Classification of Hazardous

Chemicals and Hazard Symbols

Chemical Hazards

• Flammability
• Explosion
• Oxidation
• Acute toxicity
• Long term/chronic effects
• Infectious substances
• Radioactivity
• Corrosive/Irritant
• Compressed gases
• Incompatibility

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 Hazards symbols
NFPA (The National Fire Protection Association, USA) system

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Red: Fire; Blue: Health; Yellow: Reactivity / ดนม ฟต
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The hazardous level is represented by number 0 (low) to 4 (high)
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 NFPA Rating
HEALTH (Blue)
4: Materials that, under
emergency conditions, can be
lethal.
3: Materials that, under
emergency conditions, can
cause serious or permanent
injury.
2: Materials that, under
emergency conditions, can
cause temporary incapacitation
or residual injury.
1: Materials that, under
emergency conditions, can
cause significant irritation.
FLAMMABILITY (Red)
4: Materials that rapidly or
completely vaporize at
atmospheric pressure and normal
ambient temperature or that are
readily dispersed in air and burn
readily.
3: Liquids and solids (including
finely divided suspended solids)
that can be ignited under almost
all ambient temperature
conditions.
2: Materials that must be
moderately heated or exposed to
relatively high ambient
temperatures before ignition can
occur.
1: Materials that must be
preheated before ignition can
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https://www.safetysign.com/nfpa-diamond-meanings
INSTABILITY (Yellow)
4: Materials that in themselves are
readily capable of detonation or
explosive decomposition or
explosive reaction at normal
temperatures and pressures.
3: Materials that in themselves are
capable of detonation or explosive
decomposition or explosive
reaction but that require a strong
initiating source or must be heated
under confinement before
initiation.
2: Materials that readily undergo
violent chemical change at elevated
temperatures and pressures.
1: Materials that in themselves are
normally stable but that can
become unstable at elevated
temperatures and pressures.
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 Hazards symbols
UN symbols for transportation of hazardous goods

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Hazards symbols แฟนเ า
EEC classification of dangerous substance according to
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The Globally Harmonized System of Classification and Labelling of Chemicals (GHS)

UN, A Guide to The Globally Harmonized System of 7

Classification and Labeling of Chemicals (GHS)
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GHS Classification of Hazardous Chemicals

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UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS) (in mCV)
 Comparison between EEC and GHS systems

67/548/EEC * *
GHS/CLP
Symbol Pictogram

Indication of Explosive
danger Extremely/very flammable worlevel
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Oxidising Signal word Danger < นตราย ก าwarning
Very toxic/toxic Warning
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Corrosive can

Harmful/irritating
Dangerous for the environment
Hazard statement H ###

Risk phrase R ## Precautionary P ###

Safety phrase S ## statement
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fuming hydrochloric acid (37%)

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Source: Safety Data Sheet (SDS), hydrochloric acid, Product Number 84436, Sigma-Aldrich, 2015
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http://www.weberpackaging.com/GHS-compliance-labels.html
 Flammable chemicals

• Fires probably cause the most serious

damages in the laboratory.
• Most organic compounds and some
inorganic compounds are flammable.
• Fire requires three components: fuels,
oxygen/oxidant and heat/ignition source
• Flammability is quantitatively indicated by
• Flash point (Fp): The lowest
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Flammable chemicals
• Flammability is quantitatively indicated by (cont’d)
• Autoignition temperature: The lowest temperature
at which the chemical can catch fire in the air
without an ignition source. While most organic
compounds have autoignition temperature above
200 oC, some common solvents have particularly low
autoignition temperature such as CS2 (90 oC) and
diethyl ether (160 oC). They can easily catch fire on
contacting with hot surfaces
• Explosive limit or flammable range: The range of
composition between the fuel vapor and air that can
be ignited. The larger the range, the more
dangerous the chemical.
• CS2 has a Fp of -30 oC, an autoignition temerature of 90
oC and a large exprosive limit (1 to 50%) therefore it is
13
one of the most dangerous flammable solvents.
Flammable chemicals
• Any liquids with Fp lower room temperature are regarded as
highly flammable. Anything with an Fp higher than 60 oC (140
oF) is considered non-flammable.

• Gases and solids can also be flammable. Some non-

flammable solid can be highly flammable when finely divided
such as starch and metal powder.

Classification of flammable liquid and solid according to GHS

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UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
Flammable chemicals
• Some compounds do not by its own flammable, but can give
off flammable gases upon contact with water (alkali metals,
metal hydrides, metal amides or nitrides, many
organometallic compounds) or acids (most metals). The heat
from the reaction may be sufficient to ignite the flammable
gases formed.
• Some compounds can ignite themselves by just contacting
the oxygen in the air. These “pyrophoric” compounds such as
tert-butyl lithium and other organometallic compounds are
extremely dangerous and require special storage and
handling.

15
UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
Explosives
• Type of decompositions: deflagration <
explosion < detonation.
• Explosion is highly damaging, especially in a
confined space.
• Compounds that are potentially explosive
• Compounds with close-to-zero or
positive oxygen balance (contain
enough oxygen to completely oxidize
itself) like glyceryl trinitrate, polynitro
compounds etc.

C3H5(ONO2)3 -------> 3CO2 + 2.5 H2O + 1.5 N2 + 0.5 O

2 NH4NO3 -------> 4 H2O + 2 N2 + O2

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Explosives
• Compounds that are potentially explosive (cont’d)
• Compounds or mixture that contain organic and
oxidizing parts such as polynitro compounds, organic
peroxides, quaternary ammonium perchlorate, metal
perchlorate with organic ligands, a mixture of chlorate
salt and metal powder etc.
• Endothermic compounds (alkynes, polyenes,
hydrazines, peroxides, azides etc.)
• Aldehydes, ketones, alkenes and ethers as well as
certain inorganic compounds such as metallic K and
NaNH2 can form potentially explosive peroxides upon
prolonged storage. The peroxides are particularly
dangerous when being concentrated such as during
evaporation or distillation. Diisopropyl ether is
particularly dangerous that opening of an aged bottle
17
can result in explosion due to the friction.
 Explosives
• Working with potentially explosive compounds requires
special care especially when heat or friction are likely to
involve. Work at a smallest possible scale with adequate
protection (safety shield, face screen etc.). Possession or
manufacturing of most explosive compounds requires
specific permission from the Ministry of Defense.
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Classification of explosives according to GHS

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UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
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Oxidizers (ใ Ol

• The compounds can give oxygen or oxygen

equivalents that can initiate and/or sustain
the combustion.
• Oxidizers are generally not hazardous by its
own, but are very dangerous when mixed
with reducing agents or combustible
materials, especially at high temperature.
• Some common acids are also oxidizers
including concentrated sulfuric acid and
concentrated nitric acid. The “fuming”
version of these two acids are even stronger
oxidizing agents. Another strong oxidizing
acid is perchloric acid. It must be handled
only in specialized fume hood to avoid
accumulation of dangerous perchlorates.
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Organic Peroxides
Classification of ↑

organic peroxides
according to GHS

20
UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
 Benzoyl peroxide (stabilized with 25% water)
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 Corrosives สาร ดก อน
• Definition according to US DOT: A liquid or
solid that causes visible destruction of human
skin tissue at the site of contact, or in the case
of leakage from its packaging, a liquid that has a
severe corrosion rate on steel or aluminium
(exceeding 0.25 in per year at 55 oC).
• Corrosive gases such as chlorine or anhydrous
HCl are classified as toxic gases.
• The most serious accidents are exposure to the
eyes and skins. Handling of corrosive substances
require goggles, gloves and protective coats.
• Strength of acids or bases may not correlate with the severity of
the damage it can do to human tissues . Bases are usually more
destructive than acids. Some common compounds that present
serious skin corrosion hazards include phenol (also very toxic) and
hydrofluoric acid (HF). The latter is particularly dangerous and
23
even small exposure requires immediate medical attention.
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 Web Article in mCV: Measures of Toxicity
Toxicity
• A compound under controlled circumstances is able to
produce a definite harmful effect in a biological system –
most specifically to human
• Toxicity depends on several factors: the dose (amount of
chemicals, time and frequency for exposure); the route of
exposure (ingestion, inhalation, skin contact, injection);
other factors (genders, genetics, sensitization etc.)
• Do not associate toxicity with odors. Some smelly
compounds is not so toxic, and many odorless compounds
are very toxic.
If you don’t know the details about toxicity of the compound, it
is prudent to act as though you could be susceptible to serious
toxic consequences and to therefore follow the necessary
precautions when working with chemical in the laboratory.
24
American Chemical Society, Safety in Academic Chemistry Laboratories Vol. 1 (7th Ed, 2003).
 Acute toxicity
• Regarding to the dose, all chemicals are toxic,
only at what level.
• The level of acute toxicity is expressed by LD50
(lethal dose fifty), which is the dose given to
animals (often by ingestion) that result in 50%
death. The unit of LD50 is mg/kg. The smaller
LD50 value, the more toxic the compound.
Anything with LD50 < 50 mg/kg are quite toxic.
• The dose that can kill a human can be
extrapolated by multiplication with the body
weight. (note: Me2Hg has an LD50 of 50 ug/kg)
• The term LC50 (lethal concentration fifty) can ในการไปคะ านทาน
also be found but it is expressed in term of
concentration of compound in the air (mg/L)
that can kill 50% of a specified animal species
tested. exll. Syamide
LD50 value (rat, oral): Sucrose: 30,000; NaCl 3,000; Aspirin: 200; NaCN: 6.4;
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aflatoxin B1: 0.48; tetrachlorodibenzodioxin: 2x10-5; botulinum toxin: 1x10-9 mg/kg
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https://thoughtscapism.com/2018/05/07/measures-of-toxicity/
Acute toxicity: GHS classification

27
UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
Chronic toxicity/Long term effects
• Usually workers are more likely to be exposed to smaller dose of
the same compound repeatedly.
• The effects in these circumstances may not be the same as acute
toxicity. It is also more difficult to determine what is the “safe”
exposure level.
• Some numbers that can be used as a guide to estimate how
dangerous of a specific compounds are:
• TLV (Threshold Limit Value): A concentration of the
compound in the air (ppm or mg/m3) that workers may be
repeatedly exposed day after day without adverse effect. The
figure usually expressed as TLV-TWA (exposure at 8 h/day) or
TLV-STEL (15 min exposure) (ACGIH).
• PEL (Permissible Exposure Limit) is OSHA’s equivalent of
ACGIH TLV, although the figure may not necessarily be the
same as TLV.
• IDLH – NIOSH’s Immediately Dangerous To Life or Health
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(IDLH) Values
(The same formula can be used for the conversion of mg/m3 to ppm)

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https://www2.dmu.dk/atmosphericenvironment/expost/database/docs/ppm_conversion.pdf
see TLV chart in mCV

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Chronic toxicity/Long term effects
• Sensitizers: initial exposure causes no visible effect
but on repeated exposure allergic symptom
develops
• Carcinogens: compounds that may cause cancer
According to GHS
Category 1: known or presumed to have
carcinogenic potential for humans
1A: the assessment is based primarily on human
evidence
1B: the assessment is based primarily on animal
evidence
Category 2: suspected human carcinogens
• Mutagens: substances that can cause damage to the
chromosomes
• Teratogens: substance that can affect fetal
development and/or cause birth defects, including
fetal deaths 31
UN, A Guide to The Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
Chronic toxicity/Long term effects
Examples of compounds that are known to show long term effects:
• Sensitizer: formaldehyde, dichromates, hydroquinone, DCC
• Carcinogens:
• asbestos
• Cr(VI), Ni, Cd, As compounds
• alkylating agents and epoxides
• acrylamide and acrylonitrile
• benzidines, naphthylamines
• benzene
• N-nitroso compound
• Hydrazine
• CH2Cl2, CHCl3
• phenolphthalein
• Mutagens and teratogens:
• any compounds that interact with genetic materials (such as
alkylating agents and acrylonitrile) are potentially mutagenic
and teratogens as well as carcinogenic. 32
Compressed gases
• Compressed gases are
potentially hazardous by:
• the cylinder
• the pressure
• the gas inside
• The gas cylinder must always
put upright and safely secured
to the wall or a stand by a
chain or a belt.
• Always use the right kind of
pressure regulators.
• Before turning the main valve,
make sure that the gas can
escape the system.
• Unused gas cylinders should
have the protection caps in
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place.
 Radioactivity and biological hazards
Radioactivity: by which a nucleus of an
unstable atom loses energy by emitting
radiation (, , or )
• Exposure to radiation does not
require direct contact.
• The effect of radiation may be
delayed for many years.
• Radioactive waste cannot be safely
disposed. The only way is to keep
them in a safe place until they are
completely decayed.
Biological hazards: any microbial unit
capable of presenting a risk to the well-
being of human or other animals, either
through infection or indirectly through
disruption of the environment.
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Handling of both requires special training!
Incompatible chemicals
• Many compounds do not represent special hazards on
their own, but can be very dangerous upon mixing with
another “incompatible” chemical.
• The incompatibility hazards may be classified into:
• The reaction can be strongly exothermic so that
explosive or violent reactions that may cause
splattering or rapidly pressurizing the container.
• Flammable, toxic, corrosive or dangerous products
may be produced.
• Examples of incompatible pairs include:
• acids and bases.
• oxidizing agents and reducing agents or combustible
materials.
• many chemicals are incompatible with water e.g.
alkali metal, metal hydrides, acid halides, many
35
inorganic halides, oxyhalides or anhydrides.
 see EPA compatibility chart in mCV

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https://www.orf.od.nih.gov/EnvironmentalProtection/WasteDisposal/Documents/chemical_waste_chemical_compatibility_chart.pdf