INHIBITOR

Retarding catalyst
● IS A CHEMICAL SUBSTANCE THAT, WHEN A D D E D IN A SMALL CONCENTRATION
TO AN ENVIRONMENT, EFFECTIVELY DECREASES THE CORROSION RATE
● 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 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
1. Reducing Exchange current density of hydrogen reaction

2. Reducing Exchange current density of metal reaction

3. Reducing the surface area

1. Reduction in surface of reaction
2. Reduction in electron generation
Corrosion inhibitors help in
• temporary protection during storage
• transport
• localized protection
• prevent corrosion that may result from accumulation of small
amounts of an aggressive phase.
MECHANISM OF THE INHIBITOR
• chemically adsorbed on the surface of the metal

• forms a protective thin film with inhibitor effect

• by combination between inhibitor ions and metallic surface.

• formation of a film by oxide protection of the base metal.

• reacts with a potential corrosive component present in

aqueous
media and the product is a complex
CLASSIFICATION OF
INHIBITOR
➢ Passivating (anodic) inhibitors

➢ Cathodic inhibitors
➢ Organic inhibitors

➢ Precipitation inhibitors

➢ Scavenger Inhibitors
Inorganic Inhibitors

The addition of inorganic inhibitors causes suppression of

electrochemical reaction at anodic– cathodic areas. Most of the
times, inhibitors are used in a blended form. These inhibitors
only react at an adequate level of concentration.

(A) Chromate Inhibitors

They are most effective inhibitors, but they are toxic and, hence,
their application is restricted and is not advised. In industrial
water, the threshold concentration is 120 mg/L. Chromate
inhibitors contain either Na2CrO4 or Na2Cr2O7.
Fe → Fe+2 + 2e- (Oxidation of iron)
CrO-4 +8H+3e → Cr+3 + 4H2O (Formation of Cr+3 )
Fig (1.2) : Formation of a mixed
iron oxide and chromium oxide
film
(B) Nitrites

They are effective inhibitors for iron and a number of metals

in a wide variety of waters. Like chromates, nitrites are
anodic inhibitors and they inhibit the system by forming a
passive film with ferric oxide. These are environmentally-
friendly inhibitors. Besides steel, nitrites also inhibit the
corrosion of copper.
Nitrites should not be used in open systems as they
would oxidize to nitrates in the presence of oxygen.
NO-2+O2↔2NO-3

Nitrites are not effective if presence of chloride and

sulfate .
(C)Phosphate Inhibitors

Phosphate retards corrosion by promoting the growth

of protective iron oxide films and by healing the defects
in protective films.

(D) Molybdates

Molybdenum is an alloying element which is known

to increase passivation of stainless steels of type 316.
Sodium molybdates forms a complex passivation film
at the iron anode.
The passive film can only be formed in the presence of
oxygen.
(E) Silicates
Silicates are strong anodic inhibitors and passive films can
be formed even on the corroded surface. The monomeric
silica does not provide any protection. In waters below pH
levels of
6.0 , the silicate used is Na2O.2SiO3 and with a pH greater
than 6.0, it is Na2O3.3SiO3 .
Silicate treatment also prevents dezincification in brass
and corrosion of copper.
Anodic
inhibitor

Cathodic
inhibitor
 Passivating (anodic)
● inhibitors
Passivating inhibitors cause a large anodic shift of the
corrosion potential, forcing the metallic surface into
the passivation range.

Increases the

ECorr

● There are two types of passivating inhibitors:

- 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
Organic Inhibitors

Organic inhibitors are used in the oil industry to control oil and
gas well corrosion. Most common types are long chain (C18) . The
most common types of organic inhibitors are shown below:

(1) Monoamine:
Primary amine, RNH2 Secondary amine, R2NH Tertiary amine,
R-N(CH3)2

(2) Diamines

R – NHCH2CH2CH2NH2

(3) Amides R – CONH2

 (4) Polyethoxylated
compounds
(a) Amines

(x and y vary between 2 and 50)

(b) Diamines

(x+ y+ z varies between 3–

10)
 Organic inhibitors react by adsorption on a metallic
surface. Cationic inhibitors (+), like amines, or anionic
inhibitors (−), like sulfonates, are preferentially adsorbed
depending on the charge of the metal surface (+)or(−). At
zero point of charge, there is no particular preference for
an anodic or cathodic inhibitor.

Organic
inhibitor
 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.
● 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.
Film forming in nature
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.
● 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.
Synergistic effect
Scavenger
s Oxygen, even in very small amounts, may cause serious corrosion
in feedwater lines, stage heaters, economizers, boiler metal, steam
operated equipment and condensable piping. It must, there-fore,
be removed from the closed system. The solubility of oxygen varies
with both pressure and temperature. Oxygen is the main cause of
corrosion. It reacts by consuming electrons at the cathode causing
cathodic depolarization and enhancing the rate of corrosion.
Chemicals which eliminate oxygen from the closed systems
are called scavengers. Ammonium sulfite (NH4)2SO3, and
hydrazine (N2H4) have been successfully used over the years to
eliminate oxygen. Oxygen scavengers remove oxygen as shown
below:
SCAVENGER INHIBITOR
•

Table (1.2) : Advantages and disadvantages sodium sulfite and

of hydrazine
Chemical Advantage Disadvantage

Sodium ■ Rapid reaction ■Does not reduce ferric oxide to

sulfite ■ Non-toxic magnetite
■ Contributes no solids ■May decompose to form
■Reduces ferric oxide corrosive gases
to magnetite ■Reacts less rapidly compared to
sodium sulfite

Hydrazine ■Less dosage for scavenging ■ More expensive than sodium

compared to sodium sulfite
sulfite required ■ Toxic and flammable
Inhibitor Application Techniques
Basically, there are three well-known inhibitor
application techniques:
(1) Continuous injection
(2) Batch treatment
(3) Squeeze treatment

1 . Continuous Injection
As the name suggests, inhibitors are injected in the system to
achieve inhibition objectives through the system. Normally the
inhibitor is injected into the system by means of an electric or gas
driven chemical pump. The inhibitor is added at the point of
turbulence to achieve uniform mixing. This method is used for
municipal water supplies, cooling towers and oil wells, to minimize
scaling and corrosion problems. In the continuous injection
method, a constant supply of chemicals is maintained at a
controlled
rate.
2. Batch Treatment

This is a periodic treatment in which a large quantity of

chemicals is used for an extended period of time. It is
commonly used to treat flowing oil wells. Batch treatment is
also called slug treatment. For batch treating, the tube
displacement method is employed. Several barrels of inhibitor
are pumped into the tubing at the top. The inhibitor is
displaced to the bottom of the tubing with the fluids in the oil
well. The well is closed for a specific period before operation.
The batch is used mainly to treat water with biocides.
 Squeeze
Treatment
•Continuous treatment of oil wells by inhibitors is achieved by this
method. The liquid inhibitor is pumped down through the tubing into
the oil producing geological formation under low pressure which acts
as a chemical reserve.
•In oil wells, 1–2 drums of inhibitor is mixed with 10–20 bbl of water
(1bbl (British barrel) = 36 gallons), and is pumped into the well
followed by pumping in over-flush fluid (50–75 bbl).
• The inhibitor is absorbed by the formation.
Inhibitor Efficienc y and Inhibitor
Concentration
(1) The efficiency of corrosion inhibition can be expressed
as
Einh = (CR o – CRI) / CR O
where = efficiency of a corrosion
Einh
CR o =inhibitor
corrosion rate with zero inhibitor
CRI = corrosion rate in the presence of an
inhibitor

(2) The quantity of inhibitor required for a fluid to be

inhibited can be obtained by the relationship:
Qinh =( Vf luid / 1*106) *Cinh (ppm)
where
Qinh = quantity of inhibitor, kg
Vf luid = volume of fluid to be inhibited , liters
Cinh = inhibitor concentration, ppm
 LIMITATIONS OF INHIBITORS

1. Small amount may have opposite effect

2. Contamination of the system and environment
3. Inhibitors ate toxic in nature eg arsenic
4. Effectiveness is based on the temperature and pressure conditions
Examples of Application of Inhibitors

•Petroleum Industry. Corrosion phenomena in the petroleum

industry occur in a two-phase medium of water and
hydrocarbon. It is the presence of a thin layer of water which
leads to corrosion, and rigorous elimination of water reduces
the corrosion rate to a negligible value. The inhibitors used
in petroleum industry, both in production and refining are
either oil soluble–water insoluble types or oil soluble–water
dispersible compounds.

•Packaging Industry. For transportation of

machinery,components and equipment by sea, vapor phase
cyclohexylamine and hexa- methylamine are used.
•Sour Gas Systems. A major problem is encountered in steel pipelines
in various sour gas environments. Chemical inhibition is one of the
effective methods used to mitigate sulfide induced corrosion.
Inhibitors containing alkyl ammonium ions are found to suppress
corrosion effectively.

•Potable Water Systems. Corrosion is experienced in potable

water transportation pipes of steels and cast iron. Inhibitors, such
as Ca(HCO3)2 and polyphosphates are commonly used to combat
corrosion.

•Engine Coolants. Inhibitors, such as NaCrO4 (sodium chromate),

borates and nitrites (NaNO2) and mercaptabenzothia-zole are
widely used for protection of auto-mobile engines. Chromates are a
health hazard.
Example

Calculate the dosage of sodium chromate required to be

added to 500 000 liters of
water, if the concentration of sodium chromate is 5 ppm.

Solution:
QNn2CrO4= ( VNa2CrO4/ 1*106) *CNa2CrO4 (ppm) 06 ) *5 (ppm)
=(500000Kg/ 1*1
=2.5 Kg

The Table (1.3) in the next page state some corrosive systems
and the inhibitors used to protect them.
 ADVANTAGES OF
ANODIC
PROTECTION
●Anodic protection can decrease corrosion
rate substantially.
●The primary advantages of anodic protection
are its applicability in extremely corrosive
environments and its low current
requirements.
●Anodic protection has been most extensively
applied to protect equipment used to store
and handle sulfuric acid.
Protective Coatings /
Wrapping
● The main function of coating is to provided an
effective
barrier .

● There are many methods by which we can coated the

materials, i.e.:
● Metallic coating

● Inorganic coating

● Organic coating

● Coatings may act as sacrificial anode or release

substance
Metal
coatings
Metallic coatings provide a layer that changes the surface
: properties of the workpiece to those of the metal being
applied.
●Noble – silver, copper, nickel, Cr, Sn, Pb on steel. Should

be free of pores/discontinuity because creates small anode-

large cathode leading to rapid attack at the damaged areas.
●Sacrificial – Zn, Al, Cd on steel. Exposed substrate will be

cathodic & will be protected.

●Application – hot dipping, flame spraying, cladding,

electroplating, vapor deposition, etc.

Inorganic
coating
Inorganic coatings can be produced by chemical action,
:with or without electrical assistance. The treatments change
the immediate surface layer of metal into a film of metallic
oxide or compound which has better corrosion resistance
than the natural oxide film .
● cement coatings, glass coatings, ceramic coatings,
chemical conversion coatings.
● Chemical conversion – anodizing, phosphatizing,
chromate.
Organic
coating
:
Coating liquid generally consists of solvent, resin and
pigment. The resin provides chemical and corrosion
resistance, and pigments may also have corrosion
inhibition functions.
● paints, lacquers, varnishes.
 Organic
● lining:
The difference between a polymer coating and lining is
the difference in thickness, and therefore in service
condition and protection mechanism.
● A coating is thin less than 0.5mm and a lining usually
be around 3mm.
● A lining is thick enough to be a complete barrier
between the metal and environment but coating is not.
● Lining is applied to the interior of the tank or vessel

while coating are applied at the exterior surface.