OSH for ENGINEERS

ENGG 1030

Joanne S. Dionela, ChE

5. Chemical Safety
& Hazards
Communication
Chemical Properties and Hazards 3

Hazard
is a condition or an act with the POTENTIAL to cause injury/ill-health or
damage.

Chemical
is a substance that is produced or used in a process (reaction)
involving changes to atoms or molecules. The term is sometimes
defined more broadly as "a substance".

OSHA definition: means any element, or mixture of elements and/or

compounds.
Classification of Chemicals 4

Solid Liquid Gas

General Properties of Matter 5

1. Physical Property
Any aspect of an object or substance that can be measured or perceived without
changing its identity.
Ex. Physical state: solid, liquid, gas

2. Chemical Property
any of a material's properties that becomes evident during a chemical reaction;
that is, any quality that can be established only by changing a substance's
chemical identity.
Ex. Flash point, vapor pressure
5.1 Chemical
Properties
Auto-ignition Temperature 7

• The temperature at which a product can undergo spontaneous

ignition.

• This temperature is very high – commonly in the hundreds of

degrees.
Specific Gravity/Density 8

• Specific gravity (SpG) is the ratio of the density of a substance (at a

given temperature) to the density of water at the temperature of its
maximum density.

• Numerically, SpG is equal to the density in g/cc, but is expressed as

a pure number without units.

• If the SpG of a substance is greater than 1 (the SpG of water), it will

sink in water. The substance will float on water if its SpG is less than 1
(ex. oil/petroleum products). This is important when considering
containment, cleanup, disposal and treatment alternatives.
Vapor Pressure 9

• The pressure exerted by a vapor against the sides of a closed

container.

• Vapor pressure is temperature dependent. As temperature

increases, so does the vapor pressure.

• Thus, more liquid evaporates, vaporizes or volatilizes as temperature

and vapor pressure increase.
Vapor Density 10

• The density of a gas or vapor can be compared to the density of

the ambient atmosphere.

• Vapor or gas that is greater in density than the ambient air tends to
settle to the lowest point.

• Vapor density close to the density of air or lower tends to disperse in

the atmosphere.

• In settling, dense vapor (v.d. >1) creates many hazards. If the vapor
displaces enough air to reduce the atmospheric concentration of
oxygen below 16%, asphyxia may result.
Solubility 11

• The ability of a solid, liquid, gas or vapor to dissolve in a solvent.

(basis: water)

• An insoluble substance can be physically mixed or blended in a

solvent for a short time but is unchanged when it finally separates.

• The solubility of a substance is independent of its density or specific

gravity.

• Solubility is important when determining health effects, reactivity,

dispersion, and methods of cleanup and treatment.

• Solubility is generally expressed in parts per million (ppm) or as a

percentage (0-100%).
Boiling Point 12

• Boiling point is the temperature at which liquid changes to a vapor,

or the temperature when the pressure of the liquid equals
atmospheric pressure.

• A major consideration with toxic substances on how they enter the

body.

• With high-boiling-point liquids, the most common entry is by body

contact (skin absorption). Low-boiling-point liquids are most
commonly inhaled.
Flash Point 13

• Flashpoint is the lowest temperature at which a liquid gives off

enough vapor to form an ignitable mixture with air and produce a
flame when an ignition source is present.

• The lower the flash point, the greater the danger.

Flammability/Explosive Range 14

•The range of concentrations of gases in air which will support the

explosive process bounded by measurable limits called Upper
Explosive Limits (UEL) or Upper Flammable Limit (UFL) and Lower
Explosive Limits (LEL) or Lower Flammable Limit (LFL).

•The flammable range is the optimal chemical fuel concentration in

air for the ignition and the sustenance of combustion.

•The lowest concentration of fuel in this range is the LEL/LFL. The

highest ratio that is flammable is the UEL/UFL.
Flammability/Explosive Range 15

LOWER EXPLOSIVE LIMIT (LEL) vs. UPPER EXPLOSIVE LIMIT (UEL)

AIR

COMBUSTIBLE

(TOO LEAN TO BURN) (FLAMMABILITY/ (TOO RICH TO BURN)

LEL EXPLOSIVE RANGE) UEL
100%

Gasoline Vapors: 1.4% 7.6%

5.2 Chemical
Hazards
Reactive 17

• Reacts violently with water, air, heat, or shock.

• Forms potentially explosive mixtures with water, air, or other
chemicals.
• Generates toxic gases, vapors, or fumes
• Types of Reactives:
– Metals (Sodium, Lithium – release hydrogen gas)
– Hydrides (release hydrogen)
– Peroxides (release oxygen)
– Water reactives
– Explosives (TNT, Nitroglycerine, Ammonium Nitrate)
Oxidizer 18

• Any chemical that increases the burning rate of material by readily

yielding oxygen or other oxidizing gas; or enters into a violent
reaction during which the spontaneous liberations of heat/gas is
too rapid to be safely dissipated.
• Examples:
– Oxygen
– Chlorine
Flammable Liquids 19

• A liquid that gives off vapor which can easily be ignited at normal
working temperatures.

• A flammable liquid has a flash point under 37.8°C (100 ° F).

• Vapors are released that can explode and burn at temperatures

below 37.8°C (100°F).
Combustible Liquids 20

• A combustible liquid does not catch fire as easily as a flammable

liquid.

• A combustible liquid has a flash point, above normal working

temperature from 37.8 to 93.3 °C (100 to 200 ° F).

• No ignitable vapors are released at temperatures below 38°C

(100°F).
Explosive 21

• These materials are capable of igniting spontaneously when

exposed to moist or dry air at or below 54°C (130° F).

• They will also ignite in air at or below normal room temperatures in

the absence of added heat, shock, or friction.
Corrosive 22

• Corrosive material, solid or liquid, may destroy body tissue, metal,

and plastic upon contact. Corrosives affect both organic and
inorganic matter.

• Common corrosives include halogens, acids, and bases. Acids burn

skin (Water seeker), Bases dissolve skin (Lipid seeker).

• USA’s Environmental Protection Agency (EPA)classify a waste

material as corrosive if the pH is less than or equal to 2.0 acidic or
above 12.5 basic.

• pH = measure of acidity or basicity of a solution.

1 7 15
Acid Neutral Base
Acids and Bases 23

• Strong Acids (highly corrosive) Weak Acids

- Sulfuric Acid - Boric Acid
- Hydrochloric - Carbonic Acid
- Nitric Acid - Acetic Acid

• Strong Bases (penetrate skin) Weak Bases

- Sodium Hydroxide (lye) - Amines (salts)
- Potassium Hydroxide - medicines
Toxic Chemicals 24

• Metals: Mercury, Lead Chromium, Cadmium

• Cyanides: Most common in plating operations. Forms dangerous
Hydrogen Cyanide gas when mixed with acids.
• Pesticides:
– Organophosphates
– Chlorinated Insecticides
– Herbicides
• Acute Toxins – LD50 (Lethal Dose)
• Chronic Toxins – Carcinogens, Mutagens, Teratogens.
Radioactive 25

• The process of unstable atoms trying to become stable by the

emission of energy capable of producing charged particles.

• Ionizing Radiation: (Uranium, Radium, Thorium)

– Alpha
– Beta
– Gamma, X-Rays
– Neutrons
Carcinogenic 26

• A carcinogen is a substance that causes cancer (or is believed to

cause cancer).

• A carcinogenic material is one that is known to cause cancer.

Biohazards 27

• Infectious agents presenting a risk or potential risk to the well-being

of man.
• Viruses
• Bacteria
• Needles/Sharps
• Bloodborne Pathogens found in:
– Human Blood
– Urine, body fluids or other components
Compressed Gases 28

• A compressed gas refers to a chemical which is typically stored

under pressure in cylinders.

• Compressed gases are often shipped and stored as liquids (under

pressure at low temperature) or gases (under high pressure).

• Compressed gases can be flammable, corrosive, toxic, reactive or

they may exhibit various combinations of these traits.
Cryogenic 29

• A gas that has been liquefied by lowering its temperature below -

100°C.
• The most common cryogenic chemicals used are:
– liquid nitrogen
– helium
– hydrogen
– oxygen
• Cryogens present many hazards:
– Ultra cold temperatures (Frostbite)
– Flammability
– High pressure gas, resulting in over-pressurization of containers
and pressure vessels.
– Displacement of oxygen/asphyxiation.
Static Electricity 30

• Static electricity is generated by contact and separation of

materials, such as particulates moving through a stack, gas flowing
from a nozzle at high velocity, or pouring or spraying of non-
conducting liquids or solids.

• Static electricity is also generated when:

➢Materials flow through pipes, hoses, ducts.
➢A belt runs over a pulley.
➢A person walks across a floor.
➢Static electricity accumulates to higher voltages in atmospheres
with low humidity and during dry weather.
Routes of Entry 31

•Inhalation –
breathing in the
chemical

Ingestion –
swallowing the
chemical

Absorption –
the chemical soaks
through the skin
Health Impacts 32

• Immediate / Acute
➢ Occur rapidly after single dose
• Delayed/Chronic
➢ Occur after the lapse of some time
• Reversible
➢ Affected tissues are able to regenerate (e.g. Liver)

• Irreversible
➢ Affected tissues not able to regenerate
▪ Injury to the Central Nervous System (CNS)
▪ Cancer
5.3 Hazards
Communications
Globally Harmonized System (GHS) 34

• An approach to defining and classifying

hazards for chemicals, including
pesticides.

GHS Goals:
• To promote safer transport, handling and
use of chemicals world wide.
• To facilitate international trade in
chemical products by promoting greater
consistency in regulatory requirements.
• To reduce need for testing and
evaluation.
• To assist countries in developing
strategies for sound management of
chemicals.
Globally Harmonized System (GHS) 35

These products could explode when in

contact with a flame, spark, static electricity,
heat, a shock or friction.

Explosive
Globally Harmonized System (GHS) 36

These products could burn :

•In contact with a flame, spark, static electricity,
•With heat, friction …
•In contact with air
•In contact with water, if they issue inflammable
gas
Flammable
Globally Harmonized System (GHS) 37

These products could provoke a fire or

make it worse or even provoke an explosion
if in contact with an inflammable product.

Oxidizer
Globally Harmonized System (GHS) 38

These products are gases under pressure

placed in a container :
• certain gases could explode with heat,
especially compressed gases, liquefied gases,
dissolved gases
• the liquefied freezing gases could be
responsible for burns or injuries
Compressed Gases
Globally Harmonized System (GHS) 39

These products are corrosive. Two cases :

•Substances Corrosive to Metal are substances
or mixtures that by chemical action will
materially damage, or even destroy metals
•Substances Corrosive to skin are substances
or mixtures which will produce irreversible
damage to the skin.
Corrosive
Globally Harmonized System (GHS) 40

These products poison quickly even with a slight

dose.

They could provoke diverse effects for the health :

nauseas, vomiting, headache, loss of
consciousness or some troubles which could cause
death

Acute Toxicity They could be toxic by inhalation, ingestion or skin

contact
Globally Harmonized System (GHS) 41

These products belong to one or several categories :

• Germ Cell Mutagenicity means an agent causing
an increased occurrence of mutations in
populations of cells and/or organisms.
• Carcinogenicity means a chemical substance or a
mixture of chemical substances that induce
cancer or increase its incidence.
• Reproductive Toxicity includes adverse effects on
sexual function and fertility in adult males and
Health Hazard females, as well as developmental toxicity in
offsprings.
Globally Harmonized System (GHS) 42

These products could induce several effects :

• If used with a high dose, they could poison,
• they are irritants for the eyes, the throat, the
nose or the skin
• They could induce an allergic response
• they could provoke somnolence or fainting
Irritant
 Globally Harmonized System (GHS) 43

These products belong to one of two

categories :
• Acute Aquatic Toxicity means the intrinsic
property of a material to cause injury to an
aquatic organism in a short-term exposure

• Chronic Aquatic Toxicity means the

potential or actual properties of a material to
cause adverse effects to aquatic organisms
Environmental Hazard during exposures that are determined in
relation to the lifecycle of the organism
NFPA 704: Fire Diamond 44
NFPA 704: Fire Diamond 45

Degree of Hazards

Number Degree of Hazard

4 EXTREME

3 SERIOUS

2 MODERATE

1 SLIGHT

0 MINIMAL
NFPA 704: Fire Diamond 46

Health (Color code: Blue)

4. Very short exposure could cause death or major residual injury (e.g., hydrogen
cyanide).

3. Short exposure could cause serious temporary or moderate residual injury (e.g.,
chlorine gas).

2. Intense or continued but not chronic exposure could cause temporary

incapacitation or possible residual injury (e.g., chloroform).

1. Exposure would cause irritation with only minor residual injury (e.g., turpentine).

0. Poses no health hazard, no precautions necessary. (e.g., lanolin).

NFPA 704: Fire Diamond 47

Flammability (Color Code: Red)

4. Will rapidly or completely vaporize at normal atmospheric pressure and
temperature, or is readily dispersed in air and will burn readily (e.g., propane). Flash
point below 23°C (73°F).

3. Liquids and solids that can be ignited under almost all ambient temperature
conditions (e.g., gasoline). Flash point below 38°C (100°F) but above 23°C (73°F).

2. Must be moderately heated or exposed to relatively high ambient temperature

before ignition can occur (e.g., diesel fuel). Flash point between 38°C (100°F) and
93°C (200°F).

1. Must be pre-heated before ignition can occur (e.g., soybean oil). Flash point
over 93°C (200°F).

0. Will not burn (e.g., water).

NFPA 704: Fire Diamond 48

Instability/Reactivity (Color Code: Yellow)

4. Readily capable of detonation or explosive decomposition at normal
temperatures and pressures (e.g., nitroglycerine)

3. Capable of detonation or explosive decomposition but requires a strong

initiating source, must be heated under confinement before initiation, reacts
explosively with water, or will detonate if severely shocked (e.g. fluorine).

2. Undergoes violent chemical change at elevated temperatures and pressures,

reacts violently with water, or may form explosive mixtures with water (e.g.,
phosphorus, potassium, sodium).

1. Normally stable, but can become unstable at elevated temperatures and

pressures (e.g. acetylene (ethyne)).

0. Normally stable, even under fire exposure conditions, and is not reactive with
water (e.g. helium).
NFPA 704: Fire Diamond 49

Specific Hazard (Color Code: White)

W: reacts with Water in an unusual or

BIO: Biological hazard
dangerous manner
POI: Poisonous
OX or OXY: Oxidizer
The Radioactive trefoil: is radioactive
COR: Corrosive; strong acid or base
CRY or CRYO: Cryogenic
ACID: Acid

ALK: Alkali
Transportation/UN Pictograms 50
Transportation/UN Pictograms 51

Hazard Classes
Class 1: Explosive
Class 2: Gasses (Compressed, liquefied or dissolved under pressure)
Class 3: Flammable Liquids
Class 4: Flammable Solids or Substances
Class 5: Oxidizers
Class 6: Poisonous or Infectious Substances
Class 7: Radioactive Substances
Class 8: Corrosives
Class 9: Miscellaneous Dangerous Substances
Transportation/UN Pictograms 52

UN Hazard Class Number 1 : EXPLOSIVES

Transportation/UN Pictograms 53

UN Hazard Class Number 2: COMPRESSED GASES and CRYOGENICS

Transportation/UN Pictograms 54

UN Hazard Class Number 3: FLAMMABLE and COMBUSTIBLE LIQUIDS

Transportation/UN Pictograms 55

UN Hazard Class Number 4: FLAMMABLE SOLIDS

Transportation/UN Pictograms 56

UN Hazard Class Number 5: OXIDIZERS

Transportation/UN Pictograms 57

UN Hazard Class Number 6: POISONS/TOXINS

Transportation/UN Pictograms 58

UN Hazard Class Number 7: RADIOACTIVE MATERIAL

Transportation/UN Pictograms 59

UN Hazard Class Number 8: CORROSIVE

Transportation/UN Pictograms 60

UN Hazard Class Number 9: MISCELLANEOUS DANGEROUS GOODS or

ORM-D
Other Regulated Materials (ORM-D)
Consumer commodity products or materials
that have been produced for personal or
home use. There are no labels or placards for
this group. (Examples: Spray paint and hair
spray)
Material Safety Data Sheet (MSDS) 61

What is MSDS?
• Reference material that identifies chemical characteristics and
hazards.
• Must have one for each hazardous chemical used in the work area.
• Each department must maintain MSDS file.
• Must be accessible to all employees whenever they are in their
work area.
• All hazardous materials/chemicals must have MSDS.
Material Safety Data Sheet (MSDS) 62

I. Product and company identification

II. Composition/information on ingredients
III. Hazards identification
IV. First aid measures
V. Fire fighting measures
VI. Accidental release measures
VII. Handling and storage
VIII. Exposure controls/personal protection
IX. Physical and chemical properties
X. Stability and reactivity
XI. Toxicological data
XII. Ecological information
XIII. Disposal considerations
XIV. Transport information
XV. Regulatory information
XVI. Other information
Chemical Labelling 63
Chemical Safety 64

HAZCOM VIDEO 1
5.4 Safe Chemical
Handling
Hazard Control 66

1. Elimination
- remove process/equipment, facility closure

2. Substitution
- replace with non-toxic/less hazardous product

3. Engineering control
- isolation (barrier), ventilation, grounding, safety
equipment/devices

4. Procedural or administrative controls

- safety audits, management system, 5S, etc.

5. Personal protective equipment (PPE)

- secondary control only, when hazards cannot be
reduced to ALARP level
Basic Chemical Safety Rules 67

1. Knowing what is in the product you work with. Read the labels and MSDS.

2. Properly maintaining equipment and machinery to prevent spills and leaks. Be

familiar with emergency response procedure

3. Provide sufficient and proper ventilation appropriate to reduce or extract the

chemicals in the air.

4. Follow standard procedures in safe handling of chemicals or products.

5. Use appropriate PPE.

Chemical Storage Requirements 68

1. Chemical Identification
2. Segregation/Isolation
3. Storage Cabinets /Shelves / Containers
4. Ventilation and Exhaust
5. Access and Egress
Chemical Storage Requirements 69

1. Chemical Identification
• Labels
• MSDS

Remember:
• Knowledge about the chemical, sources of information and
emergency measures are best obtained before an emergency
occurs.
Chemical Storage Requirements 70

2. Segregation/Isolation
Factors to consider:
• Severity of hazards
• Quantity of chemicals for storage
• Size and resistance of containers
• Reactivity of chemicals
➢ List of Incompatibility of Chemicals
➢ MSDS
Chemical Storage Requirements 71

3. Storage Cabinets/Shelves/Containers
• Use only approved storage cabinets.
• Never alter a flammable storage
cabinet.
• Label cabinets with the hazard class of
chemicals.
• Should be level, stable, and secured to
the wall or another stable structure
• Should have raised edges or rim
guards to prevent containers from
falling
• Should be kept free of chemical
contamination & dust
Chemical Storage Requirements 72

4. Industrial ventilation
• Ventilation is needed for chemicals and containers that may
release dangerous or damaging quantities of vapor or gases
that are flammable, corrosive, irritating or toxic or with
annoying odors.
Chemical Storage 73

5. Access and Egress

• Quick access and egress shall be
provided for all storage facilities.
• A storage plan for all storage facilities
should be considered.
• There should be evacuation and
emergency procedures to be followed in
case of leak, spill or fire within the room.
• Signage should also be provided.
Physical Handling 74

✓ Do not lift heavy load by yourself. Ask for help.

Use carts, or wagons.
✓ Gas cylinders must be capped & strapped to
carriers for transport.
✓ If chemicals are placed in bottles that are not
plastic coated use secondary containers
such as safety pails or acid buckets to carry
glass bottles of liquid chemicals.
PPE for Chemical Handling 75

✓ Follow the required PPE based on MSDS.

Basic Emergency Response 76

Public Safety
• Isolate spill or leak area for at least 50m (150ft) in all directions.
• Keep unauthorized personnel away.
• Stay upwind.
• Keep away of low areas.
• Ventilate closed spaces before entering.

Fire or explosion
Small Fire
• Dry chemical (Monoammonium Phosphate + Ammonium Phosphate), CO2,
water spray or regular Chemical foam (AFFF/AR-AFFF)

Large Fire
• Water spray, fog or regular foam.
• Use water spray or fog; do not use straight streams.
• Move containers from fire area if you can do without risk.
• Wear positive SCBA and firefighter’s protective clothing.
Basic Emergency Response 77

Spill or leak
• ELIMINATE all ignition sources.
• All equipment used when handling the product must be grounded.
• Do not touch or walk through spilled material. Stop leak if you can do without risk.
• Prevent entry into waterways, sewers, or confined spaces.
• Use vapor suppressing foam to reduce vapors.
• Absorb or cover with dry earth, sand or other non-combustible material and
transfer to containers.
• Use clean non-sparking tools to collect absorbed material.
Basic Emergency Response 78

First Aid
• Move victim to fresh air.
• Do not induce vomiting.
• Give artificial respiration if victim is not breathing.
• Administer oxygen if breathing is difficult.
• Remove and isolate contaminated clothing and shoes.
• In case of contact with substance, immediately flush kin or eyes with running
water for at least 20 minutes. Wash skin with soap and water.
• In case of burns, immediately cool affected skin for as long as possible with cold
water. Do not remove clothing if adhering to skin. Keep victim warm and quiet.
• Ensure that the medical personnel are aware of the involved and take
precautions to protect themselves.
Chemical Safety Management Program 79

1. Material Safety Data Sheet

2. Chemical Evaluation and Registration
3. Chemical Risk Assessment
4. Chemical Labelling (GHS)
5. Storage
6. Handling
7. Disposal
8. Emergency Response
9. Training
10. Management System Review
Group Work: HazCom/Chemical Safety 80

➢ Using MSDS of the assigned chemical, prepare an A3 size Chemical Safety/

Hazcom Poster/infographics covering the following minimum information:
1. Chemical Name
2. Hazards and pictograms
3. Safe Handling Requirements
4. Required Personal Protective Equipment (PPE) – show pictures/drawings
5. Emergency Response (First Aid, fire, etc.)
➢ Submit poster together with the MSDS as attachment. Due next meeting
➢ Scoring Criteria:
Completeness of information – 50%, Creativity/Graphics Design – 50%
Group 1: Acetone
Group 2: Gasoline
Group 3: Methanol
Group 4: Sulfuric Acid
Group 5: Caustic Soda
OSH for Engineers 81

Questions?