INTRODUCTION

CORROSION BASIC CONCEPTS Corrosion is a plight that faces everyone who works with metals. This introductory part aims to provide knowledge of the basic aspects of corrosion. Corrosion is the destructive attack of a material by reaction with its environment. Corrosion is a universal phenomenon and many times in spite of all precautions it has led to the failure of machines and structures.1A point of view proposed by Professor Staehle is that all engineering materials are reactive chemically and the strength of the materials depends totally upon the extent to which environments influence the reactivity and subsequent degradation of these materials. DEFINITION OF CORROSION According to Ulick.R Evans, the British Scientist who is considered the Father of corrosion science defines corrosion is largely an electrochemical phenomenon which may be defined as destruction by electrochemical or chemical agencies. Corrosion is also defined as loss of useful properties of a metallic material as a result of unwanted chemical or electrochemical reaction with environment 2. CONSEQUENCES OF CORROSION Corrosion has many serious economic, health, safety, technological and cultural consequences to our society. Corrosion costs society in three main ways:

 It is extremely expensive financially. It is extremely wasteful of natural resources It causes considerable inconvenience to human beings. Losses due to corrosion may be direct or indirect. Direct losses are Inability to use the materials Overdesign of the materials. The cost of replacement of the corroded equipments The cost of anticorrosive paintings and other protection methods. Indirect losses are Contamination of the product Products stored in corroded container Damage of the equipment. Safety i.e., sudden failure of equipment results in fire, explosion, release toxic substances Appearance: corroded materials are unpleasant to over eye. All these effects are proved in many industries like nuclear industry, chemical industry etc. Better corrosion management can be achieved using preventive strategies in non-technical and technical areas. These preventive strategies include Increase awareness of large corrosion costs and potential savings. Change the misconception that nothing can be done about corrosion

 Change policies, regulations, and standard and management practices to increase corrosion savings through sound corrosion management. Improve education and training of staff in recognition of corrosion control. Advanced design practices for better corrosion management. Advanced life prediction and performance assessment methods Advanced implementation corrosion technology through research. IMPORTANCE OF CORROSION STUDIES Increasing use of metals in the field of technology. Use of expensive metals which need more precautions. Use of high strength alloys which is more susceptible to corrosion . Increase in pollution of air and water. To increase awareness in conservation of metals. It is necessary to prevent corrosion and to know the principles and prevention methods of corrosion.3 PRINCIPLES OF CORROSION Corrosion resistance depends on many factors. Its complete and

comprehensive study requires knowledge of several fields of scientific knowledge.

Thermodynamic Principles

Metallurgical Principles

Corrosion Principles

Physical & Chemical Principles

Electrochemical Principles

i) Thermodynamic principles4 explains direction of a chemical reaction. In the case of corrosion, thermodynamic calculations can determine whether or not corrosion is theoretically possible. Physical chemistry and its various disciplines are most useful for studying the mechanisms of corrosion reactions, the surface conditions of metals, and other basic properties. ii) Metallurgical, physical and chemical principles explains corrosion behavior of a metal. Physical and chemical factors are most useful for studying the mechanisms of corrosion reactions, the surface conditions of metals, and other basic properties. Metallurgical factors frequency have a pronounced influence on corrosion resistance. In many cases the metallurgical structure of alloys can be controlled to reduce corrosion attack. iii) Electrochemical principles explains the rate of different corrosion reactions. The corrosion reaction can be represented by partial reaction such

as metal oxidation and reduction of some reducible species of the environment, both occurring simultaneously at equal rates at the mixed potential of the reaction. ELECTROCHEMICAL PRINCIPLES Corrosion of metals proceeds either by chemical (dry) or an electrochemical (wet) or by both simultaneously. Electrochemical corrosion occurs in electrically conducting media. Electrochemical corrsion5 involves two half cell reactions: anodic reaction (oxidation) and cathodic reaction (reduction). Anodic reaction : 2Fe 2Fe2+ + 4e O2 + 2H2O + 4e 4OH

Cathodic reaction :

Both anodic and cathodic reactions occur simultaneously and at the same rate on the metal surface. Corrosion occurs through the formation of electrochemical cells in which the anode corrodes and cathode is protected. There are different anodic and cathodic reactions for different alloys exposed to various environments. Current flow (tonic conduction)

The components in an electrochemical corrosion cell: An anode A cathode A conducting environment for ionic movement (electrolyte) An electrical connection between the anode and cathode (current flow). CLASSIFICATION OF CORROSION Corrosion has been classified in many different ways. Corrosion occurs due to the action of surrounding environment or medium over metals. Corrosion occurs in two ways. 1. Dry corrosion or chemical corrosion 2. Wet corrosion or electrochemical corrosion or immersed corrosion 1. DRY OR CHEMICAL CORROSION This type of corrosion involves direct chemical reaction with its environment. There is no transport of charges and metal is film free. It also includes corrosion in gaseous environment such as oxygen, halogen etc., when the product is volatile, and also corrosion in liquid metals, fused halides and liquids. There are 3 main types of chemical corrosion: 1. Oxidation corrosion 2. Corrosion by hydrogen 3. Liquid metal corrosion -

2. WET OR ELECTROCHEMICAL CORROSION This type of corrosion occurs i) ii) Where a conducting liquid is in contact with metal (or) When two dissimilar metals or alloys are either immersed or dipped partially in a solution. Electrochemical corrosion depends on the nature of corrosion product. An anodic area; M Mn+ + neCathodic reaction consumes e- with Evolution of H2 Anode : Fe Fe2+ + 2e2H+ + 2e- H2 (oxidation) (reduction)

Cathode :

Over all reaction : Fe + 2H+ Fe2+ + H2 Absorption of oxygen: Anode : Fe Fe2+ + 2eO2 + H2O + 2e- 2OH (oxidation) (reduction)

Cathode :

CORROSION RATE EXPRESSION The rate of metal removal due to corrosion is known as corrosion rate. Corrosion rates have been expressed in a variety of ways such as percentage weight loss, milligrams per square centimeter per day, and grams per square inch per hour. These do not express corrosion resistance in terms of penetration. The expression mil per year is the most desirable way of expressing corrosion rates in terms of penetration. This expression is calculated

from the weight loss of the metal specimen during the corrosion test by the formula given below. 87.6 x W Corrosion rate mm/y = aDt FORMS OF CORROSION The most common existing forms of corrosion are as follows : 1. General Attack (Uniform) corrosion This is the most common form of corrosion. It occurs when a chemical or electrochemical attack occurs over a large area in a uniform manner. This is often referred to as a general wall loss or thinning. 2. Galvanic corrosion This occurs through the electrochemical cell. It occurs when two metals in electrical contact are immersed in an electrolyte. When current flows, potential difference exists between the metals. Emf and galvanic series are used to predict the galvanic corrosion tendency of various metals. Another important factor in galvanic corrosion is the area effect or the ratio of cathodic to anodic area. The larger the cathode compared with the anode, the more oxygen reduction, or other cathodic reaction, can occur and, hence, the greater galvanic current. From the standpoint of practical corrosion resistance, the least favourable ratio is a very large cathode connected to a very small anode.

3. Cervice corrosion Cervice corrosion is a highly localized attack occurring in a cervice or an otherwise shielded area when a material is exposed to a stagnant corrosive media. Common location for cervice corrosion are : Gasket surfaces Holes Lap joints Pitting Bolt heads It occurs mainly at narrow spaces which is very small groves. 4. Pitting corrosion It is a localized attack. It results in sudden failure of equipments due to the formation of holes. It is difficult to detect as it is covered with corrosion product. It is elongated along the direction of gravity. Weight loss depends upon depth, distribution and shape of pit. 5. Intergranular corrosion Intergranular corrosion occurs when the grain boundaries are attacked in preference to the material matrix. The only difference between this and uniform corrosion is that the grains remain undamaged. This corrosion is rapid and penetrating. Metallographic examination is usually the only way to identity this corrosion mechanism.

6. Dealloying (selective leaching) Selective leaching is a process where one constituent of the alloy is removed, leaving an altered residual structure. It is a rare process. It is identified by a colour change or a drastic change in mechanical strength. 7. Erosion Erosion occurs when the velocity of the fluid is sufficient to remove the protective films from the metal surface. It is characterized by patterns that are shaped by the flow of a fluid. Impingement is caused by turbulence or impinging flow. It is commonly found in pumps, valves and at elbows. Cavitation is a mechanical damage process caused by collapsing bubbles in a flowing liquid. It results in the formation of deep pits. 8. Stress corrosion cracking Stress corrosion occurs when a material is exposed to a corrosive media while a force (stress) or pressure is applied. The material usually remains undamaged with the exception of cracks that grow through the material matrix. These cracks are usually very fine, visible only under microscopic conditions. 9. Hydrogen embrittlement Loss of ductility of a material in presence of hydrogen is known as hydrogen damage. It results in the brittle failure of ductile materials when exposed to an environment where hydrogen can enter the metal. 10. Fretting corrosion Fretting occurs when motion between surfaces either removes protective films or mechanically removes material from surfaces in relative motion.

11. High temperature corrosion High temperature corrosion is a form of material degradation that occurs at elevated temperatures, often beginning with temperatures in the range of 3040% of the melting point of the alloys. Chemical reactions are responsible for the corrosion. CORROSION MONITORING TECHNIQUES Corrosion monitoring is defined as the systematic measurement of the corrosion rate of plant materials with the objective of diagnosis and controlling corrosion. Corrosion monitoring is the practice of measuring the corrosively of process stream conditions by the use of probes which are inserted into the process and which are continuously exposed to the process stream condition. Corrosion monitoring probes can be mechanical, electrical or electrochemical devices. These probes are essential elements of all corrosion monitoring systems. Recent development of corrosion monitoring meters has helped to Obtain information of the state of operational equipment to avoid plant shutdown. Obtain information of the inter-relation between corrosion process and operating variables. Control operating conditions so that deterioration may be maintained at an acceptable rate. The most important corrosion monitoring methods are : a) Coupon method of weight loss method

b) Electrical resistance method c) Potential measurements d) Polarization resistance method e) Impedance method f) Hydrogen method 1. Non electrochemical methods a) Weight loss method This is the simplest and the most widely used method for evaluating corrosion rates and corrosion damage of the component materials. The coupons can be exposed in process medium or in a simulated medium. Coupons can be made in any size or shape depending upon the requirements. Pre weighed and previously examined test coupons are exposed in the medium for a known period of time after which they are removed, weighed and examined. The coupons inserted through a value or in a by-pass line of the process medium can be retrieved without shutting the process unit down. From the weight loss, the corrosion rates are calculated. The test coupons made from component material give the idea of corrosion processes taking place on the component. The corrosion rate of the test coupons is calculated as follows: a) The percentage of inhibition efficiency was calculated by. W1 W2 % inhibition efficiency = x 100 W1 Where, W1 and W2 are the weight loss of mild steel in uninhibited and inhibited acid solutions.

87.6 x W Corrosion rate (mm/y) = aDt

W1 W2 Surface coverage, = W1 Where, W1 and W2 are the weight loss of mild steel in uninhibited and inhibited acid solutions. b) Electrical resistance The change in electrical resistance is a measure of corrosion. Since the reduction in corrosion current is due to corrosion increase of resistance, the resistance of exposed element is measured by Kelvin Bridge. The advantage of this method is its flexibility. It can be used in aqueous, non-aqueous or vapours and for online corrosion monitoring in chemical industries. c) Gasometric method This method is reliable and accurate. The volume of gas is measured directly at constant temperature and atmospheric pressure and the metal loss is calculated. Several authors have used this technique and designed gasometric apparatus operating under controlled conditions of temperature and pressure. The main disadvantage is that this method cannot be applied to strong oxidizing medium when inhibitors used undergo reduction with H2 gas evolved and in situations when the stoichiometry of the corrosion reaction is not defined.

2. Electrochemical methods Corrosion reactions are broadly classified as activation controlled and diffusion controlled reactions. The rates of corrosion process of metals under immersed conditions are obtained from the application of mixed potential theory of Wagner and Traud for activation controlled reactions. a) Linear polarization method Stern and Geary7 have shown that there is a linear relationship between current and potential. In this method, corrosion rate is determined by measuring electric current flow between the test and an auxiliary electrode while polarizing the test electrode, with respect to a reference electrode. Electric current is applied between the test and auxiliary electrode. This current, depending upon the direction of flow, either slightly cathodically protects or anodically accelerates the corrosion of the test electrodes. For a small change in potential (+10mv), the relation between current flow and the potential is linear and follows the Stern Geary equation, which is used to estimate the corrosion current. b) Impedance measurements AC impedance measurement of the corroding system provides kinetic and mechanistic information. This technique has been widely used for the measurement of corrosion rate. The equivalent circuit of a corroding metal is represented as,

Where, Cdl = Double Layer Capacitance Rs = Solution Resistance Rct = charge Transfer Resistance Among the various A.C. techniques, the method based on faradic impedance is widely used due to the main advantage that the double layer capacitance (Cd1) and charge transfer resistance (Rct ) can be determined. Advantages AC impedance involves measurement of both capacitance and charge transfer resistance and hence this technique is more valuable. The impedance of the corroding system at various frequencies can be measured using lock in amplifier for high frequencies and fast Fourier transform technique for low frequencies. This technique uses amplitudes in the range of 5-10 mV peak to peak. Hence the perturbation is minimum and reduces the errors caused by the measurement. c) Galvanostatic method In the galvanostatic method, using a variable resistance changes current flowing between the specimen and a platinum auxiliary electrode and the potential of the specimen is measured as a function of time. d) Potentiostatic method In the potentiostatic method, the potential of the specimen is changed in steps (manually or automatically) and the current flowing in the external circuit is recorded as a function of time. For active passive metals,

potentiostatic and anodic polarization curves yield more useful information. Polarization studies are carried out for mild steel specimen of the same composition, both in the presence and absence of inhibitors. INHIBITORS A corrosion inhibitor may be defined as a substance which when added in small quantities to the aqueous corrosive environment effectively decreases the corrosion of the metal. Inhibitors are organic substances that dissolve in the corroding medium but are capable of forming a protective layer of some kind at either the anodic or cathodic areas. The parameters to be considered are : Solubility Compatibility with the corroding system Stability at different temperature and pH of the medium undesired effects of effluents containing the inhibitor pollution cost Inhibitors function by 1. Adsorption as a film in to the surface of the corroding medium 2. Inducing the formation of thick product 3. Changing the characteristics of the environment CLASSIFICATION OF INHIBITORS Inhibitors are classified on considering electrode process and environment

1. Based on electrode process: a) Anodic inhibitors These stifle the corrosion reaction, occurring at the anodic by forming a sparingly soluble compound with a newly produced metal ion. This compound is adsorbed on the metal surface forming a protective film or barrier, thereby reducing the corrosion rate. Although this type of corrosion is effective, it may be dangerous as severe local attack can happen if certain areas are left unprotected by depletion of inhibitor. Eg. chromates, phosphates or other ions transition elements with oxygen content. b) Cathodic inhibitors These are of two types: In acidic solutions, main cathodic reaction involves evolution of hydrogen. 2H+ + 2e H2

Consequently corrosion may be reduced either by slowing down the diffusion of hydrated H+ ions to the cathode or increasing the over potential of hydrogen evolution. The diffusion of H+ ions is decreased by organic inhibitors like amines, mercaptans, hetrocyclic nitrogen compounds which are capable of being adsorbed at the metal surface. In neutral solutions, main cathodic reaction involves formation of hydroxy1 ions due to oxygen absorption O 2 + H 2 O + 2 e2OH

The corrosion can be controlled either by eliminating oxygen from the corroding medium or by retarding its diffusion to the cathodic areas. The inhibitors like Mg, Zn or Ni salts to the environments are also used. c) Mixed inhibitors This type of inhibitors retards both anodic and cathodic processes. The shift in potential is smaller and the direction is determined by the relative size of the anodic and the cathodic sites. Such inhibitors will have the advantage over other inhibitors in that they control both cathodic and anodic corrosion reactions. 2. Based on environment a) Acid inhibitors It is classified into inorganic inhibitors and organic inhibitors Inorganic inhibitors The addition of salts of electropositive metals into the corrosion medium improves inhibitor. The protection is due to the reduction of electro positive ions deposition on the metal lowering the over voltage of the main cathodic depolarization reaction. The anodic behaviour of Ti and its alloy in H2SO4 and HCI has been studied and cupric ion is found to inhibit anodic dissolution reaction. Organic inhibitors The corrosion of metals and alloys in acid solution is very severe and this can be inhibited by organic inhibitors. In general nitrogen, oxygen and sulphur containing compounds with the hydrocarbon part attached to the polar

group are used as inhibitors. Many nitro and nitroso compounds have been tried as corrosion inhibitors. Organic corrosion inhibitors can be anodic, cathodic and mixed type depending on its size, carbon chain length, conjugation and nature of bonding atoms. b) Neutral inhibitors Inhibitors which are effective in acidic solutions do not function effectively in neutral solutions. In neutral solutions the interaction of inhibitors with oxide covered metal surfaces and prevention of oxygen reductions at the cathodic sites takes place. Such inhibitors protect the surface layers from aggressiveness. Some surface chelating inhibitors have been found to be efficient inhibitors in neutral solutions. c) Alkaline inhibitors The metals which form amphoteric oxides are prone to corrosion in basic solutions. Corrosion inhibitors in basic solutions mainly involves metals like Zn, Al, Cu, Fe, etc. many naturally occurring organic compounds are often used as inhibitors for metals in basic solutions, Eg. Tannin, Gelatin.

d) Vapour phase inhibitors Metals in closed space such as in parcels during storage undergo corrosion. This can be prevented by using vapour phase inhibitors. These form a thin film over certain metal surfaces especially iron and steel, thereby rendering them passive.

Advantages i) ii) Easy to apply Life of inhibitors is very long

METHODS OF CORROSION CONTROL Corrosion of metal occurs when they come in electrical contact with a corrosive environment. Various methods are available for corrosion prevention. They are : 1. Design improvement The procedure for most effective and economical method for reducing losses due to corrosion is Establish basic requirements Choose the most suitable geometric design, material of construction and protective method Carry out the final design work 2. Change of metal The corrosion resistance of metal can be greatly improved by Change of composition. Eg alloying or refining. Change of structure and heat treatment Elimination of residual tensile stress Introduction of surface compressive stresses. 3. Change of environment In many cases corrosion can be effectively controlled by changing the corrosive environment. The methods used are

 Removal of corrosive constituent Use of inhibitors. Either anodic or cathodic inhibitors. Anodic inhibitors are of three: restrainers, Incubators and Passivators 4. Change of metal / electrode potential Corrosion can be controlled by changing the electrode potential of the metal. This is done by Lowering the potential of metal in negative direction in the domain of immunity (cathodic protection). Increasing the potential of metal in positive direction in the domain of passivity (anodic protection). 5. Use of coatings The corrosion of metals which occur due to chemical or electrochemical reaction of the environment can be prevented by separating the metal from the environment. The protective coatings applied to prevent corrosion are Metallic coatings : anodic or cathodic type Non- metallic coatings : coment or paint type coatings 6. Cathodic protection The cathodic reaction is evolution of hydrogen in acid media and the reduction of oxygen in neutral or alkaline media. So, if the entire metal is made to function as cathode without the existence of any anodic sites on the metal surface, it would not undergo any corrosion. Cathodic protection may be defined as the technique of reducing the corrosion rate of metallic structures,

by making the steady state of corrosion electrical potential of the metal sufficiently more electronegative. 7. Anodic protection In this method the structure to be promoted is made anode and potential is set in the passive region. Recently organic compounds have been widely used as corrosion inhibitors for metals in acidic media (15-21).The effective and efficient corrosion inhibitors were those compounds which have -bonds and contains hetero atoms such as sulphur, nitrogen, oxygen and phosphorous which allows the adsorption of compounds on the metal surface (22-25). The organic inhibitors decrease the corrosion rate by adsorbing on the metal surface and blocking the active sites by displacing water molecules form a compact barrier film on the metal surface. The most of the organic inhibitors are toxic , highly expensive and environment unfriendly. Research activities in recent times are geared towards developing the cheap, non-toxic and environment friendly corrosion inhibitors. The present paper describes a study of corrosion protection action of Acetazolamide on mild steel in 1M HCl using weight loss and electro chemical techniques. Acetazolamide is a semisynthetic antibiotic with -electrons, heteroatoms such as S,N and O .The molecule molecular mass is 222.245 g/mol . Acetazolamide, tablet are commercially obtained as a manufactured by the sun pharmaceuticals trade name Diamox, is a carbonic an hydrase inhibitor that is used to treat glaucoma , epileptic seizures, idiopathic intracranial

hypertension (pseudotumor cerbri), altitude sickness, cystinuria, periodic paralysis and dural ectasia. Acetazolamide is available as a generic drug and is also a diuretic. As far as we know no concrete report has been published so for Acetazolamide in 1M HCl with use of weight loss and electrochemical techniques. Hence the present study , different concentrations of inhibitors were prepared and there inhibition efficiency in acidic media was investigated.

REVIEW OF LITERATURE The corrosion of iron and mild steel is a fundamental academic and industrial concern that has received a considerable amount of attention. The use of inhibitors is one of the most practical methods for protection against corrosion. Because of general aggressively of acid solutions, inhibitors are commonly used to reduce the corrosive attack on metallic materials, most of the well known inhibitors are organic compounds containing nitrogen, sulphur, and oxygen atoms. The influence of organic compounds on the corrosion of mild steel in acidic solutions has been investigated by several workers. The recent reviews of some of the drugs as a corrosion inhibitor are summarized as follows. Priyanka singh et.al., the Certrizine was investigated as corrosion

inhibitor for mild steel (MS) in 1M HCl solution by weight loss, electrochemical measurements and quantum chemical calculations. Cetirizine showed 95% inhibition efficiency even at very low concentration of 100 ppm. Polarization study indicates that Cetrizine behaves like a mixed type inhibitor. The adsorption of the inhibitor follows Langmuir adsorption isotherm. The quantum chemical calculations were applied to elucidate adsorption pattern of inhibitor molecules on steel surface10. J.Ishwara Bhat et al., have reported the corrosion inhibition of mild steel by Miconazole nitrate, an antifungal drug using potentiodynamic polarization, electrochemical impedance spectroscopy technique, and weight loss methods.

The experimental results suggested Miconazole nitrate is a good corrosion inhibitor for mild steel in 1M hydrochloric acid medium. The inhibition efficiency increased with increase in inhibitor concentration. The inhibition was assumed to occur via adsorption of the inhibitor molecule on the surface of mild steel following Langmuir adsorption isotherm11. Imran Naqvi et al., have studied the corrosion inhibition of mild steel in 1M HCl solution by Cefixime at temperature range 303-333k by weight less measurement and electrochemical techniques i.e., polarization resistance, potentiodynamic polarization and electro chemical impedance spectroscopy (EIS). The results obtained at 30C divulged that this pharmaceutical compound had established > 90% inhibition efficiency at an optimum concentration of 8.8 x 10- M. It shows that inhibition takes place by adsorption of the inhibitor on metal surface without altering the mechanism of corrosion process. The adsorption of Cefixime takes place according to Langmuirs adsorption isotherm. Kinetic parameters (activation energy, Ea and pre exponential factor,) as well as thermodynamic parameters (enthalpy, entropy and free energy of adsorption; (Sads, Hads and Gads respectively) were calculated and discoursed. Potentiodynamic polarization studies indicate that Cefixime acts as a mixed type of inhibitor12. Ahamad et al., have investigated the inhibition effect of Albendazole on the mild steel corrosion in molar hydrochloric acid was investigated using weight loss, electrochemical impedance spectroscopy (EIS) and polarization
4

techniques. The results show that Albendazole is an effective inhibitor for mild steel corrosion in 1 M HCl solutions and inhibition efficiency is >90% at inhibitor concentration of 0.4mM. Adsorption of the inhibitor of the mild steel surface followed by Langmuir adsorption isotherm. The value of free energy of adsorption (Gads) indicated that adsorption of Albendazole molecule is a spontaneous process and it adsorbs chemically as well as physically polarization studies shows that Aldendazole is a mixed type inhibitor13. N.O.Eddy et al., have been studied the inhibitive and adsorption properties of Sparfloxacin for the corrosion of mild steel in HCl have been studied using gravimetric, gasometric and thermometric methods of monitoring corrosion. Sparfloxacin is found to inhibit the corrosion of mild steel in HCl. At 303K, inhibition efficiency obtained for Sparfloxacin from gravimetric, gasometric and thermometric methods were found to range from 79.68% to 97.47%, 86.67 to 96.67% and 76.34 to 82.30% respectively. Inhibition efficiency of Sparfloxacin increased with increase in concentration of Sparfloxacin but decreased with increase in temperature. Activation energies for the inhibited reactions were higher than the value obtained for the blank. Sparfloxacin is found to be an adsorption inhibitor for the corrosion of mild steel. The adsorption of Sparfloxacin on the surface of mild steel was found to be spontaneous, exothermic and its adsorption characteristics were best described by Langmuir adsorption isotherm. The use of Sparfloxacin as an inhibitor for the corrosion of mild steel in HCl is advocated in this study 14.

OBJECTIVES Acid pickling, industrial acid cleaning, acid descaling and oil-well acidizing are the important processes involves in industries which extensively used acid solutions. Due to the aggressive nature of the acids, inhibitions are often used to reduce the corrosive attack on metals. Inhibitors are generally used in electrochemical processes to control both dissolution and acid consumption. The work on corrosion inhibition of mild steel is not expensive. Therefore, the aim of the present study was to examine the inhibitive action of Acetazolamide against the corrosion of mild steel in acidic solutions. In the present work, Acetazolamide drug have been used by physiochemical and electrochemical corrosion monitoring methods evaluated for their corrosion inhibiting performance in mild steel in 1M HCl. 1) Physio chemical methods Weight loss method 2) Electro chemical method Potentio-dynamic polarization technique Tafel plot AC impedance techniques Nyquist plot

4. EXPERIMENTAL METHODS 4.1. Materials preparation All the tests were performed on mild steel of following composition (wt %) : 0.076% C, 0.192% Mn, 0.012% P, 0.026% Si, 0.050% Cr, 0023% Al, 0.123% Cu and balance. Fe. specimens with dimensions of 1.0 x 4.0 x 0.2 cm were used for weight loss and electrochemical studies. The surface of each specimen was abraded with different emery papers (600-1200 ) and washed

with acetone. The cleaned samples were then washed with double distilled water and finally dried. Electrochemical experiments were performed using a three electrode cell assembly with mild steel samples as working electrode, platinum as counter electrode and saturated calomel (SCE) as the reference electrode. The mild steel electrode of 1.0 x 4.0 x 0.2 cm sizes with an exposed area of 1cm2 and rest being covered by epoxy resin was used as working electrode for electrochemical study. AR grade hydrochloric acid and doubly distilled water were used to prepare lM acid for all experiments. 4.2 Inhibitor Acetazolamide tablets are commercially obtained as a trade name Diamox manufactured by the Sun Pharmaceuticals Ltd.The compound is in its purest state, having molecular formula (C4H6N4O3S2) and melting point (258261C). Its chemical structure is shown in Fig (1)

Fig 1. Molecular structure of Acetazolamide N-(5 sulfamoyl 1,3,4 thiadiazol 2-yl) acetamide.

Acetazolamide is a N-S heterocyclic compound containing three oxygen atoms, four nitrogen atoms and two sulphur atoms. Hence it is expected to act as a good inhibitor. Acetazolamide is a semisynthetic antibiotic with -

electrons, heteroatoms such as S,N and O.The molecule molecular mass is 222.245 g/mol. Acetazolamide, tablet are commercially obtained as a manufactured by the sun pharmaceuticals trade name Diamox, is a carbonic an hydrase inhibitor that is used to treat glaucoma , epileptic seizures, idiopathic intracranial hypertension (pseudotumor cerbri), altitude sickness, cystinuria, periodic paralysis and dural ectasia. Acetazolamide is available as a generic drug and is also a diuretic. The range of the concentrations of inhibitor used for the inhibition is from 1.1 x 10-4 M to 10.10 x 10-4 M

4.3 Weight Loss Measurements The MS specimens used had a rectangular shape of 1.0 x 4.0 x 0.2 cm were abraded with series of emery paper (600-1200) and then washed with distilled water and finally with acetone. After weighing accurately, the specimens were immersed in beaker which contained 100ml of 1M Hcl in the absence and presence of different concentration of inhibitor at room temperature. After 3h the specimens were taken out, washed, dried and weighed accurately. Triplicate experiments were performed in weight loss test for each concentration of inhibitor and without inhibitor and average of weight loss is reported. The corrosion rate (expressed in mg cm-2) with respect to acid and inhibitor was calculated. The corrosion rate CR was calculated from the following equation. 87.6W CR (mm/y) = ---------atD

--------------->

(1)

Where W is the average weight loss of mild steel specimens, a is the total area of one mild steel specimen, t is the immersion time (3h) and D is density of mild steel in (gcm-3). The inhibition efficiency (IE%) and surface coverage () of inhibitor on the corrosion of MS was calculated as follows. W1-W2 IE(%) = --------- x 100 W1 W1-W2 = --------W1

---------------->

(2)

Surface coverage

---------------->

(3)

Where W1 and W2 are the weight losses of mild steel without and with the inhibitor respectively.

4.4. Electrochemical Measurements Three electrochemical techniques, namely DC-Tafel slope, linear polarization resistance (LPR), and ACelectrochemical impedance

spectroscopy (EIS), were used to study the corrosion behaviour. All experiments were performed in conventional three electrode cell. Three electrodes connected to potentiostat/galvanostat G 300-45050 (Gamry instruments inc., USA) Echem Analyst 5.0 software package was used for data fitting. 4.4.1 Tafel polarization and linear polarization studies The MS was the working electrode, and platinum electrode was used as an auxiliary electrode. All potentials were measured versus a saturated calomel electrode (SCE) ie. Reference electrode. Before recording the polarization curves the solution was deaerated for 20 min and the working electrode was maintained at its corrosion potential for 10 min. until a steady state was obtained. The mild steel surface was exposed to various concentrations of Acetazolamide in 100ml of 1M Hcl at room temperature. The inhibition efficiency (IE%) was calculated using the equation. Icorr Icorr(inh) Inhibition efficiency (IE%) = ---------------------- x 100 -------> (4) Icorr

Where Icorr and Icorr(inh) are the corrosion current density of mild steel in 1M HCl in absence and presence of inhibitor respectively. Tafel curves were obtained by changing the electrode potential automatically from -0.25v to 10.25v versus open corrosion potential at a scan rate of 1.0 mv S-1 to study the effect inhibitor on MS. The corresponding corrosion current (Icorr) was recorded. Tafel plots were constructed by plotting E versus log I. The corrosion potential (Ecorr), corrosion current density (Icorr) and cathodic and anodic slopes (c and a) were calculated according to known procedures. Linear polarization resistance (LPR) experiments were done from 0.02V to +0.02V versus corrosion potential at the scan rate of 0.125 V s-1. 4.4.2 EIS measurements EIS measurements were performed under potentiostatic conditions in a frequency range from 100 Hz to 0.01 Hz, with amplitude of 10mV ACsignal. The impedance diagrams were plotted in the Nyquist representation. Charge transfer resistance (Rct) values were obtained by subtracting the highfrequency impedance. The percentage inhibition efficiency was calculated using chare transfer resistance (Rct) as follows.

(Rct(inh) Rct Inhibition efficiency (IE%) = x 100 -------> (5)

Rct(inh)
Where Rct (inh) and Rct are the values of charge transfer resistance in presence and absence of inhibitor in lM HCl respectively. All experiments were measured after immersion period for 30min of mild steel in lM HCl in the absence and presence of different concentrations of inhibitor.

RESULTS AND DISCUSSION 5.1. Weight Loss Studies The values of inhibition efficiency (IE%) and the corrosion rate (CR) obtained from weight loss method at different concentrations of Acetazolamide are summarized in table 1. It follows from the data that the weight loss decreased and therefore corrosion inhibition increased with increase in inhibitor concentration. It was also observed that corrosion rate decreased with increase in inhibitor concentration. It is evident from the table that Acetazolamide inhibits the corrosion of mild steel in HCl solution at all the concentrations used in the study i.e. 1.1.x 10-4M to 10.10 x 10-4M. Maximum inhibition efficiency was obtained at the concentration 10.10 x 10-4M. The increased inhibition efficiency and decreased corrosion rate might be due to the increased adsorption and increased surface coverage () of inhibitor on mild steel surface with increase in concentration. The variation of inhibition efficiency with increase in inhibitor concentrations is shown in Fig 2.

Fig 2 Variation of Inhibition Efficiency in 1 M HCl on mild steel at different concentration of inhibitor

Inhibitio n efficiency (%)

Fig 2 Inhibitor Concentration

Table 1 weight loss measurements for MS in 1M HCl at different concentrations of acetazolamide Inhibitor concentration x 10-4 M Blank 1.1 2.2 4.4 6.6 8.8 10.10 Surface coverage 0.2939 0.3952 0.4706 0.5167 0.6223 0.8640

Weight loss (mg cm-2) 37.52 26.49 22.69 19.86 18.13 14.17 5.10

IE%

CR (mm/y)

29.39% 39.52% 47.06% 51.67% 62.23% 86.40%

131.12 92.579 79.299 69.408 63.362 49.522 17.823

5.2 Effect of immersion time The effect of immersion time was investigated by using optimum concentration 10.10 x 10-4 M of Acetazolamide for 2 to 8 hrs. The effect of immersion time on the inhibition efficiency is shown in Fig.3. It is a round that the inhibition efficiency decreases from 88.2% to 81.4% with increase in immersion time from 2 to 8 hrs.

89 88 87
IE (%)

86 85 84 83 82 81 0 1 2 3 4 5 6 7 8 9

Fig 3 Immersion time

5.3 Tafel polarization Polarization curves for mild steel in 1M Hcl at various concentrations of Acetazolamide are shown in the Fig.4 The values of corrosion potential (Ecorr), current densities (Icorr), anodic tafel slopes (ba), cathodic tafel slopes (bc), surface coverage () and inhibition efficiency(%) of Acetazolamide concentration were calculated from the curves are shown in Table 2. It is evident from the figure that both reactions where suppressed with the addition of the Acetazolamide inhibitor. The suggest that Acetazolamide reduced the anodic dissolution reactions as well as retarded the hydrogen evolution reaction on the cathodic sites. (26,27).

Fig 4: Potentiodynamic polarization curves for mild steel in 1 M HCl in the absence and present of different concentration of Acetazolamilde

It is observed that the inhibition efficiency increased with increasing ampicillin concentration and exhibited both cathodic and anodic inhibition through adsorption on the mild steel surface blocking active sites (28). There is no definite change observed in the corrosion potential (Ecorr). According to Riggs (29) and others if the displacement in E (i) is >85mV,with respect to E, the inhibitor can be seen as a cathodic or anodic type (ii) if displacement in E is < 85,the inhibitor can be seen as mixed type. In our study the maximum displacement is less than 85, which indicates that acetazolamide is a mixed type inhibitor. It is evident from the data that inhibition efficiency (IE), surface coverage () increases with increase in concentration of the inhibitor. The corrosion current density (Icorr) decreases with increase in inhibitor concentration. The maximum inhibition efficiency of 83.25% is obtained at 10.10 x 10-4 M solution of Acetazolamide.

Table 2: Electrochemical parameters and inhibition efficiency for corrosion of mild steel in lM HCl obtained by polarization method. Conc (M) Blank Ecorr mV vs SCE -472.3 Icorr (A/cm2) 598.5 Surface coverage ( ) -

ba mV/dec 82

bc mV/dec 130

IE (%)

1.1

-474.6

466.5

80

141

0.2205

22.05

2.2

-477.2

341.1

66

145

0.4300

43.00

4.4

-479.1

230.2

64

149

0.6153

61.53

6.6

-483.4

222.4

54

157

0.6284

62.84

8.8

-487.6

220.1

52

161

0.6322

63.22

10.10

-493.4

100.2

50

165

0.8325

83.25

5.4 Electrochemical Impedance Spectroscopy (EIS) Studies Corrosion inhibition of mild steel in 1M HCl solution with and without inhibitor was investaged by electrochemical impedance spectroscopy measurements. The Nyquist representations of impedance behavior of mild steel in 1M Hcl with and without addition of different concentrations of Acetazolamide are shown in the Fig.5 It is observed from the Figure. that at all concentrations range of Acetazolamide one large capacitive loop at higher frequency range followed by the one small inductive loop at lower frequency range. The diameter of the circle increased with increase in inhibitor concentration. The higher frequency capacitive loop is due to the adsorption of inhibitor molecule (30). This can be interpreted by Rs-Rp Cdl equivalent circuit, commonly known as Randle circuit (fig). which was previously used to model the ironacid interface (31) Many workers also explained the results by using randle circuit (31-36). The deviation from the perfect semi circle shape (depression) is often referred to the frequency dispersion of interfacial impedance. This behavior is due to the in homogeneity of the metal surface arising from surface roughness or interfacial phenomena (37-39). It is observed that addition of inhibitor increases the values of Rct and reduces the Cdl value. The decrease in Cdl is due to increase in thickness of the electronic double layer (40). The increase in Rct values is due to the formation of protective film on the metal / solution interface (41,42). This observation

suggests that Acetazolamide molecules function by adsorption on metal surface and thereby causing the decrease in Cdl values and increase in Rct values. The charge transfer resistance (Rct) values and the interfacial double layer capacitance (Cdl) values calculated from the cures are shown in the table 3.

1.1 X 10-4 M 2.2 X 10-4M 4.4 X 10-4M 6.6 X 10-4M 8.8 X 10-4M 10.10 X 10-4 M

Fig.5: Nyquist plot of mild steel in 1M HCl in the absence & presence of different concentrations of Acetazolamide

Table 3 electrochemical parameters and inhibition efficiency for corrosion of mild steel in 1M Hcl obtained by impedance method Inhibition efficiency (%) 69.23 69.82 70.48 72.00 73.01 82.72

Cocn (M) Blank 1.1 2.2 4.4 6.6 8.8 10.10

Rct ( cm2) 46.68 151.72 154.7 158.14 166.72 173.0 198.2

Cdl (F Cm-2) 0.619 0.535 0.493 0.479 0.449 0.410 0.402

Surface coverage () 0.6923 0.6982 0.7048 0.7200 0.7301 0.8272

5.5. Adsorption Isotherm The degree of surface coverage () for different concentrations of inhibitor in 1M HCl has been calculated from weight loss, polarization and electrochemical impedance studies. The obtained data was tested graphically for fitting suitable isotherm. Almost a straight line was obtained by plotting surface coverage () Vs log C shown in Fig. 6, which proves that the adsorption of this compound obeys Temkin isotherm.

Surface Coverage

log C x 10-4

Fig 6. Temkin adsorption isotherm for different concentrations of Acetazolamide in 1M HCl

5.6. Mechanism of Corrosion Inhibition Corrosion inhibition mechanism in acidic medium is based on the adsorption of inhibitor on the metal surface. The process of adsorption is influenced by the nature and charge of the metal, chemical structure of the inhibitor and the type of the aggressive electrolyte. The charge of the metal surface can be determined from the potential zero charge (Pzc) on the correlative scale (c) (43) by the equation. c = Ecorr Eq = o Where Eq=o is the potential of zero charge. He value of Ecorr obtained in Hcl is 470mv versus SCE. In HCl solution Acetazolanide acts as a protonated species. This protonated species are adsorbed on the metal surface through chloride bridge and reduces the corrosion. Benerijee and malhotra (44) reported the Pzc of iron in hydrochloric acid solution is -530 versus SCE. Therefore the value of is +60mV versus SCE, so the metal surface acquires slight positive charge. The adsorption of cationic Acetazolamide species does not take place and the adsorption of chloride ions occurs and surface becomes negatively charged. Now due to the electrostatic attraction, the protonated Acetazolamide molecules physically adsorbed on the metal surface and thereby giving high inhibition by Acetazolamide molecules.

5.7 CONCLUSION Acetazolanide acts as a good inhibitor for the corrosion of mild steel in 1M HCl. Potentiodynamic curves reveal that Acetazolamide is a mixed type of inhibitor. EIS measurements also indicates that the inhibitor performance increase due to the adsorption of molecule on metal surface. The result obtained from weight loss, impedance and polarization studies are in good agreement with each other. The adsorption of Acetazolamide on mild steel surface obeyed Temkins adsorption isotherm.

REFERENCES 1. Staehle.R.W, Proceedings of environment induced cracking of metals, 5 (1989). 2. F.N.spellar, corrosion causes and prevention, 8 (1957) 3. Raj Narayan, An Introduction to metallic corrosion and its prevention, 1983. 4. M.M.EI Naggar, corros. Sci.49, 226 (2007). 5. K.R.Treathwey and J. Chamberlain : Corrosion for science and Engineering 2nd Edn (1995). 6. F.Bentiss, F. Gassma, D.Barbry, L.Gengembre, H.Legrence and M.Traisnel, Appl. Surf, Sci., 252, 2684 (2006). 7. C.Wagner and W.Traud, Zeitschrift fuer electrochemic, 44, 391 (1938). 8. M.Stern and A.L.Geary, J.Electrochem.Soc., 10, 436 (1957). 9. L.L.Shrer, Corrosion, Georage Newness Ltd, Landon, 2 (1994). 10.Priyanka Singh1, Ambrish Singh1, M.A. Quraishi1*, Eno. & E.Ebenso2, Int. J. Electrochem.Sci., 7 (2012) 7065-7079. 11. J.Ishwara Bhat and Vijaya D.P. Alva, International journal of Electrochemistry volume 2011 (2011), Article ID 157576, 8 pages 12. Imran Naqvi, * A.r. Saleemi & S.Naveed, Int. J. Electrochem. Sci., 6 (2011) 146-161. 13. I.Ahamad1, R.Prasad2, Eno E. Ebenso3, & M.A. Quraishi1*, Int. J. Electrochem. Sci., 7 (2012) 3436-3452.

14. N.O.Eddy1*, S.A. Odoemelam2 and A.J. Mbaba3 African Journal of pure and applied chemistry Vol.2 (12), PP.132 138, December, 2008. 15. R.Hasanov, M.Sadikoglu, & S.Bilgic, Appl. Surf. Sci.253 (2007) 39133921. 16. A.Chetouani, B.Hammouti, T.Benhadda, & M.Daoudi, Appl. Surf.Sci.249 (2005) 375-385. 17.M.Bouklah, B.Hammouti, M.Lagrence, & F.Bentiss, Corros. Sci.48 (2006) 2831-2842. 18. M.Benabdellah, R.Touzani, A.Aouniti, A.Dafali, S.El-Kadiri, B.Hammouti, & M.Benkaddour, Mater.chem.Phys.105 (2007) 373-379. 19. A.Yildirim, & M.cetin, Corros.Sci.50 (2008) 155-165. 20. I.B.Obot, & N.O.-Obi-Egbedi, Colloids Surf. A Physicochem. Eng.Aspects 330 (2008) 207-212. 21. K.F.Khaled, & M.M. Al-Qahtani, Mater.Chem.Phys.113 (2009) 150 -158. 22. H.Ma.T.Song, H.sun, & X.Li, Thin Solid films 516 (2008) 1020-1024. 23. E.H.El Ashry, A.El Nemr, S.A. Essawy, & S.Ragab, Prog. Org. Coat.61 (2008) 11-20. 24. H.Ju.Z.P.Kai, & Y.Li, Corros. Sci.50 (2008) 865-871. 25. S.El Issami, B.Hammouti, S.Kertit, E.Ait Addi, & R.Salghi, pigment Resin Technol.36 (2007) 161-168. 26. B.G.Ateya, M.B.A. El-Khair & I.Abdel Hamed, Corros. Sci.16 (1976) 163-169. 27. W.Li, Q.He.S.Zhang, C.Pel., & B.Hou, J.Appl. Electrochem.38 (2008) 289295. 28. M.A. Quraishi, S.Ahmad, & G.Venkatachari, Bull. Electrochem. 12 (1996) 109.

29. O.L .Riggs.Jr., Corrosion Inhibition, second ed., C.C.Nathan, Houston, TX, 1973. 30.S.K. Shukla, & M.A. Quraishi, Corros. Sci., 2009, doi : 10.1016/J. corros. 2009.05.020. 31. J. Cruz.R.Martinez, J.Genesca, & E.Garcia-ochoa, J.Electroanal.chem.566 (2004) 111-121. 32. R.A.Prabhu. T.V.Venkatesha, A.V.Shanbhag, R.G.Kalkhambkar, Corros.Sci.50 (2008) 3356-3362. G.M.Kulkarni, &

33. F.Bentiss, M.Traisnel, N.Chabi, B.Mernari. H.Vezin, Corros. Sci.44 (2002) 2271-2289. 34. G.AVCI, Mater, Chem..Phys.112 (2008) 234-238.

& M.Lagrence,

35. S.K.Shukla, & M.A.Quraishi, Corros. Sci.51 (2009) 1007-1011. 36. F.Bentiss, M.Lagrence, M.Traisnel, & J.C. Hornez, Corros. Sci.41 (1999) 789-803. 37. H.Shih, & H.Mansfeld , Corros. Sci. 29 (1989) 1235-1240. 38. S.Martinez, & M.Mansfeld Hukovic, J.Appl. Electrochem.33 (2003) 1137-1142. 39. M.Elayyachy, A.El.Idrissi, & B.Hammoati, Corros.Sci. 48 (2006) 24702479. 40. M.G. Hosseini, M.Ehteshamzadeh, & T.Shahrabi, Electrochem.Acta.52 (2007) 3680-3685. 41.S.Murlidharan, K.L.N.Phani, S.Pitchumani, J.Electrochem.Soc.142 (1995) 1478-1483. & S.Ravichandran,

42. F.Bentiss, M.Traisnel, & M.Lagrenee, Corros. Sci.42 (2000) 127-146. 43. A.A.Hermas, M.S.Morad, & M.H.Wahdan, J.Appl. Electrocchem. 34 (2004) 95-102. 44. G.Benerijee & S.N.Malhotra, Corrosion (NACE) 48 (1992) 10-15.