Corrosion Science 51 (2009) 761–768

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion inhibition of mild steel by ethylamino imidazoline derivative

in CO2-saturated solution
P.C. Okafor a,b, X. Liu a,c, Y.G. Zheng a,*
a
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, 62 Wencui Road, Shenyang 110016, Liaoning Province, PR China
b
Department of Pure and Applied Chemistry, University of Calabar, P.M.B. 1115, Calabar, Nigeria
c
Department of Applied Chemistry, Shenyang Institute of Chemical Technology, Shenyang 110142, PR China

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

Article history: The corrosion inhibition and adsorption behaviour of 2-undecyl-1-ethylamino imidazoline (2UEI) on N80
Received 6 August 2008 mild steel in CO2-saturated 3% NaCl solutions was investigated using potentiodynamic polarization, elec-
Accepted 28 January 2009 trochemical impedance spectroscopy techniques and SEM observation. Inhibitor efficiency increased
Available online 4 February 2009
with increase in 2UEI concentration. Temperature studies revealed an increase in inhibition efficiency
with rise in temperature and corrosion activation energies decreased in the presence of 2UEI. A mecha-
Keywords: nism of chemical adsorption of 2UEI on the metal’s surface is proposed. The adsorption characteristics of
A. Mild steel
the inhibitor were approximated by Temkin isotherm. The inhibition efficiency of 2UEI was enhanced in
B. EIS
B. Polarization
the presence of iodide ions.
C. Acid corrosion Ó 2009 Elsevier Ltd. All rights reserved.
C. Acid inhibition

1. Introduction Nitrogen-based organic surfactants, such as imidazolines or their

Corrosion of carbon steel is a significant problem in the oil and
gas production and transportation systems and causes significant
economic loss [1,2]. Rupture as a result of corrosion of the pipe
wall frequently causes failure of petroleum and gas pipelines.
The breakdowns are followed by large losses of the products, envi-
ronmental pollution and ecological disasters [3]. The majority of oil
and gas pipelines failures result from CO2 corrosion of carbon and
low alloy steels [4,5] and occurs at all stages of production from
downhole to surface equipment and processing facilities [6]. The
mechanism of carbon dioxide corrosion is a complicated process
that is influenced by many factors and conditions [7,8]. These
range from pipeline and composition of the solution to other envi-
ronmental factors [8–12]. However, significant progress has been
achieved in understanding the mechanism of CO2 corrosion in
the oil and gas industry [7,12–18], but an understanding of its inhi-
bition mechanism and the kinetics of the inhibition process neces-
sary to quantify formulations that will provide a desirable level of
protection, remains incomplete.
The use of chemical inhibitors has been acknowledged as one,
and a very practical and most economical, method of combating
CO2 corrosion [19–21]. The inhibiting molecule retards the rate
of corrosion by acting at the metal – corrosive medium interface.
* Corresponding author. Tel.: +86 24 23928381; fax: +86 24 23894149.
E-mail addresses: pcokafor@chemist.com (P.C. Okafor), ygzheng@imr.ac.cn,
icpmkaist@yahoo.com (Y.G. Zheng).
salts have been used successfully as corrosion inhibitor in the oil
and gas industries even without an understanding of the inhibition
mechanism [22]. However, recent experimental and modelling
work on the adsorption of imidazolines on metal surfaces in CO2-
saturated solutions is throwing more light on its mechanism
[22–30].
In this work, the inhibition and adsorption behaviour of 2-unde-
cyl-1-ethylamino imidazoline (2UEI) in CO2-saturated 3% NaCl
solution was investigated using potentiodynamic polarization
and electrochemical impedance spectroscopy (EIS) techniques as
well as SEM observation. This research is concerned further with
the co-operative effects of iodide ions on the inhibition efficiency
of 2-undecyl-1-ethylamino imidazoline which has hitherto, not
been reported in the open literature for CO2 corrosion.
2. Experimental
2.1. Materials preparation
Experiments were conducted using a conventional three-elec-
trode 500 ml cell assembly with the counter electrode made of a
platinum foil and saturated calomel electrode (SCE) reference elec-
trode. N80 carbon steel cut from its parent pipe was used as the
test material and has the chemical composition shown in Table
1. The steel sheet was cut into coupons of dimension
1  1  0.8 cm. The coupons were degreased with acetone in an
ultrasonic water bath for about 10 min, air dry, embedded in

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.01.017
762 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768

Table 1 -0.5
Chemical composition of the N80 carbon steel.

Element C Si Mn P S Al Cu Nb Ni -0.6
Composition (wt%) 0.52 0.23 1.50 0.011 0.008 0.01 0.07 <0.005 0.02

-0.7

E/(VSCE)
pH 4
pH 5
-0.8 pH 6
two-component epoxy resin and mounted in a PVC holder. A cop-
per wire was soldered to the rear side of the coupon as an electrical
connection. The exposed surface of the electrode (of area 1 cm2) -0.9
was wet polished with silicon carbide abrasive paper up to 800
grits, rinsed with ethanol, placed in an ultrasonic acetone bath -1.0
-7 -5 -3 -1
for about 5 min to remove possible residue of polishing and air 10 10 10 10
dried. This was used as the working electrode during the electro- I/(A/cm )
2

chemical test.
The test medium was 350 ml 3% NaCl solutions saturated with Fig. 1. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution in
carbon dioxide gas at atmospheric pressure by continuous purging the absence of inhibitor at 25 °C after 30 min of immersion.
with carbon dioxide. The gas exit was sealed with distilled water.
When needed HCl or NaHCO3, was added to adjust the pH. The
3. Results and discussion
temperature was maintained within ±1 °C in all experiments by
placing the cell on a thermostated water bath. The pH was moni-
3.1. Potentiodynamic polarization measurements
tored with PB-10 Sartorius pH/temperature (°C) meter (with accu-
racy of ±0.01) that was carefully calibrated with two buffer
Fig. 1 shows the polarization curves obtained at 25 °C and at pH
solution (pH 4 and pH 7). Electrochemical measurements were
made using a PARSTATÒ 2273 electrochemical measurement sys- 4 to 6 in the absence of inhibitor after 30 min of exposure. Increase
in pH was observed to have little or no effect on the anodic reac-
tem connected to a computer, and an XL 30 ESEM FEG Scanning
electron microscopy was used for the corrosion surface morphol- tion. Similar observation has been made by previous researchers
[14,32] and the behaviour attributed to the increase in HCO 3 ions
ogy observation.
with pH which saturates the surface of the metal and thus inhibits
2.2. Experimental procedure the transport of the Fe2+ ion from the metal lattice. However, a de-
crease in the cathodic reaction is observed with increase in pH due
The free corrosion potential (vs SCE) was followed immediately principally to a change in the concentration of the species involved
after immersing the working electrode in the test solution until the in the cathodic reaction. Polarization parameters obtained from the
potential stabilized within ±1 mV. This was followed by EIS test, curves are as shown in Table 2.
performed over the frequency range of 100 kHz–10 mHz with a On introduction of 2UEI to the system at 25 °C and at pH 4,
signal amplitude perturbation of 5 mV. The Nyquist representa- three distinct features were observed in the polarization curves
tions of the impedance data were analysed with ZsimpWin soft- (shown in Fig. 2): The presence of the inhibitor greatly increased
ware. The charge transfer resistance (Rct), was obtained from the the corrosion potential (vs SCE) to a more positive region and the
diameter of the semicircle in the Nyquist plot, and the inhibition shifts are dependent on the inhibitor concentration. The large shift
efficiency determined from the relationship: in the corrosion potential (vs SCE) indicates that the inhibitor for
this system is probably due to the active sites blocking effect
RctðinhÞ  Rct [33]. Secondly, the anodic reaction is slightly accelerated (above
g% ¼  100 ð1Þ 0.5 V) by the presence of the inhibitor. This effect may however
RctðinhÞ
be due to the large change of the corrosion potential (vs SCE) by
where Rct and Rct(inh) are the uninhibited and inhibited charge trans- the inhibitor. Lastly, a pronounced effect is exerted on the cathodic
fer resistance, respectively. The characteristic frequencies fmax were process. The limiting current for hydrogen evolution is greatly re-
obtained from the semicircles maxima and used to calculate the duced indicating that the inhibition is confined to the hindering
capacitance from the equation: of the hydrogen reduction reaction. At pH 4 or below, direct reduc-
tion of H+ ions, 2Hþ þ 2e () H2 is important particularly at lower
1 partial pressure of CO2 [34] and hindering this reduction process
C dl ¼ ð2Þ
2pfmax Rct greatly inhibits the rate of the corrosion reaction. Also, the corro-
The potentiodynamic sweeps were conducted at a constant pH sion current density is reduced to lower values as indicated in Ta-
and sweep rate of 0.2 mV/s, and the corrosion current density, icorr, ble 3. It is observed that the current density decreased with
determined graphically by extrapolating the linear Tafel segment
of the cathodic curves to the Ecorr (vs SCE) as described previously
[30,31]. From the measured icorr values, the inhibition efficiency Table 2
Potentiodynamic polarization and electrochemical impedance spectroscopy param-
was calculated using the relationship:
eters for N80 carbon steel in CO2-saturated 3% NaCl solutions without inhibitor after
o 30 min of immersion.
icorr  icorr
g% ¼ o  100 ð3Þ Temperature (°C) pH Polarization EIS method
icorr
Ecorr (mVSCE) icorr (lA/cm2) Rt (X cm2) Cdl (F cm2)
o
where icorr and icorr are the uninhibited and inhibited corrosion cur- 25 4 701 98.1 168.9 2.0  104
rent densities, respectively. The solution and metal coupon were 5 704 85.9 216.7 1.6  104
changed after each sweep. In another set of experiments, EIS and 6 717 66.6 251.7 1.4  104
40 4 701 150.0 112.6 2.1  104
polarization measurements were taken after 3 h of immersion at
50 4 700 239.7 71.6 2.8  104
pH 4.
 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768 763

-0.2

-0.3
20 mg/l
80 mg/l
-0.4 100 mg/l
40 mg/l

-0.5

E/(VSCE )
-0.6

Blank
-0.7

-0.8

-0.9

-1.0
-7 -5 -3 -1
10 10 10 10
2
I/(A/cm )

Fig. 2. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution containing 2UEI at 25 °C and at pH 4 after 30 min of immersion.

increasing concentration of the inhibiting molecules, indicating an
inhibiting effect. The polarization curves indicate that the corro-
sion process in the presence of the inhibitor is under cathodic con-
trol. It should be noted that the parameters (pH 4, 25 °C and
30 min) was chosen to yield conditions where corrosion product
film formation is unlikely or very slow.
Fig. 3 shows the polarization curves for N80 carbon steel in CO2-
saturated 3% NaCl solutions in the (a) absence and (b) presence of
80 mg/l 2UEI at pH 4 and 25 °C after 0.5 and 3 h of exposure. In-
crease in time from 0.5 to 3 h was observed to have effects on both
the anodic and cathodic reactions in remarkable ways. The anodic
and cathodic reactions were inhibited more and the corrosion cur-
rents reduced to lower values (Table 3). In the absence of inhibitor,
trans-active, passive and trans-passive characteristics were clearly
observed after 3 h of immersion showing that exposing the metal
for longer time leads to formation of corrosion products that may
be partially protective.
In the presence of 80 mg/l 2UEI, the anodic and cathodic reac-
tions were inhibited more when exposed for 3 h than for 0.5 h
and the Ecorr (vs SCE) was reduced towards the potential in the ab-
sence of inhibitor. This is understandable considering the change in
the surface adsorption state. A combination of the corrosion prod-
uct and the inhibiting molecules lead to a more protective layer
and consequently, a lower rate of corrosion. The inhibition of the
anodic and cathodic reactions and the reduction of the potential
closer to the potential of the blank (absence of inhibitor) indicate
a change in the mode of inhibition from active sites blocking effect
(in the absence of corrosion product layer after 0.5 h of immersion)
to geometric blocking effect (in the presence of inhibitor and cor-
rosion product layer after 3 h of immersion). From Table 3, it can
also be seen from the inhibition efficiency values that 2UEI inhibits
the CO2 corrosion of N80 carbon steel to a large extent at all tem-
peratures and that the extent of inhibition is dependent on the
inhibitor concentration and immersion time.
The effect of temperature on the anodic and cathodic reactions
in the absence and presence of 80 mg/l 2UEI for N80 carbon steel in
3% NaCl solutions saturated with CO2 at pH 4 is represented in the
polarization curves shown in Figs. 4 and 5, respectively. There is a
clear acceleration of both the anodic and cathodic reactions with
an increase in temperature. Similar curves have been reported pre-
viously [35,36]. The polarization parameters for the mild steel in
the absence and presence of 2UEI are listed in Tables 2 and 3,
respectively. It can be seen that the current density increased with
temperature in the uninhibited and inhibited solutions. This is due
to the acceleration of all the processes involved in corrosion: elec-
trochemical, chemical, transport, etc. with increase in temperature

Table 3
Potentiodynamic polarization parameters for N80 carbon steel in 3% NaCl solutions saturated with CO2 at pH 4 containing inhibitors.

Temperature (°C) Systems Polarization EIS method

Ecorr (mVSCE) icorr (lA cm2) g% Rt (X cm2) Cdl (F cm2) g%
After 30 min of immersion
25 3.0% NaCl 701 98.1 – 173.0 2.0  104 –
3.0% NaCl + 20 mg/l 621 36.1 63.20 436.3 1.4  104 60.35
3.0% NaCl + 40 mg/l 607 32.3 67.07 449.5 1.4  104 61.51
3.0% NaCl + 80 mg/l 593 24.3 75.23 581.1 1.1  104 70.23
3.0% NaCl + 100 mg/l 586 12.1 87.67 618.9 1.0  104 72.05
40 3.0% NaCl 701 156.7 – 112.6 2.1  104 –
3.0% NaCl + 80 mg/l 609 25.8 83.54 475.47 0.8  104 76.86
50 3% NaCl 700 239.7 – 71.6 2.8  104 –
3.0% NaCl + 80 mg/l 629 36.9 84.61 327.04 0.8  104 78.42
After 3 h of immersion
25 3% NaCl 713 45.0 – 350.7 3.05  104 –
3.0% NaCl + 80 mg/l 644 2.2 95.04 3851.0 0.08  106 90.89
3.0% NaCl + 830 mg/l KI 716 54.8 21.78 264.1 4.51  104 32.79
3.0% NaCl + 2000 mg/l KI 716 67.98 51.07 237.5 4.05  104 47.66
3.0% NaCl + 80 + 830 mg/l KI 645 1.78 96.04 8562.0 0.11  106 95.90
3.0% NaCl + 80 + 2000 mg/l KI 650 1.19 97.36 12970.0 0.70  106 97.30
764 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768

-0.2 -0.3
o
-0.4 25 C
-0.4 a o
40 C
-0.5 o
50 C
-0.6

E/(VSCE)
-0.6
E/(VSCE )

0.5 hrs -0.7

-0.8 3.0 hrs
-0.8
-1.0
-0.9

-1.2 -1.0
-6 -4 -2 0
10 10 10 10
-0.2 b -2
I/(Acm )

-0.4 Fig. 5. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution
containing 80 mg/l 2UEI at pH 4 after 30 min of immersion.

-0.6
E/(VSCE )

0.5 hrs

-0.8 3.0 hrs 3.2. Electrochemical impedance spectroscopy (EIS) measurements

-1.0 The Nyquist plots obtained from the EIS measurements for N80
carbon steel in 3% NaCl solutions saturated with CO2 at 25 °C in the
-1.2 absence of 2UEI at different pH values and temperatures are as
10-8 10-6 10-4 10-2 100 shown in Figs. 6 and 7, respectively. The plots are characterized
I/(Acm-2) by a depressed semicircle from high to medium frequencies and
an inductive loop at low frequencies. The appearance of the induc-
Fig. 3. Effect of time on the potentiodynamic polarization curves for N80 carbon tive loop in the Nyquist plots is attributed to the adsorption of an
steel in CO2-saturated 3% NaCl solutions in the (a) absence and (b) presence of
intermediate product in the corrosion reaction. This is consistent
80 mg/l 2UEI at pH 4 and 25 °C.
with the proposed involvement of adsorbed intermediates in the
anodic dissolution of iron in acidic solution by Bockris et al. [37]
[34]. It could also be noticed that increase in temperature in- and in CO2-saturated solutions [14]. The capacitive semicircle is as-
creased the inhibition efficiencies of 2UEI suggesting chemisorp- cribed to the double layer capacitance and transfer resistance. It is
tion of the organic molecule on the surface of the metal. The observed that increasing the pH increases the semicircle as shown
apparent activation energies (Ea) for the corrosion process in the in Fig. 6 which indicates decrease in corrosion rate, and increasing
absence and presence of the inhibitor were calculated from the the temperature decreases the semicircle (Fig. 7) which indicates
condensed Arrhenius equation as follows: increase in corrosion rate. This behaviour is consistent with the
  polarization results.
icorrð2Þ Ea 1 1 Introduction of the imidazoline was observed to increase the
log ¼  ð4Þ
icorrð1Þ 2:303R T 1 T 2 capacitive semicircle as shown in the Nyquist plots (in Fig. 8)
where icorr(1) and icorr(2) are the corrosion current densities at tem- and this increase is dependent on the concentration of the imidaz-
peratures T1 (25 °C) and T2 (50 °C), respectively. The calculated acti- oline and indicates inhibition of the corrosion process. The values
vation energy values in the absence and presence of the inhibitors of Rct in the absence of inhibitors (shown in Table 2) were observed
are 28.60 and 13.37 KJ/mol, respectively. The decrease in activation to increase with increase in pH indicating decrease in corrosion
energy in the presence of inhibitor is an indication of chemical rate but decrease with increase in temperature indicating acceler-
adsorption of 2UEI on the surface of the metal [41]. ation of corrosion rate. Similar trend was observed from the polar-
ization measurements. In the presence of 2UEI, the values of Rct
(Table 3) were observed to increase with increase in the concentra-
tion of 2UEI indicative of reduction in the corrosion rate and con-
sequently increase in the inhibition efficiency of the imidazoline.
-0.4
It is also seen that the charge transfer resistance, Rct, decreases
-0.5 with the increase of temperature, resulting in a decrease in inhibi-
tion efficiency. The inhibition efficiency values obtained from the
-0.6 EIS measurements (Table 3) are observed to be in agreement with
E/(V SCE)

-0.7 those obtained from the polarization measurements.

o
25 C The double layer capacitance, Cdl was observed to decrease with
o
-0.8 40 C pH in the absence of inhibitor but increased with temperature
o
50 C (Table 2). This behaviour confirms the trend of corrosion rate with
-0.9
pH and temperature. The capacitance values were also observed to
-1.0 decrease with the introduction of 2UEI. The decrease in Cdl values
10
-7
10
-5
10
-3
10
-1 has been ascribed to a decrease in the dielectric constant and/or an
2 increase in the double electric layer thickness, due to inhibitor
I/(A/cm )
adsorption on the metal/electrolyte interface [38–40]. This implies
Fig. 4. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution in that the extent of adsorption on the metal/solution interface in-
the absence of inhibitor at pH 4 after 30 min of immersion. creases with 2UEI concentration.
 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768 765

150 pH 4
pH 5
125 pH 6

100

-Zim/(Ωcm 2)
75

50

25

0
0 25 50 75 100 125 150 175 200 225 250 275
-25
2
Zre /(Ωcm )

Fig. 6. Nyquist plots for N80 carbon steel in 3% NaCl solutions saturated with CO2 at 25 °C after 30 min of immersion.

100 25ºC
40º C
80 50º C

60
-Zim/(Ωcm 2)

40

20

0
0 20 40 60 80 100 120 140 160 180
-20
Z re /(Ωcm2 )

Fig. 7. Nyquist plots for N80 carbon steel in 3% NaCl solutions saturated with CO2 at pH 4 after 30 min of immersion.

3.3. Adsorption where h is the surface coverage (h = g%/100), c the extracts concen-
tration, K the adsorption coefficient, which represents the adsorp-
The experimental data were applied to different adsorption iso- tion–desorption equilibrium constant, and a is an interaction
therm equations and found to fit the Temkin isotherm (Fig. 9) parameter. Calculated values of K and a are 5.02  106 mol/l and
which may be formulated as: 4.79, respectively. The negative value of a indicates that repulsion
exists at neighbouring adsorption sites in the adsorption layer [41]
expð2ahÞ ¼ Kc ð5Þ while the calculated high value of K imply more adsorption than

400

Blank
300
20 mg/l
40 mg/l
80 mg/l
200
-Zim /(Ωcm 2)

100 mg/l

100

0
0 100 200 300 400 500 600 700

-100 Z re /(Ωcm2 )

Fig. 8. Nyquist plots for N80 carbon steel in CO2-saturated 3% NaCl solutions containing 2UEI at pH 4 after 30 min of immersion.
766 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768

0.85 -0.2
-0.3
0.80
2000 mg/l KI
-0.4
0.75
-0.5

E/(VSCE)
0.70 -0.6
θ

-0.7
0.65 Blank
-0.8 830 mg/l KI
0.60
-0.9 2000 mg/l KI
0.55 -1.0
-1.1
0.50
2.5 3.0 3.5 4.0 4.5 5.0 10-8 10-6 10-4 10-2 100

ln c/(mg/l) I/(Acm-2)

Fig. 9. Temkin adsorption isotherm for N80 carbon steel in CO2-saturated 3% NaCl Fig. 11. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution
solution containing 2UEI at pH 4 and 25 °C. containing KI at pH 4 and 25 °C after 3 h of immersion.

desorption and consequently better inhibition efficiency [41]. The
constant, K, is related to the standard free energy of adsorption
DGoads by the equation:
 
1 DGoads
K¼ exp
55:5 RT
The value of 55.5 being the concentration of water in solution
expressed in mole. The calculated negative value (48.18 kJ/mol)
indicates a spontaneous adsorption of 2UEI at the surface and con-
firms the proposed chemical adsorption mechanism [42–44].
The molecular structure of 2UEI (shown in Fig. 10) is composed
of a five member ring containing nitrogen elements (the head
group), a C-11 saturated hydrophobic group and a hydrophilic eth-
ylamino group attached to N1. The compound can be adsorbed on
the metal surface by the formation of an iron–nitrogen co-ordina-
tion bond and by a pi-electron interaction between the pi-electron
in the head group and iron. Though not a primary contributor to
the adsorption strength of the compound on the surface of the me-
tal, coulombic attraction between the negative charge on the metal
surface (as a result of the specific adsorption of chloride ions) and
the imidazoline derivative may also contribute to the inhibition
ability of the compound.
3.4. Effect of iodide ions additives
Fig. 11 shows the polarization curves for N80 carbon steel after
3 h of exposure in CO2-saturated 3% NaCl solution containing KI at
pH 4 and 25 °C. It is observed that the addition of iodide ion
slightly accelerated the cathodic reaction and shifts the corrosion
current density to higher values (Table 3). The anodic passivation
current density was observed to be reduced. The later effect shows
that halide ions participate in the anodic reaction, more especially
in the formation of the passive film and that iodide ions enhance
passive film formation. Generally, halide ions in acid solutions
are known to participate in forming intermediates on a corroding
steel surface and consequently inhibit or accelerate the iron anodic
dissolution by replacing some adsorbed OH ions in the anodic
process [45]. This ability increases in the order Cl < Br < I [40].
However, the effect of KI in this system seems to be overshadowed
ð6Þ by the large concentration of NaCl (3%). To further confirm this,
polarization measurements were conducted at varying concentra-
tions of NaCl in the presence of 2000 mg/l (0.2%) KI. The results ob-
tained are illustrated in the polarization curves shown in Fig. 12
and the polarization parameter given in Table 4. It is observed that
reduction in the concentration of chloride ions leads to a decrease
in the anodic current density. The passivation potential was also
observed to increase to a more positive value and diminishes at
very low NaCl concentration. This is most probably due to the in-
creased adsorbed iodide ions on active sites on the electrode sur-
face with decrease in chloride ions. However, this conclusion is
made with caution as the cooperative effects of the chloride and
the iodide ions may also have contributed to the observed changes.
Addition of halide salts to acid solutions containing organic
inhibitors has been reported to result in a cooperative effect which
inhibits iron dissolution [46]. It is thought that the ions are able to
improve the adsorption of the organic compounds. The effect of KI
additives on CO2 corrosion of N80 carbon steel in 3% NaCl solutions
is illustrated in Fig. 13. 830 mg/l KI was observed not to have
noticeable effect on the anodic and cathodic reactions in the pres-
ence of 80 mg/l 2UEI. However, 2000 mg/l KI further decreased the
corrosion current density and thus increased the inhibition effi-
ciency of the imidazoline. Enhanced inhibition performance in
-0.2 0 % NaCl
-0.3
0.1 % NaCl
-0.4
1.0 % NaCl
-0.5
3.0 % NaCl
E/(V SCE)

-0.6
-0.7
-0.8
-0.9
-1.0
N N C2H4NH2
-1.1
-7 -5 -3 -1
10 10 10 10
-2
I/(Acm )

C11H23 Fig. 12. Effects of NaCl on the polarization curves for N80 carbon steel in CO2-
saturated 3% NaCl solution containing 2000 mg/l KI at pH 4 and 25 °C after 3 h of
Fig. 10. Molecular structure of 2-undecyl-1-ethylamino imidazoline (2UEI). immersion.
 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768 767

Table 4
Potentiodynamic polarization parameters for N80 carbon steel in CO2-saturated 3%
NaCl solutions containing KI at pH 4 and 25 °C after 3 h of immersion.

Systems Ecorr (mVSCE) icorr (lA cm2)

0% NaCl + 2000 mg/l KI 708 64.08
0.1% NaCl + 2000 mg/l KI 703 61.97
1.0% NaCl + 2000 mg/l KI 711 77.16
3.0% NaCl + 2000 mg/l KI 716 67.98

-0.2
-0.3
-0.4
-0.5
E/(V SCE )

-0.6 Blank
-0.7
80 mg/l 2UEI
-0.8
830 mg/l KI + 80 mg/l 2UEI
-0.9
2000 mg/l KI + 80 mg/l 2UEI
-1.0
-1.1
10-8 10-6 10-4 10-2 100
-2
I/(Acm )

Fig. 13. Polarization curves for N80 carbon steel in CO2-saturated 3% NaCl solution
containing 2UEI and KI at pH 4 and 25 °C after 3 h of immersion.

the presence of iodide ions is also revealed in the Nyquist plots ob-
tained in the presence of 830 and 2000 mg/l iodide ion concentra-
tion in 80 mg/l 2UEI inhibited solutions. This is illustrated by the
increase in the diameter of the semicircle in the Nyquist plots
(Fig. 14) and the charge transfer resistance (Rct) (Table 3) on addi-
tion of KI and this increase is dependent on the halide ions
concentration.
Three possible models for inhibitor adsorption with the aid of
halide ions were described by Murakawa et al. [47]. (1) The adsorp-
tion of the halide ion which then attracts the inhibitor molecule to
the metal, (2) exchange of adsorption site by halide ions and organ-
ic ions (competitive) and (3) co-adsorption of inhibitor and halide
ions. A combination of these models is also feasible [47]. From the
results obtained, the first model may be applicable here, in which
the iodide ions facilitate the adsorption of the imidazoline mole-
cules thereby increasing the inhibition efficiency.

Blank
80 mg/l 2UEI
6000
80 mg/l mg/l + 830 mg/l KI
Fig. 15. Surface morphology for N80 carbon steel in CO2-saturated 3% NaCl
80 mg/l mg/l + 2000 mg/l KI
solutions in the (a) absence (blank) and presence of (b) 80 mg/l 2UEI and (c) 80 mg/l
2UEI + 2000 mg/l KI at pH 5 and 25 °C after 3 h of immersion.
4000
-Z im/(Ωcm 2)

3.5. Surface morphology

2000
The surface morphologies of the N80 carbon steel specimen in
CO2-saturated 3% NaCl solutions in the absence (blank) and pres-
ence of 80 mg/l 2UEI and 80 mg/l 2UEI + 2000 mg/l KI at pH 4
0
0 2000 4000 6000 8000 10000
and 25 °C after 3 h of immersion were examined using SEM. The
results obtained are as shown in Fig. 15(a), (b) and (c), respectively.
Z re /(Ωcm 2)
In the absence of inhibitors (Fig. 15(a)), a very rough surface was
Fig. 14. Nyquist plots for N80 carbon steel in CO2-saturated 3% NaCl solutions observed due to rapid corrosion attack of the carbon steel in the
containing 2UEI and KI at pH 4 and 25 °C after 3 h of immersion. CO2-saturated solution. The attack was relatively general with no
768 P.C. Okafor et al. / Corrosion Science 51 (2009) 761–768
evidence of localized corrosion initiation. In the presence of the
inhibitors (80 mg/l 2UEI and 80 mg/l 2UEI + 2000 mg/l KI) shown
in Fig. 15(b) and (c), respectively, the rough surface is visibly re-
duced indicating the formation of a film on the surface of the metal
and inhibiting effect of 2UEI and 2UEI + 2000 mg/l KI. A closer
inspection of Fig. 15(b) and (c) reveals that the surface film formed
in the presence of 2UEI + 2000 mg/l KI (c) seems to be more com-
pacted than in the presence of 2UEI alone (b). This behaviour is re-
lated to the proposed co-operative effects of 2UEI and KI leading to
a more compact film and enhanced inhibition efficiency.
3.6. Conclusions
2-Undecyl-1-ethylamino imidazoline (2UEI) inhibits the corro-
sion of N80 mild steel in CO2-saturated 3% NaCl solution and the
extent of inhibition is dependent on 2UEI concentration, tempera-
ture and exposure time. 2UEI mode of inhibition is due to the ac-
tive sites blocking effect in the absence of corrosion products and
geometric blocking effect in the presence of corrosion products.
The values of the corrosion activation energy in the absence and
presence of 2UEI and free Gibbs energy of adsorption indicated
that 2UEI is chemically adsorbed on the surface of the metal. Inhi-
bition efficiency of 2UEI was enhanced by the addition of KI.
Acknowledgement
PCO acknowledges the Chinese Academy of Sciences (CAS) and
the Academy of Sciences for the Developing World (TWAS) for the
CAS-TWAS Postdoctoral Fellowship.
References
[1] B. Miksic, R. Boyle, B. Wuertz, Efficacy of vapor phase corrosion inhibitor
technology in manufacturing, Corrosion 60 (2004) 515–522.
[2] F.M. Song, D.W. Kirk, J.W. Graydon, D.E. Cormack, Predicting carbon dioxide
corrosion of bare steel under an aqueous boundary layer, Corrosion 60 (2004)
736.
[3] Y.N. Mikhailovskii, A.I. Marshakov, N.A. Petrov, Monitoring of underground
pipeline corrosion condition with sensory instruments, Prot. Met. 33 (1997)
293–295.
[4] D.A. Lopez, W.H. Schreiner, S.R. de Sanchez, S.N. Simison, The influence of
carbon steel microstructure on corrosion layers: an XPS and SEM
characterization, Appl. Surf. Sci. 207 (2003) 69–85.
[5] W. Durnie, B. Kinsella, R. De Marco, A. Jefferson, A study of the adsorption
properties of commercial carbon dioxide corrosion inhibitor formulations, J.
Appl. Electrochem. 31 (2001) 1221–1226.
[6] S.L. Fu, J.G. Garcia, A.M. Griffin, Corrosion/1996, Paper no. 21, NACE
International, Houston, 1993.
[7] M.B. Kermani, A. Morshed, Carbon dioxide corrosion in oil and gas production –
A compendium, Corrosion 59 (2003) 659–683.
[8] K. Videm, A. Dugstad, Corrosion of carbon steel in an aqueous carbon dioxide
environment. Part 1: film formation, Mater. Perform. 28 (1989) 63–67.
[9] K. Videm, A. Dugstad, Corrosion of carbon steel in an aqueous carbon dioxide
environment Part 2 Solution effects, Mater. Perform. 28 (1989) 46–500.
[10] C.O.A. Olsson, D. Landolt, Passive films on stainless steels – Chemistry and
growth, Electrochim. Acta 48 (2003) 1093–1104.
[11] P.C. Okafor, S. Nesic, Effect of acetic acid on CO2 localized corrosion of carbon
steel in vapor-water two-phase horizontal flow, Chem. Eng. Com. 194 (2007)
141–157.
[12] J.K. Heuer, J.F. Stubbins, An XPS characterization of FeCO3 films from CO2
corrosion, Corros. Sci. 41 (1999) 1231–1243.
[13] C. de Waard, D.E. Milliams, First International Conference on the Internal and
External Protection of Pipes, Paper F1, University of Durham, Durham, 1975.
[14] S. Nesic, J. Postlethwaite, S. Olsen, An electrochemical model for prediction of
corrosion of mild steel in aqueous carbon dioxide solutions, Corrosion 52
(1996) 280–306.
[15] B.R. Linter, G.T. Burstein, Reactions of pipeline steels in carbon dioxide
solutions, Corros. Sci. 41 (1999) 117–139.
[16] M. Nordsveen, S. Nesic, R. Nyborg, A. Strangeland, A mechanistic model for
carbon dioxide corrosion of mild steel in the presence of protective iron
carbonate films – Part 1: theory and verification, Corrosion 59 (2003) 443–457.
[17] S. Nesic, M. Nordsveen, R. Nyborg, A. Strangeland, A mechanistic model for
carbon dioxide corrosion of mild steel in the presence of protective iron
carbonate films – Part 2: a numerical experiment, Corrosion 59 (2003) 489–
497.
[18] E. Remita, B. Tribollet, E. Sutter, V. Vivier, F. Ropital, J. Kittel, Hydrogen
evolution in aqueous solutions containing dissolved CO2: quantitative
contribution of the buffering effect, Corros. Sci. 50 (2008) 1433–1440.
[19] S. Webster, D. Harrop, A. McMahon, G.J. Partidge, Proceedings of NACE
Corrosion/1993, Paper no. 109, NACE International, Houston, 1993.
[20] S. Ramachandran, V. Jovancicevic, Molecular modeling of the inhibition of mild
steel carbon dioxide corrosion by imidazolines, Corrosion 55 (1999) 259–267.
[21] W. Durnie, R. De Marco, A. Jefferson, B. Kinsella, Development of a structure –
Activity relationship for oil field corrosion inhibitors, J. Electrochem. Soc. 146
(1999) 1751–1756.
[22] L.M. Rodrıguez-Valdez, W. Villamisar, M. Casales, J.G. González-Rodriguez, A.
Martı́nez-Villafane, L. Martinez, D. Glossman-Mitnik, Computational
simulations of the molecular structure and corrosion properties of
amidoethyl, aminoethyl and hydroxyethyl imidazolines inhibitors, Corros.
Sci. 48 (2006) 4053–4064.
[23] A. Edwards, C. Osborne, S. Webster, D. Klenerman, M. Joseph, P. Ostovar, M.
Doyle, Mechanistic studies of the corrosion inhibitor oleic imidazoline, Corros.
Sci. 36 (1994) 315–325.
[24] D. Wang, S. Lia, Y. Ying, M. Wang, H. Xiao, Z. Chen, Theoretical and
experimental studies of structure and inhibition efficiency of imidazoline
derivatives, Corros. Sci. 41 (1999) 1911–1919.
[25] X. Jiang, Y.G. Zheng, W. Ke, Corrosion inhibitor performances for carbon
dioxide corrosion of N80 Steel under static and flowing conditions, Corrosion
61 (2005) 326–334.
[26] M.A. Quraishi, M.Z.A. Rafiquee, S. Khan, N. Saxena, Corrosion inhibition of
aluminium in acid solutions by some imidazoline derivatives, J. Appl.
Electrochem. 37 (2007) 1153–1162.
[27] D. Wahyuningrum, S. Achmad, Y.M. Syah, Buchari, B. Ariwahjoedi, The
synthesis of imidazoline derivative compounds as corrosion inhibitor
towards carbon steel in 1% NaCl solution, ITB J. Sci. 40 (2008) 33–48.
[28] X. Liu, Y.G. Zheng, Effect of hydrophilic group on inhibition behaviour of
imidazoline for CO2 corrosion of N80 in 3% NaCl solution, Corros. Eng. Sci. Tech.
43 (2008) 87–92.
[29] X. Liu, Y.G. Zheng, P.C. Okafor, Carbon dioxide corrosion inhibition of N80
carbon steel in liquid- and liquid/particle two-phase flow by hydroxyethyl
imidazoline derivatives, Mater. Corros. (in press).
[30] X. Liu, P.C. Okafor, Y.G. Zheng, The inhibition of CO2 corrosion of N80 steel in
single liquid phase and liquid/particle two-phase flow by aminoethyl
imidazoline derivatives, Corros. Sci., in press, doi:10.1016/
j.corsci.2008.12.024.
[31] V.S. Reznik, V.D. Akamsin, Yu.P. Khodyrev, R.M. Galiakberov, Yu.Ya. Efremov, L.
Tiwari, Mercaptopyrimidines as inhibitors of carbon dioxide corrosion of iron,
Corros. Sci. 50 (2008) 392–403.
[32] K. Videm, Proceedings of Corrosion/2000, Paper no. 39, NACE International,
Houston, 2000.
[33] C. Cao, On electrochemical techniques for interface inhibitor research, Corros.
Sci. 38 (1996) 2073–2082.
[34] S. Nesic, Key issues related to modelling of internal corrosion of oil and gas
pipelines – A review, Corros. Sci. 49 (2007) 4308–4338.
[35] G. Zhang, C. Chena, M. Lub, C. Chai, Y. Wu, Evaluation of inhibition efficiency of
an imidazoline derivative in CO2-containing aqueous solution, Mater. Chem.
Phys. 105 (2007) 331–340.
[36] P.C. Okafor, B. Brown, S. Nesic, CO2 corrosion of carbon steel in the presence of
acetic acid at higher temperatures, J. Appl. Electrochem. (2008) 12–13 doi:
10.1007/s10800-008-9733-x.
[37] J. ÓM. Bockris, D. Dražić, A.R. Despić, The electrode kinetics of the deposition
and dissolution of iron, Electrochim. Acta 4 (1961) 325–361.
[38] A. Popova, E. Sokolova, S. Raicheva, M. Christov, AC and DC study of the
temperature effect on mild steel corrosion in acid media in the presence of
benzimidazole derivatives, Corros. Sci. 45 (2003) 33–58.
[39] S.Y. Sayed, M.S. El-Deab, B.E. El-Deab, B.E. El-Anadouli, B.G. Ateye, Synergistic
effects of benzotriazole and copper ions on the electrochemical impedance
spectroscopy and corrosion behavior of iron in sulfuric acid, J. Phys. Chem. B.
107 (2003) 5575–5585.
[40] E.E. Oguzie, Y. Li, F.H. Wang, Corrosion inhibition and adsorption behavior of
methionine on mild steel in sulfuric acid and synergistic effect of iodide ion, J.
Coll. Interf. Sci. 310 (2007) 90–98.
[41] S.A.M. Refaey, F. Taha, A.M. Abd El-Malak, Inhibition of stainless steel pitting
corrosion in acidic medium by 2-mercaptobenzoxazole, Appl. Surf. Sci. 236
(2004) 175–185.
[42] D. Shize, T. Yiling (Eds.), Interface Chemistry, High Grade Education Press,
Beijing, 1990, p. 124.
[43] S. Bilgic, M. Sahin, The corrosion inhibition of austenitic chromium–nickel
steel in H2SO4 by 2-butyn-1-ol, Mater. Chem. Phys. 70 (2001) 290–295.
[44] P.C. Okafor, E.E. Ebenso, U.J. Ibok, U.J. Ekpe, M.E. Ikpi, Inhibition of 4-
acetamidoaniline on corrosion of mild steel in HCl solutions, Trans. SAEST 38
(2003) 91–96.
[45] R.J. Chin, K. Nobe, Electrodissolution kinetics of iron in chloride solutions III.
Acidic solutions, J. Electrochem. Soc. 119 (1972) 1457–1461.
[46] P.C. Okafor, E.E. Oguzie, G.E. Iniama, M.E. Ikpi, U.J. Ekpe, Corrosion inhibition
properties of thiosemicarbazone and semicarbazone derivatives in
concentrated acid environment, Glob. J. Pure Appl. Sci. 14 (2008) 89–95.
[47] T. Murakawa, S. Nagaura, N. Hackerman, Coverage of iron surface by organic
compounds and anions in acid solutions, Corros. Sci. 7 (1967) 79–89.