Maximum Levels of Nitrogen Trichloride in

Liquid Chlorine

GEST 76/55
12th Edition
February 2012

EURO CHLOR PUBLICATION

This document can be obtained from:
EURO CHLOR - Avenue E. Van Nieuwenhuyse 4, Box 2 - B-1160 BRUSSELS
Telephone: 32-(0)2-676 72 65 Telefax: 32-(0)2-676 72 41

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Euro Chlor

Euro Chlor is the European federation which represents the producers of chlorine
and its primary derivatives.
Euro Chlor is working to:

improve awareness and understanding of the contribution that chlorine chemistry

has made to the thousands of products, which have improved our health, nutrition,
standard of living and quality of life;

maintain open and timely dialogue with regulators, politicians, scientists, the
media and other interested stakeholders in the debate on chlorine;

ensure our industry contributes actively to any public, regulatory or scientific

debate and provides balanced and objective science-based information to help
answer questions about chlorine and its derivatives;

promote the best safety, health and environmental practices in the manufacture,
handling and use of chlor-alkali products in order to assist our members in
achieving continuous improvements (Responsible Care).
***********
This document has been produced by the members of Euro Chlor and should not be reproduced in
whole or in part without the prior written consent of Euro Chlor.

It is intended to give only guidelines and recommendations. The information is provided in good
faith and was based on the best information available at the time of publication. The information is
to be relied upon at the users own risk. Euro Chlor and its members make no guarantee and
assume no liability whatsoever for the use and the interpretation of or the reliance on any of the
information provided.
This document was originally prepared in English by our technical experts. For our members
convenience, it may have been translated into other EU languages by translators / Euro Chlor
members. Although every effort was made to ensure that the translations were accurate, Euro
Chlor shall not be liable for any losses of accuracy or information due to the translation process.
Prior to 1990, Euro Chlors technical activities took place under the name BITC (Bureau
International Technique du Chlore). References to BITC documents may be assumed to be to Euro
Chlor documents.

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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
documents are based on the experiences and best practices adopted by member
companies of Euro Chlor at their date of issue. They can be taken into account in
full or partly, whenever companies decide it individually, in the operation of
existing processes and in the design of new installations. They are in no way
intended as a substitute for the relevant national or international regulations which
should be fully complied with.
It has been assumed in the preparation of these publications that the users will
ensure that the contents are relevant to the application selected and are correctly
applied by appropriately qualified and experienced people for whose guidance
they have been prepared. The contents are based on the most authoritative
information available at the time of writing and on good engineering, medical or
technical practice but it is essential to take account of appropriate subsequent
developments or legislation. As a result, the text may be modified in the future to
incorporate evolution of these and other factors.
This edition of the document has been drawn up by the Storage, Transport and
Safety Working Group (GEST) to whom all suggestions concerning possible
revision should be addressed through the offices of Euro Chlor.

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Summary of the Main Modifications in this version

Section

Nature

All

Reorganise the structure of the document with most sections

rewritten to add clarifications

5.2

Added some potential sources of NCl3 in chlorine

5.2

Added calculation of NCl3 concentration in chlorine from ammonia

in brine and ferrocyanide in salt

Added information on managing potential NCl3 concentration

increase

9.3

Added information on how to dilute NCl3 when emptying a tank

Appendix 1

Correction of figure 1

Appendix 2

Calculations of examples corrected

Appendix 3

Added

TABLE OF CONTENTS

1.

INTRODUCTION

2.

OBJECTIVES OF THE RECOMMENDATION

3.

SAFE PRINCIPLES FOR CHLORINE CUSTOMERS

4.

EXAMPLES OF NITROGEN TRICHLORIDE INCIDENTS

5.

NITROGEN TRICHLORIDE

6.

5.1.

Properties of NCl3

5.2.

Sources of NCl3 in chlorine

5.3.

The Effect of Chlorine Liquefaction

10

5.4.

The Effect of Chlorine Evaporation

10

HAZARDOUS LEVELS OF NITROGEN TRICHLORIDE

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7.

8.

9.

CONTROLLING NITROGEN TRICHLORIDE LEVELS

11

7.1.

General considerations

11

7.2.

Raw materials and utilities

12

7.3.

Chlorine Storage

12

7.4.

Mobile Containers

13

7.5.

Vaporisers

13

7.6.

Other Gas/Liquid Equipment

14

7.7.

Process and Operational Changes

15

7.8.

Emptying Equipment and Pipelines

15

7.9.

Plant Design

15

OPERATIONAL LEVELS OF NCL3 IN CHLORINE

16

8.1.

Maximum Level of NCl3 inside any Equipment

16

8.2.

Maximum Levels of NCl3 in Fixed Tanks

17

8.3.

Maximum Levels of NCl3 in Small Mobile Containers

17

8.4.

Maximum Levels of NCl3 in Bulk Transport Containers

17

REDUCING LEVELS OF NCL3 IN CHLORINE

18

9.1.

Reduction of NCl3 Formation

18

9.2.

Destruction of NCl3

18

9.2.1 For Gaseous Systems

18

9.2.2 For Liquid Systems

19

9.2.3 Alternative methods

19

9.3.

Blending of Chlorine

19

10. OTHER SAFETY MEASURES

20

10.1.

Nitrogen compounds Analysis in Brine

20

10.2.

NCl3 Analysis in Liquid Chlorine

20

10.3.

Temperature Limits

21

11. REFERENCES

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1. INTRODUCTION
Nitrogen trichloride (NCl3) is a trace compound normally found in chlorine. It is
created during the manufacturing process. When proper precautions are taken
during manufacturing and use of chlorine, it presents no hazard. However, when
concentrated it can become explosive and is one of the most dangerous materials
encountered in the chlor-alkali industry.
At high concentrations nitrogen trichloride will spontaneously decompose with a
destructive force of 30-40% of TNT. It is believed that at a concentration of 3 - 6%
NCl3 in chlorine, it can decompose spontaneously, resulting in a significant
pressure rise in enclosed systems. At approximately 13% concentration in
chlorine, the potential for catastrophic detonation exists.
Because of the hazard presented by nitrogen trichloride, there should always be a
significant safety margin between operating levels and the concentrations known
to be hazardous ideally all operations should be carried out without
concentrating the NCl3 above the normal manufactured levels.
There are well established ways of operating that minimise the possibility of
concentrating the nitrogen trichloride to hazardous levels. These ways of
operating are strongly recommended by Euro Chlor and should always be
followed. Exceptions should be limited to very special circumstances that have
been thoroughly assessed from both a technical and a risk perspective.
Nitrogen trichloride is only hazardous within liquid chlorine. It is not hazardous
when present in in chlorine gas. Nevertheless chlorine gas that condenses
deliberately or inadvertently to become liquid chlorine can be hazardous (nitrogen
trichloride being les volatile than chlorine, it will tend to accumulate in the liquid
phase).

2. OBJECTIVES OF THE RECOMMENDATION

The purpose of this recommendation is to highlight potential dangers with
accumulation of nitrogen trichloride (NCl3), which is a common impurity in liquid
chlorine, and to describe the actions, strategies and constraints that should be
observed in order to avoid risks associated with its presence.
Any chlorine user who is uncertain of potential problems which can arise from
accumulation of NCl3 in a system, should consult their chlorine supplier for
assistance in evaluating their specific risk.
A brief collation of information available on NCl3 can also be found in the World
Chlorine Council Global Safety Team newsletter 12 of December 2009.

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3. SAFE PRINCIPLES FOR CHLORINE CUSTOMERS

Although nitrogen trichloride is very hazardous at high concentrations, it is benign
at concentrations normally supplied by manufacturers, which is up to 20 mg/kg.
Nitrogen trichloride only becomes hazardous if it is concentrated, which can be
deliberate or inadvertent.
This section is provided to give chlorine customers some simple rules of thumb
that will minimise their risk of accumulating nitrogen trichloride. It must be
stressed that it is fully acceptable to operate in alternative ways under the
guidance and expertise of a knowledgeable chlorine supplier.

Do not discharge chlorine gas from a vessel containing greater than

1 tonne of liquid chlorine.

Do not continue adding liquid chlorine to a vessel from which chlorine gas
is taken.

Use preferably plug flow or flash type vaporisers. (see section 7.5)

Any operation outside these key principles requires both a proper risk assessment
and discussions with your chlorine supplier.
Chlorine suppliers should have a deeper understanding of nitrogen trichloride and
should base their operation on the rest of this document rather than these simple
principles.

4. EXAMPLES OF NITROGEN TRICHLORIDE INCIDENTS

There have been a number of incidents in which a high concentration of nitrogen
trichloride is believed to have been the cause and these are documented to
varying degrees in other publications; however the following short selection gives
examples of incidents from the past. The early incidents were generally due to
little knowledge of nitrogen trichloride and its perils within chlorine. More recent
incidents have generally happened where the actual level of nitrogen trichloride in
parts of the system has been higher than believed, despite the science being
understood. The purpose of the following information is to demonstrate that the
dangers of nitrogen trichloride are real and not merely a theoretical concept.
Early scientific incident:
Pierre Louis Dulong began experimenting with nitrogen trichloride in 1812 and as
a result of explosions lost not only two fingers but also an eye. The hazards of
testing explosive concentrations of NCl3 have restricted such experimental
investigation to a minimum.
Early industrial incidents:
In 1928 two cylinders ruptured at the Ashokan Reservoir Treatment Plant in New
York. Without any prior understanding of the hazards of nitrogen trichloride,
chlorine had been produced with around 450 mg of NCl 3 per litre of chlorine and

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then discharged as a gas. This had increased the concentration in the remaining
liquid to dangerous levels.
In 1949 at Croton Lake Gate House a chlorine drum was discharged completely
as gas. Forty minutes after complete discharge there was an explosion resulting in
the drum fracturing for almost its full circumference and a section 450mm x
275mm was blown out. The cause is generally believed to have been a high
concentration of nitrogen trichloride.
Recent industrial incidents:
In 1994 a chlorine purifier in Taft, USA exploded and debris from the explosion
was found over 60m away.
In 1998 in Yarraville, Australia there was an explosion in a flexible copper
connecting tube. During subsequent investigative work there was another
explosion in laboratory test equipment. Both were caused by nitrogen trichloride.
Overview
In many of the reported incidents the concentration of nitrogen trichloride was
significantly greater than the current typical sales specification of 20 mg/kg.
Although these higher levels were below the usually accepted dangerous
concentrations of NCl3 by a suitable safety margin, the concentrations had
unknowingly increased resulting in the incidents.

5. NITROGEN TRICHLORIDE
5.1.

Properties of NCl3

The physical properties of nitrogen trichloride are detailed in Appendix 1. The

following is a summary of the key features of the chemical.
Nitrogen trichloride is a yellow, oil-like liquid.
Nitrogen trichloride is practically insoluble in water but highly soluble in chlorine
and other materials such as benzene, chloromethanes and carbon disulphide.
Nitrogen trichloride has a boiling point of 71C (cf. chlorine at minus 34C) and a
freezing point of minus 27C.
As nitrogen trichloride is less volatile than chlorine, the relative boiling point and
volatility mean that when chlorine containing NCl3 is vaporised or evaporated, the
NCl3 in the remaining liquid phase will increase.
In pure form or at high concentrations in chlorine, NCl3 is extremely unstable. It
can decompose either spontaneously or with minimal (negligible) initiation energy.
The decomposition can be either rapid or explosive detonation.
If nitrogen trichloride detonates, the destructive force is estimated as 30-40% that
of the explosive trinitrotoluene (TNT).
If nitrogen trichloride is maintained at the typical concentrations in produced liquid
chlorine (no more than 20 mg/kg), there is no explosive risk.
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5.2.

Sources of NCl3 in chlorine

NCl3 can be formed during chlorine manufacture by reaction between chlorine and
nitrogen compounds. Nitrogen compounds in the brine used for aqueous
electrolysis are the main source of NCl3.
Considering
0.82 = the molar weight ratio between N and NH3
B = kg /h brine flow per kg Cl2 /h produced (usually about 13 in a recycled
brine circuit)
C = the conversion factor of nitrogen into NCl3 in the cell (usually between
40 to 60%)
8.6 = the molar weight ratio between NCl3 and N
1 mg/kg of NH3 in the feed brine will give 0.82 * B * C * 8.6 mg NCll3 /kg Cl2
produced or about 37 to 56 mg NCl3/kg chlorine produced with the figures here
above; should the nitrogen be completely transformed into NCl3 this would give
92 mg NCl3/kg chlorine produced.
Rock salt and solution mined salt using surface waters will contain varying levels
of ammonium and nitrate salts.
When rock salt is mined using explosives, the explosive used will normally
contain nitrogen compounds.
Water used for solution mining can contain traces of ammonium based
fertilisers.
The use of vacuum salt in brine recycle circuits tend to give very low levels of
NCl3, however ferrocyanide anti-caking agents can introduce nitrogen to the salt.
1 mg K4Fe(CN)6/kg salt completely transformed will give about 3 mg NCl3/kg
chlorine.
Unless the equipment used to store or transport the salt raw material is dedicated
to handle salt only, the salt can be contaminated by residues of other nitrogen
containing chemicals that have been inside the same equipment, such as
fertilisers.
Flocculent agents for decantation of impurities in the brine purification can be a
potential risk of contamination.
One should also pay attention to chemicals, waters and steam condensates that
are recycled in the brine loop.
Leaks of cooling water into the brine can be a cause of contamination if the water
contains nitrogen compounds.
NCl3 can also be formed from other nitrogen based impurities during manufacture
in the electrolytic cell.
The concentration of NCl3 could change due to an adjustment in process
conditions.

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It must be noted that not all nitrogen compounds are converted to nitrogen
trichloride. Nitrogen gas introduced into the chlorine gas stream is not converted
to nitrogen trichloride under the normal operating conditions existing in current
chlor-alkali production facilities. Fully oxidized forms of nitrogen, such as nitrate
salts (potassium nitrate or sodium nitrate), are not likely to form nitrogen trichloride
upon interaction with chlorine.
As a consequence of one or more of the above mechanisms, nitrogen trichloride
is commonly found as a trace compound in liquid chlorine from most suppliers.

5.3.

The Effect of Chlorine Liquefaction

Nitrogen trichloride has a much higher condensing temperature (ie boiling point)
than chlorine (71C vs minus 34C at atmospheric pressure). Therefore during
liquefaction of chlorine most of the NCl3 present in the chlorine gas phase will be
condensed into the liquid phase. Because all of the chlorine gas is not liquefied,
the concentration of nitrogen trichloride in the liquid chlorine produced will be
greater than that in the original gas.
If only a small proportion of the gas entering the liquefier is liquefied, the
concentration of NCl3 in the liquid produced will be significantly higher than in the
feed gas. See section 9.1 about controlling this.

5.4.

The Effect of Chlorine Evaporation

The high difference in partial vapour pressure between chlorine and NCl3 also
tends to concentrate the nitrogen trichloride in the liquid phase during evaporation
of chlorine.
During evaporation of chlorine, some NCl3 does evaporate although the amount
depends on the concentration of NCl3 and other possible compounds, the
temperature and the pressure.

6. HAZARDOUS LEVELS OF NITROGEN TRICHLORIDE

On the basis of experimental results, it is assessed that, on detonation, a mass of
1.5 g of pure NCl3 per cm of metallic surface wetted is capable of completely
fracturing the metal of a typical chlorine vessel and 0.3 g/cm2 is capable of
causing cracks. This means that a small deep pool (eg in a sump) is more
hazardous than the same quantity spread thinly over a large surface area.
Experimental results show that a concentration of NCl3 in chlorine greater than 3%
w/w at ambient temperature is capable of an accelerated decomposition, which is
strongly exothermic.
The levels of nitrogen trichloride that are hazardous are normally accepted as
those above 1% w/w (10,000 mg NCl3/kg chlorine).
Note: the above figures are NOT exact figures below which operation is
guaranteed to be safe. The data for the dangerous concentration of NCl 3
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varies in the authoritative texts, typically between 1% and 13% w/w.

Therefore the concentrations given above are those that are known to carry
significant hazard. This needs to be considered in conjunction with the
difficulty of knowing and measuring the precise concentration of nitrogen
trichloride at all points within a system. Also hazard assessments need to
consider the possibility of inadvertent concentration above the planned
figures. Consequently operational procedures should always ensure that
the concentration within any system is always maintained at a level that has
a large safety margin below the figures given above.
It must be stressed that the above hazardous levels are about 3 orders of
magnitude higher than those found in chlorine produced by modern
manufacturers, which is typically no more than 20 mg NCl3 /kg chlorine. Therefore
under normal operating conditions, every effort should be made to ensure that
NCl3 levels do not increase above this limit unless fully risk assessed.

7. CONTROLLING NITROGEN TRICHLORIDE LEVELS

7.1.

General considerations

The low concentration of nitrogen trichloride found in chlorine produced by Euro

Chlor members (no more than 20 mg/kg) is totally benign. The principle hazard
occurs where the nitrogen trichloride is concentrated significantly above these
levels. Wherever possible this should be avoided.
Concentration of nitrogen trichloride will happen when the chlorine is vaporised at
a higher rate than the nitrogen trichloride. The high boiling point of nitrogen
trichloride (+71C) compared to that for chlorine (minus 34C) makes it possible
that NCl3 could be concentrated in any circumstance involving the evaporation of
chlorine.
If the evaporation is part of a process in which chlorine is continually added to a
pool and evaporated, then unless appropriate designs and operational procedures
are used it can result in dangerously high levels of nitrogen trichloride
accumulating in the liquid chlorine.
In a system vaporising chlorine, the NCl3 may stabilise at a level that will depend
on the particular design and operation. It is quite possible for this equilibrium level
to be unsafe and therefore the system must be designed and controlled to ensure
that it is safe. There are standard solutions for many types of equipment to
provide this safety.
Operational upsets and maintenance activities can also result in higher than
envisaged levels of nitrogen trichloride caused by inadvertent or unexpected
evaporation of chlorine. An incident involving a large loss of containment of
chlorine could result in significant levels of NCl3 remaining after evaporation of the
spillage.

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7.2.

Raw materials and utilities

An important factor in the potential level of NCl3 in chlorine is the raw materials
used.
Raw materials include not only the salt used, but also water, settling and filter
aids, drying acid, etc., any of which could affect the levels of NCl3 in chlorine.
Some changes of raw materials are obvious, such as changes of salt supplier.
However others are less apparent, such as changes in the particular mine, moving
to a new salt seam within a mining area or changing the source of dissolving
water supply.
To ensure any changes are identified and that they cannot adversely affect the
safety of the chlorine, a regular check should be maintained on the total nitrogen
compounds in the brine. Also the level of the nitrogen trichloride in the chlorine
produced should be measured on a regular basis.
Whenever any source of raw materials is changed, a series of specific checks
should be made to ensure that a new NCl3 risk has not been introduced.

7.3.

Chlorine Storage

Chlorine bulk storage tanks should never be used to provide chlorine gas to a
user process directly because this can quickly result in unacceptably high levels of
nitrogen trichloride in the remaining liquid. Where chlorine gas is required, this
should either be taken from small transport containers (no more than one tonne)
that are completely emptied before refilling or by drawing liquid chlorine from a
storage tank and passing it through a vaporiser.
Normal operation of chlorine storage tanks sometimes involves slow or
intermittent vaporisation of chlorine (in particular to control the pressure of the
tank) and this can result in a steady increase of the concentration of NCl3 in the
liquid phase. If the storage tank is continually topped up without removing
sufficient liquid chlorine from it, the concentration of nitrogen trichloride will
increase. These activities need to be effectively controlled to ensure hazardous
NCl3 levels are not achieved. Where the NCl3 levels are known or suspected to be
higher than 20 mg/kg chlorine, care needs to be taken because:

The chlorine taken from the tank will have an elevated NCl 3 concentration
level which may be higher than anticipated and could create a hazard in
downstream equipment.

If the tank is subsequently emptied by a process involving evaporation, the

NCl3 concentration could be significantly higher than expected resulting in
either a safety margin smaller than estimated or dangerous conditions.

Where vapour is not routinely taken from the stock tank, care still needs to be
taken during the emptying and shutdown procedures to avoid any accidental
concentration of the nitrogen trichloride to hazardous levels.

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7.4.

Mobile Containers

Concentration of NCl3 occurs when chlorine is discharged in the gaseous phase

from a system containing liquid chlorine. This operation is not recommended,
except for small containers which are fully vented before refilling: decades of
experience has shown that cylinders and drums containing up to 1 tonne of
chlorine with NCl3 levels up to 20 mg/kg can be safely discharged this way.
Larger containers (in particular rail tanks, road tankers and ISO tank containers)
should not be discharged in the gas phase. If the large container has to be fully
emptied, this should be done in liquid phase as far as technically possible (with a
maximum of one tonne remaining in the liquid phase); the remaining chlorine can
be removed by complete evaporation.
Where exceptional circumstances require gas discharge from containers greater
than 1 tonne, such as in an emergency, suitable precautions must be taken, to
assess the specific equipment design and procedures and determine the
maximum concentration of NCl3 that could be reached throughout the discharge
procedure taking into account:

the initial concentration of NCl3 in the chlorine.

the increase in concentration during the discharge.

the shape of the equipment and consequent maximum mass per unit area
of the NCl3.

Good communication between supplier and customer is essential to assess

possible problems due to NCl3 accumulation.

7.5.

Vaporisers

Vaporisers can be classed in different basic groups, according to their design (see
GEST 76/47 Design and operation of chlorine vaporisers), but for our actual
purpose, vaporisers are split here into three categories.

Plug flow vaporisers (typified by a coil in bath, a double envelope or a

vertical tube vaporiser) where the chlorine passes through the vaporiser
linearly as a slug that is progressively boiled during its passage. There is
no recirculation or remixing of the chlorine with fresh chlorine entering the
vaporiser.

Constant volume vaporisers, typically with a heating device inside them,

like double envelope or kettle vaporisers. Chlorine liquid is added to the
vessel where it is boiled with the vaporised gas taken away from the
vessel.

Flash type vaporizers (like bayonet bundle) where chlorine is injected in an

overheated system that immediately flashes (evaporates) all incoming
liquid. In this kind of vaporizers, there is no liquid chlorine phase to
accumulate NCl3.

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Constant volume vaporisers maintain a pool of liquid chlorine. In such vaporisers,

liquid chlorine containing nitrogen trichloride is added to the pool and chlorine gas
with relatively little nitrogen trichloride is removed. As a result NCl3 will accumulate
in the liquid chlorine pool until equilibrium is reached. The equilibrium composition
can be calculated from the relative volatility (vapour pressures) of NCl3 and Cl2
(see Appendix 1). In these calculations, the thermal destruction of the NCl3 shall
be neglected. In the Appendix 1, the distribution of NCl3 between gas and liquid
phase is expressed as a concentration factor. The maximum level of NCl3
accumulation will therefore be directly related to the vaporiser temperature and
the NCl3 concentration in the Cl2 feed.
The vaporisation is generally carried out at temperatures at which some thermal
destruction of NCl3 will occur. The amount destroyed depends on parameters
such as liquid chlorine hold up, temperature, residence time and the equilibrium
gas-liquid composition.
The destruction of NCl3 (first order reaction) is expressed using a reaction rate
constant k, which is a function of the temperature. It is difficult to assess the exact
level of destruction because of the differing temperatures involved (chlorine bulk,
chlorine local, vessel exterior and heat exchange surface). It is therefore difficult to
predict the actual NCl3 levels that will result in the vaporiser. Ignoring NCl3
destruction in the vaporiser gives an extra operating safety margin. Nevertheless,
careful checks must still be maintained on the NCl3 levels in both the chlorine fed
to such equipment and the residual liquid. Where the equipment or process is
such that dangerous concentrations could occur, liquid must be drawn off
continually or periodically from the lowest point of the vaporiser - normally into a
purge vaporiser or a separate tank as described below.
For constant volume vaporisers, a greater safety margin can usually be achieved
by installing a purge system that continually removes liquid chlorine from the pool
to prevent NCl3 build-up. The continuous purge should have appropriate
monitoring to make sure it is functioning correctly. The purge flow is normally
vaporised completely in a relatively small dedicated plug flow vaporiser (typically a
small coil high temperature vaporiser in adequate material) to destroy the NCl3.
An alternative approach is for the purge flow to be returned to a storage tank that
has output to other destinations. This will not be suitable if the only output from
the stock tank is back to the vaporiser. Sufficient dilution shall be confirmed by
analysis.
Particular care should be taken when removing constant volume vaporisers from
service. It is essential to assess the effect this will have on nitrogen trichloride
concentrations, especially where the residual chlorine has to be vented down or
vaporised.

7.6.

Other Gas/Liquid Equipment

Some chlorine gas treatment processes make use of a liquid chlorine direct
contact pre-cooler and reboiler system which can lead to collection of high
concentrations of NCl3. Where the system operates at low temperatures, care

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must be taken to avoid a dangerous NCl3 concentration being reached. It must be

kept in mind that such a pre-cooler could contain more than one equilibrium stage
leading to much higher NCl3 concentrations in the pre-cooler bottom. In this case,
a monitored purge is necessary to control the NCl3 level.

7.7.

Process and Operational Changes

Changes to the chlorine manufacturing process or operation can affect the

amount of nitrogen trichloride produced. There are many possible changes that
can affect NCl3 levels. They include new plant, upgrading plant or equipment,
production rate changes and shutting down parts of a plant. Activities and
occurrences such as taking items of equipment out of service, recommissioning,
flow of liquid into a relief stream, flow of liquid into a heated trap vessel and
sampling can result in changes to NCl3 levels. These can not only affect
nitrogen trichloride levels in the overall process, but may also result in
disproportionately high levels of nitrogen trichloride in small parts of the system or
inside items of equipment or pipework.
Such factors should be accommodated in the plant design, but if the level of
nitrogen trichloride in the plant is unexpectedly high, the design philosophy may
become invalid. To control this, the level of the nitrogen trichloride in the plant
chlorine should be measured on a regular basis.
Whenever the chlorine producing process is changed, specific checks should be
made to ensure that the effect on the concentration of NCl3 is assessed.

7.8.

Emptying Equipment and Pipelines

When it is necessary to totally empty chlorine from a piece of equipment or

pipeline, the safest method is to remove all, or as much as possible, as liquid. This
is typically achieved by using the equipments normal discharge route or by
transferring the liquid chlorine into a storage tank. If the chlorine in the equipment
is to be vaporised and already has increased levels of nitrogen trichloride, it
should be diluted by blending (adding and purging of liquid). The target should be
that before any final vaporisation begins, the liquid chlorine pool has no more than
1000 kg and has a nitrogen trichloride concentration of no more than 20 mg/kg.

7.9.

Plant Design

Nitrogen trichloride is most hazardous when there is a possibility of complete (or

almost complete) evaporation of significant quantities of chlorine. It is especially a
problem when the final residual pool is confined to a small volume. Therefore
plant design should always consider how to minimise this risk associated with
nitrogen trichloride.
In particular the following should be considered:

How equipment will be emptied. Where possible it should be feasible to

completely empty the equipment as liquid into the process or a receiving
vessel.

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There should be no low points or sumps inside the equipment where small
quantities of liquid could accumulate.

Design of pipework should also consider the implications of low points that
could act as sumps for a pipe system or other equipment.

Ensuring that there are operating instructions that state the correct way to
start up and shut down plants, as well as to empty equipment.

Note: Horizontal chlorine drums (up to 1000 kg) and upright chlorine cylinders
(typically up to 100 kg) containing up to 20 mg/kg nitrogen trichloride are routinely
and safely discharged in the gas phase.

8. OPERATIONAL LEVELS OF NCl3 IN CHLORINE

During normal production and use of chlorine the levels of nitrogen trichloride will
be several orders of magnitude below the levels at which it is hazardous.
Historically the maximum level for chlorine sold and transported has been
maintained at a level not greater than 20 mg/kg (20 ppm w/w). At this
concentration nitrogen trichloride does not present a hazard.
As discussed in previous chapters, there are some particular processes operating
with a higher level of nitrogen trichloride (like chlorine vaporisers for example, see
also paragraph 8.1). In these circumstances special assessment must be made
to ensure that dangerous levels can never be approached.
The shutdown of equipment (for maintenance, etc.) carries a particular risk if there
is a need to evaporate significant quantities of chlorine during emptying of the
equipment. Special assessment must be made to ensure that dangerous levels of
NCl3 are never approached.

8.1.

Maximum Level of NCl3 inside any Equipment

The maximum admissible concentration of NCl3 at each point in a liquid chlorine

installation (production, storage, transport or use) should wherever possible be
limited to 20 mg/kg. Where this is not achievable, detailed risk assessments must
be carried out to ensure there are significant safety margins which prevent the
concentrations from approaching the known dangerous levels - which are a mass
of 0.3 g of pure NCl3 per cm of wetted metallic surface and an overall
concentration of 1% w/w. The assessment should consider both normal and
abnormal operations.
The safety margin should be as great as possible and under no circumstances
should operation be carried out in a way that could lead to concentrations of
greater than 1% w/w. When operating at levels approaching this, the
concentration of NCl3 should be monitored frequently. Where such monitoring is
not possible this limit should be reduced to 0.1% w/w or 1000 mg/kg.

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Furthermore when assessing the risk of operating at higher levels of nitrogen

trichloride, consideration should be given to:

The risk of unknowingly exceeding any safety margin a significant factor

in many historical incidents.

The accuracy of NCl3 concentration measurements for the method of

sampling and analysis used and the effect of the possible difference
between actual and measured levels on safety margins.

The measurement frequency and the possible variation with time of

nitrogen trichloride levels in the chlorine.

8.2.

Maximum Levels of NCl3 in Fixed Tanks

Nitrogen trichloride is normally controlled during chlorine production before the

liquefaction stage. Therefore fixed tanks will normally contain chlorine that has
nitrogen trichloride at levels below 20 mg/kg. This would normally only be
exceeded by a process upset or by evaporative procedures (see point 7.5).
Chlorine should not deliberately be stored with nitrogen trichloride at a level
greater than the 20 mg/kg. During any emptying procedures where the residual
chlorine will be removed by evaporation, the concentration of NCl3 should not be
greater than 20 mg/kg when there is 1 tonne liquid chlorine remaining in the tank.

8.3.

Maximum Levels of NCl3 in Small Mobile Containers

Chlorine is commonly taken in gaseous form from cylinders and drums containing
up to one tonne capacity. Experience shows that the standard NCl3 limit of
20 mg/kg in these small containers does not result in accumulation of dangerous
quantities of NCl3 in the later stage of emptying. Therefore small mobile
containers should not be filled with chlorine containing more than 20 mg/kg NCl3.

8.4.

Maximum Levels of NCl3 in Bulk Transport Containers

It is strongly recommended that all rail tanks, road tankers and ISO tank
containers of liquid chlorine are emptied by discharge in the liquid phase directly
into the customers storage, as recommended by Euro Chlor. The recommended
limit for NCl3 in these circumstances is 20 mg/kg.
In some emergencies, transport tanks may need to discharge chlorine gas. In
these circumstances, or in any case where there is a need to discharge chlorine in
the gas phase, a nitrogen trichloride limit should be set based upon a specific
analysis of the situation. Careful assessment of the risk is required if NCl3 levels
could exceed 20 mg/kg chlorine and, if the operation is performed out side the
chlorine producers premises, he will be involved in this risk assessment.

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9. REDUCING LEVELS OF NCl3 IN CHLORINE

The nitrogen trichloride in manufactured chlorine is normally controlled to be
no more than 20 mg/kg using one or more of the following methods. The
methods selected will depend upon the practicality and cost effectiveness for
the particular manufacturing operation.

9.1.

Reduction of NCl3 Formation

Nitrogen compounds present in salt, water etc. used to make the feed brine
should be reduced as much as practicable.

Chlorination of the brine at a pH higher than 8.5 or treatment with sodium

hypochlorite is capable of destroying a large proportion of ammonium
compounds, producing hydrochloric acid and nitrogen, which can then
easily be removed by air scrubbing the brine.

In situations where a small proportion of the manufactured chlorine gas

stream is required as liquid, there are two possible ways to achieve this:
a) Pass all of the chlorine gas through a liquefier and liquefy a small
proportion of it.
b) Pass a small proportion of the gas stream through the liquefier
and liquefy most of it. The remainder of the gas does not pass
through a liquefier.
The liquid produced by method (b) will contain less NCl3 than (a). This is
because the NCl3 is liquefied preferentially in method (a).

9.2.

Destruction of NCl3
9.2.1 For Gaseous Systems

Thermal decomposition of nitrogen trichloride can occur above 40-50C, but the
extent of decomposition will depend on the residence time. Centrifugal and dry
volumetric chlorine compressors contribute to the reduction of NCl3 content in
chlorine gas.
Ultra violet lights in the range 3600 4800 will decompose NCl3 in gas streams.
This can be done in units similar to those sometimes used to reduce the hydrogen
content of chlorine gas.
Activated carbon and metals, particularly copper base alloys at temperatures of
80-100C, can also promote the decomposition of NCl3. Great care must be taken
to avoid the risk of fire due to overheating as both NCl3 destruction and residual
water absorption on these catalysts are exothermic and iron will burn in chlorine at
elevated temperatures.
Remark: fresh activated carbon must be chlorinated slowly, starting with highly
diluted chlorine (with nitrogen for example), to avoid excessive temperature
increase.
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Chlorine gas can be scrubbed with liquid chlorine or carbon tetrachloride to extract
the NCl3; the liquid is then maintained at 50-70C for progressive destruction of
NCl3 as described in the following section.
9.2.2 For Liquid Systems
If operating at temperatures of 50-70C (such as in vaporisers, distillation units),
some of the NCl3 will be destroyed. However the evaporation of chlorine may still
result in higher levels of NCl3 than are acceptable and in these circumstances an
additional system to reduce the NCl3 is required.
Where there is accumulation of nitrogen trichloride in equipment such as a
vaporiser, removing periodically or continuously a small proportion of the chlorine
as liquid can control the maximum NCl3 level. The NCl3 in this side stream is then
destroyed separately and this is often referred to as a purge system.
There are several options for NCl3 destruction:

Vaporisation of liquid chlorine containing NCl3 at high temperature in a plug

flow vaporiser system.

Dissolving the NCl3 in a solvent such as carbon tetrachloride. The solvent

is then maintained at a temperature of 50-70C for a period long enough to
allow the decomposition of NCl3 (See TSEM 01/274 Nitrogen
Trichloride: a Continuous Challenge). NCl3 within carbon tetrachloride
can also be destroyed by combustion of the mixture.

An indication of the thermal decomposition rate constant of NCl3 is given in Figure

3 of Appendix 2.
Heating equipment containing liquid chlorine above 80C should be avoided if it
contains very high levels of NCl3 because the fast exothermic reaction could
initiate explosive decomposition.
9.2.3 Alternative methods
NCl3 can be destroyed by reaction in a number of chemical processes, e.g.
absorption of chlorine containing NCl3 in caustic soda.

9.3.

Blending of Chlorine

Where the concentration of NCl3 in liquid chlorine is too high, the NCl3
concentration can be reduced by the addition of liquid chlorine containing lower
levels of NCl3. This will have the effect of reducing the NCl3 concentration but it
will increase the mass of NCl3. The equipment will then contain more NCl3
although it will be at a lower concentration. Consequently if this liquid chlorine
were then evaporated back to the original volume, the NCl3 concentration would
be even higher. Therefore this measure is only appropriate where it then enables
the diluted liquid to be removed / drained and subsequently handled safely
elsewhere.
If necessary the process of blending and draining can be carried out repeatedly
until the concentration of NCl3 in the equipment is low enough to be safely

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evaporated to dryness. The target should be that before final vaporisation to

dryness begins there is a pool of chlorine that is no more than 1000 kg and has a
nitrogen trichloride concentration of no more than 20 mg/kg.

10. OTHER SAFETY MEASURES

10.1. Nitrogen compounds Analysis in Brine
Periodic analysis of nitrogen compounds in the brine allows the consequent
variations of NCl3 in liquid chlorine to be determined. The acceptable limits for
nitrogen compounds in the brine should take into account the local circumstances
such as electrolysis technology, the level of destruction in the gaseous chlorine,
etc.
The appropriate analysis frequency and maximum acceptable concentration
should be determined by experience taking into consideration the extent of
variation in the results obtained.
In case of change in water supply, raw materials and chemicals quality, the
analysis frequencies should be temporarily increased and the schedule adapted if
necessary.
On-line analysers have been developed, allowing continuous monitoring of the
nitrogen compounds in brine.

10.2. NCl3 Analysis in Liquid Chlorine

Analysis of NCl3 concentration is usually made on the liquid chlorine, but can also
be performed on the dry compressed gas (to give predictive information) and is
recommended on the gas flow from any NCl3 destruction unit to monitor its
performances.
The analysis of NCl3 in liquid chlorine requires special analytical equipment as
described in the Euro Chlor publication Analytical 2 Determination of
Nitrogen Trichloride in Liquid Chlorine. The analysis of low concentration of
NCl3 is the most difficult and care must be taken to avoid contamination of the
samples with other nitrogen compounds like ammonia. These analyses are
usually performed by the chlorine producers, but can be appropriate for some
consumers (for example if a constant volume vaporisation unit is used).
Regular checks at an appropriate frequency should be carried out to assess the
NCl3 levels in the system.
The appropriate analysis frequency should be determined by experience taking
into consideration the level of NCl3, the particular equipment, operating regime
and the extent of variation in the results obtained.
The following frequencies are suggested as a guide:
1. Where the peak NCl3 level is between 0.1 and 1%, analytical check should
be carried out at least once per week.
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2. Where the NCl3 level is normally between 20 mg/kg and 1000 mg/kg
(0.1%), analytical checks should be carried out at least once per month.
3. Where the NCl3 level is normally between 5 mg/kg and 20 mg/kg, the
analytical frequency should be at least once per 3 months on liquefaction
output or on the chlorine storage.
4. Where the NCl3 level is normally below 5 mg/kg, the frequency of testing
should be at least once per year.
During periods of commissioning, maintenance, process modification, process
fluctuations, shutting down and changes of raw material quality there can be a risk
of higher NCl3 levels and the frequency should be increased.
On-line analysers have been developed, allowing continuous monitoring of the
NCl3 concentration in chlorine and detect possible variations (see TSEM 05/299 On-Line Determination of Nitrogen Trichloride In Solvay Chlorine Production
Units).

10.3. Temperature Limits

Vaporisers should be designed to operate with low pressure steam at 120C
maximum (temperature to avoid chlorine-iron reaction) or using a heat transfer
fluid between steam and chlorine in which the temperature can be limited to 8090C, ensuring that the liquid chlorine containing NCl3 does not exceed 80C to
prevent rapid decomposition of NCl3.
Dedicated small coil purge vaporisers are used industrially to destroy NCl3 by
completely vaporising the plug flow. Temperature limits are set to achieve a
controlled decomposition rate, while at the same time ensuring that local
overheating of metal surfaces is avoided (for indication of the NCl3 decomposition
rate constant, see Appendix 1). Chlorine can be brought to higher temperature
using high nickel alloy vaporisers and adequate gaskets (up to 300C, depending
of the type of alloy), but precautions must be taken to cool the evaporated chlorine
before sending it into any steel equipment.
Because increasing temperature also increases the explosive decomposition rate
of NCl3, care should be taken to control the temperature of equipment handling
liquid chlorine containing high levels of NCl3 (0.1 - 1%). In this case, overheating
of chlorine should be avoided and direct electrical heating systems should not be
used.

11. REFERENCES
GEST 73/17 Low Pressure Storage of Liquid Chlorine
GEST 75/47 Design and operation of chlorine vaporisers
TSEM 01/274 - Nitrogen Trichloride: a Continuing Challenge (H.
Piersma)

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TSEM 05/299 - On-Line Determination of Nitrogen Trichloride In Solvay

Chlorine Production Units (N. Breton)
Analytical 2 Determination of Nitrogen Trichloride in Liquid Chlorine
World Chlorine Council Global Safety Team newsletter 12 of December 2009

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APPENDIX 1: PHYSICAL AND CHEMICAL PROPERTIES OF NITROGEN

TRICHLORIDE
Some physical properties are:
Molecular weight

120.38

Melting point

246 K (at 101.3 kPa) = minus 27C

Boiling point

344 K (at 101.3 kPa) = + 71C

Specific gravity (liquid)

1640 kg/m

Heat of vaporisation

31.07 kJ/mole

Vapour pressure can be calculated with the DIPPR databank (see graph 1 below)

with P = vapour pressure NCl3 (Pa)

T = absolute temperature (K)
A = 131.24

B = -8010

C = -16.91

D = 1.9677 10-5

Graph 1: Calculated pressure vapour of NCl3 as a function of temperature

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Experimental data (The Electrochemical Society Proceedings, May 19781) show

values somewhat higher than the prediction for temperatures below 50C, and
another study2 determined that the activity coefficient of diluted NCl3 in chlorine (to
correct the molar concentration) was about 13.4.
Nitrogen trichloride is an oil-like liquid, with a pungent odour; it has a low solubility
in water (2 g/kg) but is miscible in all proportions with liquid chlorine and other
chlorine compounds, such as carbon tetrachloride, chloroform, carbon disulphide
and benzene.
Nitrogen trichloride decomposes exothermically, and in the concentrated form, the
liquid behaves as a sensitive explosive, capable of rapid deflagration or
detonation. The explosion can be triggered by temperature (> 93C), shock and
light. Additionally, the explosion of NCl3 can also result from the contact with
substances like ozone, phosphorous, arsenic, alkali and organic matters.
The explosive nature of the material when present in liquid chlorine (and similar
materials) is dependent on both its concentration and on the total amount present.
Pure liquid NCl3 has been calculated as capable of generating a detonation
pressure of 5.5 to 7.5 x 10 atm. At very high concentrations in liquid chlorine it
could generate an energy release equivalent to 30-40% of the explosive force of
TNT. Concentrations > 35% by weight are readily capable of detonation by shock,
high temperature or ultra-violet light. 13% NCl3 appears to be the limiting
concentration to achieve detonation. Even at low concentrations, NCl3 will slowly
decompose; this decomposition rate increasing with temperature or in the
presence of metals such as copper or high nickel alloys. Ultra violet light can be
used to decompose NCl3 safely, when it exists as a minor component in the gas
phase.
As the concern over the explosive behaviour of NCl3 is in the context of mixtures
with liquid chlorine, the important factor is its explosive force when contained
within a typical chlorine pressure vessel with a wall thickness of 10-12 mm.
Private reports indicate that detonation of 1.5 g NCl3 (as 100%) /cm within a liquid
film would be capable of fracturing the metal, and 0.3 g/cm of surface area is
capable of overstressing the metal to the point of cracking or fissurisation. The
calculation of the potential explosive capability of an NCl3 / Cl2 mixture within a
vessel is only an approximation. As the chlorine evaporates, the concentration of
NCl3 will progressively increase, but if the residual pool covers a large area, or the
NCl3 concentration is still < 13%, the explosive potential remains small. On the
other hand, if the residual liquid is collected in a sump or bottom drain connection,
the critical mass sufficient to cause total metal failure may be reached.

Argade S.D., Balko E.N., Kramer D.A. anf J.F. Louvar Nitrogen Trichloride
Control in Chlorine Manufacture, Industrial Electrolytic Division, The
Electrochemical Society Proceedings, May 22, 1978
2

Zeller, R.L., Non-ideal solution behaviour of NCl3 in liquid chlorine, Annual

meeting of the Chlorine Institute Nitrogen Trichloride workshop, March 23, 2000.
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Experimental work has also shown that chemical decomposition of NCl 3 in liquid
chlorine and at > 3% is rapid and strongly exothermic.
The above summarises the properties of NCl3 in the presence of the much more
volatile liquid chlorine. In the presence of higher boiling impurities, which act as
inert diluents and are also found in commercial chlorine (such as bromine, C1 or
C2 chlorinated carbon compounds), the hazards from NCl3 accumulating in the
residues from evaporation are reduced by dilution. However care must be taken to
ensure that other reactive materials are not formed that could increase the
explosive hazard.
The maximum level of NCl3 that can accumulate in the liquid phase of a
continuous chlorine vaporiser can be calculated with the vapour pressure data for
NCl3 and chlorine. Assuming a perfect gas, this distribution - or concentration
factor ( mNCl3 x NCl3 / y NCl3 ) is calculated as follows with the abbreviations meaning:
pp = partial pressure
vp = vapour pressure
Pt = total pressure
y = mole fraction in gaseous phase
x = mole fraction in liquid phase
Dalton: pp

NCl3

Pt * y NCl3

Raoult: pp NCl3 vpNCl3 * x NCl3

and

ppCl2 Pt * yCl2

and

ppCl2 vpCl2 * xCl2

The concentration factor m NCl3 can be calculated from the Dalton and Raoult
equations:

pp NCl3 Pt * yNCl3 = vpNCl3 * xNCl3 mNCl3

xNCl3
yNCl3

Pt
vpNCl3

As NCl3 concentration is very small compared to chlorine concentration, we have:

yCl2 1 , so Dalton equation gives:

Pt ppCl2

and xCl2 1 , so the Raoult equation gives

ppCl2 vpCl2

The concentration factor becomes:

mNCl3

xNCl3
y NCl3

ppCl2
vp
Pt
= Cl2

vpNCl3
vpNCl3 vpNCl3

The values of distribution or concentration factor as function of the temperature

are shown in the Figure 1 below.

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Ideal theoretical solution (vapour pressure from DIPPR data bank)

Experimental values3 (concentration NCl3 in liquid hold-up related to
concentration in feed, supposing equal to the gas phase one, i.e. no NCl 3
destruction in vaporiser)
Non ideal theoretical solution4

Figure 1: Distribution of NCl3 in equilibrium between liquid chlorine and

gaseous chlorine expressed by the concentration factor m NCl3

Chlorine Institute Pamphlet 21, Nitrogen Trichloride - A collection of reports and

papers, Edition 5, October 2002, page 187.
4
Zeller R.L., Non-ideal solution behaviour of NCl3 in liquid chlorine, Annual
meeting of the Chlorine Institute Nitrogen Trichloride workshop, March 23, 2000.
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APPENDIX 2: THERMAL DESTRUCTION OF NCl3 IN A CHLORINE

VAPORISER
F kg Cl2/h
b mg NCl3/kg

F kg Cl2/h
a mg NCl3/kg
V kg Cl2
c mg NCl3/kg
Figure 2 Mass balance of a vaporiser
In the vaporiser two phenomena take place,
1) Thermal destruction of NCl3
The destruction is a 1st order reaction (mg/kg/h) and can be described with the
reaction velocity : R = k . c

[eq 1]

The destruction rate in a volume V is: G = R . V = k . c . V

[eq 2]

expressed in mg NCl3/h
2) Equilibrium NCl3 concentration between the liquid and gaseous Cl2 phase
The equilibrium is defined as the concentration factor mNCl3

c
b

[eq 3]

Calculation
The NCl3 mass balance for the vaporiser is: F . a F . b = G

[eq 4]

Substitution of [eq 2] in [eq 4] gives: F . a F . b = k . c . V

Rearrangement results in: a - b = k . c . (V/F)

[eq 5]

Introduction of the equilibrium relation [eq 3] in [eq 5] gives:

a - b = k . b . m NCl3 . (V/F)

[eq 6]

with (V/F) = the residence time in the vaporiser,

[eq 7]

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Values for k (reaction velocity constant) are given in Figure 3 here below.

reaction rate constant k

100
75
50
25

100 * log k

0
-25
-50
-75
-100
-125
-150
-175
-200
30

40

50

60

70

80

90

100

110

120

Temperature oC

Figure 3: Reaction rate constant k in h-1 for the decomposition of NCl3 in

liquid chlorine as a function of temperature
Examples are shown for the two following cases: a vertical shell and tube
vaporiser and a kettle type vaporiser.
Example 1: vertical shell and tube vaporiser
The essential characteristics of this vaporiser are:
shell diameter

= 310 mm

tube diameter

= 30 mm

wetted tube length

= 1400 mm

number of tubes

= 46

Liquid volume = /4 . L . (D2 n . d2) = 0.06 m3

With density Cl2 = 1500 kg/m3 V = 90 kg.
If the capacity of the vaporiser F= 3000 kg/h (V/F) = = 0.03 h.

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If the vaporiser is operating at an equilibrium liquid temperature of 50C, the wall

temperature of the tubes can be about 90C but the residence time at this
temperature is much shorter than (V/F) = .
Considering the average vaporiser temperature (50C) and neglecting the
destruction at the wall temperature, we obtain log k = -1.8 k = 0.0158 h-1 from
Figure 3 here above.
From Figure 1 (see Appendix 1, experimental curve) m NCl3 = about 26
With a = 10 mg/kg, b is calculated from [eq 7]:
b = 9.88 mg/kg
and c is calculated from [eq 3]:
c = 26 . b = 257 mg/kg
The destructed amount is calculated from [eq 4]:
G = 365 mg/h.
The supplied amount of NCl3 is (F . a) = 3000 . 10 = 30000 mg/h
This means that only (365 / 30000) . 100% = 1.2% is destructed in the vaporiser.
If the wall temperature of the tubes is also considered for a part of the NCl3
destruction (at 90C, log k= 0.6 and k = 4 h-1) and the corresponding volume /
local residence time is hypothetically assumed to be 5% of the global volume /
residence time (* = 0.05 . (V/F)), then the total destructed amount of NCl3,
relative to the supplied NCl3, becomes 14 % (with m NCl3 being about 20).
The results of this calculation will of course vary according to the hypothesis
considered.
Example 2: kettle type vaporiser
This kind of vaporiser (see Figure 4) contains more liquid hold up V, resulting in a
residence time = (V/F) higher than for a vertical shell/tube vaporiser.

F kg Cl2 /h
b mg NCl3 /kg Cl2
F kg Cl2/h
a mg NCl3/kg

c mg NCl3 /kg

Figure 4 - Kettle type vaporiser

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Dimensions of the kettle type vaporiser:

shell diameter

800 mm

shell length

Ls =

1600 mm

tube diameter

30 mm

tube length

Lt

1400 mm

number of tubes

n =

46

Liquid chlorine hold up, assuming the shell half filled with liquid (and all tubes are
in the liquid phase):
liquid volume V = /4 . (0.5 . D2 . Ls n . d2 . Lt) V = 0.356 m3.
With density Cl2 = 1500 kg/m3 V = 535 kg.
The capacity of the vaporiser is F=3000 kg/h and = (V/F) = 0.178 h.
We suppose that the vaporiser is operating at an equilibrium temperature of 50C.
From Figure 3 here above log k = -1.8 k = 0.0158 h-1
From Figure 1 (see Appendix 1) m NCl3 = 26
With a = 10 mg/kg, b is calculated from [eq 7]:
b = 9.3 mg/kg
and c is calculated from [eq 3] :
c = 26

b = 242 mg/kg

The destructed amount is calculated from [eq 4]:

G = 2054 mg /h
The supplied amount of NCl3 is F . a = 3000 . 10 = 30000 mg/h
This means that (2054 / 30000) . 100% = 7% is destructed in the vaporiser.
If the wall temperature of the tubes is also considered for a part of the NCl3
destruction (90C k = 4 h-1) and the corresponding volume / residence time is
hypothetically assumed to be also 5% of the global volume / residence time (* =
0.05 . (V/F)), than the total destructed amount of NCl3 relative to the supplied NCl3
becomes 49%.
The results of this calculation will of course vary according to the hypothesis
considered.
Care must also be taken here as there is in this case a much higher volume at
high temperature than for shell and tubes and the quantity of NCl3 destroyed is
highly dependent of this hypothesis.

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Conclusion
Some thermal destruction of NCl3 occurs in the vaporiser. To be at the safe side it
is recommended to calculate the destruction based on the bulk liquid chlorine
temperature (temperature in equilibrium with the operating pressure) rather than
the wall temperature because of the uncertainty of the real residence time at that
temperature..
Literature

Chlorine Institute Members Information Report Pamphlet 21 "Nitrogen

Trichloride - A Collection of Reports and Papers" Edition 5, 2002.

Zeller, R.L., Non-ideal solution behaviour of NCl3 in liquid chlorine, Annual

meeting of the Chlorine Institute Nitrogen Trichloride workshop, March 23,
2000

Mellor, Inorganic and Theoretical Chemistry, Volume VIII, pp 598 - 604.

T. Dokter - Formation of NCl3 and N2O in the reaction of NaOCl and

nitrogen compounds. Journal of Hazardous Materials 12 (1985) pp. 207,
224.

Physical properties are derived from the GMELIN and DIPPR databanks

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APPENDIX 3: CALCULATION OF THE MASS / WETTED AREA RATIO OF A

RESIDUAL POOL OF NITROGEN TRICHLORIDE IN A HORIZONTAL
CYLINDRICAL TANK
This calculation makes the following approximations:

Only the cylindrical section is considered (not the dished ends). This should
provide a conservative assessment.

The size of the pool is small - reasonable considering large pools of NCl3
are too hazardous

The vessel is absolutely horizontal - this is a potentially significant error

because the pool depth will be so small (see below for how the depth is
calculated). Inclinations of the vessel that would be totally negligible from a
process perspective may be large when compared to the pool size.

Where:
M = mass of nitrogen trichloride (g)
SG = specific gravity of fluid (= 1.64 for nitrogen trichloride)
V = volume of the pool (cm3)
A = cross sectional area of the pool (cm2)
D = vessel diameter (cm)
L = length of vessel cylindrical section (cm)
H = depth of pool (mm)
Q = angle the pool subtends at the centreline of the vessel (radians)
W = wetted area of metal (cm2)
R = ratio of mass to wetted area (g / cm2)

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Calculate the volume and cross sectional area of the pool

Calculate the area of the sector subtending angle Q

Calculate the area of the triangle above the pool area

Calculate the cross sectional area of the pool (sector minus triangle)

As Taylor series for small angle gives

The cross sectional of the pool can be approximated as

Calculate the angle in radians the pool subtends at the centreline of the vessel

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Calculate the depth of the pool in mm

Calculate the wetted area of metal

Calculate the ratio of mass to wetted area

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Industrial consumers of chlorine, engineering and equipment supply companies

world-wide and chlorine producers outside Europe may establish a permanent
relationship with Euro Chlor by becoming Associate Members or Technical
Correspondents.
Details of membership categories and fees are available from:
Euro Chlor
Avenue E Van Nieuwenhuyse 4, Box 2
B-1160 Brussels
Belgium

February 2012

Tel:

+32 2 676 7211

Fax:

+32 2 676 7241

e-mail:

eurochlor@cefic.be

Internet:

http://www.eurochlor.org

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