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Department of Physics/Electronics, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
2
Department of Chemistry, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
3
Mechanical Engineering Department, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
Accepted 5 July, 2011
The inhibitive effect of leaf extract of Euphorbia hirta on aluminium corrosion in HCl and NaOH
solutions were studied using gravimetric technique at 30 and 60C. Results obtained showed that the
leaf extract functioned as effective and excellent inhibitors in the acidic and alkaline media. Also, the
leaf extract suppressed the corrosion reaction in both media. Inhibition efficiency of the extract was
found to vary with concentration, temperature and exposure time. The leaf extracts of E. hirta
demonstrated better inhibition efficiency in the acidic medium than in the alkaline medium. The
adsorption characteristics of the leaf extract were best described by the Langmuir isotherm. Values of
the free energy of adsorption Gads were determined from the isotherm parameters and they showed that
the adsorption was spontaneous. The molecular interaction parameter () between the molecular
species of the inhibitors and the metal surface they cover was also determined. The heat of adsorption
(Qads) and apparent activation energy (Ea) were estimated from the temperature dependence of
inhibition efficiency. Physical adsorption mechanism is proposed from the obtained thermodynamic
parameters.
Key words: Adsorption isotherm, corrosion inhibition, aluminium, leaf extracts, thermodynamics.
INTRODUCTION
The study of the corrosion behaviour of aluminium in
different aggressive environments has continued to
attract considerable attention because of the many
applications of the metal. Aluminium relies on the
formation of a compact, adherent passive oxide film for
its corrosion immunity in various environments. This
surface film is amphoteric and dissolves substantially
when the metal is exposed to high concentrations of
acids or bases (Hurlen et al., 1984; Oguzie, 2007). Bared
metal surface sites become exposed to the corrodent
after the breakdown of the oxide film, leading to a
sequence electrochemical reaction as the metal
dissolves. Corrosion is accompanied by many conjugate
cathodic processes in which hydrogen gas evolution is
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RESULTS
Gravimetric technique and corrosion rates
The weight loss of the aluminium alloy in 0.5 M HCl and
0.25 M NaOH with and without the various concentrations
of leaf extract was determined after 5 h of immersion at
30C and the corrosion rate values were evaluated using
Equation 1.
(1)
The corrosion rate values were plotted against the
concentration values of the leaf extract (Figure 1). From
the bar chart, the extract showed higher corrosion rate
values in the alkaline medium than in the acidic medium.
This depicts a better corrosion inhibition in the acidic
environment than in the alkaline medium.
Inhibition efficiency
The characterization of the corrosion rate of aluminium
alloy in the inhibitor/corrodent solution was carried out by
an assessment of the inhibition efficiency (I %) using
Equation 2 below.
(2)
The bar chart representing the inhibition efficiency with
respect to the concentration of inhibitor for E. hirta in the
acidic and alkaline environments was plotted (Figure 2).
In all the concentrations, considering the approximate
rise in values, the acidic media exhibited better inhibition
efficiency than the alkaline with as much as about 10%
efficiency.
DISCUSSION
In accounting for the observed protective effect, it should
be noted that the extract comprise mixture of organic and
resinous matter, some of which have good corrosion
inhibiting abilities. The complex chemical compositions
make it rather difficult to assign the inhibiting action to a
particular constituent or group of constituents.
Nevertheless, the net adsorption of the extract organic
matter on the metal surface creates a barrier to charge
and mass transfer, thus protecting the alloy surface from
corrodent attack. The degree of protection varies for
different extracts, with notable sensitivity to the inhibitor
concentration. Tables 1, 2 and 3 are a listing of the
phytochemical components of the extract, which include
tannins, alkaloids, and essential oil. The inhibitive
properties of tannins have been attributed to the reaction
Nnanna et al.
267
Figure 1. Corrosion rates of various concentrations of E. hirta leaf extract in 0.5 m HCI and 0.25 m NaOH
on aluminium alloy AA3003.
Figure 2. Inhibition efficiencies of various concentrations of E. hirta leaf extract in 0.5 m HCI and 0.25 m
NaOH on aluminium alloy AA3003.
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S. no.
1
2
3
4
5
6
7
8
Table 2. Calculated values of inhibition efficiency (I%), apparent activation energy (Ea) and heat of adsorption (Qads) of
Euphorbia hirta extract on AA3003 aluminium alloy in 0.25M NaOH at different temperatures.
Extract concentration
Blank
0.10
0.15
0.20
0.25
0.30
Inhibition efficiency (I %)
at 30C
at 60C
85.22
80.79
81.81
85.35
85.91
Ea (kJmol-1)
Qads (kJmol-1)
4.61
68.77
49.69
61.70
59.76
57.73
-1.36
-1.04
-1.28
-1.18
-1.13
83.03
78.77
79.41
83.48
84.18
Table 3. Calculated values of inhibition efficiency (I%), apparent activation energy (Ea) and heat of adsorption (Qads) of E.
hirta extract on AA3003 aluminium alloy in 0.5 M HCl at different temperatures.
Extract concentration
Blank
0.10
0.15
0.20
0.25
0.30
80.1
83.6
82.2
83.0
82.4
Ea(kJmol-1)
Qads(kJmol-1)
0.62
45.30
18.43
9.15
37.83
35.05
-4.83
-3.18
-2.65
-1.77
-1.65
Nnanna et al.
269
Figure 3. Langmuir isotherm for E. hirta adsorption on AA3003 aluminium alloy in 0.5 m HCI.
Figure 4. Langmuir isotherm for E. hirta adsorption on AA3003 aluminium alloy in 0.25 M NaOH.
(3)
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(6)
(7)
Whereas estimates of the heats of adsorption (Qads) were
(8)
1 and 2 are the corrosion rates in respective
temperatures T1 and T2, respectively while 1 and 2 are
the degrees of surface coverage at temperature T1 and
T2 and R is the molar gas constant.
(9)
The standard free energy of adsorption, Gads, which
can characterize the interaction of adsorption molecules
and metal surface, was calculated using Equation 9. The
negative values of Gads ensure the spontaneity of
adsorption process and stability of the adsorbed layer on
the aluminium surface. Generally, the values of Gads
around -20 kJ/mol or less negative are consistent with
physisorption, while those around -40 kJ/mol or more
negative involve chemisorptions (Ebenso, 2003; Popova
et al., 2003; Oguzie, 2008). Analysis of the temperature
dependence of inhibition efficiency as well as comparison
of corrosion activation energies in the presence of
inhibitor gives some insight into the possible mechanism
of inhibitor adsorption. A decrease in inhibition efficiency
with rise in temperature, with analogous increase in
corrosion activation energy in the presence of inhibitor
compared to its absence, is frequently interpreted as
Nnanna et al.
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