INHIBITOR IS A CHEMICAL SUBSTANCE THAT, WHEN ADDED IN A SMALL CONCENTRATION TO AN ENVIRONMENT, EFFECTIVELY DECREASES THE CORROSION RATE In the oil extraction and processing industries inhibitors have always been considered to be the first line of defense against corrosion

The efficiency of inhibitor can be expressed by a measure of this improvement : The efficiency of inhibitor can be expressed by a measure of this improvement : Inhibitor efficiency (%) = Inhibitor efficiency (%) = [CR uninhibited – CR inhibited ] [CR uninhibited – CR inhibited ] CR unhibited CR unhibited or or [R p,inhibited – R p, uninhibited ] [R p,inhibited – R p, uninhibited ] R p,inhibited R p,inhibited CR : corrosion rate ; R p = polarization resistance x 100%

Inhibitor efficiency of Trans- Cinnamaldehyde (TCA) TCAppm R p Ω. cm 2 Corrosion current, mA.cm -2 Corrosion Rate, mm.y -1 Effi- ciency, %

Inhibitors are chemicals that interact with a metallic surface, or the environment this surface is exposed, giving the surface a certain level of protection. Inhibitors are chemicals that interact with a metallic surface, or the environment this surface is exposed, giving the surface a certain level of protection. Inhibitors often work by adsorbing themselves on the metallic surface by forming a film Inhibitors often work by adsorbing themselves on the metallic surface by forming a film Inhibitors slow corrosion process by: Inhibitors slow corrosion process by:  - Increasing the anodic or cathodic polarization behavior (Tafel slopes)  - Reducing the movement or diffusion of ions to the metallic surface  - Increasing the electrical resistance to the metallic surface

CLASSIFICATION OF INHIBITOR  Passivating (anodic) inhibitors  Cathodic inhibitors  Organic inhibitors  Precipitation inhibitors  Volatile corrosion inhibitors

Passivating (anodic) inhibitors Passivating inhibitors cause a large anodic shift of the corrosion potential, forcing the metallic surface into the passivation range. Passivating inhibitors cause a large anodic shift of the corrosion potential, forcing the metallic surface into the passivation range. There are two types of passivating inhibitors: There are two types of passivating inhibitors: - oxidizing anions, such as chromate, nitrite and nitrate that can passivate steel in the absence of oxygen. - oxidizing anions, such as chromate, nitrite and nitrate that can passivate steel in the absence of oxygen. - nonoxidizing ions, such as phosphate, tungstate and molybdate that require the presence of oxygen to passivate the steel - nonoxidizing ions, such as phosphate, tungstate and molybdate that require the presence of oxygen to passivate the steel

The reduction potential of chromate ion to solid Cr 2 O 3 is possible to increase the corrosion potential of steel into its passivation region but not for molybdate and tungstate.

INHIBITING MECHANISM OF NITRITES The formation of ferric oxides with the participation of nitrite ions takes place according to the following reactions (Joseph et al): The formation of ferric oxides with the participation of nitrite ions takes place according to the following reactions (Joseph et al): Formation of a lower oxide: Formation of a lower oxide: NO H + +6e = NH H 2 O NO H + +6e = NH H 2 O 9 Fe(OH) 2 = 3Fe 3 O 4 +6H 2 O+6H + +6e 9 Fe(OH) 2 = 3Fe 3 O 4 +6H 2 O+6H + +6e 2H 2 O = 2H + + 2OH - 2H 2 O = 2H + + 2OH - 9Fe(OH) 2 +NO 2 - = 3Fe 3 O 4 +NH OH - +6H 2 O

Formation of a higher oxide: Formation of a higher oxide: NO H + +6e = NH H 2 O NO H + +6e = NH H 2 O 6Fe(OH) 2 = 2Fe 3 O 4 +4H 2 O+4H + +4e - 6Fe(OH) 2 = 2Fe 3 O 4 +4H 2 O+4H + +4e - 2Fe 3 O 4 +H 2 O=3(γ-Fe 2 O 3 )+2H + +2e - 2Fe 3 O 4 +H 2 O=3(γ-Fe 2 O 3 )+2H + +2e - 2H 2 O = 2H + + 2OH - 2H 2 O = 2H + + 2OH - 6Fe(OH) 2 +NO 2 - =3(γFe 2 O 3 )+NH H 2 O+2OH - Sodium nitrite is more effective in suppressing the aggressive properties of chlorides than are benzoate and chromate. In the presence of sulfate, nitrate is slightly less effective than are chromate and benzoate.

Protective properties of sodium nitrite as function of sodium chloride concentration Protective properties of sodium nitrite as function of sodium chloride concentration C NaCl %mass C NaNO2 %mass C NaCl C NaCl T, hr Pot.mV State of metal surface corrodes protected protected protected

Chromate-base inhibitors are the least- expensive inhibitors and were used until recently in a variety of application (e.g. recirculation cooling systems of internal combustion engines, refrigeration units and cooling towers). Sodium chromate, typically in concentrations of 0.04 to 0.1% was used for this applications. At higher temperatures or in fresh water with chloride concentration above 10 ppm, higher concentration are required. If necessary, sodium hydroxide is added to adjust the pH to a range of 7.5 – 9.5. If the concentration of chromate falls below a concentration of 0.016% corrosion will be accelerated. Chromate-base inhibitors are the least- expensive inhibitors and were used until recently in a variety of application (e.g. recirculation cooling systems of internal combustion engines, refrigeration units and cooling towers). Sodium chromate, typically in concentrations of 0.04 to 0.1% was used for this applications. At higher temperatures or in fresh water with chloride concentration above 10 ppm, higher concentration are required. If necessary, sodium hydroxide is added to adjust the pH to a range of 7.5 – 9.5. If the concentration of chromate falls below a concentration of 0.016% corrosion will be accelerated.

Cathodic Inhibitors Cathodic inhibitors either slow the cathodic reaction itself or selectively precipitate on cathodic areas to increase the surface impedance and limit the diffusion of reducible species to these area. Cathodic inhibitors either slow the cathodic reaction itself or selectively precipitate on cathodic areas to increase the surface impedance and limit the diffusion of reducible species to these area. Cathodic inhibitors can provide inhibition by three different mechanisms: 1. as cathodic poisons; 2. as cathodic precipitates, and 3. as oxygen scavenger. Cathodic inhibitors can provide inhibition by three different mechanisms: 1. as cathodic poisons; 2. as cathodic precipitates, and 3. as oxygen scavenger.

Some cathodic inhibitors, such as compounds of arsenic and antimony, work by making recombination of hydrogen more difficult. These substances are very effective in acid solutions but are ineffective in environments where other reduction processes such as oxygen reduction are the controlling cathodic reactions. Some cathodic inhibitors, such as compounds of arsenic and antimony, work by making recombination of hydrogen more difficult. These substances are very effective in acid solutions but are ineffective in environments where other reduction processes such as oxygen reduction are the controlling cathodic reactions. Other cathodic inhibitors, ions such as calcium, zinc, or magnesium, may be precipitated as oxides to form a protective layer on the metal. Other cathodic inhibitors, ions such as calcium, zinc, or magnesium, may be precipitated as oxides to form a protective layer on the metal. Oxygen scavengers help to inhibit corrosion by preventing cathodic polarization caused by oxygen. Examples of this type of inhibitors are sodium sulfite and hydrazine. Oxygen scavengers help to inhibit corrosion by preventing cathodic polarization caused by oxygen. Examples of this type of inhibitors are sodium sulfite and hydrazine.

They remove dissolved oxygen from aqueous solutions; They remove dissolved oxygen from aqueous solutions; 2 Na 2 SO 3 + O 2(dissolved ox.) = 2Na 2 SO 4 2 Na 2 SO 3 + O 2(dissolved ox.) = 2Na 2 SO 4 N 2 H 4 + O 2 = N 2 + 2H 2 O N 2 H 4 + O 2 = N 2 + 2H 2 O These inhibitors will work effectively in solutions where oxygen reduction is controlling the cathodic process but will not effective in acid solution. These inhibitors will work effectively in solutions where oxygen reduction is controlling the cathodic process but will not effective in acid solution.

Organic Inhibitors Both anodic and cathodic effects are sometimes observed in the presence of organic inhibitors, but as general rule, organic inhibitors effect the entire surface of corroding metal present in sufficient concentration. Both anodic and cathodic effects are sometimes observed in the presence of organic inhibitors, but as general rule, organic inhibitors effect the entire surface of corroding metal present in sufficient concentration. Organic inhibitors, usually designated as film forming, protect the metal by forming hydrophobic film on the metal surface. Their effectiveness depends on the chemical composition, their molecular structures, and their affinities for the metal surface. Because film formation is an adsorption process, the temperature and pressure in the system is the important factors. Organic inhibitors, usually designated as film forming, protect the metal by forming hydrophobic film on the metal surface. Their effectiveness depends on the chemical composition, their molecular structures, and their affinities for the metal surface. Because film formation is an adsorption process, the temperature and pressure in the system is the important factors. Organic inhibitors will adsorbed according to the ionic charge of inhibitors and the charge of the surface. Organic inhibitors will adsorbed according to the ionic charge of inhibitors and the charge of the surface.

Cationic inhibitors, such as amines, or anionic inhibitors such as sulfonates, will be adsorbed preferentially depending on whether the metal is charge negatively or positively.The strength of adsorption bond is the dominant factor for soluble organic inhibitors. Cationic inhibitors, such as amines, or anionic inhibitors such as sulfonates, will be adsorbed preferentially depending on whether the metal is charge negatively or positively.The strength of adsorption bond is the dominant factor for soluble organic inhibitors. These materials build up a protective film of adsorbed molecules on the metal surface, which provides a barrier to the dissolution of the metal in the electrolyte. Because the metal surface covered is proportional to the inhibitors concentrate, the concentration of inhibitor in the medium is critical. For any specific inhibitor in any given medium there is an optimal concentration. These materials build up a protective film of adsorbed molecules on the metal surface, which provides a barrier to the dissolution of the metal in the electrolyte. Because the metal surface covered is proportional to the inhibitors concentrate, the concentration of inhibitor in the medium is critical. For any specific inhibitor in any given medium there is an optimal concentration.

Precipitation Inhibitors Precipitation-inducing inhibitors are film forming compounds that have general action over the metal surface, blocking both anodic and cathodic sites indirectly. Precipitation inhibitors are compound that cause the formation of precipitates on the surface of the metal, thereby providing protective layer. Hard water that is high in calcium and magnesium is less corrosive than soft water because of the tendency of the salts in the hard water to precipitate on the surface of the metal and form a protective film. Precipitation-inducing inhibitors are film forming compounds that have general action over the metal surface, blocking both anodic and cathodic sites indirectly. Precipitation inhibitors are compound that cause the formation of precipitates on the surface of the metal, thereby providing protective layer. Hard water that is high in calcium and magnesium is less corrosive than soft water because of the tendency of the salts in the hard water to precipitate on the surface of the metal and form a protective film. The most common inhibitors in this category are the silicates and the phosphates, i.e. sodium silicate is used in many domestic softeners to prevent the occurrence of rust water. In aerated hot water systems, sodium silicates protect steel, copper and brass. The most common inhibitors in this category are the silicates and the phosphates, i.e. sodium silicate is used in many domestic softeners to prevent the occurrence of rust water. In aerated hot water systems, sodium silicates protect steel, copper and brass.

However the protection is not always reliable and depends heavily on pH and a saturation index that is influenced by water composition and temperature. Phosphates also require oxygen for effective inhibition. Silicates and phosphates do not afford the degree of protection provided by chromates and nitrites; however they are very useful in situations where nontoxic additive are required. However the protection is not always reliable and depends heavily on pH and a saturation index that is influenced by water composition and temperature. Phosphates also require oxygen for effective inhibition. Silicates and phosphates do not afford the degree of protection provided by chromates and nitrites; however they are very useful in situations where nontoxic additive are required.

Volatile Corrosion Inhibitors Volatile corrosion inhibitors (VCIs), also vapor phase inhibitors (VPIs), are compounds transported in a closed environment to the site of corrosion by volatilization from a source. In boilers, volatile basic compounds, such as morpholine or hydrazine, are transported with steam to prevent corrosion in condencer tubes by neutralizing acidic carbon dioxide or by sifting surface pH toward less acidic and corrosive values. Volatile corrosion inhibitors (VCIs), also vapor phase inhibitors (VPIs), are compounds transported in a closed environment to the site of corrosion by volatilization from a source. In boilers, volatile basic compounds, such as morpholine or hydrazine, are transported with steam to prevent corrosion in condencer tubes by neutralizing acidic carbon dioxide or by sifting surface pH toward less acidic and corrosive values. In closed vapor spaces, such as shipping containers, volatile solids such as salts of dicyclohexylamine, cyclohexylamine, and hexamethylene amine are used. On contact with the metal surface, the vapor of this salt condenses and hydrolyzed by any moisture to liberate protective ions. In closed vapor spaces, such as shipping containers, volatile solids such as salts of dicyclohexylamine, cyclohexylamine, and hexamethylene amine are used. On contact with the metal surface, the vapor of this salt condenses and hydrolyzed by any moisture to liberate protective ions.

It is desirable, for an efficient VCI, to provide inhibition rapidly and to last for long periods. Both qualities depend on the volatility of these compounds, fast action wanting high volatility, whereas enduring protection requires low volatility. It is desirable, for an efficient VCI, to provide inhibition rapidly and to last for long periods. Both qualities depend on the volatility of these compounds, fast action wanting high volatility, whereas enduring protection requires low volatility.

The majority of inhibitor applications for aqueous, or partly aqueous, systems are concerned with four main types of environment: The majority of inhibitor applications for aqueous, or partly aqueous, systems are concerned with four main types of environment:  Aqueous solution of acids as used in metal- cleaning processes such as pickling for removal of rust or mill scale during the production and fabrication of metals or in the postservice cleaning of metal surfaces.  Natural waters, supply waters, and industrial cooling towers in near-neutral pH range (5 to 9)  Primary and secondary productions of oil and subsequent refining and transport process.  Atmospheric or gaseous corrosion in confined environments, during transport, storage, or any other confined operation.