PROCESS SAFETY

&
HAZARD MANAGEMENT

BY

Dr. Kanti Kumar Athankar

Chemical Engineering Department
Institute of Engineering Science
IPS Academy Indore-452012 (M.P)

Email Id: kanti.kumar@rediffmail.com

SCHEME

Source: rgpv.ac.in
 SYLLABUS
Unit I: Origin of process hazards, Laws Codes, Standards, Case Histories, Properties of
Chemical, Health, hazards of industrial substances.

Unit II: Toxicology: Toxic materials and their properties, effect of dose and exposure time,
relationship and predictive models for response, Threshold value and its definitions, material
safety data sheets, industrial hygiene evaluation.

Unit III: Fire & Explosion: Fire and explosion hazards, causes of fire and preventive methods.
Flammability, characteristics of chemical, fire and explosion hazard, rating of process plant,
Propagation of fire and effect of environmental factors, ventilation, dispersion, purifying, and
sprinkling, safety and relief valves.

Unit IV: Energy Hazards: Electrical hazards, noise hazards, radiation hazard in process
operations, hazards communication to employees, plant management and maintenance to reduce
energy hazards. Risk Analysis: Component and plant reliability, event probability and failure,
plant reliability, risk analysis.

Unit V: Analysis & Assessment: HAZOP and HAZON, event and consequence analysis (vapor
cloud modeling) Designing for safety, measurement and calculation of risk analysis.
Hazard Assessment: Failure distribution, failure data analysis, modeling for safety, safety
training, emergency planning and disaster management, case studies.
 GRADUATE ATTRIBUTES or POs
During the study of chemical engineering program, students will demonstrate the following:
1. Engineering knowledge: Apply the knowledge of basic science, and engineering fundamentals to the solution of
chemical engineering problems.
2. Problem analysis: Identify, formulate, and analyze chemical engineering problems to arrive at substantiated
conclusions using the principles of mathematics, and engineering sciences.
3. Design/development of solutions: Design solutions for chemical engineering problems and design system
components, processes to meet the specifications with consideration for the public health and safety, and the
cultural, societal, and environmental considerations.
4. Conduct investigations of complex problems: An ability to design and conduct experiments, as well as to
analyze and interpret data.
5. Modern tool usage: Create, select, and apply appropriate techniques, resources, and modern engineering and
IT tools including prediction and modeling to chemical engineering problems with an understanding of the
limitations.
6. The engineer and society: Apply critical reasoning by the contextual knowledge to assess societal, health, safety,
legal and cultural issues and the consequent responsibilities relevant to the chemical engineering practice.
7. Environment and sustainability: Understand the impact of the Chemical engineering solutions in societal and
environmental contexts, and demonstrate the knowledge of, and need for sustainable development.
8. Ethics: An understanding of professional and ethical responsibility.
9. Individual and team work: Function effectively as an individual, and as a member or leader in teams, and in
multidisciplinary settings.
10. Communication: Ability to communicate effectively. Be able to comprehend and write effective reports
documentation.
11. Project management and finance: Demonstrate knowledge and understanding of engineering and management
principles and apply this to chemical engineering problem.
12. Life-long learning: ability to engage in life-long learning in the broadest context of technological change.

Source: http://www.abet.org
Suggested Text Book
1. Crowl DA et al. Chemical Process Safety: Fundamentals with Applications 3 rd Edn.
PHI.
2. Roy E. Sanders. Chemical Process Safety: Learning from Case History 4 th Edn.
Elsevier.
3. Perry’s Chemical Engineers Handbook.
 FEW SUGGESTED READING
1. Chemical Weekly
http://www.chemicalweekly.com/home/index.php
2. Chemical Engineering News
http://cen.acs.org/index.html
3. Chemical Engineering World
http://www.cewindia.com/
“To know is to survive and to ignore
fundamentals is to court disaster.”
(Howard H. Fawcett and William S. Wood 1982)
WHAT IS SAFETY ?
The prevention of accidents through the use of appropriate
technologies to identify the hazards of chemical plant and
eliminate them before an accident occurs.

WHAT IS CHEMICAL PROCESS SAFETY ?

Chemical process safety is a technical and management
systems discipline that focuses primarily on prevention of
loss of containment. Specifically to protection against the
toxic effects of chemicals.
WHAT IS ACCIDENT ?
An accident is an unplanned, unforeseen and unexpected event
that has a negative impact on all activities of the individual
concerned.

WHAT IS DISASTER ?
A disaster is defined as a "sudden or great misfortune" or "an
event whose timing is unexpected and whose consequences are
seriously destructive.

WHAT IS RISK ?
A measure of human injury, environmental damage, economic
loss in terms of both the incident likelihood and the magnitude of
loss and injury.
WHAT IS HAZARD ?
A chemical or physical condition that has the potential for causing
damage to people, property, or the environment

PROCESS HAZARDS ANALYSIS (PHA)

An organized effort to identify and evaluate hazards associated with
chemical processes and operations to enable their control. This
review normally involves the use of qualitative techniques to identify
and assess the significance of hazards.

Source: AIChE, Center for Chemical Process Safety (CCPS) .

 FEW COMMON PHA TECHNIQUES
 Hazard and Operability Analysis (HAZOP)
 Checklist Analysis
 What If Analysis
 Failure Modes and Effects Analysis (FMEA)
 Layers of Protection Analysis (LOPA)

MANDATORY CONCEPT OF PHA

 Preparation for the PHA
 Proper team formation
 Correct and up-to-date information to support PHA
 Conduct the meetings
 Selection of appropriate techniques
 Clear documentation of PHA results
 Timely, effective implementation of PHA recommendations

Source: AIChE, Center for Chemical Process Safety (CCPS)

RISK = HAZARD + VULNERABIL
ITY
 Technical
Rehabilitation Competence

Experience Safety Program Knowledge

Management
Commitment
Support

FEATURES OF SAFETY PROGRAM

Source: AIChE, Center for Chemical Process Safety (CCPS)
Types of Chemical Plant Accidents
Potential
Potential
Types of Probability of for
for
accident occurrence economic
fatalities
loss

Moderate
Fire High ↑ Low ↓

Moderate
Explosion Moderate High ↑

Toxic release Low ↓ High ↑ Low ↓

Sources: Types of Loss For Large Chemical Plant Accidents. A Thirty year Review of One
Hundred of the Largest Property Damage Losses in the Hydrocarbon-Chemical Industries, 1987
 1%
Vapor Colud Explosions

22%
Fire

42% Explosion

Others

35%

Sources: Types of Loss For Large Chemical Plant Accidents. A Thirty year Review of One
Hundred of the Largest Property Damage Losses in the Hydrocarbon-Chemical Industries, 1987
 STATISTICS
45

40 39

35

30
26
No. of Accidents

25

20

15 13
11
10
7
5 4
3

0
Mechanical Faliure Operational Error Unknown Process Upset Natural Hazard Design Error Arson Sabotage
35
Sources: Causes for loss in the large chemical plant accidents.
30
30

25
22

20
15
15
No. of Accidents

11
10
5
5 4 4
3
2 2 2

0
n k ks s s s s ps es
em ow an te
m er ve er or ag
st s
Ta
n g al ow ss m
Sy kn eT Sy an V re Pu G
ng
n
ra
g g ng ch sT p
pi
U
to in di x es om
Pi S Pip ol tE roc C
rs sH ea P
es H
to
ea
c
roc
R P Sources: Hardware associated with largest Losses.
1.6 ACCIDENT PROCESS

Accidents are followed by three steps:

Initiation: The event that start the accident

Propagation: The event that retain or expand the accident

Termination: The event that stop the accident

Examples 1-6, (Crowl DA et al. Chemical Process Safety, pg. 16 )

Failure of a threaded 1-1/2” drain connectiono on a rich oil at the base an absorber tower in
a large (1.35 met. cub. Ft/day) gas producing plant allowed the release of rich oil and gas^ at
80 psi and -40oF. The resulting vapor cloud probably ignited from the ignition system of
engine driven recompressors ^. The 75’ high×10’ diameter absorber tower eventually
collapsed across the pipe rack and on two exchanger trains ^. Breaking pipelines added
more fuel to the fire ^. Serve flame impingement on an 11,000 hp gas turbine driven
compressor-waste heat recovery and super-heater train resulted in its near destruction.
Combustible materials get destroyed and become debris#. Indentify the initiation,
propagation, termination step for this accident.

Answer-Initiation: o; Propagation: ^; Termination: #

Accident 1.7a, (Crowl DA et al. Chemical Process Safety, pg. 20 )
Indentify the initiation, propagation, termination steps for the
accident. A contractor accidently cut into a 10-inch propane line
operating at 800 psi at a natural gas liquids terminal. The large
vapor cloud estimated to cover an area of 44 acres was ignited about
4-5 minutes later by an unknown sources. Liquid products from 5 of
26 salt dome caverns fed the fire with an estimated 18,000 to 35,000
gallons of LPGs for almost 6 hours before being blocked in and the
fires extinguished. Both engine driven fire pumps failed; one
because intense radiated heat damaged its ignition wires and the
other because the explosions broke a sight glass fuel gage spilling
diesel fuel which ignited, destroying the fire pump engine.

Answer-Initiation: o; Propagation: ^; Termination: #

Accident 1.7b, (Crowl DA et al. Chemical Process Safety, pg. 20 )
An alkylation unit was being started up after shutdown because of an electrical
outage. When adequate circulation could not be maintained in a deisobutanizer
heater circuit, it was decided to clean the strainer. Workman has depressurized
the pipe and removed all but three of the flanges bolts when pressure release blew
a black material from the flange, followed by butane vapors. These vapors were
carried to a furnace 100 feet away, where they ignited, flashing back to the
flanges.

The ensuing fire exposed a fractionation tower and horizontal receiver drums.
These drums exploded, rupturing pipelines, which added more fuel. The
explosions and heat caused loss of insulation from the 8-foot-by-122-foot
fractionator tower, causing it to weaken and fall across two major pipe lanes,
breaking piping-which added more fuel to the fire. Extinguishment, achieved
basically by isolating the fuel source, took 2.5 hrs.

Answer-Initiation: o; Propagation: ^; Termination: #

1.3 ACCIDENT AND LOSS
STATISTICS
Accident and loss statistics are important measures of the effectiveness of safety
programs. These statistics are valuable for determining whether a process is safe
or whether a safety procedure is working effectively. Following statistical methods
are available to characterize accident and loss performance.

OSHA incidence rate, Occupational Safety and Health Administration US Govt.

The OSHA incidence rate is based on cases per 100 worker years. A worker year is
assumed to contain 2000 hours (50 work weeks/year×40 hours/week). The OSHA
incidence rate is based on 200,000 hours of worker exposure to a hazard. The
OSHA incidence rate is calculated from the number of occupational injuries and
illnesses and the total number of employee hours worked during the applicable
period
Based on injuries and illness

Number of injuriesand illnesses 200,000

OSHA incidencerate 
Total hours worked by all employeesduring period covered
Based on lost workdays

Number of lost workdays  200,000

OSHA incidencerate 
Total hours worked by all employeesduring period covered
Fatal accident Rate (FAR) is used mostly by the British chemical industry. The
FAR reports the number of fatalities based on 1000 employees working their
entire lifetime. The employees are assumed to work a total of 50 years. Thus the
FAR is based on 108 working hours. The resulting equation is-

8
Number of fatalities  10
FAR 
Total hours worked by all employees during period covered

The last method considered is the fatality rate or deaths per person per year. This
system is independent of the number of hours actually worked and reports only
the number of fatalities expected per person per year

Number of fatalities per year

Fatility Rate 
Total number of peoplein applicablepopulation
Modified Problem 1.9, (Crowl DA et al. Chemical Process Safety, pg. 31 )
In 2017, 1200 man power are working in the chemical industry. In the same
tenure, industry had 38 reportable lost-time injuries with a resulting 274 lost
workdays. Evaluate the OSHA incidence rate based on injuries and lost workdays.
 CHEMICAL HAZARD SYMBOLS

Explosives Corrosive Radioactive

Toxic Harmful

Flammable
Dangerous for
environment

Oxidizing
Biohazard
Standard: It’s a set of technical definitions. It gives
all the necessary requirements for the product,
service, and operation. Ex.; ASTM, API, ISO etc.

Law/Code/Act: When governmental bodies adopt

the standard and become legally enforceable the
standard will become a law/code/act.

Specifications: Specification provide

specific/additional requirements for the materials,
components or services that are beyond the code or
standard requirements.
Example of a mobile phone charger: If you are in the USA and
traveling to India, you need an adapter to use your charger. This is
because both the country follows the different standard for power
sockets. But your USB cables will work anywhere in the world
because it is manufactured as per globally accepted standard.
 DIFFERENCE BETWEEN CODE, STANDARD & SPECIFICATION

CODE STANDARD SPECIFICATION

 Enforceable by Law or by  Globally accepted “how to  Must meet requirements by

contract instruction” contracts

 Written by government or  Written by public  Written by private

government approved body organization or by companies
government body
 Guidelines for design,
fabrication, construction  Set of technical definitions  Additional requirements,
and installation and guidelines for beyond code & standard
manufacturing
 ASME, BS, IS  Shell Design & Engineering
 ASTM, Society of Practice (DEP), EIL 
Automotive (SAE)
Engineers, ISO
 Shri Santosh Gangwar

Source: Ministry of Labour & Employment , https://labour.gov.in/industrial-safety-health

Source: Ministry of Consumer Affairs, http://www.bis.gov.in/
 INDUSTRIAL LAWS & CODES or STANDARDS
The factories Act, 23rd Sept. 1948 (Act No. 63), serves to formulating national
policies in India towards safety and health in industries. It is administered by
the Ministry of Labour and Employment. Different provisions are explained in
the 11 chapters :

CHAPTER- I Preliminary
CHAPTER -II The inspecting staff
CHAPTER -III Health
CHAPTER -IV Safety
CHAPTER -IVA Provisions relating to Hazardous processes
CHAPTER -V Welfare and grievance
CHAPTER -VI Working hours of adults
CHAPTER -VII Employment of young persons
CHAPTER -VIII Annual leave with wages
CHAPTER -IX Special provisions
CHAPTER -X Penalties and procedure
CHAPTER -XI Supplemental
Source: Ministry of Labour & Employment
INDUSTRIAL DISASTER: CASE
STUDY
Industry: Fukushima Daiichi Nuclear Disaster, Japan

Date: 11th March 2011

Reason: Failure of cooling system after  tsunami (33 ft) following the Tohoku
earthquake (9.0) on 11th March 2011.
Casualty: 200+ death; 80+ injured; 500 missing Source: BBC News
Effect of Explosion
Industry: Sherbrooke Plant Quebec, Canada

Date: 8th November 2012

Reason: Explosion
Casualty: 2 death; 17 injured
Source: Canadian Pres
Industry: West Fertilizer Plant, Texas

Date: 17th April 2013

Reason: Ammonium nitrate explosion.
Casualty: 14 death; 160 injured
Source: New York Times
Industry: Soma Underground Coal Mine Disaster, Turkey

Date: 13th May 2014

Reason: Explosion
Casualty: 200+ death; 80+ injured Source: The Guardian
Industry: Port of Tianjin, Northern China

Date: 12th August 2015

Reason: Warehouse at the port which contained hazardous and flammable
chemicals, including sodium cyanide, potassium nitrate, ammonium nitrate and
sodium nitrate.
Casualty: 173 death; 797 injured; 8 missing
Source: BBC News
Industry: DAP Fertilizer Company Chittagong, Bangladesh

Date:24th August 2016

Reason: Toxic ammonia release
Casualty: 250+ injured
Source: The Daily Star News Paper
Industry: Packaging Industry Gazipur, Bangladesh

Date:10th September 2016

Reason: Boiler explosion
Casualty: 23 death; 50+ injured
Source: Dhaka Tribute News Paper
Industry: Ordnance Factory Khamaria Jabalpur, India

Date: 25th March 2017

Reason: L70 shell was being loaded to be taken to Pulgaon (MH)
Casualty: 20+ injured
Source: Times of India
Industry: Ordnance Factory Khadki Pune, India

Date:15th June 2017

Reason: Explosion of propellants
Casualty: 02 death
Source: Dhaka Tribute News Paper
Industry: Ordnance factory Bolangir Odisha, India

Date:15th September 2017

Reason: Rejected detonators exploded at the demolition yard
Casualty: 3 injured
Source: Times of India
 UNIT-II TOXICOLOGY
1. Toxic substances definition
Route of entry & exit of toxic substance
Effects of toxic substance

2. Relationship of doses and responses

Threshold limiting values
Exposure thresholds
Airborne contaminants

3. Confined spaces hazards

4. Prevention and control

Suggested Book: Chemical Exposure and Toxic Response; Stephen K. Hall, Joana
Chakraborty, Randall J. Ruch.
 FATHER OF TOXICOLOGY

1493-1541; German-Swiss physician 2nd century BCE

Source: Encyclopedia;
britannica.com/biography/Paracelsus Courtesy : Google Images
 TOXICOLOGY
In an ancient era, toxicology was defined as the science of poisons.

“Alle Dinge sind Gift und nichts ist ohne Gift; allein die Dosis
macht, dass ein Ding kein Gift ist“.(Paracelsus, 1500)

“All things are poison and nothing is without poison; only the dose
makes that a thing is not a poison,”. (Paracelsus, 1500)

Harmless substance, such as water, can become fatal if delivered to

the biological organisms in large enough doses.

A fundamental principle of toxicology is ‘There are no harmless

substances, only harmless ways of using substances’.

Toxicology is the qualitative and quantitative study of the adverse

effects of toxicants on biological organisms.
2.1 HOW TOXIC AGENT ENTER BIOLOGICAL ORGANISM
The most common routes of entry for toxic agents are:
 Inhalation: Mouth or nose into lungs

 Ingestion: Mouth into stomach

 Injection: Cuts into skin

 Dermal absorption: Skin membrane

Entry route Entry organ Method for control

Enforcement of rules on eating and

Ingestion Mouth
drinking
Ventilation, respirators, hoods, and other
Inhalation Mouth or nose
PPE

Injection Cuts in skin Proper protective clothing

Absorption Skin Proper protective clothing

Toxic blood level concentration as a function of route of exposure

Fig. 2.1 (Crowl DA et al. Chemical Process Safety, pg. 37 )

Various Responses of Toxicants
Irreversible
 Carcinogen causes cancer
 Mutagen causes chromosome
damage
 Reproductive hazard causes
damage to reproductive system
 Teratogencauses birth defects
May or may not reversible
 Dermatotoxic affects skin
 Hernotoxic affects blood
 Hepatotoxic affects liver
 Nephrotoxic affects kidneys
 Neurotoxic affects nervous
system
 Pulmonotoxic affects lungs

2.2 HOW TOXICANTS ARE ELIMINATED FROM BIOLOGICAL

ORGANISMS
Toxicants are eliminated or rendered inactive by the following routes:
 Excretion: through the kidneys, liver, lungs, or other organs;

 Detoxification: by changing the chemical into something less harmful by

biotransformation;
2.3 EFFECTS OF TOXIC SUBSTANCE
The effects of toxic substance and exposure time can be categorized as:-
Acute effects/exposure involves a sudden dose of a highly concentrated
substance. They are usually the result of an accident (a spill or damage to a pipe
line) that results in an immediate health problem ranging from irritation to
death. Acute effect/exposure are-
 Sudden
 Severe
 Typically involve just one incident
 Causes immediate health problems

Chronic effects/exposures involve limited continual exposure over time.

Consequently, the associated health problems develop slowly and the
characteristics of chronic effects/exposure are-
 Continual exposure over time
 Limited concentrations of toxic substances
 Progressive accumulation of toxic substance in body
 Little of no awareness of exposures
 2.5 RELATIONSHIP BETWEEN DOSE & RESPONSE
Due to the age, weight, diet, general health, etc. for same dose of a toxicant biological organisms
respond in different manner. Toxicological study on a large number of individuals. Each individual is
exposed to the same dose and the response is recorded. The fraction or percentage of individuals
experiencing a specific response is plotted. The results are frequently represented by a normal or
Gaussian distribution, given by the equation.
2
1  x μ 
1   
f(x)  e 2 σ 

σ 2π

Fig 2.2 Gaussian distribution representing the biological response to exposure to a toxicant.
Source: Crowl DA et al. Chemical Process Safety, pg. 42
A normal distribution in a variate x with mean μ and variance σ2 is a statistic
distribution with probability function.
2
1  x μ 
1   
f(x)  e 2 σ 

σ 2π
f(x) is the probability of individuals experiencing a specific response, x is the
response,σ is the standard deviation, and μ is the mean.
 n

 x i f(x i )
Mean determines the location of the curve with respect to the x
Mean μ  i 1
n axis
i 1
f(x i )
n

 (x i  μ) 2 f(x i )
Variance σ2  i 1 Standard deviation or variance determines the shape
n

 f(x
i 1
i )

As the standard deviation decreases, the distribution curve becomes more sharp around the mean
value.

Fig 2.3 Effect of the σ on a normal distribution with a μ.

Example: 2.1 (Crowl DA et al. Chemical Process Safety, pg. 20)
Seventy five people were tested for skin irritation because of a specific dose of a substance.
The responses are recorded on a scale from 0 to 10, with 0 indicating no response and 10
indicating a high response. The number of individuals exhibiting a specific response is given
in the following table:
Response 0 1 2 3 4 5 6 7 8 9 10
No of Individuals affected 0 5 10 13 13 11 9 6 3 3 2

a. Plot a histogram of the number of individuals affected versus the response.

b. Determine the mean and the standard deviation.
c. Plot the normal distribution on the histogram of the original data.
N o . o f in d iv id ua ls a ffe c te d

Solution:

15

10

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

 x i f(x i )
Mean μ  i1


n
f(x i )
=4.51
i1

 (x i  μ) 2 f(x i )
Variance σ 
2 i 1
n

 f(x ) i
=2.24
i 1

Response No. of Individuals Affected 1/√2 f(x)=0.178e-0.1(x-4.51)2 f(x) 75×f(x)

0 0 0.1785 -2.02 0.024 1.77
1 5 0.1785 -1.23 0.052 3.93
2 10 0.1785 -0.63 0.095 7.16
3 13 0.1785 -0.23 0.142 10.68
4 13 0.1785 -0.03 0.174 13.05
5 11 0.1785 -0.02 0.174 13.07
6 9 0.1785 -0.22 0.143 10.72
7 6 0.1785 -0.62 0.096 7.21
8 3 0.1785 -1.22 0.053 3.97
9 3 0.1785 -2.01 0.024 1.79
10 2 0.1785 -3.01 0.009 0.66
  75        
N o . o f in d iv id u a ls a ffected

μ=4.51

f(x)  13.3e 0.1 x  4.51

2

15

13.05 13.07

10.68 10.72
10

7.16 7.21

5
3.93 3.97

1.79
0.66
0
1 2 3 4 5 6 7 8 9 10

Response
The response is plotted vs the logarithm of the dose. This form provides a
sigmoidal curve much straighter line in the middle of the response curve.

If the response of interest is death or

lethality, the response versus log dose
curve of Figure 2-7 is called a lethal
dose curve. For comparison purposes
the dose that results in 50%. This is
called the LD50. Other values such as
LD10 or LD90 are sometimes also
reported.

Fig 2.7 Response versus log dose curve,

Sigmoidal curve
If the response to the chemical or agent is minor and reversible, the curve is called
the effective dose (ED) curve.

If the response to the agent is irreversible, the curve is called the toxic dose (TD)
curve.
The relationship between the various types of response-log dose curves is shown in
following graph:

Fig 2.8 The various types of response vs. log dose curves. ED,
effective dose; TD, toxic dose; LD, lethal dose.
2.6 MODELSFOR DOSE AND RESPONSE CURVES
For single exposures the probit (probability unit) method is particularly suited,
providing a straight-line equivalent to the response-dose curve. Finney 1971
correlates the probit variable Y and probability P as:
 u2 
Y 5  
1  2 
P
 2π  1/2 

e  
du

The above relationship is plotted in Figure 2.9 and tabulated in Table 2.4

Fig 2.9 The relationship between percentages and probits.

Source: Finney, D. J. Probit Analysis, p.23, 3d ed. Cambridge University Press, 1971.
Table 2.4 Transformation from Percentages to Probits

% 0 1 2 3 4 5 6 7 8 9
0 - 2.67 2.95 3.12 3.25 3.36 3.45 3.52 3.59 3.66
10 3.72 3.77 3.82 3.87 3.92 3.96 4.01 4.05 4.08 4.12
20 4.16 4.19 4.23 4.26 4.29 4.33 4.36 4.39 4.42 4.45
30 4.48 4.5 4.53 4.56 4.59 4.61 4.64 4.67 4.69 4.72
40 4.75 4.77 4.8 4.82 4.85 4.87 4.90 4.92 4.95 4.97
50 5 5.03 5.05 5.08 5.10 5.13 5.15 5.18 5.20 5.23
60 5.25 5.28 5.31 5.33 5.36 5.39 5.41 5.44 5.47 5.5
70 5.52 5.55 5.58 5.61 5.64 5.67 5.71 5.74 5.77 5.81
80 5.84 5.88 5.92 5.95 5.99 6.04 6.08 6.13 6.18 6.23
90 6.28 6.34 6.41 6.47 6.55 6.64 6.75 6.88 7.05 7.33
% 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
99 7.33 7.37 7.41 7.45 7.51 7.58 7.65 7.75 7.88 8.09
Source: Finney, D. J. Probit Analysis, p.25, 3d ed. Cambridge University Press, 1971.
The probit relationship of transforms the sigmoid shape of the normal response
versus dose curve into a straight line when plotted using a linear probit scale, as
shown in Figure 2.10. Standard curve-fitting techniques are used to determine the
best-fitting straight line.

Fig 2.10 The probit transformation converts the sigmoidal response vs. log dose curve into a straight line when
plotted on a linear probit scale.

For spreadsheet computations, conversion from probits to percentage is given by:

 Y5  Y  5 
P  501  erf  

 Y5  2 
Example 2.3 Eisenberg reported the following data on the effect of explosion peak
overpressures on eardrum rupture in humans:
Person affected (%) Peak overpressure (N/m2)

1 16500

10 19300

50 43500

90 84300

Solution: The percentage is converted to a probit variable using Table 2-4. The
results are:
(%) Probit

1 2.67

10 3.72

50 5.00

90 6.28
 100 8.00

7.00

80
6.00 f(x) = 21.28 ln(x) − 45.37

5.00
60
Affected (%)

Probit
4.00

40
3.00

2.00
20

1.00

0 0.00
9.00 10.00 11.00 12.00 9.00 10.00 11.00 12.00

ln(overpressure, N/m2) ln(overpressure, N/m2)

Figure 2.11 Percentage affected versus the natural Figure 2.12 Probit versus the natural logarithm of
logarithm of the peak overpressure the peak overpressure
2.7 THRESHOLD LIMIT VALUES
“Threshold limit values refers airborne concentrations that correspond to
conditions under which no adverse effects are normally expected during a
worker's lifetime.”
(American Conference of Governmental Industrial Hygienists)

“Permissible exposure level”

(Occupational Safety and Health Administration)

Time weighted average: The average concentration of a given substance to which

employees may be safely exposed over an 8 hour work day or a 40 hour work
week. Workers can be exposed without adverse effect.

Short term exposure limit: The maximum concentration of a given substance to

which employees may be safely exposed for up to 15 minutes without suffering
irritation, chronic tissue change, or narcosis to a degree sufficient to increase the
potential for accidental injury.

Ceiling limit: It refers to the concentration level of a given substance that should
not be exceeded at any point during an exposure period.
OCCUPATIONAL HYGEINE
“It is the discipline of anticipating, recognition, evaluation and controlling health
hazards in the working environment with the objective of protecting workers
health and well being and safeguarding the community at large.”
(International Occupational Hygiene Association, IOHA)

“The science and art devoted to the anticipation, recognition, evaluation, and
control of those environmental factors and stresses arising in or from the
workplace, which may cause sickness, impaired health and well-being, or
significant discomfort among workers or among citizens of the community”.
(American Industrial Hygiene Association, AIHA)

Anticipation Control
+ Evaluation +
Recognition Confirm

Fundamental elements of Occupational Hygiene

 Industrial Hygiene

Identification Evaluation Control

 Workplace Hazards

Chemical Physical Ergonomic Biological

 3.2 INDUSTRIAL HYEGINE: IDENTIFICATION
 One of the most important references used during an industrial hygiene study involving
toxic chemicals is the material safety data sheet (MSDS).
 A Material Safety Data Sheet (MSDS) is a document that contains information on the
potential hazards (health, fire, reactivity and environmental) and how to work safely with
the chemical product.
The MSDS lists the physical properties of a substance that may be
required to determine the potential hazards of the substance.

MSDS are available from the following :

Chemical manufacturer,
Commercial source,
Private library developed by the chemical plant.

The industrial hygienist interpret the physical and toxicological

properties to determine the hazards associated with a chemical.
These properties are also used to develop a strategy for the proper
control and handling of these chemicals.
 3.3 INDUSTRIAL HYEGINE: EVALUATION
The evaluation phase determines the extent and degree of employee exposure to
toxicants and physical hazards in the workplace environment.

3.3.1 Evaluating Exposures to Volatile Toxicants

A direct method for determining worker exposures is by continuously monitoring
the air concentrations of toxicants on-line in a work environment. For continuous
concentration data C(t) the TWA (time-weighted average) concentration is
computed using the equation
t
1 w
TWA   C(t)dt
80
C(t) is the concentration (in ppm or mg/m3) of the chemical in the air and tw is the
worker shift time in hours.

Continuous monitoring is not the usual situation because most facilities do not
have the necessary equipment available. The samples to be obtained, representing
worker exposures at fixed points in time. If we assume that the concentration C i is
fixed (or averaged) over the period of time Ti, the TWA concentration is computed
by:
C1T1  C 2 T2  ...C n Tn
TWA 
8 hrs
If more than one chemical is present in the workplace combined exposures from
multiple toxicants with different TLV-TWAs is determined
from the equation:
n
Ci

i 1 (TLV  TWA) i

Where, n is the total number of toxicants, Ci is the concentration of chemical i

with respect to the other toxicants, and (TLV-TWA)i is the TLV-TWA for chemical
species i.

If the sum in above Eq. exceeds 1, then the workers are overexposed. The mixture
TLV-TWA can be computed from:
n

C i
(TLV  TWA) mix  i 1
n
Ci

i 1 (TLV  TWA) i
3.3.2 Estimating Worker Exposures to Toxic Vapors

Ventilation rate, Qv
Volatile rate out, kQvC
(volume/time)
(mass/time)

Evolution rate of volatile, Qm

(mass/time)
Consider the enclosed volume V, shown in above Figure. This enclosure is ventilated by a
constant volume airflow. Volatile vapors are evolved within the enclosure. An estimate of
the concentration of volatile C (mass/volume) in the air is required. Average concentration
(in ppm) of any volatile species is given by:
QmR gT
C ppm   10 6
kQ v PM
k = 0.1-0.5 for non-ideal mixing; k = 1 for perfect mixing

C concentration of volatile vapor in the enclosure (mass/volume),

V volume of the enclosure (volume),
Qv ventilation rate (volume/time),
Qm evolution rate of volatile material (mass/time),
k non-ideal mixing factor (unit less),
Rg ideal gas constant,
T absolute temperature,
P absolute pressure, and
M molecular weight of the volatile species
3.3.3 Estimating the Vaporization Rate of a Liquid
Liquids with high saturation vapor pressures evaporate faster. The evaporation
rate (mass/time) is expected to be a function of the saturation vapor pressure.
Vaporization rate can be expressed as:
MKA(Psat - p) If P >>p, then MKAPsat
Qm 
sat
Qm 
R g TL R g TL
Psat saturation vapor pressure of the pure liquid at the temperature of the liquid,
p partial pressure of the vapor,
Qm evolution rate of volatile material (mass/time),
M molecular weight of the volatile species
K mass transfer coefficient (length/time) for an area A,
Rg ideal gas constant,
TL absolute temperature of the liquid,
The gas mass transfer coefficient is estimated as: K  aD 2/3
a constant; D gas phase diffusion coefficient
Ratio of the mass transfer coefficient between species of interest K and reference
species Ko:
2/3
K  D  D Mo M 
    K  K o  o 1/3
Ko  Do  Do M  M 
Generally water is used as a reference substance; Ko=0.83 cm/s.
3.3.4 Estimating Worker Exposures during Vessel Filling Operations
Vapor concentration and vaporization rate in an enclosure resulting from a filling
operation can be estimated by:
P sat MP sat
C ppm  ( rf Vc  KA)  10 6 Qm   rf Vc  KA
kQ v P R g TL
Vc volume of the container
rf constant filling rate (1/time)
ϕ adjustment factor (ϕ =1 for splash filling; ϕ =0.5 for subsurface filling)
Example 3-7: An open toluene container in an enclosure is weighed as a function
of time, and it is determined that the average evaporation rate is 0.1 g/min. The
ventilation rate is 100 ft3/min. The temperature and pressure are 80°F and 1atm
respectively. Determine the concentration of toluene vapor in the enclosure.

Example 3-8: A large open tank with a 5-ft diameter contains toluene. Estimate
the evaporation rate from this tank assuming a temperature of 77°F and a
pressure of 1 atm. If the ventilation rate is 3000 ft3/min, estimate the concentration
of toluene in this workplace enclosure.

Example 3-9: Railroad cars are being splash filled with toluene. The 10,000 gallon
cars are being filled at the rate of one every 8 hr. The filling hole in the tank car is
4 in. in diameter. Estimate the concentration of toluene vapor as a result of this
filling operation. The ventilation rate is estimated at 3000 ft3/min. The
temperature is 77°F and the pressure is 1atm.
3.3.5 Evaluating Worker Exposures to Noise
Table 3.7 Sound Intensity Levels for a Variety of Common Activities

Sources of noise Sound intensity level (dB)

Riveting (painful 120
Punch press 110
Passing truck 100
Factory 90
Noisy office 80
Conventional speech 70
Private office 60
Average residence 50
Recording studio 40
Whisper 30
Threshold of good hearing 20
Threshold of excellent youthful hearing 10
Plog, B.A. Fundamentals of industrial Hygiene, (Chicago: National Safety Council, 1988)
Table 3-8 Permissible Noise Exposures

Sound level (dBA) Maximum exposure (hr)

90 8
92 6
95 4
97 3
100 2
102 1.5
105 1
110 0.5
115 0.25

Plog, B.A. Fundamentals of industrial Hygiene, (Chicago: National Safety Council, 1988)

Noise levels are measured in decibel by the following eq.

 I 
Noise Intensity (dB)  10log10  
 Io 
ME 3.4 INDUSTRIAL HYEGINE: EVALUATION

Elimination
Physically remove
hazard

Substitution

Replace the hazard

Isolate peoples from

Hierarchy of Controls

Engineering
controls

the hazard

Change the way

Administrative
control

peoples work

PPE

Protect the worker with personal

protective equipment
LE
How Does IH Control Workplace Hazards?

WORK PRACTICE

ENGINEERING
ADMINISTRATIVE
 Chemical Engineer’s Responsibility
 Be aware of industrial hazards and possible
effects.

 Design inherently safer systems that minimize

worker exposure to hazards.

 As a manager encourage proper safety

procedures to minimize employees exposure to
hazardous situations.
Thank You