Corrosion Engineering

Corrosion Engineering
Lecture 9
CHE 311
Factors Affecting Corrosion
 Chemical Factors
 Physical Factors
 Metallurgical Factors
Factors Affecting Corrosion-Chemical
factors
Effect of pH
 The pH is a measure of acidity or
alkalinity of a solution. A low pH can
accelerate the corrosion, but a high pH
can cause scales deposits. These scales
may form protective film such as
carbonate and hydroxides if brines are
the solution. These scales may slow
down or prevent corrosion.
 The figure shows the effect of pH on the Effect of pH on the corrosion of iron exposed to aerated water
corrosion of iron exposed to aerated at room temperature.
water at room temperature.

factors
 pH < 4
 For pH values below 4.0, ferrous oxide
(FeO) is soluble. Thus, the oxide dissolves
as it is formed rather than depositing on
the metal surface to form a film.
 In the absence of the protective oxide
film, the metal surface is in direct
contact with the acid solution, and the
corrosion reaction proceeds at a greater
rate than it does at higher pH values.
 It is also observed that hydrogen is Effect of pH on the corrosion of iron exposed to aerated water
at room temperature.
produced in acid solutions below a pH of
4, indicating that the corrosion rate no
longer depends entirely on depolarization
by oxygen, but on a combination of the
two factors (hydrogen evolution and
oxygen depolarization).
factors
 4 < pH < 10
 In the range of pH 4 to pH 10, the
corrosion rate of iron is relatively
independent of the pH of the solution.
In this pH range, the corrosion rate is
governed largely by the rate at which
oxygen reacts with absorbed atomic
hydrogen, thereby depolarizing the
surface and allowing the reduction
reaction to continue. In the range of pH
Effect of pH on the corrosion of iron exposed to aerated water
4 to pH 10, the corrosion rate of iron is at room temperature.
relatively independent of the pH of the
solution.
factors
 pH > 10
 For pH values above about pH 10, the
corrosion rate is observed to fall as pH is
increased.
 This is believed to be due to an increase
in the rate of the reaction of oxygen
with Fe(OH)2 (hydrated FeO) in the
oxide layer to form the more protective
Fe2O3 (note that this effect is not
observed in de-aerated water at high
temperatures). Fig 1: Effect of pH on the corrosion of iron exposed to aerated
water at room temperature.
factors
Acids
 Acids are the substances releasing H+ cations in aqueous solutions. This small
particle H+ cannot exist alone without any electrons, and is immediately
captured by water molecule H2O forming H3O+ cation. For simplicity, we may
write H+ in chemical reactions, but should keep in mind that H3O+ takes part in
chemical reactions, not H+.
 The presence of inorganic acids (hydrochloric HCl, sulphuric H2SO4, nitric HNO3,
phosphoric H3PO4, boric H3BO3, etc.) and organic acids (formic HCOOH, acetic
CH3COOH, citric HOC(CH2COOH)2COOH, etc.) in aqueous solutions diminish their
pH (< 7).
factors
Acids
 One may ask if lead and iron corrode in acidic solutions, but we know that
sulphuric acid is stored in carbon steel tanks cladding with lead, and carbon steel
tanks are used for transportation and storage of concentrated sulphuric and nitric
acids. Why? Not only does the pH value influence the corrosion rate of metals.
Acid type (that is anion type in the acid) also influences the corrosion resistance
of metals (Figure 2). For instance, lead begins to corrode in sulphuric acid, but
corrosion stops after formation of non-soluble salt deposits (PbSO4) on lead
surface. This deposit which stops corrosion may be called a passive film, and
depends on the concentration of sulphuric acid. If the acid concentration is high
(above 80%) the lead sulphate salt PbSO4 forming on the lead surface will
dissolve in sulphuric acid with the formation of dissolved salt Pb(HSO4)2.
Therefore, lead is used for the protection of carbon steel from corrosion in
sulphuric acid at concentrations under 70%.
 Today lead is not used for this purpose because of its ecological and safety
problems.
factors
Acids
 Concentrated sulphuric (above 60%)
and nitric (above 40%) acids favor
the formation of passive iron oxide
layers on iron and carbon steel
surfaces. Such layers protect iron
alloys from corrosion in sulphuric
and nitric concentrated acids. Any
dilution of sulphuric and nitric acids
may cause the destruction of
passive iron oxides and give rise to
intensive corrosion of iron. Fig 2: Effect of type of acid and its concentration on the corrosion rate of iron
immersed in aqueous solutions of two inorganic acids at room temperature
Phosphoric acid (H3PO4) at low
concentrations (50 to 200 ppm) and
some organic acids inhibit corrosion
of iron and carbon steel in neutral
solutions of electrolytes.
factors
Alkalis
 Alkalis are substances releasing OH− anions in water. For example, caustic solutions
of sodium (NaOH) and potassium (KOH), ammonia (NH4OH), baking soda (NaHCO3),
and soda (Na2CO3) dissolved in water give OH− anions. The more alkaline a solution
is, the higher is its pH (> 7).
 Note that there are some substances without OH groups, but when dissolved in water
they are hydrolyzed and OH− anions are released. For example,
 Therefore, the aqueous solutions of such salts (for example, soda) are alkaline.
Other salts (CaCl2, MgCl2 and NH4Cl) dissolved in water are hydrolyzed and solutions
become acidic:
factors
 All metals may be divided into five groups according to their relationship
(corrosion resistance) to pH values (Figure):
Fig 3: Influence of pH on corrosion resistance of metals. K – Relative corrosion rate.

factors
 1. The pH value does not influence the corrosion resistance of gold (Au), silver
(Ag), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), mercury (Hg),
tantalum (Ta), niobium (Nb), osmium (Os) and iridium (Ir). They are
resistant at pH = 0 to 14.
 2. Iron (Fe), chromium (Cr) and manganese (Mn) corrode at a high rate in acidic
solutions (pH < 4) and in very strong alkaline solutions (pH > 13.5) at
temperatures above 80 C. They also corrode, but at a low rate at neutral pH (6
to 8), and are resistant at pH = 9 to 13.
 3. Magnesium (Mg), titanium (Ti), hafnium (Hf), vanadium (V) and bismuth (Bi)
corrode at a high rate at low pH (in acidic solutions) and are resistant to neutral
and alkaline solutions (high pH).
 4. Molybdenum (Mo), tungsten (W) and renium (Re) are resistant to acids and
neutral solutions, but corrode in alkaline solutions.
factors
 5. The last group is large:
 Beryllium (Be), aluminum (Al), copper (Cu), zinc (Zn), Cadmium (Cd), tin (Sn), lead (Pb),
cobalt (Co), nickel (Ni), zirconium (Zr), Gallium (Ga) and indium (In).
 They corrode both in acidic and alkaline solutions and, therefore, are called the
amphoteric metals (from the Greek word amphoteros – both – the ability of some
substances to manifest acidic or alkaline properties depending on conditions). These
metals are resistant only to neutral solutions.
 It is obvious that a region of pH where high resistance exists, is different for various
amphoteric metals.
 For Example:
 Aluminum is resistant at pH = 4.5 to 8.3,
 Zinc is resistant at pH = 6.5 to 12.
 Temperature and presence of various ions in a solution may drastically change the pH
region of high resistance of the amphoteric metals.
 Strictly speaking, iron and chromium also relate to the amphoteric metals, as they
dissolve at low and very high pH (above 13.5); the higher temperature, the lower the
pH value when iron dissolves in alkaline solutions.
factors
Influence of Dissolved Salts on Corrosion
 Dissolved salts have grate effect on the corrosivitiy of the environment. Dissolved
salts change the composition of the electrolyte, and its conductivity will change. An
electrolyte becomes more conductive when it has more ions dissolved in it. For
example, salt water is more conductive than distilled water. In, general the corrosion
rate of water will increase as the conductivity of the electrolyte increases. Dissolved
acid gases ( and ) also contribute to the conductivity of the electrolyte.
 The corrosion rate depends on the salt type and its concentration. We differentiate
four groups of salts according to their influence on the corrosion of metals.
Acidic and alkali salts.

 These salts are hydrolyzed with the formation of acids or alkalies, and thus cause a
decrease or increase in the pH of the solution.
factors
Acidic salts
 salts such as ferric chloride, cupric chloride and sodium hypchlorite are especially
corrosive to carbon steel.
 For example, if there is ferric chloride (FeCl3) in water, it hydrolyzes with the
formation of hydrochloric acid as a result, the pH of the aqueous solution containing
ferric chloride salt decreases to 1–2. Many salts similar to ferric chloride may
hydrolyze in water with a drastically decreased pH.
 For example: Calcium chloride (CaCl2), magnesium chloride (MgCl2), ammonium
chloride (NH4Cl), sodium dihydrophosphate (NaH2PO4), and aluminum sulphate
Al2(SO4)3. Other examples of acid salts are:
factors
Alkali salts
Alkaline salts hydrolyze to increase solution pH that may sometimes act as corrosion
inhibitors. Examples of these salts are trisodium phosphate (Na3PO4), sodium
tetraborate, sodium silicate, and sodium carbonate (Na2CO3). Examples
 Soda ash (Na2CO3) in water hydrolyzes with OH− formation, and the pH of such a
solution will increase to above 8. The following salts hydrolyze with increasing pH:
baking soda (NaHCO3), sodium phosphate (Na3PO4), disodium hydrophosphate
(Na2HPO4), potassium cyanide (KCN), and sodium silicate (Na2SiO3).
 Salts which form deposits on a metal’s surface and protect it: brown ferric
phosphate [Fe3(PO4)2], black ferrous carbonate (FeCO3) and black iron sulphide (FeS)
on iron alloys, green-blue patina [CuCO3·Cu(OH)2] and [CuSO4·Cu(OH)2] on copper
alloys, white aluminum hydroxide (AlOOH) on aluminum alloys, white mixed corrosion
product Zn(OH)2·ZnCO3 on zinc, and gray PbSO4 on lead.
factors
Neutral salts
 which added to water cause an increase
in the corrosion rate, But with further
addition, corrosion reaches its maximum
and then decreases (Figure 4). This
dependence requires an explanation.
Example: Sodium chloride, KCl, CaSO4.
Sodium chloride NaCl:
 The figure shows the effect of sodium
chloride concentration on the corrosion
rate of iron. This figure indicates that
oxygen solubility in water decreases
continuously with NaCl concentration, Fig 4: Effect of sodium chloride
concentration on corrosion of iron
explaining the falling of corrosion rate at
higher NaCl concentration.
factors
Neutral salts - Sodium chloride NaCl
 The Seawater corresponds roughly to 3% (0.5N) sodium chloride (NaCl), which is at the
peak of the curve in figure.
Fig 5: The influence of sodium chloride concentration in water on

the corrosion rate of carbon steel
factors
Neutral salts - Sodium chloride NaCl
 If there is no electron consumer O2, corrosion decreases and the corrosion rate of
carbon steel in a 26 wt% NaCl solution (the Dead Sea!) may even be less than that in
the distilled water. Therefore, you will not observe rusted steel equipment immersed
in the Dead Sea and you will not find fish there, as dissolved oxygen is absent because
of salting out.
 Then with an increase of salt concentration in water, the more prevailing factor is the
concentration of dissolved oxygen. Therefore, the dependence of “corrosion rate –
salt concentration” is described by the curve with a maximum (see Figure 5). This is
determined by the kind of salt (electrolyte) and temperature. It is good to know that
the maximum corrosion rate for carbon steel occurs in a 3 wt% NaCl solution. This is
the mean concentration of salts in seas and oceans. Therefore, many corrosion tests
are carried out in 3 wt% NaCl solution. This is correct only regarding iron and carbon
steel. For other metals and alloys, the maximum corrosion rate may be at another
salt.
factors
Influence of Dissolved gases on Corrosion
 Dissolved gases normally present in waters causes many corrosion problems.
 The common dissolve gases are:

 Dissolved oxygen.
 Carbon dioxide
 Hydrogen sulfide
 Ammonia
factors
Dissolved oxygen (O )
2
 The term “dissolved oxygen “refers only to the oxygen gas, which is dissolved in the
water and does not refer to combined oxygen present in the water molecule.
 At 60 F and atmospheric pressure the solubility of O in air-saturated water is
o
2
approximately 8 ppm. The environment contains dissolved oxygen is termed aerated

environment.
 Dissolved Oxygen may corrodes many metals. It can cause corrosion at concentration
as low as 50 ppb. Also a small amount of Oxygen can drastically increase the
corrosivity of water that contains CO and orH S . Unequal Oxygen concentration will
2 2
lead to differential aeration cells.

factors
 Two Cathodic Reactions
 1- In acid solution:
O2  4 H   4e   2 H 2O

 Hear oxygen act as cathodic depolarizer.
 2- In natural or alkaline solutions:

O2  2 H 2O  4e  4OH 
factors
 Oxygen attack is an electrochemical reaction:
 Anodic RX: Fe  Fe2   2e
1 / 2 O2  H 2O  2e   2OH 
 Cathodic RX:
 Overall RX: Fe  1 / 2 O2  H 2O  Fe(OH ) 2
 Dissolved oxygen must be reduced in any production system. Efficient mechanical de-
aeration followed by chemical scavenges (oxygen scavenges e.g. hydrazine) reduces
dissolved oxygen to less than PPB.
Example:
 Oxygen attack in boilers
 Oxygen in the feed water will inter the boiler. Much is flashed off with steam. The
reminder can attack boiler metal and result in rapid failure of feed water lines,
economizers, boiler tubes, and condensates lines.
factors
Carbon Dioxide (CO )
2
Carbon dioxide is a corrosive gas. It is very soluble in water. It reacts with water to form
carbonic acid according to the following reaction:
CO2  H 2O  H 2CO
  
carbonic acid
 This carbonic acid is a week acid, so it does not lower pH below 4.3. However this
level is low enough to cause significant corrosion of system metal.
 Carbon dioxide inters the system with air leaking or from decomposition of sodium
bicarbonate, and sodium carbonate.
factors
Carbon Dioxide (CO )
2
 The carbonic acid ionizes to form hydrogen ions and bicarbonate ions.
H 2CO3  H   HCO3
 The bicarbonate ions ionize farther to form hydrogen ions and carbonate ions:
HCO3  H   CO32 
 The pH decreases because water becomes more acidic as hydrogen ion concentration
increases.
 This reduction in pH is responsible for CO corrosion. Carbon dioxide corrosion is
sometimes called “ sweet corrosion “.
factors
Hydrogen Sulfide (H2S)
 Hydrogen sulfide also causes blistering of steel, sulfide stress creaking, hydrogen
embitterment, and hydrogen –induced cracking. Hydrogen sulfide corrosion is
sometimes called “sour” corrosion. The corrosion reaction of H2S, water, and iron are
complex, however, the general corrosion reaction can be shown as follows:
Fe2  H 2S  FeS   2H 2
Ferrous Hydrogen Iron Hydrogen
Ions sulfide sulfide
Factors Affecting Corrosion
Microorganisms and solid particle

 Biological organisms are present in almost all aqueous environment. Some of these
are large enough to observe with the naked eyes such as barnacles, mussels, and
clams. While others are microscopic hence the name Microorganisms which lead to
the localized corrosion termed “Microbiologically Influenced Corrosion (MIC)”
 Microorganisms are microbes; they are present in water, soil, oil and air.
 Microbes can be either plants (such as bacteria, algae, fungi… etc.) or animals. Plants
are most common.

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Corrosion Engineering - Lecture 9

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water at room temperature.

Fig 3: Influence of pH on corrosion resistance of metals. K – Relative corrosion rate.

Acidic and alkali salts.

Fig 5: The influence of sodium chloride concentration in water on

 The common dissolve gases are:

approximately 8 ppm. The environment contains dissolved oxygen is termed aerated

lead to differential aeration cells.

 2- In natural or alkaline solutions:

Microorganisms and solid particle

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