B. Jegdić et al.

Chemical corrosion of metals and alloys

BORE JEGDIĆ*, JOVAN POPIĆ, BILJANA BOBIĆ, Review paper

MAJA STEVANOVIĆ ISSN 0351-9465, E-ISSN 2466-2585
1
UDC: 620.193.4:669-4
University of Belgrade, Institute of chemistry, technology and doi:10.5937/ZasMat1602205J
metallurgy, Department of electrochemistry, Belgrade, Serbia

Zastita Materijala 57 (2)

205 – 211 (2016)

Chemical corrosion of metals and alloys

ABSTRACT
In this paper, phenomena of chemical corrosion of metals and alloys in electrolyte solutions are
analyzed. It is shown that iron, chromium and other metals and alloys dissolve much faster than is
the corrosion rate determined by electrochemical methods. This means that the chemical
dissolution takes place simultaneously with the electrochemical dissolution. The chemical
dissolution does not depend on electrode potential. Under some conditions, chemical dissolution
of metals is the dominant process of dissolution. Several mechanisms of chemical corrosion are
described. Also, the consequences of chemical dissolution of various metals and alloys are
discussed, as well as the hydrogen evolution during the chemical dissolution. The process of
hydrogen evolution during the chemical corrosion is not subjected to the laws of electrochemical
kinetics.
Keywords: corrosion, chemical dissolution, electrochemical dissolution, iron, chromium.

1. INTRODUCTION
Pražak has proposed the use of correction factors
It was observed that iron, chromium and other
metals in electrolyte solutions dissolve faster than for electrochemical corrosion rates. In addition, it
their dissolution rates determined by electro- has been observed that corrosion rates obtained by
chemical methods. This indicates that simultane- electrochemical methods at elevated temperatures
ously with the electrochemical dissolution the show a significant deviation in comparison to the
chemical dissolution takes place. Several electro- results of gravimetric or analytical methods.
chemical methods were developed to determine However, electrochemical methods for determining
the corrosion rate of metals. The extrapolation of corrosion rate are still widely used, often without
Tafel lines to the corrosion potential gives the verification of the results by direct methods as the
current density of anodic dissolution of metal, weight loss method, analytical methods, etc.
which is at the same time the corrosion current There are several mechanisms of chemical
density, jcorr. Besides the Tafel extrapolation corrosion, that explain why the flowed quantity of
method, polarization measurements at low polari- electricity during the anodic dissolution of metal is
zations (Stern-Geary's method [1]) and electro- less than the quantity of electricity which is
chemical impedance spectroscopy method [2] have calculated on the basis of mass loss, using the
been widely used in practice. Many commercially Faraday's law. These mechanisms also provide an
available devices for measuring corrosion rate of explanation why the effective valence is lower than
metals and alloys were made, based on these the expected valence. The following chemical
methods. corrosion mechanisms are usually considered:
Pražak [3] has noted that in many cases values  forming metal ions of lower valence,
of corrosion rate obtained by gravimetric or analy-  mechanism of disintegration of the metal
tical methods are higher than those obtained by the surface,
polarization resistance method. For these reasons,
 mechanism by surface film control,
 mechanism of direct chemical dissolution.
*Corresponding author: Bore Jegdić
E-mail: [email protected] 2. MECHANISMS OF CHEMICAL DISSOLUTION
Paper received 25. 12. 2015.
Paper accepted 21. 01 .2016. 2.1. Forming metal ions of lower valence
Paper is available on the website: When the metal, which dissolves, forms the
www.idk.org.rs/journal ions with the valence greater than one, it can be

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B. Jegdić et al. Chemical corrosion of metals and alloys

assumed that the electrochemical reaction takes metal surface, can explain the anomalous anodic
place gradually, probably via several one-electron behaviour of metals, which is manifested by
reaction steps [4]. It was observed that during reduced current efficiency and negative differential
dissolution several metals pass through the step of effect. This behaviour has been often noticed
+
monovalent ions, in the form of Me (e.g. Cu, Zn, during dissolution of magnesium, zinc and
etc. [5,6]) or in the form of MeOH (e.g., Fe and so aluminium.
on [7]). There are different versions of this mechanism,
Ions of low valence can diffuse into the most of which are based on the fact that these
electrolyte, if they are not adsorbed on the metals are covered with a passive film. The
electrode surface. This was experimentally demon- passive film is destroyed during the anodic
+
strated by Hadži Jordanov and Dražić [8] for Zn dissolution, and then it is restored. Depending on
ions. In such cases, diffusion rate of ions with a low the composition of the solution (e.g. in the
-
valence from the electrode into the solution presence of Cl ion) the properties of the passive
depends on hydrodynamic conditions. Thus, the film change which leads to the occurrence of pits
apparently low valence depends on the on the metal surface. The negative differential
hydrodynamic conditions in the vicinity of the effect is manifested as increased hydrogen
electrode surface. However, if the intermediates of evolution with the increase in anodic current
low valence are strongly adsorbed on the electrode density. Hydrogen evolution during the anodic
surface, their diffusion in the solution cannot be polarization of Al is usually explained by the
+
expected, and therefore the reduction of the formation of Al ions and their reaction with water
apparent valence cannot be also expected. molecules, according to the following equation:
2.2. Mechanism of disintegration of metal surface
+
Al + 2H2O  Al3+ + H2 + 2OH- (1)
Mechanical disintegration of the metal surface Hydrogen evolution was also observed during
was suggested to explain the observed increase in the occurrence of stress corrosion cracking and
the concentration of metal ions in the solution, corrosion fatigue of austenitic and martensitic
above the expected concentrations. Straumanis [9] stainless steels, at anodic polarizations [12].
has analyzed the anomalous dissolution of zinc
and aluminium and concluded that the mechanical 2.4. Mechanism of direct chemical dissolution
disintegration of the investigated metals (chunk In the period from 1965. to 1980. Kolotyrkin
effect) was responsible for the low apparent and co-workers have published a number of papers
valence. According to the proposed mechanism of in which they gave experimental verification of
mechanical disintegration, the separation of atom anomalous dissolution of metals during corrosion
groups from the surface takes place during the and cathodic polarization of the metals. Metal is
dissolution of those metals. These groups of atoms cathodically polarized to different values of
are weakly bound to the surface and can be cathodic polarization over a long period of time to
transported as metal particles into the solution. If allow accumulation of the corresponding ions in the
the electrolyte is aggressive enough, e.g. the solution to a concentration high enough that its
solution of sulphuric or hydrochloric acid, the value can be determined by analytical methods.
spontaneous corrosion of the particles can be For a large number of metals it was found that total
expected in these solutions. This results with dissolution of the metals was much greater than
accumulation of metal ions in the solution in an the expected, and that the process of dissolution
amount greater than that which corresponds to the was independent on electrode potential. The
flowed quantity of electricity. Also, the hydrogen anomalous dissolution was observed in Fe, Mn,
evolution reaction takes place. Accordingly, the Co, Cr, Be, stainless steels and other metals
experimentally obtained apparent valence is lower [11,13-15].
than the expected valence. Marsh and Schaschl Figure 1 shows a polarisation diagram for
[10] have shown that iron in the sulphuric acid dissolution of several metals, which is obtained on
solution (pH 2) corrodes twice as fast due to the the basis of the metal ions concentration
mechanical disintegration (chunk effect) than it was determined by appropriate analytical methods.
expected according to the results of electro- Anodic polarization curves deviate from the linear
chemical measurements. Vorkapić and Dražić [11] Tafel behaviour on negative potentials and become
have shown that the anomalous dissolution of iron vertical, i.e. the dissolution becomes independent
in sulphuric acid during prolonged cathodic on electrode potential. In contrast to other metals,
polarization was partly caused by the mechanical the anomalous dissolution of iron depends on the
disintegration of iron. +
pH, i.e. H ions accelerate the dissolution. The
2.3. Mechanism by surface film control overall reaction of chemical dissolution for all
metals can be written as:
The mechanism of chemical dissolution, which
is controlled by the presence of protective film on M + nH2O  Mn+ + nOH- + n/2 H2 (2)

206 ZASTITA MATERIJALA 57 (2016) broj 2

B. Jegdić et al. Chemical corrosion of metals and alloys

A more complex mechanism, which is pH reactions 2 or by reactions 3-5, the total current
dependent, was proposed for Fe and Cr: density for the hydrogen evolution in dependence
M + H2O MOH + H (3) on electrode potential is the sum of the partial
cathodic current density and the appropriate
MOH + H  MOH + H
++
(4) current density for the chemical reaction (vertical
2 H  H2 (5) line C1 in Figure 2a and C2 in Figure 2b).

Figure 1 - Chemical dissolution rate dependence

on electrode potential for: (1) iron in 0.05 M H2SO4
o o
at 50 C, (2) chromium in 0.05 M H2SO4 at 50 C,
o
(3) nickel in 0.05 M H2SO4 at 50 C, (4) aluminium
o
in 0.05 M H2SO4 + 0.1 M NaCl at 25 C, (5) zinc in
o
0.05 M H2SO4 + 0.25 M Na2SO4 at 25 C, and (6)
o
manganese in 0.05 M H2SO4 at 25 C.
Reprinted with permission of Serbian Chemical
Society, Ref. [16].
According to the Kolotyrkin`s opinion, chemical
dissolution of metals, which occurs in accordance
with the reaction 2, or reaction 3-5, is independent
on electrode potential, so that the chemical
dissolution reactions are presented by vertical lines Figure 2 - Schematic presentation of rate of corrosion
in the electrochemical diagram of Wagner-Traud's processes in dependence on electrode potential. C-
type, as shown in Figure 2. Position of these lines Tafel line for cathodic hydrogen evolution, A-Tafel line
is determined by the chemical reaction of metals for anodic dissolution of metal. a) C1-chemical
with water and depends on the kind of metal, dissolution of metal with low specific rate; C2-
temperature and pH (pH-dependent reactions). chemical dissolution of metal with high specific rate.
As can be seen in Figure 2a, when the rate of The total rate is always the sum of all partial
chemical dissolution is not much higher than the processes (solid lines).
rate of electrochemical corrosion, the deviation Reprinted with permission of Serbian Chemical
from the straight line for the partial anodic current Society, Ref. [16].
density can be observed only in the region of The most important experimental results for
cathodic polarizations (vertical line C1). In the case iron, presented in the paper [17], are as follows: in
when the rate of chemical dissolution is much the region of anodic potentials the total partial
larger than the rate of electrochemical corrosion, current of hydrogen evolution deviates from Tafel
the deviation from the straight line of the partial behaviour and passes into the approximately
anodic current density can be observed far before vertical line, similar to that for the case of chemical
the corrosion potential, i.e. in the region of the real dissolution of Kolotyrkin`s type (Figure 2a). Results
anodic polarization (vertical line C2 in Figure 2b). for the anomalous hydrogen evolution are in
Previous diagrams can also be analyzed from accordance with the Kolotyrkin`s results. Also, it
the standpoint of the electrochemical reaction of was shown that the anomalous hydrogen evolution
cathodic hydrogen evolution. Considering that the was independent on the solution pH, in the range
0.5 to 3, which is in contrast to the results of
molecular hydrogen is formed by chemical

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B. Jegdić et al. Chemical corrosion of metals and alloys

Kolotyrkin and Florijanovich [15]. The results in the Dissolution of chromium occurs if its surface is
paper [17] confirm the Kolotyrkin`s model, accor- activated, e.g. by polarization with the cathodic
-2
ding to which the anomalous dissolution and hydro- current density of ~ 50 mA cm , for a few tens of
gen evolution on iron occur by the chemical seconds. In this way, the thin oxide film on
mechanism (Equation 6), simultaneously with the chromium surface is reduced, which was formed
electrochemical process: spontaneously in air. Corrosion potential of non-
Fe + 2 H2O → Fe
2+ -
+ H2 + 2 OH (6) activated surface of chromium is much more
Electronic equilibrium between the metal and positive (-0.4 V vs. SCE) than the corrosion
the solution is established when electrochemical potential of the activated surface.
partial processes occur at the same rate, i.e. at the Heumann and Diekotter [23], Wilde and Hodge
corrosion potential, regardless to the progress of a [24], Sukhotin and Khoreva [25] and Popić and
chemical reaction (Equation 6). The chemical reac- Dražić [19-21] have observed that two stable
tion does not involve the exchange of electrons. corrosion potentials are established on chromium
Thus, the corrosion potential for iron (and other in deaerated sulphuric acid solution. First corrosion
metals that chemically corrode) is determined only potential is established for the reaction of hydrogen
by the electrochemical reactions, and chemical evolution on the passive surface of chromium and
corrosion processes have no effect on it. the reaction of anodic dissolution of chromium
The results of Popić and Dražić on the metallic through the passive film. The other corrosion
chromium [18-22] are important for the explanation potential is established for the reaction of hydrogen
of the role of chemical reactions during corrosion of evolution on the activated, clean surface of
metals. Polarization measurements, analytical de- chromium and the reaction of active anodic
2+ 3+
termination of the concentration of Cr and Cr dissolution of chromium.
ions by atomic absorption spectroscopy AAS, the
Figure 3 shows also the results obtained by
volume determination of the hydrogen evolved and
volumetric measurements of the total volume of
gravimetric determination of mass loss of metals
hydrogen evolved. The volume of hydrogen
(chromium), were applied to study the anomalous
dissolution of chromium. evolved is converted into an equivalent current
density. In the cathodic region the total hydrogen
The most important results are shown in Figure
evolution (dashed line in Figure 3) is significantly
3 [22]. Anodic and cathodic Tafel slopes are
-1 greater than the electrochemical hydrogen evo-
approximately 120 mV dec with a narrow linear
region of electrode potential before passivation. Si- lution. It is also the case in the vicinity of the
milar polarisation diagrams for pH 2 and pH 3 have corrosion potential and in the region of anodic
shown that the cathodic hydrogen evolution is pH polarizations. In the region of passivation poten-
+
dependent, with the reaction order ~ 1, for H ions. tials, hydrogen evolution is significantly reduced.
Electrochemical anodic chromium dissolution is All three applied methods (volumetric, AAS and
independent on pH. measurement of mass loss) gave approximately
the same result for the chemical dissolution of
chromium, thus confirming the Kolotyrkin`s view
about chemical corrosion.
Based on the papers [19-21] the following
mechanism of chemical dissolution of chromium in
acidic solutions has been proposed:
Cr + H2O  CrOHads + H (7)
CrOHads + H3O  CrOH + H + H2O
+ +
(8)
CrOH + H3O  Cr + H2O
+ + 2+
(9)
This mechanism is similar to the mechanism of
chemical dissolution for iron which was proposed
by Kolotyrkin [15]. It should be noted that the
reaction of chemical dissolution of chromium takes
Figure 3 - Polarisation curves for Cr in 0.1 M place only on a clean metal surface. The formation
Na2SO4 + H2SO4, pH 1. Hydrogen detected on Pt of passive film inhibits this reaction, since water
ring, or volumetrically (- - -). Calculated rates of molecules cannot come into the contact with the
chemical dissolution based on (■) analytical data, metal atoms.
(●) volumetrical measurements, and (▲) In addition, it has been found that the
gravimetrical measurements. temperature influences the reaction of chemical
Reprinted with permission of Serbian Chemical dissolution of chromium more significantly than the
Society, Ref. [22]. reaction of electrochemical corrosion of chromium.

208 ZASTITA MATERIJALA 57 (2016) broj 2

B. Jegdić et al. Chemical corrosion of metals and alloys

In the paper [19] it is shown that the apparent

activation energy of chemical dissolution of
-1 -1
chromium is 63.1 kJ mol , 66.9 kJ mol for the
electrochemical reaction of anodic dissolution of
-1
chromium and 19.5 kJ mol for the electrochemical
reaction of hydrogen evolution. In accordance with
the Arrhenius equation, the rate of the process with
a higher activation energy increases more at
elevated temperatures, than the rate of the process
with a lower activation energy, as shown in Figure
4.

Figure 5 - Time dependence of total current density

of chromium dissolution and current density of
chromium electrochemical corrosion, at 333 K. The
total current density of chromium dissolution was
determined by AAS. The current density of
chromium electrochemical corrosion is determined
by Stern-Geary method.
Reprinted with permission of Serbian Chemical
Society, Ref. [26].

Figure 4 - Corrosion current density for chromium,

obtained gravimetrically (□), analytically (Δ), or
electrochemically (o) at different temperatures.
Reprinted with permission of Serbian Chemical
Society, Ref. [19].
The rate of chemical dissolution of chromium is
the difference between the total rate and the rate of
electrochemical dissolution. As can be seen in Figure 6 - pH dependence of chemical dissolution
Figure 4, the current density of chromium chemical rate for chromium.
dissolution increases more rapidly with the (Reprinted with permission of Serbian Chemical
increase in temperature than the current density of Society, Ref. [22])
electrochemical dissolution. Greater influence of The influence of texture of the metallic chro-
temperature on the rate of chemical dissolution mium and texture of the electrolytically deposited
than on the rate of electrochemical dissolution is chromium coating on the rate of chemical or
due to the differences in values of activation electrochemical dissolution is discussed in [27]. It
energies, as previously noted. was demonstrated that chromium with the texture
Figure 5 shows the time dependence of the (110) dissolves more slowly than chromium with
total dissolution current of chromium and the the texture (111). Mechanisms of hydrogen evolu-
current of electrochemical corrosion of chromium, tion on chromium during chemical and electro-
at 333 K [26]. chemical corrosion are presented in detail in [28].
The nature of corrosion potentials formed on the
The rate of chemical dissolution of chromium is chromium, and chromium-nickel stainless steels is
pH dependent, as shown in Figure 6. This suggests discussed in detail [29-31]. Chromium in deaerated
that the hydrogen ions are involved in the aqueous solutions of H2SO4, with and without
chromium chemical dissolution. NaCl, shows two stable corrosion potentials. One

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B. Jegdić et al. Chemical corrosion of metals and alloys

corrosion potential is formed on the passivated ments hydrogen evolves, whereby hydrogen
chromium surface, and the second corrosion po- evolution also is not dependent on electrode
tential is formed on the clean surface of chromium, potential, i.e. it is not subjected to the laws of
without passive film. On Cr-Ni stainless steels only electrochemical kinetics.
one corrosion potential is established [29-31]. Several mechanisms of chemical corrosion of
metals are described, such as: formation of metal
3. CONSEQUENCES OF CHEMICAL ions of lower valence, mechanism of disintegration
DISSOLUTION of metal surface, mechanism of control by surface
The consequences of chemical dissolution of film and mechanism of direct chemical dissolution.
chromium were observed in different cases. These mechanisms explain why, in chemical
The aqueous solution for electrodeposition of dissolution of metals, the measured quantity of
-3 electricity during dissolution of metal is less than
chromium contains CrO3 (up to 600 g dm ) and
-3 the quantity of electricity which is calculated by the
H2SO4 (up to 6 g dm ). The current efficiency for
deposition of chromium is 13 to 15 %. Low current mass loss method. The mechanism of direct
efficiency is usually explained by the fact that the chemical dissolution and a large number of
rate of electrochemical hydrogen evolution on the influencing factors (temperature, pH value, etc.)
chromium is 3 to 4 times greater than the rate of were discussed in more detail.
chromium precipitation. However, according to Acknowledgement
Dražić [32], this effect is the result of high rate of
chromium chemical dissolution, which takes place This work was co-financed from the Ministry of
simultaneously with the chromium cathodic Education, Science and Technological Develop-
deposition. Net deposition of chromium is achieved ment of the Republic of Serbia through projects III
when the equilibrium is established between the 45019 and TR 35021.
rate of chromium chemical dissolution and the rate
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Phys. Chem., 63 (7), 671-680.

IZVOD
HEMIJSKA KOROZIJA METALA I LEGURA
U ovom preglednom radu analizirana je hemijska korozija metala i legura u rastvorima elektrolita.
Pokazano je da se gvožđe, hrom i neki drugi metali i legure rastvaraju mnogo brže nego što je
njihova brzina korozije određena elektrohemijskim metodama. To znači da se istovremeno sa
elektrohemijskim rastvaranjem odvija i hemijsko rastvaranje, koje ne zavisi od potencijala. U
nekim uslovima hemijsko rastvaranje metala je dominantan proces rastvaranja. Opisano je više
mehanizama hemijske korozije. Takođe, razmatrane su posledice hemijskog rastvaranja različitih
metala i legura, kao i pojava izdvajanja vodonika pri hemijskom rastvaranju. Proces izdvajanja
vodonika pri hemijskoj koroziji ne podleže zakonitostima elektrohemijske kinetike.
Ključne reči: korozija, hemijsko rastvaranje, elektrohemijsko rastvaranje, gvožđe, hrom.

Pregledni rad
Rad primljen: 25. 12. 2015.
Rad prihvaćen: 21. 01. 2016.
Rad je dostupan na sajtu: www.idk.org.rs/casopis

ZASTITA MATERIJALA 57 (2016) broj 2 211