CHAPTER ONE

1.0 Introduction
Metal atoms given by nature, existing in the earth crust, do occur in chemical compounds. That
is as minerals. They are extracted upon undergoing energy consuming process. But however, the
chemical reaction producing corrosion products reverts these metals to, mostly, oxides and other
chemical products that requires same amount of energy as in the extraction (Sayyah et al., 2014).
Metals corrode in aggressive environments of acids and bases in industries for manufacturing
processes and other application like acid pickling, acid and base cleaning, acid de-scaling and oil
well cleaning (Sastri, 1998). Corrosion of metals has for long been costing so much to humanity.
And that various types of metals are used for different inevitable purposes. Steels are used in
residential and commercial structures, in bridges and trusses, in automobiles, passenger trains,
railroad cars, ships, in pipelines and storage tanks. Aluminum alloys are used in electronic
application, aircraft frames and canned food containers. Copper finds its usage in electrical
connectors, water pipes and decorative roof (McCafferty, 2010). These metals are found
prevalently to corrode at different extent and rate when exposed to some destructive conditions
in the course of their wide range of applications in various industries as construction material for
chemical reactors, roofing, heat exchange and boiler systems, storage tanks, oil and gas transport
pipelines.

Many substances, inorganic and organic compounds containing π – electrons and polar functions
with oxygen, nitrogen, or sulfur atoms have recently been widely studied as corrosion inhibitors.
Interestingly, Schiff bases are therefore researched on, to study the efficiency of inhibition of
corrosion of metals using several electrochemical methods.

1.1 Corrosion
The origin of the word corrosion is from the Latin word corrodere, meaning "to gnaw to pieces;'
(a similar origin as the word "rodent" (Svedberg et al., 2011). Corrosion is an electrochemical
process which usually occurs not by direct chemical reaction of a metal with its environment but
rather through the operation of coupled electrochemical half reaction. Broadly, Corrosion can be
defined as the destructive attack of metal by its reaction with the environment (McCafferty,
2010). Corrosion is a chemical or electrochemical oxidation process, in which the metal transfers
electrons to the environment and undergoes a valence change from zero to a positive value. The

1
environment may be a liquid, gas or hybrid soil-liquid. These environments are called
electrolytes since they have their own conductivity for electron transfer (Perez, 2004). Corrosion
can produce problems ranging from loss of heat transfer efficiency and constricted pipes to
annoyance pinhole leaks and temporary shutdowns. More serious failures are often in the form of
major floods, property damage, operating failures, lost production, and personal injury (Sulaiman
et al., 2012).

1.2 Corrosion inhibition

This is a phenomenon in which chemical substances, organic and inorganic, are added in to the
aggressive of environment of metals and metal alloys so as to inhibit the corrosion reaction.
Corrosion inhibitor is a substance which when added to a corroding medium brings about an
appreciable reduction of the corrosive action. Corrosion inhibitors are commonly added in small
amounts to acids, cooling waters, steam and other environments, either continuously or
intermittently to prevent serious corrosion (McCafferty, 2010).

1.2.1 Classification of inhibitors

Chemical substances that inhibit corrosion as reported by (Sayyah et al., 2014) are classified as
either:

1. Anodic Inhibitors: Anodic inhibitors impede the corrosion process by causing a large shift in
the corrosion potential. They are also called dangerous inhibitors, because if used in insufficient
concentrations, they cause pitting or sometimes an increase in corrosion rate. These forms a
passive film on the metal surface. Which is incurred by oxidizing agent like Chromates or non-
oxidizing agents like azelates.

2. Cathodic Inhibitors: Cathodic inhibitors are precipitation inhibitors that act by either slowing
the cathodic reaction itself, or they selectively precipitate on cathodic areas to increase circuit
resistance and restrict diffusion of reducible species to the cathodes. Some cathodic inhibitors
make the discharge of hydrogen gas more difficult, and they increase the hydrogen over voltage.
Another possible cathodic reaction is the reduction of oxygen. A three-dimensional barrier film
is formed on metal surfaces by a precipitation reaction between the cations of the corroding
metal and the inhibitor. Phosphates and silicates are precipitation-type inhibitors.

2
3. Organic inhibitors: Inhibitors adsorbed on metal surfaces mostly form a chemisorptive bonds
with the metal surface and impede electrochemical corrosive reactions. Prevalently, organic
inhibitors are chemisorptive-type inhibitors. Organic compounds constitute a broad class of
corrosion inhibitors which cannot be designed specifically as either anodic or cathodic. Anodic
and cathodic effects alone are sometimes observed in the presence of organic inhibitors, but, as a
general rule, organic inhibitors affect the entire surface of a corroding metal when present in
sufficient concentration. Both anodic and cathodic areas are inhibited differently depending on
the potential of the metal, chemical structure of the inhibitor molecule, and size of the molecule.
The inhibition is the result of adsorption of inhibitor on the metal surface. The film formed by
adsorption of soluble organic inhibitors is invisible.

However, the organic inhibitors are found to be more efficient. But on the other hand, some are
environmentally not friendly. Natural plant extract and Schiff bases are now the trending
corrosion inhibitors.

1.3 Schiff Bases

Schiff bases are typically formed by the condensation of a primary amine and an aldehyde.
Schiff bases are important intermediates for the synthesis of various bioactive compounds.
Furthermore, they are reported to show a variety of biological activities including antibacterial,
antifungal, anti-cancer and herbicidal activities (Yang and Sun, 2006). On the other hand, they
are fundamental material for synthesis of various ligands which are used as chiral auxiliaries in
asymmetric synthesis. Metal complex Schiff bases have also been used in oxidation reactions
(Jarrahpour, 2006).

1.3.1 Schiff Bases as Corrosion Inhibitors

Compounds containing functional groups with hetero atoms, which can donate lone pair of
electrons, are found to be very efficient as inhibitors against metal corrosion in many
environments. Many N-heterocyclic compounds with polar groups and/or π electrons are acting
as efficient corrosion inhibitors in acidic solutions. Schiff bases as organic compounds which
have both these features combined in one molecule, will be potential inhibitors. Schiff bases
have been reported as effective corrosion inhibitors for steel, copper and aluminum in acid
medium like hydrochloric acid, sulphuric acid, acetic acid, formic acid and bases like sodium
hydroxide and potassium hydroxide by adsorbing on the surface (Boudalia et al., 2017). The

3
adsorption is influenced by the electronic structure of the inhibiting molecules and also by steric
factors, aromaticity, electron density at the donor atoms and the presence of functional groups
(McCafferty, 1970 and Metikos-Hukovic, 1994).
1.4 Aluminum

Aluminum has atomic number of 13 with mass number of 27, belongs to group 3 period 2 of the
periodic table. It has three valence electrons making it relatively metallic. This makes it exhibits
many peculiar properties. Aluminum and its alloys offer an extremely wide range of capability
and applicability, with a unique combination of advantages that make it the material of choice for
numerous products and markets. Aluminum alloys possess a number of very attractive
characteristics which, together with their very light weight, make then extremely attractive for
many applications. It has ease of extrudability. Aluminum and its alloys application range from
transportation, industrial and packing to construction, infrastructure and aerospace (The
Aluminum Association, Inc., 1998). These applications are owing to the balanced combination of
physical, mechanical and chemical properties, such as electrical and thermal conductivities, low
density, high ductility, stability for surface treatments, good corrosion resistance, easiness of
recycling and functional advantages of extruded and cast semi-products (Yang, 1994). Elements
such as copper, lithium, manganese, magnesium, silicon and zinc are added to aluminum to form
alloys, which allows aluminum to achieve a long range of bulk properties; likewise, minor
additions provide an improvement in specific properties (Davis, 1994). Aluminum generally
exhibits passive behavior in aqueous solution due to the formation of a strong and compact
adherent passive oxide film on the surface, which affects corrosion susceptibility. The adhesive
passivating surface oxide film is amphoteric, and consequently, the metal is readily dissolved
when exposed to aggressive acidic and alkaline solutions (Umoren, 2006). Most commercial
alloys contain several types of intermetallic phases, where aluminum corrosion occurred
essentially as a micro-galvanic process between these secondary phases and the matrix alloy.
Sulfuric acid solutions are widely used for aluminum anodizing operations. Additionally,
aluminum and its alloys are designated for industrial applications to manage a large variety of
acid and alkaline solutions, but once dissolved, corrosion of the naturally-formed film can only
be controlled by efficient inhibitors. Aggressive ions (chlorides, fluorides, sulphates) attack the
oxide film locally (Nisancioglu,1992).

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1.5 Background of the study

The use of corrosion inhibitors on metal surface has become necessary due to ravages caused by
the corrosion process in the areas of economics, safety, and conservation as summarized by
Revie and Uhlig (2008). One of the most vital processes in the field of prevention of corrosion
and its control is the use of organic inhibitors. The crucial part in the mechanistic aspect of such
inhibitors is the specific interaction between certain functionalities in the inhibitors with the
corrosion active centers on the metal surface (Chitra et al., 2010). HCl and H2SO4 have been
used for drilling operations, picking baths and in descaling processes thereby causing corrosion
process on the metal surface. The corrosion of metals has become a major problem in many
industries, installation and municipal services such as water and sewage supplies due to
excessive use of acids. This problem not only cause increase in the cost, but quality and the
efficiency of the plants and that of the products get also decreased. Corrosion of metals is a
fundamental academic and serious industrial problem that has acknowledged considerable
attention (Hari et al., 2016)

1.6 Scope and of the research

Organic compounds have been reportedly used as corrosion inhibitors for corrosion of
Aluminum in acid solutions. Due to the presence of the -C=N group, an electron cloud on the
aromatic rings, the electronegative N and O atoms in the molecule, the Schiff base may be good
corrosion inhibitor. The Schiff base was synthesized for the experiment. The corrosion inhibition
study of the Schiff base on Aluminum in H 2SO4 was not yet reported. For these, the corrosion
inhibition efficiency studies of the Schiff base on Aluminum in H 2SO4 was investigated using
Weight Loss method. An adsorption isotherm which describes the adsorptive behavior of a
corrosion inhibitor and provides important clues to the nature of metal - inhibitor interaction for
the inhibition process was suitably assigned for the corrosion inhibition of Aluminum in the
presence of the Schiff base.
1.7 Statement of the problem

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Corrosion of Aluminum in oil, metallurgical and other industries is a result of an electrochemical
reaction. The electrochemical corrosion process happens in the order in which a current leaves
the structure at the anode site, passes through an electrolyte, and reenters the structure at the
cathode site. Areas which corrosion is important is in economic - costing billions in its
prevention and recovery of the damages, safety – leads to damages of properties, equipment and
lives, and conservation of resources. Several organic and inorganic substances have been
employed to inhibit the corrosion process of Aluminum, but most, are however expensive with
some environmentally unfriendly and toxic.
1.8 Justification
To inhibit the corrosion of aluminum, several measures (including anodic, cathodic and mixed
protection, lubrication, painting and electroplating) have been adopted. However, the best option
accessible for the protection of metals against corrosion involves the use of organic inhibitors –
mixed type inhibitors. Most successful inhibitors are synthesized from cheap raw materials
selected from compounds, which have hetero atom (N, O, P, S) in their aromatic or long carbon
chain. The benzoin and anthranilic acid are relatively cheap and environmentally friendly, with
the presence of N and O hetero atoms in the Schiff base as well as three aromatic benzene rings.
The suitable functional groups (C=N, COOH, and OH) and excess π – electrons in the aromatic
rings could facilitate the adsorption of the inhibitor on the metal surface thereby inhibiting the
corrosion process.
1.9 Aim And Objectives

The aim of the study is to investigate the corrosion inhibition efficiency of the Schiff base on
Aluminum surface.

The objectives are;

 To investigate the effect of temperature, time and concentration of corrodent with the
Schiff base as the inhibitor on the Aluminum surface.
 To predict the adsorption isotherm of the inhibitor on the metal by fitting adsorption data
into different adsorption isotherms.
 To characterize the type of adsorption as either chemisorption or physisorption

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1.10 Literature Review

The inhibitory effect of a new synthesized (E)-N-(4-methylphenyl)-1-(4-nitrobenzyl)

methanimine Schiff base (SBMNM) on the corrosion of aluminum in 2M H2SO4 solution was
studied using weight loss and gasometric techniques. The Schiff base was prepared using reflux
method; the characterization was carried out by electronic absorption spectra, infrared spectra,
solubility and melting point tests. The results showed that the inhibition efficiency decreased as
the temperature increased, a physical reaction mechanism is proposed. The plot of log (wi-Δw)
against time gave linear graph which suggests the reaction is a first order reaction. The
percentage efficiency was 75.43% at 1.0x10 -2M concentration of the Schiff base. The negative
free energy of adsorption obtained confirmed a spontaneous adsorption. The Langmuir
adsorption isotherm result showed a deviation from an ideal Langmuir adsorption isotherm
equation (Echem and James, 2014).

Umasankareswari and Jeyaraj (2012) studied the inhibition effect of vanillideneanthranilic acid
on the corrosion behavior of commercial aluminum in 1.0 N NaOH as corrosion medium using
weight loss, potentiodynamic polarization and electrochemical impedance measurement methods
and SEM technique. It was concluded that the inhibition efficiency increased with the increasing
concentration of the inhibitor. The maximum inhibition efficiency was found to be 59.25% at
30°C. The investigation of adsorption isotherms indicated that the inhibitor fitted Langmuir and
Temkin isotherms, fairly well. The phenomenon of physisorption is attributed to the values of
Ea, Qads and ΔG°ads. The potentiodynamic polarisation results revealed that the inhibitor act as a
mixed type inhibitor.
Another studies of compounds of poly(ionic liquid)s (PILs), derived from imidazole with
different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-
3-dodecyl-imidazolium) (PImC12), poly(1-vinyl-3-octylimidazolium) (PImC8) and poly(1-
vinyl-3-butylimidazolium) (PImC4) hexafluorophosphate) was reported. These compounds were
tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1–1 M
H2SO4) by weight loss, polarization resistance measurements and inductively coupled plasma
optical emission spectroscopy. Langmuir’s isotherms suggested film formation on bare alloy
while standard free energy indicated inhibition by a physisorption process. However, compound
PImC12 showed highest efficiency as inhibitor of 61% in highly diluted acidic solution.

7
Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The
surface film displayed general corrosion, and pitting occurred because of PILs’ partial inhibition
along with a continuous dissolution of defective patchy film on formation. A slight improvement
in efficiency was displayed by compounds having high molecular weight and a long alkyl chain,
as a consequence of steric hindrance and PIL interactions (Paulina et al., 2014).
In another study by Aouniti et al. (2016) on the adsorption and corrosion inhibition behavior of
(E)-2-methyl-N-(thiophen-2-ylmethylidene)aniline on steel in 1.0 M HCl using gravimetric
and electrochemical methods at 308K, the Inhibition efficiency increased with increase in the
concentration of the Thiophene Schiff base. The potentiodynamic polarization studies revealed
that this compound is a mixed-type inhibitor. The adsorption follows Langmuir’s isotherm.

Patel et al. (2013) also reported that a Schiff base, o-Chloroaniline-N-benzylidene (o-CANB) has
shown good inhibitive effectiveness on Aluminum in 1M HCl. The corrosion inhibition
efficiency was determined by Weight Loss method in the temperature range of 35°C-65°C. Other
two electrochemical techniques such as Electrochemical Impedance Spectroscopy and
potentiodynamic polarization were employed for the determination of corrosion inhibition
efficiency of the o-CANB at 35°C. Weight Loss method reflected that corrosion inhibition
efficiency of o-CANB increased with increasing concentration and highest corrosion inhibition
efficiency is achieved at 0.5% concentration (%V/V). At this concentration and 35°C
temperature, corrosion inhibition efficiency of o-CANB was reported 99.4%. Electrochemical
Impedance Spectroscopy method showed 94.2% at 0.1% concentration and 35°C temperature.
Potentiodynamic polarization method displayed 93.7% corrosion inhibition efficiency at 0.05%
concentration and at 35°C temperature. Weight Loss method was employed to study the effect of
temperature on corrosion inhibition efficiency. The obtained result showed that as temperature
increased in the range of 35°C to 65°C, corrosion inhibition efficiency of o-CANB was
decreased. ∆G0ads value of inhibitor was-32.6kJ/mol, and that showed about physisorption.

Three Schiff bases 2-[2-aza-2-(5-methyl(2-pyridly))vinyl]phenol (MP), 2-[2-aza-2-(5-methyl(2-

pyridly))vinyl]-4-bromophenol (MBP) and 2-[2-aza-2-(5-methyl(2-pyridly))vinyl]-4-chloro-
phenol (MCP) were studied as corrosion inhibitors for Aluminum in 0.1M HCl at 25°C.
Corrosion inhibition efficiency of the three inhibitors was increased with concentration. MP
showed highest corrosion inhibition efficiency 43.4% at 5×10 -3M as determined by

8
Electrochemical Impedance Spectroscopy method. However, Potentiodynamic polarization and
Linear Polarization Resistance showed 80.2% and 58.7% corrosion inhibition efficiency at same
concentration. Other two inhibitors MBP and MCP displayed 64.2% and 69.7% corrosion
inhibition effectiveness as calculated by Electrochemical Impedance Spectroscopy method at
5×10-3M. Potentiodynamic polarization and Linear Polarization Resistance method exhibited
84.3% and 60% corrosion inhibition efficiency at same concentration for MBP. Potentiodynamic
polarization and Linear Polarization Resistance reflected 78.6% and 44.5 corrosion inhibition
efficiency at 5×10-4M for MCP. ∆G0ads value of the three compounds is less than -20kJ/mol
which indicated about physisorption on Aluminum surface. Various quantum chemical indices
were evaluated for the determination of theoretical corrosion inhibition efficiency of inhibitors
(Yurt et al., 2006).

Novel corrosion inhibitors namely dianiline Schiff bases were synthesized and studied for
inhibiting action on corrosion of mild steel in 1M H2SO4 acid at 30°C. A preliminary screening
of the inhibition efficiency was carried out using weight loss measurements. Potentiodynamic
polarization studies showed that the Schiff bases were mixed type inhibitors. The effect of
temperature on the corrosion behavior of mild steel in 1M sulphuric acid with the addition of the
Schiff bases was studied in the temperature range from 40°C-60°C. The adsorption of these
compounds on a mild steel surface from sulphuric acid obeyed the Langmuir adsorption
isotherm. The decrease in inhibition efficiency with increase in temperature and the less negative
∆G°ads values suggested predominant physisorption of the Schiff base molecules on the steel
surface (Chitra et al., 2010).
In another report, the inhibitive action of Piper guineense (uziza leaf) extract on the corrosion of
mild steel in a 2M H2SO4 medium has been studied using weight loss method. The collected leaf
samples were rigorously grounded and squeezed, with the resultant gel extract used for the
weight loss determination at 1.0%, 2.0%, 3.0%, 4.0% and 5.0% v/v concentrations, respectively.
A rectangular mild steel coupons in a 2 M H2SO4 solution were also employed to determine the
amount of weight loss in the absence and presence of Piper guineense extract at temperatures of
303K, 313K and 323K. The results show that mild steel corrosion inhibition increases with
increasing concentrations of Piper guineense extract, showing greater efficiency at higher
temperatures of 313K and 323K. Moreover, Piper guineense extract can effectively perform as a
green and non-toxic inhibitor for mild steel corrosion in acidic environments (Anuchi and

9
Ngobiri, 2018). A similar trend is observed in two quinoline-thiazole derivatives namely, {4-[1-
aza-2-(phenyl)vinyl]-3-phenyl-2-thioxo(1,3-thiazoline-5-yl)}-N-[1-aza-2-(2-chloro(3-
quinolyl))vinyl] and {4-[1-aza-2-(4-methoxyphenyl)vinyl]-3-phenyl-2-thioxo(1,3-thiazoline-5-yl)}-
N-[1-aza-2-(2 chloro (3-quinolyl))vinyl] in their investigation as inhibitors for mild steel corrosion in
15% HCl solution by using weight loss measurements, potentiodynamic polarization and
electrochemical impedance spectroscopy (EIS) techniques. The inhibitors Inh I and Inh II show
corrosion inhibition efficiencies of 81.5% and 84.0% at a 20 ppm concentration and 95.0% and
96.3% at a 200 ppm concentration, respectively, at 333 K. It was found that the inhibition efficiency
of both the inhibitors increases with an increase in temperature and concentration of inhibitors. The
adsorption of inhibitors on the mild steel surface obeys the Langmuir adsorption isotherm ( Yadav et
al. 2014).

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 CHAPTER TWO

2.0 Materials And Methods

A Schiff base of benzoin and anthranilic acid, 2-(2-hydroxy-1,2-phenyl)ethiminobenzoic acid,
was synthesized and used to determined its corrosion inhibition efficiency on Aluminum surface
using weight loss measurements.
2.1 Materials
1000ml volumetric flasks
250ml volumetric flasks
250ml beakers
50ml beakers
Glass rod
Measuring cylinder
Tong
Emery paper
Reflux condenser
100ml round bottom flask
Hot plate
Brush
Filter paper
Magnetic stirrer
2.2 Reagents
Anthranilic acid
Benzoin
90% rectified Ethanol
Distilled water

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Sodium acetate
Sulfuric acid
2-(2-hydroxy-1,2-phenyl)ethaniminobenzoic acid

2.3 Preparation of The Schiff Base

A prepared ethanolic (0.01mol) benzoin solution was put into a 250ml round bottom flask, added
after, was ethanolic solution of (0.01mol) anthranilic acid. 3.0g of sodium acetate was then
added. The mixture was refluxed for an hour on a steam bath. The product was precipitated by
pouring the content into an ice-cold water. Which was separated and recrystallized from rectified
spirit, filtered, washed with water and dried (Aliyu and Muhammad, 2009).

2.4 Preparation of Acid Solution

The molarity of the acid was obtained using eqn. 1. The amount of acid used was obtained from
the eqn. 2. and was put into 1000ml volumetric flask containing 890ml of distilled water.

percent purity ×10 × specific gravity

Molarity= ………………………………………….. eqn 1
Molecular mass

M1V1 = M2V2……………………………………………………………………………. eqn 2

M 2V 2
V 1= ………………………………………………………………………………. eqn 3
M1
2.5 Preparation Of Inhibitor Solution
The Schiff base synthesized as described above was employed for corrosion inhibition studies.
2M H2SO4 was used as the corrodent which was prepared using distilled water. 0.01M, 0.001M,

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0.0001M and 0.00001M of the Schiff base in the corrodent was prepared in 250ml volumetric
flask from eqn 4

Molarity × Mm× 250

Mass of inhibitor (¿ grm)= …………………………………… eqn 4
1000

250 ml of 2M H2SO4 without inhibitor is considered as blank test solution.

2.6 Preparation of Test Coupons

The Aluminum sheets were cut into coupons having 2cm x 3cm x 0.01cm size using wheel
cutting machine and polished with different grade emery papers to mirror polish. Then the
coupons were washed with ethanol and distilled water, dried and weighed using electronic
balance.
2.7 Weight Loss Method
The polished aluminum coupons were immersed in hanging position in 30 ml of test solution
taken in 50ml beakers and put in oven operated at various temperatures of 313K, 333K and 343K
for time intervals of 30min each. The specimens were taken out in the time interval, cleaned with
brush, washed with running water and ethanol, dried and weighed. The change in the weight (
Δ W ) was recorded.
The Corrosion Rate (CR) in g/mm/yr was obtained using the equation below

ΔW
CR= ……………………………………………………………………..…………... eqn 5
At

Where Δ W is the change in weight in g, A is the area of the coupon in mm 2, t is the time in
years.
The surface coverage (θ) of the inhibitor is gotten through the equation below

w−wi
θ= ……………………………………………………………………………....... eqn 6
w

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where w is wight loss without the inhibitor and wi is the weight loss with the inhibitor.
The % inhibition efficiency (η) of the Schiff base was calculated using

w−wi
η= × 100 %............................................................................................................ eqn 7
w

2.8 FT-IR
The Schiff base synthesized was subjected to IR testing and characterized. Also, the coupons
were abraded with different grades of emery paper to obtain clear surface, and then dipped into
0.01M test solution. And allowed to get exposed to the medium for 30min at room temperature
and 333K. The specimens were removed, cleaned with brush, washed with water and ethanol and
dried. Then the IR spectrum of the Schiff base on the metal surface was taken using FT-IR
spectrometer within the range of 4000cm-1-250cm-1.
2.9 Adsorption Isotherm Studies
Adsorption isotherms are often shown to demonstrate the performance of organic adsorbent type
inhibitors and important in determining the mechanisms of organic electrochemical reactions.
Establishment of isotherms that describe the adsorptive behavior of a corrosion inhibitor is an
important part of its study as they can provide important clues to the nature of metal inhibitor
interaction. The most frequently used adsorption isotherms are Langmuir, Temkin and Frumkin
isotherms having the following surface coverage–bulk concentration relationships (Sastri, 1998).

θ
for Langmuir isotherm, =KC ……………………………………………… eqn 8
1−θ
for Temkin, efθ=KC ………………………………………………… eqn 9
θ
for Frumkin, efθ=KC………………...………………………….. eqn 10
1−θ

where θ is the degree of surface coverage, C is the inhibitor concentration in the solution and K
is the equilibrium constant or the molecular interaction constant, a coefficient expressing
θ
interaction between adsorbed and adsorbing molecule. The plots are usually given as log
1−θ
θ
versus log C for Langmuir isotherm, log versus θ for Frumkin isotherm and θ versus log
C(1−θ)

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C for Temkin isotherm. The plots which give straight line will be best suitable adsorption
isotherm
2.10 Calculation of Thermodynamic Parameter
The values of activation energy for steel corrosion reaction (Ea) were obtained from Arrhenius
equation. The activation energy values were calculated from the slopes of the log(CR) versus 1/T
plots. From which the values of ΔH, ΔSads, and ΔGads were calculated (Yadav et al., 2014). The
equilibrium constant for adsorption process is related to the free energy of adsorption, ΔG ads, by
the relation: ΔGads = -RT ln (55.5Kads)
where R is universal gas constant, T temperature in absolute scale, K is the equilibrium constant
for adsorption process and 55.5 concentration of water in the solution.
θ
The Kads is given by the relation K ads=
C(1−θ)
where θ is the degree of coverage on the metal surface and C the concentration of inhibitor.

CHAPTER THREE
3.1 Result
The results of the experiments that were obtained are presented in this section.
3.1.1 Schiff base
The Schiff base synthesized from equimolar ethanolic solutions of benzoin and anthranilic acid
was characterized using FT-IR. The spectrum is given in figure 1.

Figure 1. the FT-IR spectrum of the Schiff base

The FT-IR of the starting materials, benzoin and anthranilic acid was also taken and compared to
the spectrum of the Schiff base.
3.1.1.1 The FT-IR of the inhibitor adsorbed on the metal surface

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The metal – inhibitor interaction was characterized using FT-IR at room temperature and at
343K.

Figure 2. the FT-IR spectrum of the metal surface with the inhibitor adsorbed at room
temperature

Figure 3. the FT-IR spectrum of the metal surface with the inhibitor adsorbed at 333K
3.1.2 Weight loss method
The results of weight loss measurement( Δ W), corrosion rates (CR), surface coverage (Θ) and
corrosion inhibition efficiencies (%IE) of Schiff base on Aluminum surface in 2M H 2SO4
without the inhibitor and with different inhibitor concentrations of 0.0001M, 0.0001M, 0.001M
and 0.01M at different contact time of 30min, 90min and 120min and temperatures of 313K,
333K and 343K are presented in the table1. to table 3. below:

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Table 1. weight loss measurement for 30min at 313k
Conc. W1 W2 ΔW CR Θ %IE
Blank 0.9815 0.9797 0.0018 0.05256 - -
0.00001 0.9386 0.9368 0.00171 0.04992 0.05 5
0.0001 1.01067 1.009 0.001667 0.04867 0.074 7.4
0.001 0.9384 0.9368 0.001606 0.0469 0.107 10.7
0.01 0.9616 0.9603 0.00133 0.0388 0.2611 26.11

Table 2. weight loss measurement for 90min at 333k

Conc. W1 W2 ΔW CR Θ %IE
Blank 0.9547 0.9254 0.02893 0.2815 - -
0.00001 0.9225 0.9046 0.02050 0.1996 0.291 29.1
0.0001 0.9628 0.9460 0.0168 0.1635 0.419 41.9
0.001 0.9736 0.9631 0.1046 0.1018 0.638 63.8
0.01 0.9488 0.9396 0.00923 0.08983 0.68 68

Table 3. weight loss measurement for 120min at 343k

Conc. W1 W2 ΔW CR Θ %IE
Blank 0.8854 0.8274 0.05804 0.422 - -
0.00001 0.9714 0.9382 0.033 0.240 0.4314 43.14
0.0001 0.9618 0.9423 0.0195 0.142 0.664 66.4
0.001 0.9416 0.9255 0.01613 0.1177 0.722 72.2
0.01 0.9403 0.9257 0.01465 0.1069 0.747 74.7

The results of the weight loss in the presence and absence of the inhibitor for the 30min contact
showed slight difference, and varied greatly as the time increased. Figure 4. Shows the
relationships of weight loss with contact time for the different inhibitor concentration.

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 0.07
0.06
0.05
weight loss in gm

0.04
0.03
0.02
0.01
0
20 40 60 80 100 120 140
Time in min

blank 0.00001 0.0001 0.001 0.01

Figure 4. comparison of weight loss with and without inhibitor

3.1.2.1 The effect of concentration

The effect of the inhibitor concentration on the inhibition efficiency of the Schiff base is given in
Figure 5.
80
Percentage inhibition ef-

70
60
ficiency %

50
40
30
20
10
0
Concentration in M

Figure 5. Effect of concentration on the inhibition efficiency

3.1.2.2 The effect of the contact time

Time effect on the corrosion inhibitive effectiveness of the metal coupon with the inhibitor
environment on inhibition efficiency is shown in figure 6.

18
 80
Percentage inhibition efficiency 70
60
50
40
30
20
10
0
20 40 60 80 100 120 140
Time in min

0.00001 0.0001 0.001 0.01

Figure 6. Effect of time on efficiency

3.1.2.3 The effect of temperature

The relationship between the temperature and the corrosion inhibition efficiency of the inhibitor
is summarized in figure 7.

80

70
Percentage inhibition efficiency

60

50

40

30

20

10

0
310 315 320 325 330 335 340 345
Temparature in K

0.00001 0.0001 0.001 0.01

Figure 7. comparison of % efficiency with temperature difference

3.1.3 Adsorption isotherm studies

To understand the mechanism of corrosion inhibition, the adsorption behavior of the Schiff base
adsorbate on the metal surface is ascertained using the various adsorption isotherms. The degree

19
of the surface coverage (θ) as evaluated from the weight loss measurement results of Aluminum
in 2M H2SO4 in the presence and absence of the Schiff base conducted at 343K was used. The
adsorption was found to suit in to Langmuir isotherm. The plot of Log(θ/1-θ) versus C give a
straight line as given in Figure 8.
0.6

0.5

0.4

0.3
log (θ/1-θ)

0.2

0.1

0
-5.5 -5 -4.5 -4 -3.5 -3 -2.5 -2 -1.5
-0.1

-0.2
log ( C)

figure 8. Langmuir isotherm

3.1.4 Thermodynamic parameters

The activation energy was calculated with from the slope of Arrhenius plot of Log (CR) against
1/T in figure 9. The value was obtained from the equation:

………………………...…...………………………………………….…eqn 11
−Ea
lnCR= +lnA
RT

Thermodynamic parameters for the 0.01M inhibitor concentration were also evaluated, and
found to be Ea = 13.512 KJmol-1, ΔH = 10.66KJmol-1, ΔS = -166.45 KJmol-1K-1. The free
energies of adsorption ΔGads were obtained as:
Temperature ( in K ) ΔGads ( in KJmol-1K-1)
343 -27.67
333 -25.96
313 -20.36

20
 0
0.0029
-0.2 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325

-0.4
-0.6
lnCR

-0.8
-1
-1.2
-1.4
-1.6
1/T

Figure 9. Arrhenius plot in the presence of the inhibitor

3.2 Discussion
The inferences of the results obtained from the experiment are discussed in the section.

3.2.1 Schiff base

The vibration at around 1637cm-1 infers the presence of -C=N, the spectrum of the Schiff base
shows no spiking vibrations at around 3340cm-1, which indicates the disappearance of -NH 2 from
the starting material. A shift of vibration from 1638cm -1 in benzoin to 1647cm-1 in the Schiff base
shows the conversion of -C=O to -C=N.

3.2.1.1 The FT-IR of the metal surface with the inhibitor adsorbed
The spectrum shows several modes of vibration for the bonds between the metal and the Schiff
base, with the vibration bands complete different from the Schiff bases’. The vibrations are due
to chelation of the inhibitor through the lone pairs of electron the Nitrogen, the -C=N π –
electrons, the hydroxyl -OH pair of electron, the carboxylic -COOH lone pair and π – electrons,
and resonance contributed π – electrons from the 3 aromatic benzene rings.

3.2.2 Weight loss method

From the results obtained, the Schiff base acts as a good inhibitor on the corrosion of Aluminum
surface in 2M H2SO4 at all concentrations. It reduces the corrosion rates of surface significantly
at higher concentration and temperature. Which suggest about adsorption of the Schiff base on
the metal (Sorkhabi, 2005). The surface coverage of the Schiff base on the metal was also
increased with concentration of the inhibitor. Similar result was obtained with glutamic acid
Schiff base (Verma, 2014).

21
3.2.2.1 Effect of Concentration
Moreover, the weight loss was found to decrease with inhibitor concentration increase. So, the
inhibition effect increase with increase in inhibitor concentration. The concentration was
increased from 0.00001M to 0.01M, which connotes higher surface coverage, and thus resulted
in inhibition efficiency increase. In table 4., the highest loss of 0.033g was obtained at
0.00001M, while at 0.01M, the loss was 0.01465g. It can be inferred that inhibition efficiency
increase with increment in Schiff base concentration. The result agrees with the findings of
Echem and James (2014) in similar condition on Aluminum.

3.2.2.2 Effect of Temperature

It can be observed from the Table 1 to 3 that the corrosion rate increases with an in the increase
in temperature in the presence and absence of the inhibitor. The corrosion rate of Aluminum in
the absence of inhibitors increased steeply from 313K - 343 K whereas the corrosion rate
increases slowly in the presence of inhibitors. The inhibition efficiency increased from 313K to
343K, with highest effect observed at 343K. Which can be attributed that the temperature
increase shifts the equilibrium towards the right for the adsorption of Schiff base (Fragoza-Mar
et al., 2012). This hypothesis agrees with the results obtained by Yadav et al. (2014).
3.2.2.3 Effect of Time
As given in table 1 to 3, the contact time was 30min, 90min and 120min, which shows increase
in the time. The time increase exposed the coupon more even to the environment with and
without inhibitor, and that increase in corrosion inhibition efficiency was observed as the time
was increased. This is similar with what Li et al. (2014) reported.
3.2.3 Adsorption Isotherm
The adsorption of the Schiff base was found to follow Langmuir adsorption isotherm. The plot
logCR against 1/T gave a straight with about unity coefficient. The slight deviation from the
ideal behavior (R2 = 1.00) may be due to the molecular interaction among the adsorbed Schiff
base specie (Singh and Quraishi, 2011). The result indicates about chemisorption of the inhibitor.
3.2.4 Thermodynamic Parameters
From the thermodynamic parameters obtained, the negative values of ΔGads ensures the
spontaneity and feasibility of adsorption process and stability of the adsorbed layer on the
Aluminum surface. Chemisorption predominates when the ΔGads value is -40KJ/mol or lower,
while for ΔGads values of -20KJ/mol or higher, physisorption predominates (Mankowski et al.,
1978). Thus, the ΔGads values obtained suggest about both chemisorption and physisorption with

22
the lone pairs on the N and O atoms and the π-electron systems on the highly aromatic rings with
the metals respectively. This is similar with the result of Larouj et al. (2017). The value of Ea
obtained in the presence of the inhibitor is lower than that obtained in the inhibitor free solutions.
According to Umoren et al. (2008), the lower activation energy in the presence of inhibitor is an
indication for its chemisorption. The obtained value of ΔS is negative indicating that the entropy
of inhibitor molecules in the solution phase is higher than solid phase. Which tells about
spontaneity of the process (Sorkhabi et al., 2005). The positive sign of enthalpy ΔH reflect the
endothermic nature of Aluminum dissolution process meaning that dissolution of Aluminum is
difficult in presence of the Schiff base as compare in absence of Schiff base (Quraishi et al.,
2010). The results followed the findings of Yadav et al. (2014) and Verma and Quraishi (2014).
3.3 Summary
Schiff base of anthranilic acid and benzoin, 2-(2-hydroxy-1,2-phenyl)ethaniminobenzoic acid
was tested for corrosion inhibition of Aluminum in H 2SO4 using weight loss technique. The
results of the corrosion rate (CR), weight loss (ΔW), surface coverage (θ) and % inhibition
efficiency were obtained and analyzed. The finding showed that the Schiff base impedes the
corrosion rate by covering the surface of the metal. The weight loss significantly reduced with
the addition of the inhibitor. The Schiff base showed highest inhibition efficiency of 74.7% at
343K for 0.01M concentration. The efficiency increased with inhibitor concentration increase.
Also, the inhibition efficiency increased as the temperature was increased from 313K to 343K.
which indicated about chemisorption of the inhibitor on the metal surface. Increase of the contact
time increased the inhibition efficiency of the Schiff base.
The results were found to suitably fit the Langmuir adsorption isotherm with a slight deviation
from the ideal isotherm. The thermodynamic parameters were very consistent with feasibility
and spontaneity of the chemisorption of the Schiff base on the Aluminum surface. The reason for
the high inhibition efficiency of the studied Schiff base on Aluminum 2M H 2SO4 is due to the
presence of azomethine (–C=N-) group, O atoms and electron clouds on the aromatic rings
present in the inhibitor. The Schiff bases are strongly adsorbed via the donation of the lone pair
of electrons of O atom in the hydroxyl and carboxylic group and N atom in the C=N group onto
the metal surface. The atoms are, most, in the sp3 hybridized state, denoting a planar geometry.
As in the words of (McCafferty, 1970 and Metikos-Hukovic, 1994), the molecular structure, size,

23
aromaticity, electron density and suitable functional group strongly influenced the adsorption of
the inhibitor.
The FT-IR of the Schiff base and the Schiff on the metal surface was taken. The spectrum of the
Schiff base on the metal shows several vibrations that are consistent with many chemisorptive
bonds between the inhibitor and the metal.
3.4 Conclusion
The results of this study infer that the investigated Schiff base was found to impede the corrosion
process of aluminum in H2SO4 acid. The inhibition efficiency increases with concentration, time
and temperature, with maximum efficiency of 74.7% observed at 0.01M for 343K temperature.
The size, shape, orientation of the molecule and the electronic charges on the molecule aided the
degree of adsorption and effectiveness of this inhibitor. The Langmuir adsorption isotherm
suggests multi-layer adsorption of the inhibitor molecules on the metal. The positive values of
heat of adsorption ΔH, 10.66KJmol-1 indicates endothermic reaction and the ΔG ads value of -
27.67KJmol-1 and Ea value of 13.512 KJmol-1 suggested about spontaneous chemical adsorption.
The observed inhibition of the corrosion of Aluminum is assumed to be due to the adsorption of
the Schiff base molecules on the metal surface and the subsequent blocking of the metal’s active
sites. The FT-IR revealed the compound is adsorbed through the -C = N- functional group, the π
– electrons of the aromatic rings and O atoms present in the compound. Therefore, can be
industrially used to counter Aluminum corrosion in H2SO4 efficiently.

24
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