J.

Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Research Article

Journal of Atoms and Molecules

An International Online Journal
ISSN 2277 1247

A COMPARATIVE STUDY OF VITEX DONIANA AND PTEROCARPUS SOYAUXI AS

CORROSION INHIBITORS OF MILD STEEL IN HCL MEDIUM
I. M. Iloamaeke, T. U. Onuegbu, U. C. Umeobika, and Onyema C. T.
Department of Pure and Industrial Chemistry, Nnamdi Azikiwe University Awka, Anambra State,
Nigeria.
Received on: 02-02-2013 Revised on: 20-03-2013 Accepted on: 16042013
ABSTRACT:
Corrosion inhibition of mild steel using Vitex doniana (VD) and Pterocarpus soyauxi (PS) leaves
extract were studied using thermometric and gasometric methods at 30oC and 60oC. The inhibition
efficiency was found to increase as the concentration of extracts increase from 0.1g/l to 0.5g/l with
Pterocarpus soyauxi having the highest inhibition efficiency of 70.67% from Thermometric and
69.28% from gasometric method, while Vitex doniana has 68.49% from thermometric and 68.28%
from gasometric all at 30oC. Adsorption of Vitex doniana leaves extract on the surface of the mild
steel obeyed Langmuir and Tempkin adsorption isotherm while that of Pterocarpus soyauxi leaves
extract on the surface of the mild steel followed Tempkin and freudlich isotherm. From the values
obtained from the degree of surface coverage, Ea, H and G was calculated and all indicated
physical adsorption.
KEY WORDS: corrosion, inhibition, mild steel, Vitex doniana and Pterocarpus soyauxi
INTRODUCTION:
Corrosion is the chemical or electrochemical
reaction between a metal and its environment
that produces deterioration of the material and
its properties. (Eml. Meligi, 2010). It is a
problem that started gradually and ending up
* Corresponding author destroying the material or the object in which
I. M. Iloamaeke, the metal and its alloy is made of resulting to
economic waste. Acid solution is always used
Email: ifeomailoamaeke@yahoo.com
in industries for acid cleaning, prickling,
descaling, and oil well acidizing therefore,
this require the use of corrosion inhibitor in
order to retard corrosion attack on the metallic
objects. Recently, corrosion control using
plant extract has become an interesting
research because it can be easily extracted,
environmentally friendly, easily affordable,

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J. Atoms and Molecules / 3(2); 2013 / 509519
and renewable. These plants extract contained
O, N and S which are the active centre for
adsorption process on the metal surface (Peter
et al., 2009; Umoren et al., 2007; 2008a,
2008b; Arora et al 2007). The mechanism of
this process is that O, N, and S have lone pair
and electron which facilitate electron
transfer from inhibitor to the metal surface
thereby forming a compact barrier reducing
corrodent attack. When an H atom attached to
C in the ring is replaced by a substituent
group (-NH2, -NO2, -CHO or COOH), its
improves inhibition (Amathar Ram and
Bharahi Bai, 2011). The electro density in the
metal at a point of attachment changes
resulting in the retardation of the cathodic or
anodic reaction. Some of the plants extract
that have been used as corrosion inhibitors are
solanum melongena l. leaf (Ihebrodike et al.,
2010), Azwarin (Sing Ambrish and Quraishi,
2012), Tecoma stans (Saratha, 2011),
Azadricahta indica (Okafor et al., 2010), gum
extrudate from pachylobus edulis (Umoren et
al., 2008a), Kalmegh (Ambrish Singh et al.,
2010), Curry leaf (Beenakumari, 2010),
Emblica officinalis (Sarath, 2010), black
pepper extract (Dahmani et al.,2010), Cocos
nicifera l. coir dust (Eduok et al., 2012).
As contribution to the current research on
environmentally friendly, green corrosion
inhibitors, this study investigated the
inhibition effect of Vitex doniana (VD) and
Pterocarpus soyauxi (PS) on the corrosion of
mild steel in HCl corrodent using
thermometric and gasometric methods at 30oC
and 60oC.
MATERIALS & METHODS:
Preparation of Pterocarpus soyauxi and
Vitex doniana leaves extract:
1424g of Ptercarpus soyauxi leaves (PS) and
1500g of Vitex doniana leaves (VD) was air
dried in a shade for 8-12 days and ground into
powder. 350g of the powder was taken in
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Iloamaeke IM et al
1000ml round bottom flask and enough
quantity of ethanol was added as a solvent for
extraction. The round bottom flask was
covered with a stopper and left for 48hrs.
Then the resulting paste was refluxed for 5hrs
and filtered. The solvent was removed by
concentrating the filtrate to about 20%. From
this 0.1-0.5g/l concentration was made.
Specimen preparation:
Mild steel of thickness 1.4mm was obtained
locally and was mechanically cut into
coupons of 320.14cm. A small hole was
drilled at one end of the coupons for easy
hooking. The coupons were degreased in
absolute ethanol, dried in acetone and stored
in a desiccator.
Test solution preparation:
All the chemicals used were of Analytical
grade. Solution was prepared by using double
distilled water, and different concentrations of
1.0M 2.5M HCl were prepared.
Thermometric Method:
The procedure for determining this has been
described by (Ebenso, 2003a, 2003b; Umoren,
2006a). The mild steel of 2x 3 x 0.14cm was
used here. Volume of the test solution was at
100ml reagent. From the rise in temperature
of the system per minutes, the reaction
number (RN) was calculated using this:
RN (0C min-1) = (1)
Where Tm is the maximum temperature
attained by the system, Tt is the initial
temperature and t is the time (mins).
Inhibition efficiency I(%) of the inhibitors
can as well be calculated using:
I% = 100 (2)
Where RN is the reaction number in the
absence of inhibitors while the RN is the
reaction number in the presence of inhibitors.
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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Gasometric Method: Where HR is the rate of hydrogen evolution,

Mild steel of 2 x 3 x 0.144cm was used here Vt and Vi are the volume of hydrogen evolved
and this experiment was carried out at 30oC at time Tt and Ti respectively.
and 60oC.The procedure for this experiment RESULTS & DISCUSSION:
has been documented in literature (Umoren et Thermometric method
al., 2006a, 2008b). From the volume of
Table1: shows the reaction number and
hydrogen evolved per minute inhibition
inhibition efficiency (1%) of the mild steel in
efficiency (I %) and degree of surface
the presence of the ethanol extract of VD and
coverage () were calculated using equation 3
PS. It could be deduced from the result that
&4
reaction number decreases from
o -1 o -1
I% = 1 100 (3) 0.03827 Cmins to 0.02058 Cmins as the

inhibition efficiency increases from 41.23% to
68.49% while PS decreases from
= I (4)
o -1 o
0.0345 Cmins to 0.0191 Cmins as the -1

Where V1Ht and V0Ht are the volume of H2 gas inhibition efficiency increases from 45.38% -
evolve at time t for inhibited and uninhibited 70.67% with an increase in the concentration
solution respectively. Rate of hydrogen of the ethanol extract of VD and PS. This
evolution was computed using equation 5 explained that ethanol extract of VD and PS
(Obot et al., 2011) had adsorbed on the surface of the mild steel
thereby inhibiting further corrosion attack.
= (5)

Table 1: Reaction number, inhibition efficiency (I%) and degree of surface coverage of mild
steel in different concentration of ethanol extract of leaves VD and PS
Concentration of VD Inhibition Reaction number Degree of surface
inhibitor in (g/l) Efficiency (%) (oC Mins-1) coverage ()
0.1 41.23 0.03827 0.03659
0.2 43.71 0.02393 0.02133
0.3 63.55 0.02048 0.4123
0.4 67.18 0.4371 0.6355
0.5 68.49 0.6718 0.6849

Concentration of PS
inhibitor in (g/l)
0.1 0.2 0.3 0.4
0.5 45.38 46.92 66.00
68.15 70.67 0.0355 0.0345
0.0221 0.0207 0.0191 0.4538
0.4692 0.6600 0.6815 0.7067

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Gasometric Method: that VD and PS extract are good inhibitors for

Fig.1, 2, 3 and 4 showed the variation in corrosion of mild steel. Table 2 shows
volume of H2 evolved with time at 300C and different concentrations of the VD and PS
600C with different concentrations of the VD extract and inhibition efficiency. It could be
deduced from the table that inhibition
and PS extract. It could be observed from the
plot that volume of H2 evolved increased with efficiency increase as the concentrations of
the both extract increase with decrease in
time. The rate of hydrogen evolved decrease
temperature inferring physical adsorption of
as the concentrations of VD and PS extract
the VD and PS extract on the surface of the
increase compare with the blank. This result
correlated with thermometric method result mild steel.

7
Volume of hydrogen evolved (cm3)

5
blank
4 0.1g/l

3 0.2g/l
0.3g/l
2
0.4g/l
1
0.5g/l
0
0 5 10 15 20
Time (mins)

Fig.1: Volume of hydrogen evolved with time for corrosion of mild steel in 2.5M HCl in the
presence and absence of Vitex doniana at 30oC

7
volume of hydrogen evolume (cm3)

6 30OC
5 blank at 30oC
4 0.1g/l
3 0.2g/l

2 0.3g/l
0.4g/l
1
0.5g/l
0
0 5 10 15 20
time (mins)

Fig.2: Volume of hydrogen evolved with time for corrosion of mild steel in 2.5M HCl in the
presence and absence of pterocarpus soyauxi at 30oC

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

50

Volume of hydrogen evolved

40
blank
30 0.1g/l

(cm3)
20 0.2g/l
0.3g/l
10
0.4g/l
0 0.5g/l
0 5 10 15
Time (mins)

Fig.3: volume of hydrogen evolved with time for corrosion of mild steel in 2.5M HCl in the
presence and absence of Vitex doniana at 60oC

50
Volume of hydrogen

40
60OC blank at 60oC
evolved (cm3)

30 0.1g/l
20 0.2g/l

10 0.3g/l
0.4g/l
0
0 5 10 15 0.5g/l
Time (mins)

Fig.4: Volume of hydrogen evolved with time for the corrosion of mild steel in 2.5M of HCl in
the presence and absence of ethanol extract of Pterocarpus soyauxi at 60oC.

Table 2: Shows the concentration of the VD and PS extract and inhibition efficiencies at 30oC
and 60oC from gasometric method.

Concentration of the Inhibition efficiency (%) from VD Inhibition efficiency (%)

inhibitors in(g/l) extract at from PS extract at
30oC 60oC 30oC 60oC

0.1 23.51 21.11 50.64 47.41

0.2 38.35 30.20 60.16 57.03
0.3 45.13 38.39 62.08 58.96
0.4 51.06 42.29 68.22 64.25
0.5 68.22 54.98 69.28 67.80

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Adsorption Consideration
The adsorption behaviour of ethanol extract
of VD and PS was also studied by fitting data
obtained (gasometric method) from degree of
surface coverage to different adsorption
isotherms such as Langmuir, Tempkin,
Freundlich and Flory Huggin. The test
revealed that adsorption of VD extract on the
surface of the mild steel is consistent with the
assumption of Langmuir and Tempkin
Isotherms. While the adsorption of PS extract
on the surface of the mild steel obeyed
Tempkin and Freundlich adsorption
isotherms. Langmuir adsorption models can
be represented as follows equation 6 (Agrawal
et.al. 2003)
C/ = C +1/k (6)
. .
= - (9)
. .
Slope= , while intercept =
Fig.6 and 7: Shows plot of versus log C.
which was made from equation 8 and a linear
graph was obtained which confirmed
Tempkin adsorption isotherm for the
adsorption of VD and PS extract on the
surface of mild steel. Fig.8 revealed
Freundlichs adsorption isotherm of PS
extract on the surface of the mild steel and is
given by the equation 10 and 11 (Sharma and
Sharma, 1999)
= kc1/n (10)
Log = log k +
log c (11)

Taking the logarithm of equation 6, equation

7 is obtained
Log C/ = log C log K (7)
Where C is the concentration of the inhibitor
in the electrolyte, is the degree of surface
coverage of the inhibitor and k is the
equilibrium constant of adsorption.
The plot of C/ versus C (fig 5) gave linear
plots indicating that Langmuir adsorption
isotherm is applicable to the adsorption of
ethanol extract of VD on the surface of the
mild steel.
The fraction in equation 11 has been found
to be approximate to the inhibition efficiency
of the inhibitor, k and n is constant. Slope is
equal to
and intercept =l og . Therefore,
from equation 11, a plot of log inhibition
efficiency (I%) versus log c produces a
straight line that obeyed Freundlich
adsorption isotherm. (Umoren et al., 2006b;
2008c)
1.2 y = 1.464x + 0.3462
R = 0.994
1

Tempkin isotherm was also found to occur 0.8

y = 1.025x + 0.3323
according to this equation 8 (Abdullah, 2004;
C/

0.6 R = 0.9616
El etre, 2003; Ayssar et al., 2010) 30oC
0.4 60oC
Exp(-2a) = kC (8)
0.2
Where a is the Tempkin interaction
parameter, is the degree of surface coverage 0
of the inhibitor. K is the equilibrium constant 0 0.2 0.4 0.6
of adsorption and C is the concentration of the C
inhibitor in the bulk electrolyte. Rearranging
and taking logarithm of equation 8, equation 9 Fig. 5: Langmuir isotherm for the
is obtained. adsorption of vitex doniana on the surface
of mild steel.

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

0.8
0.7
y = 0.5714x + 0.7864
R = 0.9203 0.6
0.5
30oC
0.4

y = 0.3708x + 0.5746 0.3 60oC
R = 0.9927 0.2
0.1
0
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
logC

Fig 6: Tempkin isotherm for adsorption of the extract of vitex doniana on the surface of the
mild steel.

y = 0.2683x + 0.7775 0.8

R = 0.9752 0.7
0.6
y = 0.28x + 0.7546
0.5
R = 0.979
0.4

30oC
0.3
0.2 60oC

0.1
0
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
logC

Fig.7: Tempkin isotherm for the adsorption of Pterocarpus soyauxi extract on the surface of
the mild steel.

1.86
y = 0.1964x + 1.9049 1.84
log I%

R = 0.9743 1.82
1.8
1.78
1.76
1.74 30oC
y = 0.2137x + 1.8932
R = 0.9807 1.72 60oC
1.7
1.68
1.66
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
logC

Fig.8: Freundlich isotherm for the adsorption of PS extract on the surface of the mild steel.

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Thermodynamics Studies while that of PS extract increased when

The value of activation energy Ea was
calculated using Arrhenius equation.
Log
= (
.
-
) (12)
Where HR1 and HR2 are the hydrogen
evolution rate at temperature T1 and T2
respectively. Table 3 shows the values of Ea
for VD and PS extract on the surface of mild
steel. It could be inferred from the table that
the values of Ea for VD extract decreased
Hads = 2.303R [log (
compared to the value obtained from Blank
experiment which is 54.19KJmol-1. But since
none of Ea reach up to the threshold value of
80KJmol-1 required for chemical adsorption
therefore, the adsorption is by physical
adsorption mechanism (Deepai Rani and
Selvaraj, 2010). Heat of adsorption is
approximately equal to enthalpy of reaction
Hads. The values of heat of adsorption were
calculated using equation (13). (Quraish et al.,
2009; Okafor et al., 2010; Eddy et al., 2008).
) log ( )] x (13)

Where 1 and 2 are degree of surface Gads= -2.303RTlog (55.5K) (14)

coverage at temperatures T1 and T2
Where R is the gas constant, T is the
respectively. Table 3: enumerated the values temperature, K is the equilibrium constant of
of Hads at different concentrations of adsorption, 55.5 is the molar heat of
inhibitors. Hads were found to be negative in
adsorption of water. Values of K obtained
all the concentrations of the VD and PS
from intercept of Langumir, Tempkin and
extract showing that the reactions are Freundlich isotherm were used to compute for
exothermic. Values of adsorption parameter Gads according to equation 14 and the result
deduced from Langumir, Tempkin and in Table 4 and 5.
Freundlich isotherms are recorded in Table 4
and 5: From the Tables the degrees of From the result, Gads values were found to
linearity (R2) were also close to unity be negative and less than the threshold value
indicating strong adherence of the adsorption of -40KJmol-1 required for chemical
of VD and PS extract on the surface of the adsorption hence the adsorption of VD and PS
mild steel. The equilibrium constant of extract on the surface of mild steel is
adsorption of VD and PS extract on the spontaneous and follows physical adsorption
surface of the mild steel are related to the free mechanism (Eddy et al., 2007; Saratha et al.,
energy of adsorption (Gads) according to 2011; Ihebrodike et al., 2010).
equation 14
Table 3: Calculated values of Ea and H for VD and PS extract at different concentrations
Concentration Ea from VD Ea from PS H from VD H from PS
of VD and PS inhibitor in inhibitor in inhibitor in inhibitor in
inhibitor in g/l. KJ/mol KJ/mol KJ/mol KJ/mol
Blank 54.19 54.19 ------- -------
0.1 31.18 64.30 -3.88 -3.63
0.2 41.24 58.76 -10.39 -3.69
0.3 36.38 59.95 -7.72 -3.65
0.4 38.30 59.69 -9.91 -3.70
0.5 37.42 59.09 -17.05 -1.94

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J. Atoms and Molecules / 3(2); 2013 / 509519 Iloamaeke IM et al

Table 4: Langmuir and Tempkin adsorption isotherm parameters for adsorption of VD

extract on the surface of the mild steel.

Temperature
Log k Slope G (KJ/mol) R2
(oC)
Langmuir
30 0.4785 1.0250 -7.3444 0.9616
60 0.4606 1.4640 -8.1840 0.9940
Tempkin a
30 1.3764 -2.0151 -9.5141 0.9203
60 1.5410 -3.1050 -9.5870 0.9927

Table 5: Freundlich and Tempkin adsorption isotherm parameters for adsorption of PS

extract on the surface of the mild steel.

Temperature
Log k Slope G (KJ/mol) R2
(oC)
Freundlich
30 1.9049 0.1964 -11.743 0.9743
60 1.8932 0.2137 -12.889 0.9807
Tempkin a
30 0.1573 -0.2330 -9.4860 0.9752
60 0.1594 -0.2432 -10.3420 0.9790

CONCLUSION:
The mechanism of physical adsorption

was proposed from the calculated values

VD and PS extract showed inhibitive
of Ea, Hads, and Gads, obtained.
effect on corrosion of mild steel in acidic
environment.

Inhibition efficiency increase with an REFERENCES:

increase in inhibitor concentration for
both extracts.

The adsorption of VD extract on the
surface of the mild steel followed
Langmuir and Tempkin, while that of PS
extract obeyed Tempkin and Freundlich
adsorption isotherms.

PS extract proved to be better corrosion
inhibitor than VD extract since it has
higher inhibition efficiency in
thermometric and gasometric method.
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