UNIT -I

CHEMICAL SAFETY

EVALUATING HAZARDS AND ASSESSING RISKS OF CHEMICALS

INTRODUCTION

CHEMICAL SUBSTANCE

➢ A Chemical substance is a material with a specific composition .

➢ Water is an example of a chemical substance .It always has the same number of
hydrogen and oxygen
➢ Some everyday chemicals include cleaning materials, cosmetics, plastics paint,
dyestuffs, sugar, solvents, etc.
➢ A chemical substance can exist as a solid, liquid or gas and still be the same substance
.

FORM OF CHEMICALS

➢ Chemicals are present in every workplace. Even in the cleanest, most modern office
Employees may be routinely exposed to inks, toners and adhesives not to mention a
wide range of chemicals used in cleaning and maintenance.

➢ Chemicals can exist in many forms Dust, fumes, powder, Liquids, Gases, Vapour,
Mists.

TYPES OF CHEMICALS

➢ Acid
➢ Bases
➢ Oxidizing agents
➢ Reducing agents
➢ Desiccants (Dehydrating Agents )
➢ Organic
➢ Inorganic
➢ Surfactants
➢ Coagulants
➢ Dyes
➢ Adsorbents
➢ Chelants
➢ Inert
➢ Radioactive
 ➢ Explosive
➢ Photosensitive
➢ Buffer
➢ Catalysts
➢ Metals
➢ Metalloids
➢ Poisons

ACIDS
Acid , any substance that in water solution tastes sour, changes the colour of certain
indicators reacts with some metals to liberate hydrogen ,reacts with bases to form salts and
promote certain chemical reaction Ex : Mineral acids , Nitric acid , Phosphoric acids
,Carboxylic acid .

BASES
A Base is a substance that can neutralize the acid by reacting with hydrogen ions .Most bases
are minerals that react with acids to form water and salts.
Ex : Metal oxides, and metal hydroxides and ammonium hydroxide .

OXIDISING AGENT
An oxidizing agent or oxidant gains electrons and is reduced in chemical reaction.
Ex : Halogens, potassium nitrate , and nitric acid .

REDUCING AGENT
A Reducing agent is typically in one of its lower possible oxidation states and is known as the
electron donor .Ex : Earth metals , formic acid ,sulfite compounds.

DESICCANTS
A Substance having a great affinity for water and used as a drying agent
Ex : Calcium oxide or Silica gel .

ORGANIC
Organic chemicals is nothing but carbon containing compounds, Which include not only
hydrocarbons but also compounds with any number of other elements including hydrogen
contain at least ,one carbon hydrogen bond .

INORGANIC
Inorganic includes salts, Metals, Substances made from single elements and any other
compunds that don’t contain carbon bonded to hydrogen. Ex : Sodium chloride

SURFACTANTS
Surfactants are materials that lower the surface tension between two liquids or between a
liquid and a solid .Ex : Dish detergents , Sodium Lauryl Sulfate .

COAGULANTS
Coagulant treatment chemicals are used in effluent waste water treatment process for solid
removal, water clarification ,lime softening , sludge thickening Ex : aluminum salts, iron
salts, polyelectrolytes.

DYES
Dye is defined as tint or coloring agent used to change the color of something

ADSORBENTS
A Substance that attracts other materials or particles to its surface .Ex activated charcoal and
kaolin .

CHELANTS
It is the chemical compound that react with metal ions to form a stable, water soluble
complex. Specific Chelating agents Bind iron , lead, or copper

INERT
An inert chemical is one that is stable and un reactive under specified conditions.
Ex : helium , neon ,argon .

RADIOACTIVE
It is nothing but class of chemicals where the nucleus of the atom is unstable. They achieve
stability through changes in the nucleus. Ex UV rays , X rays, Alpha particles etc

EXPLOSIVE
An explosive is a reactive substance that contains a great amount of potential energy that
can produce explosion . Eg nitroglycerine , fissile isotope uranium 235.

PHOTOSENSITIVE
A Material that changes its chemical composition when exposed to electromagnetic radaition
. Eg : Material on the surface disk, coating on unexposed photo film .

BUFFER
Buffer is one which resist changes in pH When small quantities of an acid or an alkali are
added to it . Eg : ethanoic acid , sodium ethanoate .

CATALYSTS
Catalysts are substances that work to increase the speed at which a reaction happens
They speed up the rate of a reaction by lowering energy . Eg : enzyme .
METALS
Is any one of the element with a positive electrical charge ,typically with a shiny surface and
a good conductor of a heat .Eg : Lead, Gold ,Tin etc ..

METALLOIDS
Elements with properties intermediate between metals and non metals. Eg silicon, germanium
, arsenic , tellurium etc.,

POISON :
Any substance that can cause severe organ damage or death if ingested, breathed in, injected
into the body or absorbed through the skin .Eg cyanide .

ROUTES OF ENTRY
➢ Ingestion
➢ Inhalation
➢ Absorption
➢ Injection

INGESTION

An example of a solid entering body by ingestion.

1. Dust in the air can settle out on work surfaces ,cups, plates ,utensils, and food
2. The settled dust can be swallowed with food or drinks .

INHALATION (BREATHING)

➢ Airborne chemicals are breathed in through the mouth or nose

➢ The size of particles or droplets can affect where the chemical settles in the
respiratory tract .
➢ Where the chemical settles in the respiratory tract determines what symptoms or
disease
➢ will develop .

SKIN ABSORPTION

➢ Some chemicals can pass through the skin and be taken into the body’s systems.
➢ Solvents and pesticides are examples of compounds that can be absorbed through the
skin .

Examples of chemicals that may cause adverse health effects upon exposure :
 ➢ Irritants - Ammonia
➢ Sensitizer - Formaldehyde
➢ Target Organ effects - Methanol
➢ Toxic - Carbon Monoxide
➢ Reproductive Effects -Chemo Drugs .
➢ Carcinogens - Benzene .

INJECTION

➢ Injection is another way that Chemicals enter the body.

➢ Though less common in most workplaces ,it can occur when a sharp object (E.G :
Needle ) punctures the skin and injects chemical into the bloodstream.

TOXIC
➢ Any chemical or mixture having capability to harm the environment , living being’s
and to human health by any mode of exposure (if inhaled, swallowed or absorbed
through the skin is termed as toxic.

TOXICITY

➢ IDLH (Immediately Dangerous to Life and Health ) Are not occupational exposure
limits similar to the TLV.
➢ They were developed by National Institute of Occupational Safety and Health.
➢ It is that maximum level of concentration of an air borne contamination from which
one could ecape within 30 minutes without any impairing symptoms or any
irreversible health effects.
➢ It is reported in ppm .

(IDLH (Immediate Dangerous to Life or Health)

S.No CHEMICAL IDLH

1. Acetic acid 50 PPM
 2. Acrolein (2 propane ) 2 PPM

3. Acrylonitrile Ca(85PPM)

4. Acetaldehyde Ca(2000PPM)

5. Ammonia 300 PPM

6. Benzene Ca(500 PPM)

7. Bromine 3 PPM

8. HCl 50 PPM

9. Ally Alcohol 20 PPM

10. Hydrogen fluoride 30 PPM

FLAMMABLE HAZARDS

➢ Flammable liquids are among the most common hazardous chemicals found in the
laboratory .
➢ The primary hazard associated with flammable liquids is their ability to readily ignite
and burn .
➢ The National Fire Protection Association (NFPA) defines a flammable liquid as a
liquid whose flash point does not exceed 100°F (38°C).
➢ Combustable liquids exhibit multiple health hazard besides fire .
REACTIVE HAZARDS
A Reactive chemical hazards is a situation with the potential for an uncontrolled
chemical reaction with significant increases in Temperature ,Pressure or gas evolution .That
can result directly or indirectly in serious harm to people , property or the environment.

TYPES OF REACTIVE CHEMICAL HAZARDS

➢ Self -Reacting impact sensitive.

➢ Runaway Reactions.
➢ Chemical incompatibilty

SELF -REACTING IMPACT SERVICE

➢ When subjected to heat or impact ,these chemicals may readily decompose , resulting
in a potentially explosive release of energy .
➢ Ex : Organic Peroxides
➢ Copper Acetylide .
RUNAWAY REACTIONS

➢ In an out of control reaction involving a chemical or chemical mixture , the rate at

which heat is generated exceeds the rate at which it is removed through cooling
media and surroundings . Eg : Polystyrene ,Acetylne ..

CHEMICAL INCOMPATIBILITY
➢ These hazards occur when a chemical is suddenly mixed or comes into contact with
another chemical , Resulting in a violent reaction .

Ex : Strong acid and strong base , Water reactive materials ( Sodium metal and water).

EXPLOSIVE HAZARD

➢ The OSHA Standard defines an explosive as a chemical that causes a sudden almost
instantaneous release of pressure , gas and heat when subjected to sudden shock,
pressure or high temperature .

➢ Under the Department of Transportation (DOT) hazard class system, Explosives are
listed as hazard class 1.

Examples
❖ Acetylide , Diazo,nitroso, Haloamine ,Peroxide
❖ Nitrocellulose
 ❖ Di and Tri Nitro Compounds
❖ Peroxide Forming Compounds
❖ Picric acid
❖ 2,4- Dinitrophenylhydrazine
❖ Benzoyl Peroxide.

➢ Explosives materials, explosives components (additives or adhesives), and materials

such as organic solvents used in explosives processing can be toxic when inhaled,
ingested, or absorbed through the skin.

➢ The most frequently reported effect from working with explosives is a skin rash
resulting from skin contact with explosives materials, or with solvents and adhesives
used with explosives operations

PHYSICAL HAZARDS
Physical hazard are those substances which threaten your physical safety .The
most common type of physical hazards are
➢ Fire
➢ Explosion
➢ Chemical Reactivity

FIRE
There are three classes of material which uses fire symbol
Flammables can be gases , liquids or solids

❖ Combustibles are similar to flammable ,But they do not ignite as easily .

❖ Pyrophoric , or Spontaneous combustion materials burst into flame “on their own “
at temperatures below 130 degrees Fahrenheit .
❖ With flammables, combustibles ,and pyrophorics do not expose these materials to
 sparks, flames or other heat sources .

OXIDIZERS
➢ Oxidizers cause other substances to burn more easily through chemical reaction or
change .
➢ Organic Peroxides contain oxygen and act as powerful oxidizers .

EXPLOSIVE

➢ Explosive are materials which release a tremendous amount of energy in the form of
heat , light and expanding a pressure within short span of time .

➢ Water Reactive react with water and may explode , or they may release a gas which is
flammable .

➢ Unstable Reactives are chemicals that can react or can become self reactive when
subjected to shock , pressure or temperature .

NANO MATERIALS

➢ Nanomaterials are chemical substances or materials that are manufactured and used at
a very small scale.
➢ Nanomaterials are developed to exhibit novel characteristics compared to the same
material without nanoscale features, such as increased strength, chemical reactivity or
conductivity.
 ➢ Nanomaterials that are naturally occurring (e.g., volcanic ash, soot from forest fires)
or are generated as incidental (unintentional) by-products of combustion processes
(e.g., welding, diesel engines) are usually physically and chemically heterogeneous
and often termed ‘ultrafine particles’.

BIOHAZARDS

➢ Biological hazards are organisms or products of organisms that present a health

hazard to humans.
➢ These hazards can be encountered anywhere in the environment, including home,
school or work .
➢ Exposure to biological hazards in the workplace results in a significant
amount if occupationally associated disease .

TYPES OF BIO HAZARDS

➢ Biological hazards can be put into different categories .The most common biological
Hazards include
➢ Bacteria
➢ Viruses
➢ Fungi

BACTERIA

➢ Microscopic Organisms that live in soil, water, organic matter or the bodies of plants
and animals and are characterized by lack of distinct nucleus and the inability to
photosynthesize .
Examples : E Coli , TB, Tetanus .

VIRUSES

➢ Are a group of pathogens that consist mostly of nucleic acid and that lack cellular
structure. Viruses are totally depend upon their hosts of replication.
Examples : Common cold, Influenza, Measles, SARS, Hamtavirus and Rabies.

FUNGI
➢ Any major group of lower plants that lack chlorophyll and live on dead or other living
organisms.
Examples : Athlets foot, mould, smut, yeast and mushroom.
RADIOACTIVE HAZARDS

RADIATION

Radiation is energy in the process of being transmitted , which may take such forms as light,
or tiny particles much small to see .

TYPES

Alpha particle Radiation , Beta particle radiation, Gamma rays radiation , X ray radiation .

RADIOACTIVE HAZARDS

➢ Radiation decomposition i.e splitting of water into H+ and OH(-) and also splitting of
other solvents of the body.
➢ Kinetic energy of the incident photons heats up the molecules of the living tissues .
➢ Incident radiation when traveling through the body tissues knock out the bound
electrons free from their parent atoms or molecules .

INDIRECT EFFECTS
➢ Since 80% of the biological tissue is water
➢ Most of the incident radiation energy is abosrbed by the water molecules and these
are broken into very unstable and reactive components .These then react with body
molecules and cause cell damage .
➢ Due to generation of H and OH radicals, Subsequent to many series of reactions
hydrogen peroxide is formed which is highly reactive oxidizing compound and break
chemical bonds in macromolecules of the body such as protiens, Lipids, and other
nucleic acids causing cellular damage , cell death and mutations.
➢ The biological effects are enhanced by presence of oxygen which is always present in
cells .

DIRECT EFFECTS
➢ The early effect of radiation is a result of direct injury to tissues.
Simultaneous and considerable destruction to the radiosensitive cells lead to
radiation sickness.
➢ These effects appear within days or weeks after exposure and include nausea,
vomitions, malaise, diarrhea, fever, hemorrhage, loss of appetite, fall of hair, and
death.
➢ The delayed effects of radiation includes shortening of life span, leukemia,
malignant tumours and cataract .These appear after months or even many
years of exposure
 LABELLING OF CHEMICALS

Labels on hazardous chemicals identify hazards and give instructions on how to use
them safely. They help businesses identify any safety controls needed in the workplace, and
tell workers how to deal safely with a chemical.

➢ Manufacturers and importers of hazardous chemicals need to make sure they are
labeled correctly so workers using them know the hazards.

➢ A GHS label is required for any hazardous chemical intended for predominantly Use
in workplace.

A summary of the GHS hazard label requirements is provided below:

1. Product Identifier – Name of the product

2. Pictograms – Graphic giving information about the potential hazard (s) of the
product.
3. Signal Word – Descriptive word/statement that explains the potential hazard of the
product. Examples “Danger” or “Warning”
4. Hazard Statements – Explanation of the product’s potential hazard
5. Precautionary Statements – Statement(s) that convey information on how to prevent or
minimize the negative effects of coming in contact with the product. Precautionary
statements fall into 4 categories: prevention, response, storage and disposal.
6. Supplier Information – Contact information for the manufacturer/supplier of the
product including company name, address and telephone number
Workplace Container Labeling
In production work areas, chemicals are often required to be transferred from their
primary containers into secondary or workplace containers for ease of use. Workplace
containers are often smaller and can consist of various shapes that may restrict the amount
of information a label can contain. At minimum, workplace container labels should display
the following information:

● The identity of the chemical (chemical name).

● The associated hazards (signal word and/or hazard statement).
● Pictogram.
The below example summarizes the minimum recommended label elements for
workplace containers.

SAFETY DATA SHEET

safety data sheet is a technical document which provides detailed and comprehensive
information on a controlled product related to: health effects of exposure to the product
hazard evaluation related to the product’s handling, storage or use measure to protect
workers at risk of exposure emergency procedures. The data sheet may be written, printed or
otherwise expressed, and must meet the availability, design and content requirements of
WHMIS legislation. The legislation provides for flexibility of design and wording but
requires that a minimum number of categories of information be completed and that all
hazardous ingredients meeting.
SAFETY DATA SHEET CONTENT

Section : 1
Contains contact details of the person/company responsible for supplying the chemical, the
uses of the chemical, as well as the telephone number to contact in case of an emergency.

Section : 2

➢ Gives details on the hazards of the chemical and the potential effects and symptoms
resulting from use. This will help in the assessment of the risks to health, the health of
workers and the environment.

➢ All hazardous substances and mixtures must be classified and labelled according to
the CLP Regulation. Therefore, pictograms, the signal word, hazard and precautionary
statements must appear in section 2.

Section 3

➢ This section provides information on the identity, hazards and concentration of

individual substances in a mixture. In the case of a SDS for a substance, this
section provides the identity of the substance.

Section 4

Describes the necessary first aid measures to be taken in case of an accident.

Section 5

Gives specific information on fighting a fire caused by the chemical, including the
most suitable extinguishing media and protective equipment.
Section 6

Describes what actions need to be taken if there is an accidental release of the

chemical.

Section 7

Contains details on how to handle and store the chemical safely

Section 8

Gives details of the steps needed to reduce exposure, e.g. ventilation and
personal protective equipment (PPE) necessary to protect health, as well as occupational
exposure limit (OEL) values where required.
 Section 9,11,12

Provide detailed information on the physical/ chemical, toxicological and

ecological properties of the chemical.

Section 10

Contains details of any hazardous reactions that may occur if the chemical is used
under certain conditions.

Section 13

Explains how the chemical should be disposed of correctly.

Section 14

Contains information relating to the transportation of the chemical.

Section 15

Contains details on relevant EU/national legislation.

Section 16

Gives any other information relevant to the chemical e.g. training advice, full text of
hazard statements etc.

LOBALLY HARMONIZED SYSTEM OBJECTIVES OF GHS

❖ Enhance the protection of human health and environment by providing an

internationally comprehensible system for hazard communication.
❖ Provide a recognized framework for those countries without existing systems.

❖ Reduce the need for testing and evaluation of chemicals .

❖ Facilitate international trade in chemicals whose hazards have been properly
assessed and identified on an international basis

APPLICATION OF GHS

One of the objectives of the work on GHS Has been the development of a harmonized hazard
communication system through 1) Labeling and 2) Safety Data Sheets (SDS) Based on the
classification criteria developed for the GHS whereas there are 3 different type of hazards

i) Physical Hazards , ii) Health hazards iii) Environmental Hazards .

HAZARD CLASSIFICATION

I) PHYSICAL HAZARDS (16 HAZARD CLASSES)

1. Explosives
2. Flammable gases
3. Flammable aerosols
4. Oxidising Gases
5. Gases under Pressure
6. Flammable liquids
7. Flammable solids
8. Self reactive substances
9. Pyrophoric liquids
10. Pyrophoric Solids
11. Self heating substances
12. Substances and mixtures
13. Oxidising liquids
14. Organic peroxide
15. Corrosive to metals
16. Oxidising solids

ii) HEALTH HAZARDS (10 HAZARD CLASSES )

1. Acute toxicity

2. Skin corrosion

3. Serious eye damage

4. Respiratory or skin sensitization

5. Germ cell mutagenicity

6. Carcinogenity

7. Reproductive toxicity

8. Specific target Organ systemic toxicity (TOST) -Single Exposure

9. Specific target Organ Systemic Toxicity (TOST) -Repeated Exposure.

10. Aspiration Hazard.

iii) ENVIRONMENTAL HAZARD ( 1 HAZARD CLASS)

1. Hazardous to the aquatic environment .

WHMIS SYMBOLS (Workplace Hazardous material information system )

CLP HAZARD PICTOGRAM

CLP stands for Classification, Labelling and Packaging of Substances and Mixtures
Regulations. This framework was established in 2008 for the classification and labelling of
substances and mixtures in the European Union which came into force in 2009. The CLP
Regulations are based on the Globally Harmonised System (GHS) which is an international
voluntary agreement that has to be adopted through a national or regional legal mechanism to
ensure that it becomes legally binding.

Hazard pictograms alert us to the presence of a hazardous chemical. The pictograms help us
to know that the chemicals we are using might cause harm to people or the environment. The
CLP hazard pictograms are very similar to those used in the old labelling system and appear
in the shape of a diamond with a distinctive red border and white background. One or more
pictograms might appear on the labelling of a single chemical.
CLP hazard pictograms

Explosive (Symbol: exploding bomb)

Flammable (Symbol : Flame)

Oxidising ( Symbol: Flame over Circle)

Corrosive (Symbol: Corrosion)

Acute toxicity (Symbol : Skull and crossbones)

Hazardos to the Environment ( Symbol : Dead tree and fish)

 You’ll see that the old 'harmful/irritant' symbol is missing.
This has been replaced by the exclamation mark pictogram:

Gas under pressure (Symbol: Gas cylinder)

Serious health hazard (Symbol: health hazard)

Health hazard/Hazardous to the ozone layer (Symbol: Exclamation

mark) A couple of new pictograms have also been introduced:

EXPOSURE LIMITS
OEL is the concentration in the air to which nearly all workers may be
repeatedly exposed day after day without adverse health effects to themselves .

TIME WEIGHTED AVERAGE (TWA)

❖ Time weighted average (TWA) is the average workplace exposure to any hazardous
contaminant or agent using the baseline of an 8 hour per day or 40 hours per week
work schedule
❖ The TWA reflects the maximum average exposure to such hazardous contaminants
to which workers may be exposed without experiencing significant adverse
health effects over the standardized eight-hour work period.
❖ The TWA is expressed in units of parts per million (ppm) or mg/m3.
TWA may be calculated as follows:

TWA= (t1c1+t2c2+…+tncn) / (t1+t2+…+tn)

Where ci = concentration during nth interva and ti = duration of nth interval.

SHORT TERM EXPOSURE LIMIT (STEL)

➢ Short-term exposure limit (STEL) is an allowable average exposure over a short
period of time, typically 15 minutes, and should not be exceeded more than four times
in a day as long as the time weighted average is not exceeded.

➢ If the predetermined limit has been exceeded, the worker must remove him- or herself
from the hazard for at least one hour.

PERMISSIBLE EXPOSURE LIMIT (PEL)

➢ Permissible exposure limit (PEL) is a regulatory limit on the amount or concentration
of a substance in the air.

➢ This is usually based on an eight-hour time weighted average (TWA), although some
are based on short-term exposure limits (STEL).

OXICOLOGICAL PROPERTIES

LC50( Lethal Concentration)

➢ LC stands for "Lethal Concentration". LC values usually refer to the concentration of

a chemical in air but in environmental studies it can also mean the concentration of a
chemical in water.

➢ The concentrations of the chemical in air that kills 50% of the test animals during the
observation period is the LC50 value. Other durations of exposure (versus the traditional 4
hours) may apply depending on specific laws.

LD50(Lethal Dosage)

➢ LD stands for "Lethal Dose". LD50 is the amount of a material, given all at once,
which causes the death of 50% (one half) of a group of test animals. The LD50 is one
way to measure the short-term poisoning potential (acute toxicity) of a material.
➢ LD50 can be found for any route of entry or administration but dermal (applied to the
skin) and oral (given by mouth) administration methods are the most common.
 Degree of Harmfulness LD50(mg/kg)

Extreme toxic <1

Highly Toxic 1-50

Moderately toxic 51-500

Relatively harmless >15000

FLAMMABLE LIMITS
The Flammable Range (also called Explosive Range) is the concentration range of a
gas or vapor that will burn (or explode) if an ignition source is introduced.

Three basic requirements must be met for explosion to take place:

1. flammable substance - fuel

2. oxidizer - oxygen or air
3. source of ignition - spark or high heat

Below the explosive or flammable range the mixture is too lean to burn and above the
upper explosive or flammable limit the mixture is too rich to burn. The limits are
commonly called the "Lower Explosive or Flammable Limit" (LEL/LFL) and the "Upper
Explosive or Flammable Limit" (UEL/UFL).

The lower and upper explosion concentration limits for some commonly used gases are
indicated in the table below. Some of the gases are commonly used as fuel in combustion
processes.
Acetone 2.6 12.8

Acetonitrile 3 16

Acetyl chloride 7.3 19

Acetylene 2.5 100

Acrolein 2.8 31

Acrylic acid 2.4 8

Acrylonitrile 3.0 17

Allyl chloride 2.9 11.1

Allyll alcohol 2.5 18

Alyllamine 2.2 22

Ammonia 15 28

Aniline 1.3 11

Arsine 5.1 78

Benzene 1.2 7.8

ATMOSPHERIC MONITERING
➢ Monitoring is done to keep a track on quality of air with a view to collect and
improve.
➢ The best indicators are -SO2, Smoke and suspended particles.
➢ These are monitored on a daily basis and the results are collected by a central agency.
➢ SO2 - Major contaminant in urban & industrial areas which is measured by
colorimetry ,conductivity, and Amperometry
➢ Smoke index- A known volume of air is filtered through a white paper under specified
conditions & the stain is measured by photoelectric meter & expressed as μg/m3 in
air.
➢ Grit and dust measuremernt -Deposit gauge collect grit, dust & other solids which are
analysed monthly.
➢ Haze- It is traditionally an atmospheric phenomenon where dust, smoke and other dry
particles obscure the claruty of sky.

AIR QUALITY INDEX

➢ It is an index for reporting daily air quality.
➢ It tells us how clean or polluted our air is , and what associated health effects be a
concern for us.
 ➢ calculated using the measurements of average times of the chemicals ozone (O3),
sulphur dioxide (SO2), nitrogen dioxide (NO2), carbon monoxide (CO), particles
smaller than 2.5 micrometers (PM2.5), and particles smaller than 10 micrometers
(PM10).

HEALTH SURVEILLANCE

Healthy surveillance is any activity that involves getting information about an employees'
health to help protect them from health risks at work. Some are required by law (health
surveillance) and others are carried out as good practice (health checks).

Workplace control measures may not always be totally reliable. Carrying out health
surveillance can help make sure that any potential ill health effects are detected as early as
possible.

It is not a substitute for other measures to control exposure such as

➢ Improved processes
➢ Elimination of exposure
➢ Good management practice.

Purpose of health surveillance

The purpose is to maintain and protect the health and safety of employees. This is by early
detection of adverse changes to health as a result of workplace exposures. This can help you
➢ Evidence the effectiveness of existing control measures
➢ Identify where they may still be having an impact on employee health.

Some employees may need to take part in a health surveillance programme as part of their
existing contract. This could include baseline (recorded at the start of employment), ongoing
and exit health surveillance. It may also be required as a result of potential hazardous
exposures at work.
It can include various types of tests.

● Skin examination.
● Hand and arm or full body vibration tests (HAVS).
● Lung function tests - such as peak flow and spirometry.
● Hearing or vision tests – such as audiology or keystone.
● Medical tests – such as blood, urine, ECG and blood pressure
● Physical tests – such as musculoskeletal, dexterity, function, height and weight.
● Confidential health questionnaires which are industry specific and require a
detailed recorded history.

Hazardous substances
A common reason for carrying out health surveillance is due to potential exposure to
hazardous substances that could be damaging to health. These can be
● Biological agents such as fungi, bacteria, viruses
● Natural substances such as grain, flour or enzyme dusts
● Substances generated by work, such as soldering or welding fumes, or
wood dust
● Chemical products used or produced at work, such as adhesives or cleaning
agents
 UNIT -II
CLASSIFICATION & MANAGEMENT OF
HAZARDOUS CHEMICALS

CLASSIFICATION OF HAZARDOUS CHEMICALS :

The hazardous chemicals are classified into eight classes .These are under

CLASS 1 : Explosives

CLASS 2 : Gases, Compressed liquefied dissolved or deeply refrigerated ,

inflammable gases, poison (Toxic) gases .

CLASS 3 : Inflammable liquids

CLASS 4 : Inflammable solids, Substances liable to spontaneous combustion ;

substances which on contact with water emit inflammable gases .
4.1 Inflammable solids
4.2 Substances liable to spontaneous combustion
4.3 Substances , which in contact with water , emit inflammable
gases.
CLASS 5 : Oxidising substances
5.1 Oxidizing substances
5.2 Organic peroxides .
CLASS 6 : Poisonous (toxic ) and infectious substances
CLASS 7 : Radioactive Substances
CLASS 8 : Corrosives

GREEN CHEMISTRY

❖ Green Chemistry is a pro active approach to pollution prevention .

❖ It targets pollution at the design stage , before it even begins .
❖ If chemists are taught to develop products and materials in a manner that does not
use hazardous substances , then much waste , hazards and costs can be avoided .
❖ Green chemistry is designing chemical products and processes that reduce or
eliminate the use and or the generation of hazardous substances.
❖ The Design, development and implementation of chemical products and processes
that reduce or eliminate the use and generation of hazardous substances.
 12 PRINCIPLES OF GREEN CHEMISTRY

Provides a framework for learning about green chemistry and designing or

improving materials , products , processes and systems .

1. Prevent waste
2. Atom Economy
3. Less Hazardous Synthesis
4. Design Benign Chemicals
5. Benign Solvents &Auxilliaries
6. Design for Energy Efficiency .
7. Use of Renewable Feedstocks
8. Reduce Derivatives
9. Catalysts
10. Design for degradation
11. Real time analysis for pollution prevention
12. Inherently Benign Chemistry for Accident Prevention

CHEMICAL INVENTORY

Anyone responsible for an area where hazardous materials are stored is required to
maintain a complete chemical inventory in Chemicals. This includes, but is not limited to,
people in the following roles:
● Principal investigators
● Supervisors
● Storeroom managers

hazardous material: any material that, because of its quantity, concentration, physical
characteristics, or chemical characteristics, poses a significant present or potential hazard to
human health and safety or to the environment if released.

Chemical inventory records must be updated and certified annually. In addition, they must be
updated within 30 days of any significant changes to the inventory, such as a room relocation,
additions of large amounts of new chemicals, or changes in the names and phone numbers of
key contacts.

A chemical inventory should list:

1. All chemicals in the workshop

2. All products in the workshop containing chemicals-and what those chemicals are
3. All metals and other materials being worked
 4. All metal decomposition products (i.e. oxides) that result from working processes
5. A list of possible new chemicals produced by the working processes (i.e. the
formation of copper sulfate in a sodium metabisulfate (Sparex&#153;) type
pickle.

TRACKING OF CHEMICALS

A chemical tracking system (CTS) is a database of chemicals.If implemented

correctly, a CTS will reduce purchasing costs, eliminate overstocking, and reduce disposal
costs. It will also allow you to respond more effectively to accidents, fires, and other
hazardous situations.

A major part of the tracking system is a viable and effective inventory process. The
components of such a system include a centralized inventory storage location, a management
system, and personnel in charge of the program.

Steps to CTS: Walking the walk

The following are components of an effective CTS:

 Know what’s in the container—Make sure chemicals are properly labeled. Purchased
chemicals from credible suppliers should have appropriate labels. Mislabeled and
unidentified chemicals usually are the result of students and/or teachers trying to save
leftover chemicals in a new container and not creating a proper label. Be sure to use a
standard labeling system for chemicals and waste products. Also, use permanent and colorfast
ink when creating labels to prevent fading.

Don’t make storing chemicals a shell game—As soon as chemicals are spread
throughout a building in various storage areas, chemical control can be lost. The most
efficient and safest approach to chemical storage in all laboratory work, including middle
school labs, is the concept of centralization. This approach allows for a more organized,
accountable, and credible approach to tracking chemical inventory and storage.

The tenets of an effective CTS are:

1. Always update and check your inventory system prior to purchasing additional
chemicals. This will prevent overstocking and aging of chemicals.

2. Records for chemical inventories should include the following:

● Date of inventory
● Date chemical received
● Specific amount of each chemical
● Name, formula, and grade of each chemical printed on the container’s label
● Chemical hazard of each item (Material Safety Data Sheet information and
National Fire Protection Association hazard code)
● Chemical Abstract Service (CAS) registry number
● Source (supplier)
● Container type
● Hazard classification
● Required storage conditions
● Expiration date
● Storage location of each chemical
● Amount of chemical in the container.

3. Make sure new chemicals are dated upon receipt. Expired chemicals should be
removed and slated for disposal.

4. Check expiration dates when selecting chemicals, and use older stock first.

5. Inventory audits are critical to determine which chemicals are being used and
which are not. If you don’t use it, lose it.

6. Sort out and remove from the inventory human carcinogens, dermatogens (capable of
causing birth defects), reproductive toxins, and mutagens (genetic damage). Toxic materials
(cyanide salts), radioactive materials, and explosive materials should also be removed. Foster
items in the inventory which pose lesser hazards relative to corrosively, reactivity, and
toxicity.

Chemical orienteering

Use and care of chemicals can be like a hunt in the wild; success can only be met
using a good tracking system.

TRANSPORTATION OF HAZARDOUS CHEMICALS

❖ Due to unprecedented growth of chemical Industries, the proportion of

hazardous chemicals in total freight traffic is increasing at a rapid rate.
❖ Of the carriers that carry hazardous goods approximately two-thirds of them
carry flammable petroleum products including Kerosene, Petrol, LPG,
Naphtha etc.
❖ The movement of such substances is more prone to accident than the movement of
other goods.
❖ When involved in a road accident , may cause disastrous consequences like fire,
explosion, injuries, in addition to property loss and environmental pollution.
❖ Bhopal tragedy of 1984 was followed by various administrative and legislative
measures to revise and improve the overall safety condition in various industries,
specially dealing with hazardous chemicals.
❖ The safety codes and safety requirements to be followed in transportation of
hazardous materials are laid down in Central Motor Vehicles Rules.
❖ Every goods carriage carrying dangerous or hazardous goods shall display a distinct
mark of the class label appropriate to the type of dangerous or hazardous goods.
❖ Every package containing dangerous or hazardous goods shall display the distinct
class labels appropriate to the type of dangerous or hazardous goods.
❖ In the case of packages containing goods which represent more than one hazard, such
packages shall display distinct labels to indicate the hazards.
❖ Every goods carriage carrying goods of dangerous or hazardous nature shall be fitted
with a techograph, an instrument to record the lapse of running time of the motor
vehicle; time speed maintained, acceleration and declaration etc., and a spark arrester.

MANNER OF DISPLAY OF CLASS LABELS

❖ The class label shall be so positioned that the size of the label is at angle of 45
degrees to the vertical and the size of such label shall not be of less than 25 mm
square which may be divided into two portions, the upper half portion being reserved
for the pictorial symbol and the lower half for the test.

RESPONSIBILITY OF THE CONSIGNOR FOR SAFE TRANSPORT

OF HAZARDOUS GOODS

❖ The goods carriage has a valid registration to carry the hazardous goods.
 ❖ The vehicle is equipped with necessary First-aid, Safety equipments and antidotes as
may be necessary.
❖ The transporter or owner of the goods carriage has full and adequate information
about the dangerous or hazardous goods being transported.
❖ The driver of the goods carriage is trained in handling the dangers posed during
transport of such goods.
❖ Every consignor shall supply to the owner of the goods carriage full and adequate
information about the dangerous or hazardous goods, being transported as to enable
such owner and its driver:
❖ To make aware of the safety rules for transportation of hazardous materials.
❖ o make aware of the risks created by such goods to health or safety

EMERGENCY INFORMATION PANEL

❖ It is essential for every hazardous material carrier to display correctly the emergency
information panel.
❖ Emergency information panel should be legibly and conspicuously marked in each
of the three places specified.
❖ So that the emergency information panel faces to each side of the carriage and to its
rear and such panel shall contain the following information viz.,
❖ The correct technical name of the dangerous or hazardous goods in letters not less
than 50mm high.
❖ The class label of the dangerous or hazardous goods in the size of not less than
250mm square.
❖ The name and telephone number of the emergency services to be contacted in the
event of fire or any other accident in letters and numerals that are not less than 50mm
high and the name and telephone number of the consignor of the dangerous or
hazardous goods or of some other person from whom expert information and advice
can be obtained concerning the measures that should be taken in the even of
emergency.

HAZCHEM CODE
HAZCHEM - Hazardous Chemicals.

The HAZCHEM code (also called Emergency Action Code) gives vital information to fire
brigade and other emergency services on the action to be taken to combat spillage, leakage or
fire in an emergency involving a hazardous substance.

❖ The HAZCHEM code consists of a number from 1 to 4 and any one of the letters, P,
R,S, T, W, X, Y, Z followed at times by the letter E.
❖ The numbers signify the extinguishing medium to be employed

The letters signify 4 aspects viz.

1. Method of controlling spillage a) by diluting or b) by containing

2. Personal protective equipment to be worn by fire fighters
3. Reactive nature of Chemical, and
4. Need for evacuation.

HAZCHEM Code of some important and popular chemicals transported on Indian

roads .

It is important to note here that the objective of the HAZCHEM code is not to identify
the chemical carried in the vehicle. The purpose of HAZCHEM code is only to provide
guidance on the basic approach to dealing with an emergency. In interpreting the HAZCHEM
code, the following points will be useful:

1. If necessary, a fire fighting medium represented by a higher number than that

shown may be used, but not represented by a lower number.
 2. Where the letter appears as white on black, police and other non-fire service
personnel need to wear breathing apparatus only for a fire and not for a spillage,
but firemen are required to wear it in both cases.
3. Letter E indicates that the officer in charge should consider civil evacuation of the
area

The Indian Chemical Manufacturers Association (ICMA), in their publication "Code for Safe
Transportation of Hazardous Substances by Road" recommends that at least the area within a
radius of 300m should be considered for evacuation wherever 'E' appears in HAZCHEM
code.

For example for ethylene oxide with UN number 1040 and HAZCHEM code is 2PE and
would be decoded as:

2- Fog equipment is recommended (through extinguishing agents corresponding to

higher number may also be used).
P- Can be violently (V) reactive. Full body clothing with breathing apparatus is
necessary. The substance may be diluted and washed to drain.
E- Consider evacuation as first priority.

PERSONAL PROTECTIVE EQUIPMENT FOR CHEMICAL

HANDLING.
Chemical handling PPE is divided into four (4) categories, with each based on the
protection they are capable of providing. We will discuss each category below:

LEVEL A PROTECTION
Where there is a need for the highest level of skin, eye and respiratory protection, a specific
ensemble of clothing and protective gear must be used. This includes a self-contained
breathing apparatus or air respirators, a chemical protective suit designed with full
encapsulation, and inner and outer safety gloves that are chemical resistant. For the footwear,
it is important to note ahead of time whether what is required would be the worn over or the
under suit boots. Like the rest of the PPE for this level, the footwear must be chemical
resistant, and come with a steel toe.

LEVEL B PROTECTION
In situations where skin and eye irritation are not as threatening, but the respiratory dangers
are still at the highest level, then Level B protection is the safest and the best option. Apart
from the same gloves and footwear as indicated for Level A, the workers must wear chemical
resistant clothing. This means a selection of overalls and coveralls, long-sleeved jackets, a
chemical splash suit, and disposable chemical-resistant coveralls.

LEVEL C PROTECTION
This ensemble is the option for when there are airborne chemicals and substances. This
means that air-purifying respirators are a vital part of the outfit. However, the situation does
not need eye and skin protection for routine use, except that both must be within the facility
in case a time does come when it would be needed. But typically, Level C protection only
includes face masks and air-purifying respirators, and clothing, gloves and footwear as
indicated in Level B.

LEVEL D PROTECTION
The PPE needed for this level is typically just be the work uniforms that are specific to
chemical handlers. What facilities qualifying under this level would provide includes
coveralls and safety footwear, gloves and mostly disposable protection suits. Level D
protection cannot be worn if there are identified skin and respiratory hazards in the
workplace.

We have repeatedly mentioned specific clothing and protective gear in all levels, and now
we’ll explain what’s needed for chemical handling.

Eye protection, for one, should be designed in a way the eyes are not reached by chemical
splashes or infectious substances. The best way to go is chemical splash goggles, which,
unlike general safety glasses that are worn in laboratories, provide optimum protection. The
majority of the materials used for these special goggles are chemical resistant.

Then there’s the face protection or shield that are required in most instances where chemicals
are being handled. Use of these shields prevents skin damage, particularly in work where
concentrated acids and dispensing liquid nitrogen is a routine. Face shields are usually worn
along with chemical splash goggles and respiratory aids, depending on the chemicals being
handled and the specific tasks the employees deal with during the work hours.

Chemical resistant gloves are a must to ensure safety and protection for anyone who handles
or comes in contact with harmful substances and compounds, and biological and chemical
hazards. Some have light chemical resistance, which is allowed when dealing with small
volumes of organic solvents, flammable compounds and corrosive liquids. Stronger types are
required when chemical handlers will be using an apparatus under pressure. The light to
heavy chemical resistant gloves must also be worn in events where there are air or water
reactive chemicals. Insulated and heavy chemical resistant gloves are the safest option and,
thus, required when working with large volumes of chemicals. In particular, these gloves are
important in work environments where there are acutely toxic and hazardous materials and a
high likelihood of chemical spills.

Body protective clothing, another requirement in chemical handling, comes in various forms.
For the most part, they are the daily uniforms that provide protection against chemical
hazards. Some clothing comes in the form of barriers that are made of polyester and
considered excellent for splash protection, and other clothing is made of flame resistant or
other traditional materials.

Respiratory protection is a necessity in facilities assessed to have risks to worker health and
physical systems. After completion of the hazard assessment is concluded, and it is found out
that, indeed, respiratory protection is required for employees, it’s time to choose what kind of
protection is needed. Types include surgical masks, N-95 respirators, half mask, and full-face
respirators. Each type caters to specific work environments and use would be dependent on
the type of chemicals, the workplace setup, period of exposure and the risks that come with
working with the chemicals.

CHEMICAL EXPOSURE RISK ASSESMENT

The identification of hazards, the evaluation of their risks and the putting in place of control
measures to secure the health and safety of employees is a major element for managing health
and safety under the Safety, Health and Welfare at Work Act, 2005.

The Chemical Agent Regulations 2001 and 2015 point out the specific requirements
necessary to complete a Chemical Agents risk assessment of the chemical agents used in the
work place. A generic assessment is unlikely to meet the requirements of the legislation.

The Risk Assessment steps:

1. Identify the chemical hazards.
2. Consider who might be affected and how they might be harmed.
3. Evaluate the risks- what are you doing now and what further precautions are needed?
4. Document and implement your findings.
5. Update and review as required.

The first step in risk assessment is to identify the chemical hazards. A chemical inventory can
be useful. When recording all potential chemical hazards, look beyond the obvious. As well
as considering the use of chemical agents, look at chemicals or substances that may be
produced by a process, for example welding fumes, respirable crystalline silica etc.. Evaluate
the internal transport, storage and the quantities of chemicals being stored as well as waste
disposal and emergencies e.g. spill or leak. Consider all materials and mixtures, for example,
items like glues, food stuffs, cosmetics, materials used by maintenance such as oils,
gardening materials, water treatment and cleaning materials. It may be possible to group
chemicals into specific tasks and complete a task or activity based chemical risk assessment.
Check to see whether any of your chemicals are subjected to any Restrictions or
Authorisations under the REACH regulation. Again, a chemical inventory can be useful here.
Your chemical supplier can supply you with this information and must supply you with a
safety data sheet, (SDS) which should be provided with each hazardous material. The SDS is
a primary source of health and safety information. For example the SDS may have your use
included in the attached exposure scenarios (ES). It will include occupational exposure limits
where they exist or it may have derived no effect levels (DNELs). (See SDS information)
The second step is to consider who (groups of employees) might be affected and how the
material/chemical might harm them. Recognise that some employees may need special
consideration, for example, language needs of non-national workers, potential exposure of
pregnant employees etc. The different routes of exposure need to be considered e.g. dermal
exposure, absorption, inhalation, ingestion and injection. While the employer is responsible
for carrying out the risk assessment, employees should be involved.
The third step is evaluating the risks and deciding on precautions. Write down what
precautions you are already taking and apply the principles below in the following order to
determine what additional precautions are required:

➢ Eliminate the substance or substitute a less hazardous chemical

➢ Prevent exposure, for example, by containment and use of local exhaust ventilation
(Engineering controls)
➢ Organise work to reduce the number of employees that might be exposed. Challenge
how processes are carried out. Are there smarter ways of carrying out an activity so
that the potential for exposure is eliminated or reduced.
➢ Select, provide training and issue personal protective equipment (this may be required
immediately)
➢ Provide welfare facilities (first-aid and washing facilities to remove contamination)

The fourth step is to document and implement your findings. Write down your
findings and discuss them with your employees. Consultation with your employees is
necessary at every step and especially when implementing the findings of your chemicals risk
assessment. Be specific with precautions such as PPE e.g. "wear half face mask with A2P2
filter". You may need to draw up an action plan, detailing who is responsible, for what action
and when will it be carried out.
As no workplace remains the same, the fifth step is to review your risk assessment at least
once per year, and update if necessary. When changes such as new employees, machinery,
equipment or materials occur in the workplace it is necessary to review the risk assessment.
Change in work patterns such as overtime or shift work, the needs of pregnant/nursing
employees and those with special needs must also be included.

HIERARCHY OF RISK CONTROLS

Elimination and Substitution

Elimination and substitution, while most effective at reducing hazards, also tend to be the
most difficult to implement in an existing process. If the process is still at the design or
development stage, elimination and substitution of hazards may be inexpensive and simple to
implement. For an existing process, major changes in equipment and procedures may be
required to eliminate or substitute for a hazard.

Engineering Controls

Engineering controls are favored over administrative and personal protective equipment
(PPE) for controlling existing worker exposures in the workplace because they are designed
to remove the hazard at the source, before it comes in contact with the worker. Well-designed
engineering controls can be highly effective in protecting workers and will typically be
independent of worker interactions to provide this high level of protection. The initial cost of
engineering controls can be higher than the cost of administrative controls or PPE, but over
the longer term, operating costs are frequently lower, and in some instances, can provide a
cost savings in other areas of the process.
Administrative Controls and PPE

Administrative controls and PPE are frequently used with existing processes where hazards
are not particularly well controlled. Administrative controls and PPE programs may be
relatively inexpensive to establish but, over the long term, can be very costly to sustain.
These methods for protecting workers have also proven to be less effective than other
measures, requiring significant effort by the affected workers.
 UNIT -III

STORAGE & HANDLING OF

HAZARDOUS CHEMICALS

STORAGE&HANDLING OF CHEMICALS

❖ Before a new hazardous substance is recieved for storage, information concerning its
correct handling should be provided to all users .
❖ Planning and maintaining of storage areas are necessary to avoid material losses,
accidents and disasters .
❖ Good housekeeping is essential , and special attention should be paid to incompatible
substances, suitable location of products and climatic conditions .
❖ Written instructions of storage practices should be provided, and the chemical Safety
data sheets should be available in storage areas.
❖ Locations of the different classes of chemicals should be illustrated in a storage map
and in a chemical register .
❖ The register should contain the maximum allowed quantity of all chemical products
and the maximum allowed quantity of all chemical product per class.
❖ All substances should be recieved at a central location for distribution to the
storerooms, stockrooms, and laboratories.
❖ A central recieving area is also helpful in monitoring substances that may eventually
enter the waste disposal system .
❖ Stored chemicals should be examined periodically , at least annually .
❖ Chemicals with expired shelf lives and deteriorated or leaking containers should be
disposed safely .
❖ A first in ,First out system of keeping stock should be used .
❖ The storage of dangerous substance should be supervised by competant, trained
person .
❖ All workers required to enter storage areas should be fully trained in appropriate safe
work practices, and a periodic inspection of all storage areas should be carried out by
a safety officer.
❖ A fire alarm should be situated in or near the outside of the storage premises.
❖ It is recommended that persons should not work alone in storage area containing toxic
substance .
❖ Chemical storage areas should be located away from the process areas, occupied
buildings and other storage areas.

REQUIREMENTS FOR STORAGE OF VARIOUS SUBSTANCES :

LABELLING AND RELABELLING REQUIREMENTS

The label is the key to organizing chemical products for storage .Tanks and
containers should be identified with signs indicating the name of chemical product. No
containers or cylinders of compressed gases should be accepted without the following
identifyed labels .

❖ Identification of contents ‘
❖ Description of principal hazard ( eg: Flammable Liquid)
❖ Precautions to minimize hazards and prevent accidents .
❖ Correct first aid procedures ‘
❖ Correct procedure for cleaning up spills .
❖ Special instructions to medical personnel in case of an accident .

The label may also offer precautions for correct storage, such as “Keep in cool place “ or
“ Keep container dry” .When certain dangerous products are delivered in tankers, barrels or
bags and repackaged at the workplace , each new container should be relabelled so that the
user will be able to identify the chemical and recognize the risks immediately.

EXPLOSIVE SUBSTANCES

❖ Explosive substances include all chemicals, pyrotechnics and matches which are
explosives and also those substances such as sensitive metallic salts which by
themselves or in certain mixtures or when subject to certain conditions of temperature ,
shock, friction or chemical action .
❖ In the case of explosives, most countries have stringent regulations regarding safe
storage requirements and precautions to be taken in order to prevent theft.
❖ The Storage places should be situated away from other buildings and structures
so as to minimize damage in case of an explosive .
❖ Manufacturers of explosives issue instructions as to the most suitable type of
storage .
❖ The storerooms should be of solid construction and kept securely locked
when not in use
❖ No store should be near a building containing oil, grease, waste combustible
material or flammable material, open fire or flame .
❖ In some countries there is a legal requirement that magazines should be situated at
least 60 m from any power plant , tunnel, mine shaft, dam, highway,
❖ Advantage should be taken of any protection offered by natural resources
such as hills,hollows, dense woods or forests .
❖ The storage place should be well ventilated and free from dampness.
❖ Natural lighting or portable electric lamps should be used, or lighting provided
from outside the storehouse .
 ❖ Floor should be constructed of wood or other non sparking material .
❖ The area surrounding the storage place should be kept free of dry grass, rubbish or
any other material likely to burn .
❖ Black powder and explosives should be stored in seperate storehouses, and no
detonators, tool or other materials should be kept in an explosive store .
❖ Non ferrous tools should be used for opening cases of explosives .

OXIDIZING SUBSTANCES

❖ Oxidizing substances provide sources of oxygen, and thus are capable of supporting
combustion and intensifying the violence of any fire .
❖ Some of these oxygen suppliers give off oxygen at storage room temperature , but
others require the application of heat .
❖ If containers of oxidizing materials are damaged , the contents may mixed with other
combustible materials and start a fire .
❖ This risk can be avoided by storing oxidizing materials in a seperate storage place .
❖ However , this practice may not always be available as for example in dock
warehouse for goods in transit .
❖ It is dangerous to store powerful oxidizing substances near liquids that even have a
low flash point or even slightly flammable materials .
❖ It is safer to keep all flammable materials away from a place where oxidizing
substances are stored .
❖ The storage area should be cool, well ventilated and of fire resisting construction .

FLAMMABLE SUBSTANCES

❖ Hydrogen, propane, butane, ethylene, hydrogen sulphide and coal gas are the most
common flammable gases.
❖ Flammable materials should be stored in places where are cool enough to prevent
accidental ignition if the vapours mix with air .
❖ Portable , approved safety cans are the safest vessels for storing flammables.
❖ Quantities of flammable liquids greater than 1 litre should be stored in metal
containers .
❖ Two hundred litres of drums are commonly used to ship flammables, but are not
intended as long term storage containers .
❖ The stopper should be removed carefully and replaced by an approved pressure relief
vent to avoid increased internal pressure from heat , fire.
❖ When transfering flammables from metal equipment , the worker should use an
enclosed transfer system or have adequate exhaust ventilation .
❖ The storage area should be situated away from any source of heat or fire hazard.
❖ Highly flammable substances should be kept apart from poweful oxisizing agents or
 from materials which are susceptible to spontaneous combustion .
❖ When highly volatile liquids are stored any electric light fittings should be of
certified flameproof construction, and no open flames should be permitted near the
storage place .
❖ Fire extinguishers and absorbent inert gas materials such as dry sand and earth, should
be available for emergency situations.
❖ The wall, ceilings, and floors of the storage room consist of materials with at least 2
hour fire resistance.
❖ The room should be fitted with self closing fire doors .
❖ The storage room installations should be electrically grounded and periodically
inspected or equipped with automatic smoke or fire detection devices
❖ Control valves on storage vessels containing flammable liquids should be clearly
labelled , and pipelines should be painted with distinctive safety colours to indicate
the type of liquid and direction of flow .
❖ Tanks containing flammable substances should be situated on ground sloping away
from the main buildings and plant installations.
❖ If they are on the level ground, protection against fire spread can be obtained by
adequate spacing and the provision of dykes.
❖ The dyke capacity should be preferably 1.5 times that of storage tank , as flammable
liquis may be liked to boil over.
❖ No smoking should be allowed .

TOXIC SUBSTANCES

❖ Toxic Chemicals should be stored in cool, well ventilated areas out of contact
with heat, acids, moisture and oxidizing substances .
❖ Volatile compounds should be stored in spark free freezers to avoid
evaporation.
❖ Because containers may develop leaks ,storerooms should be equipped with
exhaust hoods or equivalent local ventilation devices.
❖ Open containers should be closed with tape or other sealent before being returned to
the storeroom.
❖ Substances which can react chemically with each other should be kept in seperate
stores.

CORROSIVE SUBSTANCES

❖ Corrosive substances include strong acids, alkalis and other substances which will
cause burns or irritation of the skin , mucous membranes or eyes which will damage
most materials .
❖ Typical examples of these substances include hydroflouric acid, hydrochloric acid,
sulphuric acid , nitric acid
 ❖ Such materials cause damage to their containers and leak into the atmosphere of the
storage area; some are volatile and others react violently with moisture, organic
matter or other chemicals .
❖ Acid mists or fumes may corrode structural materials and equipment and have a toxic
action on personnel.
❖ Such materials should be kept cool but well above their freezing point, since a
substnce such as acetic acid may freeze at a relatively high temperature, rupture its
container, and then escape when the temperatures rises again above its freezing point
.
❖ Some corrosive substances also have other dangerous properties ; for example
perchloric acid in addition to being highly corrosive , is also a powerful oxidizing
agent which can cause fire and explosions .
❖ Storage area for corrosive substances should be isolated from the rest of the plant or
warehouses by impervious walls and floor , with provision for safe disposal of
spillage.
❖ The floor should be made of cinder blocks , concrete that has been treated to reduce
its solubility or other resistant material.
❖ The storage area should be well ventilated .
❖ No store should be used for the simultaneous storage of nitric acid mixtures and
sulphuric acid mixtures .
❖ Sometimes it is necessary to store corrosive and poisonous liquids in special type of
containers ; for example hydrofluoric acid should be kept in leaden, gutta percha or
ceresin bottles .
❖ Carboys containing corrosive acids should be packed with kieselghur (Infusorial
earth ) or other effective inorganic insulating material .
❖ Any necessary first aid equipment such as emergency showers and eyewash bottles
zhould be provided in or immediately close to the storage place.

WATER REACTIVE CHEMICALS

❖ Some chemicals, such as sodium and potassium metals , react with water to produce
heat and flammable or explosive gases .
❖ Certain Polymerization catalysts, such as alkyl aluminium compounds react and burn
violently on contact with water .
❖ Storage facilities for water-reactive chemicals should not have water in the storage
area.
❖ Non water automatic sprinkler system should be employed.

CRYOGENS

Cryogenic liquids are liquefied gases having boiling points of less than -73.3o C (-
100o F). The primary hazards of cryogenic liquids include both physical hazards such as fire,
explosion, and pressure buildup and health hazards such as severe frostbite and asphyxiation.
Potential fire or explosion hazards exist because cryogenic liquids are capable, under the right
conditions, of condensing oxygen from the atmosphere. This oxygen-rich environment in
combination with flammable/combustible materials and an ignition source are particularly
hazardous. Pressure is also a hazard because of the large volume expansion ratio from liquid
to gas that a cryogen exhibits as it warms and the liquid evaporates. This expansion ratio also
makes cryogenic liquids more prone to splash and therefore skin and eye contact is more
likely to occur. Contact with living tissue can cause frostbite or thermal burns, and prolonged
contact can cause blood clots that have very serious consequences. All laboratory personnel
should follow prudent safety practices when handling and storing cryogenic liquids.

Handling

❖ Appropriate personal protective equipment must be worn when handling cryogenic

liquids. This includes special cryogen gloves, safety goggles, full face shield,
impervious apron or coat, long pants, and high topped shoes. Gloves must be
impervious and sufficiently large to be readily removed should a cryogen be spilled.
Watches, rings, and other jewelry should NOT be worn.
❖ Unprotected body parts must not come in contact with vessels or pipes that contain
cryogenic liquids because extremely cold material may bond firmly to the skin and
tear flesh if separation is attempted.
❖ Objects that are in contact with cryogenic liquid must be handled with tongs or
proper gloves.
❖ All precautions should be taken to keep liquid oxygen from organic materials; spills
on oxidizable surfaces can be hazardous.
❖ All equipment should be kept clean, especially when working with liquid or gaseous
oxygen.
❖ Work areas must be well ventilated.
❖ Transfers or pouring of cryogenic liquid should be done very slowly to minimize
boiling and splashing.
❖ Cryogenic liquids and dry ice used as refrigerant baths should be open to the
atmosphere. They must never be in a closed system where they may develop
uncontrolled or dangerously high pressure.
❖ Liquid hydrogen must not be transferred in an air atmosphere because oxygen from
the air can condense in the liquid hydrogen presenting a possible explosion risk.

Storage

❖ Cryogenic liquids must be handled and stored in containers that are designed for the
pressure and temperature to which they may be subjected. The most common
container for cryogenic liquids is a double-walled, evacuated container known as a
Dewar flask.
❖ Containers and systems containing cryogenic liquids should have pressure-relief
 mechanisms.
❖ Coolers and Styrofoam boxes may be used for storage of small amounts of solid
carbon dioxide (dry ice) only. Do not use coolers and Styrofoam boxes as the
primary container for the transportation and storage of liquid cryogens.
❖ Cylinders and other pressure vessels such as Dewar flasks used for the storage of
cryogenic liquids should not be filled more than 80% of capacity to protect against
possible thermal expansion of the contents and bursting of the vessel by hydrostatic
pressure. If the possibility exists that the temperature of the cylinder may increase to
above 30o C (86o F), a lower percentage (e.g., 60 percent capacity) should be the
limit.
❖ Dewar flasks should be shielded with tape or wire mesh to minimize flying glass and
fragments should an implosion occur.
❖ Dewar flasks must be labeled with the full cryogenic liquid name and should be
labeled with hazard warning information.
❖ Work and storage areas must be well ventilated.
❖ Evaporation of the liquid cryogens will displace oxygen in the room and may present
an asphyxiation hazard. Air contains about 21% oxygen and breathing air with less
than 19.5% is considered a dangerous oxygen deficient atmosphere. Concentrations
of 18% can cause dizziness and result in unconsciousness and death.

COMPRESSED GAS
The nature of chemical gas apart, the high pressure of storage amplifies the hazard of
the storage of cylinders.Following are the recommended guidelines for storage of cylinders

❖ Cylinders should be protected adequately from variation in temperatures .They should

be store in dry , cool and well ventilated place away from steam pipes, furnace,
boilers or any other potential source of heat .
❖ Cylinders should not be kept near gangways/elevators to avoid any hard object
striking them.
❖ Cylinders containing flammable gases and toxic gases shall be kept seperated from
each other and from cylinders containing other types of gases be an adequate distance
or by a suitable partition wall .
❖ Cylinders should be properly stacked taking care to prevent knocking, dropping or
rolling of cylinders .
❖ Cylinder nozzle should be suitably protected against damage.Oil or similar lubricant
should not be used on valves or other fittings of cylinders containing gas.
❖ In case of liquefied gas like liquid nitrogen , the cylinders should be stacked vertical
so that in case of defective regulator only gas would escape.
❖ The cylinder valves should be provided with security cap on the outlet to act as a
secondary means of safeguard.
❖ If there is a leak in the valve which cannot be rectified by tightening the gland nut or
spindle , the cylinder should be removed to an open space where it is less dangerous
 to life and property and necessary remedial measures should be taken.
❖ For proper identification of the chemical all cylinders shall have the proper colour as
per rule 8 of the gas cylinder rules 1981.
❖ The due date of test for cylinder should be marked on the metal ring inserted between
the cylinder valve and neck.If this date is over ,the cylinder should not be accepted
❖ Filled and empty cylinders should be tagged and kept seperately.

GENERAL GUIDELINES FOR SAFE STORAGE AND HANDLING

A. Storage in bulk

Utmost care is necessary in ensuring proper and safe storage facility for hazardous
chemicals .The following points should be given due weightage to avoid any mishap

1. Attempt should be made to find suitable less hazardous alternate chemicals, to replace the
hazardous chemical.The inventory of all hazardous chemicals for that matter must be kept
as minimum as possible.
2. The tanks should be located so as not to pose safety problems due to leakage and reaction
with other chemicals stored nearby .The environment at the location must be compatible
with the chemical stored.
3. The stored area should be declared as a prohibited area and should be provided with
fencing having at least two exits /No smoking and or /Prohibited area display boards , as
applicable should be provided at site .
4. The storage tank and foundation should be of suitable material of construction to prevent
corrosion.
5. The connections and openings to the tank should be as minimum as possible so that the
possibility of leakage and maintenance hazards are minimized.
6. The tanks should be fitted with vents/relief systems of adequate capacity discharging to
safe height.
7. The tank should have provision for emergency evacuation of its stock to a safer location
in case of emergency like fire, tank failure etc. Using pump out system.Use of double
isolation valve -Gate and global valve in series on the drain outline is recommended.
8. Each storage tank should have necessary instruments to monitor its level, pressure and
temperature preferably with remote indications at control room or field operation cabins.
9. The tank should have a dyke of suitable material (comaptable with the chemical ) of
volume equal to the volume of the larger storage tank.
a) Drain off rain water into storm water channel.
b) Route high volume spillage/leakage to suitable neutralizing pit.
c) Dicharge safe effluent to oily water system.
10 Fire access roads should be provided to storage area .The storage tanks/area
should have suitable fire protection and fire fighting facility .
11 Adequate communication facility like public address/telephone must be
made available for interacting with control room, fire stations etc.
STORAGE OF CHEMICALS IN DRUMS/CONATINER

❖ The drums should never be filled full with the liquid chemical.There should be
sufficient ullage to take care of thermal expansion.
❖ The drums should preferably be stored in a well ventilated shed with
impermeable floor sloping away from drums.
❖ There should be provision to collect accident spills for safe disposal .
❖ The drum should be stacked in a single tier with the bung (lid) up in an
orderly manner so that all parts of the storage space are accesible .
❖ Empty drums should be removed away and made free of its contents before
being kept in safety place .
❖ Periodic site inspection should be carried out to ensure there is no leakage
from any of the debris .
❖ Where Combustible solid materials are stored, the dust content of the air
must be kept below the lower explosive limit.Efficient dust collection system and
good housekeeping should be ensured

CHEMICAL STORAGE TANKS

❖ Chemical storage tanks are made of compataible material that will not react
with stored chemical.
❖ Be careful when you decide to select tank fabricator or manufacturer.Check
their products quality and track record.
❖ Always refer to appropriate standards when you are going to design a
chemical storage tank .
❖ Some of the tank ruptures were caused by defective welds .Effective
monitoring and checking including welding test during tanks fabrication are
vital .
❖ A safe distance between each tank is provided.It will prevent chain reaction
when fire occurs at one tank .
❖ There should be atleast two level indicators installed on chemical storage
tanks to avoid level instrument failure.It had better to provide level glass or
something like that for worker to check manually .
❖ Do not foget to ensure there are also temperature indicators on the chemical
Storage tanks.Decomposition reaction , which releases heat, can be easily
detected.
❖ Instrument calibration is required to ensure correct reading.Set up regular
schedule for it .
❖ Venting facilities are installed on the chemical storage tanks to
accommodate over work properly.
❖ Avoid overfilling tanks.It can be achieved by a combination of manual
 monitoring or indicating high level and automatic shut off system.
❖ Thickness and welding check may be necessary in some cases, suppose
when contained chemical is a highly corrosive .
❖ If possible use alternative methods to avoid hot work in and arround
chemical storage tanks .
❖ Monitor flammable gas and vapour before and during the hot work.
❖ Use combustible gas detector.
❖ Use written permit before hot work can be started in the storage tank.
❖ Ensure that all personnel involved in the hot work and trained well,
including contractor workers.
❖ Any drain valve installed on tanks should be equipped with valve locks ,
blind flanges or caps to avoid accidental opening .

DESIGN CONSIDERATIONS
❖ Layout
❖ Furniture and Fixtures
❖ Storage
❖ Ventilation
❖ Emergency Equipment
❖ Materials Handling
❖ Utilities
LAYOUT
❖ Space should be physically seperate from personal desk space, meeting space and
eating areas.Consider making visible separation between lab and non lab space for
instance with different flooring.
❖ Fire rated hallaway doors should have magnetic hold open features , such that door
will close in the event of alarm
❖ Doors should not be fire rated unless necessary .
❖ Entryways should have provisions for mounting emergency information posters and
other warning signal immediately outside the door .
❖ Each door from a hallaway should have a view panel to prevent accidents from
opening the door into a person on the other side and to allow individuals to see into
the work place in case of an accident.

FURNITURE AND FIXTURES

❖ Work surfaces should be chemical resistant , smooth and readily cleanable such as
chemical grade formic .
❖ Work surfaces, including computer areas, should incorporate ergonomic features,
such as adjustability, appropriate lighting and equipment layout.
❖ Benchmark areas should have knee space to allow room for chairs near fixed
instruments equipment or for procedures requiring prolonged operation .
❖ Handwshing sinks for particularly hazardous chemicals or biological agents may need
elbow or electronic controls .
❖ Wet chemical laboratories and darkrooms should have solvent resistant moved
flooring using sheet goods rather than tile, particularly in areas where fume hoods are
located.
STORAGE
❖ Cabinets for chemical storage should be of solid, sturdy construction. Hardwood or
metal shelving is preferred. Some may require ventilation .
❖ Materials of construction should be carefully considered where corrosive materials
will be stored.
❖ Allow space within the building for any central chemical and biological or radioactive
waste storage needs .
❖ Wall Shelving should have heavy duty brackets and standards and should be attached
to studs or solid blocking , For office spaces , bookcases are prefarable to wall
mounted shelving .
❖ Flammable liquid storage is not allowed below grade or near a means of egress, per
the vapour control concern.
❖ Where corrosive liquids is used it should have ample storage space low to the floors
preferably in low cabinets, such as under fume hoods .

VENTILATION

❖ The ventilation rates should ensure 8-10 air changes per hour minimum for occupied
spaces and 6 air changes per hour minimum when unoccupied .
❖ By pass style fume hoods should be used.Auxillary air hoods should not be used .
❖ Fume hoods should have recessed work surface to control spills .
❖ The location of fume hoods, supply air vents, operable windows, furniture and
pedestrian traffic should encourage horizontal, laminar flow of air into the face of
hood,perpendicular to hood opening.
❖ Hoods may have a face velocity of 100-125 linear feet per minute with the sash fully
open or at its standard configuration.
❖ Each hood must have a continuous monitoring device such as a magnetic gauge .the
device should display either air velocity or static pressure .
❖ Noise from the fume hood should not exceed 65 dBA at the face of hood .
❖ Fume hood exhaust ducts must not contain fire dampers.

EMERGENCY EQUIPMENT
❖ Units using hazardous materials must have an eyewash and safety shower within 100
feet or 10 seconds travel time from the chemical use areas.
❖ Drench hoses support , but do not replace, safety showers and eyewashes.
❖ Eyewashes and safety should have plumbed drains .
❖ Eyewashes and safety showers should be standardized at least within a building.
❖ Flooring under safety showers should be slip resistant .
❖ Windowless places and environmental chambers should have emergency lighting
❖ Alarm enunciator panels should be descriptive of the area where the alarm has
activated.
MATERIALS HANDLING

❖ Loading docks should be equipped with dockboards and should have enough room to
maneuver pallets safely .
❖ Cryogenic liquid tanks should be placed in such a manner that ntheir controls could
not accidentally be manipulated and such that they may be secured to prevent
unauthorized access.
❖ Cryogenic liquid tanks should be placed away from below grade areas where dense
vapors may collect and away from glass doors or windows.
❖ A phone should be placed near any loading area.

UTILITIES
❖ Utility Shut off controls should be located outside the laboratory
❖ Workplace should have an abundant number of electrical supply outlets to eliminate
the need for extension cords and multi plug adaptors.
❖ Electrical panels should be placed in an accesible area not likely to be obstructed .
❖ Ground fault circuit interrupters should be installed near sink and wet areas.
❖ Environmental chambers where evacuation or other alarms cannot be heard should be
equipped with strobe lighting or additional alarms.
❖ Central vaccum systems should not be used , since they are vulnerable to
contamination.
❖ All vaccum lines should have cold traps to prevent contamination .
❖ Chilled wate loops should be available for equipment in need of coding .Loops help
to avoid excessive wastewater.
 UNIT IV
CHEMICAL PROCESS SAFETY

PROCESS HAZARD ANALYSIS

A Process hazard analysis is a systematic effort designed to identify and analyse

hazards associated with processing or handling of highly hazardous material and a method to
provide information which will help workers and employers in making decisions that will
improve safety.

❖ A Process hazard analysis is analyzing all of the potential causes of consequences

that exist throughout a process
❖ These Consequences include Fire, Explosion,Release of toxic chemicalsa .
❖ During a Process hazard analysis several aspects include
Equipment,Instrumentation, Human Actions ,Other Factors.

DETERMINATION OF PHA
❖ Failure points
❖ Method of operation .
❖ Factors that could lead to accidents

PHA TEAM
❖ A Facilitator
❖ A Scribe
❖ Engineers
❖ Operators
❖ Supervisors
❖ Other workers

FACILITATOR

❖ Facilitator is a third party bought into help witha PHA .

❖ A Facilitator will help provide direction for the analysis, organize and execute the
analysis activities.
❖ Any team meeting that will be held as part of the study will be led by the
facilitator.
❖ The selection of a PHA Methodology or technique will be influenzed by many
factors including the amount of existing knowledge about the process.
❖ These considerations assist in determining the hazards and potential failure points
or failure modes in a process.
❖ All PHA methodologies are subject to certain limitation.
❖ For example checklist methodology works well when the process is very stable
and no changes are made , but its not as effective when the process has undergone
extensive change .
❖ The checklist may miss the most recent changes and consequently the changes
wouldn’t be evaluated.
❖ Another limitation to be considered concerns the assumptions made by the team or
analyst .
❖ The PHA Team can vary in size from two people to a number of people with
varied operational and technical backgrounds .
❖ Some team members may only be part of the team r a limited time.
❖ The team leader needs to be fully knowledgable in the proper implementation of
the PHA methodology that is to be used and should be impartial in the evaluation.
❖ The other full time or part time team members need to provide the team with
expertise in areas such as process technology, process design, operating
procedures and practices , including how the work is actually performed, alarms,
emergency procedures, instrumentation, maintanence procedures and any other
relavent subject he dictates.
❖ The selected team members need to be compatible and the team leader needs to be
able to manage the team, and the PHA study .
❖ The team needs to be able to work together while benefiting from the expertise of
others on the team , to resolve issues , and to forge a consensus on the findings of
study and recommendations.
❖ The application of PHA to a process may involve the use of different
methodologies for various parts of the process.
❖ For example process involving a series of unit of operations of varying sizes,
complexities, and ages may use different methodologies and team members for
each operation.
❖ Then the conclusions can be integrated into one final study and evaluation.
❖ A more Specific example is the use of a checklist PHA for standard boiler or heat
exchanger and use of a hazard and operability PHA for the overall process.
OPERATING PROCEDURES AND PRACTICES

❖ Operating Procedures describe tasks to be performed, data to be recorded, Operating

conditions to be maintained, Samples to be collected, and safety and health
precautions to be taken.
❖ The Procedures need to be technically accurate, understandable to employees, and
revised periodically to ensure that they reflect current operations .
❖ The process safety information package is to be used as a resource to better assure
that the operating procedures and practices are consistent with the known hazards of
the chemicals in the process and that the operating parameters are accurate.
❖ Operating procedures should be reviewed by engineering staff and operating
personnel to ensure that they are accurate and provide practical instructions on how to
actually carry out job duties safely .
❖ Operating procedures will include specific instructions or details on what steps are to
be taken or followed in carrying out the stated procedures.
❖ These operating instructions for each procedure should include the applicable safety
precautions and should contain appropriate information on safety implications.
❖ For example the operating procedures addressing operating parameters will contain
operating instructions about pressure limits , temperature ranges, flow rates .
❖ Another example of usingf operating instructions to properly implement operating
procedures in starting up or shutting down the process .
❖ In these cases, different parameters will be required from those of normal operation.
❖ These operating instruction need to clearly indicate the distinctions between startup
and normal operations such as the appropriate allowances for heating up a unit to
reach the normal operating operations .
❖ Also the operating instructions need to describe the proper method for increasing the
temperature of the unit the normal operating temperature parameters are achieved.
❖ Computerized process control system add complexity to operating instructions .
❖ These operating instructions need to describe the logic of the software as well as
relationship between equipment and the control system.
❖ Operating procedures are are important to training operating personnel.
❖ The operating procedures are often viewed as standard operating practices for
operations .
❖ Control room personnel and operating staff in general need to have full understanding
of operating procedures.
❖ Communication between operating personnel and workers performing work within
the process area , such as non routine tasks also must be maintained.
❖ The hazards of the tasks are to be conveyed to operating personnel in accordance with
established procedures and to those performing actual tasks .
❖ When the work is completed , operating personnel should be informed to provide
closure on the job.
EMPLOYEE TRAINING
❖ All employees, including maintenance and contractor employees , involved with
highly hazardous chemicals need to fully understand the safety and health hazards of
the chemicals and processes they work with for protection of themselves, their fellow
employees and the citizens of nearby communities.
❖ Training conducted in compliance with chemical hazard communication program
standard , will help employees to be more knowledgable about the chemicals they
work with as well as familiarize them with reading and understanding MSDS.
❖ In establishing their training programs , employers must clearly define the employees
to be trained and what subjects are to be covered in their training .
❖ Employers in setting up their training program will need to clearly establish the goals
and objectives they wish to achieve with the training .
❖ The learning goals should be written in clear measurable terms before training begins
.
❖ These goals and objectives need to be tailored to each training modules or segments.
❖ Employers should describe the important actions and conditions under which the
employee will demonstrate competance or knowledge as well as what is acceptable
performance .
❖ Hands on training where employees are able to use their senses beyond listening , will
enhance learning.
❖ For example operating personel who will work in a control room would benifit by
being trained at a stimulated control panel.
❖ Upset conditions of various types could be displayed on the stimulator and then
emplyee could go through the proper operating procedures to bring the stimulator
panel back to the normal operating parameters.
❖ A training environment could be created to help the trainee feel the full reality of
situation but of course, under controlled conditions .
❖ This realistic type of training can be very effective in teaching employees correct
procedures While allowing them to see the consequences of what might happen if
they dont follow established operating procedures.
❖ Other training techniques using videos can be very effective for teaching other job
tasks .duties or other information.
❖ Employers need to be periodically evaluate their training program to see if the
necessary skills, knowledge and routines are being properly understood and
implemented by their trained employees.

CONTRACTORS

❖ Employers who use contractors to perform work in and arround processes that involve
highly hazardous chemicals, will need to establish a screening process so that they
hire and use contractors who accompolish the desired jobs tasks without
compromising the safety and health of employees at a facility.
 ❖ For contractors , whose safety performance on the job isn’t known to the hiring
employer , the employer will need to obtain information on injury and illness rates
and experience should obtain contractor reference.
❖ Additionally the employer must assure that the contractor has the appropriate job
skills, knowledge and certifications.
❖ Contractor work methods and experience should be evaluated.
❖ Maintaining a site injury and illness log for contractors is another method employers
must use to track and maintain current knowledge of work activities involving
contract employees working on or adjacent to covered processes.
❖ Injury and illness logs of both the employer’s employees and contract employees
allow an employer to have full knowledge on process injury and illness experience.
❖ This log will also certain information which will be of use to those auditing process
must perform their work safely .
❖ Considering that contractors often perform very specialized and potentially hazardous
tasks such as confined space entry activities and non routine repair activities its quite
important that their activities be controlled while they are working on or near a
covered process.
PRESTARTUP SAFETY
❖ For new processes , the employer will find a PHA helpful in improving the design
and construction of the process from a reliability and quality point of view.
❖ The Safe operation of the new process will be enhanced by making use of the PHA
recommendations before final installations are completed .
❖ Piping &Instrumentation Diagrams are to be completed along with having the
operating procedures in place and the operating staff trained to run the process before
startup.
❖ The initial startup procedures and normal operating procedures need to be fully
evaluated as part of the presstartup review to assure a safe transfer into the normal
operating mode for meeting the process parameters.
❖ For existing processes that have been shutdown for turnarround or modification etc.
❖ The employer must assure that any changes other than “replacement in kind” made to
the process during shutdown go through the management of change procedures.
❖ Piping &instrumentation diagrams will need to be updated as well as operating
procedures and instructions .
❖ If the changes made to the process during shutdown are significiant and impact the
training program , then operating personnel as well as employees engaged in routine
and nonroutine work in the process area may need some refresher or additional
training in light of the changes .
 ❖ Any incident investigation recommendations,compliance audits need to be reviewed
as well to see what impacts they may have on the process before begining the startup.

MECHANICAL INTEGRITY

❖ Employers will need to review their maintanence programs and schedules to see if
there are areas where “breakdown” maintenance is used rather than an ongoing
mechanical integrity program.
❖ Equipment used to process, store or handle highly hazardous chemicals needs to be
designed, constructed , installed and maintained to minimize the risk of release of
chemicals.
❖ This requires that a mechanical integrity program be in place to assure the continued
integrity of categorization of equipment and instrumentation, inspections, and tests
testing and inspection.
❖ The line of defense an employer has available is to operate and maintain the process
as designed , and to keep the chemicals contained.
❖ This line of defense is backed up by the the next line of defense which is the
controlled release of chemical through ventingbto scrubbers or to surge or overflow
tanks which are designed to recieve such chemicals .
❖ These lines of defenses are the primary line of defense or to prevent unwanted
release.
❖ The secondary lines of defense would include fixed fire protection systems like
sprinklers, waterspray, monitor guns ,deluge system ,dikes, designed drianage system,
and other system would control unwanted release occurs .
❖ These primary and secondary lines of defense are what the mechanical integrity
program needs to protect and strengthen these primary and secondary lines of defense
where appropriate .
❖ The first step of the effective mechanical integrity program is to compile and
categorize a list of process equipment and instrumentation for inclusion in the
program .
❖ This list which includes pressure vessel, storage tanks, process piping relief and vent
systems , fire protection system components, emergency shutdown systems, and
alarms.
❖ For categorization of instrumentation and the listed equipment the employer would
prioritize which piece of equipment require closer security than others.
❖ Meantime to failure of various instrumentation and equipment parts would be known
from the employer’s experience with the parts, which would then influenze the
inspection and testing frequency and associated procedures.
❖ External inspections for items such as nozzles, sprinklers, pipe hangers grounding
connections , protective coatings and insulation should be carried out.
 ❖ Also erosion both internal and external needs to be considered along with the
corrosion effects for pipes and valves.
❖ Where the corrosion rate isn’t known a maximum inspection frequency is
recommended and methods of developing the corrosion rate are available in codes.
❖ The use of appropriate gaskets, packing,bolts, valves, lubricants and welding rods
need to be verified in the field.
❖ Also procedures for installation of safety devices need to be verified such as torque on
the bolts on ruptured disc installations , uniform torque on flange bolts, proper
installation of pump seals etc.
❖ If the quality of parts is a problem, it may be appropriate to conduct audits of the
equipment supplier’s facilties to better assure proper purchases of required equipment
which is suitable for its intended service
❖ Any change in equipment that may become necessary will need to go through the
management of change procedures.

NONROUTINE WORK AUTHORIZATIONS

❖ Nonroutine work which is conducted in process areas needs to be controlled by the
employer in a consistent manner .
❖ The hazards identified involving the work that is to be accomplished must be
communicated to those doing the work but also to these operating personnel whose
work could affect the safety of the process.
❖ A work authorization notice or permit must have a procedure that describes the steps
the maintenance supervisor, contractor representative or other person need to follow
to obtain the necessary clearance to get the job started.
❖ The work authorization procedures need to reference and coordinate as applicable
lockout / tagout procedures , confined space entry procedures
❖ This procedure also needs to provide clear steps to follow once the job is completed in
order to provide closure for those that need to know the job is now completed and
equipment can be returned to normal.

MANAGING CHANGE
❖ To properly manage changes to process chemicals, technology, equipment and
facilities one must define what is meant by change.
❖ In this process safety management standard , changes includes all modifications to
equipment , procedures , raw materials, and processing conditions other than
“replacement in kind”.
❖ These changes needed to be properly managed by identifying and reviewing them
prior to implementation of the change.
❖ For example , the operating procedures contain the operating parameters
(pressurelimits, temperature ranges, flow rates etc)
 ❖ While the operator must have the flexibility to maintain safe operation within the
established parameters ,Any operation outside of these parameters requires review
and approval by a written management of change procedure.
❖ Management of change covers such as changes in process technology and changes to
equipment and instrumentation.
❖ Changes in process technology can result from changes in production rates, raw
materials, experimentation, equipment unavailability, new equipment and changes in
operating condition to improve yield or quality.
❖ Equipment changes include among others in materials of construction, equipment
specification, piping pre arrangements and changes in alarms
❖ Employers need to establish means and methods to detect both technical and
mechanical changes.
❖ Temporary changes have caused a number of catastrophes over the years , and
employers need to establish ways to detect temporary changes as well as those that are
permanent.
❖ Proper documentation and review of these changes is invaluable in assuring that the
safety and health considerations are being incorporated into the operating procedures
and process.
❖ Employers may wish to develop a form or clearance sheet to facilitate the processing
of changes through the management of change procedures.

INVESTIGATION OF INCIDENTS

❖ Incident investigation is the process of identifying the underlying causes of incidents

and implementing steps to prevent similar events from occuring.
❖ The intent of an incident investigation is for employers to learn from past experiences
and thus avoid repeating past mistakes.
❖ The incidents for which wish a expects employers to become aware and to investigate
are the types of events which result in or could reasonably have resulted in a
catastrophic release.
❖ Some of the events are sometimes refered to as “near misses”, meaning that a serious
consequence did not occur but could have.
❖ Employers need to develop in house capabiility to investigate incidents that occur in
their facilities.
❖ A team needs to be assembled by the employer and trained in the techniques of
investigation including how to conduct interviews of witnesses,needed documentation
and report writing.
❖ A Multidisciplinary team is better able to gather the facts of event and to analyze
them and develop plausible scenarios as to what happened and why.
❖ Team members should be selected on the basis of their training , knowledge and
ability to contribute to a team effort to fully investigate the incident.
 ❖ Employees in the process area where the incident occured should be consulted,
interviewed, or made a member of the team.
❖ Their knowledge of the events form a significiant set of facts about the incident which
occured.
❖ The report, its findings,and recommendations are to be shared with those who can
benifit from information.

EMERGENCY PREPAREDNESS

❖ Each employer must address what actions employees are to take when there is an
unwanted release of highly hazardous chemicals.
❖ Emergency preparedness or the employers teritary lines of defense are those that will
be relied on along with the secondary lines of defense when the primary lines of
defense which are used to prevent an unwanted release fail to stop the release .
❖ Employers will need to decide if they want employees to handle and stop small or
minor incidental releases.
❖ Whether they wish to mobilize the available resources at the plant and have them
bought to bear on a more significiant release.
❖ Employers will need to select how many different emerfency prepardness or teritiary
lines of defense they plan to have and then develop the necessary plans and
procedures , and appropriately train employees in their emergency duty and
responsibilities and then implement these lines of defense .
❖ Employers at minimum must have an emergency action plan which will facilitate the
prompt evacuationn of employees due to an unwanted release of a highly hazardous
chemical.
❖ This means that the employer will have a plan that will be activated by an alarm
system to alert employees when to evacuate and the employers who are physically
impaired, will have the necessary support and assistance to get them to the safe zone
as well.
❖ The intent of these requirements is to alert and move employees to a safe zone quickly
.
❖ Delaying alarms or confusing alarms to be avoided.
❖ The use of process control centers or similar process buildings in the process area as
safe areas is discouraged.
❖ Unwanted incidental releases of highly hazardous chemicals in the process area must
be addressed by the employer as to what actions employees are to take .
❖ If the employer wants employees to evacuate the area, then the emergency action plan
will be activated.
❖ For outdoor processes where wind direction is important for selecting the safe route to
a refuge area the employer should place a wind direction indicator such as wind sock
or pennant at the highest point that can be seen throughout the process area.
 ❖ Employees can move in the direction of cross wind to upwind to gain safe access to
the refuge area by knowing the wind direction.
❖ If the employer wants specific employees in the release area to control or stop the
minor emergency or incidental release, these actions must be planned for in advance
and procedures developed and implemented.
❖ Preplanning for handling incidental releases for minor emergencies in the process area
needs to be done, appropriate equipment for the hazards must be provided , and
training conducted for these employees who will perform the emergency work before
they respond to handle an actual release .
❖ The employer’s training program, including the hazard communication standard
training is to address the training needs for employees who are expected to handle
incidental or minor releases.
❖ Preplanning for releases that are more serious than incidental releases is another
important line of defense used by the employer.
❖ When a serious release of a highly hazardous chemical occurs, the employer through
preplanning will have determined in advance what actions emplyee , to take.
❖ The evacuation of immediate release area and other areas as necessary would be
accompolished under the emergency action plan.
❖ If the employer wishes to use plant personnel such as fire brigade, spill control team a
hazardous material team , or use employees to render aid to those in immediate
release area to control the incident.
❖ One effective way to medium to large facilities to enhance coordination and
communication during emergencies for on plant operations and with local community
organizations is for employers to establish and equip an emergency control center.
❖ The emergency control center would be sited in safe zone area so that it could be
occupied throught the duration of an emergency.

COMPLIANCE AUDITS:

❖ Employers need to select a trained individual or assemble a trained team of people to

audit the process safety management system and program.
❖ A small process or plant may need only one knowledgable person to conduct an audit.
❖ The audit is to include an evaluation of the design and effectiveness of the process
safety management system and a field inspection of the safety and health conditions
and practises to verify the employer’s systems are effectively implemented.
❖ The audit should be conducted or led by a person knowledgable in audit techniques
and who is impartial towards the facility or area being audited.
❖ The essential elements of an audit program including planning, staffing, conducting
the audit, evaluation, and corrective action , follow up and documentation.
❖ Planning in advance is essential to the sucess of auditing process.
❖ Each employer needs to establish the format, staffing, scheduling, and verification
methods which details the requirements of each section of the standard.
 ❖ The names of the audit team members should be listed as part of the format as well.
❖ The checklist , if properly designed could serve as the verification sheet which
provides the auditor with necessary information to expedite the review and assure that
no requirement of these standard are omitted.
❖ This verification sheet format could also identify those elements that will require
evaluation or a response to correct deficiencies.
❖ This sheet could also be used for developing the follow up and documentation
requirements.
❖ The selection of effective audit team members is critical to the sucess of the program.
❖ Team members should be chosen for their experience, knowledge, and training and
should be familiar with the process and auditing techniques , practices and
procedures.
❖ The size of the team will vary depending upon the size and complexity of the process
under consideration .
❖ For a large , complex, highly instrumented plant, it may be desirable to have team
members with expertice in process engineering and design, process chemistry ,
computer controls, electrical hazards and classification , warehousing, and process
safety auditing.
❖ The team may use part time members to provide the depth of expertice required as
well as the for whact is actually done compared to what is written.
❖ An effective audit includes a review of those relevant documentation and process
safety information, inspection of the physical facilities , and interviews with all levels
of plant personnel.
❖ Utlilizing the audit procedure and checklist developed in preplanned stage , the
auditing team can systamatically analyze compliance with the provisions of the
standard and any other corporate policies that are relevant .
❖ Auditors should select their preplanning a sample size sufficient to give a degree of
confidence that the audit reflects the level of compliance with the standard.
❖ The audit team , through this systematic analysis, should document areas which
require corrective action as well as those areas where the process safety management
system is effective.
❖ This provides a records of the audit procedures and findings, and serves a baseline of
operation data for future audits.

SAFE PRACTICES FOR OIL STORAGE AND HANDLING

❖ Tanks may be above ground , on elevated ground or underground.

❖ In case of underground storage tanks , protection to the external surfaces of fixed
pipes shall be provided by a glass or synthetic fibre reinforced hot applied bitumen
and by surrounding the heated tank with a backfill of selected sand .
❖ This is prefered over solid skin of fine concrete through contraction .
❖ Cathodic protection should be provided where high standard of protection is required
due to soil condition.
❖ Risk analysis for the surrounding area of tankls should prefarably be undertaken while
constructing large capacity tanks beyond 20,000 Cu.M .
❖ Corrosion allowance should be specified depending on the nature of petroleum
products to be stored; its impurity level.
❖ Individual tank shall be provided with acess to roof .
❖ A Platform with railings should be provided from the top of the stairway to gauge
well and roof ladder.
❖ On floating roof tanks , non sparkling self leveling tread type rolling ladder with
suitable earthing connection to be provided.
❖ Stairs should be made of grating
❖ All staircase shall have resting/landing platform preferably for every 5m height.
❖ Number of manholes shall depend on diameter of the tank .
❖ Minimum of the flush type clean out manhole should be provided for tank under dirty
services .
❖ Drains are provided in all tanks for draining water and also for emptying the tank for
cleaning .
❖ Maximum rainfall rate on hourly basis for the past 15 years should be considered in
designing the number and size of the drains for open floating tank.
❖ Also drains shall pass the design rainfall when roof is resting at the lowest position.
❖ The inlet for these drains shall have a swing type check valve to prevent product from
flowing into roof if pipe design drain leaks/fails.
❖ Emergency drain for floating roof tank shall be provided on the roof to take care of
drainage problem and drianage of total water in case of plugging of normal roof drain
.
❖ Dip hatch or gauge hatch is used for gauging the height of the liquid in a tank as well
as to take out samples for testing.
❖ Gauge hatch shall be non sparking ( or lined with non sparking material ) and self
closing type.
❖ Gauge well pipe (with slots) should be provided for all types of tanks .
❖ This should have continous contact by means of strikes with bottle plate of the tank.
❖ Continous contact makes the tank safer with respect to static charge accumulation and
acts as a support for the gauge well pipe.
❖ Walkway with handrail on the roof of the tank should be provided to facilitate
inspection/checking of vents/flame arrestor etc.So that the movement of personnel on
roof is safer.
❖ Open vents shall be of goose neck type, covered with 4 to 8 mesh screen.
❖ Every storage tank, including its roof and all metal connections , should be
electrically continuous and be effectively earthed.
❖ Painting is essential for tank protection .
 ❖ Besides tank number , safe filling height, reference height etc
❖ Should be painted on the tank to avoid operational errors .
❖ Necessary insulation will normaly provided for heat conservation
❖ It is advisable that to provide a two meters high insulation arround the tanks having
higher surface temperature for personal protection.
❖ Also patch insulation may be provided on the shell along with spiral stairway.
❖ For safety considerations , it is desirable to keep the number of inlet/outlet
connections to tank shell to minimum.
❖ This reduces the number of flanges/valves closed to the tank.
❖ In case of more number of lines , it is desirable to take a single header and form as
manifold away from the tank.
❖ Tank manifolds shall be located outside the dyke area .
❖ The floor underneath should be paved, have curb walls and connected to drainage
system.

SAFE HANDLING & STORAGE OF LPG

❖ Form: liquefied gas.

❖ Flash point : 1040c (-1550 f)

❖ Lower explosive limit: 2.1%(v).

❖ Upper explosive limit: 9.5% (v).

❖ Boiling point: -400c.

❖ LPG is a stored as a liquid under pressure in cylinder. It is widely used for homes as a
cooking gas and industrial usage for gas cutting purpose.

❖ The major hazards of LPG are fire and explosion in case of even a minor leakage.’

❖ In case of major leakage in contained spaces asphyxiation due to deficiency oxygen may
result.

❖ LPG being colorless and order less gas LPG to find easy dedication incase of leakage (
ethyl metrication)
❖ LPG gas is heavier than air these vapors accumulated to lower levels and fair ad explosion
may results.
❖ The bulk storage of LPG should be maintained above or below ground levels.
❖ There is well ventilation needed (SMPV rule: 21).
❖ There should be separation between one vessels to another vessels.
❖ Compound / boundary should be providing for storage.
❖ The storage vessels are designed constructed tested and certified to appropriated standards.
❖ Minimum safe operating pressure is TPSI.
❖ Vessels are marked with safe operating procedure.
❖ Before filling the vessels are certified competent person approved is necessary.
❖ Storage vessels not placed in the space of flooding.
❖ LPG vessels must not stored near any other flammable (or) ignited sources.
❖ The relief value to be given the vessel at least 1.8 m above the top of the level.
❖ Electrical equipment installed near the LPG vessel etc should be need require standard and
separation and distance.
❖ Always keep the cylinder in upright position.
❖ Don’t tilt or drag the cylinder for obtain last bit of gas.
❖ When the source is not used keep the cylinder value closed.
❖ Never lit a match box checking the cylinder.
❖ In case you suspect leakage in LPG.

1) Close burner knobs and cylinder value.

2) Refix safety protection cap.
3) Execute any open fire.
4) Open window, door.
5) Don’t touch the electrical appliances switch.
6) Contact with your distributer and the service.
7) Keep their phone number in case of emergency.