Journal of Electroanalytical Chemistry 823 (2018) 234–244

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Journal of Electroanalytical Chemistry

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Kinetics and mechanism of corrosion of mild steel in new types of ionic T

liquids
⁎
A.A. Kityka, , Y.D. Rublovaa, A. Kelmb, V.V. Malyshevb, N.G. Bannyka, I. Flis-Kabulskac
a
Ukrainian State University of Chemical Technology, Gagarin Ave., 8, Dnipro, Ukraine
b
Institute of Physical Chemistry, Polish Academy of Science, Kasprzaka 44/52, Warsaw, Poland
c
University of Cardinal Stefan Wyszynski, Wóycickiego 1/3, Warsaw, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: It has been established that the corrosion of mild steel in Ethaline and Reline (choline chloride based deep eutectic
Choline chloride solvents with the ethylene glycol and urea respectively) occurs with oxygen depolarization. The rate of corrosion
Deep eutectic solvents is significantly affected by the contact time of solvents with air and temperature. These two factors determine the
Impedance physicochemical properties and play a decisive role in the rate of diffusion of the depolarizer, and hence the
Voltammetry
corrosion rate. It is shown that both solvents are hygroscopic (for 160 h of contact with air in Ethaline 15 vol% of
Raman spectroscopy
water is detected, in Reline about 7 vol%). It is noted that the rate of corrosion of mild steel in Ethaline is
SEM
noticeably higher than in Reline. However, when operating temperatures of solvents becomes ≈70 ÷ 80 °C the
corrosion rates in Ethaline and Reline is very close to each other, which is primarily due to the convergence of the
viscosity parameters. SEM studies of the surface of the steel samples showed that in Ethaline and Reline solvents
corrosion occurs with the formation of pitting and elements of subsurface corrosion. The mechanism of corrosion
is established and the essential role of chloride anions in the formation of intermediate corrosion products is
shown.

1. Introduction dedicated to the investigation of their different properties and practical

The new class of ionic liquids called deep eutectic solvents (DESs)
has become widespread in recent decades [1–3]. DESs can be an al-
ternative to traditional toxic solvents currently used in different fields
of science and technology. DESs have a lot of advantages such as a lack
of toxicity, low volatility, incombustibility, thermal and chemical sta-
bility, the wide range of electrochemical stability. DESs are safe for
humans and environment and fulfil all requirements of “green chem-
istry” [1–6].
Choline chloride is one of the most popular components of DESs. It
is a quaternary ammonium salt which can form eutectic mixtures with
very low crystallization temperature with hydrogen bond donors such
as carbamide, carboxylic acids and polyols [7–11]. The most common
DESs based on choline chloride are Ethaline and Reline [12–15]. Ethaline
is a mixture of choline chloride with ethylene glycol in the molar ratio
1:2, and Reline is a mixture of choline chloride with carbamide in the
same molar ratio. It is important to add the fact that Ethaline and Reline
are aprotic solvents contrary to a mixture of choline chloride and car-
boxylic acids.
The vast majority of modern scientific literatures on DESs are
applications [1–3]. Only very few papers concentrate on metals dis-
solution in Ethaline and Reline [16, 17] and corrosion properties of these
solvents [18, 19]. However, the corrosion process affects almost all
aspects of modern life [20], and the full implementation of ionic liquids
is impossible without knowing how corrosion proceeds [21].
First, consider the anodic dissolution of metals in DES, since these
data are extremely important in the study of the corrosion of metals.
Abbott and coauthors [16] showed that 9 metals (Ag, Au, Fe, Co, Cu, Ni,
Pb, Sn and Zn) can be electrochemically oxidized in Ethaline, including
gold. They showed that for the majority of metals studied a quasi-
passivation of the metal surface occurs, primarily due to the formation
of insoluble films on the electrode surface. Film formation can block the
electrode surface, leading to a decrease in anodic current and hence
affecting the dissolution of metal. They emphasized that the formation
of passivating salt films can be decreased with stirring or by increasing
the electrolyte temperature, thereby increasing ligand transport to the
electrode surface. It should also be noted that for some metals (iron,
cobalt and nickel) the formation film is poorly soluble [16]. At the same
time the refractory metals like molybdenum and tungsten showed al-
most no passivation in Ethaline and Reline [17]. Abbass and Binder [17]

⁎
Corresponding author.
E-mail address: kitykanna7@gmail.com (A.A. Kityk).

https://doi.org/10.1016/j.jelechem.2018.06.018
Received 23 February 2018; Received in revised form 4 June 2018; Accepted 11 June 2018
Available online 15 June 2018
1572-6657/ © 2018 Elsevier B.V. All rights reserved.
A.A. Kityk et al.
noticed that the factor affecting dissolution process of molybdenum and
tungsten is the release of chloride ions and overall mechanism is ki-
netically controlled.
The corrosion of steel [18, 19], iron [19], aluminium [18, 19],
copper [18] and nickel [19] was investigated in Ethaline and Reline.
AlHazzaa with AlNashef [18] using linear polarization resistance and
Tafel plot measurements showed that Ethaline was more aggressive
towards steel, copper, and aluminium than Reline, and steel showed
passivity in the solution Reline. However, the authors did not give the
information about the steel grade that does not allow to be assured of
the shown results. Moreover, the results using linear sweep voltam-
metry and Tafel slope analysis obtained by Abbott et al. [19] showed
that Ethaline is less aggressive to aluminium and iron than Reline. Also
in [19], there are some controversial data about corrosion of mild steel
in DESs. The linear sweep voltammetry showed, that corrosivity of
Reline > Ethaline, at the same time according to EIS Ethaline is more
aggressive to mild steel than Reline. Due to such ambiguity in the pre-
sented results, as well as the fact that lack of knowledge about corrosion
of different constructional materials, impedes a wide application DESs
in the fields of science and industry it is necessary to study in more
detail the issue of corrosion of mild steel in these media. In the present
work, a complex approach for determination of kinetics and mechanism
of corrosion of mild steel in Ethaline and Reline was employed. Tem-
perature and time dependences of corrosion process were investigated.
2. Research methodology
2.1. Chemicals and materials
Choline chloride (Aldrich, purity > 98%) was recrystallized from
isopropanol then filtered and dried under vacuum. Ethylene glycol
(Aldrich, purity > 99%), urea (Aldrich, purity > 99%) were used as
they were received. Fischer Reagent solutions No. 1 and No. 2 (Pan-Eco,
Russia) was used as they were received. The working electrode was
made of mild steel (“Altair-D”, Dnepr), the composition of which is
presented in Table 1.
2.2. Preparation and Physicochemical properties of DESs
Ethaline and Reline were prepared by 24-h stirring of the compo-
nents: choline chloride with ethylene glycol in the molar ratio 1:2 for
Ethaline, and choline chloride with carbamide in the same molar ratio
for Reline. Stirring was carried out at temperature 75 °C until homo-
geneous colourless liquids were obtained. DESs were vacuum-filtered
through a sintered glass plate.
Hygroscopicity of DESs was evaluated by water absorption as a
function of the exposure time to the open air and determined by visual
titration according to the Karl Fischer method. The method consists in
the reaction of iodine with sulphur dioxide in the presence of water to
form hydroiodic acid and sulphuric anhydride in methanol and pyridine
[22].
The sample of the analyte was titrated with a Fischer reagent until a
reddish-brown colour appeared. The content of water (φ) in percent
was calculated by the formula:
VT⋅ρ25⋅100
φ= , The surface morphology of the samples was investigated using the
m s⋅1000 (1.1)
where V – Fischer reagent amount spent on the titration of the test
sample; Т – titre of Fischer's reagent; ms – sample weight, g; ρ25 –
Table 1
Composition of working electrode (w, %).
Material С Si Mn S P
Mild steel 0.180 0.110 0.510 0.008
Journal of Electroanalytical Chemistry 823 (2018) 234–244
density of the test solution at 25 °C.
The titre of the Fischer reagent was calculated using the formula
m H2O⋅100
T= ,
m s⋅1000 (1.2)
where is mH2O – the weight of the sample of water taken to prepare a
solution of water in methanol; VH2O – Fischer reagent amount spent on
the titration of 10 cm3 of water; V1 – Fischer reagent amount spent on
the titration of 10 cm3 of methanol.
Density (ρ) of investigated DESs was measured by pycnometrical
method (pycnometer volume 5 ml) and calculated using the formula:
mDES − m 0
ρ=
m H20 − m 0 (1.3)
where m0 – mass of the empty pycnometer; mH2O – mass of the pycn-
ometer filled with distilling water; mDES – mass of the pycnometer filled
with DESs.
Dynamic viscosity (η) of DESs was measured by the glass capillary
viscometer and calculated using the formula:
η = K⋅ρ⋅τ, (1.4)
where K – viscometer's constant; ρ – density of investigated liquid; τ –
time of the leaking of investigated liquid through a calibrated capillary.
Conductivity of DESs was measured in a glass cell with two parallel
platinum electrodes by Potentiostat/Galvanostat/ZRAReference 3000
(Gamry Instruments, Inc.) and calculated using the formula:
K
χ= ,
R (1.5)
where K – cell's constant (was determined by measuring the con-
ductivity of 0.02 M solution KCl); R is a resistance of cell with in-
vestigated liquid.
2.3. Voltammetric and EIS experiments
Electrochemical investigations were performed using Potentiostat/
Galvanostat/ZRA Reference 3000 (Gamry Instruments, Inc.) in three
electrodes glass cell. A 2-mm diameter mild steel rod sealed in teflon,
graphite electrode with a high surface area, and Ag|AgCl were used as
working, counter and pseudo-reference electrode respectively. Using
pseudo-reference electrode instead of classical Ag|AgCl reference elec-
trode is typical for measurements in such systems [23].
Voltammetric measurements were made under natural aeration
conditions, in temperature range of 25–80 °C, scan rate range of
20–500 mV*s −1. After each measurement electrode surface was
cleaned by polishing. All measurements were done with automatic IR
compensation. Due to the fact that the representation of the cyclic
voltammogram greatly complicated the understanding of the process, it
was decided to present a part of the cyclic voltammogram.
EIS measurements were performed at corrosion stationary potential
(Ecorr), in the frequency range of 105 ÷ 10−2 Hz, the amplitude of po-
tential alternation 5 mV. Obtained Nyquist plots were fitted with Gamry
Echem Analyst software (by Levenberg-Marquardt Method).
2.4. Scanning electron microscopy (SEM)
scanning electron microscope FEI Nova NanoSEM 450 operating at 5 kV
in a field-free mode with the use of Everhart-Thornley detector. Prior to
observation, samples were mounted on aluminium stubs using adhesive
Cr Ni Cu As N
0.013 0.030 0.020 0.030 0.003 0.011
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A.A. Kityk et al. Journal of Electroanalytical Chemistry 823 (2018) 234–244

carbon tape and silver paste. All samples were observed without any
sputtering.

2.5. Raman spectroscopy

Raman spectroscopy was employed for identification of corrosion

products. Mild steel flat samples were immersed into Ethaline and Reline
for 30 days at ambient temperature. After removal from DESs, samples
were washed with methanol and dried. The sample immersed in dis-
tilled water and sample stored in the air were used as control samples.
Measurements were carried out using a Renishaw in Via Raman system
equipped with a 532 nm solid-state laser. The light from the laser
passed through a line filter and was focused on a sample mounted on an
X–Y–Z translation stage with a ×50 microscope objective of
NA = 0.25. The microscope was equipped with 1200 grooves/mm
grating, dielectric cut-off filters, and a 1024 × 256 pixel Peltier-cooled
RenCam CCD detector, which allowed registering the Stokes part of
Raman spectra. The spectral resolution was 4–6 cm−1 and the wave-
number accuracy was 2 cm−1, which was calibrated with the
520.6 cm−1 band of the silicon crystal. The experiments were per- Fig. 1. Corrosion potential of mild steel in Ethaline and Reline vs. time (mea-
formed under ambient conditions using backscattering geometry. For sured at 25 °C).
every sample, three randomly chosen spots in different areas of the
sample were selected, for which area of 28 × 32 μm was mapped every
4 μm, resulting in 56 spectra (168 spectra per sample). The obtained
spectra were processed with Renishaw Wire 3.4 software.

2.6. Statistical processing of measured values

The processing of the measured values was carried out by a point

statistical evaluation [24]. All measurements were repeated succes-
sively at least three times. The measured values were averaged, the
standard deviation Δx was calculated using the formula [24]:

3 3 2
∑ ⎜⎛xi − ∑ xi/3⎟⎞
i=1 ⎝ i=1 ⎠
Δx
2 (1.6)

The value of Δx did not exceed 5%.

3. Results and discussion

3.1. Corrosion potential of mild steel in Ethaline and Reline: Time
dependence. Hygroscopic of solvents
The time dependence of the open circuit potential (corrosion po-
tential Ecorr) of the steel electrode in Ethaline and Reline is shown in
Fig. 1. As can be seen from the presented data, the establishment of a
stationary potential takes some time.
In region I of Fig. 1, the change in Ecorr occurs quite sharply, which
may be due to the dissolution of the oxide film formed in the air on the
steel surface, or due to the interaction of DESs molecules with the
electrode surface. The sharp shift in the corrosion potential of steel
(Fig. 1. region I) in the negative direction is observed in both Ethaline
and Reline.
In region II of Fig. 1, the values of stationary potentials of steel in
Ethaline and Reline are stabilized and stay practically unchanged.
However, prolonged experiments showed the occurrence that of a fur-
ther decrease Ecorr (Fig. 1. region II). A significant and abrupt change in
the corrosion potential occurs during the first 72 h (Fig. 1. region II),
whereas after about 72 h the change in potential is not significant
(Fig. 1. region III). Such dependence is related to a change in the
composition of solvents. The titration of Ethaline and Reline according to
Karl Fischer's method allowed to establish that these ionic liquids are
very hygroscopic (Fig. 2). In the region of 72 h the characteristic in-
flexion is observed, which is similar to the dependencies of the corro-
sion potential vs. time (compare Figs. 1 and 2). Thus, such behaviour
Fig. 2. The rise of water content in Ethaline and Reline vs. time (measured at
25 °C).
can be caused by the change of water content in the solutions.
The appearance of water in solvents leads to a change in the phy-
sicochemical properties of Ethaline and Reline, for example, the density
and viscosity of solvents decreased and their conductivity is raised
(Fig. 3). Interesting those physicochemical properties of Ethaline and
Reline with 20% of water were almost the same.
The increasing of water content in Ethaline and Reline change not
only the nature and properties of the ionic liquids, but also effects on
their corrosion activity to mild steel. To prove or disprove our hy-
pothesis, we conducted corrosion tests of mild steel in solvents under
conditions of short-term (the region II in Fig. 1) and long-term contact
(the regions II and III in Fig. 1) of steel samples with corrosive media.
3.2. Features of corrosion process under conditions of short contact of steel
with Ethaline and Reline solvents (region II in Fig. 1). Voltammetric
measurements and effect of temperature
Voltammetric studies were carried out after a short immersion
(conditions for the region II in Fig. 1). Fig. 4 shows voltammograms
(VAG) of the steel electrode in Ethaline and Reline, obtained after im-
mersion for 10 min holding until stabilization of the stationary poten-
tial. The potential at that time is referred to as holding until

236
A.A. Kityk et al.
Fig. 3. Dependence of density (a), dynamic viscosity (b) and conductivity (c) of Ethaline and Reline on the amount of water (measured at 25 °C).
stabilization of the open circuit potential (OCP). The values of OCP
(Ecorr, mV) are presented in Table 2.
Potential scanning was carried out from the OCP to the cathodic
region, and then to the anodic one. In the cathodic region of the VAG, a
small limiting current is observed (~10–20 mA/m2), presumably asso-
ciated with the reduction of dissolved oxygen. At potentials more ne-
gative than −1.2 V, current of the hydrogen evolution is observed.
In the anodic region (at potentials more positive than ~−0,2 V) the
current of active dissolution of the steel electrode is observed, which
after reaching maximum decreases, indicating passivation of the elec-
trode surface.
The passivation of the steel surface to a passive state in the studied
solvents is probably connected with the formation of hardly soluble iron
compounds on the metal surface known as “saline” passivation. Ferric
chloride and hardly soluble iron complexes can be formed compounds
because iron, being a transition element, is a typical complexing agent.
These complexes might be formed similarly as in DESs there are formed
nickel complexes involving ethylene glycol (Eg) [Ni(Eg)3]2+,
[NiCl3(Eg)3]−, as well as chloride complexes [NiCl4]2− [25–27].
The curves in Fig. 4 show that at all scanning speeds anodic currents
in the Ethaline solvent are higher than those in Reline. As the potential
scanning rate increases, the peak currents also increase. The depen-
dence of the peak current vs. v1/2 is linear both for the Ethaline and
Reline solvents, which is typical for processes controlled by diffusion.
The diffusion control of the anodic process is also indicated by the
Semerano diagnostic criterion (Xv), which, in fact, is the angular
Fig. 4. VAG of steel electrode in the solvents Ethaline (а) and Reline (b), obtained at different scanning rates of the potential, (v 1–20, 2–50, 3–100, 4–200, 5–500 mV/
s; t = 25 °C; τ = 10 min); ip is peak current.
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Journal of Electroanalytical Chemistry 823 (2018) 234–244
coefficient of the logarithmic dependence of the peak current (ip) on the
scanning speed of the potential (v):
Xv = (Δ⋅lg⋅ip/Δ⋅lg⋅v)t,c (2.1)
As it turned out (Fig. 5), for the considered anodic dissolution
process of steel in Ethaline and Reline, the Xv values are close to 0.5,
which confirms the diffusion nature of the maximum dissolution cur-
rent.
The effect of temperature on VAG can be estimated from Fig. 6.
Fig. 6 shows that an increase in temperature leads to an increase of
the anodic currents in both solvents. The dependence of peak current on
temperature is linear. At all temperatures, the dissolution rate of steel in
Ethaline is significantly higher than that in Reline.
The increase of the currents with the increasing temperature (Fig. 6)
can be a consequence of two factors the decrease in the viscosity which
leads to faster diffusion and to the higher solubility of passivating
product.
On the basis of the obtained polarization curves and their processing
(the processing example is shown in Fig. 7), the quantitative parameters
of the corrosion process are calculated and the influence of temperature
on them is analyzed (Table 2).
Table 2 presents corrosion potential Ecorr and corrosion current icorr
determined from the Tafel plot of the VAG at various potentials. The
results show that the corrosion potentials in the entire temperature
range are in Ethaline more negative, compared to the potentials in Re-
line. Also, the corrosion rates are higher in Ethaline. This indicates a
A.A. Kityk et al. Journal of Electroanalytical Chemistry 823 (2018) 234–244

Table 2
Corrosion potentials (Ecorr) and corrosion currents (icorr) of steel electrode in Ethaline and Reline solvents.
t°C Ecorr, mV Log Icorr Icorr∙108, A icorr, mА/m2 Ecorr, mV Log Icorr Icorr∙108, A icorr, mА/m2

Ethaline Reline

25 −459 −7.432 3.698 11.777 −445 −7.564 2.729 8.692

30 −463 −7.367 4.295 13.678 −453 −7.523 2.999 9.552
40 −469 −7.355 4.416 14.064 −462 −7.496 3.192 10.167
50 −476 −7.341 4.560 14.522 −466 −7.485 3.273 10.425
60 −483 −7.293 5.093 16.220 −470 −7.445 3.589 11.431
70 −490 −7.291 5.117 16.296 −484 −7.327 4.710 15.097
80 −498 −7.253 5.585 17.787 −496 −7.268 5.395 17.183

cathodic current characterizes the reduction of oxygen on the steel

Fig. 5. The logarithmic dependence of the peak current in DESs on the potential
scanning rate (t = 25 °C).
greater corrosivity of Ethaline. However, the values of the corrosion
potentials and corrosion rates of steel in the DESs are approaching each
other with the increasing temperature. At high temperatures the cor-
rosive activities of Ethaline and Reline towards mild steel become
practically the same.
Ethaline and Reline, which were used in the work, are aprotic sol-
vents. Thus, depolarizer in the corrosion process can be either compo-
nent of these ionic liquids (carbamide, ethylene glycol, choline
chloride) or oxygen, which is dissolved due to the natural aeration of
solvents. The analysis of the literature data and obtained VAG showed
that the electroreduction of the solvent components begins at suffi-
ciently large negative potentials of ~−1.2 V, and a small initial limiting
surface.
It can be concluded that the rate of steel corrosion in these solutions
will be determined by the concentration of dissolved oxygen and the
speed of its delivery to the surface of the corroded sample, as well as the
rate of removal of corrosion products from the surface and exposure of
new surface areas to corrosion.
The corrosion activation energy (Еа corr) of the steel electrode, cal-
culated from the temperature dependences of the corrosion current,
were 5.61 kJ/mol and 10.03 kJ/mol in Ethaline and Reline, respectively.
These values are anomalously low for the activation energy (usually the
activation energy of the corrosion process, which is limited by delivery
of the depolarizer to the surface of the corroding sample, is ~20 kJ/
mol). Obviously, parameters Еа corr can be considered only as effective
activation energies or as temperature coefficients of corrosion rate. It is
possible to explain their magnitudes by taking into account the fact that
two factors, such as the concentration of dissolved oxygen and its dif-
fusion coefficient, simultaneously change with temperature, and these
factors have an opposite effect on the corrosion rate.
The amount of dissolved oxygen and the rate of its diffusion in a
solvent are quantities that directly depend on the physicochemical
properties of the liquid, hence the differences in the corrosivity of
Ethaline and Reline towards mild steel are primarily due to differences in
their physicochemical properties.
Fig. 8 shows the temperature dependences of the main physico-
chemical parameters of the DESs: the density (Fig. 8a), the conductivity
(Fig. 8b), and the dynamic viscosity (Fig. 8c).
An increase in the temperature leads to a decrease in the density of
DESs (Fig. 8a), which can easily be explained by an increase in the
mobility of ions and molecules in ionic liquids due to the destruction of
hydrogen bonds between them.
Throughout the entire temperature range, a linear character of the
density variation is observed. Density of the Reline solution was

Fig. 6. VAG for steel electrode in Ethaline (a) and Reline (b), obtained at 25 °C (1); 30 °C (2); 40 °C (3); 50 °C (4); 60 °C (5), 70 °C (6); 80 °C (7); v = 50 mV/s.

238
A.A. Kityk et al.
Fig. 7. Tafel plots for cathode and anode regions of the VAG for steel electrode in Ethaline (a) and Reline (b), obtained at 25 °C.
significantly higher than that for Ethaline. Apparently, this is due to
different nature and strength of the interaction of the components that
formed by the investigated DESs.
It is known that DESs contain vacancies (so-called “holes”), the size
of which determines the density of the liquid [28]. Thus, we can con-
clude that Reline, having a higher density, is characterized by sig-
nificantly smaller vacancies radii in comparison with Ethaline solvent.
Fig. 8b shows that the increase in the mobility of ions and molecules
of the DESs with the increasing temperature is also reflected in the
temperature dependences of the conductivity. The conductivity of
Ethaline solvent over the entire temperature range is greater than the
conductivity of the Reline solvent, being a consequence of the different
structure of the DESs.
The different size of “voids” or vacancies in Ethaline and Reline so-
lutions also affects the solvents viscosities (Fig. 8c). Fig. 8c shows that
the viscosity of Reline solvent at low temperatures (up to 40 °C) exceeds
the viscosity of the Ethaline mixture several times. Increasing the sol-
vents temperature (over 40 °C) leads to a convergence of the viscosities
of Ethaline and Reline. We observe that at a temperature of 70–80 °C the
viscosities of the DESs become practically the same.
It becomes evident that there exists a relationship between the
viscosity of the solvents, the rate of diffusion of the depolarizer, and the
rate of corrosion. Differences in the physicochemical properties of DESs
predetermine differences in the diffusion rate of oxygen dissolved in
liquids, which in turn leads to differences in its concentration at the
surface of the corroding sample and, as a consequence, to differences in
the corrosion rates of steel in Ethaline and Reline. As the experiment has
shown, the physicochemical parameters of these ionic liquids converge
when the temperature increases, which leads to a convergence of the
corrosion rates.
Fig. 8. The temperature dependence of density (a), conductivity (b), and dynamic viscosity (c) of Ethaline and Reline.
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Journal of Electroanalytical Chemistry 823 (2018) 234–244
3.3. Features of corrosion process under conditions of prolonged contact of
steel with Ethaline and Reline solvents (region III Fig. 1). Mechanism of the
corrosion process, the role of chloride ions
In the investigation of steel corrosion in DESs, the features of the
corrosion process under conditions of prolonged contact of steel sam-
ples with the investigated liquids (region III of Fig. 1) are of consider-
able importance. Only under conditions of prolonged immersion of steel
in DESs, it is possible to estimate the “true” corrosive activity of these
solvents and to approximate the model experiment to the real operating
conditions of industrial equipment.
The SEM images (Fig. 9) show pitting and damages characteristic of
subsurface corrosion (similar to blistering of the metal surface), after
prolonged contact of the steel samples with Ethaline and Reline solvents.
Subsurface corrosion is well be seen especially at the magnification of
10,000× (Fig. 10).
The analysis of the time dependence of the corrosion potential and
the obtained SEM images allows concluding that the most significant
changes on the sample surface occur on the first day of the immersion
when potential strongly change. There is no essential difference in the
appearance of samples corroded in Ethaline and Reline. Corrosion pro-
ducts in water are probably iron oxides or hydroxides (Fig. 10).
Changes in corrosive activity with time were established with the
using of Electrochemical Impedance Spectroscopy (EIS). These mea-
surements confirmed the previously described features of corrosion in
Ethaline and Reline.
Nyquist plots for steel samples in Ethaline and Reline are shown in
Fig. 11. They were obtained at various times of the sample immersion in
the DESs. The complicated shape of the obtained spectra makes it im-
possible to use the simplest Ershler-Randles circuit. Distortion of circles
A.A. Kityk et al.
Fig. 9. The SEM images (magnification 1000×) before corrosion (a) and after corrosion in water (b) and in the solvents Reline (с) and Ethaline (d) (τ = 720 h).
and appearance of “tails” suggest a complex mechanism of the corro-
sion process in the studied liquids.
The form of the impedance spectra (Fig. 11) turned out to be de-
pendent not only on the nature of the solvent but also on the time of
contact with it.
The impedance spectra are represented by a circle of irregular shape
and a “tail”. A similar distortion of the shape of the circle is often en-
countered in the case of solid electrodes, the surface of which is in-
homogeneous and rough. In our case, the steel surface is not only
heterogeneous and rough but also characterized by the appearance of
pitting during corrosion (see SEM pictures). The appearance of the
“tail” in the impedance plots is always associated with the Warburg
impedance. It is well known, the Warburg impedance is an integral
component of the impedance in cases where the investigated process is
characterized by a slow diffusion. The fact that diffusion is the de-
termining factor in the corrosion of steel in these solvents was con-
firmed by voltammetric measurements.
Radii of circles, characterizing the resistance of the corrosion pro-
cess, are in the Ethaline lower than those in Reline, this demonstrates
greater corrosivity of Ethaline towards mild steel. The radii of circles
decrease with time both in the case of Ethaline and of Reline, showing
the decrease in the corrosion resistance. A particularly sharp decrease
in the resistance occurs after 24 h of the experiment. This can be ex-
plained by the appearance of a significant number of pitting, which we
observed when receiving SEM images. The decrease in the radius of the
circles in the entire time interval and the acceleration of the corrosion
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Journal of Electroanalytical Chemistry 823 (2018) 234–244
process can be attributed to the appearance of water in the composition
of the solvents, which was proved by the titration of Karl Fischer.
Pitting and partial blocking of the surface by corrosion products
explains the presence of “tails” on the impedance spectra, which, as a
rule, are associated with the diffusion limitations of the process and are
expressed in equivalent circuits of the Warburg impedance. It should be
noted that as the contact time of steel with DESs increases, changes in
the size and shape of the “tails” are observed, which is a consequence of
changes in the diffusion of the depolarizer to the surface of the cor-
roding electrode and the diffusion of corrosion products from the
sample surface into the bulk of the solution.
Based on the obtained experimental data, two equivalent circuits for
mild steel in the DESs were proposed (Fig. 12). The first equivalent
electrical circuit (Fig. 12a) allows to estimate the impedance of the steel
electrode in Ethaline and Reline at the “initial” moment, until a large
pitting appears (this circuit includes the resistance of the solution –
Rsol, corrosion resistance – Rc, Warburg element for the final diffusion
layer – W and a constant phase element – CPE, which takes into account
the capacity of the interphase and the roughness of the surface of the
steel sample). The second equivalent circuit, describing the impedance
of the system under conditions of sufficiently long contact of the sam-
ples with DESs (Fig. 12b), allows to take into account the heterogeneity
of the surface and its unequal accessibility to the corrosion process due
to the appearance of a large pitting (similar elements appearing in the
circuit describing corrosion with pitting).
For a more detailed understanding of the corrosion mechanism and
A.A. Kityk et al. Journal of Electroanalytical Chemistry 823 (2018) 234–244

Fig. 10. The SEM images (magnification 10,000×) before corrosion (a) and after corrosion in water (b) and in the solvents Reline (с) and Ethaline (d) (τ = 720 h).

the design of a circuit that accurately describes all stages of the cor- comparison.
rosion process, the surface products formed on the samples during Kassim et al. [29] have shown, that in water the initial oxidation
prolonged immersion were analyzed. The analysis was performed with product Fe(OH)+ is oxidized to γ-FeOOH, or to Fe3O4, depending on
Raman spectroscopy using a sample immersed in distilled water for a the rate of oxidation (Fig. 13). Oxides and hydroxides of iron: hematite

Fig. 11. Nyquist impedance spectra for steel electrode after various times of immersion in Ethaline (a) and Reline (b).

241
A.A. Kityk et al.
Fig. 12. Equivalent circuits simulating a mild steel system in Ethaline and Reline solvents on the first day of corrosion (a) and after 24 h (b).
Fig. 13. Schematic diagram of the formation of solid corrosion products on iron in aqueous solutions at room temperature (Os – slow oxidation; Or– rapid oxidation;
Red – reduction) [29]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 14. Raman spectra of corrosion products of steel in distilled water (1 – α-
Fe2O3, γ-FeOOH; 2 – Fe3O4; 3 – FeO).
(α-Fe2O3), lepidocrocite (γ-FeOOH), magnetite (Fe3O4) and wustite
(FeO) were detected on corroded samples in distilled water (Fig. 14).
The obtained spectra are in good agreement with the data presented in
the literature [30–39] and with the scheme shown in Fig.13.
A detailed analysis of the Raman spectra revealed the appearance of
some additional bands in the spectra of corrosion products of steel in
Ethaline and Reline. The appearance of a band of weak intensity at
1550 cm−1 can be ascribed to amorphous carbon. In addition, a new
corrosion product appears in the surface film of samples contacting
DESs with an intense band in the range of 150 cm−1 (plot 3, Fig. 15),
which may be due to the presence of chloride ions in the solution and
the formation of FeOCl [37].
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Journal of Electroanalytical Chemistry 823 (2018) 234–244
b
According to [40], two roles are proposed for chloride ions: the role
of the catalyst of the corrosion process (the presence of chloride ions
causes the pitting corrosion) and the role of the regulator of the for-
mation of phases FeOOH, Fe2O3, Fe3O4. In the case of a catalytic role,
the chloride ions participate in the corrosion process according to the
reactions [40, 41]:
Me + Cl− → Me+Cl− + e−
Me+Cl− → Me+ + Cl−,
where Me is a metal.
Once the rust starts to grow, the surface can become positively
charged, because the hydroxyl (-OH) groups on the rust surface (FeOOH
phase) are converted to –OH2+ groups [40, 42]. Thus, the chloride ions
can move through the rust layers to the surface of the metal, creating a
noticeable acceleration of corrosion.
Moreover, Cl− ions can play an important role in the mechanism of
oxidation of Fe(OH)2+ due to the existence of Green rust, which is a
transitional hydroxyl salt of Fe (II) – Fe (III) between metallic iron and
final corrosion products [40, 43–45]. In this case, a high content of Cl−
ions in the solution promotes the formation of FeOOH.
The formation process according to [46] can be as follows:
(Fe2 +, Fe3 +) + Cl− + OH → FeOCl
FeOCl + OH− → γ‐FeOOH + Cl
Based on the obtained results, it can be assumed that the scheme for
the formation of corrosion products in the DESs will differ from the
scheme shown in Fig. 13 by the presence of a new stage the formation
of FeOCl (Fig. 16).
Thus, it can be concluded that the chloride ions present in large
quantities in DESs solutions affect the mechanism of corrosion of steels
in the investigated media leading to acceleration of the process.
A.A. Kityk et al.
Fig. 15. Raman spectra of corrosion products of steel in Ethaline (a) and Reline (b) (1 – α-Fe2O3, γ-FeOOH; 2 – Fe3O4; 3 – FeOCl).
Fig. 16. Schematic diagram of the formation of solid products of corrosion of iron in DESs at room temperature (Os – slow oxidation; Or – rapid oxidation; Red –
reduction). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
4. Conclusions
The process of corrosion of mild steel in the DESs proceeds with
oxygen depolarization. The rate of corrosion of steel in the solvent
Ethaline at temperatures of 25–60 °C is significantly higher than the
corrosion rate in Reline. However, at higher temperatures of ~70–80 °C,
the values of corrosion rates and corrosion potentials become close to
each other. Apparently, the differences in corrosion rates are primarily
due to differences in the physicochemical properties of the used sol-
vents.
Based on the obtained results, it was concluded that the corrosion
mechanism in the investigated media might be complex, with a sig-
nificant role played by chloride ions, which can lead to an acceleration
of corrosion. Despite the higher corrosion rate in Ethaline as compared
with Reline, there is no significant difference in the corrosion me-
chanism of mild steel in these two solvents.
Acknowledgments
The authors are particularly grateful for the help in setting up the
research tasks and discussing the results to professors of the Ukrainian
State University of Chemical Technology Danilov F. I. and Protsenko V.
S.
This work was supported by the Ministry of Education and Science
of Ukraine [grant number 0116U006897].
References
[1] Q.H. Zhang, K.D. Vigier, S. Royer, F. Jerome, Deep eutectic solvents: syntheses,
properties and applications, Chem. Soc. Rev. 41 (2012) 7108–7146.
243
Journal of Electroanalytical Chemistry 823 (2018) 234–244
[2] E.L. Smith, A.P. Abbott, K.S. Ryder, Deep eutectic solvents (DESs) and their appli-
cations, Chem. Rev. 114 (2014) 11060–11082.
[3] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R.L. Reis, A.R.C. Duarte, Natural deep
eutectic solvents - solvents for the 21st century, ACS Sustain. Chem. Eng. 2 (2014)
1063–1071.
[4] V.S. Protsenko, L.S. Bobrova, F.I. Danilov, Physicochemical properties of ionic li-
quid mixtures containing choline chloride, chromium (III) chloride and water: ef-
fects of temperature and water content, Ionics (2016) 1–7.
[5] F. Endres, D. MacFarlane, A. Abbott, Electrodeposition from Ionic Liquids, Wiley
VCH, 2008.
[6] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, Novel solvent
properties of choline chloride/urea mixtures, Chem. Commun. 99 (2003) 70–71.
[7] A.P. Abbott, G. Capper, D.L. Davies, K.J. McKenzie, S.U. Obi, Solubility of metal
oxides in deep eutectic solvents based on choline chloride, J. Chem. Eng. Data 51
(2006) 1280–1282.
[8] H.G. Morrison, C.C. Sun, S. Neervannan, Characterization of thermal behavior of
deep eutectic solvents and their potential as drug solubilization vehicles, Int. J.
Pharm. 378 (2009) 136–139.
[9] A.P. Abbott, G. Capper, K.J. McKenzie, K.S. Ryder, Voltammetric and impedance
studies of the electropolishing of type 316 stainless steel in a choline chloride based
ionic liquid, Electrochim. Acta 51 (2006) 4420–4425.
[10] D. Shah, F.S. Mjalli, Effect of water on the thermo-physical properties of Reline: an
experimental and molecular simulation based approach, Phys. Chem. Chem. Phys.
16 (2014) 23900–23907.
[11] V.S. Protsenko, A.A. Kityk, D.A. Shaiderov, F.I. Danilov, Effect of water content on
physicochemical properties and electrochemical behavior of ionic liquids con-
taining choline chloride, ethylene glycol and hydrated nickel chloride, J. Mol. Liq.
212 (2015) 716–722.
[12] R.B. Leron, A.N. Soriano, M.H. Li, Densities and refractive indices of the deep eu-
tectic solvents (choline chloride + ethylene glycol or glycerol) and their aqueous
mixtures at the temperature ranging from 298.15 to 333.15 K, J. Taiwan Inst.
Chem. Eng. 43 (2012) 551–557.
[13] E.S.C. Ferreira, C.M. Pereira, A.F. Silva, Electrochemical studies of metallic chro-
mium electrodeposition from a Cr(III) bath, J. Electroanal. Chem. 707 (2013)
52–58.
[14] S. Salomé, N.M. Pereira, E.S. Ferreira, C.M. Pereira, A.F. Silva, Tin electrodeposition
from choline chloride based solvent: influence of the hydrogen bond donors, J.
Electroanal. Chem. 703 (2013) 80–87.
[15] C.A. Nkuku, R.J. Lesuer, Electrochemistry in deep eutectic solvents, J. Phys. Chem.
A.A. Kityk et al.
B 111 (2007) 13271–13277.
[16] A.P. Abbott, G. Frisch, J. Hartley, W.O. Karim, K.S. Ryder, Anodic dissolution of
metals in ionic liquids, Prog. Nat. Sci.: Mater. Int. 25 (2015) 595–602.
[17] Q. Abbas, L. Binder, Anodic dissolution of refractory metals in choline chloride
based binary mixtures, ECS Trans. 33 (2011) 57–67.
[18] M. AlHazzaa, I. AlNashef, Electrochemical corrosion behavior of steel, copper, and
aluminum in selected ionic liquids, Proceedings of the 7th Saudi Engineering
Conference, KSU, Riyadh, 2007, pp. 193–204.
[19] A.P. Abbott, E.I. Ahmed, R.C. Harris, K.S. Ryder, Evaluating water miscible deep
eutectic solvents (DESs) and ionic liquids as potential lubricants, Green Chem. 16
(2014) 4156–4161.
[20] A. Groysman, Corrosion for Everybody, (2010).
[21] F. Ropital, Current and future corrosion challenges for a reliable and sustainable
development of the chemical, refinery, and petrochemical industries, Mater. Corros.
60 (2009) 495–500.
[22] E. Scholz, Karl Fischer titration determination of water - chemical, Lab. Pract.
(1984) 138.
[23] G.A. Snook, A.S. Best, A.G. Pandolfo, A.F. Hollenkamp, Evaluation of a Ag/Ag+
reference electrode for use in room temperature ionic liquids, Electrochem.
Commun. 8 (2006) 1405–1411.
[24] S.V. Branovits'ka, R.B. Medvedêv, Yu Ya Fíalkov, Obchyslyuvalna matematyka ta
prohramuvannya: Obchyslyuvalna matematyka v khimiyi i khimichniy tekhnolo-
hiyi [Computational Mathematics and Programming: Computational Mathematics
in Chemistry and Chemical Technology], (2004) (In Ukrainian).
[25] A.P. Abbott, A. Ballantyne, R.C. Harris, J.A. Juma, K.S. Ryder, G. Forrest, A com-
parative study of nickel electrodeposition using deep eutectic solvents and aqueous
solutions, Electrochim. Acta 176 (2015) 718–726.
[26] C.D. Gu, J.P. Tu, Thermochromic behavior of chloro-nickel(II) in deep eutectic
solvents and their application in thermochromic composite films, RSC Adv. 1
(2011) 1220–1227.
[27] A.A. Kityk, D.A. Shaiderov, E.A. Vasil'eva, V.S. Protsenko, F.I. Danilov, Choline
chloride based ionic liquids containing nickel chloride: physicochemical properties
and kinetics of Ni(II) electroreduction, Electrochim. Acta 245 (2017) 133–145.
[28] A.P. Abbott, J.C. Barron, K.S. Ryder, D. Wilson, Eutectic-based ionic liquids with
metal-containing anions and cations, Chem. Eur. J. 13 (2007) 6495–6501.
[29] J. Kassim, T. Baird, Electron microscope studies of corrosion products in water at
room remperature, Corros. Sci. 22 (1982) 147–158.
[30] R.J. Thibeau, C.W. Brown, R.H. Heidersbach, Raman spectra of possible corrosion
products of iron, Appl. Spectrosc. 32 (1978) 532–535.
[31] S.J. Oh, D.C. Cook, H.E. Townsend, Characterization of iron oxides commonly
formed as corrosion products on steel, Hyperfine Interact. 112 (1998) 59–66.
244
Journal of Electroanalytical Chemistry 823 (2018) 234–244
[32] D.L.A. de Faria, S. Venâncio Silva, M.T. de Oliveira, Raman microspectroscopy of
some iron oxides and oxyhydroxides, J. Raman Spectrosc. 28 (1997) 873–878.
[33] S.M. Vovk, A.N. Tolstykh, L.M. Sharygin, V.I. Denisov, V.B. Podobedov, Raman-
scattering measurements on corrosion films, At. Energy 69 (1990) 782–783.
[34] R.K.S. Raman, B. Gleeson, D.J. Young, Laser Raman spectroscopy: a technique for
rapid characterisation of oxide scale layers, Mater. Sci. Technol. 14 (1998)
373–376.
[35] I.S. Molchan, G.E. Thompson, R. Lindsay, P. Skeldon, V. Likodimos, G.E. Romanos,
P. Falaras, G. Adamova, B. Iliev, T.J.S. Schubert, Corrosion behaviour of mild steel
in 1-alkyl-3-methylimidazolium tricyanomethanide ionic liquids for CO2 capture
applications, RSC Adv. 4 (2014) 5300–5311.
[36] K. Jallad, Chemical imaging of iron oxides and oxyhydroxides using near infrared
Raman imaging microscopy, Mater. Sci. Technol. 17 (2001) 1479–1486.
[37] E. Hazan, Y. Sadia, Y. Gelbstein, Characterization of AISI 4340 corrosion products
using Raman spectroscopy, Corros. Sci. 74 (2013) 414–418.
[38] M. Bouchard, D.C. Smith, Catalogue of 45 reference Raman spectra of minerals
concerning research in art history or archaeology, especially on corroded metals
and coloured glass, Spectrochim. Acta A Mol. Biomol. Spectrosc. 59 (2003)
2247–2266.
[39] J. Alcántara, B. Chico, J. Simancas, I. Díaz, D. de la Fuente, M. Morcillo, An attempt
to classify the morphologies presented by different rust phases formed during the
exposure of carbon steel to marine atmospheres, Mater. Charact. 118 (2016) 65–78.
[40] F.R. Pérez, C.A. Barrero, A.R.H. Walker, K.E. García, K. Nomura, Effects of chloride
concentration, immersion time and steel composition on the spinel phase formation,
Mater. Chem. Phys. 117 (2009) 214–223.
[41] F. Corvo, N. Betancourt, A. Mendoza, The influence of airborne salinity on the at-
mospheric corrosion of steel, Corros. Sci. 37 (1995) 1889–1901.
[42] X. Cao, C.C. Xu, Effect of chloride on the atmospheric corrosion of simulated artifact
iron in NO3-bearing pollutant environment, Acta Metall. Sin. 19 (2006) 34–42.
[43] P. Refait, J.-M.R. Genin, The oxidation of ferrous hydroxide in chloride-containing
aqueous media and pourbaix diagrams of green rust one, Corros. Sci. 34 (1993)
797–819.
[44] P. Refait, M. Abdelmoula, J.-M.R. Genin, Mechanisms of formation and structure of
green rust one in aqueous corrosion of iron in the presence of chloride ions, Corros.
Sci. 40 (1998) 1547–1560.
[45] P. Refait, J.-M.R. Génin, The mechanisms of oxidation of ferrous hydroxychloride β-
Fe2(OH)3Cl in aqueous solution: the formation of akaganeite vs goethite, Corros.
Sci. 39 (1997) 539–553.
[46] D.H. Xia, S.Z. Song, J.H. Wang, H.C. Bi, Y.X. Jiang, Z.W. Han, Corrosion behaviour
of tinplate in NaCl solution, Trans. Nonferrous Metals Soc. China 22 (2012)
717–724.