Agenda

• Recap of previous class

• Flash Point
• Explosive limits
• Problems
• Assignment
Ground Rules
• This is not a college. Perfection is not important
• Application of theory is important
• No exams. Do not study marks
• Here student can be better than teacher
• Training is to develop interest on study
• When you take interest on study, you are creating positive energy
with your colleagues and family members
Problem:
Air contains 5 ppm of diethylamine (TLV-TWA of 10 ppm), 20 ppm of cyclohexanol (TLV-TWA of 50 ppm),
and 10 ppm of propylene oxide (TLV-TWA of 20 ppm). What is the mixture TLV-TWA and has this level
been exceeded?

TLV mixture = (y1=Y2+y3)/(y1/TLV1+y2/TLV2+y3/TLV 3)

y1= 5ppm, TLV 1=10ppm
y2=20 ppm, TLV 2=50 ppm
Y3= 10 ppm, TLV 3=20 ppm

If y1+y2+y3 > TLV mixture, safety precautions to be taken

Or
y1/TLV1+y2/TLV2+y3/TLV 3 >1.0,

Safety precautions to be taken

Flash Point
• Flash point is the lowest temperature at which a liquid can gives off
vapor to form an ignitable mixture in air near the surface of the liquid
Explosive Limits
• lower explosive limit (LEL) Lowest concentration (percentage) of a gas or vapor in air
capable of producing a flash of fire in presence of an ignition source (arc, flame, heat).
• upper explosive limit (UEL) The highest concentration of a gas or vapor (percentage by
volume in air) above which a flame will not spread in the presence of an ignition source
(arc, flame, or heat). Concentrations higher than UEL are “too rich” to burn.
• Atmospheres with a concentration of flammable vapors at or above 10 percent of the
lower explosive limit (LEL) are considered hazardous when located in confined spaces.
However, atmospheres with flammable vapors below 10 percent of the LEL are not
necessarily safe
• Lower flammability limit (LFL): The lowest concentration (percentage) of a gas or a vapor
in air capable of producing a flash of fire in the presence of an ignition source (arc, flame,
heat). The term is considered by many safety professionals to be the same as the lower
explosive level (LEL)
Problem:
Determine the 8-hr TWA worker exposure if the worker is exposed to toluene vapors
as follows:
Duration of Measured exposure concentration (hr) (PP~)
Duration of exposure ppm
2hr 110
2hr 330
4hr 90

TWA =CITl + C2T2 + C3T3 / 8

- - 110 x (2) + 330 x(2) + 90 x(4)/ 8
= 155 ppm.
Because the TLV for toluene is 100 ppm, the worker is overexposed. Additional control
measures need to be developed. On a temporary and immediate basis all employees
working in this environ- ment need to wear the appropriate respirators.
Assignement
Description Benzene Toluene
Molecular weight 78.11 92.13
Specific gravity 0.88 0.866
TLV (ppm) 0.5 20

Saturation vapour pressures:

ln(Psat) =A-(B/(C+T))
Where Psat is the saturation vapour pressure in mmHG. T is the temperature in K and A, B and C are the
constants
A B C
Benzene 15.9 2788.9 -52.36
Toluene 16.01 3096.5 -53.67
Compute the concentration (in ppm) of the saturated vapour with the air above the solution of pure
toluene
Compute the concentration (in ppm) of the equilibrium vapour with air above a solution of 50% toluene
and benzene.
The temperature is 80F and pressure is 1 atm
Compute the density of pure air and compute the density of air contaminated with 100 ppm benzene.
Do the densities of these two gases differ enough to ensure higher concentration on the floors and other
lower spots? The temperature is 70F and pressure is 1 atm.
Data Given:
Part a) Compute the concentration (in ppm) of the saturated vapour with the air above
the solution of pure toluene

ln(Psat) =A-(B/(C+T)) where Psat in vapour pressure in mmhg and T is Kelvin

Temperature = 80 F = (80-32)/1.8 =26C

=26+273 = 299K

Pressure = 1atm = 760 mmhg

Component = Pure Toluene solution (x=1.0)

Component A B C
Toluene 16.01 3096.5 -53.67
Raoults law:

Partial pressure = Vapour pressure x mole fraction in liquid state

Step1: Calculate the vapour pressure using Antoini equation

ln(Psat) =A-(B/(C+T)) = 3.42

Psat = exp (3.42) =30.64 mmHg

Partial Pressure of Toluene = 30.64 mmHg

Total Pressure = 760 mmHg

Mole fraction in vapor phase = Partial Pressure / Total Pressure

= 30.64/760 = 0.04
Mole Percentage = 4%= 40,000 ppm

1) Is it flammable?
2) Is the operator is safe to operate?
3) What precautions to be taken?
What happens , it it chilled to 4.4 C?

y =1.1%

The lower explosive limit of Toluene 1.2%

There is no fire risk.

However, there is health risk

If it is chilled to -65C or below, Vapour concentration is 19 ppm.

There is no safety Risk.

Is it economical?

Options are

a) Closed handling
b) PPE ( please chat the PPE for Toluene)
 Assignment 1

Prove that hexane flash point is -26C at 1 atm pressure

Collect following data from reliance sources

Antoini constants
Part b.
Compute the concentration (in ppm) of the equilibrium vapour with air above a solution of 50%
toluene and benzene

Is it % mole?
Is it % weight?
Is it % volume?

For Industrial purpose, I consider it as %Volume because

GC gives % Volume
 Step 1: Convert % volume = % weight
Volume x specific gravity = weight

Step 2: Convert % weight into % mole

Weight/Molecular weight =moles

Component x (Volume fraction) Density Weight Weight fraction % weight Molecular weight Mole %mole

Benzene 0.5 0.88 0.44 0.50 50.40092 78.11 0.64 54.51

Toluene 0.5 0.866 0.433 0.49 49.59908 92.13 0.53 45.48

Total 1   0.873 1 100   1.1836154 100

 Step 3:
Find the vapour pressure using antoini equation ln (Psat) = A-(B/(C+T))

Component x A B C T in K ln (Psat) = A-(B/(C+T)) Psat mmHg

Benzene 0.54 15.9 2788.8 -52.36 299.6667 4.62 101.83

Toluene 0.45 16.01 3096.5 -53.67 299.6667 3.42 30.64

Step 4:
Calculate the partial pressure using Raoults law: Partial pressure = vapour pressure x mole fraction in
liquid state

ln (Psat) = Partial
Component x A B C T in K A-(B/(C+T)) Psat mmHg Pressure

Benzene 0.54 15.9 2788.8 -52.36 299.6667 4.623312487 101.83079 54.98863

Toluene 0.45 16.01 3096.5 -53.67 299.6667 3.422431063 30.643822 13.78972

Step 5:

Using Daltons law: Total pressure= p1 + p2+p3+…

Given : Total pressure is 1 atm =760 mm hg
Componen ln (Psat) = Psat Partial
t x A B C T in K A-(B/(C+T)) mmHg Pressure
299.666
Benzene 0.54 15.9 2788.8 -52.36 7 4.62 101.83 54.98
299.666
Toluene 0.45 16.01 3096.5 -53.67 7 3.42 30.64 13.78
air               691.22
Tota               760

Step 6:
Compute the vapour composition y= partial pressure /total pressure *100

Componen ln (Psat) = Psat Partial y=p/Ptotal

t x A B C T in K A-(B/(C+T)) mmHg Pressure *100
Benzene 0.54 15.9 2788.8 -52.36 299.66 4.62 101.83 54.98 7.23
Toluene 0.45 16.01 3096.5 -53.67 299.66 3.42 30.64 13.78 1.81
air               691.22 90.95
Tota               760 100
Assignment 2

Is the mixture flammable?

Give reason

Is this mixture toxic if inhaled?

Give reason

How will make this mixture safe from flammability and toxic point of view
Part C:
Compute the density of pure air

Ideal Gas law , PV =nRT

n/V =P/RT
=1.0133 x 10^5 /(8314 x 294)
= 0.014 kg moles/M3
= 1.202 kg/M3
Part D:
Compute the density of pure air and compute the density of air contaminated with
100 ppm benzene.

Compoisitio Density
Component n Mol wt Avearge mol wt (PM/RT)

Air 0.99 29 29.4911 1.22

Benzene 0.01 78.11   

Assignment 3:

Do the densities of these two gases differ enough to ensure higher concentration on the floors
and other lower spots? The temperature is 70F and pressure is 1 atm.

If it is higher than the TLV of benzene, what precautions to be taken:

1) Type of PPE to be used

2) What should be the capacity of AHU?

3) What should be height of exhaust duct from the floor level?

4) How will you treat the exhaust from the duct?

5) Can you use scrubber?

6) Provide details of instruments used for occupational Hygiene study.

7) How will you measure the mixture TLV?

Part 4:
What is the safe TLV for the mixture?

TLV mixture = (y1+y2)/ (y1/TLV1 = y2/TLV2)

Component Partial Pressure TLV y y1/TLV (y1+y2)/(y1/TLV 1+y2/TLV2)

Benzene 54.98862508 0.5 0.799505 1.60

Toluene 13.78971972 20 0.200495 0.010 0.62

total 68.7783448  1   
Assignment 4:
• How will you monitor the TLV on the shop floor for this mixture of
solvent?
• While unloading the centrifuge, monitor the TLV of the mixture. If the
observed value is more than the calculated mixture TLV, what
precautions to be taken?
• How will you train the operator for the above case?
Type and explanation Typical techniques
Enclosures Enclose hazardous operations such as
sample points. Seal rooms, sewers,
ventilation, and the like. Use analyzers
and instruments to observe inside
equipment. Shield high-temperature
surfaces.
Local ventilation Use properly designed hoods.
Use hoods for charging and discharging.
Use ventilation at drumming station. Use
local exhaust at sample points. Keep
exhaust systems under negative pressure
Personal protection As last line of Use safety glasses and face shields. Use
defense. aprons, arm shields, and space suits.
Wear appropriate respirators; airline
respirators are required when oxygen
concentration is less than 19.5%
For continuous concentration data C(t) the TWA (time-weighted average) concentration is computed
using the equation

TWA =1/8 (Integrate C(t) dt for 0 to tw)

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.
CITl + C2T2 + . . . + CnT,
TWA =
8 hr
 Assignment 5

The TLV-TWA for a substance is 150 ppm. A worker begins a work shift at 8 A.M. and
completes the shift at 5 P.M. A one-hour lunch break is included between 12 noon and
1 P.M., where it can be assumed that no exposure to the chemical occurs.
Problems 105
The data were taken in the work area at the times indicated. Has the worker exceeded the TLV specification?
Concentration
Time (PP~)
8:10 A.M. 110
9:05 A.M. 130
10:07 A.M. 143
11:20 A.M. 162
1212 P.M. 142
1:17 P.M. 157
2:03 P.M. 159
3:13 P.M. 165
4:01 P.M. 153
5:00 P.M. 130
Assignment 6

A substance has a TLV-TWA of 200 ppm, a TLV-STEL of 250 ppm, and a TLV-C of 300
ppm. The data in the following table were taken in a work area:
Concentration
Time (PP~)
8:01 A.M. 185
9:17 A.M. 240
10:05 A.M. 270
11:22 A.M. 230
12:08 P.M. 190
1:06 P.M. 150
2:05 P.M. 170
3:09 P.M. 165
400 P.M. 160
5:05 P.M. 130
A worker on an 8-hour shift is exposed to this toxic vapor. Is the exposure within compliance? If not, what
are the violations? Assume that the worker is at lunch between the
hours of 12 noon to 1 P.M. and is not exposed to the chemical during that time.
Self Study
• Environmental protection agency (EPA)
• OSHA
• Environmental protection act
• National Institute for Occupational Safety and Health (NIOSH)
• Risk Management Plan,1996
• Occupational hygiene monitoring equipments
• Indoor air quality
• Fugitive emission monitoring
• Ventilation testing and balancing
Quiz
• Above the flash point, fire can not happen
• Yes/No

• How to convert volume to weight

1) Divide by density
2) Multiply by density

• How to convert to weight to moles

1) Divide by density
2) Multiply by density
• Increasing the temperature …….. Risk of fire
• 1) Reduces
• 2) Increases
• 3) Cannot say
• Mixture TLV will be …than the individual TLV
• 1) More
• 2) Less
• 3) In between