APPLICATION NOTE
MEASURING HYDROGEN CHLORIDE AND CHLORINE
This application is focused on measuring
hydrogen chlorine (HCl) and chlorine
(Cl2), which are corrosive materials. There
are many metal alloys such as Inconel®,
Hastelloy®, and Monel®, with different
corrosion resistant properties that can be
considered depending on the application.
CHLORINE
Chlorine is a chemical element in the halogen group with
a high electron affinity. It is a strong oxidizing agent,
which is a concern when measuring chlorine itself or other
chemicals, such as water (H2O), in chlorine. The reaction
of chlorine with hydrogen or hydrogen-containing
compounds can be considered an oxidation reaction and
is likely to produce HCl. The issues associated with HCl
sampling and measurements are discussed below.
Chlorine gas is a toxic gas and is used to sterilize drinking
water, disinfect swimming pools and to manufacture
many consumer products such as paper, dyestuffs, textiles,
petroleum products, medicines, antiseptics, insecticides,
foodstuffs, solvents and plastics, especially PVC.
100% dry chlorine at temperatures up to 70oC may be
used with stainless steels, but moist chlorine is considered
unsatisfactory as it removes protective oxide layers from
most steels. Therefore, moisture measurement is vital in
chlorine plants.
Even titanium is not fully resistant to chlorine. Hastelloy is
resistant to a variety of concentrations of moist chlorine.
Inconel has been found effective for chlorine gas mixtures
at elevated temperatures. Monel (often Monel 400, a
copper-nickel alloy) is not so resistant to wet chlorine.
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IPS-4 ANALYZER
Each application in chlorine environment could be
different and has to be looked at on its own metrics.
Special metals such as those above are expensive,
especially if measuring cells and sample components
are both required to be specially manufactured. So,
compromise solutions, where occasional replacement of
less resistant materials will be necessary, may be more
customer-acceptable.
When measuring chlorine or other gases excluding
moisture, use a sample chiller to dry the gas if the water
concentrations are in percent or high parts-per-million
(ppm) levels. For longer lifetimes of metal sample system
components, reduce moisture even further by using
chemical driers such as a molecular sieve.
In chlorine plants, moisture measurements are often made
to ensure they do not rise above (typically) 15 ppmv,
because significant corrosion may occur above this level.
Where possible, using halogenated plastics such as PVDF
for sample tubing is recommended.
Significant levels of ammonia, acetylene, hydrogen, or fuel
gas may react explosively with chlorine.
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CHLORINE MEASUREMENT SUMMARY

Chlorine, being a symmetric molecule, does not absorb in
the infrared, but can be measured in the UV spectrum where
AMETEK IPS-4 analyzers have been used for measuring Cl2 in
gas mixtures, as well as ethylene dichloride (EDC).
HYDROGEN CHLORIDE
Hydrogen chloride is a diatomic molecule, consisting of a
hydrogen and a chlorine atom connected by a single covalent
bond. Since the chlorine atom is much more electronegative
than the hydrogen atom, the covalent bond between the
two atoms is quite polar. Consequently, the molecule has
a large dipole moment with a negative partial charge δ- at
the chlorine atom and a positive partial charge δ+ at the
hydrogen atom, which make HCl highly polar and soluble in
water and other polar solvents.
Upon contact, H2O and HCl combine to form hydronium
cations H3O+ and chloride anions Cl- through a reversible
chemical reaction:
Where HCl and moisture are present, the sample in the gas
phase should be kept above the acid dew point temperature.
Temperatures above 100oC will usually be more than adequate.
Condensed HCl reacts with most metals forming hydrogen
(and denaturing the metal to a salt). Stainless steel is not
resistant to hydrochloric acid. Hastelloy C is largely resistant
but, for long-term reliability, the concentration of HCl should
be as low as possible. As with chlorine, plastics are much
more resistant than metals, including PP, PVC, PTFE, PVDF,
and PFA.
CONCLUSION
The issue with these measurements is potential corrosion
of the analyzer and sample conditioning system. Clearly,
the lifetime of these components is a primary customer
question and varies depending on the concentrations, and
stream operating conditions. The table below summarizes
the solutions AMETEK recommends for analyzing some of the
more common corrosive materials.

HCI + HO2 H3O+ + Cl- Analyte Solution

Dry chlorine UV Photometer
The resulting solution is called hydrochloric acid and is a Use corrosion-resistant plastics or metals where
Wet (>15 ppm H2O) chlorine
strong acid. Even in the absence of water, hydrogen chloride possible - UV

can still act as an acid. Because of its acidic nature, hydrogen Dry HCI IR Photometer (Note that low ppm levels are difficult)
chloride is corrosive in the presence of moisture. Either dry or raise above acid dew point temperature
Wet (>15 ppm H2O) HCI Corrosion-resistant materials will extend lifetime
Dry HCl is not generally a concern to us from a sampling IR Photometer (Note that low ppm levels are difficult)
viewpoint. It will react easily with water to form hydrochloric Sampling as for wet chlorine
Water in chlorine
acid, which is a problem when it condenses. It is important to IR Photometer
keep a sample containing both HCl and H2O above the acid Raise above acid dew point temperature
dew point which means heating the sample lines and parts in Water in HCI Corrosion-resistant materials will extend lifetime
contact with the sample, efficiently. IR Photometer

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© 2019, by AMETEK, Inc. All rights reserved. Printed in the U.S.A. is A-0439 Rev 4 (0219)
One of a family of innovative process analyzer solutions from AMETEK Process Instruments.
Specifications subject to change without notice.

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