Gum arabic as a potential corrosion inhibitor

for aluminium in alkaline medium and its

adsorption characteristics
S.A. Umoren and I.B. Obot
Department of Chemistry, Faculty of Science, University of Uyo, Uyo, Nigeria
E.E. Ebenso and P.C. Okafor
Physical Chemistry Unit, Department of Pure and Applied Chemistry, University of Calabar, Calabar, Nigeria, and
O. Ogbobe and E.E. Oguzie
Department of Polymer and Textile Engineering and Electrochemistry/Materials Science Research Laboratory,
Federal University of Technology, Owerri, Nigeria

Abstract
Purpose – To investigate the inhibitive effect of gum arabic (GA) for the corrosion of aluminium in alkaline (NaOH) medium and
determine its adsorption characteristics. The present work is another trial to find a cheap and environmentally safe inhibitor for aluminium
corrosion.
Design/methodology/approach – The inhibition efficiency (%I) has been evaluated using the hydrogen evolution (via the gasometric assembly) and
the thermometric methods at 30 and 408C. The concentrations of GA (inhibitor) used were 0.1-0.5 g/l and the concentrations of NaOH (the corrodent)
were 0.1-2.5 M. The mechanism of adsorption inhibition and type of adsorption isotherms were proposed from the trend of inhibition efficiency with
temperature, Ea, DGads and Qads values.
Findings – GA inhibited the corrosion of aluminium in NaOH solutions. The inhibition efficiency increased with increase in GA concentration and with
increase in temperature. Phenomenon of chemical adsorption is proposed for the inhibition and the process followed the Langmuir and Freundlich
adsorption isotherms. The results obtained in this study for the %I were comparable for the two methods used and were corroborated by kinetic and
thermodynamic parameters evaluated from the experimental data.
Research limitations/implications – Further investigations involving electrochemical studies such as polarization method will enlighten more on the
mechanistic aspect of the corrosion inhibition.
Originality/value – This paper provides new information on the possible application of GA as an environmentally friendly corrosion inhibitor even in
highly aggressive alkaline environments. It has not been published elsewhere.

Keywords Alkalinity, Corrosion inhibitors, Metals

Paper type Research paper

1. Introduction inhibitors has attracted considerable attention because they

Some investigations have been made recently into the use of
naturally occurring substances to inhibit corrosion of metals
in acidic environments. Plant extracts including their leaves
and tubers and their corrosion inhibitive properties have been
widely examined (Loto, 1990; Zakvi and Mehta, 1988; Kar
et al., 1998; Verma and Mehta, 1998, 1999; Ebenso et al.,
1996, 2004; Ekpe et al., 1994; Sakthievel et al., 1999; Ramesh
et al., 2001; Avwiri and Igho, 2003; El-Etre, 2001, 2003;
Muller, 2004). It has been shown that the inhibitive effect of
some plants solution extract has been attributed to the
presence of tannin in their chemical constituents (Martinez,
2002). Investigation of natural substances as corrosion
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Anti-Corrosion Methods and Materials
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[DOI 10.1108/00035590610692554]
have been shown to be low cost, ecologically friendly and
possess no threat to the environment.
Gum arabic (GA) which is the subject of the present
investigation is a dried, gummy exudate obtained from
various species of Acacia trees of the leguminosae family. It is
water soluble and a complex mixture of arabinogalactan,
oligosaccharides, polysaccharides and glucoproteins (Chaplin,
2003; Abdallah, 2004). In practical terms, gums are defined
as molecular structures, tending to high molecular mass,
usually with colloidal properties, that, in an appropriate
solvent produce gels or suspensions of high viscosity or
solutions of low matter content that can absorb water at ten
times their weight. GA is a useful hydrocolloid, emulsifier,
texturizer, film former and stabilizer.
Investigations into the use of natural substances as
corrosion inhibitors have been conducted in acidic medium
and there seem to be scanty reports on corrosion inhibition of
metals in alkaline environments using natural substances. In
this present work, the corrosion inhibition of aluminium in
NaOH using GA at 30 and 408C using hydrogen evolution
and thermometric methods has been investigated.

277
 Gum arabic as a potential corrosion inhibitor
S.A. Umoren et al.
2. Experimental
2.1 Materials preparation
The sheets of aluminium, AA 1060 type and purity of 98.5
per cent used for this study were obtained from the System
Metal industries limited, Calabar, Nigeria. Each sheet was
0.8 mm in thickness and were mechanically pressed cut into
5 £ 4 cm coupons. These coupons were used as cut without
further polishing. However, they were degreased in ethanol,
dried in acetone and stored in a moisture free desiccator
before their use in corrosion studies. Coupons of the same
dimension (5 £ 4 £ 0.8 cm) were used for both hydrogen
evolution and thermometric methods. The concentrations of
inhibitor (GA) (BDH supplies chemicals, England) prepared
and used in the study were 0.1-0.5 g/l. The concentrations of
NaOH (BDH laboratory supplies, England) (the corrodent)
used were 0.1-2.5 M.
2.2 Hydrogen evolution technique
The volume of hydrogen evolved was determined following
the procedures previously described elsewhere (Ebenso et al.,
1996, 1999, 2001, 2003, 2004; Ebenso, 1998, 2003; Ekpe
et al., 2001). A 100 ml solution of 0.1-2.5 M solution of
NaOH was introduced into the reaction vessel connected to a
burette through a delivery tube. The initial volume of air in
the burette was recorded. An aluminium coupon of weight 2 g
was dropped into the solution of NaOH and the reaction
vessel quickly closed to prevent any escape of H2 gas.
However, the volume of H2 evolved from the corrosion
reaction was monitored by the depression (in ml) in the
paraffin oil level. The depression in paraffin oil level was
monitored every 10 s for 300 s. The same experiment was
repeated in the presence of inhibitor (GA) having the
concentration range 0.1-0.5 g/l with a corrodent (NaOH)
concentration of 1 M.
The inhibition efficiency (%I) was calculated using the
equation:
 
Vi
Ipercent ¼ 1 2 H £ 100 ð1Þ
V oH
where V iH is the volume of H2 gas evolved at time t in the
presence of inhibitor (GA) and V oH for the blank (absence of
GA) (Ebenso et al., 2004).
2.3 Thermometric method
The reaction vessel and procedure for determining the
corrosion behaviour by this method has been described
elsewhere by other authors (Mylius, 1922; Shams Eldin and
Khedr, 1992; El-Etre, 2001). The volume of the test solution
was kept at 50 ml. The initial temperature in all experiments
was kept at 308C. The temperature was measured to ^ 0.058C
on a calibrated thermometer (0-1008C). This method allowed
for the evaluation of the reaction number (RN). The RN is
defined as:
Tm 2 Ti
RNð8C min21 Þ ¼ ð2Þ
t
where Tm and Ti are the maximum and initial temperatures,
respectively, of the system studied when put into reaction
vessel and t is the time (min) taken to reach the maximum
temperature.
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Anti-Corrosion Methods and Materials
Volume 53 · Number 5 · 2006 · 277 –282
The inhibition efficiency (%I) was evaluated from
percentage reduction in the RN namely:
RNaq 2 RNwi
Ipercent ¼ £ 100 ð3Þ
RNaq
where RNaq is the RN in the absence of inhibitor (GA), i.e.
blank (2 M NaOH) and RNwi the RN of aqueous 2 M NaOH
in the presence of the inhibitor (GA) (Abd-El Nabey et al.,
1985; Ebenso et al., 2004).
3. Results
Results obtained in this study are presented in Tables I-III
and Figures 1-7. Figure 1 shows the variation of volume of
hydrogen evolved with time for aluminium in different
concentrations of NaOH without GA at 30 and 408C.
Inspection of Figure 1 shows that the hydrogen evolution
starts after a certain time from the immersion of the
aluminium coupon in the test solution. It may be expected
that this time corresponded to the period/time needed by the
base to destroy the pre-immersion oxide film and is known as
incubation period. Figure 2 shows the volume of hydrogen
evolved during the corrosion reaction of aluminium in 1 M
NaOH containing different concentrations of GA measured
as a function of reaction time at 30 and 408C. Figure 3
shows the temperature – time curves for the dissolution of
aluminium in 1 M NaOH containing different concentrations
of the inhibitor (GA). Inspection of Figure 3 shows that as the
concentration of the inhibitor increased, the time required to
reach maximum temperature (Tm) increased and the rate of
temperature rise decreased, that is, the inhibition efficiency
increased with the increase in the concentration of the
inhibitor. Figure 4 shows the relationship between the RN,
RN and the logarithm of inhibitor concentration. The curve
consists of an initial decreasing portion along which the RN
decreased with increasing concentration of GA and then the
rate of decrease became smaller. As the concentration of GA
increased further, the value of RN decreased with
concentration. This seems to suggest that the inhibitor
formed a monolayer on the surface of aluminium (Mousa
et al., 1988).
Table I shows the calculated values of inhibition efficiency
(%I), degree of surface coverage (u) and corrosion rate (mdd)
for GA. From Table I, it is clearly seen that the corrosion rate
of aluminium in NaOH decreased with addition of inhibitor
compared to the blank. Also, the corrosion rate decreased
with increase in the concentration of the inhibitor. This is an
indication that the GA showed a significant inhibitive effect
on aluminium corrosion in the alkaline environment. Table II
compares the inhibition efficiency for GA obtained from the
thermometric and hydrogen evolution methods. The two
methods are comparable within limits of the concentration
studied. Figure 5 shows the plot of inhibition efficiency
against inhibitor concentration at both temperatures. Non-
linear plots were obtained. Table III shows calculated values
of activation energy (Ea) and heat of adsorption (Qads) for GA
for aluminium corrosion in NaOH. A plot of logarithm of %I
versus logarithm of inhibitor concentration is shown in
Figure 6 (Freundlich adsorption isotherm) while that of
Langmuir adsorption isotherm is shown in Figure 7 (plot of
C/u against C).
 Gum arabic as a potential corrosion inhibitor Anti-Corrosion Methods and Materials
S.A. Umoren et al. Volume 53 · Number 5 · 2006 · 277 –282

Table I Calculated values of corrosion rate (mdd), inhibition efficiency and degree of surface coverage (u) for GA from hydrogen evolution data
Corrosion rate Degree of surface
(mdd) 3 102 3 Inhibition efficiency (%I) coverage (u)
Concentration of GA (g/l) 308C 408C 308C 408C 308C 408C
Blank 4.0 8.1 – – – 0.28
0.1 3.6 6.1 19.09 28.41 0.19 0.28
0.2 3.4 5.7 35.23 45.22 0.35 0.45
0.3 3.3 5.4 44.34 55.41 0.44 0.55
0.4 3.1 5.1 47.14 61.41 0.47 0.61
0.5 3.0 5.0 50.24 74.16 0.50 0.74

Table II Comparison of inhibition efficiency (%I) from hydrogen From Figure 1, it could be seen that the volume of
evolution at 408C and thermometric method hydrogen evolved increased with increase in the concentration
of the corrodent (NaOH) at 308C. A similar trend was
Inhibition efficiency (%I) observed at 408C but with rather higher values. This could be
Concentration of GA (g/l) Hydrogen evolutiona Thermometricb attributed to the fact that an increase in concentration
increased the rate of chemical reaction. Figure 2 also shows
0.1 28.41 31.34
that the volume of H2 evolved was markedly reduced in the
0.2 45.22 49.14
presence of the inhibitor (GA) compared to the blank which is
0.3 55.41 60.99
an indication that GA actually inhibited the corrosion of
0.4 61.23 62.83
aluminium in the alkaline environment. Also as could be
0.5 74.16 75.86 shown from Figure 2, the volume of H2 evolved decreased
Notes: a obtained using Equation (1); b obtained using Equation (3) with increase in concentration of the inhibitor. The volume of
H2 evolved at 408C was higher than at 308C.
In all cases, the inhibition efficiency and degree of surface
coverage (u) were found to increase with increase in the
Table III Calculated values of activation energy, Ea (kJ mol2 1) and heat concentration of inhibitor (GA) and with increase in
of adsorption, Qads (kJ mol2 ) for GA for aluminium corrosion in NaOH temperature. The highest inhibition efficiency (74.16 per cent)
Activation energy, Heat of adsorption, was obtained with 0.5 g/l and at 408C (Table I). The increase in
Concentration Ea(kJ mol2 1) Qads (kJ mol2 1) inhibition efficiency with increase in temperature is suggestive
of GA (g/l) 30-408C 30-408C of chemical adsorption mechanism. A similar trend was
reported by Abdallah (2004), which studied guar gum as a
Blank corrosion inhibitor and attributed this behaviour to the increase
0.1 130.17 39.86 of surface coverage (u) by the adsorption of the inhibitor on the
0.2 125.59 32.98 metal surface. El-Etre (2003) also reported a similar
0.3 82.64 34.85 observation for the inhibitive action of Opuntia extract.
0.4 86.63 44.76
4.1 Adsorption/thermodynamic considerations
0.5 80.43 82.50
In discussing the adsorption characteristics for this study, the
surface coverage (u) data was very useful. A linear relationship
was obtained at all concentrations studied at both 30 and
4. Discussion 408C which indicates that the experimental data fits the
The dissolution of aluminium in NaOH starts from the moment Freundlich adsorption isotherm (Figure 6). All the isotherm
the metal is introduced into the corrodent. Aluminium dissolves plots indicate that plot of lower temperature (308C) are under
in NaOH according to the chemical reaction: the plot of higher temperature (408C) studied which further
indicates chemical adsorption proposed. The adsorption
3
Al þ OH2 þ H2 O ! AlO22 þ H2 ð4Þ isotherm of Langmuir was tested for its fit to the
2 experimental data. Linear plots were obtained at 30 and
The mechanism of the process takes into consideration the 408C (Figure 7) which also indicates that the experimental
influence of the passivating surface oxide film. Introduction of data fits Langmiur adsorption isotherm given by:
aluminium into NaOH leads to adsorption of the OH2 ions C 1
¼ þc ð6Þ
primarily on the surface oxide film. Owing to the acidic property u b
of the oxide film, it is chemically attacked and this leads to where “C” is the inhibitor concentration and u is the degree of
subsequent dissolution of the oxide film as shown in the reaction surface coverage. Similar observations have also been
below (Mousa et al., 1988): reported (Abdallah, 2004) that the adsorption of guar gum
Al2 O3 2OH2 ! 2AlO2 2 þ H2 O ð5Þ follows Langmiur adsorption isotherm. El-Etre (2003) also
reported that the adsorption of Opuntia extract follows the
The heat generated from the above reaction accelerates further Langmiur adsorption isotherm. It is worthy of mention here
dissolution of the oxide and activates the dissolution of that, the u values obtained with the thermometric method also
aluminium exposed to the aggressive medium. obey the Langmiur adsorption isotherm.

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S.A. Umoren et al. Volume 53 · Number 5 · 2006 · 277 –282

Figure 1 Variation of volume of hydrogen, VH, with time for the Figure 2 Variation of volume of Hydrogen, VH with time (secs) for the
dissolution of aluminium in different concentrations of NaOH at (a) dissolution of aluminium in 1.0 M NaOH in the presence of GA of
308C and (b) 408C different concentrations at (a) 308C and (b) 408C

The inhibition of aluminium corrosion by GA may be attributed

to the presence of arabinogalactan, oligosaccharides,
polysaccharides and glucoproteins since these compounds
contain oxygen and nitrogen atoms which are the centres of
adsorption. Furthermore, GA is a polysaccharide compound
containing repeated heterocyclic pyrane moiety (Abdallah,
2004). The presence of hetero oxygen atoms in the structure Figure 3 Temperature – time curves for the dissolution of aluminium in
makes possible its adsorption by co-ordinate type linkage blank and different concentration of GA
through the transfer of lone pairs of oxygen atoms.
The values of the activation energy, Ea (Table III) were
calculated with the help of the Arrhenius equation:
 
r2 Ea 1 1
log ¼ 2 ð7Þ
r1 2:303R T 1 T 2
where r1 and r2 are the corrosion rates at temperatures T1 and
T2, respectively.
The values of Ea decreased with increase in the concentration
of GA. The values were greater than 80 kJ mol2 1 which goes
further to support the assertion that chemical adsorption is
proposed. The values of heat of adsorption (Qads) were
calculated using the following equation:
    
u2 u1
Qads ¼ 2:303R log 2 log
1 2 u2 1 2 u1
values were positive and ranged from 32.98 to 82.50 kJ mol2 1
 
T1 £ T2 (Table III). The positive Qads values show that the adsorption
£ kJ mol21 ð8Þ and hence inhibition efficiency increased with rise in
T2 2 T1
temperature also supporting chemical adsorption.
where u1 and u2 are degree of surface coverage at temperatures The values of free energy of adsorption, DGoads were
T1 and T2, respectively. It is clearly seen that in all cases, the Qads obtained from the intercept of the Freundlich adsorption

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 Gum arabic as a potential corrosion inhibitor Anti-Corrosion Methods and Materials
S.A. Umoren et al. Volume 53 · Number 5 · 2006 · 277 –282

Figure 4 Plot of RN against Log of inhibitor concentration Figure 7 Langmuir adsorption isotherm plot of C/u versus C
(V 308C B 408C)

values obtained are an indication that the inhibitor (GA) was

Figure 5 Plot of inhibition efficiency (%I) against inhibitor
concentration (V308C B 408C)
Figure 6 Freundlich adsorption isotherm plot of log %I versus log C
(V 308C B 408C)
spontaneously adsorbed on the metal surface. Generally, values
of DGoads up to 220 kJ mol2 1 are consistent with electrostatic
interactions between the charged metal which signifies physical
adsorption while values more negative than 240 kJ mol2 1
(obtained in this study) involved charge sharing or transfer from
the inhibitor molecules to the metal surface to form coordinate
type of bond which signifies chemical adsorption (Bilgic and
Sahin, 2001). It is seen in the study that the inhibition efficiency
for the corrosion of aluminium in the presence of GA increased
with increase in concentration. This also implies that adsorption
of GA increases with increase in GA concentration. The
adsorbed intermediate formed at the aluminium surface by the
interaction with GA is probably a complex. At lower
concentration of GA, the adsorption intermediate formed
may be soluble complex, giving rise to low inhibition efficiency.
At higher concentration, the complex formed is insoluble and
the higher values of inhibition efficiency due to complex arise
from the blocking of most of the activities on the aluminium
surface due to the increased surface coverage.

5. Conclusions
.
GA shows significant inhibitive effect on aluminium
corrosion in alkaline environment.
.
Inhibition efficiency increased with increase in inhibitor
concentration. Inhibition was probably brought about by
the adsorption of the inhibitor on the metal surface of
oligosaccharides, polysaccharides, glucoproteins and
arabinoglactan constituents of GA on the surface of
the aluminium.
.
Phenomenon of chemical adsorption is proposed for the
calculated values of Ea, Qads and DGoads obtained. The
isotherm plot and calculated with the help of the following increase in temperature increased the inhibition efficiency
equation (Abdel and Saed, 1981): of GA which further confirmed that the adsorption
  process was chemical in nature.
u .
The mean DGoads value was negative which suggest that
log C ¼ log 2 log B ð9Þ
12u GA was strongly adsorbed on the metal surface. The
values of DGoads at both temperatures studied indicated
where log B ¼ 21:74 2 ðDGads =2:303RTÞ and C is the spontaneous adsorption of the inhibitor, and this is usually
inhibitor concentration. characteristic of strong adsorption with the metal surface.
DGoads at 308C was 2 162.69 and 2213.49 kJ mol2 1 at 408C. .
The adsorption process for GA followed the Langmuir
The mean value of DGoads was 2 188.09 kJ mol2 1. The negative and Freundlich adsorption isotherms.

281
 Gum arabic as a potential corrosion inhibitor
S.A. Umoren et al.
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Corresponding author
E.E. Ebenso can be contacted at: eno_ebenso@yahoo.com