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IJSRES Internat ional Journal of Scient if ic Research in Environmental Sciences
www.i jsrpub.com
August 2013
Volume 1, Issue 8
Pages 166 216
Table of Contents
Article Author(s) page Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel in CO2-Saturated Brine
Vagif M. Abbasov, Hany M. Abd El-Lateef, Sevinc A. Mamedxanova, Leylufer. I. Aliyeva, Teyyub A. Ismayilov, Musayev J. Ilham, Orkhan A. Aydamirov, Fariz A. Amirov
166
Livestock Products and Environment Maryam Asghari 179
Host Preference and Performance of Fruit Flies Bactrocera zonata (Saunders) and Bactrocera cucurbitae (Coquillett) (Diptera: Tephritidae) For Various Fruits and Vegetables
Muhammad Sarwar, Muhammad Hamed, Bilal Rasool, Muhammad Yousaf, Mureed Hussain
188
The Inhibitory Properties of Organic Pest Control Agents against Aphid (Aphididae: Homoptera) on Canola Brassica napus L. (Brassicaceae) Under Field Environment
Muhammad Sarwar 195
A Review of Genetic and Epigenetic Mechanisms in Heavy Metal Carcinogenesis: Nickel and Cadmium
Zienab Saedi, Shahin Gavanji, Sahar Davodi
202
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013 Available online at http://www.ijsrpub.com/ijsres
ISSN: 2322-4983; 2013 IJSRPUB
http://dx.doi.org/10.12983/ijsres-2013-p166-178
166
Full Length Research Paper
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the
Corrosive Performance of Carbon Steel in CO2-Saturated Brine
Vagif M. Abbasov1, Hany M. Abd El-Lateef
1, 2*, Sevinc A. Mamedxanova
1, Leylufer. I. Aliyeva
1, Teyyub A.
Ismayilov1, Musayev J. Ilham
1, Orkhan A. Aydamirov
1, Fariz A. Amirov
1
1Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, AZ1025 Baku, Azerbaijan
2Chemistry Department, Faculty of Science, Sohag University, 82524 Sohag, Egypt
*Corresponding Author: [email protected]
Received 26 April 2013; Accepted 07 June 2013
Abstract. Two surfactants [sodium and potassium salts of naphthenic acids] were synthesized by liquid-phase oxidation
process of the naphtha fraction of the Baku crude oil and their chemical structure was confirmed by FT-IR spectroscopy. The
surface tension at 298K was measured; the critical micelle concentration (CMC) and some surface active parameters were
calculated. The inhibition efficiency (%) of these surfactants has been studied by both Linear polarization resistance corrosion
rate and Potentiodynamic polarization measurements at 50 C. The data showed that, the presence of investigated inhibitors
results a high decrease in the corrosion rate. The inhibition efficiency increases with an increase in the inhibitor dose, getting
maximum inhibition efficiency 99.48% at 100 ppm of potassium salt. The Tafel polarization results indicate that the inhibitors
act as mixed inhibitors. Tafel slopes are approximately constant and independent on the inhibitor concentration. The adsorption
of the inhibitors on the carbon steel surface obeys Langmuirs adsorption isotherm. The thermodynamic parameters of
adsorption revealed a strong interaction between the inhibitors and the corroding carbon steel surface.
Key words: Petroleum acids, Carbon Steel, surfactants, corrosion inhibition, Carbon Dioxide Corrosion.
1. INTRODUCTION
Corrosion of carbon steel is a significant problem in
the oil and gas production and transportation systems
and causes significant economic loss (Okafor et al.,
2009). CO2 corrosion of carbon steels has been one of
the most common corrosion problems in oil and gas
industry. Carbon dioxide dissolves in the presence of
a water phase, forming carbonic acid, which is
corrosive to carbon steel (Lopez et al., 2003a). The
understanding of CO2 corrosion mechanisms under
the effects of many mechanical and environmental
factors, such as flow, temperature, pressure, oilwater
ratio, pH, solution chemistry, and corrosion product
layer, has been of great concern in corrosion field
(Yin et al., 2009).
The use of inhibitors is one of the most practical
methods for protection against corrosion. The
inhibitors, which reduce corrosion on metallic
materials, are inorganic inhibitors, organic inhibitors,
surfactant inhibitors and mixed material inhibitors. Surfactants are special type of organic compounds and
exhibit unique properties due to their amphiphilic
molecule. This is the reason of their wide application
in the field of inhibition of metals against corrosion. A
molecular layer of surfactants is formed as a result of
this attraction with the construction of a hydrophobic
barrier, which prevent the contact of the metal surface
with the environment. The surfactant inhibitors have
many advantages such as high inhibition efficiency,
low price, low toxicity and easy production (Abbasov
et al., 2013a; Abbasov et al., 2013b; Abd El-Lateef et
al., 2012a; Stoyanova et al., 1997; Abdallah et al.,
2009; Joseph and Rajendran, 2001). The adsorption of
the surfactant on the metal surface can markedly
change the corrosion-resisting property of the metal
(Abd El-Lateef et al., 2012b), and so the study of the
relationship between the adsorption and corrosion
inhibition is of great importance.
Salts of naphthenic acids, which are naphthenates,
are widely used as hydrophobic sources of metal ions
in diverse applications. Metal naphthenates
are coordination complexes. They have the formula
M(naphthenate)2 or are basic oxides with the formula
M3O(naphthenate)6. The naphthenates are highly
soluble in organic media, such as paints. They have
industrial applications including
synthetic detergents, lubricants and corrosion
inhibitors (Nora et al., 2005).
In this study, two surfactants (sodium and
potassium salts of naphthenic acids) were synthesized
by liquid-phase oxidation process of
the naphtha fraction of the Baku crude oil. The surface
activities of these surfactants were determined. The
applicability of these surfactants as corrosion
inhibitors for carbon steel were estimated by Linear
polarization resistance corrosion rate and
mailto:[email protected]://en.wikipedia.org/wiki/Naphthahttp://en.wikipedia.org/wiki/Crude_oilhttp://en.wikipedia.org/wiki/Coordination_complexhttp://en.wikipedia.org/wiki/Detergenthttp://en.wikipedia.org/wiki/Lubricanthttp://en.wikipedia.org/wiki/Naphthahttp://en.wikipedia.org/wiki/Crude_oil
Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
167
Potentiodynamic polarization measurements in CO2-
saturated 1% NaCl solution at 50 C.
2. MATERIALS AND METHODS
2.1. Chemical composition of carbon steel alloy
The rotating disk working electrodes for tests were
made of carbon steel grade 080A15 and have an area
of 4.55 cm2
with a chemical composition (wt%) C
0.18%, Si 0.17%, Mn 0.70%, P 0.011%, S 0.03%, Ni
0.0%, Cr 0.01% and Fe balance. The data was
provided by European Corrosion Supplies Ltd
2.2. Synthesis of Surfactant inhibitors
The surfactants used as inhibitors were synthesized in
our laboratory based on petroleum acids. The new
series of the complex surfactants were synthesized
from naphthenic acids isolated from light oil fractions
(Tb= 180-350 C) (Abbasov et al, 2012c). Two types
from inhibitors were synthesized in high purity by the
following compositions: [R-COONa (I) and R-COOK
(II)]. The chemical structure of the synthesized
surfactants was characterized by using FT-IR,
Spectrum BX spectrometer using KBr disks.
2.3. Preparation of solutions
The aggressive solution, 1% NaCl, was prepared by
dissolving of analytical grade NaCl in distilled water.
The concentration range of the prepared surfactants
was from 25 to 100 ppm used for corrosion
measurements. All inhibitors solutions were prepared
using distilled water.
2.4. Corrosion measurements
The measurements were performed on the rotating
cylinder electrode. This electrode was used for one
time. The reference electrode was Ag/AgCl Electrode
to which all potentials are referred.
Before beginning the experiment, the prepared 1%
- of sodium chloride solution was stirred by a
magnetic stirrer for 60 min in 1000 ml cell. Then this
cell was thermostated at 50 C for 1 hour under a CO2
pressure of 0.9 bars. The solution was saturated with
carbon dioxide. To remove any surface contamination
and air formed oxide, the working electrode was kept
at1500 mV (Ag/AgCl) for 5 min in the tested
solution, disconnected shaken free of adsorbed
hydrogen bubbles and then cathodic and anodic
polarization was recorded. ACM Gill AC instrument
connected with a personal computer was used for the
measurements.
2.4.1. Potentiodynamic polarization measurements
The extrapolation of cathodic and anodic Tafel lines
was carried out in a potential range 100 mV with
respect to corrosion potential (Ecorr) at scan rate of 1
mV/s.
2.4.2. Linear polarization resistance corrosion rate
The LPR method is ideal for plant monitoring offering
an almost instantaneous indication of corrosion rate,
allowing for quick evaluation of remedial action and
minimizing unscheduled downtime. The prepared 1%
- of the solution sodium chloride was stirred by a
magnetic stirrer for 60 min in 4000 ml. The prepared
solution poured into the 4 glass beakers (1000 ml for
each one). Then these beakers were placed on a heater
at 50 C for 1 hour under a pressure of 0.9 bars. The
solution was saturated with carbon dioxide. After
that, the electrodes were placed in the medium and are
connected through a potentiometer ACM GILL AC.
The surface of working electrode is cleaned by
acetone before using, these electrodes are using for
one time. After 1 hour, except for 1 beaker, the
remaining 3 is fed with the suitable amount of
inhibitor and continued supply of CO2 under pressure
of 0.9 bar until the end of the experiment.
The potential of the working electrode was varied
by a CoreRunning programme (Version 5.1.3.)
through an ACM instrument Gill AC. The
CoreRunning programme converts a corrosion current
in mA/cm2 to a corrosion rate in mm/year. A
cylindrical carbon steel rod of the composition
080A15 GRADE STEEL was used as a working
electrode. Gill AC technology allows measure DC and
AC signals using standard Sequencer software. A
small sweep from typically 10 mV to +10 mV at 10
mV/min around the rest potential is performed.
2.5. Surface tension measurements
The surface tensions were determined by DuNouy
Tensiometer, Kruss Type 8451 and the temperature
was maintained precisely at 25 C. Critical micelle
concentration (CMC) values of surfactants were
determined, according to the break points in plots of
the surface tension versus ln molar concentration of
investigated surfactants.
3. RESULTS AND DISCUSSION
3.1. Chemical structure of the synthesized
surfactants
The FT-IR spectrum of the naphthenic acid, shows a
broad OH stretch found at 3200-2700 cm-1
; the strong
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013
168
signal at 1712 cm-1
was due to a carbonyl group
(C=O). The strong signal at 1289 cm-1
was due to a C-
O stretch; the signal at 1369 cm-1
was due to a C-O-H.
The FT-IR absorption spectra of inhibitor II
confirmed that, the disappearance of OH band of acid
(broad band), this confirmed that, the replacement of
H atom in carboxylic group by K atom to form
COOK. FTIR spectra confirmed the expected
functional groups in the synthesized anionic
surfactant.
3.2. LPR corrosion rate
The linear- polarization-resistance (LPR) corrosion
rate bubble-test method involves evaluating the
corrosion of a given metal in simulated brine saturated
with CO2 at a temperature equivalent to that in the
field. During the test, CO2 gas is sparged continuously
into the test solution. The rate of corrosion is
determined instantaneously with the LPR corrosion
rate technique, in which a small direct-current voltage
is applied to a pair of identical electrodes and the
resultant current is measured.
Figure 1 shows that, the change in corrosion rate
(CR) with time for carbon steel in CO2-saturated 1%
NaCl solution containing different concentrations
form inhibitor II (K-salt) at 50 C. The inhibitor was
added after 1 hour of exposure because at this time the
corrosion potential got stable, allowing the
measurement of the CR prior the injection of the
inhibitor. The initial corrosion rate, without inhibitor,
was measured to be between 3.45 and 5.03 mm y-1
. It
can be observed from Figure 1 that, the CR, in the
absence of inhibitor, tends to increase with time. The
increase in CR has been attributed to the galvanic
effect between the ferrite phase and cementite (Fe3C)
which is a part of the original steel in the non-oxidized
state and accumulates on the surface after the
preferential dissolution of ferrite (-Fe) into Fe2+
(Staicopolus, 1963). Fe3C is known to be less
active than the ferrite phase. Therefore, there is a
preferential dissolution of ferrite over cementite,
working the former as the anode and latter as the
cathode, favoring the hydrogen evolved reaction
(HER) during the corrosion process (Crolet et al.,
1998; Videm et al., 1996).
Variation of the corrosion rate for inhibitor II at
different concentrations is presented in Figure 1.
Corrosion parameters were calculated on the basis of
LPR corrosion rate test. The inhibition efficiency (
%) and surface coverage () were calculated
according to the following equations:
where CRo is the corrosion rate without inhibitor
and CRi is the corrosion rate when inhibitor is present.
It can be seen that the presence of inhibitors results a
high decrease in the rate of corrosion. In the case of
these inhibitors, the corrosion rate decreases as the
inhibitor concentration increases, getting maximum
inhibition efficiency ranged between 98.49 and
99.48% at 100 ppm after 20 hour of exposure (Table
1). This trend may results from the fact that
adsorption and surface coverage increase with the
increase in concentration; thus the surface is
effectively separated from the medium (El-Sayed et
al., 2010).
Table 1 shows the calculated values of corrosion
rates, the inhibition efficiencies and the surface
coverage in the absence and presence of different
concentrations of different inhibitors at 50 C. A
general trend is observed in presence of the studied
inhibitors, a decrease in the corrosion rate of carbon
steel in presence of these surfactants compared to the
blank (inhibitor free solution). By increasing the
concentration of the surfactants, a further decrease in
corrosion rate of carbon steel was observed. The
maximum inhibition efficiency (%) was obtained at
100 ppm of inhibitors.. This indicates that the
inhibitory action of the inhibitors against carbon steel
corrosion can be attributed to the adsorption of these
molecules on the metal surface, limits the dissolution
of carbon steel, and the adsorption amounts of
surfactants on carbon steel increase with
concentrations in the corrosive solutions (Taleb and
Mohamed, 2011).
Figure 2 shows the variation of the corrosion rate
with time for carbon steel in CO2-saturated brine
containing 100 ppm from different surfactants at 50
C. This plot indicates that, the presence of different
inhibitors decreases the rate of corrosion. The data
indicate that, the inhibition efficiency of carbon steel
in CO2-saturated brine in the presence of inhibitor II
(K-salt) more than that obtained of inhibitor I (Na-
salt).
The high inhibition efficiency obtained in CO2-
saturated solution in the presence of studied inhibitors
can be attributed to the formation of a protective film
of iron carbonate (FeCO3) as follows (Lopez et al.,
2003b):
Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
169
The anodic dissolution for iron in carbonic acid
solutions gives ferrous ions (Ogundele and White,
1986).
Fe Fe2+
+ 2e- (7)
According to these processes, a corrosion layer
was formed on the steel surface. The properties of the
formed layers and its effect on the corrosion rate are
important factors to take into account when studying
the corrosion of steels in CO2 environments. Ogundele
and White suggested that, iron carbonate, FeCO3, may
be important in the formation of protective layers on
steel surface (Ogundele and White, 1986). The
formation of iron carbonate can be explained by using
the following Eq. (Migahed et al, 2006).
Fe2+
+2
3CO FeCO3 (8)
3.3. The extrapolation of cathodic and anodic Tafel
lines
The inhibiting effect of the synthesized compounds on
the corrosion reaction of carbon steel in CO2-saturated
NaCl solution was investigated using the
electrochemical polarization method. The polarization
technique was adopted to determine both cathodic and
anodic polarization curves. It is also used to calculate
the corrosion currents from the extrapolation of Tafel
lines to pre-determined open circuit potential. This is
achieved by measuring the potentialcurrent
characteristics of the metal/solution system under
consideration with the aid of a potentiostat.
Figure 3 shows the influence of inhibitor I
concentrations on the Tafel cathodic and anodic
polarization characteristics of carbon steel in CO2-
saturated solution at scan rate 1 mV/s and at 50 C.
Corrosion parameters were calculated on the basis of
cathodic and anodic potential versus current density
characteristics in the Tafel potential region (Tremont
et al, 2000; Schultze and Wippermann, 1987). Steady
state of open circuit corrosion potential (Ecorr) for the
investigated electrode in the absence and presence of
the studied inhibitor was attained after 4560 min
from the moment of immersion. Corrosion current
density (Icorr) of the investigated electrodes was
determined (El-Sayed, et al, 2011), by extrapolation of
cathodic and anodic Tafel lines to corrosion potential
(Ecorr). The inhibition efficiency expressed as percent
inhibition (%) is defined as:
Where Iuninh. and Iinh. are the uninhibited and
inhibited corrosion currents. The inhibited corrosion
currents are those determined in the presence of the
studied surfactants used in this investigation. The
uninhibited corrosion currents were determined in
pure (inhibitor free) CO2-saturated 1% NaCl solution
at the same temperature. It can be seen that the
presence of surfactants molecule results a marked
shift in both cathodic and anodic branches of the
polarization curves towards lower current densities.
This means that, the inhibitors affect both cathodic
and anodic reactions. It was found that, both anodic
and cathodic reactions of carbon steel electrode
corrosion were inhibited with increasing concentration
of synthesized inhibitors. These results suggest that
not only the addition of synthesized inhibitors reduce
anodic dissolution but also retard the hydrogen
evolution reaction.
The electrochemical parameters Ecorr, Icorr,
inhibition efficiency (%), anodic and cathodic Tafel
slopes (a , c) obtained from the polarization
measurements were listed in Table 2. The data
exhibited that, the corrosion current density (Icorr)
decreases, and the inhibition efficiency (%) increases
as the concentration of inhibitors is increased. These
results suggest that retardation of the electrodes
processes occurs, at both cathodic and anodic sites, as
a result of coverage of these sites by surfactants
molecules. The results also indicate that, the
percentage inhibition efficiency ( %) of the inhibitor
(II) is greater than that of the inhibitor (I), thereby;
firmly agree with aforementioned results of LPR
corrosion rate.
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013
170
Fig. 1: Variation of the Corrosion rate with time for carbon steel in CO2-saturated 1 % NaCl solution containing different
concentrations of inhibitor II (K-salt) at 50 C.
Fig. 2: Variation of the Corrosion rate with time for carbon steel in CO2-saturated 1% NaCl solution containing 100 ppm of
different inhibitors at 50 C.
The corrosion potential Ecorr values of all
synthesized inhibitors were shifted slightly toward
both cathodic and anodic directions and did not show
any definite trend in CO2-saturated brine. This may be
considered due to the mixed-type behaviour of the
studied inhibitors. It can be observed, the shift in Ecorr
that is characteristic of anodic and anodic/cathodic
inhibitor (Lpez et al, 2005). It was explained that this
shift in Ecorr is due to active sites blocking effect that
occurs when an inhibitor is added (Cao, 1996). In the
case of CO2 corrosion the anodic and cathodic
reactions are the oxidation of iron and the reduction of
hydrogen, respectively (Nordsveen et al., 2005). If it
is considered that the active sites on the metal surface
are the same for both reactions before adding the
inhibitor, it is logical the change in Ecorr when the
inhibitor is present because its adsorption change
those active sites and therefore the anodic and
cathodic reaction rates (Farelas and Ramirez, 2010).
The fact that the slopes of the cathodic (a) and
anodic (c) Tafel lines in Table 2 remain almost
unchanged upon addition of the inhibitors. These
results indicate that this inhibitor acts by simply
blocking the available surface area. In other words,
the inhibitor decreases the surface area for corrosion
of the investigated metal, and only causes inactivation
Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
171
of a part of the surface with respect to corrosive
medium. On the other hand, the cathodic Tafel slopes
(c) are also found to be greater than the respective
anodic Tafel slopes (a). These observations are
correlated with the fact that the cathodic exchange-
current density values are less than those of the anodic
counter parts. It can be concluded that the overall
kinetics of corrosion of carbon steel alloy in CO2
saturated solution are under cathodic control.
For all studied inhibitors, the common ground was
that the corrosion current density decreased and the
inhibition efficiency increased with increasing
inhibitors concentration. The highest inhibition
efficiency was 98.49 % for inhibitor II (K-salt) at100
ppm.
Table 1: The corrosion parameters obtained from LPR corrosion rate measurements for carbon steel electrode in CO2-
saturated brine in the absence and presence of various concentrations of investigated surfactants at 50 C.
Fig. 3: Tafel polarization curves for carbon steel in CO2-saturated 1% NaCl solution containing different concentration of
inhibitor (I) at 50 C.
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013
172
Table 2: Corrosion parameters obtained from Tafel polarization for carbon steel in CO2-saturted 1% NaCl solution
in the absence and presence of different concentrations of the prepared surfactants at 50 C.
3.4. Surface tension and surface active properties
The values of surface tension () were measured at
303 K for various concentrations of the synthesized
surfactants. The measured values of () were plotted
against ln of the surfactant concentration, ln C (Fig.
4). The intercept of the two straight lines designates
the CMC, where saturation in the surface adsorbed
layer takes place. The plot showed that the surfactant
was molecularly dispersed at low concentration
leading to a reduction in surface tension. This
reduction increases with increasing concentration. At
high concentration, however, when a certain
concentration was reached (CMC), the surfactant
molecules form micelles, which were in equilibrium
with the free surfactant molecules (Migahed et al.,
2006).
The surface active properties of the surfactant,
effectiveness (cmc), maximum surface excess (max),
and minimum area per molecule (Amin) were
calculated using the following equations (Rosen,
1978):
Where /lnC is maximum slope, 0 is the surface
tension of pure water, cmc the surface tension at
critical micelle concentration, NA is the Avogadros
number (6.023 1023
molecules/mol), R is the molar
gas constant (R= 8.314 J/(mol K)) and T is the
absolute temperature = (tC+273), o
micG is the Gibbs
free energy of micellization, 0
adsG is the Gibbs free
energy of adsorption (Badawi et al., 2007).
The data presented in Table 3 show some of the
surface active properties for the investigated
surfactants. The results indicate that, the consequent
increase in of max leads to crowding at the interface,
which causes a decrease in Amin values. The values of
effectiveness (cmc) at 298 K indicate that the prepared
compounds gives large reduction of surface tension at
CMC, so that, these compounds acts as effective
corrosion inhibitors for carbon steel in CO2- saturated
1% NaCl solutions.
The free energy changes of micellization and
adsorption showed negative sign showing the
spontaneity of the two processes at 25 C (Table 3).
Moreover, 0
adsG increase in negativity thano
micG .
That showed the higher tendency of these surfactants
towards adsorption rather than micellization. Then the
adsorption will be accompanied with micellization at
last. The tendency towards adsorption was referred to
Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
173
the interaction between the aqueous phases and the
hydrophobic chains which pump the surfactant
molecules to the interface (Alsabagh et al., 2006).
Table 3: The critical micelle concentration and surface parameters of the synthesized surfactants
3.5. Adsorption isotherm and thermodynamic
parameters
Basic information on the interaction between the
inhibitor molecules and metal surfaces could be
provided from the adsorption isotherms. The values of
surface coverage () which were defined as in the
following equation:
A correlation between and inhibitor
concentration in the corrosive medium can be
represented by the Langmuir adsorption isotherm (Tao
et al., 2009).
Where Kads is the equilibrium constant of the
inhibitor adsorption process and Cinh. is the inhibitor
concentration.
Plots of Cinh/ versus Cinh yielded a straight line as
shown in Fig. 5, which suggested that at 323 K the
adsorption of investigated inhibitors on metal surface
obeyed Langmuir adsorption isotherm model. This
isotherm assumed that the adsorbed molecules
occupied only one site and there was no interaction
with other molecules adsorbed. The linear regression
coefficients (r) and the slopes parameter were shown
in Table 4. All correlation coefficient (r > 0.997)
indicated that the inhibition of carbon steel by studied
surfactants was attributed to the adsorption of
inhibitors on the metal surface. However, the slopes of
the Cinh/ versus Cinh plots were close to 1 and
showed a little deviation from unity which meant non-
ideal simulating (Badawy et al., 2006) and unexpected
from Langmuir adsorption isotherm. They might be
the results of the interactions between the adsorbed
species on the metal surface (Migahed et al., 2003;
Azim et al., 1974).
Kads values could be calculated from the intercepts
of the straight lines on the Cinh/ -axis, the Kads was
related to the standard free energy of adsorption, o
adsG ; with the following equation (Flis and
Zakroczymski, 1996):
The value 55.5 in the above equation was the molar
concentration of water in solution in mol/L (Azim et
al., 1974). The relatively high value of the adsorption
equilibrium constant (Kads; Table 4) reflects the high
adsorption ability of these surfactants on the metal
surface (Abd El-Lateef et al., 2012c). It is also noted
that, the high value of Kads for inhibitor II indicate
stronger adsorption on the carbon steel surface than
the inhibitor I. Large values of Kads imply more
efficient adsorption hence better inhibition efficiency
(Refay et al., 2004).
The high and negative values of free energy of
adsorption (o
adsG ) indicate spontaneous adsorption
and strong interaction of the inhibitor molecule with
the carbon steel surface. Generally, values of o
adsG
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013
174
up to -20 kJ mol-1
are consistent with physisorption,
while those around -40 kJ mol-1
or higher are
associated with chemisorption as a result of the
sharing or transfer of electrons from organic
molecules to the metal surface to form a coordinate
bond (Farhat and Quraishi, 2011). In the present
study, the o
adsG values obtained for the surfactants I
and II on carbon steel in CO2-saturated 1 % NaCl
solution are -44.71 and -45.92 kJ mol-1
, respectively.
This indicates that the adsorption of studied inhibitors
is typical chemisorption.
Fig. 4: Change of surface tension () with the concentration of the surfactants at 25 C.
Fig. 5: Langmuir plots for inhibitors I and II in CO2-saturated brine obtained from the extrapolation of cathodic and anodic
Tafel lines at 50 C.
4. CONCLUSION
In this research, Linear polarization resistance
corrosion rate and Potentiodynamic polarization
measurements were used to study the corrosion
inhibition of carbon steel in CO2-saturated 1% NaCl
solution using sodium and potassium salts of
naphthenic acids as corrosion inhibitors. The results
can be summarized as follows.
a) The synthesized surfactant acts as an effective
corrosion inhibitor for carbon steel in CO2-saturated
1% NaCl solution.
b) The inhibition efficiency increased with
increasing concentration of the inhibitor.
Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
175
c) The inhibition efficiency (%) reached to 99.48
% at 100 ppm of the inhibitor II.
d) Polarization measurements showed that the
inhibitors act as mixed inhibitor.
e) The adsorption of the inhibitors on the metal
surface obeys Langmuir adsorption isotherm.
f) The higher value of the equilibrium adsorption
constant (Kads. = 3.65 105) reflects the high
adsorption ability of the inhibitors molecules on the
surface of carbon steel.
Table 4: Thermodynamic parameters for the adsorption of inhibitors I and II in CO2-saturated brine on the
carbon steel surface at 323 K
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Abbasov et al.
Inhibitive Effect of Some Natural Naphthenates as Corrosion Inhibitors on the Corrosive Performance of Carbon Steel
in CO2-Saturated Brine
177
Prof. Dr. Vagif Maharram Abbasov, Doctor of chemical sciences (DSC), Azerbaijan National Academy
of Sciences, Institute of Petrochemical Processes, Director of Institute of Petrochemical Processes. He
is a Member of the Editorial Board of "Processes of Petrochemistry and oil refining journal" (Chief
Secretary). He is a Member of the American Chemical Society. He is an author on 250 papers in
international journals and more than 35 books. V. M. Abbasov has carried out the thorough researches
in the field of synthesis of antistatic additives to hydrocarbon liquids including to jet fuels. He for the
first time proposed the possibility for producing the displaced complexes of nitroalkanes and organic
acids with the transition metals, developed on their basis the high efficient and polyfunctional antistatic
additive. This additive was tested and commercialized in perm plant of aircraft engines. V. M. Abbasov
with coworkers has created in 1997 the polyfunctional waxy deposit corrosion inhibitor "Parkorin-1",
the commercial tests have been carried out in the Azerbaijan oil fields, jointly exploited by Turkish- Azerbaijan and by
TSNIIKP (Moscow city) has been recommended for application.
Dr. Hany M. Abd El-Lateef was born in Sohag, Egypt, in 1982. He received the master degree in
physical chemistry from the University of Sohag, Sohag, Egypt, in 2009, since that has worked in
different projects in the field of corrosion science. In 2010, he joined the department of chemical
resistance of materials and corrosion protection, institute of petrochemical processes, Azerbaijan
National Academy of Sciences, as a PhD student. He is one of the Editorial board of Chemistry Journal.
He is an author on 30 papers in international journals and two books. Hany is one of NACE
membership.
Dr. Sevinc A. Mamedxanov, Doctor of chemical sciences, Azerbaijan State Oil Academy. She is an
author on 50 papers in international journals. She obtained degree in Master of Science in
Petrochemistry from Azerbaijan State Oil Academy. She received his first degree in applied chemistry
from Azerbaijan State Oil Academy. Her research is focused on the Synthesis of various surfactants,
compounds soluble in oils and fuels, and their investigation as corrosion inhibitors, additives to fuels,
oils, polymeric stabilizers, development of theoretical bases for selecting corrosion inhibitors and
additives.
Prof. Dr. Leylufer Imran Aliyeva Doctor of Technical Sciences, Azerbaijan National Academy of
Sciences, Institute of Petrochemical Processes, Head of department. She is a Member of the Editorial
Board of "Processes of Petrochemistry and oil refining journal". She is an author on 180 papers in
international journals and more than 18 books. Her work focused on the synthesis of nitroalkanes
metallocomplexes, high-molecular amines and creation of polyfunctional antistatic additives, corrosion
inhibitors, inhibitor-bactericides and study of their action mechanism. She has created the high efficient
polyfunctional sulfurated hydrogen corrosion inhibitors based on -olifins with working capacity in the
media with H2S, CO2 content more than 25% vol.
http://www.google.com.eg/url?sa=t&rct=j&q=azerbaijan+neft+academy&source=web&cd=1&cad=rja&ved=0CDEQFjAA&url=http%3A%2F%2Fen.wikipedia.org%2Fwiki%2FAzerbaijan_State_Oil_Academy&ei=b1mFUb68HK6w4QTDl4CoDg&usg=AFQjCNGRjlbJ79143AtSz1mBwpRSBndHUA&bvm=bv.45960087,d.Yms
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 166-178, 2013
178
Dr. Teyyub A. Ismayilov, Doctor of chemical sciences, Azerbaijan National Academy of Sciences,
Institute of Petrochemical Processes. He is an author on 50 papers in international journals. T. A.
Ismayilov has carried out the thorough and extensive researches in the field of creation of the corrosion
inhibitors and obtained the following important results: on the basis of carbamide and amines there has
beer created a new method for synthesis of phosphate complexes and organized on their basis the
production and application of polyfunctional corrosion inhibitors.
Musayev Javidan Ilham is a Ph.D student in the sphere of quality control at the State Economic
University of Azerbaijan. He received his first degree from The State Economic University in 2009
awarded with Bachelor of Science. He obtained Master degree of Science from The State Economic
University in 2012. His current research is focuses on synthesis and the review in quality of sulfonation
of acids and saline acids on plant origin.
Orkhan A. Aydamirov obtained his first degree from the Baku State University in chemistry in 2011.
He is junior researcher in Petrochemical Institute of Azerbaijan National Academy of Sciences. His
current research is focuses on corrosion inhibitors and conservation fluids. To date, he has published
several scientific articles related to corrosion inhibitors. He also interests in alternative energy sources
and biomass.
Dr. Fariz A. Amirov is an Assistant Professor in Azerbaijan State Oil Academy. He has more than 22
years research experience in the field of Petrochemistry. He has published over 70 refereed articles in
professional journals/proceedings. Dr. F. A. Amirov research has focused on alleviating problems
associated with oil industry issues from corrosion. He is editor and reviewer of some international
journals.
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 179-187, 2013 Available online at http://www.ijsrpub.com/ijsres
ISSN: 2322-4983; 2013 IJSRPUB
http://dx.doi.org/10.12983/ijsres-2013-p179-187
179
Review Paper
Livestock Products and Environment
Maryam Asghari
Researcher in Environmental Economics and International Trade and Assistant Professor at Shahid Ashrafi Esfahani
University, Esfahan, Iran; Email: [email protected]
Received 14 May 2013; Accepted 07 June 2013
Abstract. Increasing demand for livestock products, together with changes in international trade, is placing pressure on the
livestock sector both to adapt and expand. There is an increasing tendency to greater selectivity as to parts of the animal used
for food and therefore, there is a trend from multi-purpose to single-purpose animals, with the production of animal protein the
overriding objective. The aim of this paper is the examination of livestock products effects on environmental quality as
agricultural trade liberalization happens in the six countries of Gulf Persian region, over 1980-2012. Our results show that this
is an N-shaped EKC between income and the agricultural land expansion in this region. We find that livestock production
decreases the percentage annual growth of agricultural land area use in this region as trade in agriculture sector is libered and
the form of EKC has not changed when we enter livestock production index of the different countries, as agriculture trade is
libered, in our model.
Key words: Agriculture Trade Liberalization, Livestock Products, Environmental Quality, Environmental Kuznets Curve,
Gulf Persian Region
1. INTRODUCTION
The livestock has been well knit with the socio-
economic fabric of our rural economy and played an
important role in the employment and income
generation. The developed countries of the world have
already well recognized the importance of livestock
for employment and income generation and have
devolved around their agriculture a prosperous,
progressive and forward looking livestock enterprise.
The major components through which livestock
contribute to the agricultural income are milk and
milk products, meat and eggs.
Livestock production is an important resource
ensuring global food supply, meeting the increasing
demand for protein and supporting human livelihood
and well-being. Both extensive and intensive livestock
production systems require attention and intervention
to promote fewer negative and more positive impacts
on social, economic, and environmental aspect, all
within a global context.
In the developing countries, the income elasticity
of demand for livestock products is high as compared
to cereals. It is also high as compared to the developed
economies. This implies that with rising per capita
income, the demand for these products would rise
faster in the Third World countries.
Livestock production can contribute to poverty
reduction and economic growth in those poor
countries that are not fully exposed to globalized food
markets. In rapidly growing and developed
economies, market barriers and economies of scale
will continue to push smallholders out of production,
thus alternative livelihoods need to be sought in other
sectors.
Standard economic theory concludes that
liberalised agricultural trade increases social welfare.
By specialising in the production of food and fibre
products for which it has comparative advantage, each
countrys allocative market efficiency can be
improved, thus permitting higher national and global
economic growth. The returns from that higher level
of growth enhance individual incomes, which in turn
raise national welfare.
Further liberalization of agricultural trade can
affect environmental quality and the pattern of natural
resource use through several, possibly offsetting, and
effects. Further agricultural trade liberalization can
affect the scale of production, the composition of
goods produced in an economy, and the technologies
used to produce output.
The rapid increase of intensive (confined) livestock
production and the land and livelihood needs of
extensive production (rangeland grazing) are crucial
challenges. The livestock sector emerges as a very
significant contributor to environmental problems at
every scale from local to global, including land
degradation, climate change and air pollution, water
shortage and pollution and loss of biodiversity.
By improving allocative market efficiency through
liberalised trade, the country enjoys higher economic
growth and incomes, but the growth also generates
negative pollution effects from the increased scale of
economic activity. Increased incomes raise the social
mailto:[email protected]
Asghari
Livestock Products and Environment
180
demand for environmental quality which translates
into policies that shift product composition and
techniques of production to meet public
environmental objectives via less pollution and more
positive environmental services.1
By expanding the scale of livestock production,
trade liberalization can increase pollution. However,
countervailing forces will tend to offset the scale
effect by encouraging an economy to use cleaner
technologies to produce output and by encouraging
specialization in the production of less pollution-
intensive goods.
Total emissions of greenhouse gases (GHGs) from
agriculture, including livestock, depend on the source
(US EPA, 2006; IPCC, 2007) and on the proportion of
land conversion that is ascribed to livestock activities.
Land-use change is complex and driven by a range of
drivers, although it is possible to see some strong
historical associations between land abundance,
application of science and technology, and land-use
change in some regions (Rosegrant et al., 2009)
The implications of livestock demand increases on
land use in the future are perhaps best discussed in
relation to the different livestock production systems
that occur globally. Confined livestock production
systems in industrialized countries are the source of
much of the worlds poultry and pig meat production,
and such systems are being established in developing
countries to meet increasing demand. Future trends for
these essentially landless production systems are
outlined in Steinfeld et al. (2006), who describe a two-
step process: as developing countries industrialize,
large-scale monogastric production systems spring up
and tend to be located close to urban centers to
minimize the problems associated with product
conservation and transportation. In the second step,
transport infrastructure and technology develop
sufficiently so that these intensive livestock systems
are located further away from the centers of demand
for the products. This movement can help to reduce
some of the economic costs of production (via lower
land and labor costs), improve access to feed
resources via reduced feed transportation costs, and
may also reduce (or make it easier to deal with) some
of the environmental and human and livestock health
issues associated with intensive, industrialized
production (Steinfeld et al., 2006). If this two-step
characterization of this process is broadly correct, then
in the future these largely landless systems will
become concentrated outside peri-urban areas,
particularly in regions with good access to long-
1 - Note in this simple conception of the process adapted
from Runge [1995], structural effects are not broken out
separately but can be interpreted to fall within the product
and technology categories.
distance transportation facilities (ports, railways)
and/or with good access to plentiful feed resources.
There are likely to be strong regional differences in
the growth of industrial (confined) livestock
production systems.
This paper attempts to quantify the effect of
livestock production, when trade is libered in
agriculture sector, on agricultural land use expansion.
The remainder of the paper is organized as follows.
Section II presents the relation between growth and
environment. Section III specifies the empirical model
and the data and discusses the empirical results, while
Section VI concludes.
2. ECONOMIC GROWTH AND
ENVIRONMENT
The issue of worldwide environment has received
more attention than ever, since global warming and
other environmental problems are becoming more and
more serious. In particular, an urgent subject for all
authorities who are responsible for environmental
policies is to understand and predict how the
environmental quality will evolve over time.
At the 67th annual meeting of the American
Economic Association in 1954, Simon Kuznets
delivered the presidential address Economic Growth
and Income Inequality and suggested that, as per
capita income increases, income inequality also
increases at first but then, after some turning point,
starts declining (Kuznets, 1955). This changing
relationship between per capita income and income
inequality can be represented by an inverted-U-shaped
curve, known as the Kuznets curve, for which Kuznets
was awarded the Novel prize in economics in 1971.
The Kuznets curve hypothesis posits that initially, at
lower levels of per capita income, income distribution
is skewed toward higher income levels so that income
inequality is high. As income rises, skewness is
reduced and income inequality becomes lower.
The environmental Kuznets curve (EKC for short)
is referred to as the hypothesis that the relationship
between environmental degradation and per capita
income exhibits an inverted-U shape. The logic of the
EKC relationship is rather intuitive. In early stages of
industrialization, pollution grows rapidly because high
priority is given to increasing material output, and
people are more interested in income than
environment. In the later stage, however, as income
rises, the willingness to pay for a clean environment
increases by a greater proportion than income,
regulatory institutions become more effective for the
environment, and pollution level starts declining.
The EKC hypothesis is usually described by three
effects: (a) the effect of the scale of economic activity,
(b) the effect of the changes in the structure of
International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(8), pp. 179-187, 2013
181
economic activity and (c) the effect of income on the
demand for pollution abatement efforts (Panayotou,
2000). The first effect is a monotonically increasing
function of income: the larger the scale of economic
activity the higher the level of pollution, all else being
equal. The second effect reflects the changes in the
composition of the economic activity toward sectors
of varying pollution intensity: a shift from agriculture
to industry implies higher pollution while a shift from
industry to services reverts this trend. The third effect
is a monotonically decreasing function of income and
it reflects the growing demand for environmental
quality with higher income levels (Kukla-Gryz, 2009).
Theoretical models on the EKC relationship can be
classified into several categories; e.g., static vs.
dynamic, macroeconomic vs. microeconomic, long
term vs. short term, deterministic vs. stochastic. This
paper adopts the classification based on static and
dynamic models. The primary reason is that most
theoretical studies in the literature mainly focus on the
macroeconomic production and/or the utility of a
representative agent without uncertainty. While static
models are classified into production-based models
and utility-based models, dynamic models are
classified further to include policy-based models and
the real options approach (Kijima, al. 2010)
Note that most of the theoretical papers succeed
only to illustrate an inverted-U-shape pattern and few
of them shows an N-shaped pattern. It is therefore
required to develop sophisticated models that are
flexible enough to explain the actual environment-
income relationship and to predict how the
environmental quality will evolve in future within a
unified framework. Such theoretical models supported
by ample empirical studies can be useful for
environmental policy makers, because the evolution
of pollution is linked not only with a development
path or economic growth, but also with policy
response. See, e.g., Grossman and Krueger (1995),
Magnani (2001).
Conventional EKC studies employ functional
forms where results can be evaluated with respect to
the presence or absence of a turning point (TP) and
the significance of the parameters computed (Agras
and Chapman, 1999). The following equation shows
that a reduced functional form is applied to find out
the best possible relationships between environmental
pollution level and economic growth:
Yit = i + 1Xit + 2X2it
+ 3X
3it + 4Zit + it (1)
where Y is environmental indicators, X is
income and Z relates to other variables of influence
on environmental degradation. Here, the subscript i
is a country, t is time, is constant, is error
term while k is the coefficient of the k
explanatory variables (Chow, 2006; Dinda, 2004;
Ekins, 1997; Shafik, 1994). Eq. (1) provides us with a
method to test several forms of environment-
economic development/growth relationships.
The model (1) provides important information as
to the form of the relationship between environment
and economic growth. Namely, if 01 ( 01 ,
respectively) while 032 , then there is a
monotonically increasing (decreasing) relationship
between income x and environment y. If, on the other
hand, 01 , 02 and 03 , then we observe
an inverted-U-shaped relationship, the original EKC
pattern. Note that, in this case, the turning point of the
curve is given by2
1*
2
x . Finally, if 01 ,
02 and 03 , then we come up with an N-
shaped relationship. Of course,
when 0321 , this indicates that there is no
relationship between income x and environment y.
The other cases are not of interesting the EKC
literature.
However, some papers are skeptical about the EKC
hypothesis, and some criticize the concept and
methodology of empirical studies. For example, a
variety of time series, cross-section and panel data
analyses indicate that the empirical results are
sensitive to the sample of countries chosen and to the
time period considered (Grossman and Krueger, 1993;
Selden and Song, 1994; Hill and Magnani, 2002). The
results may change by the choice of scaling factors to
be used in regression models (Borghesi, 2001). Also,
empirical studies are based on reduced-form models
that assume specific functional forms a priori to
estimate the environment-income relationship.1 In
reality, the environment-income relationship could be
more complicated than the assumed functional forms
(see, e.g., Section 4 in Borghesi, 2001). Hence, it is
not sufficient to conclude an EKC relationship based
on such empirical studies and, as Pearson (1994)
argues, more sophisticated techniques of curve fitting
should be investigated, so that our findings are not
determined by specific functional forms. The fitted
function should be decided, based on theoretical
research, for the complex bi-directional relationship
between environmental quality and economic-social
development. A comprehensive review of the
empirical literature examining the EKC hypothesis is
presented by Soumyananda (2004) and Verbeke and
Clercq (2006).
Asghari
Livestock Products and Environment
182
Using new international data, Hettige et al. (2000)
test the environmental Kuznets curve (EKC)
hypothesis for industrial water pollution. They
measure the effect of income growth on three
determinants of pollution: the share of industry in
national output, the share of polluting sectors in
industrial output, and end-of-pipe (EOP) pollution
intensities (per unit of output) in the polluting sectors.
They find that the industry share of national output
follows a Kuznets-type trajectory, but the other two
determinants do not. When combined, their results
imply rejection of the EKC hypothesis for industrial
water pollution: it rises rapidly through middle-
income status and remains roughly constant thereafter.
Mills et al. (2009) test this environmental Kuznets
curve (EKC) using estimates of per capita income and
deforestation rates (index of biodiversity threat) for 35
tropical countries. They introduce the use of quantile
regression and spatial filtering to reanalyze this data,
addressing issues of heteroskedasticity and spatial
autocorrelation. They note that preliminary analysis
using these methods provides some initial evidence
for an EKC. However, a series of panel analyses with
country-specific dummy variables eliminated or even
reversed much of this support. A closer examination
of conservation practices and environmental
indicators within the countries, particularly those
countries that drove our initial support, suggests that
wealth is not a reliable indicator of improved
conservation practice. Their findings indicate that an
EKC for biodiversity is overly simplistic and further
exploration is required to fully understand the
mechanisms by which income affects biodiversity.
3. EMPIRICAL MODEL
1.3. Our Model
In the above discussions, we have seen that livestock
products are a key determinant of agricultural land-
use expansion. So, we need to a new model to the
cross-country analysis of agricultural land use
expansion. The model should concentrate on
explaining agricultural land use expansion, 1 itit AA ,
on the other hand, agricultural land-use increasing
have a nonlinear quadratic relationship according to
the EKC hypothesis. Hence, the long-run steady-state
relationship between land-use increasing, livestock
prod