Industrial Hygiene

Estimating Worker Exposures to

Toxic Vapors
2
Enclosure volume, V
Concentration of volatile, C
(Mass/ Volume)
Ventilation rate, Q
v

(Volume/ Time)
Evolution rate of volatile, Q
m

(Mass/ Time)
Volatile rate out, kQ
v
C
(Mass/ Time)
3
k varies from 0.1 to 0.5
Example
4
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 ft
3
/min. The temperature is
80F and the pressure is 1 atm. Estimate the
concentration of toluene vapor in the enclosure,
and compare your answer to the TLV for toluene of
50 ppm.
Solution
5
Because the value of k is not known directly, it must
be used as a parameter.







Because k varies from 0.1 to 0.5, the concentration is
expected to vary from 18.9 ppm to 94.3 ppm.
Estimating the Vaporization Rate
of a Liquid
6

Liquids with high saturation vapor
pressures evaporate faster.


Hence, the evaporation rate (mass/time) is a
function of the saturation vapor pressure.
Estimating the Vaporization Rate
of a Liquid
7
For vaporization into stagnant air, the
vaporization rate is proportional to the
difference between the saturation and partial
pressure of the vapor.



P
Sat
is the saturation vapor pressure of the
pure liquid at the temperature of the liquid and
p is the partial pressure of the vapor in the
bulk stagnant gas above the liquid.
Estimating the Vaporization Rate
of a Liquid
8
9
Above equation is used to estimate the vaporization rate of volatile
from an open vessel or from a spill of liquid.
10
The gas mass transfer coefficient is estimated using the relationship
where
a is a constant and
D is the gas-phase diffusion coefficient
11
It is used to determine the ratio of the mass transfer coefficients
between the species of interest K and a reference species K
O
The gas-phase diffusion coefficients are estimated from the
molecular weights M of the species
Example
12
A large open tank with a 5-ft diameter contains
toluene. Estimate the evaporation rate from this
tank assuming a temperature of 77F and a
pressure of 1 atm. If the ventilation rate is 3000
ft
3
/min, estimate the concentration of toluene in
this workplace enclosure. TLV for toluene is 50
ppm.

For water
Solution
13
The molecular weight of toluene is 92. The mass
transfer coefficient is estimated from following
Equation, using water as a reference:
14
The pool area is
The evaporation rate is
15
The concentration is estimated using Equation
16
The concentration will range from 460 ppm to
2300 ppm, depending on the value of k.

Because the TLV for toluene is 50 ppm,
additional ventilation is recommended, or the
amount of exposed surface area should be
reduced.
17
The amount of ventilation required to reduce
the concentration from 2300 ppm to 50 ppm is



This represents an impractical level of general
ventilation.
Potential solutions:
containing the toluene in a closed vessel or
using local ventilation at the vessel opening.
Estimating Worker Exposures
during Vessel Filling Operations
18
Estimating Worker Exposures
during Vessel Filling Operations
19
For vessels being filled with liquid, volatile
emissions are generated from two sources as
shown in Figure.
1. Evaporation of the liquid, represented by
Equation and


2. Displacement of the vapor in the vapor space
by the liquid filling the vessel.
Estimating Worker Exposures
during Vessel Filling Operations
20
The net generation of volatile is the sum of the
two sources:

(Q
m
)
1
= source resulting from evaporation and
(Q
m
)
2
= source resulting from displacement

The source term (Q
m
)
1
is computed using
Equation
Estimating Worker Exposures
during Vessel Filling Operations
21

(Q
m
)
2
is determined by assuming that the
vapor is completely saturated with the volatile.

Generally, an adjustment is introduced for less
than saturated conditions.
Estimating Worker Exposures
during Vessel Filling Operations
22
Let

Estimating Worker Exposures
during Vessel Filling Operations
23

r
f
V
c
= volumetric rate of bulk vapor being
displaced from the drum (volume/time).

If
v
is the density of the volatile vapor, then

r
f
V
c

v
= mass rate of volatile displaced from
the container (mass/time).
24
and it follows that
It can be modified for container vapors that are not saturated with
the volatile.

Let represent this adjustment factor; then,
Using the ideal gas law,
Estimating Worker Exposures
during Vessel Filling Operations
25
For splash filling (filling from the top of a
container with the liquid splashing to the
bottom), = 1.

For subsurface filling (by a dip leg to the
bottom of the tank), = 0.5.

The net source term resulting from filling:
Estimating Worker Exposures
during Vessel Filling Operations
26
Vapor concentration (in ppm) in an enclosure
resulting from a filling operation assuming T =
T
L
:




In practical situations, the evaporation term
KA is much smaller than the displacement
term and can be neglected.
Example
27
Railroad cars are being splash-filled with
toluene. The 10,000-gal 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 ft
3
/min.
The temperature is 77F and the pressure is 1
atm.
Solution
28
29
As expected, the evaporation term is small compared to the
displacement term.
30
The actual concentration could range from 69 ppm to 344 ppm,
depending on the value of k.

Sampling to ensure that the concentration is below 50 ppm is
recommended.

For subsurface filling, =0.5, and the concentration range is
reduced to 35-172 ppm.
Ventilation
31