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Role of hydrazine/reducing agent to

develop the magnetite protective layer
in boiler?
Published on February 27, 2017

Nikhilesh Mukherjee Follow

31 6 12
Author and Consultant

Electrochemical corrosion of iron

It is the general tendency of metals to become oxidized again, through loss of electrons.
When metal loses electrons or oxidized, it also loses metal, M ---- > M++ + e. This
oxidizing tendency of a metal is the driving force for corrosion. Corrosion is a redox
reaction. Corrosion occurs at the anode, where metal oxidizes and dissolves. At cathode
, reduction takes place. An electrical potential difference exists between anode and
cathode .Current flows [ electron] through the metal from the anode to the cathode.

Reaction at anode

For steel, the typical anodic oxidation reaction is: Iron is oxidizing to Fe++ , ferrous ion
at anode, Fe = Fe2+ + 2e
Reaction at cathode

O2 gets reduced to OH- ions at cathode, O2 + H2O + 2e = 2OH, Fe++ ions are
combining with OH- ions to form Fe(OH)2, ferrous hydroxide, Fe2+ + 2OH =
Fe(OH)2. The ferrous hydroxide then combines with oxygen and water to produce ferric
hydroxide, Fe(OH)3, 4 Fe(OH)2 + O2 + 2 H2O --> 4 Fe(OH)3. Ferrric
hydroxide dehydrates to rust, Fe2O3, Fe(OH)3 FeO(OH) + H2O . FeO(OH)
Fe2O3 + H2O. Rust consists of hydrated iron(III) oxide, Fe2O3nH2O and iron ( III)
oxide hydroxide ,(FeO(OH), Fe(OH)3).

What is magnetite layer in boiler?

Magnetite is an iron oxide, [Fe3O4]. It deposits in the form of thin layer on boiler steel
surface and passivates the surface and thus protects the surface from corrosion.

Iron has a number of different oxides depending on the amount of Oxygen present.
Magnetite with low oxygen content is very stable and stubborn and provides a good
protective barrier. Hematite, [ Fe2O3] which is another very common iron oxide form
on steel has a higher oxide content and tends to be porous and less stable and therefore
not a desirable oxide layer on steel surface.

While, both magnetite (Fe3O4) & hematite (Fe2O3) are iron oxides, the oxidation state
of iron (Fe) is not the same for both oxides. Hematite contains only the 3+ type of Fe.
Magnetite in contrast contains both 2+ and 3+ Fe.

How magnetite forms?

This is often achieved by using a boiler water treatment programme.

Magnetite forms on boiler system metal surfaces from the following overall reaction:

3Fe + 4H2O = Fe3O4 [magnetite] + 4H2

This reaction requires oxygen-free atmosphere and alkaline boiler water [pH 9.0-9.3] to
convert iron to magnetite, Fe3O4. Unless the atmosphere is reducing, magnetite
(Fe3O4) is not stable under oxidizing conditions and it will be oxidized to -Fe2O3.

Magnetite can convert to hematite in presence of excess oxygen

4Fe3O4 + O2 ------- > 6Fe2O3

Role of hydrazine/ reducing agent

To maintain a reducing atmosphere and alkaline pH we use ammonia [NH4OH] and

hydrazine [N2H4] which is a strong reducing agent. Hydrazine removes oxygen from
the system, N2H4 (aq)+ O2 (g) ----> N2 (g) + 2H2O (l).

In addition, hydrazine in presence of ammonia can also assist formation of magnetite

In reaction system containing NH4OH and N2H4, there are two processes forming
magnetite. In the first process: NH4OH < = > NH4+ +OH-

Fe2+ + 2Fe3+ +8OH- ---------- > Fe3O4 + 4H2O

In the second process, hydrazine acting as an oxidant can form [NH3OH]+; the
[NH3OH]+ cations can also react with Fe2+ to form Fe3O4:

3Fe2+ + [NH3OH]+ +6OH- --------- > Fe3O4 + NH4- + 3H2O In the same time, by
these reactions, the hydrazine eliminates oxygen from the system, protecting Fe2+ ions.

Hydrazine also reacts with the hematite (Fe2O3) layer on the boiler tubes if it has
formed and forms magnetite.

N2H4 + 6Fe2O3 -- > 4Fe3O4 + N2 + 2H2O, Its a redox reaction

Both magnetite (Fe3O4) & hematite (Fe2O3) are iron oxides. However, the oxidation
state of iron (Fe) is not the same for both oxides. Hematite contains only the 3+ type of
Fe. Magnetite in contrast contains both 2+ and 3+ Fe.

Under properly-managed OT or AVT(O) programs, magnetite becomes interspersed and

covered with a layer of ferric oxide hydrate (FeOOH). This modified iron oxide forms a
much tighter layer than magnetite. Keys to these programs are the correct oxygen
concentrations and very high-purity water. If contaminants, say from a condenser tube
 leak, enter the condensate, serious problems will be the result.

Nikhilesh Mukherjee
Author and Consultant Follow
62 articles

6 comments Newest

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maklub mostofa 2w
Maritime Professional
Dear sir,good day. I am a sailor. I have little confusion about the protection layer. Is it possible to form
hydrogen layer at the cathode? As some books hints about polarising hydogen layer.
Like Reply 2

Nikhilesh Mukherjee 2w
Author and Consultant
Pl ref to this reference, https://en.wikipedia.org/wiki/Rust
Like Reply

Nikhilesh Mukherjee 2w
Author and Consultant
In acidic pH, H+ ions are produced at cathode.
Like Reply

RENIL K.G 2mo

CEO at ACQUASOLUTIONS LLC
Like it Sir....
Like Reply

There are 4 other comments. Show more.

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