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In fact, the economic impact of corrosion is much bigger than many realize. According to a 2001
report by CC Technologies Laboratories Inc., the cost of corrosion within the U.S. alone was $276
billion annually. Of this, $121 billion was spent to manage corrosion, while the remaining $155 billion
was incurred as a net loss to the economy. Utilities, particularly water and sewer systems, suffer the
biggest economic impact, with motorized vehicles and transportation coming a close second.
Because metallic corrosion is an ongoing electrochemical process, it's crucial to know the essential
nature of electrochemical reactions to properly inhibit corrosion and reduce its impact on structures.
In this article, we'll discuss the mechanisms of corrosion by covering the details of:
Electrochemical reactions
The Daniell cell
The anodic method
Faraday's law
The cathodic method
Surface area impact
Electrochemical Reactions
An electrochemical reaction is outlined as a reaction involving the transfer of electrons. It's also a
reaction that involves oxidation and reduction. The very fact that corrosion consists of a minimum of
one chemical reaction and one reduction reaction isn't entirely obvious because both reactions are
usually combined in one piece of metal (e.g. Zn), as illustrated schematically below.
Figure 1: Electrochemical reactions during the corrosion of Zn in air-free HCL.
In Figure 1, a bit of Zinc immersed in acid solution is undergoing corrosion. At some point on the
surface, Zn is transformed to Zn ions losing electrons. These electrons go through the solid
conducting metal to alternative sites on the metal surface, wherever hydrogen (H) ions are reduced
to hydrogen gas consistent with the following equation:
Therefore, in electrochemistry, anodic and cathodic reactions are occurring simultaneously and at
equivalent rates. However, corrosion happens solely in the areas that function as anodes.
The difference in corrosion potential between the two metals will usually cause a scenario that's
referred to as galvanic corrosion, which was named in honor of its discoverer, Luigi Galvani.
This situation is common in natural corrosion cells wherever the setting is the electrolyte that
completes the corrosion cell. The conduction of a liquid atmosphere like soil, concrete, or water has
usually been associated with its corrosivity.
The short-hand description within the following equation is valid for each Daniell cell configuration.
This equation identifies the zinc electrode as the anode because it is negative in the case of a
spontaneous reaction, while the copper electrode is the cathode due to its positive charge.
We can write the general anodic reaction occurring throughout corrosion by examining the above
equations as:
That is, the corrosion of metal "M" leads to the chemical reaction of metal "M" to an ion with a
valence charge of n+ and therefore the release of "n" electrons. The worth of n, of course, depends
totally on the character of the metal. Some metals, like silver, are univalent, whereas multivalent
iron, titanium, and uranium possess positive charges as high as +6. This equation is a general one
and it applies to any and all corrosion reactions.
According to Faraday’s law, the reaction with one mole of silver would need one mole of electrons,
or one Avogadro's number of electrons (6.022 x 1023). The charge carried by one mole of electrons
is known as one Faraday (F). One Faraday equals 96,485 C/(mole of electrons). Uniting Faraday’s
main beliefs with specific electrochemical reactions of acknowledged stoichiometry gives us the
following equation:
The change in the concentration of H ions, or the increase in hydroxyl (OH) ions, may be shown by
testing pH levels to find surfaces on which cathodic reactions are taking place. There can be many
cathodic reactions encountered throughout the corrosion process. They include the following:
Oxygen Reduction
Oxygen reduction is a common cathodic reaction because oxygen exists within the atmosphere
and in solutions exposed to the environment. Although not frequent, metal ionreduction and metal
deposition will cause severe corrosion problems, for instance: the plating of copper ions, which are
created upstream in a water circuit, on the inner aluminum surface of a radiator. Therefore, the use
of a copper conduit in a water-based circuit where aluminum is also present should generally be
avoided.
All corrosion reactions are merely combinations of one or many of the above cathodic reactions in
conjunction with an anodic reaction. Thus, each case of liquid corrosion may be reduced to those
equations in most cases, either on an individual basis or in combination. Take into account the
corrosion of Zn (zinc) by water or wet air. By multiplying the Zn oxidization reaction by 2 and
summing this with the oxygen reduction reaction, one obtains the following equation:
The products of this reaction are Zn2+ and OH-, which at once react to make insoluble Zn(OH)2.
Likewise, the corrosion of Zn by copper sulfate represented within the following equation is simply
the summation of the oxidization reaction for Zn and the metal deposition reaction involving copper
(II) ions:
During corrosion, more than one oxidation and one reduction reaction might take place. In the
corrosion of Zn in a concentrated HCL solution containing dissolved oxygen, for example, two
cathodic reactions are possible. One is an evolution of H, while the other is the reduction of oxygen.
Because there are two cathodic reactions or methods that consume electrons, the general corrosion
rate of zinc is overstated. Thus, it is typically more corrosive than air-free acids, and removing
oxygen from acid solutions can typically make these solutions less corrosive. This is a typical
method for reducing corrosivity in many settings. Oxygen can be removed by either chemical or
mechanical means.
By taking the relative anodic (Sa) and cathodic (Sc) surface areas (and their associated current
densities ia and ic expressed in units of mA/cm2), this equation can be expressed in terms of
current densities.
The importance of the surface area ratio (Sc/Sa) of the above equation is notably vital when it comes
to several varieties of localized corrosion, such as pitting and stress-corrosion cracking. It has great
implications for the occurrence of corrosion in dissimilar metals as well.
It is simple to know that the result of a particular quantity of anodic current focused on a small area
of a metal surface will be much bigger than when the same quantity of current is dissipated over a
much larger area. This is an important amplifying issue of the anodic current when Sc/Sa is greater
than one and a stifling factor when it is less than one.
The cause of current density may be seen when two dissimilar metals are joined (here it's Cu and
Fe), which are shown diagrammatically in Figure 3 below.
Figure 3: The areas affected by dissimilar metals, where "a" shows rivets of steel on copper
plates, while "b" shows rivets of copper on steel plates.
When steel rivets are part of copper plates, the corrosion of the cathodic copper plates will be low,
while the corrosion of the small anodal steel rivets will be high. On the other hand, if copper rivets
are joining steel plates, corrosion on the copper will be high, while corrosion of the steel plates will
hardly be noticeable.
Corrosion Prevention
In this article, we examined corrosion as an electrochemical phenomenon by which
materials/structures are deteriorated.Electrochemical reactions of corrosion are discussed in detail
with the help of the Daniell cell, the anodic method, the cathodic method, Faraday's laws, and
surface area effects. Because we can prevent corrosion if we thoroughly understand the
electrochemistry of corrosion, manufacturers and users of corrosion products should be attentive to
the electrochemical mechanisms behind corrosion.
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Tags: Chemical Corrosion Prevention
Related Terms: Electrochemical Reaction Faraday's Law Anode Cathode Oxidation Reduction Galvanic
Corrosion Surface Area Impact
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Md. Ohiduzzaman
Md. Ohiduzzaman is a freelance writer and researcher. He holds master of science degree in
applied chemistry and chemical technology as well as master's degree in development studies. He
started his career in a pharmaceutical company than worked for a legislative institution. He has more
than 16 years of work experience in legislative institutions, three years of which he spent in project
management. During his professional work, he helped lawmakers in policy making and overseeing in
the field of ICT, science technology, industries and forest environments.
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