sAFetY / Loss Prevention

To know is to survive and to ignore

fundamentals is to court disaster.
- H. H. Fawcett
 INGREDIENTS OF SAFETY
To record want needs to be done
To do what is needed
To record what is done
• System Positive attitude, and use fundamentals of
Understand
willingness
safetytoin design, construction and
• Attitude work for operation of plants
required
success
• Fundamentals
Learn from
• Experience experience of
history and others
• Time in organization.

• You Time to train and get trained

Time to record results
Everyone is Time to share experiences
responsible

Safety is equal in importance to production

 DEFINATIONS
• HAZARD: A chemical or physical condition that has the
potential to cause damage to people, property, or the
environment.
• ACCIDENT: The occurrence of a sequence of events
that produce unintended injury, death, or property
damage. It refers to event and not the result of event.
• SAFETY: The prevention of accidents through the use of
appropriate technologies to identify the hazards of a
chemical plant and eliminate them before an accident
occurs.
• RISK: A measure of human injury, environmental
damage, or economic loss in terms of both the incident
likelihood & the magnitude of the loss or injury.
 ACCIDENT PYRAMID

DISABLING INJURY
1
MINOR INJURY
100
PROPERTY DAMAGE
500
NO DAMAGE /
1000 NEAR MISSES

Property Damage + loss of production + loss to environment + loss of life

All must be considered in loss prevention.
 Loss Prevention
• It includes:
– Hazard identification,
– Technical evaluation,
– Design of new engineering features to prevent
loss.
 OSHA
Occupational Safety and Health Administration.
• It’s a US government body
• Its responsible for ensuring that workers are
provided with safe working environment.

Occupational Safety: Aims at creating safe

working conditions to avoid occupational
disease.
Occupational Injury: It is any injury such as cut,
fracture, sprain, etc which results from a
work.
 OSHA
Occupational illness: any abnormal condition or
disorder, other than the one resulting from
occupational injury, caused by exposure to
environmental factors associated with
employment.
It includes acute and chronic illness or disease
which may be caused by inhalation, ingestion,
absorption or direct contact.
 OSHA
• Lost work days: number of days on which the
employee would have worked but could not
because of occupational injury or illness.
• The number of days include all days on which
due to injury or illness an employee
– Would have worked but could not
– was assigned a temporary job
– Worked on permanent job less than full time
– Worked on permanent job but could not perform all
duties normally connected to it.
 OSHA
WHO defines Health as
“ A state of complete physical, mental & social well being &
not merely absence of disease.
Good Industrial health means good working conditions &
other facilities for good health & sound state of mind.
Health Administration : It is setting up & implementation of
a system for administering industrial health.
Proper Health Admistration results in:
 Low rate of Absenteeism
 Low rate of labour turn over
 Satisfaction and discipline among workers.
 Good performance & higher productivity.
 Decreased accidents and occupational disease
 Improved moral of workers.
 Statistics
• Determine whether the process is safe or
if a safety procedure is working effectively.
• 3 systems to be considered
– OSHA incidence Rate
– Fatal Accident Rate (FAR)
– Fatality Rate
 OSHA Incidence Rate
• Based on cases per 100 worker years.
• 1 worker year = 2000 hrs (50 work week x 40 hrs/week)
• It is calculated from number of occupational injuries &
illness & the total number of employee hrs worked during
the applicable period

• OSHA IR = (Number of Injuries & illness x 2,00,000)

(Total hrs worked by all employees during
period under consideration)
• It can also be calculated based on lost workdays instead
of injury or illness
• Provides information on all types of work related injuries
and illness including fatalities
• Provides better representation of worker accidents.
 FAR
• This stats is mainly used by British Chemical companies.
• Reports the number of fatalities based on 1000
employees working their entire lifetime.
• The employees are assumed to work a total of 50 years
• FAR is based on (50 years x 50 weeks x 40 hrs) =
100000

FAR = number of fatalities x 100000000

Total hrs worked by all employees during period
covered
 Fatality Rate
• It considers the fatality rate or deaths per person per
year.
• It is independent of number of hrs actually worked &
reports only the number of fatalities expected per person
per year.
• It is useful for performing calculations on the general
population where the number of exposed hrs is poorly
defined.

Fatality Rate = Number of fatalities per year

Total number of people in applicable
population
 Accident Process
• Initiation : the event that starts the
accident
• Propagation: the events that maintain or
expands the accident
• Termination: the event/s that stop the
accident or diminish it in size.
 Defeating Accidents
• Diminish Initiation: grounding, bounding,
inerting, explosion proof electrical, guards,
maintenance procedures, work permits, etc.
• Diminish Propagation: emergency material
transfer, reduce inventories of flammable
materials, equipment spacing and layout,
nonflammable MOC, etc.
• Increase Termination: Firefighting equipment &
procedure, relief systems, sprinkler systems.
 Seveso, Italy
• Town with 17,000 inhabitants, 15 miles from
Milan.
• Product: Hexachlorophene, a bactericide.
• Side product: TCDD
(Tetrachlorodibenzoparadioxin)
• TCDD: Most potent toxic known to humans.
• It is fatal even in the dose of 10-9 times the body
weight.
• It is insolube in water hence it can not be
contaminated.
• On July 10, 1976, the reactor went out of control.
2 kg of TCDD was released through relief
forming white cloud over Seveso.
• The subsequent heavy rains washed down
TCDD in soil
• Approx. 10 miles were contaminated
• 600 people were evacuated, 250 cases of
chlorace were reported and 2000 blood test
were carried.
 Inherent Safety
• Relies on chemistry and physics to prevent accidents
rather than on control systems, interlocks, redundancy,
and special operating procedures to prevent accidents.
• Inherently safer plants are tolerant of errors and are
often the most cost effective.
• A process that does not require complex safety
interlocks and elaborate procedures is simpler, easier to
operate, and more reliable.
• Smaller equipment, operated at less severe
temperatures and pressures, has lower capital and
operating costs.
Chapter 2
• Toxicology is the science of poisons.
• Paracelsus, an early investigator in 1500 stated that “ All
substances are poisons, there is none which is not a
poison.”
• The RIGHT dose differentiates between a poison and
remedy.
• Toxicology is defined as the quantitative and qualitative
study of the adverse effects of toxicants on biological
organisms.

A Toxicant can be chemical or physical agent, including

dust, fiber, noise, etc.
There are no harmless substances, only harmless ways
of using substances
• The toxicity of a chemical or physical
agent is a property of the agent describing
its effect on biological organisms.
• Toxicity is a measure to the degree to
which something is toxic.
• Toxic hazard is the likelihood of damage to
biological organisms based on exposure
resulting from transport and other physical
factors of usage.
 Types of toxic entities
• Chemical: include inorganic and organic
chemicals eg, lead, mercury, ethyl alcohol,
etc.
• Biological: it is the cause – effect
relationship between the toxic agent and
the host immune system.
• Physical: sound and vibrations, heat and
cold, x-rays, gamma rays, radiations, etc.
 How toxicants enter Biological
Organisms
• After the toxicant enters the organism, it moves into the
bloodstream and is eventually gets eliminated or it is
transported to the target organ. The damage is exerted
at the target organ.
• Ingestion: through the mouth into the stomach. It is the
route of most immediate poisoning that may lead to
accidental death.
• Inhalation: through the mouth or nose into the lungs.
It is more common, and can be much more harmful
than ingestion.
• Injection: through cuts into the skin. It results in highest
blood level concentration.
• Dermal absorption: through skin membrane. It is an
often unsuspected route of exposure.
 SKIN
• The skin plays important roles in both the dermal absorption and
injection routes of entry.
• Injection includes both entry by absorption through cuts and
mechanical injection.
• The absorption properties of the skin vary as a function of location
and the degree of hydration.
• The presence of water increases the skin hydration and results in
increased permeability and absorption.
• Few chemicals show remarkable skin permeability. Phenol, for
example, requires only a small area of skin for the body to absorb an
adequate amount to result in death.
• The skin on the palm of the hand is thicker than skin found
elsewhere. However, this skin demonstrates increased porosity,
resulting in higher toxicant absorption.
 RESPIRATORY SYSTEM
• Plays a significant role in toxicants entering the body through
inhalation.
• The upper respiratory system is composed of the nose, sinuses,
mouth, pharynx (section between the mouth and esophagus), larynx
(the voice box), and the trachea or windpipe.
• It is responsible for filtering, heating, and humidifying the air.
• Fresh air brought in through the nose is completely saturated with
water and regulated to the proper temperature by the time it reaches
the larynx.
• The mucus lining in the upper respiratory tract assists in filtering.

• The upper respiratory tract is affected mostly by toxicants that

are water soluble. These materials either react or dissolve in the
mucus to form acids and bases.

• Upper respiratory toxicants include hydrogen halides (hydrogen

chloride, hydrogen bromide), oxides (nitrogen oxides, sulfur
oxides, sodium oxide), and hydroxides (ammonium hydroxide,
sodium dusts, and potassium hydroxides).
• The lower respiratory system is composed of the lungs and its smaller
structures, including the bronchi and the alveoli.
• The bronchial tubes carry fresh air from the trachea through a series of
branching tubes to the alveoli.
• The alveoli are small blind air sacs where the gas exchange with the blood
occurs. An estimated 300 million alveoli are found in a normal lung.
• Small capillaries found in the walls of the alveoli transport the blood; an
estimated 100 ml of blood is in the capillaries at any moment.

• Toxicants in the lower respiratory tract affect the alveoli by physically

blocking the transfer of gases (as with insoluble dusts) or reacting
with the wall of the alveoli to produce corrosive or toxic substances.
• Phosgene gas, for example, reacts with the water on the alveoli wall to
produce HCl and carbon monoxide.
• Toxicants include monomers (such as acrylonitrile), halides (fluorine,
chlorine, bromine), and other miscellaneous substances such as
hydrogen sulfide, phosgene, methyl cyanide, acrolein, asbestos dust,
silica, and soot.
• Particles > 5 um : filtered by the upper respiratory system.
• Particles betn 2 and 5 um reach the bronchial system.
• Particles < 1 um reach the alveoli.
 Elimination of Toxicants from
Biological Organisms
• Excretion:
• Mainly through the kidneys, liver, lungs, or other organs.
• The kidneys eliminate substances that enter the body by ingestion,
inhalation, injection, and dermal absorption.
• The toxicants are extracted by the kidneys from the bloodstream
and are excreted in the urine.
• Toxicants that are ingested into the digestive tract are frequently
excreted by the liver.
• Chemical compounds with molecular weights greater than about
300 are excreted by the liver into bile.
• Compounds with lower molecular weights enter the bloodstream
and are excreted by the kidneys.
• The lungs are also a means for elimination of substances,
particularly those that are volatile.
• Other routes of excretion are the skin (by means of sweat), hair, and
nails.
• Detoxification:
• The digestive tract tends to selectively detoxify certain agents.
• The liver is the dominant organ in the detoxification process.
• The detoxification occurs by biotransformation, in which the
chemical agents are transformed by reaction into either harmless or
less harmful substances.
• Biotransformation reactions can also occur in the blood, intestinal
tract wall, skin, kidneys, and other organs.

• Storage:
• This process involves depositing the chemical agent mostly in the
fatty areas of the organism but also in the bones, blood, liver, kidney
and in the fatty tissues.
• Storage can create a future problem if the organism's food supply is
reduced and the fatty deposits are metabolized; the stored chemical
agents will be released into the bloodstream, resulting in possible
damage.
 TOXICOLOGICAL STUDIES
• A major objective of a toxicological study
is to quantify the effects of the suspect
toxicant on a target organism.
• Before undertaking a toxicological study,
the following items must be identified:
1. The toxicant: The toxicant must be identified with
respect to its chemical composition and its
physical state. For example, benzene can exist in
either liquid or vapor form. Each physical state
preferentially enters the body by a different route
and requires a different toxicological study.
 TOXICOLOGICAL STUDIES
2. the target or test organism: The test organism can range from
a simple single cell up through the higher animals. The
selection depends on the effects considered and other factors
such as the cost and availability of the test organism
3. the effect or response to be monitored: For studies of genetic
effects, single-cell organisms might be satisfactory. For studies
determining the effects on specific organs such as the lungs,
kidneys, or liver, higher organisms are a necessity.
4. the dose range: The dose units depend on the method of
delivery. For substances delivered directly into the organism
(by ingestion or injection), the dose is measured in milligrams
of agent per kilogram of body weight.
5. The period of the test: The period of the test depends on
whether long- or short-term effects are of interest. Acute
toxicity is the effect of a single exposure or a series of
exposures close together in a short period of time. Chronic
toxicity is the effect of multiple exposures occurring over a long
period of time
 Dose v/s Response
• Biological organisms respond differently to the
same dose of a toxicant.
• These differences are a result of age, sex, weight,
diet, general health, genetic factor, environmental
conditions and other factors
 Dose – Response relation
• For comparison purposes the dose that
results in 50% lethality of the subjects is
frequently reported. This is called the
LD50dose (lethal dose for 50% of the
subjects).
• If the response to the chemical or agent is
minor and reversible (such as minor eye
irritation), the response-log dose curve is
called the effective dose (ED) curve. Values
for ED50, ED10, and so forth are also used.

Finally, if the response to the agent is toxic (an indesirable response that
is not lethal but is irreversible, such as liver or lung damage), the
response - log dose curve is called the toxic dose, or TD curve.
• Toxic dose low (TDLO): The lowest dose of a substance introduced
by any route, other than inhalation, over any given period of time,
and reported to produce any toxic effect in humans or to produce
tumorigenic or reproductive effects in animals.
• Toxic concentration low (TCLO): The lowest concentration of a
substance in air to which humans or animals have been exposed for
any given period of time that has produced any toxic effect in
humans or produced tumorigenic or reproductive effects in animals.
• Lethal dose low (LDLO): The lowest dose, other than LD50 of a
substance introduced by any route, other than inhalation, which has
been reported to have caused death in humans or animals.
• Lethal dose fifty (LD50): A calculated dose of a substance which is
expected to cause the death of 50 percent of an entire defined
experimental animal population. It is determined from the exposure
to the substance by any route other than inhalation.
When several chemicals are involved, the
toxicants might interact
• additively: the combined effect is the sum
of the individual effects, Organophosphate
pesticides (for example, dialiphos, naledand parathion)
exhibit such additivity of effects.
• Synergistically: the combined effect is more
than the individual effects,
Carbon tetrachloride and ethanol (ethyl alcohol) are
individually toxic to the liver, but together they produce
much more liver injury than the sum of their individual
effects on the liver.
• Potentiately: presence of one increases the
effect of the other, Isopropanol, for example, is
not hepatotoxic in itself. Its combination with carbon
tetrachloride, however, increases the toxic response to
the carbon tetrachloride.
• Antagonistically: both counteract each
other.
ethyl alcohol (ethanol) can antagonize the toxic effects
of methyl alcohol (methanol) by displacing it from the
enzyme that oxidizes the methanol
1. functional: Produces opposite effects on the same physiologic function.
For example, phosphate reduces lead absorption in the gastrointestinal
tract by forming insoluble lead phosphate.
2. chemical: Reacts with the toxic compound to form a less toxic product.
For example, chelating agents bind up metals such as lead, arsenic, and
mercury.
3. dispositional: Alters absorption, metabolism, distribution, or
excretion. For example, some alcohols use the same enzymes in
their metabolism:
• ethanol--------> acetaldehyde-------> acetic acid
• methanol------> formaldehyde------> formic acid
• The aldehydes cause toxic effects (hangover, blindness). Ethanol is more
readily metabolized than methanol, so when both are present, methanol is
not metabolized and can be excreted before forming formaldehyde. Another
dispositional antagonist is Antabuse which, when administered to alcoholics,
inhibits the metabolism of acetaldehyde, giving the patient a more severe
prolonged hangover.
4. receptor:
Occurs when a second chemical either binds to the same tissue receptor as the
toxic chemical or blocks the action of receptor and thereby reduces the toxic
effect. For example, atropine interferes with the receptor responsible for the

toxic effects of organophosphate pesticides .

 THRESHOLD LIMIT VALUES
• The lowest value on the response versus dose
curve is called the threshold dose.
• Below this dose the body is able to detoxify and
eliminate the agent without any detectable effects.
• In reality the response is only identically zero when
the dose is zero, but for small doses the response
is not detectable.
• Units
– in parts per million (ppm) for gases;
– in milligrams per cubic meter (mg/m³) for particulates
such as dust, smoke and mist.
 TLV-TWA
TLV-TWA: Time-weighted average for a
normal 8-hour workday or 40-hour work
week, to which
• nearly all workers can be exposed, day
after day, without adverse effects.
• Excursions above the limit are allowed if
compensated by excursions below the
limit.
 TLV-STEL
TLV-STEL: Short-term exposure limit. The maximum
concentration to which workers can be exposed
• for a period of up to 15 minutes continuously without
suffering (1) intolerable irritation, (2) chronic or
irreversible tissue change, (3) narcosis of sufficient
degree to increase accident proneness, impair self-
rescue, or materially reduce worker efficiency,
• provided that no more than 4 excursions per day are
permitted, with at least 60 minutes between exposure
periods, and provided that the daily TLV-TWA is not
exceeded.
 TLV - C
• TLV-C: Ceiling limit. The concentration
that should not be exceeded, even
instantaneously.
 Examples
Chemical TLV – TWA TLV – STEL TLV – C
Hydrogen Sulfide 10 15 20
Sulfur dioxide 2 5
Benzene 0.5 2.5
Phenol 5 15.5
Ammonia 25 35
Hydrogen 2
Chloride
Carbon 5 10
tetrachloride
INDUSTRIAL HYGIENE
 Steps
• Industrial hygiene is a science devoted to the
identification, evaluation and control of occupational
conditions that cause sickness or injury.

The three phases of IH project are:

• Identification
• Evaluation
• Control
 PSM
• Process Safety Management was developed after the
Bhopal accident (1985), to prevent similar accidents. It is
recognized by industry and the government as an
excellent regulation that will reduce the number and
magnitude of accidents -if it is understood and practiced
as intended.
• The PSM standard has 14 major sections: employee
participation, process safety information, process hazard
analysis, operating procedures, training, contractors,
pre-startup safety review, mechanical integrity, hot work
permits, management of change, incident investigations,
emergency planning and response, audits, and trade
secrets.
Employee participation
• Requires active employee participation in all the major elements of
PSM.
• Employers must develop and document a plan of action to specify
this participation.

Process Safety Information

• It is compiled and made available to all employees to facilitate the
understanding and identification of hazards.
• This information includes block flow diagrams or process flow
diagrams, process chemistry, and process limitations, such as
temperatures, pressures, flows, and compositions.
• Consequences of process deviations are also required.
 Process hazard analysis (PHA)
• Must be performed by a team of experts, including
engineers, chemists, operators, industrial hygienists, and
other appropriate and experienced specialists.
• The PHA needs to include a method that fits the
complexity of the process, a hazards and operability
(HAZOP) study for a complex process, and for less
complex processes a less rigorous process, such as
what-if scenarios, checklists, failure mode and effects
analysis, or fault trees.
• Every PSM process needs an updated PHA at least
every five years after the initial analysis is completed.
 Operating Procedure
• To facilitate the safe operation of the plant procedure must be documented.
These instructions need to be clearly written and must be consistent with
the process safety information.
• They need to cover, at a minimum, initial startup, normal operations,
temporary operations, emergency shutdown, emergency operations,
normal shutdown, startup after normal and emergency shutdowns,
operating limits and consequences of deviations, safety and health
considerations, hazardous properties of the chemicals, exposure
precautions, engineering and administrative controls, quality control
specifications for all chemicals, special or unique hazards, and safety
control systems and functions.
• Safe work practices also need to be documented, such as hot work,
lockout, and confined space.
• These operating procedures are updated frequently, with the frequency
being set by the operating personnel.
Effective training program
• Helps employees understand the hazards associated
with the tasks they perform.
• Maintenance and operations personnel receive initial
training and refresher training.
• Operators need to understand the hazards associated
with every task, including emergency shutdowns,
startups, and normal operations.
• Refresher training is given every three years and more
often if necessary; the operators decide on the frequency
of the refresher training.
Contractors
• They are trained to perform their tasks safely to the same extent as
employees.
• Even when selecting contractors, the employees need to consider the
contractors' safety performance in addition to their skills.

Pre-startup safety review

• It is a special safety review that is conducted after a modification to the
process or operating conditions has been made and before the startup. In
this review a team of reviewers ensures that
(1) the system is constructed in accordance with the design specifications,
(2) the safety, maintenance, operating, and emergency procedures are in
place,
(3) the appropriate training is completed, and
(4) the recommendations from the PHA are implemented or resolved.
 The mechanical integrity
• This section of the PSM standard ensures that the equipment,
piping, relief systems, controls, and alarms are mechanically sound
and operational. The requirements include
(1) written procedures to maintain functioning systems,
(2) training regarding preventive maintenance,
(3) periodic inspections and testing based on vendor
recommendations,
(4) A process to correct deficiencies, and
(5) a process to ensure that all equipment and spare parts are suitable.
 Management of change
• This section of the PSM standard employees are
required to develop and implement documented
procedures to manage changes in the process
chemistry, process equipment, and operating
procedures.
• Before a change occurs (except for replacement- kind), it
must be reviewed to ascertain that it will not affect the
safety of the operation.
• After the change has been made, all the affected
employees are trained, and a pre-startup review is
conducted.
 Incident investigation
• Employers must investigate all incidents that have or
could have resulted in a major release or accident within
48 hours of the event.
• The regulation requires an investigation team composed
of people, including operators, who are knowledgeable
about the system.
• After the investigation, the employers are required to
appropriately use the investigation recommendations.
• The intent of the PSM element for emergency planning
Emergency planning and response
• It is to require employers to respond effectively to the release of
highly hazardous chemicals.
• Although the regulation requires this activity for companies with
more than 10 employees, this element should be part of a program
for even the smallest organizations that handle hazardous
chemicals.

Audits
• employers are required to certify that they have evaluated their
compliance with the standard at least every three years.
• The recommendations from the audit must be followed.
• The audit reports need to be retained as long as the process exists.
 Identification
• All potential hazards should be identified.
• In chemical industries, identification requires the concerted
efforts of industrial hygienists, process designers,
operators, laboratory personnel & management.
• Potential hazards and methods of contact are identified &
recorded.
• This step requires thorough study of the chemical process,
operating conditions & operating procedures.
• The sources of information include process design
descriptions, operating instructions, safety reviews,
equipment vendor descriptions, information from chemical
suppliers, and information from operating personnel.
 Identification
• The quality of this identification step is often a
function of the number of resources used and
the quality of the questions asked.
• Determining the Potential for hazards to result in
an accident is a part of identification step.
• It is often necessary to collate and integrate the
available information to identify new potential
problems resulting from the combined effects of
multiple exposures.
• This list of potential hazards & their risk is used
during the evaluation and control phase.
 MSDS
• Most important document used for identification
of hazards.
• MSDS are available from Chemical
manufacturer, commercial source or literature.
 Information from MSDS
• Product Information: product identifier (name), manufacturer and
suppliers names, addresses, and emergency phone numbers
• Hazardous Ingredients
• Physical Data
• Fire or Explosion Hazard Data
• Reactivity Data: information on the chemical instability of a product
and the substances it may react with
• Toxicological Properties: health effects
• Preventive Measures
• First Aid Measures
• Preparation Information: who is responsible for preparation and date
of preparation of MSDS
 EVALUATION
• The evaluation phase determines the extent and
degree of employee exposure to toxicants and
physical hazards in the workplace environment.
• Sudden exposures to high concentrations,
through large leaks, may lead to immediate
acute effects such as unconsciousness, burning
eyes, or fits of coughing. There is rarely lasting
damage to individuals if they are removed
promptly from the contaminated area, ready
access to a clean environment is important.
 EVALUATION
• Chronic effects, arise from repeated exposures to low
concentrations, mostly by small leaks.
• Many toxic chemical vapors are colorless and odorless
(or the toxic concentration might be below the odor
threshold). Small leaks of these substances might not
become obvious for months or even years. There may
be permanent and serious impairments from such
exposures.
• Special attention must be directed toward preventing and
controlling low concentrations of toxic gases. In these
circumstances some provision for continuous evaluation
is necessary; that is, continuous or frequent and periodic
sampling and analysis is important.
• For continuous concentration data, C(t) the TWA (time-
weighted average) concentration is computed using the
equation

where
• C(t) is the concentration (in ppm or mg/m3) of the
chemical in the air and
• t, is the worker shift time in hours.

• The integral is always divided by 8 hours, independent of

the length of time actually worked in the shift. Thus, if a
worker is exposed for 12 hours to a concentration of
chemical equal to the TLV-TWA, then the TLV-TWA has
been exceeded, because the computation is normalized
to 8 hours.
• The more usual case is for intermittent samples to be obtained, representing
worker exposures at fixed points in time.
• If we assume that the concentration Ciis fixed (or averaged) over the period
of time Ti, the TWA concentration is computed by

• If more than one chemical is present in the workplace, one procedure is to

assume that the effects of the toxicants are additive.
• The combined exposures from multiple toxicants with different TLV-TWAs is
determined from the equation:

where
• n is the total number of toxicants,
• Ciis the concentration of chemical i with respect to the other toxicants, and
• (TLV-TWA), is the TLV-TWA for chemical species i.
• If the sum in Equation exceeds 1, then the workers are overexposed.
• The mixture TLV-TWA can be computed from

• If the sum of the concentrations of the toxicants in the

mixture exceeds this amount, then the workers are
overexposed.

• For mixtures of toxicants with different effects (such as an

acid vapor mixed with lead fume) the TLVs cannot be
assumed to be additive.
 Noise
• Noise levels are measured in decibels. A decibel (dB) is
a relative logarithmic scale used to compare the
intensities of two sounds. If one sound is at intensity I
and another sound is at intensity Io, then the difference
in intensity levels in decibels is given by:

• Thus a sound 10 times as intense as another has an

intensity level 10 dB greater.
• An absolute sound scale (in dBA for absolute decibels) is
defined by establishing an intensity reference.
• For convenience, the hearing threshold is set at 0 dBA
 EXPOSURE TO TOXIC VAPORS
C be the concentration of volatile vapor It can be applied to the
(masslvolume), following types of exposures:
Qv, be the ventilation rate (volume/time), •a worker standing near a
k be the nonideal mixing factor (unitless), varies pool of volatile liquid,
from 0.1 – 0.5 for most practical situations, •a worker standing near an
Qm, be the evolution rate of volatile material opening to a storage tank,
(massltime). •or a worker standing near
R, is the ideal gas constant, an open container of volatile
liquid.
T is the absolute ambient temperature,
P is the absolute pressure, and This analysis is frequently
M is the molecular weight of the volatile species. required in enclosed
spaces, above open
containers, where drums
are filled or in the area of
spills.
 ESTIMATING THE
VAPORIZATION OF LIQUID
• Liquids with high saturation vapor pressures evaporate
faster.
• As a result, the evaporation rate (mass/time) is expected
to be a function of the saturation vapor pressure

• Qm, is the evaporation rate (mass/time),

• M is the molecular weight of the volatile substance,
• K is a mass transfer coefficient (length/time) for an area
A,
• Rg, is the ideal gas constant, and
• TL is the absolute temperature of the liquid.
• For many situations, Psat >>p,
 ESTIMATING THE
VAPORIZATION OF LIQUID

• the concentration (in ppm) of a volatile,

resulting from evaporation of a liquid:

• Ko is mtc for reference species.

• Water is most frequently used as a
reference substance; it has a mass
transfer coefficient of 0.83 cm/s.
 Estimating Worker Exposures
during Vessel Filling Operations
• For vessels being filled with liquid, volatile emissions are generated
from two sources
1) Evaporation of liquid 2) displacement of the vapor in vapor space
by filling liquid.
 Estimating Worker Exposures
during Vessel Filling Operations
(Qm)1, represents the source resulting from evaporation and
(Qm)2 represents the source resulting from displacement

For splash filling (filling from the top of a container with the liquid splashing to
the bottom), Φ = 1. For subsurface filling (by a dip leg to the bottom of the
tank), Φ =0.5.

Vc, be the volume of the container (volume),

rf be the constant filling rate of the vessel (time-1),
 CONTROL
• CONTROL: refers to application of appropriate
technology to reduce workplace exposures to acceptable
levels.

• Respirators should be used only

– on a temporary basis, until regular control methods can be
implemented;
– as emergency equipment, to ensure worker safety in the event of
an accident;
– as a last resort, in the event that environmental control
techniques are unable to provide satisfactory protection.
• Respirators always compromise worker ability. A worker
with a respirator is unable to perform or respond as well
as a worker without one.
 VENTILATION
For environmental control of airborne toxic material the
most common method:
– Ventilation can quickly remove dangerous concentrations of
flammable and toxic materials.
– Ventilation can be highly localized, reducing the quantity of
air moved and the equipment size.
– Ventilation equipment is readily available and can be easily
installed.
– Ventilation equipment can be added to an existing facility.
• Ventilation is based on two principles:
(1) dilute the contaminant below the target
concentration,
(2) remove the contaminant before workers are
exposed.
 VENTILATION
• Ventilation systems are composed of
fans and ducts. The fans produce a
small pressure drop (less than 0.1 psi)
that moves the air.
 LOCAL VENTILATION
• The most common example of local
ventilation is the hood.
• A hood is a device that either completely
encloses the source of contaminant and/or
moves the air in such a fashion as to carry
the contaminant to an exhaust device.
• An enclosed hood completely contains the
source of contaminant.
• An exterior hood continuously draws
contaminants into an exhaust from some
distance away.
 DILUTE VENTILATION
• If the contaminant cannot be placed in a hood and must
be used in an open area or room, dilution ventilation is
necessary.
• dilution ventilation always exposes the worker but in
amounts diluted by fresh air.
• Dilution ventilation always requires more airflow than
local ventilation; operating expenses can be substantial.
• The following restrictions should be considered before
implementing dilution ventilation:
– The contaminant must not be highly toxic.
– The contaminant must be evolved at a uniform rate.
– Workers must remain a suitable distance from the source to
ensure proper dilution of the contaminant.
– Scrubbing systems must not be required to treat the air before
exhaust into the environment.
 CHEMICAL PLANT CONTROL
TECHNIQUES
1) Substitution : use of chemicals and equipments which are less hazardous.
• Use welded pipe v/s flanges
• Use solvents that are less toxic
• Use of mechanical guages
• Use of chemicals with high BPs
• Use of water as HT fluid instead of oil.
2) Attenuation: use of chemicals under conditions that make them less
hazardous.
• Reduce process temperature and pressure
• Refrigerate storage vessel
• Operate at conditions where reactor run away is not possible
3) Isolation: Isolate equipment &/or source of hazard.
• Place control rooms away from other rooms
• Proper plan layout
4) Intensification: Reduced quantity of Chemicals
• Use continuous small reactors instead of large batch reactors
• Reduce inventories of Raw material
• Reduce process hold up
• Low inventory
 CHEMICAL PLANT CONTROL
TECHNIQUES
1) Enclosures: Enclose drum or equipment & place under negative pressure.
• Sample points should be enclosed
• Shield high temp surface
• Convey dusty materials pneumatically
2) Local Ventilation: Enclosed drum or equipment & place under negative pressure.:
• Use properly designed hoods
• Use ventilation at drumming station
• Keep exhaust systems under neg. pressure
3) Dilute Ventilation:
• Design rooms with good ventilation
4) Wet Methods:
• Clean vessels chemically v/s sand blasting
• Use water sprays for cleaning
• Clean areas frequently
5) Good Housekeeping: keep toxic & dusts contained
• Use disks around tanks n pumps
• Provide water and steam connection for cleaning
• Well designed sewer system
6) Personal Protection: As last line of defense