H260 P R O D U C T F I L E

H261 Chemicals which react

violently with water
EUH014
MANAGEMENT OF CHEMICAL ACCIDENTS
HEALTH - ENVIRONMENT

Version 0 - September 2013

www.prevor.com
 H260
H261 CONTENTS
CHEMICALS WHICH REACT VIOLENTLY WITH WATER

EUH014
MANAGEMENT OF CHEMICAL ACCIDENTS
HEALTH - ENVIRONMENT

1. KEY POINTS p3
1.1 Definitions p3
1.2. Uses p4
2. LABELLING P5

3. CHEMICAL CHARACTERISTICS p6

4. CORROSIVITY p9

5. EXOTHERMICITY p12

6. MANAGEMENT OF ASSOCIATED RISKS p14

6.1. Collective protective measures p14
6.2. Individual protective equipments p15

7. EMERGENCY RESPONSE TO SPLASHES p16

7.1. Evaluation of washing methods p16
7.2. Experimental evidence p17
7.3. Classification of solutions p20

8. MANAGING SPILLAGES p21

8.1. Evaluation of spillage collection methods p21
8.2. Experimental evidence p22
8.3. Feedback p24

9. WASHING AND COLLECTING ADVICE p25

9.1. Washing advice of a chemical splash p25
9.2. Collecting advice p30
10. DOCUMENTARY REFERENCES p31
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Management of chemical accidents / Health - Environment
 1. KEY POINTS

1.1. DEFINITIONS

Chemicals which react with water are considered as dangerous substances or mixtures. This
danger represents an entirely separate class in the CLP1 labelling system, from the moment that
release of flammable gases results from the contact of said products with water.
The former European classification of chemicals (Directive 67/548/CE) included two risk phrases
for substances and preparations which react with water:
• The risk phrase “R 14 – Reacts violently with water”, was assigned to substances
which strongly react with water, by virtue of their physical-chemical properties, but without
necessarily leading to the release of a flammable gas or an explosion.
• The risk phrase “R15 – Contact with water liberates extremely flammable gases”
was assigned to substances and preparations when, during a test-assay (test method A12,
regulation (EC) 440/2008 of the 30/05/2008) ignition occurred, or that the flow of flammable
gas generated exceeded the limit value of 1l/kg/h.
In the CLP labelling system, the R14 phrase has been replaced by the phrase “EUH014 – Reacts
violently with water”.
It applies “to substances and mixtures which react violently with water, such as acetyl chloride,
alkaline metals, titanium tetrachloride”, according to the definition in CLP. This hazard statement,
which does not exist in the GHS2, has been added by the European Union.
The phrase R15 corresponds to the new hazard class “Substances and mixtures which, in contact
with water, release flammable gases”, which is divided into 3 categories (hazard statements
H2603 and H2614). These are “Liquid or solid substances or mixtures which, through reaction
with water, are capable of igniting spontaneously or releasing flammable gases in dangerous
quantities”, according to the CLP definition.

1 - CLP : Classification Labelling Packaging, European regulation N°1272/2008/EC

2 - GHS : Globally Harmonised System
3 - H260 : In contact with water releases flammable gases which may ignite spontaneously
4 - H261 : In contact with water releases flammable gases
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Chemicals which react violently with water - H260/H261 - EUH014
 The reaction must take place at ambient temperature. Then, different criteria are taken into
account for a classification into 3 categories:

CATEGORY CRITERIA
Vigorous reaction with water releasing a gas capable of igniting spontaneously
1 OR
Rather vigorous reaction with water releasing a flammable gas > or = 10 l/kg/min

Rather vigorous reaction with water releasing a flammable gas > or = 20 l/kg/h and
2 which does not meet the classification criteria in category 1

3 Slow reaction with water releasing a flammable gas > or

= 1 l/kg/h and which does not meet the classification criteria in categories 1 and 2

Furthermore, if a spontaneous ignition occurs (for example ignition of a solvent due to a

temperature increase), the tested substance or mixture is then classified as a substance or
mixture which on contact with water releases flammable gases.

1.2. USES

All these chemicals are used for their high reactivity:

•
Organomagnesium compounds, or Grignard reagents, are very useful as synthesis
intermediates in the pharmaceutical industry.
• Metal hydrides, such as lithium aluminium hydride (LiAlH4), are also used in organic
chemistry for their strong capacity to produce hydrides.
• Lithium is used in lithium batteries, installed as such to power, for example, mobile phones.
• Phosphoryl chloride (POCl3) is used in the manufacture of photovoltaic panels.
• Titanium tetrachloride (TiCl4) is used for the production of titanium, white titanium oxide
pigment, artificial glass pearls, for the production of smoke screens or the surface treatment
of glass bottles.

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Management of chemical accidents / Health - Environment
 Given their reactivity and their frequent use, it is not uncommon that accidents occur with
chemicals which react strongly with water. The problem is twofold:
• Achieve an optimal and active decontamination for exposed personnel in the event
of splashes on the body, capable of limiting the consequences of the specific physical/
chemical properties of these chemicals.
•C
 apable of absorbing this type of substance in the event of ground spillage, in order to
preserve the environment5 and limit explosive and inflammable reactions.

2. LABELLING

Products reacting with water while releasing flammable gases will be labelled in the following
manner, according to the previously cited test results:

CLASSIFICATION CATEGORY 1 CATEGORY 2 CATEGORY 3

GHS pictograms

Signal word Danger Danger Danger

H260: In contact
with water releases H261: In contact H261: In contact
Hazard statement flammable gases with water releases with water releases
which may ignite flammable gases flammable gases
spontaneously
P223 P223
Precautionary statement P231 + P232
P231 + P232 P231 + P232
Prevention P280
P280 P280
Precautionary statement P335 + P334 P335 + P334
P370 + P378
Response P370 + P378 P370 + P378
Precautionary statement
P402 + P404 P402 + P404 P402 + P404
Storage
Precautionary statement P501 P501 P501
Disposal
Table 2.12.2 of the CLP regulations

Products which react violently with water will be labelled in Europe with the wording of the statement
EUH14 – Reacts violently in contact with water.
There is no pictogram or associated signal word.

5 - Here this is taken to mean preservation of the environment and management of chemical spillages. 5
Chemicals which react violently with water - H260/H261 - EUH014
 3. CHEMICAL CHARACTERISTICS

Chemicals which react strongly with water can be classified according to chemical families:

• Alkaline metals, such as lithium (Li), sodium (Na) or potassium (K)

• Chlorosilanes (chlorinated silicon compounds), such as trichloromethylsilane (CH3SiCl3)

•M
 etal alkyls such as aluminum, zinc, magnesium, or lithium alkyls (organometallics)

• Acid chlorides (of general formula R-COCl)

•C
 ertain Lewis acids, such as titanium trichloride (TiCl4) and phosphorous pentachloride (PCl5)

•M
 etal phosphides such as aluminum phosphide (AlP) or magnesium phosphide (MgP)

• P hosphorus sulphides (such as P4S10 dimer form of diphosphorus pentasulphide)

• S ulfonyl isocyanates (R-SO2-NCO)

•M
 etal hydrides (LiAlH4)

The chemical reactions on contact with water may be of different types:

> It can be a hydrolysis with oxidation of alkaline metals:

2 Na + 2 H2O 2 Na+ + 2 OH- + H2(g)

A release of hydrogen gas (H2) takes place and the residue is very alkaline, because of hydroxide
ion OH- presence.

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Management of chemical accidents / Health - Environment
 > It can be a decomposition reaction of the substance in contact with water:

TiCl4 + 2 H2O TiO2 + 4 HCl (g)

CH3COCl + H2O CH3COOH + HCl (g)

AlP + 3 H2O Al(OH)3 + PH3 (g)

Al(C2H5)3 + 3 H2O Al(OH)3 + 3 C2H6 (g)

LiAlH4 + 4 H2O LiOH + Al(OH)3 + 4 H2 (g)

CH3C6H4SO2NCO+H2O CH3C6H4 SO2NHCOOH CH3C6H4SO2NH2+CO2(g)

> It may involve hydration reactions, such as with oleum (SO3) :

SO3 + H2O H2SO4

A more interesting classification may be proposed if the nature of the products derived from the
decomposition by water is taken into account. Distinction needs to be made between reactions
with water releasing:

• Hydrogen gas (H2),

• Hydrogen chloride (HCl), or any other halogen hydride (HBr, HF, HI)

• Phosphine (PH3)

• Alkanes (methane, ethane, etc.)

• Carbon dioxide (CO2)

• Hydrogen sulphide (H2S)

Releases following contact with water are violent. They are generally accompanied by a strong
heat increase, leading in the worst cases to an explosion (such as with the release of phosphine
– example of phosphorous fires) or to a fire. Gas emission, if it does not ignite, can carry along
vapours of all reagents present with possible intoxications and/or depletion of ambient oxygen.

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Chemicals which react violently with water - H260/H261 - EUH014
 For example, in the decomposition reaction of titanium tetrachloride with water, a plume of
hydrogen chloride and titanium compounds (TiO2, TiCl4 that has not yet reacted) is formed.

As in nature, exceptions do exist and chemicals in other forms than gas can be released!

For example, calcium carbide reacts with water to form acetylene and solid lime:

CaC2 + 2 H2O C2H2g + Ca(OH)2

ΔH = -130 kJ/mol (-31,1 kcal/mol)

Another example is methoxysilanes (e.g. vinyltrimethoxysilane), which release liquid methanol at

ambient temperature.

H2C=CH-Si-(OCH3)3 + 3H2O 3 CH3OH + H2C=CH-Si(OH)3

Chemicals which react violently with water can be classified depending on hazards resulting from
gas emissions.

Following contact with water, there can be release of:

• Flammable gases (sometimes spontaneously ignitable) such as hydrogen gas or alkanes,

such as methane, ethane, etc...

• Corrosive products such as hydrochloric acid, bromic acid, phosphorous acid, sulphuric
acid, propionic acid, etc...

• Toxic gases such as carbon dioxide, hydrogen sulphide, methanol, phosphine (gas which
is also flammable) or hydrofluoric acid (corrosive and toxic gas).

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Management of chemical accidents / Health - Environment
 4. CORROSIVITY

Cutaneous or ocular splashes which react violently with water can generate a double or even
triple hazard:

• If the chemical is irritant/corrosive, a chemical injury can develop.

• L esions caused may then be more severe due to the exothermic nature of the reaction with
water. Heat can induce further thermal burns.

• Finally, a risk of toxicity may exist, depending on by-products released.

In addition, a physical risk of explosion or

fire is not negligible (see the chapter on the
management of associated risks).

The corrosiveness of chemicals reacting

with water will be linked to the nature of by-  
products released.   Figure 1 : Illustration of a chemical and
thermal lesion – source: Turbomeca

> When hydrogen chloride (HCl) is released, it can be responsible for skin, eyes and respiratory
mucous membrane chemical lesions, on account of its acid character. On contact with moisture,
it is transformed into hydrochloric acid. The induced injuries are due to contact with the H+ proton
which is released. Lesions concern the respiratory tracts, to a greater or lesser degree with,
apart from the risk of corrosion, that of initial bronchospasm, which can be more or less severe.
In addition, exists the possibility of secondary onset of Brooks syndrome6, even after a single
exposure. Furthermore, the hydrochloric acid inhalation may lead to an acute pulmonary oedema,
through a toxic alveolar mechanism, which can be more or less delayed in the hours following
contact. It is therefore advisable to remain vigilant and to place the victim under observation for
24 hours to avoid a real fatal risk ; thus explaining the classification of hydrogen chloride as a
toxic substance through inhalation.

6 - Asthma with a non-immunological mechanism, induced by irritants

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Chemicals which react violently with water - H260/H261 - EUH014
 > Hydrogen bromide and hydrogen iodide, HBr and HI, which can be released depending on the
initial halogen (respectively Br or I), are also highly corrosive. HF, hydrofluoric acid, is known for
its corrosive properties on one side, linked to the production of the H+ hydrogen ion, and its toxic
properties on the other, linked to the production of the F- fluoride ion.
During hydrolysis reaction of chlorinated phosphides, the release of hydrogen chloride is
accompanied by a release of phosphoric acids:

> Phosphorous acid, H3PO3, corrosive diacid:

PCl3 + 3 H2O H3PO3 + 3 HCl

> P hosphoric acid, H3PO4, a triacid which is also corrosive but which is in solid form as soon as
the temperature returns to ambient temperature:

POCl3 + 3 H2O H3PO4 + 3 HCl

> When the hydroxyl ion, OH-, is released, it can cause alkaline chemical lesions:

2 K + 2 H2O 2 K+ + 2 OH- + H2(g)

Precisely in this type of reaction with alkaline metals (such as potassium or

sodium), the released dihydrogen (H2) is an extremely flammable gas, which can
lead to a deflagration on contact with air.

> Phosphine (PH3) is a very toxic and corrosive gas and is used as a source of organophosphorous
compounds. There is then formation of H° radicals, through an oxidation reaction with oxygen,
capable of spontaneous ignition.
A massive dose of inhaled phosphine is necessary to be fatal (400 ppm for 30 minutes
to 1 hour) but the first serious symptoms can occur as of an exposure of several hours at
concentrations of 5/10 ppm.

> Hydrogen sulphide (H2S) is a very toxic and highly flammable gas, without corrosive
activity. It has the particularity of being highly odorous when it is at low concentration (fetid
odour when it is at a concentration below 5 ppm) and becomes odourless when it is at a
concentration above 10 ppm. Its toxicity threshold is 14 ppm. H2S is thus non odorant when
it is toxic. Specific H2S detectors exist for indicating the presence of this gas.

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Management of chemical accidents / Health - Environment
 > Carbon dioxide (CO2) is mainly released when sulphonyl isocyanates, come into contact

with water.

It does not present a corrosive danger. The corresponding carbamide acid, which is also
released, will be responsible for certain corrosiveness, due to its more or less acid character.
Urea, which can also be a by-product of the hydrolysis, is non corrosive.

> Alkanes do not represent a corrosive danger. On the other hand, they can be flammable.

> Hydrogen gas (H2) does not represent a corrosive hazard, but is likely to react with the
ambient oxygen in a noticeable violent and exothermic combustion reaction, with only a little
spark, or a small temperature rise.

TYPE OF PRODUCT HAZARD OF

FAMILY EXAMPLE
REACTION RELEASED PRODUCT RELEASED
Alkaline metals Reductive HO- Corrosive Na + H2O NaOH + H2
Chlorosilanes Electrophilic HCl Corrosive gas ClSiMe3 + H2O HOSiMe3 + HCl
Acyl
Electrophilic HX, X halogen Corrosive gas RCOCl + H2O RCOOH + HCl
halogenides
Lewis acids
(metal Electrophilic HX, X halogen Corrosive gas TiCl4 + 2 H2O TiO2 +4 HCl
halogenides)
Basic / Flammable liquids /
Metal alkyls alkanes CH3MgBr + H2O CH4 + MgBr+ + HO-
nucleophilic gases

Basic / NaH + H2O NaOH + H2

Metal hydrides H2 Flammable gas
reductive LiAlH4 + 4 H2O LiOH + Al(OH)3 + 4 H2
Basic / Flammable,
Metal phosphides PH3 AlP + 3 H2O Al(OH)3 + PH3
nucleophilic explosive, toxic gas
Basic /
Metal sulphides H2S Toxic gas Al2S3 + 6 H2O 2 Al(OH)3 + 3 H2S
nucleophilic

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Chemicals which react violently with water - H260/H261 - EUH014
 5. EXOTHERMICITY

By reacting more or less violently on contact with water, all of the chemicals studied in this file will
lead to a more or less significant release of heat.
This heat release may be quantified in a theoretical manner, by calculating the enthalpy of reaction
ΔH. This value represents the amount of energy involved. When this value is negative, this means
that the reaction is exothermic and thus, releasing heat.
FOR EXAMPLE:

POCl3(l)+ 3 H2O(l) H3PO4(aq) + 3 HCl(aq)

ΔH7 = -323 kJ/mol

TiCl4(l) + 2 H2O(l) TiO2 + 4 HCl(aq)

ΔH7 = -237 kJ/mol

The increase in temperature will vary according to the initial chemical substance and its capacity
to react more or less quickly with water.
The associated maximum increase in temperature may be measured experimentally. Since
titanium tetrachloride is one of the chemicals which react the most violently with water, its
hydrolysis is monitored in a beaker, by adding a continuous volume of water.

For example, on an initial sample of 1 ml of 99% titanium chloride, when water is added to dilute
it, the temperature reached at the start of the addition rises to 72°C, and then very quickly returns
to a value below 30°C once the first 3 millilitres of water have been added.

7 - Calculated theoretically, considering an excess of water.

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Management of chemical accidents / Health - Environment
 Temperature evolution during the addition of water to 1 ml of 99% TiCl4 in a beaker

80

70

60
Temperature (°C)

50

40 Water T° (°C)

30

20

10

0
0
5
1
2
3
4
5
6
7
8
9
10

38 0
00
15
20

22 0
25 0
30 0
35 0
25
50
0
0
0
10 0
15 0
17 0
20 0
0,

5
0
5
0
10
20
30
50
0
0
5
0
Volume (ml)

This experiment is carried out in a closed environment. It is thus less representative of a

real washing simulation, where the wash-off effect is reproduced. When the same type of
experiment is carried out in a dynamic washing situation, the rise in temperature is less
important.
For example, by simulating the wash-off effect of washing a splash of titanium tetrachloride
with water, it is then observed that the maximum temperature reached in the first few seconds
does not exceed 55°C. After 20 seconds, the reaction temperature comes down to around
30°C.

Temperature evolution during washing with water with

wash-off effect on 1 ml of 99% TiCl4
60

50
Temperature (°C)

40

30

20
Water T° (en°C)
10

0
0
9
18
27
36
45
54
63
72
81
90

1
0
9
8
99

8
7
6
5
4
3
2

7
6
5
10
11
12
13
14
15
16
17
18
18
19
20
21
22

Time (seconds)

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Chemicals which react violently with water - H260/H261 - EUH014
 6. MANAGEMENT OF ASSOCIATED RISKS

For chemicals releasing flammable gases on contact with water, the first risk is physical and
precautionary measures must be taken in the same way as for highly flammable products.

6.1. COLLECTIVE PROTECTIVE MEASURES

> First of all, the safest possible work processes should be designed: automation, self-contained
work operations, planned organisation of maintenance and repair operations in the event of an
incident, design of strict storage conditions.

> Chemicals that react when coming into contact with water must be identified and stored
independently of aqueous chemicals, to avoid the risk of any contact in the event of leaks.

> Just as important the storage sites of these chemicals do not include any water pipes. These
types of chemicals must be stored in such a way that any contact with water is impossible,
even in the event of flooding.

> Implement a system of use in isolation and provide for a suction system at work stations. While
handling, avoid the proximity of water or other chemicals in order to limit further accidents in
the event of flames or explosion8.

> The chemicals must be kept away from moisture and, if possible, from air (INRS, 2011)

THESE CHEMICALS MUST NEVER BE POURED DOWN THE SINK.

8 - Glove box or, failing this, an experimental system that avoids air contact
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Management of chemical accidents / Health - Environment
> T hen, and failing this, set up a regular control of potentially emited fumes suctions.

> It is also necessary to install a retention tank to recuperate liquids.

> F irefighting measures: pressurized dry chemical and/or CO2 extinguishers must be readily
available. The use of specific extinguishing agents based on graphites or special dry powders
for metal fires may also be justified, particularly for lithium and other mineral elements.
Failing this, sand must be available to estinguish the flames and limit contact with air
moisture (INRS FT 183, 2000).

6.2. INDIVIDUAL PROTECTIVE EQUIPMENTS:

> Protective clothing

> Gloves resistant to chemicals used
> Protective glasses or face screen
> Safety shoes
> Chemical cartridge respirator, for short operations, or supply-air respirator.

Since some gases emitted may be toxic, it is advisable that fire fighting personnel is equipped
with self-contained breathing apparatus with a full facepiece. Absorbents must also be
available to collect any leaks and thus limit the risks of an explosion / fire.

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Chemicals which react violently with water - H260/H261 - EUH014
 7. EMERGENCY RESPONSE TO SPLASHES

7.1. EVALUATION OF WASHING METHODS

7.1.1. WASHING WITH WATER

We have thus seen previously that although these chemicals react violently with water,
decontamination with water is however recommended within the context of first aid since a
continuous washing enables a very rapid return to body surface ambient temperature.
Washing with water also makes it possible to remove a large part of the chemical from the
surface of body tissues, by mechanical removal. However, it will not have any action on by-
products released. This can lead to dangerous situations for first aid or emergency services
personnel who will be faced with emanations of by-products from the reaction of the chemical
with water while washing the injured person.
For example, R-methoxysilane type compounds generate methanol on contact with water.
Methanol is a toxic substance through ingestion and inhalation. In addition to the victim, the
persons present during the decontamination are going to be exposed (Lazzeri D, 2009). The
responders must therefore be equipped with suitable personal protective equipment.

7.1.2. WASHING WITH AN ACTIVE SOLUTION

Setting up an active washing helps to keep the wash-off and dilution effects of washing with
water, while optimising the decontamination process of the irritant chemicals.
Diphoterine® solution meets these efficiency requirements. Its hypertonicity limits the penetration
of caustic substances in depth and helps to create an inverse flux from the interior towards the
exterior, of skin or eye.
Its amphoteric and chelating properties will enable washing optimisation by acting on irritant and
corrosive chemicals. Its effect is nevertheless limited with hydrofluoric acid and fluorides in acid
medium.
Products which generate hydrofluoric acid (HF) on contact with water, such as boron trifluoride
(BF3), need to be identified. Washing with Hexafluorine® solution will respond to the twofold
corrosive and toxic hazard of HF.

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Management of chemical accidents / Health - Environment
 7.2. EXPERIMENTAL EVIDENCE

Experimentally, the efficiency of washing with an amphoteric and chelating solution such as
Diphoterine® solution can be shown during an in vitro splash simulation, compared to washing
with water.
If we return to the previous example of titanium tetrachloride (TiCl4):
The chemical action of Diphoterine® solution on hydrochloric acid released is represented by a
decrease of the pH in solution, whereas washing with water only results into a dilution:

Addition of Diphoterine® solution or tap water to 1 ml of 99% TiCl4

3
pH

1
physiologically
acceptable pH
-1 Diphoterine®
solution pH
Water pH
-3

-5
0 200 400 600 800 1000
Volume (ml)
Figure 2 : In vitro simulation of static washing of a TiCl4 splash with Diphoterine®
solution compared with water.

This can also be verified with another substance which reacts strongly with water, such as
boron tribromide.
On contact with water, the chemical reaction is as follows:

BBr3 + 3 H2O B(OH)3 + 3 HBr

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Chemicals which react violently with water - H260/H261 - EUH014
 This reaction is exothermic and generates heat if it is carried out via static washing simulation
(experimental temperature of 85°C during the addition of one millilitre of water to a millilitre of
boron tribromide – Figure 3).
In dynamic washing situation, the temperature will not exceed 40°C, only for several seconds, and
it will return very quickly to ambient temperature.

Simulation of washing 1 ml of BBr3 with Previn® solution or tap water

40
7
35
5

Temperature (°C)
30
pH

3
Previn® pH
25
1 Water pH
physiological pH

-1 20 T °C
T °C water

-3 15
0 30 60 90 120 150
Time (s)

Figure 3 : In vitro simulation of dynamic washing of a splash of BBr3 with Previn®

solution (molecule similar to Diphoterine® solution commercialised in Germany),
compared to water.

In Figure 3, the wash-off effect of the two washing solutions is identical and the action of washing
will limit in both cases any additional heating. The action of Diphoterine® / Previn® solutions on
bromic acid is illustrated by the pH value, which rapidly returns to a physiologically acceptable pH
zone (in 20 s and after adding 60 ml) whereas for a same volume of added water, the pH remains
at a corrosive value. A volume of water almost 10 times greater is necessary to reach the same
physiological pH.

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Management of chemical accidents / Health - Environment
 Without the dynamic effect of washing, the sole action of Diphoterine® solution on the corrosive
character of a chemical which reacts with water can be monitored by pHmetry, according to
the volume of the washing solutions added.
Take the example of 96% p-toluene sulphonyl isocyanate [CAS n°4083-64-1]:

:
Where “R” designates the group:

R-SO2-NCO + H2O R-SO2-NH-COOH R-SO2-NH2 + CO2

The gas emitted is carbon dioxide (CO2), without specific danger.

Carbamide acid, R-SO2-NH2, which is also a reaction by-product, is corrosive.

Evolution of pH during dosage of 1 ml of 99% p-toluenesulphonyl

isocyanate with Diphoterine® solution or tap water
6

5
pH

4
Diphoterine® solution pH
Water pH
Physiologically
3 acceptable pH

2
0 2 4 6 8 10 12 14 16 18 20
Time (s)

Figure 4 : In vitro simulation of static washing of a splash of 1 ml of p-toluene

sulfphonyl isocyanate with Diphoterine® solution or tap water.

Figure 4 shows that a volume of 6 ml of Diphoterine® solution is sufficient to reach the

physiologically acceptable pH zone.

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Chemicals which react violently with water - H260/H261 - EUH014
 7.3. CLASSIFICATION OF SOLUTIONS

Diphoterine® solution thus appears as a first aid choice to wash chemical splashes reacting
violently to water, and thereby generating corrosive products.
In the specific case where hydrofluoric acid is one of the acids coming from the reaction of a
chemical with water, you are adviced to use first aid Hexafluorine® solution, specific for splashes
due to hydrofluoric acid, or fluorinated salts in acid medium.

CLASSIFICATION OF DIPHOTERINE® AND HEXAFLORINE® SOLUTIONS

> Washing solutions of corrosive and irritant chemicals (Hexafluorine® solution is dedicated to
emergency washing splashes of hydrofluoric acid and its derivates)

> Medical device of class IIa

> CE 0459 marking, delivered by G-MED

> Manufactured by PREVOR laboratory

> Read carefully advice given on instructions for use, on labelling, or at the end of this
document in section”9.1 washing instructions”

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Management of chemical accidents / Health - Environment
 8. MANAGING SPILLAGES

8.1. EVALUATION OF SPILLAGE COLLECTION METHODS

8.1.1. CONVENTIONAL METHOD OF SPILLAGE COLLECTION

Conventionally, spillages are absorbed by natural or synthetic products. One can mention sand,
sepiolite, diatomaceous earth or synthetic absorbents based on polypropylene. The absorption
residue is then collected, temporarily stored and treated with hazardous solid waste.
Two problems can be linked to the collection of reactive chemicals by conventional absorbents:
> First, during their absorption, chemicals which react violently with water can react with
moisture in the air (there can then have release of dangerous gases). The absorption of
chemical products which react with water, using a conventional absorbent, does not reduce
the risks associated with the chemical.
> Then, if the residue is stored with other solid humid wastes, there can be a delayed exothermic
reaction with these other wastes, release of heat and dangerous gases. This delayed reaction
can be even more dangerous as unexpected by operators.

In all cases, the absorption residues must be stored in appropriate sealed airtight containers.
One may sometimes consider treating them with excess water so as to neutralize the hazard
linked to the reactivity of the chemical with water (e.g:organometallic). The addition of water
will not however have any action on gases released. This can lead to dangerous situations
for the personnel who are going to be faced with emanations of products stemming from the
reaction of the chemical with water. This delicate operation will have to be carried out with all
necessary precautions.
For example, TiCl4 generates gaseous HCl on contact with moisture in the air. HCl is a corrosive
gas that will contaminate all persons present at the accident site (Kapias T, 2005). In case of
spillage of this type of chemicals, the personnel present should therefore be evacuated rapidly
and the responders should be equipped with appropriate individual protective material.

21
Chemicals which react violently with water - H260/H261 - EUH014
 8.1.2. ABSORPTION WITH AN ABSORBENT/NEUTRALISING PRODUCT

Absorption of a chemical which reacts violently with water, with a neutralising absorbent,
makes it possible to keep the solidification notion of a hazardous liquid derivative and to
neutralise corrosive species that could form during the reaction of the chemical with water.
Trivorex® absorbent answers to these efficiency requirements.
Its amphoteric properties will help acting on a large majority of irritant and corrosive chemical
by-products (HCl, HBr, HF, PH3, NaOH, etc...). In addition, its absorption capacity enables the
absorbtion of any flammable by-products that could form.

8.2. EXPERIMENTAL EVIDENCE

Experimentally, we have demonstrated the absorption efficiency of boron tribromide (BBr3) by

Trivorex® absorbent.
On contact with water, the chemical reaction is the following:

BBr3 + 3 H2O B(OH)3 + 3 HBr

As we have seen previously, this reaction is

exothermic and generates heat if it is carried out in
an enclosed space. Furthermore, boron tribromide
reacts with air moisture during simple exposure and
bromic acid (HBr) is formed (see figure 5).

Figure 5 : BBr3 before absorption

If a spillage of boron tribromide is absorbed by a
non-neutralising absorbent, one is faced with two
problems. First, the absorption residue still contains
boron tribromide. The later continues to react with
moisture in the air through an exothermic reaction.
Moreover, bromic acid can continue to be formed
after absorption (sometimes visible in the form of
white fumes, see figure 6). It will then be necessary
to take all possible precautions to collect the residue,
store it (protect from moisture, and limit any contact
with other products/wastes), before treating it
Figure 6 : 5ml BBr3 absorption by 20g of sepiolite subsequently.
22
Management of chemical accidents / Health - Environment
In the case of the absorption of boron tribromide by Trivorex® absorbent, several processes
will take place. Part of the boron tribromide is going to be neutralised by the Trivorex®
absorbent, which enables the residue containing boron tribromide not to be stored.
Moreover, bromic acid, released by-product, will also be neutralised by Trivorex® absorbent,
as soon as water is added. Finally, the presence of a coloured indicator helps to indicate if
part of the chemical has not been neutralised and whether necessary precautions need to
be taken when handling the residue.
In the case of boron tribromide, addition of water to the trivorexation residue is necessary
in order to completely eliminate the corrosive hazard. A release of carbon dioxide (CO2) is
observed, product of the neutralisation reaction. There is then no longer a risk of emission
of bromic acid, and the residue has a neutral pH.

Quantity of Quantity
Boron
Trivorex® of water
tribromide pH Observations
absorbent added
(5 ml)
( g) (ml)

Pink residue
Not BBr3 still reacts with
Absorption 5 /
available moisture (white fumes)
(Figure 7)

Water favours the

neutralisation with
Trivorex® absorbent
Neutralisation 15 4 >5
(disappearance of fumes
and effervescence)
(Figure 8)

PHOTOGRAPHS:

Figure 7 : absorption, less fumes: Figure 8 : absorption/neutralisation

(BBr3+ Trivorex® absorbent, after 1 minute) BBr3 + Trivorex® absorbent + water

23
Chemicals which react violently with water - H260/H261 - EUH014
 Quantity of Trivorex® absorbent (Kg) to
add for 1 l of product spilled
Product
Family Example
released
Absorption Neutralisation*

Chlorosilanes ClSiMe3 HCl 0.25 0.5

Acetyl Pivaloyl
HCl 1 1.5
chloride chloride
BBr3 HBr 0.5 2
Lewis acids
(metal TiCl4 HCl 1.5 4.5
halogenides)
POCl3 HCl 1 10
* : With addition of water

In conclusion, Trivorex® absorbent enables easy collection of all types of chemical product, as
well as an indication of hazard and neutralisation of part of spillage hazards.

8.3. FEEDBACK

The photovoltaïc industry uses phosphoryl chloride (POCl3) for doping cell emitters. POCl3 is a
liquid that reacts with water to form phosphoric acid and hydrogen chloride:

O=PCl3 + 3 H2O O=P(OH)3 + 3 HCl

In the event of spillage, this means limiting contact with moisture. By using Trivorex® absorbent,
the acids generated are neutralised, thus making collection safe.

24
Management of chemical accidents / Health - Environment
    
> P OCl3 reacts with moisture   onitoring the neutralisation > A bsorption/neutralisation
>M
in the air: a white fume is reaction using a coloured finished.
released from the poorly indicator.
sealed bottle.
Parts of a video produced by the Air Liquide firm

9. WASHING AND COLLECTING ADVICE

9.1. WASHING ADVICE OF A CHEMICAL SPLASH

To decontaminate an ocular or cutaneous splash, we strongly recommend never delaying

washing which, for maximum efficiency, must begin as soon as possible, in other words
within seconds following the accident. Ideally, management of the incident should take place
within one minute following the splash. In a similar vein, soiled clothing must be removed very
quickly because with some chemicals of this class, the risk of ignition is very real. It is therefore
advisable to remove clothing at the start of washing so that once again precious seconds are
not wasted during which the chemical begins to react with the biochemical components of the
body tissues with which it is in direct contact.
The mechanical effect of washing the surface of the skin or the eye makes it possible to
eliminate a large quantity of the chemical received.
Chemicals which react with water can generate irritating, corrosive or toxic substances.

Generally speaking, the following protocol aims to optimise the way in which
incidents are managed and to minimise chemical ocular or cutaneous-mucous
membranes burn lesions.

25
Chemicals which react violently with water - H260/H261 - EUH014
 WASHING PROTOCOL

•S
 tart washing within one minute following the splash, beginning with the
uncovered areas.
•R
 emove clothes and/or contact lenses.
 apidly continue washing the unclothed areas.
•R
•D
 o not put back on clothing soiled by the washing or by the chemical.
• Consult a specialist.

GENERAL INSTRUCTIONS FOR WASHING

• Never delay washing.

• F or optimal effectiveness, use Diphoterine® or Hexafluorine® solutions as first-
line action.
• Use the entire contents of the container.
• F ailing this, use water and wash as quickly as possible with Diphoterine® or
Hexafluorine® solutions.
• In the case of a washing started after one minute, extend the washing of the
affected surface from 3 to 5 times the contact time. It is not useful to continue
washing for more than 15 minutes for a delayed ocular wash.
• Then seek medical advice urgently.

In the case of a cutaneous or ocular splash, we recommend carrying out very rapid and
prolonged washing with Diphoterine® solution or with Hexafluorine® solution in the particular
case of splashes with hydrofluoric acid or fluorinated salts in acid medium.

In case of ocular splashes:

• F or a contact time less than 10 seconds, use the SIEW (sterilised individual eyewash).
• F or a response time of 1 minute, use a 500 ml eyewash.
• F inally, in order to facilitate the return to a physiological osmolarity zone, we recommend
ending washing with the use of Afterwash II® solution, isotonic to cornea.

26
Management of chemical accidents / Health - Environment
In the case of cutaneous splashes (hand, forearm, neck, etc...) and a contact time less than
a minute, use a Micro DAP. For extended splashes on the body and a contact time less than one
minute, use a Portable Autonomous Shower (DAP containing 5 litres).
In the case of a skin splash of hydrofluoric acid, use a DAP of Hexafluorine® solution.

> In the case of chemical and thermal lesions, the chemical burn injury must be treated first,
then the thermal burn. Washing can then be continued, or a water gel compress may be
used.

>G
 iven the reactive potential of these chemicals with water, in the event of abundant
splashing or in the absence of possibility of rinsing within several seconds following the
splash, the medical and safety supervisors may recommend, in their accidental protocol
management on the place of the accident, an immediate wiping of the skin splashes
before starting washing with water or with specific active decontamination solutions.
This measure could thus contribute to removing an important quantity of product before it
reacts, in contact with the skin, with sweat.

> Do note that INRS underlines the importance of prolonged washing. The pain feeling
disappearance does not indicate washing’s end. It is thus necessary to use all of the
dispenser in accordance with the body surface to be decontaminated.

> If oral mucosa have been affected by the splash, rinse the victim’s mouth with Diphoterine®
solution (or with Hexafluorine® solution when appropriated) and then spit it out.

If the ear canal has been affected, rapidly wash with Diphoterine® solution (or with
Hexafluorine® solution when appropriated) by instilling 500 ml in the ear canal, leaning the
head to one side, to enable the flow of the liquid out of the ear. Ideally the solution is slightly
warmed up to limit the triggering of dizziness. As with any unilateral ear bath with a liquid
at ambient temperature, a dizzy feeling, can occur without any serious consequences. It will
spontaneously disappear after a few minutes.

>D
 iphoterine®, Hexafluorine® and Afterwash II® solutions are medical devices of class IIa.
Do read carefully instructions for different dispensers which can be found on prevor.com
website.

27
Chemicals which react violently with water - H260/H261 - EUH014
 Protocol for Diphoterine® solution use
In cases of corrosive or irritant chemical splashes on skin or eyes*.

ACTION WITHIN THE FIRST MINUTE

Use
Action within 1 LIS
the first 10 seconds
50 ml
Use
Intervention after
10 seconds
1 LPM
500 ml

3
Use
% of body 1 MICRO DAP
surface
100 ml

Use
9 % of body
surface
1 MINI DAP
200 ml

Use
+ 9 de
of body
% surface 1 DAP
5 litres

®
* Limited efficacy on hydrofluoric acid or its derivatives in an acidic medium. Hexafluorine solution is better adapted for this use.

In compliance with the law, this medical device is a regulated health product bearing the certified EC marking by LNE/G-MED accredited
body by ANSM in France.
28
Management of chemical accidents / Health - Environment
Protocol for Hexafluorine® solution use
In cases of hydrofluoric acid splashes or its derivatives in an acidic medium*

ACTION WITHIN THE FIRST MINUTE

Use
To wash one eye 1 LPM
500 ml

Use
To wash a body 1 DAP
5 litres

In all cases, washing must be followed by a medical examination.

Depending on the company’s recommended medical protocol,

apply locally a specific antidote such as calcium gluconate.

In the case of delayed washing, the application of an antidote is

justified because of the systemic effect involved in this kind of situation.

* Limited efficacy on alkaline chemicals. Diphoterine® solution is better adapted for this use.

In compliance with the law, this medical device is a regulated health product bearing the certified EC marking by LNE/G-MED accredited
body by ANSM in France.
29
Chemicals which react violently with water - H260/H261 - EUH014
 9.2. COLLECTING ADVICE

Given the reactive potential of chemicals classified H260/261 with water, in the event of
spillage, it is necessary to use a non-flammable absorbent. In all cases, absolutely avoid the
use of absorbent paper which risks catching fire on contact with these chemicals.
Non-neutralising absorbents do not make it possible to limit the reaction of the spilled product
classified H260/261 with moisture in the air. Corrosive (or toxic) gases can be emitted or a
significant rise in temperature can occur, once the product has been absorbed, creating a new
danger. It is therefore advisable to neutralize the residue with a suitable product.
A neutralising absorbent, such as Trivorex®, makes it possible to both absorb the chemical that
reacts violently with water and to neutralize its corrosiveness.

30
Management of chemical accidents / Health - Environment
 We strongly recommend absorbing-solidifying and neutralising spillages of
chemicals which react violently with water using TRIVOREX® absorbent in a
well-ventilated area. Ensure that the appropriate respiratory apparatus is used
when dealing with the fumes of the spilled chemical.
The absorption-solidification is carried out at the site of the spill. To rapidly
absorb-solidify the liquid (within a minute), it is necessary to add from 0.5
to 1.5 times the quantity by weight of TRIVOREX® absorbent with respect to the
quantity of spilled liquid.
Neutralisation can be carried out either, at the site of the spill or, in another
area, better suited to waste treatment. It is sometimes necessary to add water
to the Trivorexation residue in order to totally eliminate the corrosiveness of the
residue.

10. DOCUMENTARY REFERENCES

• Agency for Toxic Substances and Disease Registry, US Department of Health and Human Services, Toxicological
profile for titanium tetrachloride, September 1997
•C
 lare Robert A. and Krenzelok Edward P., Chemical burns secondary to elemental metal exposure: Two case
reports, The American Journal of Emergency Medicine, Volume 6, Issue 4, July 1988, 355-357
• E ldad A, Chaouat M, Weinberg A, Neuman A, Ben Meir P, Rotem M, Wexler MR., Phosphorous pentachloride
chemical burn--a slowly healing injury, Burns. 1992 Aug; 18(4):340-1.
• L . Fernie, P. Wright, T. Kapias, Water Reactive Materials: Incorporation into Safety and Environmental Risk
Assessments, Process Safety and Environmental Protection, Volume 85, Issue 2, 2007, Pages 162-168
• T. Kapias, R.F. Griffiths, Accidental releases of titanium tetrachloride (TiCl4) in the context of major hazards--spill
behaviour using REACTPOOL, Journal of Hazardous Materials, Volume 119, Issues 1-3, 17 March 2005, 41-52
• INRS, Fiche toxicologique FT5, méthanol, Edition 2009 [French]
• INRS, Fiche toxicologique FT13, chlorure d’hydrogène et solutions aqueuses, Edition 2010 [French]
• INRS, Fiche toxicologique FT32, sulfure d’hydrogène, Edition 2009 [French]
• INRS, Fiche toxicologique FT179, phosphine, Edition 2008 [French]
• INRS, Fiche toxicologique FT183, lithium, Edition 2000 [French]
• INRS, Stockage des produits chimiques, Edition 2011 [French]
• L azzeri D., Pieri M, Lazzeri S, Colizzi L, Giannotti G, Pagnini D, Stabile M, Gatti GL, Massei A., Silane coupling
agent chemical burns: a risk for medical personnel too, Burns 35 (2009), 600-605
• Thanabalasingham T, Beckett MW, Murray V., Hospital response to a chemical incident: report on casualties of
an ethyldichlorosilane spill, BMJ. 1991 Jan 12;302(6768):101-102

31
Chemicals which react violently with water - H260/H261 - EUH014
HAZARD AND PRECAUTIONARY STATEMENTS

H260 : In contact with water releases flammable gases which may
ignite spontaneously
H261: In contact with water releases flammable gases
EUH 014: Reacts violently with water
P223: Keep away from any possible contact with water, because of
violent reaction and possible flash fire
P231: Handle under inert gas
P232: Protect from moisture
P280: Wear protective gloves / protective clothing / eye protection /
face protection
P334: Immerse in cool water / wrap in wet bandages
P335: Brush off loose particles from skin
P370/378: In case of fire: Use… for extinction
P402: Store in a dry place
P404: Store in a closed container
P501: Dispose of contents/container to …

A N T I C I PAT E A N D S AV E
Toxicology Laboratory & Chemical Risk Management