REVIEW

Safety of chlorine production

and chlorination processes
Most chlorine production is obtained by electrolysis of NaCl aqueous solution. Other processes to produce
chlorine involve the electrolysis of KCl or HCl aqueous solutions, the electrolysis of molten NaCl at high
temperature and the Deacon process. In most cases, chlorine is a by-product in the production of caustic
soda, potassium hydroxide, sodium metal or is recovered from HCl using HCl aqueous solution electrolysis
or gas–solid reaction in the Deacon process.
Chlorination reactions are part of various processes in the chemical industry, to manufacture heavy
chemicals, specialty chemicals, pesticides and pharmaceuticals, in inorganic and organic chemistry. They
are valuable tools in organic synthesis.
The hazards of chlorine production and chlorination processes involve:

- Gas phase explosion, i.e., self-ignition, deflagration and detonation in the gas phase.
- Runaway reaction or thermal explosion, deflagration and detonation in the condensed phase.

Gas phase explosion hazard with chlorine as an oxidizer is present in the production of chlorine by
electrolysis, in gas phase chlorination processes and in chlorination reactions carried out in the condensed
phase.
Gas phase chlorination processes are continuous processes operating either in the flammable range like
burners or outside the flammable range in loop reactors or loop processes where chlorine is the controlling
reactant.
When chlorination is carried out by chlorine injection in the liquid phase, gas phase explosion hazard
is related to chlorine evolution in the vapour phase, giving a flammable mixture with the solvent or
reaction mixture vapour. Hazard assessment is achieved by comparing the gas phase composition with the
flammable area of the gaseous mixture. Self-ignition is also considered because the self-ignition temperature
of gaseous fuels in chlorine atmosphere is lower than in air or oxygen and often close to the ambient
temperature.
The relevant flammability data is the flammability limits, LFL, UFL, minimum oxidizer concentration
(MOC), auto-ignition temperature (AIT), of fuels in chlorine and the explosion characteristics Pmax and KG
for deflagration in chlorine.
A collection of flammability data is given for the reader convenience, collected in the literature or obtained
in our own experimental facility, a specially designed 20 L Hastelloy C 276 sphere with 200 bar pressure
resistance, ambient to 300 8C initial temperature, easily opened for frequent cleaning. This apparatus allows
precise determination of the flammability limits, self-ignition temperature, explosion overpressure, rate of
pressure rise and flame speed.
Runaway reaction hazards in chlorination reactions are related to a series of dangerous process situations
or process deviations such as:

- Delay in reaction initiation.

- Reaction mixture instability.
- Production and accumulation of unstable species like chloramines, nitrogen tri-chloride, chloro-nitroso
compounds, alcohol hypo-chlorites.
- Demixing or separation of unstable species in case of chlorination reactions made in aqueous solution,
because the chlorinated compounds are less soluble in water than the initial reactant.
A full review of runaway reaction hazards in chlorination reactions is given with examples from the
literature and from the laboratory.

1074-9098/$30.00 ß Division of Chemical Health and Safety of the American Chemical Society 5
doi:10.1016/j.chs.2004.08.002 Elsevier Inc. All rights reserved.
By Jean-Louis Gustin
INTRODUCTION—CHLORINE
PRODUCTION AND USE
Most chlorine production is obtained
by electrolysis of NaCl aqueous solu-
tions. Different processes are also
used. Their importance depends on
the area considered.
In 1996, the mercury cell process
accounted for 53% of the chlorine pro-
duction in France, 64% in Europe and
39% worldwide. The diaphragm cell
process accounted for 32% of the pro-
duction in France, 25% in Europe and
45% worldwide. The membrane cell
process accounted for 15% of the pro-
duction in France, 11% in Europe and
16% worldwide.
For environmental reasons, the
installation of new mercury cell plants
is not allowed in Europe and the exist-
ing plants must meet the ever more
demanding regulation for mercury
emission control. The importance of
the diaphragm cell process should
not increase as long as diaphragms
are made of asbestos. New plants are
using the more environment friendly
membrane cell process.
The process for the electrolysis of
NaCl aqueous solutions to produce
caustic soda may apply to the electro-
lysis of KCl aqueous solutions as well,
for the production of potassium hydro-
xide.
For the production of sodium metal,
the electrolysis of molten NaCl at 650 8C
is used. This process accounts for 2% of
the chlorine production in France.
The electrolysis of HCl aqueous
solutions using a diaphragm cell pro-
Jean-Louis Gustin is process safety
consultant since 1984 within the for-
mer Rhône-Poulenc, Aventis, and now
Rhodia, working in the field of chem-
istry and runaway reactions. He is
affiliated with Rhoditech 24 Avenue
Jean-Jaurès, F69153 Décines-Char-
pieu, France (Tel.: +4 72 93 57 14;
fax +4 72 93 59 68; e-mail: jean-louis.-
gustin@eu.rhodia.com).
A short version of this paper was pre-
sented to the Eurochlor seminar held
in Leipzig, Germany, 1997, and was
published by Eurochlor under the
reference GEST 97/242.
6 Chemical Health & Safety, January/February 2005
cess is used for the recycling into chlor-
ine of HCl aqueous solutions produced
by chlorination processes. The HCl
produced by TiO2 chlorine processes
may be recycled into chlorine using the
Deacon process.
The chlorine produced by electroly-
sis of NaCl, KCl, or HCl aqueous solu-
tions is obtained wet of water and is
corrosive for current metallic materials
of construction except titanium. The
wet gas is dried as soon as possible
by cooling to above 12 8C to prevent
chlorine hydrate formation, often by
direct contact with cold water, filtra-
tion of the water aerosol and washing
with 98% sulphuric acid in a column,
to reach a water concentration of less
than 20 mg/kg chlorine. Then carbon
steel equipment dried to a dew point of
40 8C under atmospheric pressure
may be used to process dry chlorine
(see Process diagram 1).
The dry gaseous chlorine is then
washed with liquid chlorine in a bub-
ble-cap tray column operated at
35 8C under atmospheric pressure
to remove nitrogen tri-chloride from
the gaseous chlorine and cool the gas
before compression. This column is
also intended to separate chlorinated
organic compounds from gaseous
chlorine before compression in plants
where this chlorinated organic con-
centration is significant (see Process
diagram 2).
NCl3 and the chlorinated organic
compounds condense or dissolve in
liquid chlorine in the column bottom,
which is routinely admitted in a
so-called re-boiler where carbon tetra-
chloride is often added to extract
nitrogen tri-chloride and allow its sub-
sequent disposal/destruction. Carbon
tetrachloride is a suitable solvent to
extract NCl3 because it cannot be
further chlorinated and has an atmo-
spheric boiling point of 77 8C versus
71 8C for NCl3.
The re-boiler is intended to allow
chlorine to vaporize and return to
the column.
The re-boiler is either operated cold
(0 to 5 8C) in which case NCl3 is allowed
to accumulate in this vessel and must be
further disposed, or the re-boiler is
operated hot (45 to 60 8C) in which case
the re-boiler is intended to thermally
decompose NCl3 and is equipped with
a condenser. In between is a grey zone
where the temperature is not carefully
controlled, allowing NCl3 to accumu-
late and subsequently decompose. This
processing step is subject to many pro-
blems and accident case histories con-
cerning the disposal/destruction of the
NCl3 solutions.
The gaseous chlorine is then lique-
fied by compression and cooling thus
providing a further purification step for
the liquid chlorine and allowing the
storage and transport of liquid chlor-
ine.
Total liquefaction of the chlorine
produced is difficult and may cause
problems due to the presence of gas-
eous impurities (H2, CO2, CO, O2, N2).
A fraction of the chlorine production is
not liquefied and is used on site at least
for the production of bleach. This gas-
eous chlorine is rich in gaseous impu-
rities and called residual chlorine.
The chlorine consumer plants are
best situated near the chlorine produc-
tion plants, to limit chlorine transport.
However, this is not always so for his-
torical reasons or for small consumer
plants. Therefore, a fraction of the
chlorine produced is liquefied to
obtain good purity chlorine and allow
chlorine to be transported to remote
consumer plants. In France and in
Europe as well, the capacity of liquid
chlorine storage facilities is limited by
the regulation. In France, chlorine sto-
rage vessels as well as loading and
unloading stations must be enclosed
in a housing connected to a scrubber
using caustic soda, to control acciden-
tal releases. The capacity of the scrub-
ber is typically 5,000 kg/hour chlorine
in air destruction.
Most chlorine storage facilities are
operated at or near ambient tempera-
ture, under the liquid vapour pressure.
There are limited examples of cryo-
genic chlorine storage facilities oper-
ated at 35 8C and atmospheric
pressure, as a buffer storage between
chlorine production and local con-
sumption. About 10% of the chlorine
production is transported to a remote
consumer plant. Bulk chlorine trans-
port in Europe is by rail tanks. The use
of road trucks is very limited. The use
of barges or boats was considered in
northern Europe, it is more wide-
spread in the USA.
Process diagram 1. Chlorine line of an electrolysis plant.
One tonne cylinders and bottles are
used to supply chlorine to small con-
sumers and for water treatment.
Chlorine is an important raw material
in the chemical industry. The main uses
are in the production of PVC (40%),
chlorinated solvents (25%), Phosgene
(10%), other organics (10%), inorganic
and miscellaneous products (15%).
Quite similar to oxygen, chlorine is
used as an oxidizer in a wide range of
chemical processes where it is reacted
with organic and inorganic com-
Process diagram 2. Washing/cooling column and re-boiler.
Chemical Health & Safety, January/February 2005
pounds to produce chlorinated pro-
ducts or intermediates. A wide range
of useful products are obtained such
as bleach, metallic chlorides, reactive
monomers to manufacture plastics,
heat exchange fluids, chlorinated
solvents and intermediates in organic
synthesis to produce specialty
chemicals, pesticides and pharmaceu-
ticals.
Chlorine is involved in a wide range
of process situations including gas
phase reactions in a burner or in a loop
reactor, on a catalyst bed, solid /gas
reactions in a fluid bed, gas/liquid
reactions in a packed column, gas/
liquid reactions by injecting chlorine
in a liquid phase in a semi-batch pro-
cess or in a continuous process. The
reaction of chlorine takes place with-
out catalyst, in the presence of a cata-
lyst or in photochemical reactions.
Compared to oxygen, chlorine is a
more reactive gas because it is pro-
cessed as a pure gas whereas oxygen
is often reacted using air. More pro-
blems would occur with oxygen if the
use of pure oxygen was widespread in
the chemical industry.
Compared to pure oxygen, chlorine
is even more reactive. The self-ignition
temperature of gaseous mixtures of
organic vapours with chlorine is much
lower than that of their mixtures with
oxygen. Natural light can split the
chlorine molecule to produce reactive
chlorine radicals. Many reactions of
chlorine take place near the ambient
temperature. The combustion of iron
in chlorine can be initiated at tempera-
tures slightly above 100 8C.
Chlorine is toxic to man and ani-
mals. Many chlorinated compounds
are also toxic.
The TLV
TWA is 0.5 ppm and the
STEL/C is 1 ppm. The effects of expo-
sure to chlorine may be described as
follows.
Below 1 ppm, detection of the smell by
normal subject.
7
1 to 5 ppm, slight irritation of the upper
breathing path.
5 to 8 ppm, irritation of the upper
breathing path and of the eyes.
15 to 20 ppm, immediate severe irrita-
tion of the upper breathing path, strong
cough and choking.
30 ppm, breathing is difficult, pain to
breast, nausea, vomiting.
40–50 ppm, chemical tracheobronchi-
tis, severe lung edema may appear up
to 72 hours later.
Above 50 ppm, depending on the
exposure time, loss of consciousness
and death.
For all the above reasons, the chemical
processes where chlorine is involved
are submitted to careful safety studies
where the specific chemical properties
of chlorine are considered.
THERMAL EXPLOSION HAZARD IN
THE CONDENSED PHASE
Chlorine is a strong oxidizer. Mixtures
of chlorine and organic fuels may have
a high energy content and are unstable.
The thermal instability of condensed
phases containing chlorine can appear
in various process conditions.
Example of Chlorine Accumulation Due
to a Delay in the Chlorination Reaction
Initiation
When chlorine is injected in a liquid
reaction mixture, the chlorination
reaction may not start immediately
allowing chlorine to accumulate in
the reaction mixture. The reaction
may start suddenly when a large con-
centration of chlorine is present in the
reaction mixture and give a severe run-
away reaction producing a large quan-
tity of insoluble HCl. An example of
such an induction period in chlorina-
tion is mentioned in the literature for
the chlorination of ketones in metha-
nol.1 To avoid this type of incident, the
reaction onset should be checked
before allowing a large concentration
of un-reacted chlorine to be dissolved
in the liquid phase.
Examples of Dangerous Process
Situation in Chlorination Reactions
When chlorine is reacted with an
organic fuel in a liquid reaction mix-
ture, highly unstable substitution pro-
8 Chemical Health & Safety, January/February 2005
ducts may be obtained. This process
situation is dangerous in two cases:
- if a high concentration of unstable
chlorination product is obtained in
the condensed phase and
- if a chlorinated liquid phase sepa-
rates from the bulk liquid phase
‘‘by segregation’’.
The latter situation is frequent in the
chlorination of aqueous solutions of
organic reactants because the chlori-
nated products are less soluble in water
than the initial reactants.
Examples of this dangerous process
situation are the synthesis of alcohol
hypo-chlorites by injecting chlorine in
an alkaline aqueous solution of alco-
hol, the formation of nitrogen tri-
chloride by chlorination of certain
‘‘dangerous’’ nitrogen containing com-
pounds, the chlorination of oximes
in aqueous solution, the radical or
photochemical chlorination of succi-
nimide.
Alcohol Hypochlorites
Traugott Sandmeyer described the
synthesis of methyl and ethyl hypo-
chlorites2,3 and suffered severe injuries
due to explosions during the experi-
ments. In Sandmeyer’s method to
obtain alcohol hypochlorites, chlorine
is injected into an aqueous solution of
alcohol and caustic soda with a mole
ratio alcohol/sodium hydroxide of 1,
under cooling at 0 8C. The alcohol
hypochlorite separates by decantation.
When chlorine does not dissolve any
longer in the solution, chlorine injec-
tion must be interrupted to avoid the
alcohol hypochlorite decomposition
under acidic conditions. The method
was described for the synthesis
of methyl hypochlorite and ethyl
hypochlorite. Methyl hypochlorite is
a volatile yellow oil with a boiling point
of 10 to 12 8C under 726 mmHg. Ethyl
hypochlorite has an atmospheric boil-
ing point of 36 8C. The liquids are
flammable in air. They decompose
slowly under alkaline conditions and
with violence under acidic conditions.
The Sandmeyer method may be
applied to water soluble alcohols.
Roland Fort and Leon Denivelle4
described the synthesis and properties
of a series of other alcohol hypochlor-
ites obtained following Sandmeyer’s
method and proposed other methods
of solvent extraction to obtain those
alcohol hypochlorites which cannot be
obtained directly using Sandmeyer’s
method.
In most process instances, the forma-
tion of alcohol hypochlorites is
unwanted for process safety reasons.
However, the formation of alcohol
hypochlorites is possible in waste-water
treatments where alcohols are present,
using chlorine or bleach. This is a very
frequent process situation. The accu-
mulation of alcohol hypochlorite is pos-
sible under alkaline conditions. The
solubility limits of the hypochlorite in
water depend on the alcohol chain
length. Methyl hypochlorite is soluble
in water and should not separate unless
the alcohol concentration in the waste
water is very high (of several percents by
weight). Under acidic conditions, alco-
hol hypochlorites are unstable and
should decompose readily or behave
like chlorinating reagents, contributing
to the water treatment. One should take
care if the yellow oil separates from the
bulk liquid. Methyl and ethyl hypo-
chlorites may detonate in the liquid
phase.
Nitrogen Trichloride
The oxidation of organic compounds
containing nitrogen in their formula
(amines, amides, cyanides, urea) using
chlorine, gives unstable chloramines.
The very unstable nitrogen trichloride
is finally obtained. NCl3 is only slightly
soluble in water and can separate from
aqueous solutions giving a very sensi-
tive yellow dense oil. NCl3 can also be
obtained by chlorination of aqueous
solutions containing ammonium ions,
ammonium nitrate, ammonium sul-
phate, ammonium chloride or ammo-
nia. The formation of nitrogen
trichloride is possible in chlorination
processes and in water treatment using
chlorine or bleach.
Due to the presence of ammonium
ions and amine impurities in the salt,
and to the use of nitrogen containing
flocculants for salt processing or to the
contamination of the salt by dangerous
nitrogen containing impurities, nitro-
gen trichloride is present in the crude
chlorine produced by electrolysis of
NaCl or KCl brines. Nitrogen trichlor-
ide may also be present in the chlorine
produced by electrolysis of HCl aqu-
eous solutions but is absent from the
chlorine produced by electrolysis of
molten NaCl due to the high tempera-
ture conditions in this particular pro-
cess.
NCl3 compound was first obtained
by Pierre Louis Dulong (1785–1838)
by chlorination of ammonium chloride
solutions. Dulong was seriously
injured by several explosions of liquid
NCl3.5
NCl3 is liquid under normal tem-
perature and pressure conditions.
The theoretical atmospheric boiling
point is 71 8C. The density of the liquid
is of 1.635 g/cm3 at ambient tempera-
ture, so the liquid may accumulate
undetected under water. The pungent
odour of NCl3 is that of dirty chlori-
nated swimming pools. The vapour
pressure of the pure liquid is
150 mmHg @ 20 8C and 80 mmHg @
0 8C. Due to its high vapour pressure
under ambient temperature, the liquid
tends to evaporate quickly. NCl3 is
toxic. The recommended occupational
exposure limit in France is of 0.1 ppm
and the TLV-STEL is of 0.3 ppm.
Occupational exposure can occur in
indoor swimming pool areas and in
cleaning operations using bleach.
The heat of decomposition was
determined in carbon tetrachloride
solutions: DH = 54.7 kcal/mol or
DH = 457 kcal/kg NCl3. In this
decomposition, 1 mol of nitrogen and
3 mol of chlorine are produced per
2 mol of NCl3. The solvent is left unaf-
fected in this decomposition.
Liquid NCl3 can detonate in the
condensed phase. The constant
volume detonation of the liquid
produces a maximum pressure of
5,500 bar and a maximum temperature
of 2,128 8C.
NCl3 vapour is also unstable and may
explode above 93 8C or under the influ-
ence of light. The limits of the gas phase
explosive decomposition range in a P
versus T diagram are as follows:
Upper limit: 40 mmHg at 20 8C,
70 mmHg at 40 8C, 115 mmHg at 60 8C.
Lower limit: 10 3 mmHg at room
temperature.
The lower explosive limit is difficult
to distinguish from the slow reaction.
Between the lower limit and the
upper limit, the decomposition is
explosive and presents a flame propa-
gation phenomenon. In the dark, NCl3
decomposition flame has a pink colour
at low concentration. Above the upper
limit NCl3 vapour decomposes follow-
ing a slow reaction mode. NCl3 is
thought to detonate also in the gas
phase but the study of this detonation
in shock tubes is difficult due to the
problem of obtaining a high vapour
concentration.
The very low LEL of NCl3 makes
possible the initiation of gas phase
explosion of flammable chlorine + fuel
mixtures by NCl3 vapour at trace con-
centration.
Nitrogen trichloride is miscible with
liquid chlorine even at chlorine atmo-
spheric boiling point of 35 8C. NCl3 is
also soluble in carbon tetrachloride
and chloroform. Other solvents are
sometimes mentioned like benzene,
ether, carbon disulfide but one should
avoid solvents which may be chlori-
nated by NCl3 or chlorine because the
solution obtained may be unstable and
react violently. NCl3 is a chlorinating
reactant. Solutions of 12–15 wt.%
NCl3 in carbon tetrachloride or
chloroform are expected to be stable
under ambient temperature but would
decompose above 60 8C.
The decomposition exotherm
obtained in DTA under temperature
scan conditions, is influenced by the
test cell wall material. The decomposi-
tion pattern shows a chemical accel-
eration phenomenon in titanium or
stainless steel closed cell, and a slow
decomposition exotherm in closed
glass ampoule. In other words, the
decomposition of liquid NCl3 presents
an autocatalytic behaviour and is cat-
alyzed by metals like carbon steel,
stainless steel and titanium. This parti-
cular behaviour finds some industrial
application in NCl3 thermal destruc-
tion processes used in chlorine pro-
duction.
Case Histories Concerning Nitrogen
Trichloride in Chlorine Purification
Processes
A long time ago, the liquid chlorine
used to wash nitrogen trichloride from
gaseous chlorine in the bubble-cap tray
column described above, was collected
in one tonne cylinders for use in the
Balard reaction, to produce bromine
by chlorination of brine containing
sodium bromide. An operator felt that
a one tonne cylinder was self-heating
above ambient temperature. The cylin-
der did not rupture but it was clear that
the NCl3 concentration in this residual
chlorine was not well controlled and
that this method of NCl3 disposal was
not safe.
Further to this incident, the process
was modified and carbon tetrachloride
was added to the chlorine purification
column re-boiler to allow NCl3 extrac-
tion. The NCl3 solution in liquid chlor-
ine was continuously discharged from
the column bottom to the re-boiler,
degassed and the NCl3 in CCl4 solution
continuously decomposed in a carbon
steel vessel by raising the solution
temperature to 45–60 8C. No serious
incident occurred with this type of
destruction process.
In another example, NCl3 was
extracted by adding a mixture of car-
bon tetrachloride and chloroform to
the purification column re-boiler.
The NCl3 in liquid chlorine solution
was admitted to the re-boiler, degassed
and withdrawn batch-wise to be sent
to incineration. No serious incident
occurred with this type of destruction
process.
However, the control of NCl3 con-
centration in the CCl4, chloroform and
chlorinated organics solution is critical
since NCl3 may decompose violently on
heating. A runaway reaction accident is
described on this process in a pamphlet
by the American Chlorine Institute.6A
An off-line re-boiler used to degas chlor-
ine from a NCl3 in CCl4, chloroform and
chlorinated organics solution before
its disposal, exploded on October 17,
1967 in a PPG facility at Lake Charles,
Louisiana. The NCl3 concentration was
deduced from the concentration in the
column bottom after the incident, to be
only of 8.5 wt.% NCl3. This solution
could self-heat above the ambient tem-
perature of 22 8C and the decomposi-
tion could runaway causing the re-
boiler vessel rupture under an estimated
pressure of 51 bar and temperature of
100 8C.
Another accident case history on the
same type of installation at an unspe-
cified location was also reported in a

Chemical Health & Safety, January/February 2005 9

letter of February 3, 1995 issued by the
Chlorine Institute.6B
In this accident, a double block ball
valve system was installed on the liquid
chlorine line between the washing col-
umn bottom and the re-boiler, because
the previously installed single ball
valve did not close properly. As the
plant was shut down for maintenance,
shortly after the process modification,
the pipe between the two ball valves
and the ball valves themselves were
destroyed by an explosion, causing a
chlorine release which killed two
operators.
The column drain pipe flange was
then sealed using a blind flange and it
was a decided to pump a drum of
carbon tetrachloride in the washing
column bottom. While this was imple-
mented a second explosion occurred
in the concrete trench below the
washing column where the NCl3 in
liquid chlorine solution from the col-
umn bottom had been collected. This
second explosion severely injured one
operator. As the NCl3 concentration
was kept low in this plant column re-
boiler, a fast increase of the NCl3
concentration in the crude chlorine
was suspected due to an unexpected
contamination of the salt, brine or
chlorine itself. A possible source of
contamination was ammonia present
in the cooling water used in direct
contact with gaseous chlorine from
the electrolysis room. Also, the deci-
sion to install a double block valve
system and ball valves on the drain
pipe from the washing column bottom
to the re-boiler was wrong since a
NCl3 decomposition could have been
anticipated in this closed pipe and in
the ball valve bodies. The name given
to the equipment may be misleading.
Of course the washing column may
wash also chlorinated organics from
gaseous chlorine and it is also a pre-
cooler for gaseous chlorine before
compression. However, it is impor-
tant to state that this equipment is
also designed to collect nitrogen tri-
chloride, a very unstable detonating
compound. Also the column re-boiler
is designed to evaporate chlorine from
the carbon tetrachloride solution, but
it is also a purge tank or a buffer tank
before the solution disposal if it is kept
at low (0 to 5 8C) temperature or a
10
chemical reactor to decompose NCl3
if it is operated at high (45 to 60 8C)
temperature.
Recommended NCl3 Concentration
Limits in Commercial Chlorine
Trace concentration of NCl3 is also
present in bulk liquid chlorine shipped
to customers. Following Eurochlor
recommendations, the NCl3 concen-
tration should not exceed 20 ppm in
1,000 kg chlorine cylinders, 10 ppm in
20,000 and 50,000 kg rail tanks and
2 ppm above 300,000 kg chlorine
inventory.7
The withdrawal of chlorine from the
gaseous phase is forbidden for contain-
ers of 1,000 kg and more to avoid con-
centrating NCl3 in the vessel.
The accumulation of NCl3 in chlor-
ine vaporizers operating continuously
is possible if the operating temperature
is too low. If the vaporizer operating
temperature allows enough NCl3
decomposition, accumulation does
not occur.
The recommended frequency of
NCl3 control in chlorine production
is given by Eurochlor depending on
the observed concentration.7
Case Histories Concerning Nitrogen
Trichloride in Waste Treatments Using
Chlorine or Bleach
At least one accident is known where
liquid NCl3 could separate in a waste-
water treatment where bleach was
used to oxidize cyanide ions. After an
agitation failure, the actuation of a
bottom valve triggered the detonation.
NCl3 was suspected to have collected
in a dense layer in the vessel bottom.
Direct chlorination would lead to the
same dangerous situation. It was men-
tioned that the pH was not well con-
trolled and became too acidic despite
the fact that bleach was used. This
would be even easier if direct chlorina-
tion had been used. One should take
care that NCl3 may be obtained in
waste-water treatments using chlorine
or bleach as an oxidizer if the water
contains ammonium ions, cyanides,
amines, amides, urea, ammonia or
any ‘‘dangerous’’ nitrogen containing
compound.
In another incident, the cyanide
containing sludge produced by a cal-
cium carbide oven was submitted to
Chemical Health & Safety, January/February 2005
chlorine injection to reduce their cya-
nide content. As the operators were
weeping very much, it was determined
that cyanogen chloride, ClCN, was
evolving from the liquid. The forma-
tion of cyanogen chloride is possible by
reaction of chlorine with inorganic
cyanides under acidic conditions. It
was decided to replace chlorine injec-
tion by the use of bleach to prevent this
unwanted gas evolution. This sad story
shows that oxidizing conditions are
not always obtained and that other
volatile intermediates may also be
formed.
Bromination processes and the pro-
cessing of bromine containing reac-
tants produce waste solutions
containing inorganic or organic bro-
mides. The incineration of these wastes
would produce bromine which cannot
be released as is in the atmosphere.
Some organic bromine product produ-
cers offer the reprocessing of these
wastes to recover bromine using the
Balard reaction. The bromide contain-
ing waste is chlorinated in a glass
packed column where chlorine is
injected in the column bottom and
bromine is evolving in the column
upper part where the liquid waste is
fed, as usual to carry out the Balard
reaction. In this process, a very low
level of contamination of the waste
by dangerous nitrogen containing
compounds is safety critical, either
for the organic and inorganic compo-
nents. In particular, the presence of
ammonium ions may cause explosions
due to the formation of nitrogen tri-
chloride in the glass column.
Accumulation of Unstable Chlorinated
Compounds in The Bulk Liquid Phase
The accumulation of unstable chlori-
nated products in the bulk liquid phase
is most likely when a solvent is used
where this product is soluble. The most
common example is nevertheless the
accumulation of NCl3 produced by
electrolysis of KCl or NaCl salt con-
taining ammonium ions, in a NCl3
removal process using extraction in
carbon tetrachloride. If NCl3 is not
continuously thermally decomposed,
high NCl3 concentrations in the CCl4
solution are obtained with a potential
runaway decomposition hazard as
described above.
Miscellaneous Examples
Example of unstable compound
obtained by chlorination of oximes in
aqueous solution
The chlorination of organic com-
pounds with a N–O bound will leave
this chemical bound unaffected. For
example the chlorination of organic
nitro-compounds does not affect the
nitro groups. The chlorination of oxi-
mes gives chloro-oximes or chloro-
nitroso compounds8,9 which can
demix from aqueous solutions giving
an unstable dense oil. For example, the
chlorination of acetaldoxime gives the
water soluble chloro-acetaldoxime
which isomerises to chloro-nitro-
soethane, both unstable compounds.
The latter gives an unstable dimer, a
blue oil, which demix from aqueous
solutions. This blue oil may decompose
violently.
This is another example of the
demixion of an unstable chlorinated
compound from aqueous solutions.
This ends in process situations similar
to NCl3 formation and demixion.
Example of unstable solid obtained by
chlorination reaction
N-bromosuccinimide is a very com-
mon brominating reactant. But what
about N-chlorosuccinimide? This pro-
duct can be obtained by radical or
photochemical chlorination of succi-
nimide in aqueous solution. After crys-
tallization, the wet solid is recovered
but it must be handled with care. The
solid explodes on contact with iron.
The use of a plastic shovel is recom-
mended to handle it.
Recommendations
When chlorine is reacted with organic
reactants, especially if nitrogen con-
taining compounds or ammonium ions
are present, the possible formation
of unstable chlorinated compounds
should be considered. Any segregation
of a separate phase from the bulk liquid
is potentially dangerous and should be
investigated carefully. The separation of
an unstable liquid phase may induce a
high vapour pressure of the unstable
product in the gas phase because the
gas phase is in equilibrium with the
separated unstable liquid. This problem
should be considered. If no segregation
Chemical Health & Safety, January/February 2005
occurs, the process situation is safer,
however it is necessary to check for
low concentration of unstable chlori-
nated compounds (NCl3, alcohol hypo-
chlorites, others, etc.) in the bulk liquid
phase.
GAS PHASE EXPLOSION HAZARDS
Gas Phase Explosion Hazards in
Chlorine Production
In chlorine production by electrolysis
of NaCl or KCl brine or HCl solutions,
chlorine is obtained in the anodic com-
partment and hydrogen is obtained in
the cathode compartment of the elec-
trolysis cell. In the mercury cell pro-
cess, hydrogen is evolved in the
amalgam decomposer, allowing a bet-
ter separation between chlorine and
hydrogen. In the diaphragm or mem-
brane cell process the partial mixing of
the two gases is more straightforward
and the quality of the two gas separa-
tion relies on the pressure equilibrium
between the cathode and anode com-
partments and on the tightness of the
cell assembly.
As hydrogen is flammable in chlor-
ine, explosions may occur if the com-
position of the two gases enters the
flammable range of H2 + Cl2 mixtures.
The lower flammability limit of hydro-
gen in chlorine is: 3.5 vol.% H2. Above
this limit, the mixture is flammable and
may give violent explosions in vessels.
The upper flammability limit of
hydrogen in chlorine is: 89 vol.%
hydrogen. Up to this concentration,
the mixture of hydrogen and chlorine
is flammable. These limits concern the
combustion and deflagration of the gas
mixture.
The mixtures of hydrogen and chlor-
ine are known to detonate. The lower
limit for the detonation of hydrogen in
chlorine is: 17.5 vol.% H2, the upper
limit of the detonation range is:
83 vol.% hydrogen.
Many severe explosions of H2 + Cl2
mixtures occurred in the history of the
electrolysis process due to process fail-
ure or incorrect operation. The gas
phase explosion hazard makes the
total liquefaction of chlorine a difficult
process since the hydrogen concentra-
tion in the residual chlorine may rise
above the lower flammability limit of
hydrogen in chlorine, allowing gas-
phase explosion to occur. In case of
the gas-phase ignition in residual
chlorine containing H2, the combus-
tion heat can initiate the combustion of
carbon steel in chlorine, causing a
chlorine release to the atmosphere.
Therefore, total liquefaction is avoided
by sending residual chlorine to a
bleach production unit or to an on-site
consumer unit.
The hydrogen produced by electro-
lysis processes must be washed with
caustic soda and dried before use in
burners or in other processes. When
hydrogen with trace concentration of
chlorine is released to the atmosphere,
spontaneous ignition of the stack exit
may occur, especially by sunny
weather.
The corrosion of carbon steel con-
tainers by wet chlorine may produce
enough hydrogen to allow the hydrogen
concentration in the container to rise
above the LFL in chlorine, making a
gas-phase explosion possible. The
hydrogen is produced by the reaction
of carbon steel with hydrochloric acid
formed by hydrolysis of chlorine giving
hydrochloric acid and hypochlorous
acid. For this reason, it is important to
keep the water concentration in chlor-
ine below the recommended limit.
Gas Phase Explosion Hazards in
Chlorination Reactions
Continuous or loop gas phase reactors
Gas phase explosion hazard is present
when chlorine is mixed with a fuel in
the gas phase. The fuel may be hydro-
gen, a solvent or organic vapour,
ammonia, etc.
When chlorine is reacted with a fuel
in a burner, as in the manufacture of
HCl from hydrogen and chlorine most
incidents occur when the burner is set
on-stream, either by lighting the burner
with a pilot flame or by preheating the
gas and the burner. Of course the gas
mixture is in the flammable range and
explosions occur due to mal-opera-
tion.
Loop reactors are used to react
chlorine with organic reactants in the
gas phase. The substrate may be hydro-
carbons or mixtures of hydrocarbons
with chlorinated hydrocarbons. In this
type of process, chlorine is the control-
11
ling reactant and the reaction is ture with the reactant, product, solvent (1) Lowering the fuel vapour pressure
controlled by the chlorine to substrate or reaction mixture vapour. Here blan- below the Lower Flammability
mole ratio to obtain the desired keting is difficult as in other oxidation Limit in chlorine by lowering the
product. Under normal operating processes because the oxidizer is process temperature.
conditions, the reaction mixture is bubbled through the liquid reaction (2) Raising the fuel vapour pressure
not flammable, the fuel (substrate) mixture. above the Upper Flammability
concentration is above the upper As far as possible, it is recommended Limit in chlorine by raising the
flammability limit. On reactor start- to keep the reactor gas phase composi- process temperature.
up, the reactor is preheated to a tem- tion outside the flammable range. Var- (3) Blanketing the gas phase by flush-
perature above the auto-ignition tem- ious methods are used: ing the reactor gas phase with an
perature, where the slow reaction
of chlorine with the substrate is active.
The substrate vapour is circulated
in the loop and then chlorine is fed
to the loop reactor. The reaction
of chlorine must be initiated immedi-
ately. As the chlorination reaction
is exothermic, cooling is provided
in the loop to control the temperature.
Problems may arise if the chlorina-
tion reaction does not start immedi-
ately. The chlorine concentration
will increase in the loop, the gas phase
composition will enter the flammable
range and on reaction initiation, the
reactor will explode. Of course, inter-
locks are necessary to interrupt the
chlorine inlet flow and provide blan-
keting to the gas phase if the reaction
exotherm is not detected immediately
on chlorine injection.
Continuous gas phase reactors are
used for the chlorination of butadiene
to obtain dichlorobutenes, intermedi-
ates in the production of chloroprene.
The start-up procedure is similar to
that of gas phase loop reactors and
also the process conditions above the
upper flammable limit of butadiene at
the process temperature. A good con-
trol of the start-up conditions is also
necessary.
When chlorine is reacted with a fuel
on a catalyst bed, incorrect operation
will result in catalyst burn-out or gas
phase explosion before or after the
catalyst. Here the determination of
the fuel gas flammable limits in chlor-
ine are of interest if the feed gas is not
in the flammable range in normal pro-
cess conditions.

Semi-batch or continuous gas/liquid

reactors
When chlorine is injected or bubbled
in a liquid phase containing a reactant
and/or a solvent in a stirred reactor,
chlorine evolution in the reactor gas
phase may produce a flammable mix- Figure 1. 20 L sphere for gas explosion experiments, open.

12 Chemical Health & Safety, January/February 2005

 inert gas such as nitrogen, CO2,
HCl.
To keep the reactor gas phase below
the LFL in chlorine (method 1) is the
safer method where only proper tem-
perature control is necessary.
To keep the reactor gas phase above
the UFL in chlorine (method 2) may
not be quite safe. On start-up the tem-
perature must be set to the process
normal value ensuring enough fuel
vapour pressure before chlorine injec-
tion. If a condenser is used where the
fuel vapour pressure is depleted, the
gas flow composition may enter the
flammable range. Glass condensers
are better not used or protected from
light.
Blanketing (method 3) is a difficult
technique when the chlorine flow evol-
ving from the liquid reaction mixture
may change as the reaction goes to
completion.
If chlorine does not evolve in the gas
phase in normal process conditions, an
inert gas flush in the reactor gas phase
is recommended (see below). If a
chlorine flow evolves from the liquid
reaction mixture unreacted, enough
inert gas flush must be provided in
the reactor gas phase to lower the
chlorine concentration below the
minimum oxidizer concentration
(MOC) of the fuel flammable range.
If HCl is released in the gas phase,
this gas contributes to the reactor gas
phase blanketing. However, one
should take into account rapid
changes in the process conditions, if
the wanted chlorination reaction stops
due to catalyst depletion or reactant
consumption. More unreacted chlor-
ine can be released in the gas phase, the
HCl production can disappear. There-
fore, monitoring of the gas phase chlor-
ine concentration using a chlorine
analyzer is recommended.
Self-ignition, Deflagration and
Detonation in the Gas Phase
Self-ignitions of gaseous mixtures con-
taining chlorine and a fuel, near the
ambient temperature, are known. Self-
ignitions can turn into severe deflagra-
tions or detonations.
Self-ignition occurs in mixtures with
a composition both in the flammable
range and outside the previously deter-
Chemical Health & Safety, January/February 2005
mined flammable range. This phenom-
enon can be explained as follows:
- The self-ignition temperature of gas-
eous mixtures is not a clear-cut limit.
It is best represented by an induction
period versus temperature relation.
Self-ignition will be observed at
lower temperature if a longer induc-
tion period is allowed.
- Near the self-ignition temperature,
the flammable area is enlarged to a
wide range of equivalence ratios.
- When long induction periods are
necessary, weak ignition sources
can initiate the explosion, such as
light, wall effects, tar deposits, cata-
lyst deposits on the wall, NCl3
decomposition flame.5,10
- The slow reaction of chlorine with
organic fuels may modify the gas
phase composition allowing it to
enter the flammable range.
A combination of these influences may
explain the above mentioned self-igni-
tion phenomenon outside the flamma-
ble range.
Example of self-ignition of solvent
vapour in chlorine
In a chlorination process using diox-
ane as a solvent, the reactor gas phase
was found to present a self-ignition
phenomenon if chlorine was allowed
to evolve in the reactor gas phase. After
a first ignition, a series of subsequent
Figure 2. 20 L sphere for gas explosion experiments, closed.
self-ignitions were observed as if the
ignition delay was reduced by the pre-
vious ignitions. The reactor wall was
found to be covered with a soot deposit
produced by the combustion of diox-
ane in chlorine.
Further to this incident, the self-igni-
tion of gas phase mixtures of dioxane
and chlorine was thoroughly investi-
gated by F. Battin-Leclerc.11,12 Diox-
ane is sometimes mentioned as a
solvent for chlorination processes13
whereas self-ignitions of dioxane +
chlorine mixtures are easily obtained
near the ambient temperature.
The flammable limits of dioxane +
chlorine mixtures were determined in
a 4.6 L explosion vessel together with
the explosion overpressures and max-
imum rates of pressure rise.13 The
explosion overpressures obtained are
of the same order of magnitude of that
of explosion of gaseous fuel in air but
half of the expected thermodynamic
explosion overpressures in chlorine.
The gas phase detonation of gaseous
mixtures of dioxane and chlorine was
successfully investigated in shock tubes
by A. Elaissi.14,15 The detonation pro-
ceeds in shock tubes leaving behind a
soot deposit, with a velocity half of that
expected from the Chapman-Jouguet
theory. This mixture was shown to be
very sensitive to detonation compared
to mixtures of fuel in air or oxygen.
The full investigation of this example
shows that mixtures of organic fuels
13
with chlorine can exhibit self-ignition Table 1. Flammability Limits of Gaseous Fuels in Chlorine Data of Mal’tseva17,18
followed by deflagration and detona- Fuel Temperature (8C) LFL (vol.%) UFL (vol.%)
tion thus explaining violent explosions
observed in the past. Hydrocarbons
CH4 20–22 5.6 63.0
C2H6 20–22 4.95 55.4
EXPERIMENTAL SET-UP TO STUDY C3H8 20–22 4.30 50.0
EXPLOSION LIMITS, EXPLOSION C4H10 20–22 3.31 49.5
CHARACTERISTICS AND SELF- C5H12 20–22 2.42 43
IGNITION OF GASEOUS MIXTURES
Alcohols
CH3OH 70 13.8 73.5
A new explosion vessel, a 20 L sphere, C2H5OH 83 5.06 64.1
was built to investigate gas phase C3H7OH 102 3.03 51.5
explosions with special attention for C4H9OH 120 2.53 48.8
experiments using chlorine as an oxi- C5H11OH 143 1.98 37.6
dizer. See Figures 1 and 2.
This new facility allows the measure- Carboxylic acids
ment of: HCOOH 105 27.62 82.0
CH3COOH 122 15.83 56.0
- The flammability limits of gaseous C2H5COOH 145 9.33 50.8
mixtures using various ignition C3H7COOH 170 7.81 49.8
sources: single spark, fusing wire, C4H9COOH 190 5.84 48.8
chemical ignition sources.
Chloro-alkanes
- The explosion characteristics, i.e.,
CH3Cl 20 10.2 56.0
explosion overpressure and maxi-
CH2Cl2 50 16.7 52.9
mum rate of pressure rise.
CHCl3 Not combustible
- The laminar burning velocity
C2H5Cl 20 8.98 49.2
deduced from the pressure–time hist-
1,2-C2H4Cl2 100 16.4 36.8
ory of the explosion.16 The pressure
C2H3Cl3 Not combustible
is recorded at a rate of 20,000
C3H7Cl 60 6.88 41.8
Points/s.
C3H6Cl2 100 9.95 35.0
- The self-ignition temperature and
C3H5Cl3 Not combustible
induction period of gaseous mix-
C4H9Cl 100 5.42 44.5
tures, down to a few minutes. Sam-
pling is possible to check for gas NB compositions are in percents by volume. Isomers are not specified. Refer to the original
phase reaction. papers.
- Flash points in chlorine.
of 10 to 20 bar according to the ing is ensured before ignition using a
The main features of this explosion
expected explosion pressure. The ves- propeller mixer. Central ignition is
vessel are:
sel temperature can be set between made using spark, hot wire or a pyr-
- Hastelloy C276 walls to lower wall ambient temperature and 300 8C. Mix- otechnic ignition source.
effects, i.e., to prevent the reaction of
chlorine with fuel before ignition, Table 2. Flammability Limits of Gaseous Fuels in Chlorine Data Published by
catalysed by stainless steel. Dokter19 and Medard20
- The vessel is made of two half- Fuel Temperature (8C) LFL (vol.%) UFL (vol.%) Reference
spheres connected through a flange
H2 3.5 89 19
assembly kept tight by clamps.
CH4 5.51 63 19
CH4 100 3.6 66 19
The upper half-sphere is fixed, CH4 200 0.6 19
the lower half-sphere is movable, using CH3Cl 10.2 63 19
a pneumatic jack, to allow quick open- C2H6 4.95 58.8 19
ing of the vessel for frequent cleaning.
Combustion in chlorine produces soot H2 8 86 20
deposits on the walls, which may pro- CH4 20 5.6 70 20
mote or prevent ignition of subsequent CH4 100 3.6 20
mixtures. Cleaning after each positive CH4 200 0.6 20
test is necessary to obtain reliable flam- C2H6 6.1 58 20
mable limits in chlorine. C3H8 5 40 20
The vessel design pressure is CH3Cl 10 63 20
200 bar, thus allowing initial pressure CH2Cl2 16 53 20

14 Chemical Health & Safety, January/February 2005

Table 3. Flammability Limits of Gaseous Fuels in Chlorine Dokter19 and Medard20 published
Fuel Temperature (8C) LFL (vol.%) UFL (vol.%) Apparatus some more data collected in Table 2,
together with interesting discussions.
CH3Cl 25 7 65 (C) Further flammability data obtained
C3H8 70a 2 60 (S) either using our 4.6 L stainless steel
C3H6Cl2 200b 4.5 (S) cylinder described in Ref. 13 (C) or
(CH3)3COCH3 60 2 33 (C) our 20 L Hastelloy C sphere (S) are
1,4-Dioxane 80 2.5 41 (C) given in Table 3.
CH3COOH 120 5 36 (C) Miscellaneous data can be found in
Acetone 60 4.5 60 (C) the literature, like the flammability lim-
Chloro-benzene 130 7.5 43.5 (S) its of benzene in chlorine:21 LFL = 8
Toluene 160 3.5 50 (S) vol.%, UFL = 52 vol%.
2-Chloro-toluene 150 5 45 (C) The experimental data is given under
Chloro-toluene 160 4 (S) atmospheric initial pressure, unless
Di-chloro-toluene 160 6 (S) otherwise specified.
Tri-chloro-toluene 160 9 (S)
2-Fluoro-toluene 100 4 37 (C) Self-ignition Temperatures
a b
(C): 4.6 L cylinder; (S): 20 L sphere. Po = 1.7 atmosphere abs. Po = 1.3 atmosphere abs. Data on self-ignition temperature of
gaseous mixtures of fuel and chlorine
are given by Mal’tseva,18 Dokter19 and
REVIEW OF FLAMMABILITY DATA was introduced after evacuation, and others. A collection of data is given in
OF GASEOUS MIXTURES allowed to vaporize. Then chlorine Table 4.
CONTAINING CHLORINE was admitted in the explosion vessel.
Mixing was only by molecular diffusion
Flammability Limits (no stirring). A 10 min waiting time was CONCLUSION
A review of flammability limits of gas- observed before ignition by a spark.
eous mixtures containing chlorine was Our comment on this method is that Owing to the importance of chemical
first given by Mal’tseva, Roslovskii and the wall material is correct, mixing is reactions involving free chlorine in the
Frolov.17,18 The experimental set-up poor or not effective and the waiting chemical industry, the collection of
used to obtain these data was a dou- time before ignition is too long and experiences and experimental data is
ble-wall vertical glass cylinder, 80 mm may have allowed the mixture to react of great interest. This should contri-
in diameter and 120 mm high. The before ignition. The results are sum- bute more to process safety than infor-
experiment initial temperature was set marized in Table 1 for the reader con- mation on less dangerous chemicals or
by thermostating the vessel. The fuel venience. processes. It is surprising that only
limited effort or support is devoted to
collect safety data on chlorination
reactions. The literature on the safety
Table 4. Auto-ignition Temperature of Gaseous Fuels in Chlorine of chlorination reactions is very lim-
ited compared to the literature on oxi-
Fuel AIT in Chlorine (8C) Author
dation reactions using oxygen. The
CH4 318 18 author hopes that this contribution
C2H6 280 18 will promote further experimental
Dimethyl ether Ambient 18 work in this field. The new 20 L explo-
C1–C3 carboxylic acids 300–320 18 sion vessel, specially designed to study
C4–C7 carboxylic acids 230–190 18 the flammability of gaseous mixtures
C2–C4 carboxylic anhydrides 290–215 18 containing chlorine as an oxidizer will
C3–C5 ketones 325–205 18 allow the determination of reliable
C1–C8 alcohols 225–210 18 data at a reasonable cost, for a wide
C2–C7 aldehydes 110–160 18 range of initial conditions.
H2 207 19
CH3Cl 215 19
CH2Cl2 262 19 References
C2H6 205 19 1. Gallucci, R. R.; Going, R. Chlorination
C3H6 150–100 19 of aliphatic ketones in methanol. J. Org.
1,2-C3H6Cl2 180 19 Chem. 1981, 46, 2532–2538.
Dioxane (0.26 ATA) 100 10,11 2. Sandmeyer, T. Uber aethyl and methyl-
hypochlorit. Berichte D. Chem. Ge-
Chloro-benzene >165 20 L sphere
sellschaft, 1886, Jahrg. XIX, 857–861.
C3H8 (1.7 ATA) 165 20 L sphere 3. Sandmeyer, T. Uber den Aethylester
C3H6 (1.7 ATA) 60 20 L sphere der unterchlorigen Säure. Berichte D.

Chemical Health & Safety, January/February 2005 15

 Chem. Gesellschaft, 1885, Jahrg. XVIII,
1767–1769.
4. Fort, Roland; Denivelle, Leon Recher-
ches sur les hypochlorites d’alcoyle.
C.R. Acad. Sci. 1954, 234, 1109–1115.
5. Baillou, Françoise. Proprietés explo-
sives du Trichlorure d’Azote gazeux.
Thesis dissertation, Université d’Or-
léans, France, 27 September 1990.
6. (A). Nitrogen Trichloride, A Collection
of Reports and Papers. The Chlor-
ine Institute, Report, no. 21, Ed. 2;
New York, 1975;
(B). Chlorine Precooler Drain Piping
Explosion, Report of February 3,
1995. The Chlorine Institute; L
Street, N.W. Washington, DC
20036, 2001.
7. Maximum Level of Nitrogen Tri-chlor-
ide in Liquid Chlorine, Document
GEST 76/55, 9th ed.; Eurochlor, Brus-
sels, September 1990.
8. Piloty,; Steinbock, Berichte, 1902, 35,
3113.
9. Steinkopf, W.; Mieg, W.; Herold, J.
Berichte, 1920, 53, 1148.
10. Baillou, F.; Lisbet, R.; Dupré, G.;
Paillard, C.; Gustin, J. L. Gas phase
16
explosion of nitrogen trichloride: Ap-
plication to the safety of chlorine
plants and chlorination processes. 7th
International Symposium on Loss Pre-
vention and Safety Promotion in the
Process Industries. Taormina, Italy,
May, 1992, (Paper no. 106).
11. Battin-Leclerc, F. Reaction du 1,4-
Dioxanne Gazeux en Présence D’oxy-
gène ou de Chlore. Thesis dissertation,
INPL-ENSIC, Nancy, France, 15 Jan-
uary 1991.
12. Battin-Leclerc, F.; Marquaire, P. M.;
Come, G. M.; Baronnet, F.; Gustin, J.
L. Auto-ignition of gas phase mixtures
of 1,4-dioxane and chlorine. 7th Inter-
national Symposium on Loss Preven-
tion and Safety Promotion in the
Process Industries. Taormina, Italy,
May, 1992, (Paper no. 82).
13. Gustin, J. L. Gas-phase explosions of
mixtures of organic compounds with
chlorine. 6th International Symposium
Loss Prevention and Safety Promotion
in the Process Industries. Oslo, Nor-
way, June 19–22, 1989, (Paper no. 91).
14. Elaissi, Abdelkrim. Propriétés Explo-
sives des Mélanges 1,4-Dioxanne +
Chemical Health & Safety, January/February 2005
Chlore en Phase Vapeur. Thesis dis-
sertation, University of Orleans,
France, 14 March 1994.
15. Elaissi, A., Dupré, G., Paillard, C.
Paper Presented at the 8th Interna-
tional Symposium Loss Prevention and
Safety Promotion in the Process In-
dustries, Antwerpen, 1995.
16. Bradley, D.; Mitcheson, A. Mathema-
tical solutions for explosions in sphe-
rical vessels. Combust. Flame, 1976,
26, 201–217.
17. Mal’tseva, A. S.; Sushchinskiy, V. L.
Sov. Chem. Ind. 1971, January, 23–25.
18. Mal’tseva, A. S.; Rozlovskii, A. T.;
Zhurnal Vses. khim. Ob-va im. Men-
deleeva, 1974, 19(5), 522–551.
19. Dokter, T. Fire and explosion hazards
of chlorine-containing systems. J. Ha-
zard. Mater. 1985, 10, 73–87.
20. Medard, L. Les explosifs occasionnels,
vol. 1 Lavoisier ed.; Paris, 1987, (pp.
172–173).
21. Calingaert, G.; Burt, W. IEC, 1951,
43(10), 1341.