Corrosion Inhibition Arabian Journal

S. A. Umoren and M. M.
Solomon
EFFECT OF HALIDE IONS ADDITIVES ON THE

CORROSION INHIBITION OF ALUMINUM IN HCl BY
POLYACRYLAMIDE
S. A. Umoren* and M. M. Solomon
Department of Chemistry, Faculty of Science, University of Uyo, PMB 1017 Uyo, Nigeria
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*Corresponding Author:
E-mail: saviourumoren@yahoo.com
Phone: +234-802-3144-384
______________________________________________________________________________
Paper Received May 19, 2009; Paper Revised August 18, 2009; Paper Accepted October 7, 2009
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The Arabian Journal for Science and Engineering, Volume 35, Number 2A
July 2010
S. A. Umoren and M. M. Solomon
ABSTRACT
The influence of bromide and iodide ions on the inhibitive effect of polyacrylamide (PA) on aluminum corrosion
in HCl solution was studied using weight loss, hydrogen evolution, and thermometric techniques at 30 and 60oC. The
results show that the halide additives synergistically increased the inhibition efficiency of polyacrylamide. The
increase in inhibition efficiency (%I) was found to be more pronounced in I- than Br- ions. The observed difference
in behavior of both halide additives could be linked to the differences in their atomic radii as well as
electronegativity. The values of synergism parameter (S1) obtained for the halides are greater than unity, suggesting
that the improved inhibition efficiency of polyacrylamide caused by the addition of the halide ions is due to
synergistic effect. Corrosion inhibition could be attributed to adsorption of inhibitor molecules on the Al surface via
physical mechanism. The adsorption process followed the kinetic-thermodynamic model of El-Awady adsorption
isotherm. These results were further corroborated by kinetic and thermodynamic parameters for corrosion and
adsorption processes evaluated from experimental data.
Key words: polyacrylamide, aluminum, corrosion, adsorption isotherms, synergism, halides
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July 2010
EFFECT OF HALIDE IONS ADDITIVES ON THE CORROSION INHIBITION OF

ALUMINUM IN HCl BY POLYACRYLAMIDE
1. INTRODUCTION
Aluminum is an abundant metallic chemical element which is widely used throughout the world for a wide range
of applications. It relies on the formation of a strong adherent and a continuous film on its surface for corrosion
resistance on exposure to the atmosphere. However, in some instances, aluminum may be exposed to a high
concentration of acids and alkalis, which usually leads to the dissolution of the passive films. It is therefore
necessary for it to be protected from corrosion in these environments. The appropriate way is to isolate the metal
from corrosive agents present in solutions by the use of corrosion inhibitors. Organic compounds containing oxygen,
nitrogen, or sulphur have been found suitable for this purpose, and their action is attributed to adsorption onto the
surface of the metal/solution interface [14]. Polymers, both naturally occurring and synthetic ones, have been
studied as metal corrosion inhibitors. Interest in them arose from their stability in acid media, low cost, and the
presence of multiple adsorption sites in their molecular structure for bonding with a metal surface [5]. Among those
studied to date include polyethylene glycol, polyvinyl alcohol, polyacrylamide, carboxyl methylcellulose, poly
(aminoquinone), polyethylene glycol methyl ether (PEGME), polyvinylpyrrolidone and polyethylenimine, poly
(4-vinylpyridne), and poly (diphenylamine) [613], to mention but a few.
It has been established that the presence of halide ions in solution enhances the inhibition efficiency of most
inhibitors. It is generally accepted that the halide ions facilitate adsorption of organic cations during metal corrosion
by forming intermediate bridges between the metal surface and the positive end of the organic inhibitor. Some
authors have reported the synergistic effect of halide ions in combination with some organic compounds [1419] and
naturally occurring substances [2023]. In each case, the synergistic effect of the halide ions increases in the order
Cl-< Br-< I-. This may be attributed to the atomic radii, as well as the electronegativity, which increase in the order
Cl- < Br- < I- and Cl- > Br-> I- , respectively, in the halogen series.
In our laboratory, a series of reports have been highlighted on the synergistic effect of halide ions on the
corrosion of aluminum in acidic environment using naturally occurring substances [2426] and polymeric materials
in acidic/alkaline media [2730]. As part of our contribution to the growing interest of exploring polymers as
corrosion inhibitors, the present work reports the inhibitive effect of polyacrylamide on aluminum corrosion in HCl,
including the synergistic effect of bromide and iodide ions using gravimetric, hydrogen evolution, and thermometric
techniques at 30 and 60oC.
2. EXPERIMENTAL
2.1. Materials
An aluminum sheet supplied by First Aluminum Company, Nigeria Limited, Port Harcourt, Nigeria with the
following composition (Wt %): Si 0.22851 , Fe 0.57828 , Cu 0.008090 , Mn 0.27315 , Mg 0.0731,
Zn 0.10291, Ti 0.01229 , Cr 0.005732, Ni 0.00548, V 0.01229, Pb 0.07663, and the balance Al was used
for the study. Each sheet was 0.9 mm in thickness and was mechanically press cut into 5 cm x 4 cm coupons. These
coupons were used without further polishing. However, for surface treatment, they were degreased in absolute
ethanol, dried in acetone, and stored in desiccators free from moisture before being used in the corrosion studies.
Polyacrylamide (Hi-tek polymers, Japan) [Mn: 50,000 g mol-1] was used as the inhibitor in the concentration range of
1 x 10-5 1 x 10-4 M. The hydrochloric acid (HCl) (Sigma-Aldrich) concentration was 0.5M prepared from
analytical grade reagent. Potassium bromide and iodide (KBr, KI, Sigma-Aldrich) were used in the concentration
range of 1 5mM. For the systems containing PA and halide mixtures, a fixed concentration of KBr and KI (5mM)
was used while the concentration of PA was varied. All preparations were made using doubly distilled water. The
study was conducted at 30 and 60oC and the temperature was maintained using a thermostated water bath.
2.2. Gravimetric Technique
In the gravimetric measurements, clean weighed aluminum coupons were immersed completely in 250ml beakers
containing 200ml of the corrodent (HCl) and inhibitors with the aid of glass rods and hooks. The beakers were
placed in a constant thermostated bath maintained at 30 and 60oC. The coupons were retrieved at 24-hour intervals
progressively for 168 hours (7 days), and immersed in 70% nitric acid for 2 minutes at room temperature. They
were scrubbed with a bristle brush under running water, dried in acetone, and weighed [31].
The differences in weight of the coupons before and after immersion in different test solutions were taken as the
weight loss. It was then used to calculate the corrosion rate using the formula [32]
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CRWL (mmy) =
87.6W
At
(1)
where W is the weight loss (mg ), is the density of the specimen (gcm-3), A is the area of the specimen (cm2), and t
is the exposure time (h).
The inhibition efficiency of PA and PA in combination with halides acting as inhibitor in 0.5 M HCl was
calculated using the following expression:
CR
CR inh
% I = blank
x 100
CR blank
(2)
where CRblank and CRinh are the corrosion rate in the absence and presence of the PA and PA halide mixtures,
respectively.
2.3. Hydrogen Evolution Technique
The apparatus and procedure followed was similar to that previously described [2729]. The gasometric
assembly is essentially an apparatus that measures the volume of gas evolved from a reaction system. It
consists essentially of a two-necked round bottom flask which serves as the reaction medium containing
the corrodent and the metal coupons. Other components are a separating funnel, a burette fitted with
taps, and an outer glass jacket that serves as a water condenser. In this technique, 100mL of different test
solutions were introduced into a reaction vessel, which was connected to a burette through a delivery tube. The
initial volume of air in the burette was recorded. Aluminum sheets of dimensions 5 cm x 4 cm were carefully
dropped into the test solution of HCl and the reaction vessel was quickly closed to avoid any escape of hydrogen gas.
The volume of hydrogen gas evolved from the corrosion reaction was monitored by the depression (in cm3) in the
paraffin oil level. This depression was monitored at fixed time intervals. From the volume of hydrogen gas evolved,
the corrosion rate was computed using the following expression:
CR H =
V t V i
tt t i
(3)
where Vt and Vi are the volumes of hydrogen evolved at time tt and ti, respectively.
The inhibition efficiency (%I) was calculated using Equation (2).
2.4. Thermometric Technique
The apparatus consists essentially of a two-necked reaction flask to which a thermometer is fitted. The reaction
flask is lagged to prevent heat losses to the surroundings. In this technique, the corrodent (HCl) concentration was
kept at 2M and 50 ml of the test solution was used. Aluminum coupons were completely immersed in HCl without
the inhibitor and with different concentrations of the inhibitors and inhibitorrhalide mixtures. The temperature
changes with the dissolution of aluminum were followed accordingly at various time intervals by means of a
thermometer (0100oC) measured to the nearest + 0.05oC.
This method enabled the computation of the reaction number (RN) defined by the equation
T i
(4)
t
where Tm and Ti are the maximum and initial temperatures, respectively, and t is the time (min) taken to reach the
maximum temperature. The inhibition efficiency (%I) was calculated from percentage reduction in the RN given by
Equation (5)
RN aq RN wi
(5)
%I =
x 100
RN aq
RN
C / min
)=T
where RNaq and RNwi are the reaction numbers of in the absence and presence of the additives, respectively.
3. RESULTS AND DISCUSSION
3.1. Gravimetric Measurements
The weight loss method has proved to be useful in monitoring the corrosion of metals in different aqueous media
because of its simplicity and reliability. Some authors have reported comparable results between the weight loss
technique and other techniques of corrosion monitoring, such as polarization measurements, hydrogen evolution,
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July 2010
thermometric methods, and electrochemical impedance spectroscopy [3336]. The loss in weight of aluminum in 0.5
M HCl in the absence and presence of polyacrylamide, halides, and polyacrylamideehalides mixtures after 168
hours of immersion was evaluated at temperatures of 30 and 60oC. Figure 1 shows the plot of weight loss versus time
for the dissolution of aluminum in the absence and presence of polyacrylamide, halides, and polyacrylamidehalides
mixtures at (a) 30oC and (b) 60oC. Inspection of the figure shows a decrease in weight loss of aluminum in the
presence of halides and polyacylamide compared to the blank. Further reduction in weight loss was observed in the
presence of PA in combination with halides with the most significant decrease obtained for PAKI mixtures at both
temperatures. Examination of the figure also reveals that the weight loss of aluminum in the absence and presence of
halides, polyacrylamide, and polyacrylamidehalides mixtures increases with increase in temperature.
Figure 1: Variation of weight loss against time for aluminum corrosion in 0.5M HCl in the absence
and presence of halides, PA and PA halide mixtures at (a) 30 and (b) 60oC
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The calculated values of corrosion rate and inhibition efficiency for the different systems studied from the weight
loss measurements are presented in Table 1. Results given in the table clearly indicate that the corrosion rate of
aluminum in HCl was found to reduce in the presence of polyacrylamide compared to its absence. This is an
indication that PA afforded the inhibition of acid induced corrosion of aluminum. Further reduction in corrosion rate
was also observed on addition of halide ions to polyacrylamide. It is also seen in the table that corrosion rate in the
presence of PA alone and on addition of the halides decreases with increase in PA concentration but increases with a
rise in temperature. At the temperatures studied, the reduction in corrosion rate in the presence of the halides was
found to be in the order PA + KBr > PA + KI.
Table 1. Calculated Values of Corrosion Rate, Inhibition Efficiency and for Aluminum Corrosion in 0.5M
HCl for Different Systems at 30 and 60oC from Weight Loss Measurements
Systems/concentration
Corrosion rate (mm/yr)

o
30 C
60 C
Inhibition efficiency (I %)
30oC
60oC
Blank
2.69
5.87
5mM KBr
0.99
3.45
62.9
41.2
5mM KI
0.83
2.57
69.2
56.2
-5
1 x 10 M PA
1.32
3.83
51.3
34.8
-5
3 x 10 M PA
1.13
3.15
57.6
46.3
-5
5 x 10 M PA
1.08
2.90
60.2
50.6
-5
7 x 10 M PA
1.02
2.76
61.8
52.9
-4
1 x 10 M PA
0.97
2.55
63.6
56.6
1 x 10-5M PA + 5mM KBr
0.86
3.17
65.4
45.9
-5
0.82
2.98
68.0
49.2
-5
0.75
2.73
69.5
52.6
-5
0.73
2.72
72.2
53.5
-5
1 x 10 M PA + 5mM KBr
0.58
2.09
78.4
64.4
1 x 10-5M PA + 5mM KI
0.69
2.48
74.3
57.8
3 x 10 M PA + 5mM KI
0.68
2.36
74.7
59.8
5 x 10-5M PA + 5mM KI
0.65
2.18
75.8
62.9
-5
0.61
2.02
77.3
65.6
-4
0.50
1.78
81.0
69.7
-5
The inhibition efficiency was observed to increase with increase in concentration of polyacrylamide and was
greatly enhanced on addition of the halide ions. The required enhancement of inhibition efficiency of polyacrylamide
on the addition of halide ions was more pronounced with iodide ion compared to bromide ion. This may be attributed
to the differences in atomic radii as well as electronegativity of the halide ions, which increases in the order I- > Br- >
Cl- and Cl- > Br- > I- , respectively. Inspection of the results presented in the table further revealed that inhibition
efficiency decreases with increase in temperature, suggesting a physisorption mechanism.
It is generally accepted that the inhibitive power of polymers are related to cyclic rings and heteroatoms (oxygen
and nitrogen) which are the centers of adsorption. The inhibition of aluminum corrosion by polyacrylamide could be
attributed to adsorption of PA through the oxygen and nitrogen atoms on the aluminum surface, which creates a
barrier isolating the metal from attack by the aggressive anions of the acid. In acid solution, PA may exist in both
protonated and molecular species, which can affect the corrosion process to different extents depending on their
relative proportion. The decrease in inhibition efficiency with increase in temperature observed in this study is an
indication that PA molecules were physically adsorbed onto the metal surface. Physical adsorption is a result of
electrostatic interactions between charged metal surface and protonated species in the bulk solution, while
chemisorption is characterized by adsorption of molecular species (uncharged molecules) on a heterogeneous
surface. It is pertinent to conclude that adsorption of protonated PA species by electrostatic interaction with chloride
ion adsorbed on the aluminum surface is the predominating factor rather than the participation of molecular species
in this study.
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July 2010
3.2. Hydrogen Evolution Technique

Experiments were also undertaken using the hydrogen evolution technique. Figure 2 shows variation of volume
of H2 evolved with time for aluminum dissolution in 2M HCl in the absence and presence of halides,
polyacrylamide, and polyacrylamidehalides mixtures at (a) 30oC and (b) 60oC. From the figures, it can be seen that
the volume of H2 evolved increases with time. The volume of H2 evolved was observed to appreciably reduce in the
presence of polyacrylamide and halides compared to the free acid solution. Further reduction in the volume of H2
evolved was observed on the introduction of Br- and I- ions into the solution containing PA. The volume of H2
evolved is also seen to increase with increase in temperature. This shows that the polyacrylamide alone and in
combination with halides retards the dissolution rate of aluminum in the acidic solution more at lower temperatures
than at higher temperatures. The figure also revealed that the most remarkable reduction in the volume of H2 evolved
was observed with a polyacrylamideiodide ion combination at both 30 and 60oC.
Figure 2: Variation of volume of H2 evolved against time for aluminum, corrosion in 2M HCl
in the absence and presence of halides, PA and PA halide mixtures at (a) 30 and 60oC
The corrosion rates of aluminum in the absence and presence of various additives were calculated using Equation
(4) and the corresponding values at different temperatures are presented in Table 2. The results show that corrosion
rates increase with increase in temperature but decrease in the presence of halides, polyacrylamide, and
polyacrylamidehalides mixtures. The inhibition efficiency (%I) obtained from the hydrogen evolution
measurements are also presented in Table 2. From the table, inhibition efficiency is enhanced on the addition of
halide ions to polyacrylamide but decreases with increase in temperature. This is in agreement with the trend
reported for weight loss measurement. The inhibition efficiency increases with increase in the concentration of PA. It
is also found to increase markedly on the addition of Br- and I- ions, with the most profound effect noticed in the
presence of I- ions.
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Table 2. Calculated Values of Corrosion Rate, Inhibition Efficiency for Aluminum Corrosion in 1M HCl
for Different Systems at 30 and 60oC from Hydrogen Evolution Measurements
Corrosion rate (cm3/min)

30oC
60oC
30oC
60oC
Blank
5mM KBr
5mM KI
1 x 10-5M PA
3 x 10-5M PA
5 x 10-5M PA
7 x 10-5M PA
1 x 10-4M PA
3.36
2.33
1.23
1.39
0.94
0.78
0.49
0.33
10.23
9.55
7.38
6.90
6.70
6.60
5.75
5.02
30.65
62.86
58.63
72.02
76.79
85.42
90.00
6.65
27.86
32.55
34.51
35.48
43.79
50.93

0.42
0.40
0.36
0.20
0.20
6.06
5.48
5.33
4.38
3.63
87.50
88.10
89.29
94.04
94.04
40.75
46.42
47.89
57.15
64.52
1 x 10-5M PA + 5mM KI
3 x 10-5M PA + 5mM KI
5 x 10-5M PA + 5mM KI
7 x 10-5M PA + 5mM KI
1 x 10-4M PA + 5mM KI
0.37
0.23
0.16
0.13
0.09
5.60
4.80
4.10
3.7
3.18
88.99
94.05
95.24
96.13
97.32
45.26
53.08
59.92
63.39
68.91
3.3. Thermometric Technique

The dissolution of aluminum in 1M HCl in the absence and presence of halides, polyacrylamide, and
polyacrylamidehalides mixtures was also studied using the thermometric technique. Figure 3 shows the
temperaturetime curve for aluminum corrosion in 2M HCl in the absence and presence of the additives.
Examination of the figure reveals that in the absence of the additives (blank), the temperature increases gradually to
attain a maximum value due to the exothermic corrosion reaction, and gradually decreases again. However, in the
presence of the additives, an interesting behavior was observed in which the temperature accompanying the
dissolution of aluminum was lower compared to the blank and took a longer time to reach the maximum value. This
behavior reflects the high inhibition efficiency (%I) obtained for the PA and PAhalide mixtures toward aluminum
dissolution in the acidic medium.
Figure 3: Variation of temperature with time for aluminum, corrosion in 2M HCl in the
absence and presence of halides, PA and PA halide mixtures
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July 2010
The calculated values of reaction number (RN) and percentage reduction in reaction number (inhibition
efficiency) for the different systems studied from the thermometric measurement are given in Table 3. It is clear
from the table that reaction number decreased more in the presence of the additives compared to the blank solution.
The table also shows that reaction number decreases with increase in the concentration of the additives. The
percentage reduction in reaction number (inhibition efficiency) followed the trend reported for weight loss and
hydrogen evolution measurements. It increases with increase in concentration of PA and was appreciably improved
on addition of the halide ions, the iodide ion giving the most remarkable improvement.
Table 3: Calculated Values of Reaction Number and Percentage Reduction in Reaction Number (Inhibition
Efficiency) for Aluminum Corrosion in 1M HCl for Different Systems from Thermometric Method
Reaction number (oC/min)
Blank
1.53
5mM KBr
0.54
64.71
5mM KI
041
73.01
-5
1 x 10 M PA
0.61
60.13
-5
3 x 10 M PA
0.53
65.34
-5
5 x 10 M PA
0.48
68.63
-5
7 x 10 M PA
0.43
71.89
1 x 10-4M PA
0.38
75.16
0.45
70.58
-5
0.43
71.89
-5
0.40
73.86
-5
0.38
75.16
-5
0.33
78.43
1 x 10-5M PA + 5mM KI
0.23
84.96
-5
0.21
86.27
-5
0.20
86.93
-5
0.19
87.58
-4
0.19
87.58
3.4. Effect of Halide Ions and Synergistic Consideration

Results obtained from the study show that the inhibition efficiency of PA was remarkably improved on addition
of Br- and I- ions. For instance, inspection of Table 1 reveals that in the presence of the highest concentration of PA
studied (1x10-4 M), the inhibition efficiency is 63.7% at 30oC. On addition of 5mM KBr and KI, the inhibition
efficiency increases to 78.4% and 81%, respectively. Similar observations, which were ascribed to synergistic effect,
had been reported [16,18,23] by other authors. The role of the anions in improving the inhibition efficiency of
organic compounds has been explained as due to the specific adsorption of these anions, which then creates an
excess negative charge towards the solution and favors more adsorption of the organic cations [37]. Other authors
opined that the feasible adsorption of organic cations in the presence of halide ions may be due to the formation of an
intermediate bridge, the negative ends of the halide metal dipoles being oriented towards solution [38]. The
improved inhibition efficiency of PA in the presence of the halide ions increases in the order I- > Br-. This may be
explained on the basis that iodide ions play an essential role in reducing the repulsive forces between PA polycation
head groups and stabilized physical adsorption, so a close packed layer at the metal surface may be formed [39]. The
strong chemisorption of iodide ions on the metal surface is responsible for the synergism effect of iodide ion in
attraction with cations. In addition to electrostatic effect, some covalent bonding to the metal must be involved. The
large size and ease of polarizability of iodide facilitate the electron pair bonding. In short, the adsorption of inhibitors
between the metal and solution interface is usually accepted as the formation of electrostatic or covalent bonding
between the adsorbates and metal surface atoms. In other words, halide ions will adsorb on the metal surface by
creating oriented dipoles with their negative ends towards solution, thus increasing the adsorption of the organic
cations on the dipoles, and as a result, a positive synergistic effect arises.
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123
The synergistic parameter (S1) was evaluated from inhibition efficiency values obtained from the three methods
using the relationship initially given by Aramaki and Hackermann and reported elsewhere [18,20]:
S1 =
1 I 1+ 2
1 I 1'+ 2
(6)
where I1+2 = I1 + I2, I1 is inhibition efficiency of the halides, I2 is the inhibition efficiency of inhibitor
(polyacrylamide), and I1+2 is measured inhibition efficiency for the inhibitor in combination with the halides.
The values obtained are listed in Table 4. S1 approaches 1 when no interaction between the inhibitor compounds
exist, while S1>1 points to a synergistic effect. In the case of S1< 1, the antagonistic interaction prevails, which may
be attributed to competitive adsorption. The results in the table show that the synergistic parameter (S1) for the
halides is greater than unity, suggesting the enhanced inhibition efficiency caused by the addition of halide ions to
the polyacrylamide is due to synergistic effect.
Table 4. Synergism Parameter for the Halides from the Three Methods at 30oC
Halides
Synergism parameter (S1)

Weight loss
Hydrogen evolution
Thermometric
KBr
1.88
1.28
1.81
KI
1.89
1.89
1.82
3.5. Adsorption Isotherm

As far as the inhibition process is concerned, it is generally assumed that the adsorption of the inhibitors at the
metal-aggressive solution interface is the first step in the inhibition mechanism [40]. Considering the dependence of
inhibition efficiency on inhibitor concentration, as shown in Table 1, it seems probable that the inhibitor acts by
adsorbing and blocking the available active center on the aluminum surface. In other words, the inhibitor decreases
the active center for aluminum dissolution. The values of degree of surface coverage from weight loss
measurements, ( = %I/100), assuming a direct relationship between surface coverage and inhibition efficiency for
different concentrations of inhibitor (PA) and inhibitorhalide mixtures at 30 and 60oC studied, have been used in
explaining the adsorption process. Langmuir adsorption isotherm was tested for its fit to the experimental data. The
characteristic of Langmuir adsorption isotherm is given by the equation
C
1
+C
K ads
(10)
The plot of C/ as a function of C (inhibitor concentration) is shown in Figure 4. Although the figure gives a
linear plot with high correlation coefficient (0.99), the deviation of the slopes from unity (Table 4) (for ideal
Langmuir isotherm) can be attributed to the molecular interaction among the adsorbed inhibitor species, a fact that
was not taken into consideration during the derivation of Langmuir equation. This deviation necessitated the fitting
of the experimental data into El-Awadys kinetic thermodynamic model. The isotherm is expressed as

Log
= LogK + y logC
1
(11)
where y is the number of inhibitor molecules occupying one active site, is the surface coverage, C is the
concentration , K is the equilibrium constant of the adsorption process, and Kads = K1/y where 1/y represents the
number of active sites of the metal surface occupied by one molecule of inhibitor [41]. Kads is related to the free
energy of adsorption Gads by the equation
K ads =
o
G ads
1
exp
55.5
RT
(12)
where R is the molar gas constant, T is the absolute temperature, and 55.5 is the concentration of water in solution
expressed in mol dm-3.
124
July 2010
25
PA (30oC)
PA (60oC)
PA + KBr (30oC)
PA + KBr (60oC)
20
PA + KI (30oC)
C/ x 10-5 ( M)
PA + KI (60oC)
15
10
0
1
10
C x 10-5 (M)
Figure 4: Langmuir adsorption isotherm plot for aluminum corrosion in 0.5M HCl
for PA and PA halide mixtures at different temperatures
Figure 5 shows the plot of El-Awadys kinetic thermodynamic adsorption isotherm model. Linear plots were
obtained indicating that the adsorption of PA alone and in combination with halide ions can be approximated by ElAwadys kinetic thermodynamic model. Adsorption parameters derived from the model are given in Table 5.
Results in the table show that the values of K are very low and decrease with increasing temperature, suggesting
physical adsorption of the PA and PAhalides on the aluminum surface. The low values of K also indicate weak
interaction between the adsorbed species. The values of 1/y obtained are more than unity, indicating that the PA and
PAhalides are attached to more than one active site on the aluminum surface. These results may suggest that the
inhibitor was vertically adsorbed on the aluminum surface while the occurrence of flat adsorption by the studied
compound (PA) may be completely ruled out [41].
Table 5. Adsorption Parameters from Langmuir and El-Awady et al. Isotherms for Aluminum
in 0.5M HCl Containing PA and PA Halide Mixtures
Systems
PA
PA + KBr
PA + KI
July 2010
Temperature (oC)
Langmuir
El-Awady
Slope
R2
Goads
(kJ/mol
1/y
R2
30
3.35
0.99
-5.09
1.48
14.71
0.90
60
4.25
0.99
-4.22
0.50
11.11
0.89
30
2.79
0.99
-5.16
1.56
15.63
0.92
60
3.28
0.99
-5.15
1.04
10.42
0.95
30
2.71
0.99
-5.69
2.49
25.00
0.84
60
3.09
0.99
-4.29
0.53
15.87
0.91
125
0.7
0.6
0.5
0.4
0.3
Log (/1-)
0.2
0.1
0
PA (30oC)
-0.1
PA (60oC)
PA + KBr (30oC)
-0.2
PA + KBr (60oC)
PA + KI (30oC)
-0.3
PA + KI (60oC)
-0.4
-5
-4.5
-4.3
-4.1
-4.0
Log C
Figure 5: El-Awady adsorption isotherm plot for aluminum corrosion in 0.5M HCl
for PA and PA halide mixtures at different temperatures
3.6. Kinetic and Thermodynamic Studies

The mode of inhibitor adsorption on the metal surface can be probed by varying the temperature during the
corrosion process. The use of two temperatures to establish the mode of inhibitor adsorption on the surface of a
corroding metal has been reported by some authors [42 44] and has been found to be adequate. The values of the
activation energy Ea were calculated using the Arrhenius equation
log
CR 2
Ea 1 1
=

CR1 2.303R T 1 T 2
(13)
where CR1 and CR2 are the corrosion rates at temperatures T1 and T2, respectively. The values obtained are presented
in Table 6. The result shows that Ea increases markedly in the presence of polyacrylamide and polyacrylamide
halide mixtures compared to the blank. The higher value of Ea in the presence of polyacrylamide and
polyacrylamidehalide mixtures compared to the blank is attributed to physical adsorption mechanism [45]. As a
consequence, corrosion inhibition is assumed to occur primarily through physical adsorption of the inhibitor
molecules on the aluminum surface, giving rise to the deactivation of these surfaces to hydrogen atom
recombination. A similar result has been reported in our earlier publication [42]. An estimate of heat of adsorption
(Qads) was obtained from the trend of surface coverage with temperature as follows:

T T
Q ads = 2.303R log 2 log 1 x 1X 2 kJmol 1
1 2
1 1 T 2 T1
(14)
where 1 and 2 are are degrees of surface coverage at temperature T1 and T2, respectively, and R is the molar gas
constant. The calculated values of heat of adsorption are given in Table 6. From the table, it is clear that Qads values
are negative. The negative values of Qads show that the adsorption and, hence, inhibition efficiencies decreased with
a rise in temperature, thus also supporting the proposed physisorption mechanism. The free energy of adsorption was
obtained from the relationship expressed in Equation (12) and the calculated values are given in Table 5. From the
table, it is seen that the values of Goads increased with an increase in temperature, a phenomenon which indicates
that the adsorption of the inhibitor onto the aluminum surface was unfavorable with increasing experimental
temperatures as a result of desorption of adsorbed inhibitor from the metal surface. The values of Goads are negative,
which reveals the spontaneity of the adsorption process and the stability of the adsorbed layer on the aluminum
surface. Since the values of Goads of 40 kJmol-1 are usually accepted as a threshold value between chemisorption
and physiosorption, the obtained values of Goads for the studied inhibitor are below 40 kJmol-1, which is consistent
with electrostatic interactions between charged molecules and charged metal, which are indicative of physiosorption.
126
July 2010
Table 6. Calculated Values of Activation Energy (Ea) and Heat of Adsorption (Qads)
for Aluminum in 0.5M HCl for the Different Systems
Activation energy (Ea) (kJ/mol)

o
30 60 C
Heat of adsorption (Qads) (kJ/mol)

30 60oC
Blank
26.68
5mM KBr
44.29
-24.47
5mM KI
43.20
-18.48
-5
1 x 10 M PA
43.90
-29.82
-5
3 x 10 M PA
43.33
-23.06
-5
5 x 10 M PA
43.37
-22.58
-5
7 x 10 M PA
43.43
-23.05
-4
1 x 10 M PA
43.06
-21.37
44.15
-27.49
-5
43.93
-25.57
-5
43.45
-24.82
-5
43.50
-21.93
-5
43.16
-19.31
1 x 10-5M PA + 5mM KI
44.28
-2.25
43.57
-21.69
5 x 10-5M PA + 5mM KI
43.42
-20.89
-5
42.89
-18.91
-4
42.76
-16.86
-5
4. CONCLUSIONS
Polyacrylamide was found to be an efficient inhibitor of aluminum corrosion in HCl at lower temperatures.
Inhibition efficiency increased with increase in the concentration of polyacrylamide and synergistically increased on
addition of halide (Br- and I-) ions with the most profound effect obtained with iodide ion. The physisorption
phenomenon is proposed from the kinetic and thermodynamic parameters (Ea, Goads, and Qads) obtained. The
adsorption process for polyacrylamide and polyacrylamidehalide mixtures followed the kinetic-thermodynamic
model of El-Awady et al. The synergistic parameter evaluated was found to be greater than unity, which indicates
that the phenomenon of synergism exists between PA and halide ions.
REFERENCES
[1]
S. A. M. Refaey, F. Taha, and M. Abd El-Malek, Inhibition of Stainless Steel Pitting Corrosion in Acidic Medium
by 2-Mercaptobenzoxazole, Appl. Surf. Sci., 236(2004), p. 175.
[2]
A. K. Maayta and N. A. F. Al-Rawashdeh, Inhibition of Acidic Corrosion of Pure Aluminum by Some Organic
Compounds, Corros. Sci., 46(2004), p. 1129.
[3]
M. Bouklah, B. Hammouti, M. Benkaddour, and T. Benhadda, Thiophene Derivatives as Effective Inhibitors for
the Corrosion of Mild Steel in 0.5M H2SO4, J. Appl. Electrochem., 35(2005), p. 1095.
[4]
M. A. Quraishi and H. K. Sharma, Thiazo1es as Corrosion Inhibitors for Mild Steel in Formic and Acetic Acid
Solutions, J. Appl. Electrochem., 35(2005), p. 33.
[5]
A. Yurt, B. Butun, and B. Duran, Effect of the Molecular Weight and Structure of Some Novel Water Soluble
Triblock Copolymers on the Electrochemical Behavior of Mild Steel, Mater. Chem. Phys., 105(2007), p. 115.
[6]
H. Ashassi-Sorkhabi and N. Ghalebsaz-Jeddi, Inhibition Effect of Polyethylene Glycol on Corrosion of Carbon

Steel in Sulphuric Acid, Mater. Chem. Phys., 92(2005), p. 480.
[7]
S. K. Sathiyanarayanan, K. Balakrishnan, S. K. Dhawan, and D. C. Trivedi, Influence of Poly(aminoquinone) on

Corrosion Inhibition of Iron in Acid Media, Appl. Surf. Sci., 252(2005), p. 966.
July 2010
127
128
[8]
S. Rajendran, S. P. Sridevi, N. Anthony, and A. J. Amairaj, Corrosion Behavior of Carbon Steel in Polyvinyl
Alcohol, Anti-Corros. Method Mater., 52(2005), p. 102.
[9]
C. Jeyaprabha, S. Sathiyanarayanan, K. N. L. Phani, and G. Venkatachari, Investigation of the Inhibitive Effect of

Poly (diphenylamine) on Corrosion of Iron in 0.5M H2SO4 Solutions, J. Electroanal. Chem., 585(2005), p. 250.
[10]
Y. Jianguo, W. Lin., V. Otieno-Alego, and D. P. Schweinsberg, Polyvinylpyrrolidone and Polyethylenimine as

Corrosion Inhibitors for the Corrosion of a Low Carbon Steel in Phosphoric Acid, Corros. Sci., 38(1996), p. 587.
[11]
Y. Abed, B. Hammouti, F. Touhami, A. Aouniti, S. Kertit, A. Mansri, and K. Elkacemi, Poly (4-vinylpyrindine)
(P4VP) as Corrosion Inhibitors of Armco Iron in Molar Sulphuric Acid Solution, Bull. Electrochem., 17(2001),
p. 105.
[12]
A. K. Dubey and G. Singh, Corrosion Inhibition of Mild Steel in Sulphuric Acid Solution by Using Polyethylene
Glycol Methyl Ether (PEGME), Portugaliae Electrochim. Acta, 25(2007), p. 221.
[13]
K. S. Khairou and A. El-Sayed, Inhibition Effect of Some Polymers on the Corrosion of Cadmium in a
Hydrochloric Acid Solution, J. Appl. Polym. Sci., 88(2003), p. 866.
[14]
E. E. Oguzie, L. Unaegbu, C. N. Ogukwe, B. N. Okolue, and A. I. Onuchukwu, Inhibition of Mild Steel Corrosion
in Sulphuric Acid Using Indigo Dye and Synergistic Halide Additives, Mater. Chem. Phys., 84(2004), p. 363.
[15]
E. E. Ebenso, Effect of Halide Ions on the Corrosion Inhibition of Mild Steel in H2SO4 Using Methyl Red, Part 2,
Bull. Electrochem., 20(2004), p. 551.
[16]
E. E. Ebenso, Synergistic Effect of Halide Ions on the Corrosion Inhibition of Aluminum in H2SO4 Using 2Acetylphenothiazine, Mater. Chem. Phys., 79(2003), p. 58.
[17]
M. Abdallah, E. E. Helal, and A. S. Fouda, Amino-Pyrimidine Derivatives as Inhibitors for Corrosion of 1018
Carbon Steel in Nitric Acid Solution, Corros. Sci., 48(2006), p. 639.
[18]
G. K. Gomma, Corrosion of Low-Carbon Steel in Sulphuric Acid Solution in Presence of Pyrazole Halides
Mixtures, Mater. Chem. Phys., 55(1998), p. 241.
[19]
M. Th. Makhlouf, S. A. El-Shatory, and A. El-Said, The Synergistic Effect of Halide Ions and Some Selected
Thiols as a Combined Corrosion Inhibitors for Pickling of Mild Steel in Sulphuric Acid Solution, Mater. Chem.
Phys., 43(1996), p. 76.
[20]
E. E. Oguzie, Studies on the Inhibitive Effects of Occimum Viridis Extracts on the Acid Corrosion of Mild Steel,
Mater. Chem. Phys., 99(2006), p. 441.
[21]
E. E. Oguzie, A. I. Onuchukwu, P. C. Okafor, and E. E. Ebenso, Corrosion Inhibition and Adsorption Behavior of
Ocimum Basilicum Extract on Aluminum, Pigm. Resin Technol., 35(2006), pp. 6370.
[22]
E. E. Oguzie, Inhibition of Acid Corrosion of Mild Steel by Telfaria Occidentalis Extract, Pigm. Resin Technol.,
34(2005), p. 321.
[23]
E. E. Oguzie, Corrosion Inhibition of Aluminum in Acidic and Alkaline Media by Sansevieria Trifaciata Extract,
Corros. Sci., 49(2007), p. 1527.
[24]
S. A. Umoren., I. B. Obot, and E. E. Ebenso, Corrosion Inhibition of Aluminum Using Exudates Gum from
Pachylobus Edulis in the Presence of Halide Ions in HCl, E-J. Chem., 5(2008), p. 355.
[25]
S. A. Umoren and E. E. Ebenso, Studies on the AntiCorrosive Effect of Raphia Hookeri Exudates GumHalide
Mixtures for Aluminum Corrosion in Acidic Medium, Pigm. Resin Technol., 37(2008), p. 173.
[26]
S. A Umoren, O. Ogbobe, and E. E. Ebenso, Synergistic Inhibition of Aluminum Corrosion in Acidic Medium by
Gum Arabic and Halide Ions, Trans. SAEST, 41(2006), p. 74.
[27]
E. E. Ebenso, U. J. Ekpe, S. A. Umoren, E. U. Jackson, O. K. Abiola, and N. C. Oforka, Synergistic Effect of

Halide Ions on the Corrosion Inhibition of Aluminum in Acidic Medium by Some Polymers J. Appl. Polym. Sci.,
100(2006), p. 2889.
[28]
S. A. Umoren, E. E. Ebenso, P. C. Okafor, U. J. Ekpe, and O. Ogbobe, Effect of Halide Ions on the Corrosion
Inhibition of Aluminum in Alkaline Medium Using Polyvinyl Alcohol, J. Appl. Polym. Sci., 103(2007), p. 2810.
[29]
S. A. Umoren., I. B. Obot, and I. O. Igwe, Synergistic Inhibition Between Polyvinylpyrollidone and Iodide Ions on
Corrosion of Aluminum in HCl, The Open Corros. J., 2(2009), p. 1.
[30]
S. A. Umoren., E. E. Ebenso, and O. Ogbobe, Synergistic Effect of Halide Ions and Polyethylene Glycol on the
Corrosion Inhibition of Aluminum in Alkaline Medium, J. Appl. Polym. Sci., 113(2009), p. 3533.
[31]
National Association of Corrosion Engineers (NACE). Corrosion Basics: An Introduction. Houston, Texas, 1984,
pp. 214230.
July 2010
[32]
D. A. Jones, Principles and Prevention of Corrosion, 2nd Edition. Upper Saddle River, New Jersey, USA: PrenticeHall Inc., 1996, p. 32.
[33]
M. M. El-Naggar, Corrosion Inhibition of Mild Steel in Acidic Medium by Some Sulfa Drugs Compounds,
Corros. Sci., 49(2007), p. 2226.
[34]
S. A. Umoren and E. E. Ebenso, The Synergistic Effect of Polyacrylamide and Iodide Ions on the Corrosion
Inhibition of Mild Steel in H2SO4, Mater. Chem. Phys., 106(2007), p. 387.
[35]
A. Y. El-Etre, Inhibition of Aluminum Corrosion Using Opuntia Extract, Corros. Sci., 45(2003), p. 2495.
[36]
M. Lebrini, F. Bentiss, H. Vezin, and M. Lagrenee, The Inhibition of Mild Steel Corrosion in Acid Solutions by
2,5-bis (4-pyridyl)-1,2,3-thiadiazole: Structure-Activity Correlation, Corros. Sci., 48(2006), p. 1291.
[37]
E. E. Oguzie, Y. Li, and F. H. Wang, Corrosion Inhibition and Adsorption Behavior of Methionine on Mild Steel
in Sulfuric Acid and Synergistic Effect of Iodide Ion, J. Coll. Interf. Sci., 310(2007), p. 90.
[38]
L. Niu, H. Zhang, F. Wei, S. Wu, X. Cao, and P. Liu, Corrosion Inhibition of Iron in Acidic Solution by Alkyl
Quaternary Ammonium Halides: Correlation Between Inhibition Efficiency and Molecular Structure, Appl. Surf.
Sci., 252(2005), p. 634.
[39]
A. Frignani, G. Trabanelli, F. Zucchi, and M. Zucchini, in Proceeding of Fifth European Symposium on Corrosion
Inhibitors, Ferrara, 1980.
[40]
T. Y. Soror and M. A. El-Ziady, Effect of Cetyl Trimethyl Ammonium Bromide on the Corrosion of Carbon
Steel in Acids, Mater. Chem. Phys., 77(2003), p. 697.
[41]
E. A. Noor, Inhibition of Mild Steel Corrosion in Phosphoric Acid Solutions by Some N-Heterocyclic
Compounds in the Salt Form, Corros. Sci., 47(2005), p. 33.
[42]
I. B. Obot, N. O. Obi-Egbedi, and S. A. Umoren, The Synergistic Inhibitive Effect and Some Quantum Chemical
Parameters of 2, 3-Diaminonaphthalene and Iodide Ions on the Acid Corrosion of Aluminum, Corros. Sci.,
51(2009), p. 276.
[43]
P. C. Okafor, M. E. Ikpi, I. E. Uwah, E. E. Ebenso, U. J. Ekpe, and S. A. Umoren, Inhibitory Action of

Phyllanthus Amarus Extracts on the Corrosion of Mild Steel in Acidic Media, Corros. Sci., 50(2008), p. 2310.
[44]
Y. Ren, Y. Luo, K. Zhang, G. Zhu, and X. Tan, Lignin Terpolymer for Corrosion Inhibition of Mild Steel in 10%
Hydrochloric Acid Medium, Corros. Sci., 50(2008), p. 4147.
[45]
A. S. Fouda, A. A. Al-Sarawy, and E. E. El-Katori, Pyrazolone Derivatives as Corrosion Inhibitors for C-Steel in
Hydrochloric Acid Solution, Desalination, 201(2006), p. 1.
July 2010
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S. A. Umoren and M. M.

EFFECT OF HALIDE IONS ADDITIVES ON THE

S. A. Umoren and M. M. Solomon

S. A. Umoren and M. M. Solomon

EFFECT OF HALIDE IONS ADDITIVES ON THE CORROSION INHIBITION OF

S. A. Umoren and M. M. Solomon

S. A. Umoren and M. M. Solomon

S. A. Umoren and M. M. Solomon

Corrosion rate (mm/yr)

1 x 10-5M PA + 5mM KBr

S. A. Umoren and M. M. Solomon

3.2. Hydrogen Evolution Technique

S. A. Umoren and M. M. Solomon

Corrosion rate (cm3/min)

1 x 10-5M PA + 5mM KBr

3.3. Thermometric Technique

S. A. Umoren and M. M. Solomon

1 x 10-5M PA + 5mM KBr

3.4. Effect of Halide Ions and Synergistic Consideration

S. A. Umoren and M. M. Solomon

Synergism parameter (S1)

3.5. Adsorption Isotherm

S. A. Umoren and M. M. Solomon

S. A. Umoren and M. M. Solomon

3.6. Kinetic and Thermodynamic Studies

S. A. Umoren and M. M. Solomon

Activation energy (Ea) (kJ/mol)

Heat of adsorption (Qads) (kJ/mol)

1 x 10-5M PA + 5mM KBr

H. Ashassi-Sorkhabi and N. Ghalebsaz-Jeddi, Inhibition Effect of Polyethylene Glycol on Corrosion of Carbon

S. K. Sathiyanarayanan, K. Balakrishnan, S. K. Dhawan, and D. C. Trivedi, Influence of Poly(aminoquinone) on

S. A. Umoren and M. M. Solomon

C. Jeyaprabha, S. Sathiyanarayanan, K. N. L. Phani, and G. Venkatachari, Investigation of the Inhibitive Effect of

Y. Jianguo, W. Lin., V. Otieno-Alego, and D. P. Schweinsberg, Polyvinylpyrrolidone and Polyethylenimine as

E. E. Ebenso, U. J. Ekpe, S. A. Umoren, E. U. Jackson, O. K. Abiola, and N. C. Oforka, Synergistic Effect of

S. A. Umoren and M. M. Solomon

P. C. Okafor, M. E. Ikpi, I. E. Uwah, E. E. Ebenso, U. J. Ekpe, and S. A. Umoren, Inhibitory Action of

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