Green Corrosion Electrochemistry: Cheilocostus Speciosus Extract (CSE) Investigated Electro-Analytically As A Potential Green Corrosion Inhibitor For Copper Within Acidic Solution

International Journal of Emerging Trends in Engineering and Development Issue 7, Vol.
1 (January 2017)
Available online on http://www.rspublication.com/ijeted/ijeted_index.htm ISSN 2249-6149
Green Corrosion Electrochemistry: Cheilocostus Speciosus Extract (CSE)

Investigated Electro-analytically as a Potential Green Corrosion Inhibitor for
Copper within Acidic Solution
Hala M. Hassan*1, Ahmed M. Eldesoky2, Awad Al-Rashdi3 and Hytham M. Ahmed4

1*
Textile Technology Department, Industrial Education College, Beni-Suef University, Egypt and Chemistry
Department, Faculty of Science, Jazan University, KSA.
2
Engineering Chemistry Department, High Institute of Engineering &Technology (New Damietta), Egypt and Al-
Qunfudah Center for Scientific Research (QCSR), Chemistry Department, Al-Qunfudah University College, Umm
Al-Qura University, KSA.
3
Al-Qunfudah Center for Scientific Research (QCSR), Chemistry Department, Al-Qunfudah University College,
Umm Al-Qura University, KSA.
4
Pharmaceutical Analysis Department, Faculty of Pharmacy, Damanhour University, Damanhour, Egypt.
ABSTRACT:
For the first time, the investigation and characterization of Cheilocostus Speciosus
Extract, as a potential green corrosion inhibitor for copper within acidic aqueous solutions is
been reported. The inhibition efficiency was calculated based on the data using weight loss,
potenodynamic polarization, electrochemical impedance spectroscopy and electrical frequency
modulation. The values reported in this manuscript were 73.47% for weight loss, 88.2 for
potenodynamic polarization, 89.3 for electrochemical impedance spectroscopy and 90.8 for
electrical frequency modulation. The temperature effect upon the corrosion behavior at different
concentrations was also studied over the temperature range from 25 to 40 C by weight loss
method. Polarization curves revealed that the investigated extract is a mixed type inhibitor. The
inhibition efficiency increased proportionally with the investigated extract concentration and
decreased with the solution temperature. The adsorption of the inhibitor on the copper surface
was found to obey the Langmuirs adsorption isotherm. The results obtained from chemical and
electrochemical techniques are in good agreement with each other.
Keywords: Copper, Cheilocostus Speciosus Extract, Green inhibitor, Langmuirs Adsorption

Isotherm and Electrochemical Impedance Spectroscopy.
1. INTRODUCTION:
Many metals and alloys used in different human activates are susceptible to different
forms of corrosion due to their exposure to different corrosive media. Copper has been one of the
more important materials in industry owing to its high electrical and thermal conductivity,
mechanical workability and its relatively noble metal properties. Corrosion is the destructive
Page 72 2017 RS Publication, rspublicationhouse@gmail.com
International Journal of Emerging Trends in Engineering and Development Issue 7, Vol. 1 (January 2017)
surface phenomenon which affects copper and almost all metals, known as the attack of metals
or alloys by their environment, by chemical or electrochemical reactions to form more stable
compounds. When copper is corroded, many of its important properties such as heat and
electricity conductivity are affected. Thus, recent investigators have been attracted by the
corrosion of copper and the process of its inhibition. It requires strong oxidants for this corrosion
or chemical dissolution. The Electrolytic plating and chemical dissolution are the two main
processes used in fabrication or electronic devices. Corrosion inhibitors which used in acidic
solutions are generally used to decrease the rate of corrosion during the acid cleaning and
descaling. The possibility of controlling the dissolution rate of copper surface at a desired value
by adding inhibitors to the corroding environment has attracted many researchers, and until now,
various possible inhibitors have been investigated for copper-acidic system [1-3].
Some methods and compounds have been used as corrosion inhibitors for copper metal
in acidic media such as inorganic, organic, amines, amino acids, triphenylamine derivatives,
thiole group compounds, potassium ethyle xanthate, phthlazine and self-assembled monolayers
such as dodecanethiol (DT). Although several synthetic organic compounds represent good
anticorrosive activity, most of them are highly toxic causing severe hazards to both human and
the environment. Because of the toxicity of most of thesecorrosion inhibitors, this has
necessitated the use of environment-friendly inhibitors. Among the eco-friendly inhibitors,
natural products find a prominent place. The extracts of several parts of many plants have gained
importance as environmentally acceptable, easily available, biodegradable, and renewable
sources of materials for a wide range of corrosion prevention applications. Thus, finding
naturally occurring substances as a potential corrosion inhibitor is a subject of great practical
significance. Plant extract is an alternative way to use corrosion inhibitors as they exhibit several
more advantages such as low-cost and environmental safe [10].
The purpose of the present study is to determine the influence of eco-environmental

friendly green inhibitor leaves extracts Cheilocostus Specious on the corrosion of copper in
acidic media. A comparison table illustrates the inhibition efficiency values for other friendly
green inhibitors employed in the corrosion inhibition of copper-acidic media was also reported.
Crpe Ginger or Cheilocostus (CSE) is depicted in Fig. 1 belongs to the genus Cheilocostus and
the family Costus specious.

a) b)
Fig. 1: The Cheilocostus Specious a) Main features and b) a photograph of the plant [21]
Costus is a group of perennial herbaceous plants in the family (Costaceae described by

[2,3]
Linnaeus as a genus in 1753 . It is an economically important medical plant for its content of
high value secondary metabolites, bioactive compounds. It is widespread through tropical and
subtropical regions of Asia, Africa, and the Americas.
The purpose of this work is to investigate the protection efficiency of the green corrosion
inhibitor Cheilocostus Speciosus Extract (CSE) on copper corrosion in 1M HNO3 by Tafel
polarization, weight loss, electrochemical impedance spectroscopy (EIS), and the
electrochemical frequency modulation (EFM) techniques without and with the inhibitor was
studied to measure the inhibition efficiency.
2. EXPERIMENTAL METHODS
2.1. Materials and Solutions
The copper electrode was made from 99.98 percent pure copper rode as a working
electrode purchased from Sigma- Aldrich (UK) and used as received. The rod was mounted into
a glass tube and fixed by araldite leaving a circle surface geometry of 1 cm diameter to contact
the test solution. Prior to each experiment, the working electrode was polished with different
grades of emery paper up to 1200 grade. Prior to the experiment, the working electrode was
polished with different grades of emery paper up to 1200 grade, then cleaned ultrasonically in
acetone for 2 min, followed by a rinse in double-distilled water.
A platinum sheet electrode was used as counter electrode, and the reference was a
saturated calomel electrode (SCE). The three electrodes were connected to a conventional
electrolytic cell of 100 ml capacity. The aggressive acidic solution used to emulate the acidic
conditions employed industry was prepared by dilution of analytical reagent grade 70% HNO 3
with bi-distilled water. Stock solution of a 1000 ppm CSE was used to prepare 25-150 ppm
concentration range by dilution by the appropriate amount of purified water with 18.2 M. Cm
conductivity.
2.2. Preparation of Plant Extracts
Fresh aerial parts of CSE sample were crushed into a mortar creating a fine powder. The
powdered materials (250 g) were soaked in 500 ml of dichloromethane for 5 days and then
subjected to repeated extraction with 5 50 ml until exhaustion of plant materials. The extracts
obtained were then concentrated under reduced pressure using rotary evaporator at temperature
below 50C. The solid extract was collected after dichloromethane evaporation and subsequently
it was prepared for application as corrosion inhibitor.
[18]
Chemical studies and characterization have demonstrated that the CSE constituents
are phytochemical isolated from roots as: 24-hydroxytriacontan-26-one and 24-
hydroxytriacontan-27-one along with methyl triacontanoate, diosgenin, sitosterol, 8-hydroxy
triacontane-25-one and methyl triacontanoate. 5-stigmast-9(11)-en-3-ol was also
characterized. The roots of this plant also contain -sitosterol--D-glucoside, prosapogenins A
and B of dioscin, dioscin, gracillin, 3-O-[-L-rhamnopyranosyl(12)--D-glucopyranosyl]-26-
O-[-Dglucopyranosyl]- 22-methoxy-(25R) furost-5-en-3,26diol, protodioscin and
methylprotodioscin. Other components identified were 31-norcycloartanone, cyloartanol,
[19,20]
cycloartenol and cycloalaudenol . The structures of the main phytoconstituents which are
Protodiosan, Octasonoic acid, Dioscin, Diosgenin, Gracillin and Cycloartanol are depicted in
Scheme 1.
CH3
CH3 OH CH3
OH H
OH O
O O
CH3 H OH
HO O
H H HO
O OH
HO HO O HO
CH3 O CH3
HO OH
OH
Protodioscin
H3C R
CH3 CH3 CH3 CH3
Octasonoic acid
CH3
CH3
CH3 O
OH
OH
O
CH3 H H
HO O CH3
H H
O
HO HO O
CH3 O CH3
HO OH
OH
Dioscin
H
CH3 CH3
O
H3C
O
CH3
HO
Diosgenin
H
CH3 CH3
O
H3C
O
CH3
OH
O O
O
HO
HO
O
OH
HO
OH
HO O O
CH3
H H
H H
OH OH
Gracillin

H2C
H3C
CH3
H3C
CH3
H3C O
H3C O H3C
O
H3C CH3
Cycloartanol
Scheme 1: Structures of Protodiosan, Octasonoic acid, Dioscin, Diosgenin, Gracillin and Cycloartanol.
Scheme 1 illustrates the structures of the main phytoconstituents which were isolated
from Cheilocostus Speciosus Extract (CSE).
Cheilocostus speeciosus Extract CSE chemical constituents are organic which have heteroatoms
[19,21]
or -electrons , enabling the adsorption on the surface of copper and therefore inhibiting
[22]
corrosion. The Langmuir adsorption isotherm and in some cases Temkin isotherm can
describe the physical adsorption.
2.3. Weight Loss Method
Copper square specimens of size 2cm 2cm 0.2cm for weight loss measurements were
polished to a mirror finish using different grades of abrasive paper from 400 up to 800, immersed
in methanol and washed with bidistilled water, dried before being weighed and immersed into
the test solution.
The weight loss measurements were carried out in a 100 ml capacity glass beaker
placed in water thermostat at 25C. The specimens were then immediately immersed in the test
solution without or with the desired concentration of the investigated compound. Triplicate
specimens were exposed for each condition and the mean weight losses were reported in order to
verify reproducibility of the experiments.
2.4. Electrochemical Measurements
2.4.1. Potentiodynamic Polarization Measurements

Polarization experiments were carried out in a conventional three-electrode cell with
platinum gauze as the auxiliary electrode (1 cm2) and a saturated calomel electrode (SCE)

coupled to a fine Luggin capillary as reference electrode. The working electrode was in the form
of a square cut from copper sheet of equal composition embedded in epoxy resin of
polytetrafluoroethylene so that the flat surface area was 1 cm2. Prior to each measurement, the
electrode surface was pretreated in the same manner as the weight loss experiments. Before
measurements, the electrode was immersed in solution at natural potential for 30 min. until a
steady state was reached. The potential was started from - 600 to + 400 mV vs. open circuit
potential (Eocp). All experiments were carried out in freshly prepared solutions at 25C and
results were always repeated at least three times to check the reproducibility.
2.4.2 Electrochemical Impedance Spectroscopy Measurements

Impedance measurements were carried out using AC signals of 5 mV peak to peak
amplitude at the open circuit potential in the frequency range of 100 kHz to 0.1 Hz. All
impedance data were fitted to appropriate equivalent circuit using the Gamry Echem Analyst
software.
2.4.3 Electrochemical Frequency Modulation Technique

EFM experiments were performed with applying potential perturbation signal with
amplitude 10 mV with two sine waves of 2 and 5 Hz respectively. The choice for the frequencies
[23]
of 2 and 5Hz was based on three arguments . The larger peaks were used to calculate the
corrosion current density (icorr), the Tafel slopes (c and a) and the causality factors CF-2 and
CF-3 [24]. All electrochemical experiments were carried out using Gamry instrument PCI300/4
Potentiostat/Galvanostat/Zra analyzer, DC105 corrosion software, EIS300 electrochemical
impedance spectroscopy software, EFM140 electrochemical frequency modulation software and
Echem Analyst 5.5 for results plotting, graphing, data fitting and calculating.
3- Results and Discussion
3.1. Weight Loss Measurements

First, we turn our attention to the investigation and studies of weight loss
measurements. Fig. 2 represents the weight loss-time curves for copper in 1 M HNO3 in the
absence and presence of Cheilocostus Speciosus Extract (CSE). The weight loss method at
different concentrations (25150 ppm) was performed where it is observed from Fig. 2 that the
weight loss varies with the CSE concentration. The weight loss increases inversely with the CSE

inhibitor concentration in 1 M HNO3. The inhibitory behavior of the compound against copper
corrosion can be attributed to the adsorption of CSE inhibitor on the copper surface, which limits
the dissolution of the metal by blocking its corrosion sites and increase the inhibition efficiency,
hence decreasing the corrosion rate.
The weight loss values are used to calculate the corrosion rate (R) in mmy-1 by Eq. (1):
R = (weight loss in gram x 8.75 x 104) / DAT (1)
where D: copper density in g cm-3, A: exposed area in cm2 and T: exposure time in hours.
The inhibition efficiency (%IE) and the degree of surface coverage () were calculated from Eq.
(2):
% IE = x 100 = [(R* - R) / R*] x 100 (2)
where R* and R are the copper corrosion rates in the absence and in the presence of
inhibitor, respectively.
Table 1 collects the values of inhibition efficiency obtained from weight loss method at
different concentrations of CSE (25150 ppm) in 1 M HNO3 at 25C. The weight loss decreased,
and therefore the corrosion inhibition strengthened, with increase in inhibitor concentration. This
trend may result from the fact that adsorption and surface coverage increases with the increase in
CSE inhibitor concentration; thus, the surface is efficiently separated from the medium as well as
the reduction of copper corrosion rate in 1M HNO3.
7
Blank .
25 ppm.
50 ppm.
6 75 ppm.
100 ppm.
125 ppm.
150 ppm.
5
-2
4
Weight loss, mg cm
0
0 30 60 90 120 150 180
Time,min
Fig. 2: Weight loss-time curves for the dissolution of copper in the absence and presence of different
concentrations of Cheilocostus Speciosus Extract (CSE) in 1 M HNO3 at 25oC.

Table 1: Variation of inhibition efficiency (%IE) of Cheilocostus Speciosus Extract (CSE)

with its different concentrations at 25oC from weight loss measurements at 60 min
immersion in 1 M HNO3.
Compound Conc., CR % IE
ppm mg cm-2 min-1
Blank 0.049
--- ----
0.023 52.90
25
0.019 61.83
50
(CSE) 0.017 65.45
75
0.016 67.71
100
0.014 70.69
125
0.013 73.47
150
3.2. Adsorption Isotherm

It is generally assumed that the adsorption of the inhibitors on the metal surface is
[25]
essential step in the inhibition mechanism . To calculate the surface coverage () it was
assumed that the inhibitor efficiency (% IE) is due mainly to the blocking effect of the adsorbed
[26]
species so (% IE = x100) . To gain insight into the adsorption mode of CSE on copper
surface, the surface coverage values from weight loss technique were theoretically fitted into
different adsorption isotherms and the values of correlation coefficient (R2) were used to
determine the best-fit isotherm. Fig. 3 shows the plot (C/) vs. (C), which is typical of Langmuir
adsorption isotherm at different temperatures. The slope deviation from unity is a result of
interactions effect between adsorbing inhibitor molecules and the copper metal surface and
change in heat adsorption with the increasing surface coverage [27], [28], factors that were ignored
in the deviation of Langmuir isotherm.
The Langmuir isotherm is given by Equation (3) [29]:
(3)
where (C) is the inhibitor concentration and (K) is the equilibrium constant of adsorption
process which is also related to the standard free energy of adsorption (Gads) by Equation (4):

(4)
Using equation (4) 55.5 value represents the concentration of water in solution expressed
in mole per liter, (R) the universal gas constant and (T) the absolute temperature. The calculated
(Gads) values were also given in Table 2. The negative values of (Gads) ensure the
spontaneity of the adsorption process and the stability of the adsorbed layer on the copper
[30]
surface . Values of G in the region of -40 kJ mol-1 or higher involve charge sharing or
transfer from the inhibitor molecules to metal surface to form coordinate type of bond
(chemisorption); those of order of -20 kJ mol-1 or lower indicate a physisorption [31, 32]
. The
calculated (Gads) values recorded in Table 2 were less negative than -20 kJ mol-1 represents the
adsorption mechanism of CSE on copper in 1 M HNO3 solution because of physisorption. The
lower negative values of (Gads) indicate that this inhibitor is not strongly adsorbed on the
copper surface. Moreover, the adsorption heat can be calculated per the Vant Hoff equation [33]:
Ln Kads = H0ads/RT+ const (5)
That is:
Ln (K2ads/K1ads) = H0ads/R(1/T2-1/T1) (6)
where H is the adsorption heat, R is the gas constant, T is the absolute temperature,
K1 and K2 are the adsorptive equilibrium constants at T1 and T2, respectively. In consideration
that the experiments precede at the standard pressure and the solution concentrations are not very
high, which are close to the standard condition, the calculated adsorption heat thus can be
approximately regarded as the standard adsorption heat Hads. The negative values of H
recorded in Table (2) presents the exothermic behavior of the adsorption of CSE on the copper
surface. Finally, the standard adsorption entropy Sads can be calculated by the following Eq.
(7):
Sads= (Hads -Gads) /T (7)
The (Sads) values from Table 2 are positive, which are opposite to the usual expectation
that the adsorption is an exothermic process and always accompanied by a decrease of entropy.
The reason can be explained as follows: the adsorption of CSE inhibitor molecules from the
aqueous solution can be regarded as a quasi-substitution process between the CSE in the aqueous
[34-37]
phase and water molecules at the electrode surface [H2O(ads)] . In this situation, the

adsorption of CSE is accompanied by the desorption of water molecules from the copper surface.
Thus, while the adsorption process for the inhibitor is believed to be exothermic and associated
[38]
with a decrease in entropy of the solute, the opposite is true for the solvent . The
thermodynamic values obtained are the algebraic sum of the adsorption of CSE inhibitor
molecules and the desorption of water molecules. Therefore, the gain in entropy is attributed to
the increase in solvent entropy. The positive values of (S0ads) suggest that the adsorption
process is accompanied by an increase in entropy, which is the driving force for the adsorption of
CSE on the copper surface. Table 2 clearly shows all the above calculated thermodynamic
parameters.
0.30
O 2
0.28 (25 C,R =0.998)
O 2
(30 C,R =0.995)
0.26 O 2
(35 C,R =0.995)
0.24 O 2
(40 C,R =0.991)
0.22
0.20
/c
0.18
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16
Conc (g/l)
Fig. 3: Langmuir adsorption plots for copper dissolution in 1M HNO3 are containing various
concentrations of Cheilocostus Speciosus Extract (CSE) at different temperatures.

1.8
2
Langmuir,R =0.995
1.7
1.6
logKads
1.5
1.4
1.3
3.18 3.20 3.22 3.24 3.26 3.28 3.30 3.32 3.34 3.36
-1
1000/T,K
Fig. 4: (log kads) vs. (1/T) for the corrosion of Copper in 1M HNO3 in the presence of Cheilocostus
Speciosus Extract (CSE).
Table 2: Thermodynamic parameters for the adsorption of Cheilocostus Speciosus Extract (CSE) on
copper surface in 1M HNO3 at different temperatures
Langumir Isotherm
Temp. Kads - G5ads - H5 - S5

K M-1 kJ mol-1 kJ mol-1 J mol-1K-1
298 55.555 19.9 50.3 66.6
303 42.918 19.5 50.3 64.5
308 30.864 19.0 50.3 61.8
313 21.008 18.3 50.3 58.6
3.3. Effect of Temperature
The effect of temperature on the inhibited acid-metal reaction is highly complex,

because many changes occur on the metal surface, such as rapid etching and desorption of the
inhibitor and the inhibitor itself, in some cases, may undergo decomposition and/or
rearrangement. Generally, the corrosion rate increases with the rise of temperature. It was found
that the inhibition efficiency decreases with increasing temperature and increases with increasing
the concentration of the inhibitor. The activation energy (E*a) of the corrosion process was
calculated using Arrhenius Eq. (8) [39]:
K =A exp (-E*a / RT) (8)
where K the corrosion rate, A is Arrhenius constant, R is the gas constant and T is the
absolute temperature. The values of activation energies E*a can be obtained from the slope of the
straight lines of plotting log K vs. 1/T in the presence and absence of CSE at various
temperatures are shown in Fig. 5 and in Table (3), it is noted that the values of activation energy
increase in the presence of inhibitor and with increase the concentration of the inhibitor. This is
due to the presence of a film inhibitor on the copper surface. The activation energy for the copper
corrosion 1 M HNO3 was found to be 42.4 kJ mol-1 which is in good agreement with the work
[40] [41,42]
carried out by Fouda et al. and others . An alternative formulation of the Arrhenius
equation is the transition state symbolized by Eq. (9) [43]:
K = RT/Nh exp (S*/R) exp (- H*/ RT) (9)
where h is Plancks constant, N is Avogadros number, S* is the entropy of activation and

H* is the enthalpy of activation.
Fig. 6 shows a plot of log (K / T) vs. (1/T). Straight lines are obtained with a slope of (
H*/2.303 R) and an intercept of (log R/Nh + S*/2.303 R) from which the values of H* and S*
are calculated and listed in Table 3. From inspection of Table 3 it is clear that the positive values
of H* reflect that the process of adsorption of the inhibitors on the copper surface is an
endothermic process indicating to chemisorption process. Typically, the enthalpy of a
chemisorption process approaches 100 kJ mol-1 [44]
. More interesting behavior was observed in
*
Table 3 positive S values are accompanied with endothermic adsorption processes. Those
values are in good agreement with that we expected, when the adsorption is an endothermic
process, it must be accompanied by an increase in the entropy energy change and vice versa [45].
CSE represented inhibiting properties for all the studied temperatures and the values of % IE
decrease when temperatures increase. This shows that the inhibitor has experienced a significant
decrease in its protective properties by increasing temperature. This decrease in the protective
properties of the inhibitor with increase in temperature is a result of two effects; a certain

drawing of the adsorption-desorption equilibrium towards desorption (meaning that the strength
of adsorption process decreases at higher temperatures) and roughening of the metal surface
which results from enhanced corrosion. These results suggest that physical adsorption may be the
type of adsorption of the inhibitor on the copper surface.
-1.0
-1.2
-1
logkcorr, mg cm min
-1.4
2
Blank,R2=0.93
-1.6 Conc.25ppm,R2=0.98
Conc.50ppm,R2=0.97
Conc.75ppm,R2=0.97
-1.8 Conc.100ppm,R2=0.97
Conc.125ppm,R2=0.98
Conc.150ppm,R2=0.98
-2.0
3.18 3.20 3.22 3.24 3.26 3.28 3.30 3.32 3.34 3.36
-1
1000/T,K
Fig. 5: Arrhenius (log k vs 1/T) for corrosion of copper in 1M HNO3 in the absence and presence of
different concentrations of Cheilocostus Speciosus Extract (CSE).
-3.4
-3.6
-1
logkcorr/T, mg cm min K
-1
-3.8
2
-4.0
Blank,R2=0.92
Conc.25ppm,R2=0.98
-4.2 Conc.50ppm,R2=0.97
Conc.75ppm,R2=0.97
Conc.100ppm,R2=0.97
Conc.125ppm,R2=0.97
-4.4
Conc.150ppm,R2=0.98
3.18 3.20 3.22 3.24 3.26 3.28 3.30 3.32 3.34 3.36
-1
1000/T,K
Fig. 6: Plots of (log k/T) vs.1/T for corrosion of copper in 1 M HNO3 in the absence and presence of
different concentrations of Cheilocostus Speciosus Extract (CSE).

Table (3): Activation parameters for copper corrosion in the absence and presence of various
concentration of Cheilocostus Speciosus Extract (CSE) in 1M HNO3.
Activation Parameters
Conc., *
E a H* -S*
ppm
(kJ mol-1) (kJ mol-1) (J mol K-1)
Blank 42.4 17.0 137.5
25 61.0 25.5 78.6
50 68.3 28.3 57.9
75 69.5 29.2 51.8
100 69.2 29.1 53.7
125 71.5 30.8 41.7
150 72.4 30.5 44.7
3.4. Potentiodynamic Polarization Measurements

Theoretically, copper can hardly be corroded in the deoxygenated acid solutions, as
copper cannot displace hydrogen from acid solutions according to the theories of chemical
thermodynamics [46-48]. However, this situation will change in nitric acid. Dissolved oxygen may
be reduced on copper surface and this will allow corrosion to occur. It is a good approximation to
ignore the hydrogen evolution reaction and only consider oxygen reduction in the nitric acid
solutions at potentials near the corrosion potentials [49].
Polarization measurements were carried out in order to gain knowledge concerning the
kinetics of the cathodic and anodic reactions. Fig. 7 shows the polarization behavior of copper
electrode in 1 M HNO3 in the absence and presence of various concentrations of CSE. Fig. 7
indicates that both the anodic and cathodic reactions are affected by the addition of investigated
CSE and the inhibition efficiency increases as the inhibitor concentration increases. Therefore,
the cathodic reaction is more inhibited, meaning that the addition of CSE reduces the anodic
dissolution of copper and retards the cathodic reactions. Thus, investigated CSE is considered as
mixed type inhibitor. The values of electrochemical parameters such as corrosion current
densities (icorr), corrosion potential (Ecorr), the cathodic Tafel slope (c), anodic Tafel slope (a)
and inhibition efficiency (% IE) were calculated from the curves of Fig. 7 and are listed in Table
4. The results in Table (4) revealed that the corrosion current density decreases after the addition
of inhibitor in 1M HNO3 and % IE increases by increasing the inhibitor concentration. In the
presence of inhibitor Ecorr was enhanced with no definite trend, indicating that CSE act as
mixedtype inhibitor in 2 M HNO3. The inhibition efficiency was calculated using the Equation
10:
% IEp = [(iocorr icorr) / iocorr] x100 (10)

where iocorr and icorr are the uninhibited and inhibited corrosion current densities,
respectively.
Table (4) represents that the slopes of the anodic a and cathodic c Tafel lines remain
almost unchanged upon addition of CSE, giving rise to a nearly parallel set of anodic lines, and
almost parallel cathodic plots results. Thus, the adsorbed inhibitor acts by simple blocking of the
active sites for both anodic and cathodic processes. Therefore, the adsorbed inhibitor decrease
the surface area for corrosion without affecting the corrosion mechanism of copper in 1M HNO3
solution, and only causes inactivation of a part of the surface with respect to the corrosive
medium [50,51].
0.8
Bla nk .
25 ppm.
0.6
50 ppm.
75 ppm.
0.4 100 ppm.
125 ppm.
Potential, mV vs SCE.
0.2 150 ppm.
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1
-2
log icorr, mA cm .
Fig. 7: Potentiodynamic polarization curves for the corrosion of Copper in 1M HNO3 in the absence and
presence of various concentrations Cheilocostus Speciosus Extract (CSE) at 25C.

Table 4: The effect of concentration of the investigated concentrations of Cheilocostus Speciosus Extract
(CSE) on the free corrosion potential (Ecorr), corrosion current density (icorr), Tafel slopes (a & c),
inhibition efficiency (% IE), and degree of surface coverage for the corrosion of Copper in 1 M HNO 3 at
25 oC.
-Ecorr., icorr. X 10-5 a X 10-3 c X 10-3

Compound Conc., ppm. % IE
mV(vs SCE) A cm-2 mV dec-1 mV dec-1
Blank
405 9.90 83.7 232.5 ---- ----
25 338 8.80 102.9 238.5 0.111 11.1
50 446 7.74 109.7 270.5 0.218 21.8

(CSE)
75 115 6.98 103.4 263.4 0.295 29.5
100 277 1.91 171.9 482.9 0.807 80.7
125 838 1.88 137.9 420.1 0.810 81.0
150 258 1.17 93.5 146.1 0.882 88.2
3.5 Electrochemical Impedance Spectroscopy (EIS)

EIS is a well-established and powerful technique in the study of corrosion. Surface
properties, electrode kinetics and mechanistic information can be obtained from impedance
[52-56]
diagrams . Fig. 8 shows the Nyquist (a) and Bode (b) plots obtained at open-circuit
potential both in the absence and presence of increasing concentrations of investigated CSE at
25C. The capacitive loop was found to increase in size with CSE addition leads to gradual
formation of a barrier on the surface of copper metal. Figure (8a) shows that at a fixed CSE
inhibitor concentration the increase in the capacitive loop size is enhanced. Bode plots are shown
in figure (8b) represents that the total impedance increases with the inhibitor concentration (log Z
vs. log f).
In addition, (log f vs. phase), and Bode plot displays the continuous increase in the phase
angle shift, is directly correlated with the increase of inhibitor adsorbed on the copper surface.
The Nyquist plots do not yield perfect semicircles as expected from the theory of EIS. The
deviation from ideal semicircle was generally attributed to the frequency dispersion [57] as well as
to the in homogeneities of the surface. EIS spectra of the CSE were analyzed using the
equivalent circuit which is shown in Fig. 9. Fig. 9 indicates that a single charge transfer reaction

and fits well with our experimental results. The constant phase element, CPE, is introduced in the
[58]
circuit instead of a pure double layer capacitor to give a more accurate fit . The double layer
capacitance, Cdl, for a circuit including a CPE parameter (Y0 and n) were calculated from Eq.
(11) [59]:
Cdl = Y0 n-1 / sin [n (/2)] (11 )
where Y0 is the magnitude of the CPE, = 2fmax, fmax is the frequency at which the imaginary
component of the impedance is maximal and the factor n is an adjustable parameter that usually
lies between 0.50 and 1.0.
After analyzing the shape of the Nyquist plots, it is concluded that the curves
approximated by a single capacitive semicircle, indicate that the corrosion process was mainly
charged-transfer controlled [60, 61]. The general shape of the curves is very similar for all samples
(in presence or absence of inhibitors at different immersion times) indicating no change in the
[62]
corrosion mechanism . Table 5 illustrates that the Rct values increase with the concentration
of the inhibitor.
The inhibitor addition enhances the Rct values in acidic solution. The obtained results
indicate that values of double layer capacitance are also brought down to the maximum extent in
the presence of inhibitor and the decrease in the values of CPE follows the order like that
obtained for icorr. The decrease in CPE/Cdl results from a decrease in local dielectric constant
and/or an increase in the thickness of the double layer, suggesting that organic derivatives inhibit
[63, 64]
the copper corrosion by adsorption at metal/acid . The inhibition efficiency was calculated
from the charge transfer resistance data from Equation 12[65]:
% IEEIS= [1 (Rct/Rct)] x100 (12)
where Roct and Rct are the charge-transfer resistance values without and with inhibitor
respectively.

500 a
Blank .
25 ppm.
450
50 ppm.
75 ppm.
400
100 ppm.
125 ppm.
350
150 ppm.
300
-2
Zimg , ohm cm
250
200
150
100
50
-50
-200 0 200 400 600 800 1000 1200 1400 1600 1800
-2
Zreal , ohm cm .
10
b
1000
0
-10
log Zmod, ohm cm .
-2
-20
100
Zph, deg
-30
Blank . -40
25 ppm.
10 -50
50 ppm.
75 ppm.
100 ppm. -60
125 ppm.
150 ppm. -70
1
0.01 0.1 1 10 100 1000 10000 100000 1000000
log F, Hz.
Fig. 8: EIS Nyquist plots (a) and Bode plots (b) for copper in 1 M HNO3 in the absence and presence of
different concentrations of Cheilocostus Speciosus Extract (CSE) at 25oC.

Fig. 9: Equivalent circuit model used to fit experimental EIS
Table 5: Electrochemical kinetic parameters obtained by EIS technique for copper in 1M HNO3 without
and with various concentrations Cheilocostus Speciosus Extract (CSE) at 25oC.
Conc., Rs Y, x 10-6 Rct, Cdl x 10-5

Compound n x 10 -3
% IE
ppm. cm2 1 sn cm2 Fcm2
Blank 1.895 90.82 782.8 103.0 6.20 --- ---
25 1.855 94.64 777.0 107.3 5.72 0.040 4.0
50 2.242 104.3 764.0 110.7 5.66 0.069 6.9
)CSE) 75 1.366 103.5 764.5 120.7 5.49 0.147 14.7
100 1.831 109.6 786.4 802.6 5.45 0.872 87.2
125 1.899 112.5 770.7 915.9 4.90 0.888 88.7
150 1.963 93.12 786.6 965.8 4.84 0.893 89.3
3.6. Electrochemical Frequency Modulation Technique (EFM)

EFM is a nondestructive corrosion measurement technique that can directly and quickly
determine the corrosion current values without prior knowledge of Tafel slopes, and with only a
small polarizing signal. These advantages of EFM technique make it an ideal candidate for
[66]
online corrosion monitoring . The great strength of the EFM is the causality factors which
serve as an internal check on the validity of EFM measurement. The causality factors CF-2 and
CF-3 are calculated from the frequency spectrum of the current responses. Fig. 10 shows the
EFM Intermodulation spectrums of copper in nitric acid solution containing different CSE
concentrations at 25oC. The harmonic and intermodulation peaks are clearly visible and are much

larger than the background noise. The two large peaks, with amplitude of about 200 A, are the
response to the 40 and 100 mHz (2 and 5 Hz) excitation frequencies. It is important to note that
between the peaks there is nearly no current response (<100 nA). The experimental EFM data
were treated using two different models: complete diffusion control of the cathodic reaction and
the activation model. For the latter, a set of three non-linear equations had been solved,
assuming that the corrosion potential does not change due to the polarization of the working
[67]
electrode . The larger peaks were used to calculate the corrosion current density (icorr), the
Tafel slopes c and a and the causality factors CF-2 and CF-3. These electrochemical
parameters were listed in Table 6. The data presented in Table 6 show that, the addition of CSE
at a given concentration to the acidic solution decreases the corrosion current density, indicating
that CSE inhibit the corrosion of copper in 1 M HNO3 through adsorption. The causality factors
obtained under different experimental conditions are approximately equal to the theoretical
values (2 and 3) indicating that the measured data are verified and of good quality. The inhibition
efficiencies % IEEFM increases proportionally by increasing the inhibitor concentration and was
calculated from Equation (13):
% IEEFM = [1-(icorr/ iocorr )] x 100 ( 13)

o
where i corr and icorr are corrosion current densities in the absence and presence of inhibitor,
respectively.


Fig. 10: EFM spectra copper in 1M HNO3 in the absence and presence of different concentrations of
Cheilocostus Speciosus Extract (CSE) at 25oC.
Table 6: Electrochemical kinetic parameters obtained by EFM technique for Copper in the absence and
presence of various concentrations of Cheilocostus speciosus Extract (CSE) in 1M HNO3 at 25oC.
icorr
Conc., c X 10-3 a X 10-3
Compound A CF-2 CF-3 C.R % IE
ppm mV dec1 mVdec1
cm-2
Blank 138.1 59.8 341.3 1.92 2.93 133.10 --- ---
25
16.78 70.3 128.8 1.85 2.80 16.17 0.878 87.8
50
16.63 64.7 129.5 1.80 3.07 16.03 0.879 87.9
75
16.38 68.4 124.4 1.82 3.02 15.79 0.881 88.1
)CSE)
100
14.56 63.5 117.0 1.86 2.86 14.03 0.894 89.5
125
13.99 67.6 131.2 1.83 2.93 13.48 0.899 89.9
150
12.72 65.8 101.3 1.77 2.95 12.26 0.908 90.8
3.7. Mechanism of Inhibition
Most organic inhibitors contain at least one polar group with an atom of nitrogen or
sulphur or in some cases selenium and phosphorus. The inhibiting properties of many
compounds are determined by the electron density at the reaction center [68].
With increase in electron density in the center, the chemisorption between the inhibitor
[69, 70]
and the metal are strengthened . The plant CSE is composed of numerous naturally
occurring organic compounds. Accordingly, the inhibitive action of CSE could be attributed to

the adsorption of its components on the copper surface. The constituents of CSE were
phytochemical isolated from roots as 24-hydroxytriacontan-26-one and 24-hydroxytriacontan-
27-one together with methyl triacontanoate, diosgenin, sitosterol, 8-hydroxy triacontane-25-one
and methyl triacontanoate. In addation, 5-stigmast-9(11)-en-3-ol were also characterized. The
roots of this plant also contain -sitosterol--D-glucoside, prosapogenins A and B of dioscin,
dioscin, gracillin, 3-O-[-L-rhamnopyranosyl(12)--D-glucopyranosyl]-26-O-[-
Dglucopyranosyl]- 22-methoxy-(25R)furost-5-en-3,26diol, protodioscin and
methylprotodioscin. Other components identified were 31-norcycloartanone, cyloartanol,
cycloartenol and cycloalaudenol [19,20].
Most of these phytochemicals are organic compounds that have center for -electron
and presence of hetero atoms such as oxygen and nitrogen; hence, the adsorption of the inhibitor
on the surface of copper is enhanced by their presence. The inhibition efficiency of methanol
extracts of CSE is due to the formation of multi-molecular layer of adsorption between copper
and some of these phytochemicals. Results of the present study have shown that CSE inhibits the
acid induced corrosion of copper by virtue of adsorption of its components onto the copper
surface. The inhibition process is a function of the metal, inhibitor concentration, and
temperature as well as inhibitor adsorption abilities, which depends on the number of adsorption
sites. the adsorption showed that both physisorption and chemisorption are involved in the
inhibition process. This can be explained to the fact that corrosion inhibitor CSE has many
different chemical constituents, which some can be adsorbed as chemisorption which indicate
that inhibitor molecules are adsorbed strongly on the metal surface through coordinate type bond
and physisorption which indicate that the electrostatic interaction of the charged molecule and
the charged surface of the metal, suggesting that the adsorption of inhibitor involves both
electrostatic adsorption and chemisorption.
This explains the fact that adsorbed organic molecules can influence the behavior of
electrochemical reactions involved in corrosion processes in several ways. The action of organic
inhibitors depends on the type of interactions between the substance and the metallic surface.
The interactions can bring a change either in electrochemical mechanism or in the surface
available for the process [71].

4. CONCLUSIONS
The obtained results indicate that Cheilocostus Speciosus Extract can be used as an
effective green corrosion inhibitor for copper surface in 1M HNO3 media.Reasonably good
agreement was observed between the values obtained from the poteniodynamic polarization,
weight loss, electrochemical impendence spectroscopy and electrochemical frequency
modulation (EFM) techniques.CSE inhibitor plays a vital role in providing protection against
corrosion. The selection of the inhibitor is important for environmental protection. The eco-
friendly plant extract and pharmaceutical compounds are a growing trend to use as corrosion
inhibitors. Most of these compounds are environmentally-friend.The obtained results from all
electrochemical measurements showed that the inhibition efficiency increases with the
concentration of CSE inhibitor and decreases with the increasing of temperature. The double
layer capacitances decrease with respect to blank solution when the CSE plant extract is added.
The adsorption of CSE extract inhibitor on the surface of copper in 1M HNO3 solution follows
Langmuir isotherm. The negativity of the free energies of adsorption and adsorption heat means
that the adsorption process is spontaneous and exothermic. The inhibition efficiencies data
obtained from all different independent quantitative techniques are comparable and show the
validity of the results.
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Green Corrosion Electrochemistry: Cheilocostus Speciosus Extract (CSE) Investigated Electro-Analytically As A Potential Green Corrosion Inhibitor For Copper Within Acidic Solution

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International Journal of Emerging Trends in Engineering and Development Issue 7, Vol.

Green Corrosion Electrochemistry: Cheilocostus Speciosus Extract (CSE)

Hala M. Hassan*1, Ahmed M. Eldesoky2, Awad Al-Rashdi3 and Hytham M. Ahmed4

Keywords: Copper, Cheilocostus Speciosus Extract, Green inhibitor, Langmuirs Adsorption

The purpose of the present study is to determine the influence of eco-environmental

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Costus is a group of perennial herbaceous plants in the family (Costaceae described by

2.1. Materials and Solutions

CH3 CH3 CH3 CH3

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2.3. Weight Loss Method

2.4. Electrochemical Measurements

2.4.1. Potentiodynamic Polarization Measurements

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2.4.2 Electrochemical Impedance Spectroscopy Measurements

2.4.3 Electrochemical Frequency Modulation Technique

3- Results and Discussion

3.1. Weight Loss Measurements

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Table 1: Variation of inhibition efficiency (%IE) of Cheilocostus Speciosus Extract (CSE)

3.2. Adsorption Isotherm

The Langmuir isotherm is given by Equation (3) [29]:

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Ln Kads = H0ads/RT+ const (5)

Ln (K2ads/K1ads) = H0ads/R(1/T2-1/T1) (6)

Sads= (Hads -Gads) /T (7)

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0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16

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Temp. Kads - G5ads - H5 - S5

298 55.555 19.9 50.3 66.6

303 42.918 19.5 50.3 64.5

308 30.864 19.0 50.3 61.8

313 21.008 18.3 50.3 58.6

3.3. Effect of Temperature

The effect of temperature on the inhibited acid-metal reaction is highly complex,

K =A exp (-E*a / RT) (8)

K = RT/Nh exp (S*/R) exp (- H*/ RT) (9)

where h is Plancks constant, N is Avogadros number, S* is the entropy of activation and

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3.4. Potentiodynamic Polarization Measurements

% IEp = [(iocorr icorr) / iocorr] x100 (10)

0.2 150 ppm.

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-Ecorr., icorr. X 10-5 a X 10-3 c X 10-3

25 338 8.80 102.9 238.5 0.111 11.1

50 446 7.74 109.7 270.5 0.218 21.8

100 277 1.91 171.9 482.9 0.807 80.7

125 838 1.88 137.9 420.1 0.810 81.0

150 258 1.17 93.5 146.1 0.882 88.2

3.5 Electrochemical Impedance Spectroscopy (EIS)

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Cdl = Y0 n-1 / sin [n (/2)] (11 )

% IEEIS= [1 (Rct/Rct)] x100 (12)

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Fig. 9: Equivalent circuit model used to fit experimental EIS

Conc., Rs Y, x 10-6 Rct, Cdl x 10-5

Blank 1.895 90.82 782.8 103.0 6.20 --- ---

25 1.855 94.64 777.0 107.3 5.72 0.040 4.0

50 2.242 104.3 764.0 110.7 5.66 0.069 6.9

K = RT/Nh exp (S/R) exp (- H/ RT) (9)