Corrosion Behaviour of Carbon Steel in

Wet and Dry Chlorine

GEST 10/362
Edition 2
January 2013

EURO CHLOR PUBLICATION

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E-mail: eurochlor@cefic.be Internet: http://www.eurochlor.org
 GEST 10/362
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RESPONSIBLE CARE IN ACTION

Chlorine is essential in the chemical industry and consequently there is a need

for chlorine to be produced, stored, transported and used. The chlorine industry
has co-operated over many years to ensure the well-being of its employees, local
communities and the wider environment. This document is one in a series which
the European producers, acting through Euro Chlor, have drawn up to promote
continuous improvement in the general standards of health, safety and the
environment associated with chlorine manufacture in the spirit of Responsible
Care.
The voluntary recommendations, techniques and standards presented in these
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be modified in the future to incorporate evolution of these and other factors.
This edition of the document has been drawn up by the GEST (Storage, Transport
and Safety Working Group) to whom all suggestions concerning possible revision
should be addressed through the offices of Euro Chlor.

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MAIN MODIFICATIONS IN THIS EDITION

Section Nature
3.2 Addition of precautions linked to possible dissolution of
protective ferric chloride layer by condensation of gaseous
chlorine

TABLE OF CONTENTS
1. INTRODUCTION 5
2. IRON CORROSION DUE TO PRESENCE OF MOISTURE 5
2.1. Gaseous chlorine 9
2.2. Liquid chlorine 10
2.3. Conclusion 11
3. DESTRUCTION OF THE FERRIC CHLORIDE LAYER 12
3.1. Sublimation and chlorine-iron fire 12
3.2. Dissolving 14
3.3. Melting 15
3.4. Erosion 15
4. REFERENCES 15

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1. INTRODUCTION
The materials of construction that can be used with chlorine are highly
dependent on the moisture content of the chlorine (gas or liquid); the most
common are described in document GEST 79/82 – Materials of Construction
for Use in Contact with Chlorine.
The usual material for dry chlorine is carbon steel. Steel reacts with the chlorine
and produces ferric (III) chloride (FeCl3). This ferric chloride forms a thin skin on
the metal surface as ferric chloride or ferric chloride hydrates. This skin will
protect the remaining material from corrosion, provided that it is prevented
from disappearing through sublimation, dissolution, melting and/or erosion.
In this document it will be explained how these phenomena leading to the
destruction of the protective ferric chloride layer can be avoided so that the
(carbon) steel can be used as an excellent material of construction for dry
chlorine applications.
This recommendation is based on a presentation made by P.C. Westen (Akzo) at
the 1993 Euro Chlor Technology Seminar (TSEM 93/192 – How to Use Steel and
Titanium Safely)

2. IRON CORROSION DUE TO PRESENCE OF MOISTURE

Ferric chloride can form various hydrates with water. The water vapour pressure
and the concentration of water at the prevailing temperature determine which
hydrate is formed and whether that particular hydrate will melt. These
conditions are explored below with reference to the equilibrium values.
Iron reacts with chlorine as follows:
2 Fe + 3 Cl2  2 FeCl3 + reaction heat
The solid ferric chloride, formed in this reaction, is a very hygroscopic salt. It
can form five different hydrates with water, depending on the water
concentration: FeCl3.nH2O with n = 2, 2.5, 3.5, 6 or 10.
These solid hydrates have their own melting temperature and the melting point
of the different hydrates is much lower than the melting point (Tm=304C) of
solid FeCl3.
Between these hydrates there exist eutectics with even lower melting points.
The system of FeCl3-H2O and the hydrates is shown in a T-x (temperature–
composition) phase diagram in the Figure 1 here below.

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Fig. 1 The T-x Phase diagram of FeCl3-H2O investigated in 1892 (see H.W.
Bakhuis-Roozeboom Z.Physik Chem 1892, 10, 477 & Landolt-Börnstein,
Springer Verlag, 1962, Vol. II, Chapter 26-3, p. 138
The lower part of the diagram corresponds to ice and solid FeCl3 hydrates, the
upper part represents the liquid solution of FeCl3 and H2O.
As long as water (ice), FeCl3 and its hydrates remain solid, and if no erosion of
the layer takes place, corrosion cannot occur because no electrolyte can be
formed. These solid hydrates even protect the iron from further attack by
chlorine in the same way as FeCl3 does.

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The weak point of this protection is that by supplying some more water the
ferric chloride hydrates can deliquesce, and/or by increasing the temperature
they can melt (going to the left side, respectively upward in the diagram).
In that case a concentrated solution (electrolyte) of FeCl3 is formed, being very
aggressive against iron, steel and many other alloys.
A ferric chloride solution is corrosive, because it is an electrolyte, a strong
oxidizer and an acid.
The corrosive power of a concentrated ferric chloride solution is shown in the
table below (AkzoNobel internal report). In the table the corrosion rate is
presented in mm per year for a 45 % (saturated) FeCl3 solution at room
temperature which is stirred and in contact with Cl2:

Material Corrosion rate (mm/y) Corrosion behaviour

Carbon steel 187 even attack

Copper 52 even attack

Nickel 53 pitting

Copper-nickel 70/30 67 even attack

Stainless steel 316 L 20….80 heavy pitting

Hastelloy C 0.003 passive up to 80oC

Titanium Grade 2 0.002 passive

Tantalum pure 0.001 passive

Note on the table: the corrosion rate of carbon steel is so fast (0.5 mm/day!)
that a pipe wall or a vessel can be perforated within one week or even less.
Stainless steel shows severe pitting. Hastelloy C can be used (up to about. 80°C).
Titanium and tantalum are completely resistant even above this temperature,
but keep in mind that titanium does not resist to dry chlorine!
Using safely carbon steel with chlorine means therefore that it is essential to
prevent ferric chloride and its hydrates from deliquescing and/or melting.
Each hydrate has its own equilibrium water vapour pressure. These vapour
pressures are exponential functions of the temperature and are given in Fig. 2
here below together with the vapour pressures of water, ice, chlorine-hydrate
and 95% H2SO4.

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Fig. 2 Arrhenius plot of log PH2O as function of the 1/T partial water vapour
pressure of FeCl3 hydrates and solutions
At water vapour pressures in the gaseous phase below 1 mbar (and the
corresponding water concentration in liquid chlorine) a solid ferric chloride
hydrate will be formed, preventing corrosion (except sublimation and/or
erosion). Water vapour pressure in the gas phase and water concentration in the
liquid chlorine are related via the equilibrium solubility as function of
temperature.
As long as these hydrates are solids, below their melting temperature and in
equilibrium with their partial vapour pressure/water concentration, they will not
corrode the steel. But they can act as drying agents and collect water by forming
higher hydrates (2.5 --> 3.5 --> 6), eventually plugging the piping and valves, like
chlorine-hydrate can do. When melting afterwards, e.g. at a plant shutdown, the
melt will lead to heavy corrosion.
Normally one can accept the forming of some lower hydrates (e.g. FeCl3.2H2O)
with a high melting temperature and also somewhat higher water concentrations
(about 5.3 mbar water vapour pressure).

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2.1. Gaseous chlorine

For gaseous chlorine, the table shows which values of water vapour pressure at
the indicated temperatures are in balance with the lowest form of hydrate,
FeCl3.2H2O (laboratory values in line with the Fig. 2 here above).

Temperature (°C) Water vapour pressure (mbar)

in balance with FeCl3.2H2O

0 0.095

20 0.34

40 1.15

60 3.4

70 5.3

73 5.8 (melting point)

80 8.4

90 12.5

100 19

110 28

At water vapour pressures below the values shown here above (or below the
equivalent line in Fig. 2), no ferric chloride hydrate will be formed at the
corresponding temperature; only anhydrous solid ferric chloride will be present
with some water in the vapour phase. Consequently no ferric chloride liquid
phase will arise when temperature is increased, and no corrosion will take place.
Remark on the low water content eutectic
According to the thermodynamic (Fig. 1) there is an eutectic corresponding to
84% FeCl3. Below its melting temperature (66°C) a solid mixture of FeCl 3.2H2O
and FeCl3 should be formed with an average concentration in water between 18%
(FeCl3.2H2O) and 0%. At a higher temperature this solid mixture would melt
partially to give a liquid with a composition between 18% and 0% and a solid that
would be FeCl3.2H2O or pure FeCl3, depending on the average initial composition
of the solid (below or above the eutectic). The vapour pressure in equilibrium
with the liquid mentioned here would then be lower than the values in the
above table (valid for FeCl3.2H2O); this would lead to the formation of a
corrosive salt, even at quite low vapour pressure.
Nevertheless, experience shows that this is not the case, and that the kinetics of
the reactions most probably explains that there is this low melting eutectic is
not causing troubles: practically we can assume that only pure solid FeCl 3 will be

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formed when the vapour pressure is below the equilibrium with FeCl3.2H2O at
the given temperature.
To get a better understanding of these phenomena a few examples will be
presented.
Example 1:
The maximum allowed water content of gaseous chlorine at 80°C and a total
pressure of 1 bara is 8,4 mbar. At a pressure of 1 bara the max allowable water
content is then 0.84 vol% (8.4/1000*100%). This is 8400 ml water vapour per m3
of gas. 8400 ml water vapour at 80°C and 1 bara is equal to 5150 mg water per
m3. 1 m3 of chlorine gas at 80°C and 1 bara contains 2.42 kg chlorine. So the
water content may be equal to 2143 mg/kg. No corrosion through deliquescence
will occur below this water content.
Example 2:
The maximum allowed water content of gaseous chlorine at 80°C and a total
pressure of 1 bara is 8,4 mbar. At a pressure of 10 bara the max allowable water
content is then 0.084 vol% (8.4/10000*100%). This is 840 ml water vapour per m3
of gas. 840 ml water vapour at 80°C and 10 bara is equal to 5150 mg water per
m3. 1 m3 of chlorine gas at 80°C and 10 bara contains 24.16 kg chlorine. So the
water content may be equal to 213 mg/kg. No corrosion through deliquescence
will occur below this water content.
Example 3:
The maximum allowed water content for gaseous chlorine at 20°C and a total
pressure of 1 bara (at which there is no hydrate formation/contamination) is
0.34 mbar. At this temperature and pressure this is equal to 86 mg water per kg
gas.
Given the melting points of the different ferric chloride hydrates, no liquid
phase can arise at water vapour pressures below 5.3 mbar, and no corrosion will
therefore occur. For water vapour pressures over 5.3 mbar, melting (and hence
corrosion) will occur.
When, at temperatures below 70°C, the water vapour pressure is over the value
indicated in the table, but lower than 5.3 mbar, solid hydrates will form and
cause incrustation. These hydrates will melt when the temperature is increased
over 70°C, exposing the bare metal and causing corrosion.
2.2. Liquid chlorine
In liquid chlorine, as well, no liquid hydrate should be formed. The critical limit
of 5.3 mbar water vapour pressure therefore also applies in this case.
Liquid hydrate will not form in liquid chlorine if the concentration of water in
the chlorine is lower than the values given in the table below; only liquid water
will then be mixed in the liquid chlorine.

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Temperature mg H2O/kg Nr of hydrate

°C liquid Cl2 molecules

0 48 10

10 34 6

20 24 6

30 17.5 3.5

40 13 3.5

50 9 2.5

60 7.5 2.5 - 2

70 5.3 2

For all these values, water vapour pressure in the gaseous state is 5.3 mbar.
Water of hydration for the various forms of ferric chloride hydrate is also stated.
Example 4
A water vapour pressure of 5.3 mbar is reached at 20°C over liquid chlorine
containing 24 mg water/kg chlorine.
Let the pressure in this system be 10 bara. The water concentration in the
gaseous phase then is:
(5.3/10000) . 106 = 530 ml/m3 = 130 mg/kg
In either phase, the water will be in equilibrium with solid FeCl3.6H2O.
2.3. Conclusion
Using carbon steel with chlorine safely means that it is essential to prevent
ferric chloride and its hydrates from deliquescing and/or melting. At water
vapour pressures below 1 mbar and at a corresponding water concentration in
the liquid chlorine, it can be seen from figure 2 that solid ferric chloride
anhydrous or hydrated will be formed, giving protection and preventing
corrosion (except if erosion)..
Note: one has to be aware that this crucial vapour pressure counts everywhere
in the system. This will be explained with the following example. The chlorine
gas is dried to 1 mbar at atmospheric conditions and 20°C. The water content is
254 mg/kg after the drying. Assume this gas is compressed to 10 bara. The water
vapour pressure after this compression is then 10 mbar so corrosion can occur.
For most systems where working pressures are lower than 12.5 bara, it is advised
to dry the chlorine below 20 mg/kg at a pressure of 1 bara (80 vol. ppm) to avoid
corrosion of the downstream carbon steel equipment (see GEST 79/82 –
Materials of Construction for Use in Contact with Chlorine).

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If higher pressures are obtained, a lower water content of the dried chlorine
should be achieved (for example 5 mg/kg at a pressure of 1 bara which
corresponds to 20 vol. ppm allows compression up to 50 bara without risk of
downstream carbon steel corrosion).
These values can easily be reached by drying with sulphuric acid at ambient
pressure and temperature as can be seen in the figure below where the vapour
pressure of water is presented as function of the sulphuric acid concentration
and the temperature.

Water vapor pressure as fuction of temperature and

sulfuric acid oncentration

0.10000
water vapor pressure in mbar

0.01000
90% H2SO4
92% H2SO4
94% H2SO4
0.00100 96% H2SO4

0.00010
10 20 30 40 50
temperature in C

Fig 3 Water vapour pressure as function of temperature and acid

concentration

3. DESTRUCTION OF THE FERRIC CHLORIDE LAYER

3.1. Sublimation and chlorine-iron fire
Ferric chloride is a fairly volatile substance (melting point 304°C; boiling point
315°C), therefore the protective ferric chloride skin is subject to sublimation
when the temperature increases. In such cases the iron is exposed and fresh
ferric chloride is formed. The reaction of chlorine with iron is exothermic.
Thermal conduction, radiation to the environment and evaporation of solid ferric
chloride usually ensure that the heat of reaction is dissipated without causing a
considerable increase in temperature.
In certain situations, determined by reaction rate and transport of heat and
matter, the generated heat exceeds the dissipated heat. If this is the case, the
chlorine-iron reaction sustains itself, temperature increases rapidly and a
chlorine-iron fire results.

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Whether or not a chlorine-iron fire starts, is determined by the following

factors:
for chlorine: Liquid or gas state
flow rate
pressure
temperature
presence of other gases
for iron: surface area
mass
temperature
heat dissipation (to system and environment)
surface condition (roughness and cleanness, i.e. presence
of contaminants such as grease and paint)
Practice has shown, and tests confirmed, that in the current robust design of
piping, tanks, vessels, pumps, and valves, the risk of a sustained reaction is not
high for temperatures up to 170°C 1; above this temperature, the reaction speed
increases exponentially. At the lower temperatures, ferric chloride sublimation
slows down the reaction.
According to an internal AkzoNobel research reports2, there is a distinct effect
of ferric chloride sublimation for temperatures above 120°C. Corrosion will then
proceed at a rate of more than 0.1 mm of steel per year 3. This temperature
must therefore be regarded as a safe design limit. Public literature4 gives an
explanation on the decreasing sublimation speed over time at 120°C and 8 hours
the speed is 0.03 mm/yr and at 15 minutes it is 5 times higher. Another author5
gives a corrosion speed of 0.1 mm/yr at 130°C.
One should take into account that temperatures in dead end of systems (ex.
valves of piston compressors) might be higher than at the location of the
temperature measurement.
When new piping is commissioned, the absence of the ferric chloride skin and
the possible presence of metal pellets left from welding operations, metal chips,
cleaning cloths, oil, etc., increase the risks of a chlorine-iron fire.
Other causes for a chlorine-iron fire are:
 Welding on or near chlorine piping.

1 Conservative value (some publications refer to 200°C or even 250°C

2 H.W. Nicolai KNZ report 55, 22-9-1952 and F. Van Westen KNZ report n° 528 26-7-1961
3 Some references mention even 0.25 mm/yr
4 G. Heineman et al, Ind. Eng. Chem. 38 n° 5 1946 pages 497 – 499
5 C.M Schillmoller Chem. Eng. Vol 87 n° 5 March 1990 page 55

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 A fire in or near a chlorine pipe. (Think of a chlorine-hydrogen reaction in

the pipeline).
 Improper use of service liquids reacting with chlorine, e.g. in instruments
or membrane compressors.
 Oil left behind in the system, e.g. from pressure-testing with
contaminated water
 Local temperature peaks caused by faulty control of electric tracing,
coinciding with stagnating throughput.
 Use of steam with a too high temperature in evaporators or pipeline
tracing (one should be attentive to saturate superheated steam behind
high pressure steam expansion)
 Cleaning of pipes with unsuitable materials, such as methanol.
 Overheating of pumps, blowers, or compressors.
 Backflow of materials reacting with chlorine.
3.2. Dissolving
Iron chloride is slightly soluble in liquid chlorine, so some of the protective layer
will slowly be dissolved towards equilibrium. The most likely location of this
mechanism is at spot points where chlorine gas is condensing (intentionally or
accidentally, which should always be avoided), as it will not already be carrying
any iron chloride and some physic/mechanical conditions foster this dissolution.
The solubility increases with extremely low moisture (< 3 mg/kg) and increasing
temperature (see figure 1 on page 6) and so such liquid chlorine could be
corrosive to iron. This process is influenced by diffusion into the chlorine bulk
(also increasing with temperature) and usually rather slow; over years it can
nevertheless result in significant loss of metal and it should be considered during
the definition of appropriate inspection schemes.
During opening and cleaning of equipment for maintenance, when the chlorine is
purged out, ferric chloride will hydrolyse in the presence of water or moist air.
If the cleaning medium is water, it should be removed and the equipment should
be dried before taking into service. In case of remaining water, the corrosion
will take place and continue until all of the water has been used to form ferric
chloride hydrate, with the number of molecules of crystallization water per
chloride molecule going as high as 10. This ferric chloride may be formed by
something like the following mechanism.
First, the highly oxidative ferric ion reacts with iron to form ferrous ions:
2 Fe3+ + Fe  3 Fe2+
The chlorine then converts ferrous ions back to ferric ions:
2 Fe2+ + Cl2  2 Fe3+ + 2 Cl
Remark: the following corrosion reaction will also occur
Cl2 + Fe  FeCl2

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3.3. Melting
Ferric chloride hydrate (in solid crystalline form) is not corrosive, but as these
hydrates can melt and form free water as temperature goes up, the presence of
ferric chloride hydrate is a potential risk. When the ferric chloride hydrate
melts, corrosion occurs according to the reactions as seen in previous paragraph.
3.4. Erosion
Tests by the AkzoNobel Corrosion Department have not indicated any erosion
from liquid chlorine at velocities up to 7 m/sec. Because of turbulence in bends,
at welded joints, and after valves, the maximum velocity for liquid chlorine in
pipelines should be limited to 2 m/s for practical reasons.
Two-phase flow must be prevented (flashing, formation of gas bubbles), in view
of the high velocities occurring locally.
With gaseous chlorine, erosion did not occur at all; therefore economical
considerations determine the speed in pipelines with gaseous chlorine.

4. REFERENCES
 GEST 79/82 – Materials of Construction for Use in Contact with
Chlorine
 TSEM 93/192 – How to Use Steel and Titanium Safely
 H.W. Nicolai KNZ report 55, 22-9-1952 and F. Van Westen KNZ report n°
528 26-7-1961
 G. Heineman et al, Ind. Eng. Chem. 38 n° 5 1946 pages 497 – 499
 C.M Schillmoller Chem. Eng. Vol 87 n° 5 March 1990 page 55

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