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CORROSION INHIBITORS UNIT-7

CHE-545-172
DR IME B.OBOT

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INTRODUCTION
Methods of corrosion Protection:
• (a) Changing the electrode potentials:
 Cathodic protection
 Anodic Protection
• (b) Changing the nature of materials:
 Corrosion Resistance Alloy
 Metallic Coatings
• (c) Changing the corrosive environment:
 Corrosion Inhibitors: Any chemical substance which when added to a
solution (usually in a small amounts) increases the corrosion resistance. It
modifies the electrochemical reaction by their action from the solution
side of the metal/solution interface.
 Efficiency of corrosion inhibitor is calculated as follows for general
corrosion: %I = io-i/io × 100
Where io is the corrosion current density without inhibitor and i is the
corrosion current density in the presence of inhibitor.

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INTRODUCTION
• Corrosion inhibitors can be used in the following
industries:
 Portable (drinking) water
 Cooling water systems
 Automobile Engine coolants
 Acid pickling (cleaning) solutions
 Steel rebar in concrete
 Oil recovery
 Storage
 Oil transportation
 Mining

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Corrosion Inhibitors and its
Applications

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TYPES OF CORROSION INHIBITORS
• There are two main types:
• (i) Adsorption Inhibitors and (ii) Film forming Inhibitors
(i) Adsorption Inhibitors: These inhibitors form a chemisorption
bond with the metal surface to impede ongoing
electrochemical dissolution reactions.
• Most organic inhibitors are chemisorption type-inhibitors.

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TYPES OF CORROSION INHIBITORS
• (ii) Film-forming Inhibitors:
• There are two types of film forming inhibitors:
• (a) Passivating (b) Precipitating inhibitors.
 Passivating Inhibitors works by promoting the formation of
passive film on the surface. They maybe oxidizing or non-oxidizing
agents. Examples of oxidizing passivators are chromate and
nitrite. Ex. of non-oxidizing passivating inhibitors are benzoates
and phosphonates. The non-oxidizing passivators first adsorbed
on the metal surface before forming passive films. Note:
adsorption is also important with passivating inhibitors.
 Precipitating inhibitors: In this type of inhibitor, a precipitation
reaction between cations of the corroding metal and the inhibitor
deposits a 3D-barrier film on the metal surface. Phosphates and
silicates are typical examples.

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OTHER CLASSIFICATION
• Inhibitors can also be classified into Anodic,
Cathodic and Mixed Type depending on
which partial electrochemical reaction is
affected.
• Anodic: Example chromates
• Cathodic: Example Phosphates
• Mixed type inhibitors: Example organic
inhibitors like amines and imidazolines.

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Corrosion Inhibitors in Acidic solution
• Most of the known mechanisms of corrosion inhibitors evolved from
studies in acidic solutions.
• This is because the dissolution of air formed surface film allow focus on
direct interaction of inhibitor and clean metal surface.
• Mechanistic studies assumes deaerated solution and cathodic H2
evolution in acid medium. Oxygen cathodic reaction is not considered at
pH below 2-4.
• Some practical applications for corrosion inhibitors in acid environment
include: commercial pickling (cleaning) processes, storage and transport
of acids, in oil and gas production, pulp and paper industries, cleaning of
corroded metal artifacts.
• Corrosion inhibition in deaerated acidic solution finds application in the
inhibition of the propagation of localized corrosion processes such as
crevice corrosion, pitting corrosion and stress corrosion cracking where
the internal local electrolyte becomes both acidic and depleted in
oxygen.
• Most inhibitors chemisorb in acid medium which sometimes is
proceeded with physisorption.
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CHEMISORPTION OF CORROSION INHIBITORS
• Chemisorption involves an actual
charge transfer or charge sharing
between the inhibitor molecule and
the metal surface.
• The main characteristics of
chemisorbed inhibitors are high heat
of adsorption, persistence and
specificity.
• Chemisorbed inhibitors usually
contains N, S or O atoms. This atoms
donate electrons to the d-orbitals of
the metal atoms.
• The order of increasing inhibition is
shown.
• Direct evidence of chemisorption
have been gained through studies
such as FT-IR, XPS and radiotracer
measurements.

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EFFECT OF INHIBITOR CONCENTRATION
• Generally inhibition efficiency of an
inhibitor increase with
concentration.
• As a result, corrosion rate decreases.
• As concentration increases and
corrosion rate decreases, adsorption
of the inhibitor on the metal surface
increases till it reaches a maximum
where further increase in
concentration, decreases inhibition
efficiency.
• For chemisorption a monolayer is
formed at this maximum adsorption.

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CHEMICAL FACTORS IN THE EFFECTIVENESS
OF CHEMISORBED CORROSION INHIBITORS
• The three principal factors affecting the
effectiveness of a chemisorbed inhibitors
are:
The electron donor ability of the
inhibitors
The size of the molecule
Solubility.
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CHEMICAL FACTORS IN THE EFFECTIVENESS OF
CHEMISORBED CORROSION INHIBITORS
• The electron donor ability of the inhibitors
• The estimate of the ability of a molecule to act as electron donor is given by its base
strength.
• Stronger bases are better electron donors than are weak bases.
• Organic bases are protonated in acid medium:
• As the molecule approaches the metal surface it loses its proton so its lone pair of
electrons can interact with the metal surface. RNH2 + H+ →RNH3
• The base strength is usually given by Ka values:
• Ka = [RHN2][H+]/[RNH3+] or by pKa = log 1/Ka
• The greater the pKa values the greater is the base strength.
• A greater base strength in turn means a greater tendency for electron donation and
chemisorption.

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CHEMICAL FACTORS IN THE EFFECTIVENESS OF
CHEMISORBED CORROSION INHIBITORS
• The size of the molecule:
• In general the larger the molecular size, the better the inhibitor (other factors
being equal).
• However, with very large molecules such as polymers, there may be steric
hindrance problem when a large molecule attempt to fit onto a surface already
partially occupied with previously occupied molecules.
• Complete surface coverage by large molecules may sometimes be very difficult to
achieve.
• Solubility of the organic molecule:
• Less soluble molecule has a greater chance to be adsorbed than soluble
molecules.

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EFFECT OF WATER ON ADSORPTION OF
CORROSION INHIBITOR
• When a metal is immersed in an aqueous solution,
the metal surface becomes covered with water
molecules. In order to adsorbed onto the metal
surface, the organic molecule must first displace
these adsorbed water molecules.
• The adsorption of organic molecules from aqueous
solution is thus a replacement reaction:
• Org (soln) + nH2O(ads)→ Org(ads) + nH2O
• The overall free energy of the reaction
involved by organic and water molecules and
is given by ∆Gads = ∆Gadsorg - n∆GadsH2O
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COMPETITIVE VS CO-OPERATIVE ADSORPTION
• When the solution contains absorbable anions, such as Cl- and I-, organic
inhibitors must compete with these ions for sites on the metal surface.
• This process of competitive adsorption is shown below: In this type of
adsorption, the protonated inhibitor loses its associated proton on entering the
electrical double layer and chemisorbs by donating electron to the metal.
• The protonated inhibitor can electrostatically adsorb on the halide covered
surface through its hydrogen ions. This is called co-operative adsorption.

(a) Competitive and (b) co- Evidence of co-


operative adsorption operative adsorption
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THE POTENTIAL OF ZERO CHARGE (PZC)
• The metal side of the metal/solution interface
can have an excess od deficiencies of electrons.
• That means it can have a negative or a positive
charge.
• These can attract both positive or negative
charges to the metal surface.
• The electrode potential at which the metal
surface can have a zero charge is called the PZC.
• The closer a metal is to its PZC, the easier it is for
neutral organic compound to adsorb on to the
metal surface.
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THE POTENTIAL OF ZERO CHARGE (PZC)
• Above (more positive than)
the PZC the adsorption of
negatively charged ions is
favoured.
• Below (more negative
than) the PZC the
adsorption of positively
charged ions is favoured.

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EFFECT OF MOLECULAR STRUCTURE
• Molecular structure is important in determining
effectiveness of adsorption type inhibitor.
• This is because the molecular structure influences both the
electron donating and adsorption properties of the inhibitor.
• In general aliphatic amines are better corrosion inhibitors
than aromatic amines.
• Also heterocyclic amines are better corrosion inhibitors than
aromatic amines.
• Consider the molecules below (with similar area and
solubilities), the electron donating abilities (base strength)
and inhibition efficiency increases in the following order:

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EFFECT OF MOLECULAR STRUCTURE
• The electron donating groups like -CH3 will
increase electron density on the ring and
increase protection on metal surface.
• The substitution of -CH3 at Para-position has
more inductive effect than the substitution at
meta-position is more.
• Thus, the order of inhibition efficiencies for
methyl substituted pyridines are:

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Adsorption Isotherm
• Adsorption isotherm relates the concentration of the inhibitor in
solution to the amount of inhibitor taken up by the surface.
• The surface coverage of inhibitor is important for corrosion
inhibition effectiveness.
• There are several types of adsorption isotherm. But the two most
important ones frequently used for corrosion inhibition studies
are Langmuir and Temkin adsorption isotherms.
• Langmuir isotherm: Ɵ/1-Ɵ=KC, rearranging gives:
C/Ɵ =1/K+C; A plot of C/Ɵ vs C will produce a straight line with unit
slope if Langmuir isotherm is obeyed.
• Temkin isotherm : Ɵ =2.303RT/r log C +2.303RT/r logK`
Plot of Ɵ vs log C gives a linear portion. r is Temkin parameter and K`
is adsorption constant.

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Differences between Langmuir and
Temkin isotherms

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Corrosion Near Neutral Solution
• Corrosion in Acid solution differs from the
one in neutral solution (open to air) because
of two reasons:
In acid solution, the metal is oxide free but in
neutral solution, the surface is covered with
oxides.
In acid solution the main cathodic reaction is
hydrogen evolution while in air saturated
neutral solution it is oxygen reduction.

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Effect of Oxide Film on
Corrosion Inhibition.
• Corrosion Inhibitors can adsorbed strongly with a surface even if it
is oxide covered,
• For oxide covered surfaces, corrosion inhibitors in neutral media
must also compete with water molecules for adsorption sites just
like the case in acid media.
• The heat of adsorption in the next table are for near zero
coverages.
• The values are well within the range expected for chemisorption.
• The values also show strong adsorption of water molecules on
oxide surfaces.
• Oxidizing inhibitors, like chromate react with the oxide covered
surface and are incorporated into the passive film.
• Phosphates are incorporated into the passive film by exchange
with surface oxide or hydroxide ions.

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Heat of Adsorption for organic molecules on
metals, oxides or oxide covered surfaces.

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Chelating compounds as Corrosion Inhibitors.
• Chelating compounds are organic molecules with atleast two
polar functional groups capable of ring closure with a metal
cation.
• The functional groups may either be basic –NH2 which can
form bond by electron donor or acidic group –COOH, which
can coordinate with metal cations after the loss H+
• Example of chelates are EDTA, mercaptoacetic acid and 8-
hydroxyquinoline etc.
• Chelates may interact with metal ions which is in the oxide
film or they may react with metal cation which are first
produced by metallic dissolution.
• In the latter case, a complex of high molecular weight and
lower solubility is precipitated near the metal surface and a
barrier film is formed. 25
Surface Chelates Mechanisms

Sarcosine Type Surface Chelates-Mechanism of inhibition

Steric Effect in Surface Chelation


Rigid nature of phenanthroline
favours inhibition compared with
Flexible nature of bipyridine.

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Chromates and Chromate replacement
• Chromates (CrO42-) are excellent corrosion inhibitors when
added to aqueous solution.
• They are also used to treat metals to form corrosion-
resistant ‘conversion’ coating.
• However, Cr6+is a known carcinogen.
• This concern has led to increase interest in finding
replacement for chromates.
• However a lack of fundamental understanding of how
chromates are such excellent corrosion inhibitors has
complicated the search for its replacement.
• Some studies on chromate replacement include:
 Some compounds analogous to chromates such as
molybdates (MoO42-), tungstates (WO42-), vanadates (VO42-
or VO3-), Phosphates (PO42-), Cerium salts, natural products,
etc.
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New Approaches to Corrosion Inhibition

• The new approach in corrosion inhibition


studies is the search for cheap and
environmentally friendly molecules to
replace toxic ones.
• Two approaches common are:
Using biological molecules. Ex. Amino acids,
peptides, catechol, vitamins etc.
Use of nontoxic, biodegradable molecules.
Ex. Plant extracts.
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Example of Green corrosion Inhibitors

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Vapour Phase Corrosion Inhibitors
• These are inhibitors used to protect against atmospheric
corrosion in gaseous atmospheres that contains moisture or
other corrosive agents such as Cl-, SO2 and H2S.
• They can also be called Volatile corrosion Inhibitors (VCI)
• The inhibitors are applied in the vapour phase.
• They volatilize and adsorb on all surfaces located in an
enclosed space.
• They are used to protect metal surfaces in storage or
transport as well as to protect electronic materials such as
circuit boards.
• They can provide corrosion protections for months or years.
• They can be solid or liquids and are often volatile amines.
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Vapour Phase Corrosion Inhibitors
• Liquids VCIs can be impregnated in papers or
polymeric films while solids VCIs can be
contained in porous bags or sachets.
• Solid phase VCIs have vapour pressures in the
range of 10-4-10-6 mmHg (10-4-10-2 Pa).
• Two new research directions for VCIs:
 Fundamental understanding of VCI interaction
with metals using modern surface
characterization tools.
 Search for Environmentally friendly VCIs.

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EXAMPLES OF VCIs.

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