J Bio Tribo Corros (2017) 3:31
DOI 10.1007/s40735-017-0092-1
Novel Ionic Liquid Compound Act as Sweet Corrosion Inhibitors
for X-65 Carbon Tubing Steel: Experimental and Theoretical
Studies
M. A. Migahed1 • M. M. EL-Rabiei2 • H. Nady2,3 • Amr. Elgendy1
E. G. Zaki1 • M. I. Abdou1 • E. S. Noamy1
Received: 16 April 2017 / Revised: 3 May 2017 / Accepted: 19 May 2017 / Published online: 30 May 2017
 Springer International Publishing Switzerland 2017
Abstract Three novel ionic liquid-based imidazolium
gemini dicationic compounds (I, II and III) synthesized,
characterized by FTIR and 1HNMR spectroscopic tech-
niques and were evaluated as corrosion inhibitors for X-65
carbon tubing steel in oil well formation water under sweet
environment by electrochemical techniques. The inhibition
effect was found effected by the inhibitor concentration
and the spacer length in their chemical structure. Adsorp-
tion of the investigated inhibitors obeyed Langmuir iso-
therm which shows a mixed type of adsorption mechanism.
SEM and EDX techniques investigate the surface mor-
phology and show less damage for inhibited sample.
Finally, theoretical calculations study the influence of
inhibitors structure on the inhibition efficacy to give a
hypothetical interpretation about inhibitors performance.
Keywords Sweet corrosion  Ionic liquids  SEM  DFT
calculations
1 Introduction
Carbon tubing steel (C-steel) is usually employed as a part
of transportation and production in oil industry due to its
low-cost, easy fabrication and excellent properties [1–4].
& Amr. Elgendy
Amr_elgendy40@yahoo.com
1
Egyptian Petroleum Research Institute,
Nasr City 11727, Cairo, Egypt
2
Chemistry Department, Faculty of Science, Fayoum
University, Fayoum, Egypt
3
Chemistry Department, Faculty of Science and Arts in
Qurayat, Al-Jouf University, Sakaka, Kingdom of Saudi
Arabia
•
But it faces serious corrosion problems when exposed to
aggressive medium as formation water, which gathered as
the most corrosive and serious environment in oil field
processes. Sweet corrosion of C-steel given a great atten-
tion in recent years, Because CO2 gas found naturally in
wells or inject during enhanced oil recovery techniques.
With the presence of water phase, CO2 dissolves to form
weak carbonic acid [5–10]. This acid is more destructive if
compared with solution of strong acid at a given pH as
shown by Eqs. (1, 2).
CO2ðgÞ  CO2ðaqÞ ð1Þ
CO2ðaqÞ þ H2 O  H2 CO3ðaqÞ ð2Þ
Sweet corrosion mainly occurs in the form of general
and localized corrosion. Injection of inhibitors accepted as
the most practical and economically cost-effective method
minimizes the corrosive attack on metals [11, 12]. Unfor-
tunately, many efficient inhibitors are toxic which increases
the demand to synthesize eco-friendly inhibitors [13]. Ionic
liquids (ILs) compounds are recently used as corrosion
inhibitors in oil industry process to protect equipment. ILs
compounds have low melting point, high conductivity and
negligible vapor pressure so it is considered as environ-
mental corrosion inhibitor, and many ILs are based on
imidazolium compounds as cations [14–17]. Sasikumar
et al. [18] have investigated the inhibition behavior of
1-decyl-3-methylimidazolium tetra fluoroborate for mild
steel in acidic medium. It was found that this compound
shows a good inhibition performance for mild steel in 1 M
HCl solution. Tawfik [19] has synthesized and evaluated
the inhibition performance of three ionic liquid-based
gemini cationic surfactant for carbon steel corrosion in
acidic environment, and it was found that the three ionic
liquids (IL2, IL3 and IL6) containing quaternary N with
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31 Page 2 of 19 J Bio Tribo Corros (2017) 3:31

long alkyl-saturated chains (cation) and bromide (anion) Table 1 Physical properties and chemical composition of deep oil
showed corrosion inhibition properties for the protection of well formation water used in this investigation
carbon steel in aqueous 1.0 M HCl. The performance of Value Unit
these compounds is depending on forming a protective
Physical properties
layer among metal and the corroding medium. Adsorption
of inhibitor may be occured through physisorption and/or pH 3.2
via chemisorption, the former involve electrostatic attrac- Turbidity 272 FAU
tion between the charged metal and charged inhibitor Density 1.060 g/cm3
molecules but the later involve charge transfer and for- Salinity as NaCl 82,257 mg/L
mation of a coordinate-type bond between the inhibitor and Total hardness 3564 mg/L
metal surface [20–22]. Here in this work, novel ionic liq- Chemical properties
uid-based imidazolium dicationic inhibitors were synthe- Ionic species
sized from low-cost dicarboxylic acids to mitigate Sulfide 788 mg/L
corrosion of X-65 steel under sweet condition by different Calcium 2776 mg/L
electrochemical techniques. Additionally, the surface Barium 28 mg/L
morphology of X-65 samples was studied by SEM and Strontium 39 mg/L
EDX. Finally, the inhibition performance correlated with Chloride 49,980 mg/L
theoretical calculations as in the literature many research- Iron 58.45 mg/L
ers found a clear relationship between the molecular
structures of the synthesized inhibitors and their inhibition
efficiency.
was raised up to 200 C for 6 h, and when the splitting
water was close to demanded amount, the mixture was
2 Materials and Experimental Work cooled down. Then (0.1 mol) of obtained product was
refluxed with (0.2 mol) chlorododecane in the presence of
2.1 Composition of X-65 Steel ethanol at 70 C for 72 h to obtain the diquaternary ionic
liquid compounds. The product compound was permitted
The working electrode was prepared from X-65 steel in to cool, then purified by diethyl ether and left to dry
cylindrical shape with 0.5 cm2 exposed surface area, hav- [23–25].
ing the following composition (in wt%): 0.09% (C), 1.52% Chemical structure of the prepared inhibitors was con-
(Mn), 0.02% (Cr), 0.04% (Ni), 0.004% (Mo), 0.02% (Cu), firmed by FTIR and 1HNMR spectroscopic techniques:
0.002% (V) and the rest is mainly Fe. A copper wire was
• (IR) Infrared spectra analyses performed using (FTIR)
patched to the back side of the electrode as an electrical
Fourier transform infrared spectrophotometer (ATI
connection.
Mattson Series FTIRTM).
• Nuclear magnetic resonance spectra 1H (NMR) analy-
2.2 Electrolyte Solution
ses recorded by BRUKER spectrometer at 400 MHz
using dimethyl sulphoxide as a solvent, and the
The corrosive medium used in this examination is the
trimethylsilane peak taken as the zero (0.0 ppm).
formation water which naturally flows with oil production
obtained from Qarun Petroleum Company, Egypt (QPC).
The chemical composition of this water is listed in Table 1 2.4 Electrochemical Measurements
test medium purging with CO2 from an external source as
the display in Fig. 1. Corrosion measurements as open-circuit potential, Tafel
polarization and electrochemical impedance spectroscopy
2.3 Synthesis of Evaluated Inhibitors were conducted using a Volta lab 80 (Tacussel-Radiometer
PGZ 402) potentiostat controlled by Voltamaster-4 soft-
Synthesis of investigated inhibitors was performed in two ware model at 25 C. In a conventional three-electrode
steps as shown in Scheme 1. Diethylenetriamine (DETA) Pyrex glass 250-ml cell with a platinum counter electrode
was refluxed with dicarboxylic acids (succinic, adipic and (CE), X-65 as working electrode and saturated calomel
sebacic acid) (2:1 molar ratio) in 100 mL xylene as the (SCE) as a reference electrode to which all potentials were
solvent at 140 C for 3.5 h. When the theoretically calcu- referred. The working electrode was polished before each
lated amount of water was removed, the solvent was experiment with a series of abrasive silicon carbide papers
removed by distillation. After that, the reaction temperature up to 2500 grit, cleaned with bi-distilled water, engrossed

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J Bio Tribo Corros (2017) 3:31
Fig. 1 Schematic
representation for the
electrochemical cell used in this
work
in acetone to remove polishing residue and then engrossed
in corroded medium for 90 min until a steady-state
potential was attained. EIS test was implemented at OCP
within a frequency range from 100 kHz to 50 mHz using
ten steps per frequency decade. AC signal with 10 mV
amplitude was applied to perturb the system [26]. The
polarization curves measured change the electrode poten-
tial from -800 to -300 mV automatically with scan rate
2 mV/s. corrosion current densities values calculated using
the Tafel extrapolation interim of ±200 mV with respect to
OCP.
2.5 Surface Observation and EDX Analysis
The change in the surface morphology of CS sheets (pol-
ished, uninhibited and inhibited) after engrossing samples
for 15 days in the corroding medium in the absence and
presence of 300 ppm of inhibitor (I) was examined by
using Quanta 250 FEG (Field Emission Gun, FEI associ-
ation, Netherlands), scanning electron magnifying
Page 3 of 19 31
instrument supplied with EDX spectroscopy system. EDX
study depends on the interaction between X-ray radiations
and the surface of CS sheets, and this interaction recorded
as voltage signals by the X-ray detector and data sent to a
pulse processor, which measures the signs and passes them
into an analyzer to examine the data and display it [27].
2.6 Surface Tension Measurements
The surface tension (c) for the synthesized inhibitors was
measured with a direct technique using a Du Nouy Ten-
siometer (Krüss K6 tensiometer) at 25 C. Different con-
centration from inhibitors was prepared in double-distilled
water (72 mN/m). The platinum ring was rinsed several
times in acetone prior each analysis. Surface tension values
for each concentration were measured three times for all
samples within 2-min wait between each reading and then
take the average of these values. CMC value was detected
at the break point in the plot between (c) and (–ln c (conc))
of synthesized ionic liquid [28].
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31 Page 4 of 19
Scheme 1 Synthesis of ionic liquid-based imidazolium gemini dicationic inhibitors (I, II and III)
2.7 Computational Study
Quantum chemical calculations for ILs compounds were
geometrically set by 3-21 G** basis set with Hyperchem
7.5 using density functional theory (DFT). Quantum
parameters as energy of the highest occupied (ELUMO) and
lowest unoccupied (EHOMO) molecular orbitals, energy gap
(DEL–H = ELUMO - EHOMO), hardness (g), electronega-
tivity (X), dipole moment (l), number of electron trans-
ferred (DN) and softness (r) = 1/g were calculated [29].
3 Results and Discussion
3.1 Characterization of Inhibitors
The structure of the investigated inhibitors (I, II and III)
confirmed by FTIRTM spectroscopy shows the following
absorption bands agreement to the reported characteristics.
Inhibitor (I) (2, 20 -(ethane-1, 2-diyl) bis (1-(2-aminoethyl)-
1-dodecyl-4, 5-dihydro-1H-imidazol-1-ium) dichloride as a
representative sample shows the following absorption bands
1649,1332 cm-1 corresponding to (C=N of imidazole ring);
1552 cm-1, corresponding to the (N–H) bending absence of
C=O band at 1720 cm-1 confirms the cyclization of amide
compound; 2929 and 2915 cm-1 (CH3 and CH2),
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J Bio Tribo Corros (2017) 3:31
respectively, 3367 cm-1 corresponding to vN–H; and 1063,
669.02 cm-1 for the asymmetric and symmetric stretching
N?–C as seen in Fig. 2.
1
HNMR spectroscopy shows d = 7.79 ppm (t, 4H of
2NH2 group), d = 2.57 ppm (m, 8H of 2C2H4 group),
d = 3.2, 3.3 ppm (m, 50H of 2C12H25 group),
d = 3.4 ppm (t, 8H of 4CH2 group in the imidazole ring
attached to quaternary and t nitrogen), d = 2.4, 2.5 ppm (q,
4H of 2CH2 group of the aliphatic spacer), d = 2.4,
2.57 ppm (t, 4H of C2H4 spacer group), d = 1.36 ppm CH2
attached quaternary nitrogen of the imidazoline ring and
the carbon of aliphatic chain and d = 0.85 ppm (t, 6H of
2CH3 group at the end of the aliphatic chain) as displayed
in Fig. 3.
3.2 Electrochemical Measurements
3.2.1 OCP Results
Figure 4a–c shows the potential–time curves of CS elec-
trode engrossed in test medium saturated with CO2 was
measured as function of immersion time versus (SCE) in
the absence and presence of various concentrations of
inhibitor (I, II and III) at 25 C, respectively. All mea-
surements were carried out until steady-state potential was
recognized at which (Ioxidation = Ireduction). In blank
J Bio Tribo Corros (2017) 3:31 Page 5 of 19 31

Fig. 2 FTIR spectrum of ionic liquid inhibitor (I) as representative sample

Fig. 3 1HNMR spectrum of ionic liquid inhibitor (I) as representative sample

solution, potential was decreased toward negative values addition of inhibitor to the corroding medium produces a
indicating the initial dissolution process of the pre-im- slight positive shift which was attributed to development of
mersion air-formed oxide film and the attack on the bare a protecting film from inhibitors molecule on metal-active
metal until steady state attended by the way [30]. With sites surface [31].

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31 Page 6 of 19 J Bio Tribo Corros (2017) 3:31

Fig. 4 OCP measurements of

carbon steel immersed in oil
well formation water saturated
with CO2 in the absence and
presence of different
concentrations of a inhibitor (I),
b inhibitor (II) and c inhibitor
(III) at 25 C

3.2.2 EIS Measurements Nyquist plots, a single, depressed and capacitive-like

EIS measurements were performed at OCP to enhancement
data about the efficiency of the synthesized inhibitors on
X-65 CS electrode engrossed in the test medium containing
various concentrations of inhibitors. Nyquist and Bode
plots are seen in Figs. 5a–c and 6a–c, respectively. In
semicircle was appeared in the absence and after adding
inhibitor. The diameter of Nyquist plots increases as con-
centration increased which refers to inhibitor molecules are
adsorbed on the metal surface and corrosion decreases
under the charge transfer mechanism [32]. The slightly
depressed nature of semicircle is attributed to dispersion in

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J Bio Tribo Corros (2017) 3:31 Page 7 of 19 31

frequency due to different physical phenomena as inho-
mogeneity and roughness of the solid during corrosion
[33]. EIS spectra were fitted with a suitable equivalent
circuit (EC) as displayed in Fig. 7.
Parameters as film resistance (Rf), film double-layer
capacitance of ILs inhibitor (Cf) and double-layer capaci-
tance (Cdl) are listed in Table 2.
The values of inhibition efficiency (g%) are estimated
from Rct values by the following equation:


g% ¼ 1  RctðuninhÞ =RctðinhÞ  100 ð3Þ
Rct(inh) and Rct(uninh) are the charge movement resistance
values in the presence and absence of the inhibitor,
respectively. The impedance data revealed that values of

Fig. 5 Nyquist impedance

curve of carbon steel immersed
in oil well formation water
saturated with CO2 in the
absence and presence of
different concentrations of
inhibitor. a Inhibitor (I),
b inhibitor (II) and c inhibitor
(III) at 25 C

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31 Page 8 of 19 J Bio Tribo Corros (2017) 3:31

Fig. 6 Bode curve of carbon

steel immersed in oil well
formation water saturated with
CO2 in the absence and
presence of different
concentrations of inhibitor of
different concentrations of
a inhibitor (I), b inhibitor (II)
and c inhibitor (III) at 25 C

Rct and Rf increase while Cf decreases gradually with
increase in concentration of the three synthesized inhibitors
as displayed in Fig. 8 due to the formation of a protecting
film from inhibitor molecule between the metal and solu-
tion [34, 35]. Decrease in Cdl values due to increase in the
thickness of adsorbed film at the electrode surface by
exchanging water at solution/metal interface with ILs
molecules confirms that corrosion is controlled by a charge
transfer process [36]. In phase angle plots when concen-
tration of ILs is greater than 100 ppm, there are two time
constant peaks, which indicates that an adsorbed film from
inhibitor is formed. Inhibition efficiency obtained from EIS
of synthesized inhibitors shows the following sequences:
III \ II \ I. The change in efficiency values obtained from
Tafel and EIS techniques was attributed to the difference in
the statues of electrode surface in the two techniques [37].
3.2.3 Tafel Polarization Results
Figure 9a–c shows the polarization measurements of CS
electrode engrossed in the test medium in the presence and
absence of various concentrations (50–300 ppm) of ionic
liquid inhibitors (I, II and III) at 25 C. The electrochem-
ical polarization parameters as bc and ba are the cathodic

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J Bio Tribo Corros (2017) 3:31 Page 9 of 19 31

51.0
65.2
69.2
75.2
86.8
47.7
61.6
68.4
74.7
83.4
42.1
57.0
68.0
73.2
82.2
Table 2 Electrochemical parameters for carbon steel engrossed in corrosive medium in the absence and presence of different concentrations of inhibitors obtained from electrochemical

g%

–
Rct (ohm cm2)

1759.0
291.5
594.0
837.6
947.0

556.5
758.8
923.3

503.5
678.2
912.2
1175
2214

1153

1087
1638
0.99
0.95
0.93
0.92
0.91
0.89
0.91
0.87
0.88
0.85
0.83
0.90
0.83
0.81
0.79
0.78
n2
Fig. 7 Equivalent circuit (EC) used to simulate impedance data for
carbon steel in oil well formation water saturated with CO2 gas

Cdl (lF/cm2)
and anodic Tafel slopes, respectively. Corrosion potential
Ecorr, corrosion current density (icorr), polarization resis-

47.05
43.61
36.03

61.82
45.42
42.56
32.85

75.82
46.23
43.09
34.57
31.6

32.2

34.5
149.3
tance (RP) and percent of inhibition efficiency (g%) were

30
calculated from polarization curves and given in Table 3.
The percent of inhibition efficacy (g%) and the values of
Rp were calculated with the following equations [38, 39]:

Rf (X cm2)
h ¼ 1  iinh =iuninh ð4Þ
g% ¼ ð1  iinh =iuninh Þ  100 ð5Þ
13.8
23.7
31.2
39.8
47.1
51.3
18.2
22.3
29.1
35.8
42.5
15.9
17.4
19.3
22.2
24.5
Rp ¼ ba bc =2:303iinh ðba þ bc Þ SternGeary equation
ð6Þ
0.93
0.92
0.91
0.88
0.87
0.86
0.90
0.92
0.89
0.88
0.86
0.92
0.89
0.86
0.85
0.83
where iinh and iuninh represent the values of corrosion
n1

current density in the presence and absence of inhibitor,

respectively; it is worth noting that with adding inhibitor
the values of corrosion current density and corrosion rate
Cf, (lF cm2)

increase as shown in Figs. 10 and 11, respectively. But the

inhibition performance increase with increase in concen-
tration of ILs inhibitors as shown in Fig. 12. By inspection
9.2
8.7
7.3
6.5

9.2
8.3
6.8

9.7
8.5
7.1
15.6
10.3

11.8
10.6

12.3
11.9
of Tafel slopes bc, ba and Ecorr values in Table 3, for all
inhibitors the inhibitive action is of a mixed type (anodic
and cathodic) as they are almost constant and independent
of inhibitor concentration compared to the blank, and so
Rs (ohm cm2)

the synthesized compounds not affect the metal dissolution

mechanism but effect on corrosion rate (Figs. 10, 11, 12).
0.591
0.138

0.245
9.392
0.864
0.964

6.703
1.34
5.00
1.07

2.18
7.11
5.85

6.09
8.10
13.2

The difference between inhibitors efficiency may be

attributable to the spacer length, and inhibitor with longer
spacer has low performance due to longer distance
between the two head hydrophobic groups in the gemini
impedance spectroscopy at 25 C
Conc. (ppm)

structure decreases the charge density of head groups and

lower adsorption of inhibitor [40–42].
Blank

100
200
300

100
200
300

100
200
300
25
50

25
50

25
50

3.3 Surface Tension Results

Figure 13 shows the variation surface tension (c) of vari-

Inhibitors

ous concentrations of the synthesized inhibitors (I, II and

III) at 25 C. It was found that c values decrease with
(III)
(II)
(I)

surfactants concentration increase until critical micelle

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31 Page 10 of 19
Fig. 8 Change of charge transfer resistance with concentration of
inhibitor (I, II and III) for carbon steel in oil well formation water
saturated with CO2 at 25 C
concentration reached. CMC represents the value of con-
centration at which it becomes favorable for surfactant
molecules to form micelles and decrease interaction of
either their head groups or their tail groups with the sol-
vent, CMC values determined at the crossing of the two
linear portions of curve c versus -lnC of inhibitor con-
centration. The obtained values of CMC, cCMC, effective-
ness of surface tension reduction(pCMC), surface excess
concentration (Cmax), minimum area per molecule(Amin),
Gibbs free energy of micellization DGmic and adsorption
DGads, PC20 were calculated and given in Table 4 using
the following equations [43, 44].
pCMC ¼ c  cCMC
Cmax ¼ ð1=nRT Þðoc=olnCÞ
T 
Amin ¼ 1016 =ðNmax Þ
 where T is the absolute temperature in kelvin, R is the
DGmic ¼ 2:303nRTlogðCMCÞ
 
DGads ¼ DGmic  ð0:006  pcmc  Amin Þ
Pc20 ¼ logc20
c is the surface tension of pure water, cCMC is the surface
tension at CMC, R is the gas constant and ðoc=olnCÞ is
T profound physisorption while those more negative than
the slope of c versus –lnC, N is Avogadro’s number,
n taken as 3 for dimeric surfactant and PC20 is the con-
centration at which c diminished by 20 mN/m. From data
in Table 4, it was found the CCMC for synthesized surfac-
tants increase and pCMC decrease with longer spacer length,
also Amin values decrease with shorter spacer length
because shorter spacer makes the head groups are more
tightly at the air/solution interface and this increase their
effectiveness [45]. DGads are always more negative than
the DGmic, prove spontaneity of the two processes and the
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J Bio Tribo Corros (2017) 3:31
synthesized compounds favors adsorption than micelliza-
tion [46]. For surfactants used as corrosion inhibitor it
should show a low CMC value and high effectiveness,
from Table 4 parameter the order of effectiveness is
(I) [ (II) [ (III) which is in great agreement with experi-
mental measurements.
3.4 Adsorption Isotherm
Adsorption is essential method that provides fundamental
information about the interaction between inhibitor mole-
cules and CS surface [47]. Two essential forms of
adsorption can occur at the surface of electrode, i.e.,
physical adsorption and/or chemical adsorption. Similarly
to many imidazolium inhibitors, adsorption of investigated
inhibitors fitted with Langmuir isotherm in which Cinh/h
plotted against Cinh for the inhibitors as displayed in
Fig. 14. Langmuir adsorption calculated by this Eq. (14)
[48]:
Cinh= ¼ Kads þ Cinh
h ð13Þ
where Cinh is inhibitor molar concentration, h degree of
surface coverage and Kads is the standard adsorption con-
stant, obtained from the reciprocal of the intercepts on Y-
axis. The regression coefficient is around unity
(r2 [ 0.9998) indicating that the inhibition of assessed
inhibitors is attributed to their adsorption [49]. The slope of
a plot is around 1. This deviation from unity clarified on the
basis of the interaction between the adsorbed inhibitor
ð7Þ molecules on the surface of metal by mutual attraction or
repulsion, also from Kads the values of DGads obtained by
ð8Þ next equation [50]:
DGads ¼ RTlnð55:5Kads Þ ð14Þ
ð9Þ
ð10Þ
universal gas constant (8.314 J/mol K) and the value 55.5
ð11Þ is the water molar concentration. The values of DGads and
Kads of inhibitor (I, II, and III) are listed in Table 5. The
ð12Þ
negative sign of DGads indicates that the inhibitor mole-
cules are spontaneously adsorbed onto the metal surface,
generally, DGads value up to -20 kJ/mol or lower is
-40 kJ/mol are profound chemisorption. The large values
of Kads indicate a strong adsorption property [51]. Calcu-
lated DGads values indicated that inhibitors could adsorb
on CS surface engrossed in corroding medium by mixed
sort (physical and also chemical).
3.5 Quantum Investigation
Quantum chemical calculations were utilized to made
correlation between inhibitor structure and their inhibition
J Bio Tribo Corros (2017) 3:31
Fig. 9 a–c Potentiodynamic
polarization curve of carbon
steel in oil well formation water
saturated with CO2 in the
absence and presence of
different concentrations of
a inhibitor (I), b inhibitor (II)
and c inhibitor(III) at 25 C
efficacy [52]. Figure 15 shows Frontier molecular distri-
butions (HOMO and LUMO) for the investigated inhibi-
tors. It can be seen that the HOMO spreads along the
imidazoline ring and the LUMO mainly concentrated in
halogen regions opposite to the HOMO. From density
functional theory, the energy of EHOMO and ELUMO has
important roles in predicting the adsorption centers in
inhibitor molecules, i.e., as EHOMO values increase as
electron donation of inhibitors molecule to empty metal d-
orbitals and adsorption increases. Alternatively, the ability
of inhibitor molecules to receive an electron is associated
Page 11 of 19 31
with ELUMO values, i.e., the lower its values the easier to
inhibitor to accept an electron from a metal surface. Energy
gap DEL–H is related to the stability index of any inhibitor.
Thus, the higher DE values of an inhibitor the lower its
efficiency because the ionization potential will be high and
the energy requested to eliminate an electron from the
outer occupied orbital will be high [53]. Quantum param-
eter is computed and recorded in Table 6, and from this
parameter it is clear that EHOMO values are in order
(I [ II [ III) which suggest the electron donation of IL(I)
is the highest and so adsorb in C-steel surface to great
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31 Page 12 of 19 J Bio Tribo Corros (2017) 3:31

Table 3 Polarization parameters for carbon steel engrossed in corrosive medium in the absence and presence of different concentrations of
inhibitors obtained from potentiodynamic curves at 25 C
Inhibitors Conc. (ppm) -Ecorr (mv Icorr (lA/ Corr. Rate ba (mV -bc (mV Rp h g%
vs. SCE) cm2) (lm/Y) dec-1) dec-1) (ohm.cm2)

(I) Blank 578.5 125.9 1472 355.0 120.2 439.03 – —-

25 569.9 29.8 348.0 151.4 120.7 630.8 0.763 76.3
50 560.1 25.4 303.0 159.2 121.9 769.73 0.794 79.8
100 556.7 19.17 224.2 131.6 151.2 1270 0.848 84.8
200 538.2 16.3 190.8 131.7 251.3 1710 0.870 87.0
300 534.3 12.05 140.9 142.8 265.5 2410 0.904 90.4
(II) 25 559.7 38.1 445.1 180.7 188.5 931.12 0.698 69.8
50 541.9 25.9 303.7 173.7 165.3 1170 0.794 79.4
100 544.4 25.18 294.4 134.1 222.1 1050 0.80 80.0
200 538.4 18.8 220.4 126.4 181.2 1250 0.850 85.0
300 528.5 12.96 151.6 143.8 252.4 2280 0.897 89.7
(III) 25 565.1 82.0 959.0 234.7 164.8 428.61 0.349 34.9
50 542.3 27.0 315.3 149.3 121.8 717.61 0.786 78.6
100 549.5 25.2 295.0 172.8 168.6 1190 0.799 79.9
200 535.2 19.0 222.6 145.6 179.6 1380 0.849 84.8
300 498.3 14.56 170.2 139.8 229.0 1910 0.884 88.4

Fig. 10 Change of corrosion

current density with
concentration of inhibitor (I, II
and III) for carbon steel in oil
well formation water saturated
with CO2 at 25 C

extent, but ELUMO and DE values are in reverse order Usually, inhibitors which have higher EHOMO values
(III [ II [ I), which indicate the high ability of inhibitor have more electrons donating to the electrode surface and
(I) to accept electron and over inhibitor (II and III) and so so, (v) values will decrease when increasing the inhibition
the inhibition efficacy increase in the order (I [ II [ III). effectiveness. The values of (v), (r) softness of the inhi-
When the global hardness increases, the reactivity increa- bitor and the numbers of transferred electrons are com-
ses and so decreases the inhibition ability inhibitor. Values puted as follows [55, 56].
of (g) were calculated by Eq. (15), which shows that
inhibitor I has lower hardness value if compared to inhi- 1
X¼ ðEHOMO þ ELUMO Þ ð16Þ
bitors II and III [54]. 2
1 r ¼ 2ðELUMO  EHOMO Þ ð17Þ
g¼ ðEHOMO  ELUMO Þ ð15Þ
2

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J Bio Tribo Corros (2017) 3:31 Page 13 of 19 31

Fig. 11 Change of corrosion

rate with concentration of
inhibitor (I, II and III) for
carbon steel in oil well
formation water saturated with
CO2 at 25 C

Fig. 12 Change of inhibition

efficacy with concentration of
inhibitor (I, II and III) for
carbon steel in oil well
formation water saturated with
CO2 at 25 C

Fig. 13 Change of surface

tension (c) with –ln C inhibitor
(I, II and III) for carbon steel in
oil well formation water
saturated with CO2 at 25 C

Xinh  XFe molecule, respectively, that measures the resistance of an

DN ¼ ð18Þ
2ðginh þ gFe Þ
where, Xinh and XFe are the absolute electronegativity of the
inhibitor and iron molecule, respectively, which related to
the ability of the molecule to pull electron toward itself;
ginh and gFe are the absolute hardness of Fe and inhibitor
atom to a charge transfer. According to Lukovits’s study,
the inhibition efficiency increases by increasing ability of
these inhibitors to donate an electron to the metal surface
[57]. To calculate DN, the theoretical values of XFe
(7 eV/mol) and gFe (0 eV/mol) are used. From Table 6, it

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Table 4 Surface tension parameters of inhibitors (I, II and III) at 25 C

Inhibitors CMC (mol/l) cCMC (mN/m) pCMC (mN/m) Cmax (mol/cm2) Amin (Å2) DGmic kJ/mol DGads kJ/mol Pc20 (mol/l)

(I) 9.4E-04 33.9 38.4 7.58E-11 218.9 -17.2 -22.3 6.63

(II) 1.82E-03 36 36.3 7.50E-11 221.29 -16.1 -20.9 6.15
(III) 3.38E-03 39 33.3 7.22E-11 229.80 -15.0 -19.6 5.48

Fig. 14 Langmuir adsorption

isotherm curve (Ci/h vs. Ci)
from polarization data for
synthesized inhibitor on carbon
steel surface in oil well
formation water saturated with
CO2 at 25 C

Table 5 Thermodynamic
Inhibitor Slope Regression coefficient (r2) Kads (M-1) DGads (kJ/mol
parameter for adsorption of the
synthesized inhibitor for carbon (I) 1.08 0.9995 81,717.6 -37.97
steel in oil well formation water
saturated with CO2 at 25 C (II) 1.09 0.9986 61,509.0 -37.27
(III) 1.03 0.9897 26,826.7 -35.21

is evident that DN values are in the order: (I [ II [ III)
indicate that inhibitor (I) has the highest electron donation,
according to this calculation it is expected that inhibitors
are donors of electrons, and CS surface is the electron
withdraw, which is in complete agreement with results
obtained from experimental work.
3.6 SEM and EDX Characterization
Scanning electron microscope is an important tool to
study the metal surface morphology and assure the
interaction between inhibitor and metal surface. In this
work, the SEM photomicrographs recorded for X-65
carbon steel sample in tested medium (blank) and
inhibited medium with the optimal concentration of
inhibitor (I that have the highest inhibition) results shown
in Fig. 16a–c. Where Fig. 16a shows smooth surface
contains minor scratches obtained during abrasion is free
from pits and a characteristic inclusion, which may be an
oxide inclusion [58]. While when CS sample engrossed
in corrosive medium without inhibitor for 15 days, SEM
image shows severely damaged and very rough surface
by chloride attack as shown in Fig. 16b. But Fig. 16c
shows the SEM photomicrograph of CS sample after
treated with 300 ppm of inhibitor (I) in test medium for
the same time a significantly smooth surface shown and
less damaged compared with Fig. 16b reveals that
selected inhibitor exhibits a good protecting layer on CS
surface through the development of a protective film. In
order to assure the presence of layer from inhibitor and
show its composition, EDX spectra recorded in Fig. 17a–
c where Fig. 17a shows EDX spectrum of polished CS
sample with high surface properties, but the EDX spectra
Fig. 17b in the presence of O and Cl are maybe due to
corrosion products. By adding 300 ppm of inhibitor (I),
CS sample surface enhanced by the existence of char-
acteristic peak of nitrogen, furthermore, decrease in
oxygen and chloride contribution relative to blank sample
as in Fig. 17c attributed to the development of protecting

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J Bio Tribo Corros (2017) 3:31 Page 15 of 19 31

Fig. 15 HOMO and LUMO orbital occupation for the investigated inhibitors (I, II and III)

Table 6 Quantum chemical

Inhibitors EHOMO (eV) ELUMO (eV) DE (eV) I (eV) A (eV) X (eV) g (eV) r (eV-1) DN
calculations of the investigated
inhibitors using density (I) -1.68 0.61 2.29 1.68 -0.61 0.535 1.145 0.87336 2.29
functional theory (DFT)
(II) -3.97 0.9 4.87 3.97 -0.9 1.55 2.56 0.38986 1.122
(III) -4.91 0.98 5.89 4.91 -0.98 1.965 2.945 0.33955 0.985

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31 Page 16 of 19
Fig. 16 SEM micrographs for X-65 carbon steel surface. a abraded sample, b after immersion in test solution for 15 day, c after immersion in
test solution containing 300 ppm of inhibitor (I) at 25 C
film from inhibitor molecules [59] which is adherent to
the surface lead to a high level of inhibition.
4 Conclusion
Impact obtained from this investigation revealed numerous
conclusions:
1. Ionic liquid-based inhibitors synthesized from low-cost
dicarboxylic acid were found to have good inhibition
efficiency for X-65 carbon steel engrossed in oil well
water under sweet environment.
2. The length of the spacer in ILs structure is the key
effect on percent of inhibition and the order of
inhibition is (I [ II [ III).
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J Bio Tribo Corros (2017) 3:31
3. The surface tension measurements revealed that com-
pound (I) acquire the lowest CMC if compared with
compound (II, III) and inhibitors have a stronger
tendency to adsorb rather than to micellize. Adsorption
of the synthesized inhibitor is of mixed type (ph-
ysisorption and chemisorption) as concluded from
Gibbs free energy values obtained from Langmuir
adsorption model.
4. SEM photographs demonstrated that the inhibitor
molecules formed a good protecting film on the
surface of carbon tubing steel by isolating its surface
from the corrosive medium.
5. Quantum parameters confirmed the high inhibition
efficiency of inhibitor (I) over II and III which agree
with experimental results.
J Bio Tribo Corros (2017) 3:31 Page 17 of 19 31

Fig. 17 EDX micrographs for

X-65 carbon steel surface.
a abraded sample, b after
immersion in test solution for
15 day and c after immersion in
test solution containing
300 ppm of inhibitor (I) at
25 C

Acknowledgements This work was encouraged by the Egyptian
Petroleum Research Institute (EPRI). The authors are greatly Dr E.
A. Khamis for her support to provide quantum chemical calculations.
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