CHAPTER ONE

1.0 INTRODUCTION

1.1 BACKGROUND OF THE STUDY

Aluminum is a very important metal. It is used in numerous industries e.g. as a construction

material for roofs, cans, foils, kitchen utensils, window frames, beer kegs and airplane parts ,

staircases, railings, shelves, and other several applications (Abd El-Aal, 2009). Aluminum is a

very active metal so that it corrodes quickly in the aqueous solutions. For these reasons the

industrial use of corrosion inhibitors is often a good solution to prevent corrosion phenomena

and to provide more acceptable life time of metallic structure (Trbanelli, 2011). Most of the

reported corrosion inhibitors are organic compounds containing heterocyclic atoms (nitrogen,

oxygen, sulphur and phosphorous), aromatic ring or triple bonds are commonly used to reduce

the corrosion attack of Aluminum in aqueous solution (Fouda et al., 2006). The inhibitory effects

of organic compounds arise from their adsorption properties (such as functional groups, steric

factors and aromaticity) which depend on the structure of such organic compounds.

Corrosion is the degradation of a metal either by the direct chemical or electrochemical reaction

when in contact with aqueous corrosive surroundings. It is an endless and costly problem, often

difficult to eradicate completely. It is a foremost problem that has safety, conservation and

economic impacts in various chemical, motorized, metallurgical, natural and medical

engineering applications and more particularly in the design of a much more varied number of

mechanical parts which equally vary in size, functionality and useful lifespan (Sharma and

Mudhoo, 2011).

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Corrosion prevention would be more practical than trying to eliminate it completely. Given that

the environment plays an important role in corrosion, corrosion mechanisms can be as varied as

the environment to which substance is exposed and thus may be complex to understand. Factors

that causes corrosion include reactivity of metal, presence of impurities, presence of air,

moisture, gases like sulphur dioxide and the presence of electrolytes. Corrosion prevention and

retardation are aimed at addressing these factors (Sastri, 2014). In this research work methyl red

will be used as a corrosion inhibitor to check its effects (behaviour) on Aluminium in acidic

medium. It has been observed by various authors (Maklouf et al., 1995; Ita and Edem, 2000;

Ebenso et al., 2004 and Onen, 2006) that functional groups such as >C=C<, -N=O, -N=N,

>C=O, SO32-, aromatic rings e.t.c play important roles in inhibition effectiveness of compounds.

The compound was therefore chosen because it shares similar functional groups.

1.2 STATEMENT OF THE PROBLEM

The industrial cost involved in preventing problems such as corrosion, scale, wax and hydrate

deposition during oil and gas, food and beverage etc transport is high, and so there is

considerable drive from these industries to find cheap and effective additives to control these

problems. Corrosion causes tremendous harm to the nation‟s economy. About 10% of iron and

steel as well as aluminium and its alloys produced annually are lost to corrosion (Onen, 2000).

Corrosion can cause life threatening damage to metal and alloy structures causing financial

punishment in terms of renovation, replacement product losses safety and environmental

pollution (Pani et al., 2013). Metal degradation may result in elevated productivity lose arising

from the malfunctioning of the corroded instruments and contamination of main industrial

products (e.g. chemical products) by the aqueous corrosion product (Murulane et al., 2012).

Leakage of products leads to lose in efficiency. If the corrosion contaminated materials are left

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untreated, the industry may have to face equipment failure due to these harmful effects corrosion

is an unattractive observable fact that must be prevented. (Ebenso et al., 2012).

1.3. AIM AND OBJECTIVES

The aim of this work is to evaluate inhibitory and adsorption behavior of methyl red on

aluminum in acidic medium with the following objectives:

i. to determine the corrosion inhibition potential of methyl red (MR) on aluminum.

ii. to determine a suitable adsorption isotherm for the corrosion inhibition of aluminum in

acidic medium.

iii. to determine the effect of temperature variation on the inhibition process.

iv. to evaluate the surface morphology of Al in the absence and presence of Methyl red

(MR).

1.4. THE SCOPE OF THE STUDY

The need for studying corrosion inhibition of metals/alloys using effective, inexpensive and non-

toxic corrosion inhibitors cannot be over emphasized. This is necessary especially at a time when

government and various industries spend huge sums of money trying to combat the menace of

corrosion of body and engine parts of their machines and locomotives.

In the light of this, the study is confined in scope to the use Methyl red (MR) to inhibit the

corrosion of Aluminium in HCl at 303K and 313K, respectively.

The choice of this material is also predicated on the fact that it is less expensive and readily

available than the conventional corrosion inhibitors. Aluminium is chosen because it is widely

used in metallurgical, chemical, food processing/packaging and oil industries. Aluminiun used

for this study was obtained from new market in Wukari, Taraba state, Nigeria.

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Although the study is limited to the use of Aluminium and the inhibitor at 303K and 313K, its

findings may be applicable to other metals/alloys in similar environment(s). Since most of our

industries operate under similar environmental conditions, chances are that, they may be faced

with similar corrosion problems.

1.5. JUSTIFICATION OF THE STUDY

Azo dye (Methyl red) is a good inhibitor that can be used in the study of the adsorption behavior

in terms of corrosion inhibition. It contains polar atoms such as Nitrogen, Hydrogen, etc. and

functional groups such as >C=C<, -N=N,>C=O, aromatic rings e.t.c play important roles in

inhibition effectiveness of Aluminuin. Due to its nature, the lone pair of electrons present on

these atom is pump on to the metal surface; loss of the electron from the metal surface can be

avoided. Thus corrosion inhibitions take place because of the adsorption of the inhibitor

molecules on the metal surface, therefore forming a protective film. The study will provide the

basis for the evaluation of methyl red as a good inhibitor for aluminum metal.

1.6 THE SIGNIFICANCE OF THE STUDY

This study is based on the premise that corrosion inhibition and protection of metals/alloys play

very important role in the chemical, manufacturing, construction, food and beverages, oil and gas

industry of the economy. The study therefore provides the basis for the evaluation of Methyl red

(MR), as suitable alternative to highly expensive and non-environmentally friendly corrosion

inhibitors of Aluminium, such as chromium oxide, polyethylene chloride e.t.c.

Corrosion inhibition studies of Aluminium have before now been carried out using various

methods - weight loss and gasometric techniques, electrochemical and analytical techniques,

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polarization and impedance measurements etc. In this work, weight loss technique is used in

carrying out the analysis.

Inhibition characteristics of MR, determined in this study provide a spectrum of applications of

great advantages to the automobile, aviation, construction, food and beverages as well as oil and

gas industries.

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 CHAPTER TWO

2.0 LITERATURE REVIEW

The term corrosion is the deterioration of material by chemical interaction with their

environment. The term corrosion is sometimes also applied to the degradation of plastics,

concrete and wood, but generally refers to metals/alloys. Corrosion may also be defined as the

destructive attack of a metal/alloy by chemical or electrochemical reaction with its environment

(Hussain et al., 2010). Corrosion can also be considered as a redox process in which an oxide

coating is formed on the surface of the metal/alloy undergoing the process. It therefore requires

oxygen and moisture to occur. It involves the transfer of electrons along the surface of the metal

under the influence of a potential difference (Onen, 2000).

The corrosion occurs because of the natural tendency for most metals to return to their natural

state; e.g. iron in the presence of moist air will revert to its natural state, iron oxide. Metals can

be corroded by the direct reaction of the metal to a chemical; e.g. reactions of aluminum with

dilute sulphuric acid. Corrosion reactions are electrochemical in nature. They involve the transfer

of charged ions across the surface between a metal and the electrolyte solution in which it is

immersed (Hussain et al., 2010).

2.1 CHEMISTRY OF CORROSION

Corrosion reactions are electrochemical in nature. They involve the transfer of charge ions across

the surface between a metal and the electrolyte solution in which it is immersed (Hussain et al.,

2010). There two types of electrode reaction occurring at the metal surface anodic and cathodic.

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Anodic reaction involves oxidation: electrons appear on the right hand side of the equation. For

example, metallic ion produces ferrous ion by the anodic reaction.

Fe Fe2+ + 2e- (anodic)............................................................... (1)

2H2O + O2 + 4e- 4 OH- (cathodic)................................................... (2)

Fe2+ +2OH- Fe (OH) 2 (chemical)..................................................(3)

Cathodic reaction involves electrochemical reduction: electron appear on the left hand side of the

equation. In corrosion process the most common cathodic reaction is the electrochemical

reduction of dissolve oxygen according to the equation:

O2 +2H2O + 4e- 4OH- ................................................................ (4)

2.2 TYPES OF CORROSION

2.2.1 General or Uniform Corrosion.

Difference in electrical potential occur on the surface of a piece of metal due to small difference

in chemical composition, phase difference, amount of cold work, etc. these differences set up

small corrosion cells each with anode and cathode. (Sangeetha et al., 2011). Corrosion continues

until the metal is consumed or the film of rust formed on the surface set up a barrier to the

electrolyte.

2.2.2 Galvanic or Bi-metallic Corrosion.

Galvanic corrosion takes place between two different metals, or coatings which are joined

together in the presence of an electrolyte. Each metal has potential difference from any other

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metal when place in an electrolyte. A series can be built up of all the metals relative to each other

(Eddy et al., 2010).

2.2.3 Pitting corrosion

Pitting corrosion occur in materials that have a protective film layer such as corrosion product or

when coating breaks down. The expose metal gives up electrons easily and the reaction initiates

tiny pits with localized chemistry supporting rapid attack (Sangeetha et al., 2011)

2.2.4 Intergranular Corrosion

Corrosion occurs at some grain boundaries due to difference in potential between the anodic

grain boundaries and the cathodic grains. Sensitized stainless steel where carbides have been

precipitated in the grain boundaries during improper heat treatment or in the heat affected one of

weld, are particularly susceptible to intergranular corrosion. (Sangeetha et al., 2011).

This form of corrosion results from the localized attack at an adjacent to the grain boundaries

with relative little corrosion of the grain. Material with precipitated phase or impurities at the

grain boundaries can be more susceptible to this form of corrosion. As a result, the alloys

disintegrate due the grains falling.

2.2.5 Filiform Corrosion

This corrosion appears as a network of corrosion trials, of a wormlike structure, particularly

beneath thin organic coatings. Salt containing chlorides, which have been left on the surface

prior to coatings. Are suspected (Nnanna et al., 2010).

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2.2.6 Crevice Corrosion

This corrosion occurs when there is a difference in ion, or oxygen. Concentration between the

metal and its surroundings. Oxygen starvation in an electrolyte at the bottom of a sharp V-

section will set up an anodic site in the metal that then corrodes rapidly. Local segment

conditions often develop in confined spaces, such as under a lap joint or a washer, and can lead

to that area becoming anodic with respect to the remaining area of the metal, which remain

exposed to aerobic condition and becomes cathodic.

2.2.7 Stress Corrosion Cracking.

Failure is due to the simultaneous influence of static tensile stress and a corrosive environment

and this is specific to a particular metal. The stresses may be internal such as those caused by

cold water, welding, and heat treatment or external forces caused by mechanical stresses set up

by assembly practices. A good example of this form of corrosion is 316 stainless in marine

environments but if stressed the steel will fail by stress corrosion cracking (Sangeetha et al.,

2011)

2.2.8 Erosion Corrosion

Erosion Corrosion is the removal of metal by the movement of fluids against the surface. The

combination of erosion and corrosion can provide a severe rate of corrosion. In this form of

corrosion because of relative movement between the corrosive fluid and the metallic surface the

rate of the metal deterioration is increased. The corrosion manifests as grooves, waves, rounded

holes, etc. exhibiting usually a directional pattern. In passive alloys the mechanical abrasion

wears off the protective layer that inhibits corrosion. (Sangeetha et al., 2011).

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2.3 CHEMISTRY OF INHIBITION

In chemistry, an inhibitor is a substance that delays, slows or prevents a chemical reaction. It

may also be called a negative catalyst.

There are three common classes of inhibitors:

Corrosion inhibitor: A corrosion inhibitor decreases the rate of oxidation of metal.

Enzyme inhibitor: In chemistry and biology, an enzyme inhibitor binds to an enzyme, lessening

its activity. Enzyme inhibitors may be reversible or irreversible.

Reaction inhibitor: A reaction inhibitor is any substance that decreases the rate of a chemical

reaction. Corrosion inhibitors and enzyme inhibitors are both types of reaction inhibitors.

Reaction inhibitors are classified by their potency as strong, moderate, or weak.

There are many different kinds of molecules that inhibit or promote enzyme function, and

various mechanisms exist for doing so. In some cases of enzyme inhibition, for example, an

inhibitor molecule is similar enough to a substrate that it can bind to the active site and simply

lock the substrate from binding. (Onen, 2000).

2.4 CORROSION INHIBITORS

A corrosion inhibitor is a substance which when added in part per million (ppm) concentration to

a corrosive environment minimizes or prevents corrosion.

These substances can absorb both physically and chemically at the metal-solution interface and

obstruct the contact surface between the metal and the corrosive agent (Ebenso et al., 2012). A

corrosion inhibitor should have a readily adsorption capacity on the metal surface through either

physiosorption or chemisorptions process (Murulan et al., 2012). Due to their industrial

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importance, most corrosion inhibitors have been synthesized from economical raw materials or

chosen from compounds containing heteroatom in their aromatic or long carbon chain.

Over the years, significant efforts have been deployed to discover appropriate corrosion

inhibitors of natural starting point in various corrosive media (Fouda et al., 2006). In acid media,

nitrogen based materials and their derivatives, sulphur-contaning compounds, aldehyde,

thioaldehyde, acetylenic compounds and various alkaloids for example palavering, strychnine,

quinine and nicotine are also use as inhibitors. In natural media, benzoate, nitrite, chromate and

phosphate act as good inhibitors.

Inhibitors decrease or prevent the reaction of the metal with the media. Use of inhibitors is one of

the simple methods to protect different metals against corrosion under the acidic medium for

cleaning decaling and pickling. (Devarayan et al., 2012)

2.4.1 Properties of corrosion inhibitors

 Strong adsorption onto metal surface

 Increasing or decreasing the anodic and /or cathodic reaction

 Decreasing the diffusion rate for the reactants to the surface of the metal.

 Decreasing the electrical resistance of the metal

2.5 TYPES OF CORROSION INHIBITORS

2.5.1 Anodic Inhibitors

Anodic inhibitors usually act by forming a positive oxide film on the surface of the metal causing

a large anodic shift of the corrosion potential. This shift forces the metallic surface into the

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passivaion region. They are also sometimes referred to as passivator. Chromate, nitrate,

tungstate, molybdate are some examples of anodic inhibitors (Autolab, 2011).

2.5.2 Cathodic Inhibitors.

Cathodic inhibitors act by slowing the cathodic reaction itself or selectively precipitating on the

cathodic areas to limit the diffusion of reducing species to the surface, the rate of the cathodic

can be reduced by the use of cathodic poison. However, cathodic poison can also increase the

susceptibility of a metal to hydrogen induced cracking since hydrogen can also be absorbed by

metal during aqueous corrosion or cathodic charging (Autolab, 2011).

2.5.3 Mixed Inhibitors.

Mixed inhibitors work by reducing both the cathodic and the anodic reaction. They typically film

forming compounds that cause the formation of precipitation on the surface blocking by anodic

and cathodic sites indirectly. Hard water that is high in calcium and magnesium is less corrosive

than the soft water because of the tendency of the salts in the hard water to precipitate on the

surface of the metal forming protecting film (Autolab, 2011). The most common inhibitor of this

category are the silicates and the phosphates. Sodium silicate for example is used many domestic

water softeners to prevent the occurrence of rust water. In aerated hot water reliable and depends

heavily on pH. Phosphate also required oxygen for effective inhibitor. Silicate and phosphate do

not afford the degree of protection provided by the chromates and nitrate; however, they are very

useful in situation where non-toxic additives are required.

2.5.4 Volatile corrosion inhibitors.

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Volatile corrosion inhibitors (VLC), are also known as vapor phase inhibitors (VPI), are

transported in a closed environment to the site f corrosion by volatilization from a source. In

boiler basic compounds, such as morphine or hydrazine, are transported with steam to prevent

corrosion the condenser tubes by neutralizing acidic carbon dioxide or by shifting surface pH

towards less acidic and corrosive values. In closed vapor space, such as shipping containers,

volatile solids such as salts of dichlohexylamine, cyclohexhlamine and hexamethylene amine are

used (Autolab, 2011).

When these inhibitors come in contact with the metal surface, the vapor of these salts condenses

and is hydrolyzed by any moisture to liberate protective ions. It is desirable, for an efficient

VLC, to provide inhibition rapidly while lasting for long periods. Fast action wanting high

volatility while enduring protection requires low volatility.

2.6 ADSORPTION

Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a

surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process

differs from absorption, in which a fluid (the absorbate) is dissolved by or permeates a liquid or

solid (the absorbent). Adsorption is a surface phenomenon, while absorption involves the whole

volume of the material, although adsorption does often precede absorption (James et al., 2018).

The term sorption encompasses both processes, while desorption is the reverse of it.

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Figure 2.1; Brunauer, Emmett and Teller's model of multilayer adsorption is a random

distribution of molecules on the material surface.

Like surface tension, adsorption is a consequence of surface energy. In a bulk material, all the

bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of the

material are fulfilled by other atoms in the material. However, atoms on the surface of the

adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract

adsorbates. The exact nature of the bonding depends on the details of the species involved, but

the adsorption process is generally classified as physisorption (characteristic of weak van der

Waals forces) or chemisorption (characteristic of covalent bonding). It may also occur due to

electrostatic attraction. (Sing and Kenneth, 1998).

The word "adsorption" was coined in 1881 by German physicist Heinrich Kayser (1853–1940).

(Dickin, 2005).

2.6.1 Isotherms

The adsorption of gases and solutes is usually described through isotherms, that is, the amount of

adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (for liquid phase

solutes) at constant temperature. The quantity adsorbed is nearly always normalized by the mass

of the adsorbent to allow comparison of different materials. To date, 15 different isotherm

models have been developed.

2.6.1.1 Freundlich equation

The Freundlich equation or Freundlich adsorption isotherm, an adsorption isotherm, is an

empirical relationship between the quantity of a gas adsorbed into a solid surface and the gas

pressure. The same relationship is also applicable for the concentration of a solute adsorbed onto

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the surface of a solid and the concentration of the solute in the liquid phase. In 1909, Herbert

Freundlich gave an expression representing the isothermal variation of adsorption of a quantity

of gas adsorbed by unit mass of solid adsorbent with gas pressure (Adamson, 1997). This

equation is known as Freundlich adsorption isotherm or Freundlich adsorption equation. As this

relationship is entirely empirical, in the case where adsorption behavior can be properly fit by

isotherms with a theoretical basis, it is usually appropriate to use such isotherms instead (see for

example the Langmuir and BET adsorption theories). The Freundlich equation is also derived

(non-empirically) by attributing the change in the equilibrium constant of the binding process to

the heterogeneity of the surface and the variation in the heat of adsorption (Freundlich and

Herbert, 1907).

Figure 2.2; Freundlich's original data for adsorption of acetic acid (Burke et al., 1991) and a fit

according to Freundlich's exponential law.

2.6.1.1.1 Derivation

The Freundlich adsorption isotherm is mathematically expressed as

Θ=C1P1/C2

Where C1 and C2 are constants, correspondent to supporsing that aadsorption enthalpy change

linearly with pressure P

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2.6.1.1.2 Limitation of Freundlich adsorption isotherm

Experimentally it was determined that extent of gas adsorption varies directly with pressure, and

then it directly varies with pressure raised to the power 1/n until saturation pressure Ps is

reached. Beyond that point, the rate of adsorption saturates even after applying higher pressure.

Thus, the Freundlich adsorption isotherm fails at higher pressure.

2.6.1.2 Langmuir adsorption model

The simplest physically plausible isotherm is based on three assumption

 Adsorption cannot proceed beyond monolayer coverage.

 All sites are equivalent

 The ability of a molecule to adsorb at a given site is independent of the occupation of

neighboring sites (i.e. there are no interaction between the adsorbed molecules).

The dynamic equation is given as

A(g) + M(surface) AM(surface).

With the rate constant Ka for adsorption and Kd for desorption. The rate of change of the surface

coverage dθ/dt, due to adsorption is proportional to the partial pressure of A and the number of

vacant sites N(1-θ), where N is the total number of site.

dθ/dt = KaPN(1-θ)

The rate of change of θ due to desorption is proportional to the number of adsorbed species, Nθ

dθ/dt = -KdNθ

At equilibrium there is no net change (i.e. the sum of the two rate is equal to zero).

θ= αP/1+αP-----------------------------Langmuir isotherm

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Where α= Ka/Kd

A continuous monolayer of adsorbate molecules covering a homogeneous flat solid surface is the

conceptual basis for this adsorption model (Hanaor et al., 2014).

2.6.1.2.1 Basic hypotheses of the model

Inherent within this model, the following hypotheses (Masel and Richard 1996), are valid

specifically for the simplest case: the adsorption of a single adsorbate onto a series of equivalent

sites onto the surface of the solid.

The surface containing the adsorbing sites is a perfectly flat plane with no corrugations (assume

the surface is homogeneous). However, chemically heterogeneous surfaces can be considered to

be homogeneous if the adsorbate is bound to only one type of functional groups on the surface.

The adsorbing gas adsorbs into an immobile state. All sites are energetically equivalent and the

energy of adsorption is equal for all sites. Each site can hold at most one molecule of A (mono-

layer coverage only). No (or ideal) interactions between adsorbate molecules on adjacent sites.

When the interactions are ideal, the energy of side-to-side interactions is equal for all sites

regardless of the surface occupancy. (Galaineau et al., 2018).

2.6.1.2.2 Limitations of the model

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The Langmuir adsorption model deviates significantly in many cases, primarily because it fails

to account for the surface roughness of the adsorbent. Rough inhomogeneous surfaces have

multiple site-types available for adsorption, with some parameters varying from site to site, such

as the heat of adsorption. Moreover, specific surface area is a scale dependent quantity and no

single true value exists for this parameter (Hanaor et al., 2014).

Thus, the use of alternative probe molecules can often result in different obtained numerical

values for surface area, rendering comparison problematic.

The model also ignores adsorbate/adsorbate interactions. Experimentally, there is clear evidence

for adsorbate/adsorbate interactions in heat of adsorption data. There are two kinds of

adsorbate/adsorbate interactions: direct interaction and indirect interaction. Direct interactions

are between adjacent adsorbed molecules, which could make adsorbing near another adsorbate

molecule more or less favorable and greatly affects high-coverage behavior. In indirect

interactions, the adsorbate changes the surface around the adsorbed site, which in turn affects the

adsorption of other adsorbate molecules nearby.

2.6.1.3 BET theory.

Brunauer–Emmett–Teller (BET) theory aims to explain the physical adsorption of gas molecules

on a solid surface and serves as the basis for an important analysis technique for the

measurement of the specific surface area of materials. The observations are very often referred to

as physical adsorption or physisorption. In 1938, Stephen Brunauer, Paul Hugh Emmett, and

Edward Teller published the first article about the BET theory in the Journal of the American

Chemical Society (Brunauer et al., 1938). The BET theory applies to systems of multilayer

adsorption and usually utilizes probing gases (called the adsorbent) that do not chemically react

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with material surfaces as adsorbates (the material upon which the gas attaches to and the gas

phase is called the adsorptive) to quantify specific surface area. Nitrogen is the most commonly

employed gaseous adsorbate used for surface probing by BET methods. For this reason, standard

BET analysis is most often conducted at the boiling temperature of N2 (77 K).

2.6.1.3.1 Concept

BET model of multilayer adsorption, that is, a random distribution of sites covered by one, two,

three, etc., adsorbate molecules.

The concept of the theory is an extension of the Langmuir theory, which is a theory for

monolayer molecular adsorption, to multilayer adsorption with the following hypotheses:

 gas molecules physically adsorb on a solid in layers infinitely;

 gas molecules only interact with adjacent layers; and

 the Langmuir theory can be applied to each layer.

 the enthalpy of adsorption for the first layer is constant and greater than the second (and

higher).

 the enthalpy of adsorption for the second (and higher) layers is the same as the enthalpy

of liquefaction.

The resulting BET equation is

V = CZ .
Vmom (1-Z)[1-(1-C)Z]

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Where Z = P/P*

P* is the vapor pressure above the lager adsorbate,c is referred to as the BET C-constant, Vmom

is the volume correspond to monolayer coverage.

C = e(ΔdesH*-ΔvapH*)/RT

We suppose that equilibrium, a fraction θ 0 of the surface sites are unoccupied, a fraction θ 1 is

covered a monolayer, a fraction θ 2 is covered by a dilayer. The number of adsorbed molecule is

therefore

N = Nsites(θ1 + 2θ2 + 3θ3 + ……..).

Θ0 = 1-α1P .

1-(α1-α0)P

2.6.1.3.2 BET plot

Figure 2.3; The BET plot graph.

2.6.1.3.4 Applications

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Cement and concrete

The rate of curing of concrete depends on the fineness of the cement and of the components used

in its manufacture, which may include fly ash, silica fume and other materials, in addition to the

calcinated limestone which causes it to harden. Although the Blaine air permeability method is

often preferred, due to its simplicity and low cost, the nitrogen BET method is also used.

When hydrated cement hardens, the calcium silicate hydrate (or C-S-H), which is responsible for

the hardening reaction, has a large specific surface area because of its high porosity. This

porosity is related to a number of important properties of the material, including the strength and

permeability, which in turn affect the properties of the resulting concrete. Measurement of the

specific surface area using the BET method is useful for comparing different cements. This may

be performed using adsorption isotherms measured in different ways, including the adsorption of

water vapour at temperatures near ambient, and adsorption of nitrogen at 77 K (the boiling point

of liquid nitrogen). Different methods of measuring cement paste surface areas often give very

different values, but for a single method the results are still useful for comparing different

cements.

Activated carbon

Activated carbon strongly adsorbs many gases and has an adsorption cross section of 0.162 nm2

for nitrogen adsorption at liquid-nitrogen temperature (77 K). BET theory can be applied to

estimate the specific surface area of activated carbon from experimental data, demonstrating a

large specific surface area, even around 3000 m2/g. However, this surface area is largely

overestimated due to enhanced adsorption in micropores (Rouquerol, 2007) and more realistic

methods should be used for its estimation, such as the subtracting pore effect (SPE) method.

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Catalysis

In the field of solid catalysis, the surface area of catalysts is an important factor in catalytic

activity. Inorganic materials such as mesoporous silica and layered clay minerals have high

surface areas of several hundred m2/g calculated by the BET method, indicating the possibility

of application for efficient catalytic materials.

2.7 METHYL RED.

Methyl red (2-(N,N-dimethyl-4-aminophenyl) azobenzenecarboxylic acid), also called C.I. Acid

Red 2, is an indicator dye that turns red in acidic solutions. It is an azo dye, and is a dark red

crystalline powder. Methyl red is a pH indicator; it is red in pH under 4.4, yellow in pH over 6.2,

and orange in between, with a pKa of 5.1 (IB chemistry 2004). Murexide and methyl red are

investigated as promising enhancers of sonochemical destruction of chlorinated hydrocarbon

pollutants. Methyl red is classed by the IARC in group 3 - unclassified as to carcinogenic

potential in humans. (Kumar et al., 2012).

Figure 2.4; Chemical Structure of Methyl Red. (Clarke and Kirner, 1941)

2.7.1 Properties.

Methyl red displays pH dependent photochromism, with protonation causing it to adopt a

hydrazone/quinone structure. Methyl Red has a special use in histopathology for showing acidic

22
nature of tissue and presence of organisms with acidic natured cell walls. Methyl Red is

detectably fluorescent in 1:1 water:methanol (pH 7.0), with an emission maximum at 375 nm

(UVA) upon excitation with 310 nm light (UVB), ( Kumar et al., 2012).

2.8 ALUMINIUN

Aluminium (aluminum in American and Canadian English) is a chemical element with the

symbol Al and atomic number 13. Aluminium has a density lower than those of other common

metals, at approximately one third that of steel. It has a great affinity towards oxygen, and forms

a protective layer of oxide on the surface when exposed to air. Aluminium visually resembles

silver, both in its color and in its great ability to reflect light. It is soft, non-magnetic and ductile.

It has one stable isotope, 27Al; this isotope is very common, making aluminium the twelfth most

common element in the Universe. The radioactivity of 26Al is used in radiodating. (USGS, 2018).

Figure 2.5; Aluminium sample.

Chemically, aluminium is a weak metal in the boron group; as is common for the group,

aluminium forms compounds primarily in the +3 oxidation state. The aluminium cation Al 3+ is

small and highly charged; as such, it is polarizing, and bonds aluminium forms tend towards

covalency. The strong affinity towards oxygen leads to aluminium's common association with

oxygen in nature in the form of oxides; for this reason, aluminium is found on Earth primarily in

23
rocks in the crust, where it is the third most abundant element after oxygen and silicon, rather

than in the mantle, and virtually never as the free metal. (Meija et al., 2016).

2.8.1 APPLICATIONS OF ALUMINIUM.

The global production of Aluminium in 2016 was 58.8 million metric tons. It exceeded that of

any other metal except iron (1,231 million metric tons).

Aluminium is almost always alloyed, which markedly improves its mechanical properties,

especially when tempered. For example, the common aluminium foils and beverage cans are

alloys of 92% to 99% aluminium (Dunster et al., 2005). The main alloying agents are copper,

zinc, magnesium, manganese, and silicon (e.g., duralumin) with the levels of other metals in a

few percent by weight (Raycraft et al., 2018). Aluminium, both wrought and cast, has been

alloyed with: manganese, silicon, magnesium, copper and zinc amongst others. For example, the

Kynal family of alloys was developed by the British chemical manufacturer Imperial Chemical

Industries.

Figure 2.6; Aluminium can

The major uses for aluminium metal are in:

24
1. Transportation (automobiles, aircraft, trucks, railway cars, marine vessels, bicycles,

spacecraft, etc.). Aluminium is used because of its low density;

2. Packaging (cans, foil, frame, etc.). Aluminium is used because it is non-toxic (see below),

non-adsorptive, and splinter-proof;

3. Building and construction (windows, doors, siding, building wire, sheathing, roofing,

etc.). Since steel is cheaper, aluminium is used when lightness, corrosion resistance, or

engineering features are important;

4. Electricity-related uses (conductor alloys, motors, and generators, transformers,

capacitors, etc.). Aluminium is used because it is relatively cheap, highly conductive, has

adequate mechanical strength and low density, and resists corrosion;

5. A wide range of household items, from cooking utensils to furniture. Low density, good

appearance, ease of fabrication, and durability are the key factors of aluminium usage;

6. Machinery and equipment (processing equipment, pipes, tools). Aluminium is used

because of its corrosion resistance, non-pyrophoricity, and mechanical strength.

7. Portable computer cases. Currently rarely used without alloying (Sanders, 2005), but

aluminium can be recycled and clean aluminium has residual market value: for example,

the used beverage can (UBC) material was used to encase the electronic components of

MacBook Air laptop, Pixel 5 smartphone or Summit Lite smartwatch (Ross, 2013).

25
 CHAPTER THREE

3.0 MATERIAL AND METHODOLOGY

3.1 MATERIALS

3.1.1 EQUIPMENT/ APPARATUS

i. Beakers

ii. Desiccators

iii. Water bath

iv. Volumetric flask

v. Digital weighing balance

vi. Meter rule

26
vii. Thermometer (100 c)0

3.1.2 REAGENTS/MATERIALS

i. Aluminum sheet

ii. Methyl red

iii. Ethanol

iv. Distil water.

3.2 METHODS

3.2.1 Sample collection.

Aluminium used for this analysis was obtained locally from new market in Wukari, Taraba state,

Nigeria and the Methyl red was obtained from Chemistry Laboratory, Benue State University in

Markudi.

3.2.2 Preparation of the Aluminum metal.

The aluminum metal used for this study was mechanically press-cut 3×4cm coupons of 0.025cm

thickness. The coupons were examined carefully to check for rough edges, which could

influence the corrosion monitoring process. Surface treatment of the coupon was done by

degreasing in absolute ethanol and risen with distilled water. They were then store in moisture

free desiccators before corrosion study commence. (Onen et al., 2011).

3.2.3 Preparation of the Inhibitor

About 0.0269, 0.0808, 0.1347, 0.1885 and 0.2693g of Methyl red was weighed using the digital

analytical balance and dissolved in 500 cm3 beaker containing water and warmed (for complete

dissolution). This solution was then transferred into a 1000cm 3 volumetric flask and more water

27
added up to the 1000cm3 mark to obtain 0.0001, 0.0003, 0.0005, 0.0007 and 0.001mol.dm -3 of

the solution respectively.

Concentrations of 0.20-1.00 mol.dm-3 HCl will also be prepared and used as corrodent. (Onen et

al., 2011).

3.3 WEIGHT LOSS MEASUREMENTS.

In the weight loss measurements, five 250mL beaker (in two sets) were labeled A, B, C, D and E

containing 0.20, 0.40, 0.60, 0.80 and 1.00 mol.dm 3 HCl solution respectively. Another five sets

of beaker containing 0.0001, 0.0003, 0.0005, 0.0007 and 0.001mol.dm-3 concentration of the

Methyl red respectively. One set of each was placed in a water bath maintained at 303K and

313K. The aluminum coupons were suspended in the beaker with the aid of glass hooks. The

coupons were retrieved from their corrodent solution at 24hours interval progressively for 168

hours (i.e. 7days). Further measurement was carried for the inhibitor (MR) solutions. (Onen et

al., 2011).

The weight loss was calculated using the formula:

W= (Wi-Wf) .......................................................................................................................... 3.1.

Where w is the weight loss of coupons, W i is the initial weight of aluminum coupon and W f is

the final weight of aluminum coupon after immersion. (Onen et al., 2011).

The inhibition efficiency of Methyl red acting as inhibitor was calculated using the formula:

IE% = Wo-W1 × 100 ……………………………………………………………………… 3.2.

Wo

28
 Where Wo and W1 are the weight losses (g) for aluminum in the presence and absence of

additives respectively in HCl solution at the same temperature. (Onen et al., 2011).

The degree of surface coverage, Ѳ is given by the equation:

Ѳ = Wo-W1 ……. …………………………………………………….………………… 3.3.

Wo
The corrosion rate (p) of aluminum in the different corrosion medium and Methyl red was

determined for a 120 hours’ immersion period from weight loss using the formula.

CR = ∆W ……. …………………………………………………….………………… 3.4.

DAT
Where W = weight loss (g), D = destiny of the specimen (g/cm 3), A = area of the specimen (cm 2)

and T is the exposure time (hours). (Onen et al., 2011).

The activation energy values obtained in the study were computed from the transformed

Arrhenius equation:

…………………………………………………….. 3.5.

where R is the gas constant, 𝞺1 and 𝞺2 are corrosion rates at T1 and T2 respectively (Akhmetov et

al., 1989).

The rate constants, k, were obtained from the linear plots of logarithm W versus time, t (days)

while the half –life, t1/2, values were calculated using the following equation:

t1/2 = 0.693/k ………………………………………………………………………… 3.6

29
The values of heat of adsorption, Qads, for the study were determined from the following

…………………………………….3.7

where θ1 and θ2 are degree of surface coverage at 303K and 313K respectively (Yadav, 1999 and

Onen, 2007).

CHAPTER FOUR

RESULTS

Tables 4.1, 4.2, 4.3, 4.4 and 4.5 show calculated values for weight loss and corrosion rate,

calculated values for Surface coverage and Inhibitor efficiencies, Kinetic data for aluminum

corrosion in 1.0M HCl solution with inhibitor (Methyl Red), Peak List of XRD analysis on

Aluminum and Qualitative Analysis Results of XRD analysis on aluminium. Figures 4.1 – 4.9.

Show Graph of Weight loss against Inhibitor conc. at 303K and 313K, plot of corrosion rate

against Inhibitor conc. at 303K and 313K, plot of inhibitor efficiency against inhibitor conc. at

30
303K and 313K, Plot of log of Weight loss versus time, t (day) at 303K and 313K, the SEM and

XRD analysis.

Table 4.1: Calculated values for Weight loss, Corrosion rate, Surface coverage and Inhibitor

efficiencies at 303K and 313K.

Inhibitor Weigh Loss Corrosio Rate Inhibito Efficienc Surface Coverage

conc. t (∆w) n (CR) ×10-5 r y (Ѳ)

(IE%)
(mol/dm3)

303K 313K 303K 313K 303K 313K 303K 313K

31
Blank

A.C.F

0.0001 0.3216 0.3530 2.0529 2.4178 30.2145 21.5178 0.3022 0.2152

0.0003 0.3402 0.3488 1.9244 2.3901 39.5507 41.4113 0.3955 0.4141

0.0005 0.2939 0.3659 1.7663 2.1989 53.4379 50.6873 0.5344 0.5069

0.0007 0.2805 0.3209 1.6257 2.0548 62.5294 59.819 0.6253 0.598

0.0010 0.2517 0.2997 1.5127 1.9814 71.0756 66.6869 0.7108 0.6669

32
 f(x) = NaN x + NaN
R² = 0 0.4

f(x) = − 62.9016393442623 x + 0.370368852459016

0.35 R² = 0.670712623754668

0.3

0.25
Weight loss (∆w)

0.2 303K
(g)

Linear (303K)
313K
Linear (313K)
0.15

0.1

0.05

0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012

Inhibitor Concentration (mgdm-3)

Figure 4.1: Graph of Weight loss against Inhibitor conc. at 303K and 313K.

33
 f(x) = NaN x + NaN
R² = 0

0.00003

0.000025
f(x) = − 0.00541622929100364 x + 2.49025365721269E-05
R² = 0.941510218214753

0.00002
Corrosion Rate
(CR)

0.000015 303K
Linear (303K)
313K
Linear (313K)

0.00001

0.000005

0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012

Ihibitor Concentration (mol.dm-3)

Figure 4.2: Plot of corrosion rate against Inhibitor conc. at 303K and 313K.

34
 f(x) = NaN x + NaN
R² = 0 80

70 f(x) = 48392.262295082 x + 22.8604836065574

R² = 0.921002850792844

60

50
Inhibitor Efficiency
(IE%)

40 303K
Linear (303K)
313K
Linear (313K)
30

20

10

0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012

Inhibitor Concentration (mol.dm-3)

Figure 4.3: Plot of inhibitor efficiency against inhibitor conc. at 303K and 313K.

35
 f(x) = NaN x + NaN
R² = 0 0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5

-0.1

-0.2

-0.3
Log of Weight

303K
Loss

Linear (303K)
Linear (303K)
313K
-0.4 Linear (313K)

-0.5 f(x) = 0.02633 x − 0.61617

R² = 0.99229672391415

-0.6

-0.7

Time, t (Day)

Figure 4.4: Plot of log of Weight loss versus time, t (day) at 303K and 313K.

36
Table 4.3: Kinetic data for aluminum corrosion in 1.0M HCl Solution with inhibitor (Methyl

Red) at 303K and 313K.

Inhibition Rate constant Half-life t1/2 Activation Heat of

conc. energy absorption

k(sec-1) (sec)
3
Ea(kJmol-1)
(mol/dm ) Qads (kJmol-1)

303K 313K 303K 313K

0.0001 0.0184 0.0142 37.6630 48.8028 16.3363 -45.5852

0.0003 0.017 0.0149 40.7647 46.5101 21.6209 -7.69709

0.0005 0.0138 0.0134 50.2174 51.7164 21.8576 -11.0057

0.0007 0.0133 0.0192 52.1053 36.0938 23.3672 -11.3963

0.0010 0.0135 0.0177 51.3333 39.1525 26.9285 -20.472

37
4.2 SEM ANALYSIS

Scanning electron microscopy provide morphology and structural image of nanomaterials.

Surface analysis was carried out using SEM on aluminum metal, in presence and absence of the

inhibitor.

Fig. 4.5(a) Pictorial view of aluminum metal from SEM Analysis in absence of inhibitor.

38
Fig. 4.5(b) Pictorial view of aluminum metal from SEM Analysis in presence of inhibitor

39
4.3 XRD ANALYSIS.

X-ray diffraction analysis determines the crystallographic structure, elemental as well as the

oxide composition of the material.

The structural analysis was carried out on aluminum using XRD.

4.3.1 Main Graphics, Analyze View:

Counts
FAc_20220330_142755_G03_S03_M03

100

50

0
10 20 30 40 50 60 70

Position [°2Theta] (Copper (Cu))

Figure 4.6. Main graphics analyze view of aluminum metal from XRD Analysis.

40
Table 4.3. Peak List of XRD analysis on Aluminum

Pos. [°2Th.] Height [cts] FWHM Left d-spacing Rel. Int. [%]
[°2Th.] [Å]

8.2029 9.73 0.9446 10.77886 9.85

40.8508 4.45 0.9446 2.20907 4.51

45.5579 58.08 0.3149 1.99117 58.80

58.8818 17.21 0.3149 1.56846 17.43

65.9400 98.77 0.3149 1.41664 100.00

4.3.2 Qualitative Analysis report.

Table 4.4. Qualitative Analysis Results of XRD analysis on Aluminium.

PHASE NAME FORMULA

Magnesium Aluminum ( Al10.35 Mg0.65 O16 )

Oxide

Aluminum, syn Al

Quartz SiO2

Garnet 3 ( Ca , Fe , Mg, O, Al , Fe)

Alunite KAl3( SO4)2 (OH)6

41
Figure 4.7. Phase Data View of aluminum metal from XRD Analysis.

42
4.3.3 Quantitative Analysis Report.

Table 4.5. Table of Results

Dataset Magnesium Aluminum, Quartz Garnet Alunite

syn
Aluminum

Oxide

Weight 0.6(2) 80(20) 3(24) 1.2(15) 15(4)

Fraction,
wt%

43
Figure 4.8. Multiple Profile of aluminum metal from XRD Analysis

44
 Magnesium Aluminum Oxide
0.6(2)
Aluminum, syn 80(20)
Quartz 3(24)
Garnet 1.2(15)
Alunite 15(4)

Figure 4.9. Plot of results of aluminum metal from XRD Analysis.

45
 CHAPTER FIVE

5.0 DISCUSSION, CONCLUSION AND RECOMMENDTION.

5.1 Effect of Inhibitor (MR) Concentration on Aluminum Corrosion.

Fig. 4.1. Show variation of weight loss with inhibitors concentration for aluminum in 1.0M HCl

with various concentration of Methyl Red (MR) at 303K and 313K, respectively. This graph

reveals that weight loss was lowest at 0.0010mol/dm3 (highest concentration of inhibitor

studied). This indicates that (MR) inhibits corrosion of aluminum to some extent, with inhibition

increase with increasing inhibitor at lower temperature. With the addition of inhibitor (MR) the

inhibition efficiency (% IE) and surface coverage were found to increase while corrosion rates

decrease with increasing concentration in the order:0.0010mol/dm 3 ≤ 0.0010 mol/dm3 at 303K

(71.08% efficiency) and at 313K (66.69% efficiency).

5.2 Effect of Inhibition Efficiency (IE%) on Inhibitor Concentration.

Fig.4.5: Illustrates the evaluation of inhibition efficiency of (MR) against inhibitor concentration

of aluminum corrosion in 1.0M HCl solution after 24 hours’ immersion respectively for different

temperatures. The increase in the inhibition efficiency with concentration may be due to

adsorption of (MR) onto the aluminum surface through the non-bonding electrons pairs on N and

O atoms as well as the ӆ-electrons of the aromatic ring.

5.3 Effect of Corrodent Concentration and Temperature on Aluminum Corrosion.

Corrosion rate was observed to be higher at 313K and 303K. A plot of log of weight loss of

aluminum specimen against time (days) in 1.0M HCl solution for 120 hours are shown in Figure

46
4.4 indicate that the weight loss decrease as the number of days increase and increase as the

temperature increase.

Table 4.1 and 4.2 show variation of weight loss and corrosion rate with days for aluminum in

1.0M HCl at 303K and 313K with (MR). It was observed that weight loss and corrosion rate of

aluminum increase with concentration of HCl solution. This could be attributed to the fact that

rate of chemical reaction increase with increase in acid concentration and temperature.

5. 4 SEM ANALYSIS

Surface analysis was carried out using SEM on aluminum metal, in presence and absence of the

inhibitor. A significant surface damage was observed on aluminum metal which was immersed

in 1.0M HCl Figure 4.5(a) indicates that the surface was highly corroded. The surface of the

corroded area was protected by the addition of the inhibitor as evident from Figure 4.5(b) surface

morphology and the presence of the inhibitor at the optimum concentration exhibited a smooth

surface indicating restricted corrosion unlike Figure 4.5(a) the SEM image clearly indicate that

the metal surface was protected from corrosion in the presence of Methyl Red which is acting as

an inhibitor. The result is in good agreement with the weight loss measurements.

5.5 XRD ANALYSIS.

The structural analysis was carried out on aluminum using XRD. It was observed that the

aluminum sheet used was crystalline in nature with the elemental composition of magnesium

aluminum oxide, aluminum syn, Quart, Gamet and Alunite having the weight fraction (wt%) of

0.6(2), 80(20), 3(24), 1.2(15) and 15(4).

47
The peaks of each of the above compositions were also observe from the plot of %intensity

against surface coverage (Ѳ), with Aluminum syn having the highest peak. This therefore

confirmed that Aluminum can be used for corrosion studies.

5.6 Inhibition Mechanism

Table 4.2 shows calculated values of activation energy Ea. The average value of the activation

energy, Ea for inhibitor is 22.02 kJmol -1 is lower than 40.0 kJmol-1 indicating that the compound

is physically adsorbed on the aluminum.

Physically adsorption requires that the average Ea be ≤ 40.0 kjmol -1 and present inhibition

efficiency increases at lower temperatures. This agrees with an earlier report by (Onen, 2011).

5.7 Thermodynamic considerations

The values of heat of adsorption Qads are negative for aluminum corrosion as shown in table 4.2

this implies that the inhibition process is spontaneous. This is a strong characteristic of strong

interaction with the metal/alloy surfaces. It is also an indication that adsorption and inhibition

efficiency decrease in temperature which agree with experimental data. This interaction causes a

change on the surfaces available for the process or in the electrochemical process mechanism.

CONCLUSION

The use of Methyl Red as corrosion inhibitor decrease the acid corrosion of aluminum to

appreciable extent being physically adsorbed on the metal surface. The efficiency (% I E) of

inhibitor increase with increase in the inhibitor concentration and decrease with increase in

temperature. The values of Qads obtained at 303K and 313K are negative, indicating that the

48
inhibitor is strongly adsorbed on aluminum surface and the adsorption process is spontaneous.

The data obtained from this study fit well into the Langmuir adsorption isotherm.

RECOMMENDATION:

 I therefore recommend the use of Methyl Red (MR) as a corrosion inhibitor of other

metals and alloys in various environments.

 Methyl Red (MR) should be use in industries as replacement for toxic chemicals.

 Methyl Red (MR) should be use as alternative for highly expensive and non-

environmentally friendly corrosion inhibitor of aluminum.

49
 REFERENCES

Abd El Aal, E.E; Abd El, W. S., (2009); “Galvanostatic study of the breakdown of

znppassivity by sulphate anions as Corrosion inhibitors for mild steel in hydrochloric acid

solution”, Corrosion Science, 51, 1780-1788.

Adamson, A.W (1997). Physical chemistry of surfaces. p. 393.

Akhmetov, B. Novichenko, Y and Chapurin, V., (1989). Physical and Colloid Chemistry, 1 st

Edition, mir publishers, Moscow. 172.

Auatolab B.V., (2011) part 5-corrosion inhibitors. Aulab application Note COR06.

Brunauer, Stephen; Emmett, P. H.; Teller, Edward (1938). "Adsorption of Gases in

Multimolecular Layers". Journal of the American Chemical Society. 60 (2): 309–319.

Burke GM, Wurter DE, Buraphacheep V, Berg MJ, Verg-pedersen P, Schottelius DD, (1991).

“Modern selection for the adsorption of Phenobarbital by activated charcoal”.

Pharmaceutical Research; 8(2):228-231.

Devarayan k., Mayakrishnan, G., and Nagarajan, S. (2012) Green inhibitors for Corrosion of

metals: a review. Chemical science review letters, 1,1-8

Dickin, A.P. (2005). "In situ Cosmogenic Isotopes". Radiogenic Isotope Geology. Cambridge

University Press.

Dunster A.M., Mouhnier F., Abbott B., Conroy A., Adams K., Widyatmoko D. (2005). "Added

value of using new industrial waste streams as secondary aggregates in both concrete and

asphalt" (PDF). Waste & Resources Action Programme.

50
Ebenso EE, Kabanda M.M., Arslan T., Saracoglu M, Kandermirli F, Murulane L.C, Sing A.K.,

Shukla S.K., Hammoti B, Khaled K.F., Quraishi M.A., Obot I.B., Eddy N.O., (2012)

Quantum chemical investigation on quinoline derivatives as effective corrosion inhibitors

for mild steel in acidic medium. International Journal of Electrochememical Sciences.

7:5643-5676.

Ebenso, E.E; Okafor, P.C; Ibok, U.J; Ekpe, U.J and Onuchukwu, A.I (2004). “The Joint Effects

of Halide ions and Methylene blue on the Corrosion Inhibition of Aluminium and Mild

Steel in acid Corrodent”, Journal of Chemical Society of Nigeria, 29 (1): 15-26.

Eddy, N.O., stoyanov, S.R and Ebenso, E. (2010). Fluoroquinolones as corrosion inhibitors for

mild steel in acidic medium; experimental and theoretical Studies, International Journal

of Electrochememical Sciences. 5, 1127-1150.

Fouda A.S., AL-Sarawy A.A., El- Katori E.E., (2006) Pyrazolone derivatives as corrosion

inhibitors for C-steel HCl solution. Desalination

Freundish, Herbet. (1907). “Uber die Adsorption in Losungen” Zentschrift fur physikahsch, chie-

stochonetun and verwandschaftshehre 57(4), 385-470.201, 1-13.

Galarneau, Anne; Mehlhorn, Dirk; Guenneau, Flavien; Coasne, Benoit; Villemot, Francois;

Minoux, Delphine; Aquino, Cindy; Dath, Jean-Pierre (2018-10-31). "Specific Surface

Area Determination for Microporous/Mesoporous Materials: The Case of Mesoporous

FAU-Y Zeolites" (PDF). Langmuir. American Chemical Society (ACS). 34 (47): 14134–

14142.

Goel R, Siddiqi WA, Ahmed B, Hussan J, (2010) Corrosion inhibition of mild steel in HCl by

isolated compounds of Riccinus communis (L). E-journal of Chemistry. 7 (supp 1):

S319-S329.

51
H. T. Clarke & W. R. Kirner (1941). "Methyl Red". Organic Syntheses.; Collective Volume, 1,
p. 374.

Hanaor, D. A. H.; Ghadiri, M.; Chrzanowski, W.; Gan, Y. (2014). "Scalable Surface Area

Characterization by Electrokinetic Analysis of Complex Anion Adsorption" (PDF).

Langmuir. 30 (50): 15143–15152.

IB chemistry Higher Level: "Archived copy". Archived from the original on 2004-09-22.

Ita, B.I and Edem, C.A (2000). “Inhibition of Steel Corrosion in Hydrochloric acid solutions by

Green S Erythrosine dyes”. Global Journal of Pure Applied Sciences, 60 (20): 239-252.

Jacek Jagiello and James P. Olivier. “2d-NLDFT adsorption model for carbon shit-shaped pores

with surface energetical heterogeneity and geometrical corrugation” Carbon 55, 70-80.

Kumar Das, Diganta; Goswami, Priyanka; Barman, Champa; Das, Biva (2012-12-30). "Methyl
Red: A Fluorescent Sensor for Hg2+ over Na+, K+, Ca2+, Mg2+, Zn2+, and Cd2+".
Environmental Engineering Research. Korean Society of Environmental Engineering:
75–78.

Lyle, J.P.; Granger, D.A.; Sanders, R.E. (2005). "Aluminum Alloys". Ullmann's Encyclopedia

of Industrial Chemistry. Wiley-VCH.

Maklouf, M.T; Gomma, G.K; Wahdam, M.H and Khalil, Z.H (1995). “Effect of Cyanine Dye

solvent interaction on Electrochemical Corrosion behaviour of Low Carbon Steel in Acid

medium”, Materials Chemistry and Physics, 40: 119-128.

Masel, Richard (1996). Principles of Adsorption and Reaction on Solid Surfaces. Wiley

Interscience. p. 240.

Meija, Juris, Tyler B. Coplen, Micheal Berglind, Willian Brand, Paul De Bievre, Manfred

Gronnig, Norman E. Holden, Johannan Irregeler, Robert D. Loss, Thomas Walczjk.

52
 (2016). "Atomic weights of the elements 2013 (IUPAC Technical Report)". Pure and

Applied Chemistry. 88 (3): 265–91.

Mudhoo A, Khamis E (2011) adsorption studies, modeling and use of green inhibitors in

corrosion inhibition: an overview of recent research, green corrosion inhibitors: status

in developing countries. Sharma S.K., (ed) Green Corrosion chemistry and

engineering. Wiley-VCH publications, Weinheim, P 319.

Murulane L.C., Kabanda M.M., Ebenso Eno E., (2012) density functional theory and

Quantitative structure-activity relationsip studies of some quinoxaline derivatives as

potential corrosion inhibitors for copper in acidic medium. International Journal of

Electrochememical Sciences.7:8713-8733.

Nnanna L.A., Onwuagba B.N., Mejeha I.M., Okeoma K.B., (2010) inhibition Effects of some

plant extracts on the acid corrosion of aluminum alloy, African Journal of pure and

applied chemistry, 4 (1), p, 11-16. Sci 7:5035-5056

Onen A.I., Maltera O.N., and Ebenso E.E., (2011) Corrosion inhibition potential and adsorption

behavior of bromophenol blue and thymol blue dyes on mild steel in acidic medium.

International journal of electrochemical science. 8:2884-2897.

Onen, A.I (2000). “Determination of the Amount of Corrosion of Iron using different

Concentrations of two Alkali Halides with time”, Yedzaram Journal of Science and

Technology, 1 (1): 74-89.

Onen, A.I (2006). “Influence of Halide ions on the Corrosion Inhibition of Aluminium in H 2SO4

using Alizarin Red”, Nigerian Journal of Polymer Science and Technology, 5 (1): 357-

371.

53
Onen, A.I (2007). “The Effect of Molecular Structure of P-Aminobenzenesulphanilamide and its

Derivatives on Corrosion Inhibition of Mild Steel in HCl-1”, Journal of Chemical

Society of Nigeria, 32 (1): 227-236.

Ross, R.B. (2013). Metallic Materials Specification Handbook. Springer Science & Business

Media.

Rouquerol, J.; Llewellyn, P.; Rouquerol, F. (2007), "Is the bet equation applicable to

microporous adsorbents?", Studies in Surface Science and Catalysis, Elsevier, 160, pp.

49–56.

Raycraft E. R., Brown T.J., Idome N.E., Shaw R.A., Hobbs S.F., Everret P. (2018). World

mineral Production, (2012-2016). British Geography Survey.

Sangeetha, M., Rajendran, S., smuthumegela, T. & Krishnaeni, (2011). A.Green corrosion

Inhibitor- an overview.

www.sitwam.org.rs/zm/2011/N01/zm52.13.09/06.

Sastri, S. (2014). “Corrosion processes and the use of corrosion inhibitors in managing corrosion

in underground pipeline,” in underground pipeline corrosion: cathodic protection and

high efficiency coating, pp. 127-165,

Sing, Kenneth S.W. (1998). "Adsorption methods for the characterization of porous materials".

Advances in Colloid and Interface Science. 76–77: 3–11.

Trbanelli, G.” Inhibitors an old remedy for a new challenge,”Corrosion. Sciences., vol 47(6), pp

410- 419.,2011.

54
United States Geological Survey (2018). "Bauxite and alumina" (PDF). Mineral Commodities

Summaries.

Yadav, P.N.S (1999). “Molecular Structure of Heterocyclic compounds and their Inhibitive

Action for Corrosion of Grade 1100 Aluminium in dilute HCl”, British Corrosion

Journal, 34 (1): 51-56.

55