosion
protection. The “ionic liquids” have several fascinating properties such
as lower melting point (lower that 100 °C), high polarity, low toxicity,
lower vapor pressure, very high thermal and chemical stability that
make them ideal candidature to replace highly volatile traditional
toxic corrosion inhibitors. Literature survey reveals that several synthet-
ic ionic liquids have been used as effective corrosion inhibitors for mild
steel (or carbon steel) in various electrolytic media. Likhanova et al. [47]
synthesized two ionic liquids namely, 1,3-dioctadecylimidazolium bro-
mide (ImDC18Br) and N-octadecylpyridiniumbromide (PyC18Br) using
conventional and microwave heating methods, respectively and inves-
tigated their inhibition performance on mild steel corrosion in 1 M
 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414 407

Table 1
classification of ionic liquids and their common features.

SN Types of ionic Some typical examples Remark

liquids
(Classes)

1 Neutral ionic Anions are associated with cations

liquids with weal electrostatic interaction,
low melting point, low viscosity,
used as inert solvent, good thermal
and electrochemical stability

2 Acidic ionic ionic liquids with acidic cations or

liquids acidic anion, enhanced solubility
in water, possess good catalytic
efficiency

3 Basic ionic These ionic liquids are basic in nature

liquids due to presence of on or more amine
group (1˚, 2˚ or 3˚ amine)

4 Functionalized Ionic liquids that has a covalently

ionic liquids bound functional group on the
cation and/or anion

5 Supported
Ionic Liquids

H2SO4 using several experimental techniques. They were observed that
studied ionic liquids acted as good corrosion for mild steel in aqueous
acid solution. Their adsorption on metallic surface takes place via chem-
isorption mechanism which obeyed the Langmuir adsorption isotherm.
Potentiodynamic polarization results revealed that studied ionic liquids
behaved as mixed type inhibitors. These authors were proposed a
mechanism of corrosion inhibition on the basis of results obtained
from SEM-EDX, XRD and Mossbauer analyses. Tuken et al. [48] studied
the inhibition performance of the 1-ethyl-3-methylimidazolium
dicyanamide (EMID) on mild steel corrosion in 0.1 M H2SO4 using
several experimental techniques. Results showed that EMID inhabits
metallic corrosion by adsorbing on the metallic surface which was con-
firmed by decreased values of Cdl and increased surface coverage in
presence of the inhibitor. The adsorption of the EMID over metallic sur-
face obeyed the Langmuir adsorption isotherm. Zhang and Hua [49] in-
vestigated the inhibition performance of two ionic liquids namely 1-
butyl-3-methylimidazolium chlorides (BMIC) and 1-butyl-3-
methylimidazolium hydrogen sulfate ([BMIM]HSO4) on mild steel cor-
rosion in 1 M HCl using electrochemical and weight loss experiments.
Results showed that the inhibition efficiency of both ionic liquids
408 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414

obeyed the order: ([BMIM]HSO4) N (BMIC). They were found that ad- Table 2 (continued)
sorption of these compounds on mild steel surface obeyed the Langmuir Electrochemical ---- CO2 [67]
techniques
adsorption isotherm. Potentiodynamic study suggested that both ionic
liquids acted as mixed type inhibitors. The effect of temperature (303–

Electrochemical), Langmuir 2M [68]

Table 2 AFM, dynamic adsorption HCl
ionic liquids as corrosion inhibitors for mild steel in different electrolytic media, their light scattering isotherm,
(DLS), FT-IR mixed type
mode of adsorption and techniques used for evaluation of the inhibition performance. and DFT
Synthetic Scheme and/ or chemical structure of ionic liquids Techniques Nature of Electro Ref.
adsorption lytic
media
Electrochemical Langmuir 3.5% [51]
and scanning adsorption NaCl Electrochemical, ---- NaCl [69]
electron isotherm, surface analysis (pH 3.8
microscopy Mixed type techniques and pH
6.8)
Electrochemical Flory-Hug 2M [70]
measurements gins H2SO4
Experimental, Langmuir 1M [52, adsorption
quantum adsorption HCl 53] isotherm,
chemical, isotherm, Mixed type
Monte Carlo Mixed type
simulation

Weight loss, Langmuir 1M [71]

electrochemical adsorption HCl
Gravimetric, Langmuir 1M [54] measurements, isotherm,
electrochemical, adsorption HCl QSAR, mixed type
Quantum isotherm, quantum
chemical Mixed type chemical
calculations calculations

Gravimetric, Langmuir 1M [55]

electrochemical adsorption HCl
isotherm, Electrochemical ---- CO2 [72]
Mixed type Capture
system
Electrochemical, Langmuir 1M [56]
Quantum adsorption HCl
chemical isotherm,
calculations Mixed type
(DFT)

Electrochemical Flory−Hug 2M [73]

and surface gins HCl
Electrochemical, Flory– 3.5% [57]
analysis adsortion
Scanning Huggins NaCl
isotherm,
electron adsorption
mixed type
microscopy isotherm,
Mixed type weight loss, Flory−Hug 0.5 M [74]
electrochemical, gins H2SO4
Weight loss, Langmuir 1M [58] SEM, and isotherm,
electrochemical, adsorption HCl quantum mixed type
SEM, AFM, isotherm, chemical
contact angle Mixed type calculation
method

Weight loss, --- Open [59]

electrochemical, and Weightloss, Langmuir 1M [75]
SEM, DFT control electrochemical, isotherm, H2SO4
methods led SEM, AFm mixed type
environ but IL3
ments behave as
cathodic
Weight loss, Langmuir 1M [60,
type
electrochemical adsorption HCl 61]
isotherm, Weight loss, Langmuir 1M [76]
Mixed type electrochemica isotherm, H2SO4
l, SEM mixed type
electrochemical, Langmuir 1M [62]
SEM adsorption HCl,
isotherm, 1M
Mixed type H2SO4
Electrochemica ---- Ethanol [77]
l polarization solution
electrochemical, Langmuir 1M [63] test, SEM
spectroscopic, adsorption HCl,
SEM, DFT, isotherm,
QSAR and Mixed type
Monte Carlo electrochemical, Langmuir 1M [78]
simulation spectroscopic isotherm, HCl
analyses, mixed type
quantum
chemical
calculations
Electrochemical, ---- 0.01M [64]
Immersion, NaCl
SEM

Gravimetric, Langmuir 1M [65]

electrochemical, adsorption H2SO4 Weight loss, ---- Arabian [79]
SEM isotherm electrochemical Gulf
Sea-
water

weight loss and Langmuir Product [66]

polarization adsorption ion
techniques isotherm, water
mixed
 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414 409

Table 2 (continued) isotherm. Polarization study suggested that investigated ionic liquid
weight loss, Langmuir 2M [80] acted as mixed type inhibitor. Tseng and coworkers [87] investigated
electrochemical adsorption H2SO4
isotherm, and the corrosion characteristics of carbon steel, 304 stainless steel (304 SS)
mixed type 3.5%
NaCl and pure titanium (Ti) in aluminum chloride–1-ethyl-3-
potentiodynamic Langmuir 1M [81] methylimidazolium chloride ionic liquid for the first time. These authors
polarization, adsorption HCl
linear isotherm, reported the active-to-passive transition behavior for CS sample. Among
polarization mixed type
and weight loss the tested materials 304 SS exhibited the maximum stability in the high
chloride environment. The most peculiar finding was that Ti was severally
corroded in the ionic liquid because it does not undergo passivation. The
ionic liquid in non-aqueous, low-oxygen and high halogen containing
Electrochemical, Langmuir 1M [82] showed different corrosion behavior and mechanism. Similar observation
SEM, EDX, adsorption HCl
contact angle isotherm, has been reported by other authors for different metals including copper,
measurement mixed type nickel and stainless steel [88]. Recently, the inhibition behavior of 1,4-
di[1-methylene-3-methyl imidazolium bromide]-benzene on mild steel
corrosion in 1 M H2SO4 have been studied using electrochemical and sur-
Weight loss Langmuir 1M [83] face analysis methods [89]. The ionic liquid under taken in the study in-
and adsorption HCl
electrochemical isotherm, hibits metallic corrosion by adsorbing on the surface which mechanism
methods mixed type
obeyed the Langmuir adsorption isotherm. The adsorption mechanism
Weight loss Langmuir 1M [84] was supported by SEM, EDX and AFM analyses. Polarization study reveals
and DFT adsorption HCl
studies isotherm that studied ionic liquid acted as mixed type inhibitor. The ongoing dis-
cussion reveals that although, several classes of ionic liquids have been
used as effective inhibitors for mild steel corrosion in various aggressive
Weight loss Langmuir 1M [85]
and adsorption HCl/ media, however, imidazole based ionic liquids have been used most ex-
electrochemical isotherm, 1M
methods mixed type H2SO4 tensively [47–53,58–65,67–81,83–85,92].

Electrochemical, Mixed 1M [90]

Quantum, type HCl 2.2. Ionic liquids as corrosion inhibitors for aluminum
surface
analysis
methods Aluminum is the second most commonly used metal due to its sev-
eral fascinating properties like its low atomic mass and negligible stan-
Weight loss, Langmuir 0.5M [91] dard electrode potential. Similar to mild steel, it is sensitive to corrosion
electrochemical adsorption H2SO4
methods isotherm, particularly in the aqueous alkaline medium which is attributed due to
mixed type
dissolution of protective surface film of aluminum oxide in presence of
Weight loss Langmuir 1M [92]
and adsorption H2SO4 hydroxyl ions (OH−) that makes very negative potential. Several organ-
electrochemical isotherm,
polarization mixed type ic and inorganic compounds have been used previously in order to pro-
methods
tect dissolution of protective surface oxide film and ultimately decrease
the corrosion rate. Moreover, recently several plants extracts have been
used as efficient corrosion inhibitors for aluminum. The criteria behind
selection of plant extracts as corrosion inhibitors is based on the fact
that they are environmental friendly and acceptable, readily available,
relatively less expensive, presence of several active constituents, and
can be isolated using simple extraction procedures. However, employ-
ment of the ionic liquids as corrosion inhibitors is limited as literature
333 K) was also investigated on both the ionic liquids. Finally, several survey reveals that only few works are available describing the corro-
activation and thermodynamic parameters such as energy of activation sion inhibition performance of ionic liquids. Zhang and Hua [93] studied
(Ea), enthalpy of activation (ΔH), entropy of activation (ΔS), adsorption the inhibition performance of few newly synthesized ionic liquids namely 1-
constant (Kads) and Gibb's standard free energy (ΔG°) were calculated in butyl-3-methylimidazoliumchlorides (BMIC), 1-hexyl-3-methylimidazolium
order to explain the mechanism of adsorption and corrosion inhibition of chlorides (HMIC) and 1-octyl-3-methylimidazoliumchlorides (OMIC) on alu-
both the ionic liquids. Zheng et al. [50] studied inhibition performance of minum corrosion in in 1 M HCl using electrochemical and weight loss
two purchased ionic liquids namely 1-octyl-3-methylimidazolium bro- methods. Results showed that inhibition efficiencies of studied ionic liquids
mide ([OMIM]Br) and 1-allyl-3-octylimidazolium bromide ([AOIM]Br) increase with increasing their concentration and obeyed the order:
on mild steel corrosion in 0.5 M H2SO4 using weight loss, electrochemical, OMIC N HMIC N BMIC. Potentiodynamic study revealed that all ionic liquids
scanning electron microscopy (SEM) and Quantum chemical calculations acted as mixed type inhibitors. Moreover, adsorption of these ionic liquids
techniques. Both ionic liquids were purchased from Lanzhou Green chem on aluminum surface followed the Langmuir adsorption isotherm. Several ki-
ILS, LICP.CAS.China. Results showed that both the ionic liquids acted as netic and thermodynamic parameters were also derived by these authors in
good corrosion inhibitors and their adsorption on the metallic surface order to provide the mechanism of corrosion inhibition. Shetty and Shetty
obeyed the El-Awady thermodynamic–kinetic model. Potentiodynamic [94] reported an ecofriendly approach of corrosion protection of 6061 Al-15
results suggested that both ionic liquids acted as slightly cathodic type in- alloy by 1,3-bis(2-oxo-2-phenylethyl)-1H-imidazol-3-ium bromide (OPEIB)
hibitors. Table 2 represents the corrosion inhibition properties of several in 0.1 M H2SO4 solution using electrochemical impedance spectroscopy and
other ionic liquids that have been employed as inhibitors for mild steel potentiodynamic polarization, scanning electron microscopy (SEM) and en-
corrosion in electrolytic media [51–85]. The chitosan based ionic liquid ergy dispersive X-ray (EDX) spectroscopic methods. Results showed that
was synthesized using oleic acid and p-toluene sulfonic acid and its corro- OPEIB acted as good corrosion inhibitors and its inhibition efficiency increases
sion inhibition efficiency was determined using several electrochemical with concentration. Several activation and thermodynamical parameters
measurements [86]. Results of the investigated study revealed that pres- were calculated in order to explain the mechanism of adsorption and corro-
ence of the ionic liquid in the chloride containing corrosive medium de- sion inhibitors. Adsorption of the OPEIB on aluminum surface obeyed the
creased the rate of metallic dissolution as well as hydrogen evolution. Temkin adsorption isotherm. Potentiodynamic study revealed that studied
Adsorption of the ionic liquid followed the Langmuir adsorption ionic liquids acted as mixed type inhibitor. Arellanes-Lozada et al. [95]
410 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414
synthesized three poly(ionic liquid)s (PILs), namely (poly(1-vinyl-3-dodecyl-
imidazolium) (PImC12), poly(1-vinyl-3-octylimidazolium) (PImC8) and
poly(1-vinyl-3-butylimidazolium) (PImC4) hexafluorophosphate) using im-
idazole with different alkylic chain lengths and studied the inhibition proper-
ties of these ionic liquids on aluminum alloy AA6061 in 0.1–1.0 M H2SO4
solution using weight loss tests, polarization resistance measurements and in-
ductively coupled plasma optical emission spectroscopy. The inhibition effi-
ciencies of these inhibitors obeyed the order: (PImC12 N PImC8 N PImC4).
Adsorption of these ionic liquids followed the Langmuir adsorption isotherm.
Polarization study suggested that investigated ionic liquids acted as mixed
type inhibitors. Four newly synthesized quaternary ammonium based surfac-
tants in the series of hexanediyl-1,6-bis-(diethyl alkyl ammonium bromide),
designated as CmC6Cm(Et)·2Br (m = 10, 12, 14, 16), were synthesized and
evaluated as inhibitors for aluminum corrosion in 1 M hydrochloric acid solu-
tion using weight loss, gasometric and SEM methods [96]. Results showed
that all studied surfactants act as good inhibitors for acidic corrosion of alumi-
num and their inhibition performance increases with increasing carbon chain
length at same concentration. They inhibit corrosion by becoming adsorbate
at metal/electrolyte interfaces and their adsorption on metallic surface obeyed
the Langmuir adsorption isotherm. Trombetta et al. [97] studied the stability
of the aluminum in 1-butyl-3methylimidazolium tetrafluoroborate ionic liq-
uid and ethylene glycol mixtures using electrochemical impedance spectro-
scope (EIS). These authors observed that there is decrease in polarization
resistance and increase in the capacitance related with the passive oxide di-
electric properties on increasing the ethylene glycol and/or water content in
the mixtures. Presence of salts namely Na2B4O7.7H2O and NaH2PO4 in the
mixtures, stabilize the oxide payer form over the metallic surface and thereby
reduce the changes of metallic corrosion. The inhibition behavior of 1,3-bis(2-
oxo-2-phenylethyl)-1H-imidazol-3-ium bromide (OPEIB) on 6061 Al-15 vol.
pct. SiC(p) composite in 0.1 M H2SO4 acid solution was studied by Shetty and
Shetty [98] using electrochemical (EIS and PDP), SEM and EDX methods. The
investigated ionic liquid exhibits the maximum efficiencies of 96.7% and 94%
using PDP and EIS methods, respectively. Potentiodynamic polarization study
further reveals that studied ionic liquid behaves as cathodic type inhibitor and
its adsorption on the composite surface followed the Temkin adsorption. Li et
al. [99] study the inhibition behavior of tetradecylpyridinium bromide (TDPB)
on aluminum corrosion in 1 M hydrochloric acid solution using weight loss
and electrochemical methods. Results of the investigation showed that
TDPB inhibits the aluminum corrosion by adsorbing on the metallic surface.
The adsorption of the TDPB followed the Langmuir adsorption isotherm. Po-
larization study suggested that TDPB acts as cathodic type inhibitor for acidic
aluminum corrosion. Bermudez and coworkers [100] investigated the surface
interactions of seven alkylimidazolium ionic liquids with aluminum alloy Al
2011using immersion test. The immersion experiments for aluminum corro-
sion was carried out in 1 wt% and 5 wt% of 1-ethyl,3-methylimidazolium tet-
rafluoroborate (IL1) in water. Results showed that neat solution of ionic
liquids did not cause any corrosion. The inhibition behavior was discussed
on the basis of SEM, EDX, XPS and XRD techniques.
2.3. Ionic liquids as corrosion inhibitors for copper and zinc
Copper and its alloys have been extensively employed in industries
for various applications such as building construction, electricity, elec-
tronics, coinages, ornamental and formation of industrial equipment
due to their relatively good thermal, electrical, mechanical and corro-
sion resistance properties [101]. However, in presence of aggressive an-
ions like chloride, sulfate and nitrate these materials undergo sever
attack resulting into loss of these materials due to corrosion occurs
[102,103]. Several attempts have been used to retard these unwanted
processes among which use of organic inhibitors is one of the best
methods of corrosion protection. In view of this several classes organic
compounds such as triazole, thiazole, imidazole, tetrazole, indole and
its derivatives have been extensively used as corrosion inhibitors for
cooper and its alloys particularly in aggressive acid solutions. Similarly,
zinc and its alloys have been used extensively particularly in petroleum
and chemical industries [102]. However, these industries are
characterized by a constant fluctuation in the pH (low and high pH),
which results into loss of mechanical properties of these materials due
to corrosion. Similar to corrosion protection of other metals and alloys,
the use of organic corrosion inhibitors is one of the best methods of cor-
rosion protection of zinc. These inhibitors become effective by
adsorbing on the metallic surface in which lone unshared electron
pairs of heteroatoms and π-electrons of double, triple and aromatic
rings act as adsorption centers. Similar to the aluminum the use of
ionic liquids as corrosion inhibitors for copper and zinc is also limited
as literature survey revealed that only few ionic liquids have been
used as corrosion inhibitors for these materials. Qi-Bo and Yi-Xin
[104] newly synthesized three ionic liquids namely 1-butyl-3-
methylimidazolium hydrogen sulfate ([BMIM]HSO4), 1-hexyl-3-
methylimidazolium hydrogen sulfate ([HMIM]HSO4), and 1-octyl-3-
methylimidazolium hydrogen sulfate ([OMIM]HSO4) and studied their
inhibition efficiency on copper corrosion in 0.5 M H2SO4 using electro-
chemical impedance spectroscopy and potentiodynamic polarization
techniques. The inhibition efficiency of the ionic liquids follows the
order: [OMIM]HSO4 N [HMIM]HSO4 N [BMIM]HSO4. Results obtained
by these authors showed that adsorption of the studied ionic liquids
followed the Langmuir adsorption isotherm. Polarization study re-
vealed that these ionic liquids behaved as mixed type inhibitors. Gabler
et al. [105] studied the inhibition performance of two ionic liquids
namely (2-hydroxyethyl)-trimethyl-ammonium (IL1) and Butyl-
trimethyl-ammonium (IL2) with identical anions; bis(trifluoromethyl-
sulfonyl)imide on CuSn8P and steel 100Cr6, purchased from Metal Su-
permarkets (Brunn am Gebirge, Austria) using inductively coupled
plasma optical emission spectrometry (ICP-OES) scanning electron mi-
croscopy (SEM) with energy dispersive X-ray spectrometry (EDX) and
X-ray photoelectron spectroscopy (XPS) in water in the absence and
presence of 1.5% of the ionic liquids. Espinosa et al. [106] studied the in-
hibition performance of two new protic (PIL) and four aprotic (APIL)
namely triprotic di[(2-hydroxyethyl)ammonium] succinate (MSu)
and the diprotic di[bis-(2-hydroxyethyl)ammonium] adipate (DAd)
and 1-ethyl-3-methylimidazolium phosphonate ([EMIM]EtPO3H); 1-
ethyl-3-methylimidazolium octylsulfate ([EMIM]C8H17SO4); 1-hexyl-
3-methylimidazolium tetrafluoroborate ([HMIM]BF4) and 1-hexyl-3-
methylimidazolium hexafluorophosphate ([HMIM]PF6) on corrosion
of copper using contact angle, SEM, AFM, EDX and XPS analyses.
Manamela et al. [106] studied the inhibition performance of two ionic
liquids; 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF− 4 ]
and 1-decyl-3-methylimidazolium tetrafluoroborate [DMIM][BF− 4 ] on
corrosion of zinc in 1 M HCl using gravimetric analysis and theoretical
Density Functional Theory (DFT) approach, using the B3LYP functional.
Results showed that both the ionic liquids acted as good corrosion in-
hibitors and their inhibition efficiencies increases with increasing
their concentrations. The inhibition efficiencies of the ionic liquids
obeyed the order: [DMIM][BF− −
4 ] N [BMIM][BF4 ]. Values of activation en-
ergy (Ea) and enthalpy of activation (ΔH) suggested that both the ionic
liquids adsorbed over the surface through physisorption mechanism.
Adsorption of these ionic liquids on metallic surface followed the Lang-
muir adsorption isotherm.
2.4. Ionic liquids as corrosion inhibitors for magnesium
Unlike active light metals such as aluminum and titanium, magnesium
based alloys do not form protective passivating film. Moreover, these alloys
easily react with the components of environment to from hydroxides, ox-
ides, carbonates film that are highly porous, inhomogeneous and poorly
bonded that cannot provide satisfactory protection to the metals against
corrosion. Among the available methods of corrosion protection, organic
coating is one of the best methods. Huang et al. [107] has presented an
early review on the corrosion protection of magnesium by some ionic liq-
uids. However, present review article is describing the few recent advances
in the utilization of ionic liquids as corrosion inhibitors. Sun et al. [108] have
investigated the inhibition effect of six phosphonium cation based ionic
 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414 411

liquids (ILs)namely, tetradecyltrihexyl phosphonium diphenylphosphate (1), 4. Mechanism of corrosion inhibition

tetradecyltrihexyl phosphonium dibutylphosphate (2), tetradecyltrihexyl
phosphonium bis(2-ethylhexyl) phosphate (3), tetradecyltrihexyl phospho- Similar to most of the organic corrosion inhibitors, ionic liquids (ILs)
nium diisobutyl dithiophosphinate (4), tetradecyltrihexyl phosphonium inhibit metallic corrosion by blocking the anodic and cathodic sites
bis(2,4,4-trimethyl pentyl) phosphonate (5), and tetradecyltrihexyl present over the metallic surface [116–118]. Therefore, inhibition of
phosphonium O,O-diethyl dithiophosphate on magnesium alloys using metallic corrosion in presence of ionic liquids involves blocking of anod-
electrochemical and surface investigation methods. ic oxidative metallic dissolution as well as cathodic hydrogen evolution
reactions [117,118]. The mechanism of metallic (M) corrosion inhibi-
tion by ionic liquids in sulfuric acid has been described below. The inhi-
3. Ionic liquids as corrosion inhibitors: DFT study bition mechanism of metallic corrosion by ionic liquids in other protic
acidic solutions such as in HCl and HNO3 will be similar because of
Nowadays, several computational methods particularly, DFT based their similar nature. The only difference in their nature is that they pos-
quantum chemical calculations have been emerged as potential tools sess different counter ions (Cl−, NO− 3 ) rather than sulfate ion of sulfuric
for studying the interactions between inhibitors and metallic surface. acid. According to Likhanova et al. [118], anodic dissolution of metals
Superiority of the DFT based computational analysis is based on the (M) in aqueous acidic solution e.g. H2SO4) can be represented as follows
facts that these calculations provide mechanistic information about [118]:
metal-inhibitor interactions and can be performed for inhibitor mole-
cules even before their synthesis. The DFT calculations provide several M þ nH2 O↔MðH2 OÞnads ð1Þ
important parameters such as energies of highest occupied molecular
h i
orbital (EHOMO), lowest unoccupied molecular orbital (ELUMO), energy
MðH2 OÞnads þ SO4 2− ↔M ðH2 OÞn SO2−
4 ð2Þ
band gap (ELUMO − EHOMO = ΔE), global electronegativity (χ), global ads
hardness (η) and softness (σ), fraction of electron transfer (ΔN) and di- h i  
pole moment (μ). The values of these parameters are being utilized in M ðH2 OÞn SO2−
4 →M ðH2 OÞn SO4 ads þ 2e− ð3Þ
ads
order to explain the metal-inhibitor interactions. In general, value of
EHOMO is related with electron donating ability, while the value of  
ELUMO related with the electron accepting ability of the inhibitor mole- M ðH2 OÞn SO4 ads →M2þ þ OH− þ SO2−
4 þH
þ
ð4Þ
cules [44–46]. A higher value of EHOMO and lower value of ELUMO associ-
ated with high inhibition performance. The inhibition efficiency of However, in presence of ionic liquids, anodic reactions can be repre-
inhibitor increases with decreasing the energy band gap (ΔE). A sented as follows:
high value of global electronegativity (χ) is related with lower elec-
tron donating ability and therefore, the value of electronegativity M þ n H2 O↔MðH2 OÞnads ð5Þ
(χ) inversely related with the inhibition efficiency order [44–46]. In- h i
hibition efficiency of the inhibitor molecules decreases with increasing MðH2 OÞnads þ SO2− 2−
4 ↔M ðH2 OÞn SO4 ð6Þ
ads
the hardness (η) and decreasing the softness (σ). Generally, inhibition
performance of the inhibitor molecules increases with increasing their
þ −
dipole moment (μ), however, negative trends of the inhibition effi- MðH2 OÞn SO2−
4 ads þ ILsC →MðH2 OÞn SO4 ILsC ads ð7Þ
ciency is also reported by several authors [44–46]. Lastly, the value
þ
of electron transfer gives direct information about the relative extent MðH2 OÞn SO4 ILsC−
ads þ ILsC
of metal-inhibitor interactions. A high value of ΔN is associated with þ SO4 →ðMðH2 OÞn SO4 ILsC−
2− þ 2− þ
ads ILsC SO4 =ILsC ð8Þ
high charge transfer and therefore high inhibition efficiency [44–46,
71].
M þ X− ↔ðMX− Þads ð9Þ
The DFT based quantum chemical calculations have also been
employed to describe the adsorption behavior of some ionic liquids on  
the metallic surface. Our research group [71] studied the adsorption ðMX− Þads þ ILsC þ ↔ MX− ILsC þ ads ð10Þ
behavior of four imidazolium-based ionic liquids, namely 1-propyl-3-
methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([PMIM][NTf2), where, ILsC+ and X− represent the cationic counter part of the ionic liq-
1-butyl-3-methylimidazoliumbis(trifluoromethyl-sulfonyl) imide uids (mostly organic) and anionic counter part of the ionic liquid, re-
([BMIM][NTf2), 1-hexyl-3-methylimidazolium bis(trifluoromethyl-sul- spectively. It is important to me mention that the concentration of
fonyl) imide([HMIM][NTf2]), and 1-propyl-2,3-methylimidazolium sulfate ions is much higher as comared to the concentration of anionic
bis(trifluoromethyl-sulfonyl) imide ([PDMIM][NTf2]) on mild steel cor- counter part of the ionic liquids (X−) that results into formation of
rosion in 1 M HCl using experimental and quantum chemical calculations. [M(H2O) SO2−4]ads in larger proporsion than [MX−]ads. Nevertheless,
The inhibition efficiency of these ionic liquids follows the experimental these both anionic charged species attracted oppositively charged cat-
trend: [PDMIM][NTf2] N [HMIM][NTf2] N [BMIM][NTf2] N [PMIM][NTf2]. ionic counter part of the ionic liquids (ILsC+) by electrostatic force of at-
The values of EHOMO and ELUMO are well satisfied the experimental order traction (physisoprtion) and forms monomolecular layer as an insoluble
of inhibition efficiency. Results showed that [PDMIM][NTf2] exhibited complex on the metallic surface [118,119]. The adsortion of the ILsC+ on
the lowest value of ΔE and therefore related with the highest chemical metallic surface causes change in the surface polarity which induces the
reactivity and inhibition efficiency. The values of dipole moment (μ) adsorption of the sulfate and X− ions again which results into multimo-
and the molecular volume (MV) did not show any regular trends. lecular layer [118,120]. The multimolecular layers are stabilized by
However, the values of global softness (σ) again show that the Vanderwaal's cohesion force acting beteween organic moeity of the
[PDMIM][NTf2] is most soft molecule among the tested compounds ionic liquids which causes a more claosely adsorbed film at metal/elec-
thereby associated with highest chemical reactivity and inhibition trolyte interfaces. Generally, the cationic part (ILsC+) interacts with the
efficiency. The quantum chemical calculations study provides good metallic surface and forms the multimolecular layers while rest of the
insight about the inhibition mechanism and well supported the ex- part of the ionic liquids form hydrophobic hemi-micelles, ad-micelles
perimental order of inhibition efficiency. Similar observations were and/or surface aggregation [118,121]. The adsorbed multimolecular
reported for few other metals and alloys in several corrosive media layers of the ILs isolate the metal (M) from corrosive enviroment and
[109–115]. protect from corrosive dissolution.
412 C. Verma et al. / Journal of Molecular Liquids 233 (2017) 403–414
The cathodic hydrogen evolution reaction (HER) can be represented
by following simple stoichimmetry equation [122]:
H2 O þ 2e− ↔H2ðgÞ þ 2OH−
Generally, the hydrogen evolution reaction (HER) follows two very
common mechanism that is, Volmer-Heyrovsky mechanism represent-
ed by Eqs. (12) and (13) or according to the Tafel hydrogen evolution
mechanism represented by Eq. (14). In acidic medium, the Volmer-
Heyrovsky and –Volmer-Tafel hydrogen evolution mechanism have
been shown below [122–124]:
M þ H3 Oþ þ e− ↔MHads þ H2 O
MHads þ H3 Oþ þ e− ↔H2 þ M þ H2 O
MHads þ MHads ↔H2 þ 2M
During the first step of cathodic reactions hydrogen ions (or hydro-
nium ions) first adsorbed on the metallic surface by Volmer mechanism
followed by discharge of hydrogen gas by Heyrovsky and Tafel mecha-
nism represented by represented by Eqs. (13)–(14). All these reactions
do not occur with the same rate. Generally, a slow reaction step is
followed by a fast reaction step [125]. If the Volmer reaction is fast,
then Heyrovsky and/or Tafel reactions occur with slower rate and vice
versa. Presence of the organic corrosion inhibitors (ILs) in the corrosive
solution may retards/or slow down the formation of MHads or retard the
electron transfer to the hydronium ions and suppress the Heyrovsky
reactions (13). In general, in corrosive medium, the adsorbed hydrogen
on metallic surface recombined and evolved as the bubbles of hydrogen
gas. The formation of bubble and its evolution is the second step in the
HER. The formation of hydrogen gas either occurs through hydrogen
atom-atom combination as denoted by Volmer-Tafel Eq. (14) or may re-
sults through hydrogen atom-hydrogen ion combination as represented
by Volmer-Heyrovsky Eq. (13) [125].
In the presence of inhibitors (ILs), cathodic can be represented as
follows:
M þ ILsC þ þ e− ↔MðILsC Þads
Initially, adsorption of hydronium ions and evolution of hydrogen
gas occur at cathodic sites, simultaneously. At cathode, the cationic
part of ionic liquids (ILsC +) starts competing with hydrogen ions
for electrons [118,126]. In general, ILsC+ has larger molecular size
and therefore replaces greater number of water molecules from the
metallic surface. After, their adsorption cationic part of the ILs ac-
cepts electrons from the metal (M) which results into the formation
of electrically neutral ionic liquids (inhibitors). The neutral species
transfer (donation) their non-bonding (of heteroatoms) and π-elec-
trons into the d-orbitals of the surface metallic atoms resulting into
the formation of co-ordinate bonds between metal and ILs (chemi-
sorption) as reported for several organic conventional inhibitors
[118,120,127]. However, metals are already electron rich species;
this type of donation causes inter electronic repulsion which interns
results into transfer of electrons from d-orbitals of the surface metal-
lic atoms to antibonding molecular orbitals of the ILs (retro-dona-
tion). Both donation and retro-donation strengthen each other
through synergism [126,128].
5. Conclusions and future perspectives
On the basis of ongoing discussion it can be concluded that ionic
liquids are green and sustainable inhibitors for corrosion of metals
and alloys [23–25]. The superiority of the use of ionic liquids as cor-
rosion inhibitors as compared to traditional volatile (toxic) corro-
sion inhibitors is based on the fact that they possess several
fascinating properties such lower volatility, non-inflammability,
non-toxic nature, chemical stability, high solubility in the polar sol-
vents and their ability to easily adsorb on the metallic surface [23–
ð11Þ 33]. Extensive literature survey reveals that several ionic liquids
have been successfully investigated as inhibitors for ferrous and
non-ferrous metals and alloys in almost various kinds of corrosive
environments [34–123]. Similar to traditional volatile corrosion in-
hibitors, ionic liquids inhibit metallic corrosion by adsorbing on the
metallic surface. The adsorption of the ionic liquids generally fol-
lows the Langmuir [117,118,123,124]. In a few cases Temkin ad-
sorption isotherms have also been reported [94,99]. Adsorption of
the ionic liquids over the metallic surface results into formation of
ð12Þ protective film which isolates the metals (alloys) from the corrosive
environment and thereby inhibits corrosion [117,118]. Among the
ð13Þ several available ionic liquids, imidazole based ionic liquids have
been most extensively used [47–53,58–65,67–81,83–85,92–95].
ð14Þ The mechanism of corrosion inhibition by ionic liquids proposed
by Likhanova et al. [118] suggests that adsorption of ionic liquids
over the metallic surface results the replacement of previously
adsorbed water molecules from the metallic surface. Extensive dis-
cussion on the use of ionic liquids as corrosion inhibitors reveals
that several ionic liquids have been used for ferrous metal and
alloy; however their use for non-ferrous metals such as aluminum,
zinc, copper and magnesium is scare. Therefore, the use of ionic liq-
uids as corrosion inhibitors for non-ferrous materials should be
explored. Although, some reports [71,109–115] are available de-
scribing the adsorption behavior of ionic liquids on metallic surface
using DFT based quantum chemical calculations, however, the use
of this technique should be further explored owing to its green na-
ture to understand the mechanistic aspects of corrosion inhibition.
A comparison between traditional volatile inhibitors and ionic liq-
uids as inhibitors has been discussed in separate section. In summa-
ry, the use of ionic liquids as corrosion inhibitors is preferred as
compared to traditional volatile (toxic) corrosion inhibitors due to
their several advantageous physiochemical properties including
their high solubility, non-toxic, high conductivity, and non-flamma-
bility, less volatility as well as high chemical stability and more im-
portantly due to their “green and sustainable” nature.
ð15Þ
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