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Imidazoline Derivatives as Corrosion

Inhibitors of Carbon Steel in Crude Oils
and Associated Water
a a a
S. T. Keera , N. A. Farid & K. Z. Mohamed
a
Egyptian Petroleum Research Institute , Nasr City , Cairo , Egypt
Published online: 07 Jun 2012.

To cite this article: S. T. Keera , N. A. Farid & K. Z. Mohamed (2012) Imidazoline Derivatives
as Corrosion Inhibitors of Carbon Steel in Crude Oils and Associated Water, Energy
Sources, Part A: Recovery, Utilization, and Environmental Effects, 34:15, 1371-1383, DOI:
10.1080/15567036.2010.481657

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 Energy Sources, Part A, 34:1371–1383, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567036.2010.481657

Imidazoline Derivatives as Corrosion Inhibitors of

Carbon Steel in Crude Oils and Associated Water

S. T. KEERA,1 N. A. FARID,1 and K. Z. MOHAMED1

1
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

Abstract Corrosion and corrosion inhibition of carbon steel in various types of

crude oils and associated water (formation water) have been studied using electro-
chemical and weight loss measurements. The corrosion rate of carbon steel depends
critically on the types of formation water. The influence of three amino ethyl imi-
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dazoline derivatives, aminoethylimidazoline of linolenic acid, aminoethylimidazoline

of oleic acid, and aminoethylimidazoline of propionic acid on the corrosion of car-
bon steel in these aggressive solutions was studied at different concentrations and
temperatures. The inhibition efficiency of these inhibitors decreases in the order:
aminoethylimidazoline of linolenic acid > aminoethylimidazoline of oleic acid >
aminoethylimidazoline of propionic acid. The adsorption of imidazoline derivatives
obeys the Langmuir adsorption isotherm. The thermodynamic parameters indicate
that imidazoline derivatives inhibitors are physically adsorbed on the carbon steel
surface. The influence of oleic imidazoline inhibitor was studied in fluids having
different oil/water ratios. The data revealed that the corrosivity of an oil/water fluid
generally increases with the increase of water cut.

Keywords carbon steel, corrosion, crude oil, formation water, imidazoline

1. Introduction
Corrosion is a serious problem in oil and gas production. The type and extent of corrosion
in oil and gas production depends on fluid composition, such as the oil type, oil/water
ratio, water salinity, gas type, and gas contents (Keera, 2001; Efird, 1991; Lotz et al.,
1991; Perdomo et al., 2002). Crude oil produced from offshore oil fields is associated
with varying proportions of water called formation waters (Warren and Smalley, 1994).
The corrosion of steel in crude oil/brine mixtures is a function of the specific crude oil
and the percentage of brine in the mixture (Malinowky, 1975). The ions present in the
formation water can affect the corrosion rate by changing the electrical conductivity of
water (Deyab, 2007).
The water salinity affects the solubility of gases that have a great influence on the
corrosivity of the environment. The presence of sodium chloride in concentrations of up
to 1 wt% increases the corrosion rate, because it prevents the formation of a protective
FeS film on the carbon steel surface (Efird and Janinsk, 1989).
Corrosion damage is frequent and very severe in oil transportation pipelines. A
number of factors may influence inhibition in multiphase pipelines, such as temperatures,
water-oil partitioning, water chemistry, and flow condition (Nyborg, 2003).

Address correspondence to Dr. Safaa Keera, Egyptian Petroleum Research Institute, Nasr City,
Cairo 11727, Egypt. E-mail: keerasafaa@yahoo.com

1371
 1372 S. T. Keera et al.

Some corrosion inhibitors function by chemisorption on the metallic surface, forming

complexes with the metal, thereby neutralizing and/or absorbing the corrodent. Among
the most commonly used inhibitors are the quaternary ammonium salts, organic amine
derivatives, and imidazoline derivatives (Keera, 2001).
Corrosion inhibitor containing oleic imidazoline and its precursor oleic amide species
is used for the oil-water-iron system (Mchohan, 1991). The importance and usefulness
of oleic imidazoline inhibitors in oil and gas pipelines has been studied in detail by
several researches (Mercer, 1976). The influences of three imidazoline type compounds
on the corrosion inhibition of carbon steel in hydrochloric acid solution have been studied
(Mohamed et al., 2004).
The aim of the current work is to study the inhibitive performance of three imida-
zoline derivatives on the corrosion of carbon steel exposed in environments of different
formation water and various oil/water ratios at various temperatures using weight loss
and potentiodynamic polarization measurements.
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2. Experimental

2.1. Electrolytes
Crude oil from the Western Desert of Egypt besides two of formation water was used
for this study.
Three amino ethyl imidazoline derivatives [aminoethylimidazoline of linolenic acid
(AEIL), aminoethylimidazoline of oleic acid (AEIO), and aminoethylimidazoline of
propionic acid (AEIP)] were synthesized and investigated as corrosion inhibitors for
the aggressive electrolyte solutions.

2.2. Experiments
The physico-chemical characteristics of the crude oils were determined using the standard
method of analysis for petroleum products (ASTM, 1991) and (IP, 1990).
The formation water sample was separated from the crude oil by using chloroform
through a glass separating funnel in several runs. The water sample was then filtered
using ashless filter papers (Whatman No. 42) before being subjected to analysis (Greeberg
et al., 1989). Analysis of the studied formation water was determined in accordance with
standard test methods of analysis, APHA (Greeberg et al., 1989; ASTM, 1976, 1988,
1989, 1992) and/or API (API, 1968).
Potentiodynamic polarization measurements were performed using EG&G poten-
tiostat/galvanostat with model 352 corrosion software. The electrochemical experiments
were performed in a cell assembly, which consisted of a platinum counter electrode
as an auxiliary electrode, a saturated calomel electrode (SCE) as a reference electrode,
and a carbon steel as a working electrode. The working electrode was machined into a
cylindrical form, 2 cm long with a cross sectional diameter of 1 cm. The electrode was
mounted in glass tubing using Araldite in such a manner that only its cross-sectional
area was exposed to the electrolyte (Keera and Deyab, 2005, 2008). The electrode
was immersed in 100 ml of the formation water, in both the absence and presence
of (1  10 3 –30  10 3 M) of the inhibitors, AEIL, AEIO, and AEIP, at 20, 40, and
60ı C. Weight loss measurements were carried out in aggressive solutions of different
oil/water ratios.
 Imidazoline Derivatives 1373

3. Results and Discussion

3.1. The Physico-chemical Characteristics of the Crude Oil

The physico-chemical characteristics of the crude oil were determined and are given in
Table 1. It is clear that nitrogen content and total acid number are 0.29% and 0.20 mg
KOH/g, respectively. The high sulphur content (3.67%), low API gravity (18.55), and the
high vanadium concentration (43.58 g/g) give detection for the crude oil corrosivity.

3.2. Chemical Analysis of the Formation Water Samples

Chemical analysis of the formation water samples (A3 and A2 ) was carried out and
presented in Tables 2 and 3. It is clear that formation water A3 (Table 3) is characterized
by a high concentration of divalent and trivalent cations, which agrees with Table 2 for
higher total dissolved solids, salinity, and acidic values for the A3 than A2 .
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3.3. Potentiodynamic Polarization Behavior of Carbon Steel in

Formation Water
Potentiodynamic polarization behavior of carbon steel in formation water (A2 ) was carried
out in the absence and presence of various concentrations (1  10 3–30  10 3 M) of the
three inhibitors and 40ıC to clarify the influence of the organic molecule chain length
on the inhibiting performance of carbon steel in the test solution. The electrochemical
parameters of this study are tabulated in Table 4 and shown in Figure 1.

Table 1
Physicochemical characteristics of the
studied crude oil sample

Characteristics Results

Density, g/ml
 At 40ı C 0.9260
 At 15.6ı C 0.9421
Specific gravity, at 60/60ıF 0.9430
API gravity 18.55
Viscosity, cSt, at 40ıC 199.9
Pour point, ı C 18
Sulphur content, m % 3.67
Nitrogen content, m % 0.29
Carbon residue content, m % 11.87
Water content, vol% 1.0
Water and sediment content, vol% 2.0
Total acid number, mg KOH/g 0.20
Salt content, ppm 183
Copper corrosion 1b
Ash content, m % 0.0279
Vanadium concentration, g/g 43.58
 1374 S. T. Keera et al.

Table 2
General properties of the formation water samples

Sample/Properties A3 A2

Oil content, % 0.054 0.053

pH at 25ıC 3.3 7.1
Density at 15ı C, g/ml 1.0989 1.088
Specific gravity at 60/60ıF 1.0998 1.089
Conductivity at 25ıC S/cm 156,200 152,600
Resistivity at 25ıC, ohm/m 0.0640 0.0655
Total dissolved solids, mg/L 133,730 122,670
Salinity, mg/L 131,959 98,969.31
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It is elucidated that the aminoethyl imidazoline of linolenic acid (AEIL) gave the
best inhibition efficiency, which is due to the presence of three double bonds besides
the longest aliphatic constituents at the imidazoline ring. The presence of more than
one double bond in the inhibitor molecule is beneficial to inhibition efficiency due to
the increase of the number of active sites, the electron densities, and the molecular size
(Mohamed et al., 2004).
This means that, at a given concentration, the inhibitor efficiency decreases in the
following order I > II > III. The maximum inhibition efficiency of the inhibitors AEIL,
AEIO, and AEIP reached 77, 67, and 54%, respectively, at a concentration of 1610 3 M
and seemed to be steady.

Table 3
Cation and anion concentrations in the
formation water samples

Concentration,
g/g A3 A2

Sodium 30,213 36,699

Potassium 933 714
Calcium 12,000 3,632
Magnesium 6,660 4,125
Lithium 48 22
Iron 53 1.34
Aluminum <0.307 —
Strontium 211 83.3
Chloride 79,975 59,981
Sulphate 53.3 120
Fluoride 34.3 1.75
Bromide 985.5 301
Nitrate — 197
 Imidazoline Derivatives 1375

Table 4
Electrochemical polarization parameters for the corrosion of carbon steel in formation
water A2 containing various concentrations of (AEIL), (AEIO), and (AEIP) at
temperature 40ıC

Concn., R, Ecorr , Icorr , Ba , Bc , Rp,

Inh M  103 mpy mV  A cm 2 mV dec 1 mV dec 1 K  cm 2 , % 

(AEIL) Blank 19.26 689.5 42.0 126.2 332.9 0.95 — —

1 13.29 654.6 28.97 100.2 316.9 1.21 31.0 0.31
4 10.40 608.2 22.68 92.9 31.0 1.36 46.0 0.46
8 7.08 573.9 15.43 87.2 285.1 1.95 63.4 0.634
12 5.76 549.2 12.56 87.0 260.9 2.26 70.1 0.701
16 4.39 526.3 9.57 100.3 218.6 2.90 77.2 0.772
20 4.41 530.5 9.62 86.9 225.0 2.83 77.1 0.771
25 4.37 525.0 9.53 85.0 218.0 2.78 77.3 0.773
30 4.39 531.0 9.58 85.8 220.0 2.80 77.2 0.772
(AEIO) 1 13.83 672.6 30.16 109.6 302.7 1.10 28.2 0.28
4 11.19 640.9 24.40 107.2 299.3 1.40 41.9 0.42
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8 9.10 591.5 20.61 106.4 246.8 1.58 52.8 0.53

12 7.65 569.0 16.67 101.9 231.0 1.84 60.3 0.60
16 6.28 527.9 13.70 95.9 220.2 2.12 67.4 0.67
20 6.32 530.0 13.78 95.7 220.0 2.10 67.2 0.67
25 6.26 531.9 13.65 96.0 221.0 2.13 67.5 0.68
30 6.28 532.0 13.69 96.2 222.3 2.13 67.4 0.67
(AEIP) 1 15.82 658.0 34.48 117.3 245.6 0.98 17.9 0.18
4 12.02 621.9 26.21 115.4 165.9 1.13 37.6 0.38
8 9.63 599.2 20.99 113.3 158.7 1.09 50.0 0.50
12 9.23 569.1 20.12 110.0 150.3 1.37 52.1 0.52
16 8.90 536.4 19.41 112.1 150.0 1.44 53.8 0.54
20 8.94 540.0 19.49 113.6 150.2 1.44 53.6 0.54
25 8.88 535.9 19.36 112.0 150.5 1.44 53.9 0.54
30 8.92 536.0 19.45 112.1 150.6 1.43 53.7 0.54

3.4. The Influence of the Type of Formation Water as

Aggressive Solution
The influence of adding various concentrations (1  10 3 –30  10 3 M) of the inhibitor
(AEIL) on the corrosion inhibition of carbon steel in formation water A2 and A3 at
different temperatures (20, 40, and 60ı C) was carried out and an example is presented
in Table 5. Some examples of the electrochemical polarization curves of this behavior
are shown in Figure 2.
Table 5 elucidates that the inhibitor efficiency increased gradually with increasing in
the inhibitor concentration and attained its maximum value of 86% at 20ı C at the optimal
concentration of 16  10 3 M followed by a steady state. It can be concluded that, at a
low inhibitor concentration, the corrosion of steel is inhibited due to the adsorption of the
inhibitor molecules on the steel surface by the hydrophilic head groups. The hydrophobic
chain may be oriented towards the aqueous medium and may also be arranged horizontally
to the steel surface (Osman et al., 1997). An increase in the efficiency is observed when
the concentration of the inhibitor increases and reaches around a specific concentration
known as critical micelle concentration. At higher inhibitor concentration far above the
critical micelle concentration (CMC), the corrosion inhibition reaches a steady state. This
 1376 S. T. Keera et al.
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Figure 1. Variation of the inhibition efficiency with logarithmic concentration of AEIL, AEIO,
and AEIP in formation water A2 at 40ıC.

behavior is attributed to the saturation of the steel surface with the inhibitors’ molecules
and the formation of a multilayer. It also may be attributed to a change in the orientation
of the adsorbed molecules at the interface resulting from hydrophobic interaction between
chains. In this situation, it is likely that the molecules bind perpendicularly to the surface
leading to more adsorbed molecules and, thus, saturation of the steel surface with the
inhibitor molecules (Gomma and Wahdan, 1994).
Figure 3 illustrates that increasing inhibitor concentration caused an increase in
the inhibition efficiency followed by a decrease, then the inhibition efficiency increased
again. As can be seen from the data, at a very low concentration range (1  10 3 –
8  10 3 M), the inhibition efficiency increased up to 79.5% at 20ı C due to adsorption of
the inhibitor molecules with complete coverage of the steel surface by a monomolecular
layer. When the concentration increased from 12  10 3 to 16  10 3 M, an unexpected
decrease in the inhibition efficiency occurred. This may be due to the presence of divalent
and trivalent cations, e.g., Ca2C , Mg2C, and Al3C in the formation water (A3 ) with
high concentration. These cations depressed the surfactant adsorption onto the steel
surface from 79.5 to 65.2% (Ofor, 1996) at 16  10 3 M. Once the concentration
exceeded that of 16  10 3 M, more inhibitor molecules may overcome the effect
of divalent and trivalent cations present in the aggressive solution approach to the
surface forming a multilayer film; consequently, a maximum inhibition efficiency of the
inhibitor is attained around the critical micelle concentration at the optimal concentration
 Imidazoline Derivatives 1377

Table 5
Electrochemical polarization parameters for the corrosion of carbon steel in formation
water A2 containing various concentrations of aminoethyl imidazoline of linolenic acid
(AEIL) at different temperatures (20, 40, and 60ı C)

Concn., R, Ecorr , Icorr , Ba , Bc , Rp,

T , ıC M=L  103 mpy mV  A cm 2 mV dec 1 mV dec 1 K  cm 2 , % 

20 Blank 10.94 668.9 23.86 119.3 201.4 1.37 — —

1 6.26 611.1 13.66 118.6 207.8 1.83 42.7 0.43
4 4.72 572.5 10.28 72.9 170.0 2.15 56.9 0.57
8 3.14 527.0 6.84 69.2 167.8 2.20 71.3 0.71
12 2.57 511.5 5.61 70.0 139.5 3.61 76.5 0.77
16 1.54 495.5 3.35 73.6 120.5 4.81 85.9 0.86
20 1.56 502.0 3.41 74.0 122.0 5.86 85.7 0.86
25 1.60 508.1 3.48 75.0 122.9 5.80 85.4 0.85
30 1.53 488.5 3.34 73.0 120.0 5.90 86.0 0.86
40 Blank 19.26 689.5 42.01 126.2 332.9 0.95 — —
1 13.29 654.6 28.97 100.2 316.9 1.21 31.0 0.31
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4 10.40 608.2 22.68 92.9 301.0 1.36 46.01 0.46

8 7.08 573.9 15.43 87.2 285.1 1.95 63.4 0.63
12 5.76 549.2 12.56 87.0 260.9 2.26 70.1 0.70
16 4.39 526.3 9.57 100.3 218.6 2.90 77.2 0.77
20 4.41 530.5 9.62 86.9 225.0 2.83 77.1 0.77
25 4.37 525.0 9.53 85.0 218.0 2.78 77.3 0.77
30 4.39 531.0 9.58 85.8 220.0 2.80 77.2 0.77
60 Blank 27.33 704.9 59.59 127.3 552.8 0.70 — —
1 19.71 683.3 42.99 117.7 287.2 0.83 27.9 0.28
4 15.85 655.2 34.56 116.2 282.5 1.03 42.0 0.42
8 12.02 645.8 27.24 143.8 245.9 1.28 56.0 0.56
12 10.14 631.9 22.11 100.1 249.2 1.40 62.9 0.63
16 8.20 618.2 17.88 89.7 245.0 1.59 70.0 0.70
20 8.42 620.0 18.35 90.0 245.6 1.56 69.2 0.69
25 8.06 619.5 17.58 90.0 247.0 1.63 70.5 0.71
30 8.20 618.6 17.88 91.2 246.0 1.62 70.0 0.70

20  10 3 M. Another decrease in the efficiency is attained at concentrations far above

the CMC.
The decrease in the inhibition efficiency in this region may be due to intermolecular
attraction between the adjacent hydrophobic tails of the adsorbed molecules, which
takes place by dispersion and Van der Waal forces (Zhao and Brown, 1996). This
interaction pushes the adsorbed molecules to be oriented perpendicular to the steel
surface. Hence, there are no sufficient molecules in the medium to adsorb onto the steel
surface and, thus, blocking the active sites on its surface. For this reason, the inhibition
efficiency towards corrosion of these samples decreases in spite of raising the inhibition
concentration.

3.5. Influence of Temperature

It is clear that the efficiency decreases with raising temperatures as shown in Figure 3.
This may be due to desorption of some adsorbed inhibitor molecules from the metal sur-
face at higher temperatures (Gomma and Wahdan, 1994) suggesting physical adsorption
of the inhibitor molecules on the steel surface.
 1378 S. T. Keera et al.
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Figure 2. Potentiodynamic polarization curves of carbon steel in formation water (A2 ) and (A3 )
in the absence and presence of different concentrations of AEIL inhibitor at 20ıC.

It is possible to use the activation energy Ea as an inhibition criterion. This was

calculated from the Arrhenius equation (Putilova et al., 1960).

Icorr D A exp. Ea =RT /;

where Icorr is the reaction rate, A is constant, Ea is the activation energy of the carbon
steel dissolution reaction, T is absolute temperature, and R is the universal gas constant.
A logarithm of the corrosion rate against the reciprocal of temperature .1=T / gives Ea
and the results are given in Table 6. It is clear that Ea values are higher in the presence
of the inhibitor than that in the uninhibited one. This indicates a more efficient inhibiting
 Imidazoline Derivatives 1379
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Figure 3. The dependence of the inhibition efficiency of AEIL inhibitor in formation water (A3 )
at 20, 40, and 60ıC.

effect that can be attributed to the thickening of the electric double layer and supports
the hypothesis that molecules can form micelles on the metal surface.
An alternative formulation of the Arrhenius equation is (Bochris and Swinkels, 1964):

Icorr D RT =N h exp.Sa0 =R/ exp. Ha0 =RT /;

where h is Plank’s constant, N is Avogadro’s number, Sa0 is the entropy of activation,

and Ha0 is the enthalpy of activation. The values of Ha0 and Sa0 were calculated
and listed in Table 6. The positive signs of the enthalpies (Ha0 ) reflect the endothermic
nature of the steel dissolution process. Large and negative values of entropies (Sa0 )
imply activated complex in the rate determining step.

Table 6
Thermodynamic activation parameters for carbon steel in formation water (A2 ) in
presence of AEIL inhibitor at 20, 40, and 60ı C
1
Compound Ea , kJ mol Ha0 , kJ mol 1
Sa0 , J mol 1 K 1

Blank 19.1 16.4 162.3

1  10 3 M 23.9 21.2 150.5
8  10 3 M 28.7 26.2 139.4
16  10 3 M 34.7 32.2 124.6
 1380 S. T. Keera et al.

Table 7
Thermodynamic parameters for the adsorption of AEIL inhibitor in formation water
(A2 ) on the carbon steel at different temperatures
0 0 0
Gads , Hads , Sads ,
2
Temp, K Kads R kJ mol 1 kJ mol 1 J mol 1 K 1

293 500 0.9971 24.9

313 359 0.9963 25.8 10.217 50
333 310 0.9964 26.9

3.6. Adsorption Isotherm

The degree of surface coverage (‚) of the carbon steel surface as a function of the
inhibitor concentration can be represented by plotting Cinh =‚ versus Cinh according to
the relation: Cinh =‚ D 1=KCCinh to explain the best isotherm to determine the adsorption
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process. The relation was found to be linear, which indicates that the inhibitor adsorbed
on the carbon steel surface according to Langmuir adsorption isotherm.
It can be seen (Table 7) that the adsorption coefficient (Kads ) decreases with an
increase in the experimental temperature, meaning probably that there was desorption of
some adsorbed inhibitor molecules from the metal surface at higher temperatures, which
confirms the physical adsorption of the inhibitor.
0 0
The standard free energy of adsorption, Gads , the heat of adsorption, Had , and
0
the standard adsorption entropy, Sads , can be calculated using the relationship:
0 0 0
Gads D Hads TSads ;
0
Kads D 1=55:5 exp. Gads =RT /:

The value 55.5 is the concentration of water in solution in mol l 1 (Flis and Zakroczymski,
1996).
The thermodynamic data obtained for AEIL using the adsorption isotherm are de-
0
picted in Table 7. The negative values of Gads ensure the spontaneity of the adsorption
process and stability of the adsorbed layer on the steel surface. The negative values
around 20 kJ mol 1 indicate that the adsorption mechanism of the inhibitor on the
carbon steel surface in formation water was typical of physisorption (Deyab et al., 2007).
0
The calculated value of the Hads for the adsorption of AEIL is 10.217 kJ mol 1 ,
indicating that this inhibitor can be considered physically adsorbed. The positive value
0
of Sads (50 J mol 1 K 1 ) indicates that an increase in disordering takes place in going
from the reactants to the metal-adsorbed species reaction complex (Do, 1998).
0
Hads can be also deduced from the integrated version of the Van’t Hoff equation
expressed by Do (1998):
0
Ln K D Hads =RT C constant.

3.7. Corrosion Inhibition of Carbon Steel in Petroleum–water

Mixtures (Effect of Oil/Water Ratio)
The effect of oil/water ratio on the performance of oleic imidazoline derivative inhibitor
has been examined. The measurements have been examined in different oil/water ratios,
 Imidazoline Derivatives 1381
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Figure 4. Inhibition efficiency-concentration curves at different oil/water (A2 ) ratios of oleic

imidazoline inhibitor.

20/80, 60/40, 50/50, and 80/20, in the absence and presence of various inhibitor concen-
trations (20–120 ppm) of the inhibitor AEIL in the aggressive solution (A3 ) using weight
loss measurements.
The data clearly show that the corrosivity of an oil/water fluid generally increases
with the increase of water cut. In the presence of a small amount of water in relation to
oil (20% water), corrosion is negligible. This is attributed to the formation of an adhering
layer of crude oil on the metal surface, which tends to prevent direct contact of the steel
with the aqueous corrosive phase (Greenwell, 1953).
At a 50/50 oil/water ratio, the inhibitor accelerated the corrosion instead of inhibition,
as shown in Figure 4. Blair (1954) interpreted that corrosion under some conditions may
be accelerated by oil wetting of the metallic surface. Hydrogen ions may be established
between certain oil-wet and water-wet areas. In effect, the water-wet areas become
cathodic because of ready wettability of hydrogen ions, while the oil-wet areas become
anodic due to the deficiency of hydrogen. Very little variation in the corrosion inhibitor
performance was observed on increasing the inhibitor concentration in excess of 100 ppm.
It confirms that the adsorption of imidazoline inhibitor from oil into oil wet Fe is fast
and follows a Langmuir isotherm to give monolayer coverage at a solution concentration
of about 100 ppm.

4. Conclusion
1. The corrosion rate of carbon steel depends critically on the types of formation
water.
2. The corrosion rate of carbon steel in an oil/water fluid, increases with the increase
of water cut.
 1382 S. T. Keera et al.

3. The inhibition efficiency of the studied inhibitors decreases in the order: AEIL >
AEIO > AEIP.
4. The inhibition of the imidazoline derivatives is due to the adsorption on the carbon
steel surface and blocking of the active sites and the adsorption follows Langmuir
adsorption isotherm.

References
API. 1968. API Recommended Practice for Analysis of Oil-field Waters. APIRP 45, 2nd Ed. Dallas,
TX: American Petroleum Institute.
ASTM. 1976, 1988, 1989, 1992. ASTM Standards. Vols. 11.01 and 11.02. Philadelphia, PA:
American Society for Testing and Materials.
ASTM. 1991. ASTM Standards for Petroleum Products and Lubricants (I–III). Vols. 05.01–05.03.
Philadelphia, PA: American Society for Testing and Materials.
Blair, C. M. 1954. Corrosion 10:105.
Bochris, J. O., and Swinkels, D. A. J. 1964. Adsorption of n-Decylamine on solid metal electrodes.
Downloaded by [UNICAMP] at 18:53 17 June 2015

J. Electrochem. Soc. 111:736.

Deyab, M. A. 2007. Effect of cationic surfactant and inorganic anions on the electrochemical
behavior of carbon steel in formation water. Corro. Sci. 49:2315–2328.
Deyab, M. A., Abo Dief, H. A., Eissa, E. A., and Taman, A. R. 2007. Electrochemical investigations
of naphthenic acid corrosion for carbon steel and the inhibitive effect by some ethoxylated
fatty acids. Electrochimica Acta. 52:8105.
Do, D. 1998. Adsorption Analysis: Equilibria and Kinetics. New York: Imperial College Press.
Efird, K. D. 1991. Mater. Perform. 30:63.
Efird, K. N., and Janinsk, R. J. 1989. Corrosion 45:63.
Flis, J., and Zakroczymski, T. J. 1996. Impedance study of reinforcing steel in simulated pore
solution with tannin. Electrochem. Soc. 143:2458.
Gomma, G. K., and Wahdan, M. H. 1994. Temperature coefficient of corrosion Inhibition of steel
by adenine. Bull. Chem. Soc. Jpn. 76:2621.
Greeberg, A. E., Trussell, R. R., and Clesceri, L. S. (Eds.). 1989. Standard methods for the
examination of water and wastewater. Standard Methods for the Examination of Water and
Wastewater, 17th Ed. Washington: APHA-AWWA-WPCF.
Greenwell, H. E. 1953. Studies on water-dependent corrosion in sweet oil wells. Corrosion 9:307.
Institution of Petroleum (IP). 1990. IP Standards for Analysis and Testing of Petroleum Products,
Vols. 1 and 2. London: Institution of Petroleum.
Keera, S. T. 2001. Inhibition of steel by alkylamine ethoxylate in petroleum production. Br.
Corrosion J. 36:261.
Keera, S. T., and Deyab, M. A. 2005. Colloids and Surfaces A: Physicochem, Eng. Aspects 266:
129.
Keera, S. T., and Deyab, M. A. 2008. Impedance spectroscopy a technique for studying corrosion
inhibition of carbon steel in formation water by surfactants. Egypt. J. Petrol. 17:53.
Lotz, U., Vanbodegom, L., and Cowhand, C. 1991. Effect of type of oil or gas condensate on
carbonic acid. Corrosion 47:635.
Malinowky, M. S. 1975. An experimental study of oil-water and air-oil flowing mixtures in
horizontal pipes. M.S. Thesis, Tulsa, OK: University of Tulsa.
Mchohan, A. J. 1991. Colloids & Surf. 59:187.
Mercer, A. D. 1976. Corrosion, 2nd Ed., Vol. 2. Kent, England: L. L. Schrier, Buttsworth, Sevenoater,
p. 18.
Mohamed, K. Z., Keera, S. T., and Farid, N. A. 2004. Imidazoline derivatives as corrosion inhibitors
for mild steel in hydrochlorid acid solution. Egypt. J. Petrol. 13:87.
Nyborg, R. 2003. Corrosion control in oil and gas pipelines. Explor. Prod.: Oil & Gas Rev. 2:79.
Ofor, O. 1996. J. Coll. Interf. Sci. 179:323.
 Imidazoline Derivatives 1383

Osman, M. M., Omar, A. M., and Al- Sabagh, A. A. M. 1997. Corrosion inhibition of benzyl
triethanol ammonium chloride and its ethoxylate on steel in sulphuric acid solution. Mater.
Chem. Phys. 50:271.
Perdomo, J. J., Gonzalez, J. J., and Viloria, A. 2002. Mater. Perform. 2:76.
Putilova, L. N., Balezin, S. A., and Barannik, V. P. 1960. Metallic Corrosion Inhibitors. Oxford:
Pergamon Press, p. 27.
Warren, E. A., and Smalley, P. C. 1994. North Sea Formation Waters Atlas. Geological Society
Memoir No. 15, Petroleum Exploration Society of Great Britain.
Zhao, J., and Brown, W. 1996. Comparative study of adsorption isotherm measurements. J. Phys.
Chem. 100:3775.
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