CHE61403 – Safety in Process Plant Design

Tutorial 2
Lecturer : Eunice Phang S.W.
Chapter 3

1. Determine the mixture TLV at 25°C and 1atm pressure of a mixture derived from the following
liquid: (P saturated heptane = 46.4mmHg, P saturated toluene = 28.2mmHg)
Component Mole % Species TLV (ppm)
Heptane 50 400
Toluene 50 20

Solution:
𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 = 46.4 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻
𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 28.2 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻
Using Raoult’s law, the partial pressures in the vapour are determined:
𝑝𝑝𝑖𝑖 = 𝑥𝑥𝑖𝑖 𝑝𝑝𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
pheptane = (0.5)(46.4mm Hg) = 23.3 mm Hg
ptoluene = (0.5)(28.2mm Hg) = 14.1 mm Hg
The total pressure of the toxicants is (23.2+14.1) = 37.3 mm Hg.

Using Dalton’s law the mole fractions on a toxicant basis are:

23.2 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻
𝑦𝑦ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 = = 0.622
37.3 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻
𝑦𝑦𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 1 − 0.622 = 0.378
The mixture TLV is computed using equation 3-4
1
𝑇𝑇𝑇𝑇𝑇𝑇𝑚𝑚𝑚𝑚𝑚𝑚 = = 48.9𝑝𝑝𝑝𝑝𝑝𝑝
0.622 0.378
+
400 20
Because the vapour will always be the same concentration, the TLVs for the individual species in
the mixture are
TLVheptane = (0.622)(48.9ppm) = 30.4ppm
TLVToluene = (0.378)(48.9ppm) = 18.5ppm

1
 CHE61403 – Safety in Process Plant Design
Tutorial 2
Lecturer : Eunice Phang S.W.
2. A process plant inventories the following chemicals: vinyl chloride, methyl ethyl ketone, ethylene
oxide, styrene, and cyclohexane. Determine the hazards associated with these chemicals. What
additional information might you request to perform an appropriate assessment of the risk
associated with these chemicals?

Solution: The following information is obtained from various sources, e.g. MSDS (you may add more if
you have additional information from other resources)

Vinyl chloride: Colourless liquid or gas, faintly sweet odour, boiling point = -13.9°F, TLV = 5ppm in
air. VC is an irritant via inhalation and to skin, eyes, and mucous membranes, causes skin burns by
rapid evaporation and freezing. Severe fire and explosion hazard; when heated to decomposition, it
emits toxic phosgene gas.

Methyl Ethyl Ketone: Also known as 2-butanone, colourless liquid, sweet odour. Boiling point =
79.6°C. TLV – 200ppm. Moderate absorption via oral route, low via dermal. A strong irritant. Affects
peripheral nervous system. Dangerous fire hazard. Moderate explosion hazard.

Ethylene oxide: Colourless gas at room temperature. TLV – 10ppm. A powerful irritant to skin, eyes,
and mucous membrane. High concentration can cause pulmonary edema. Very dangerous fire hazard
when exposed to heat and flame.

Styrene: Colourless, oily liquid. TLV – 40ppm. Mutagenic. A skin and eye irritant, a known
carcinogen. Does not vaporize sufficiently to reach a concentration that can kill animals in a few
minutes. Dangerous fire hazards. Will polymerize if not inhibited, possible explosively.

Cyclohexane: Colourless liquid with pungent odour. Boiling point – 80.7°C. TLV – 300ppm. Moderate
irritant via inhalation and oral routes. Irritant to skin, dangerous fire hazard. Can explode when mixed
with N2O4.

2
 CHE61403 – Safety in Process Plant Design
Tutorial 2
Lecturer : Eunice Phang S.W.
3. Air contains 4ppm of carbon tetrachloride (TWA 5ppm) and 25ppm of 1,1-dichloroethane (TWA
100ppm). Compute the mixture TLV, and determine whether this value has been exceeded?

Solution:
∑ 𝐶𝐶𝑖𝑖 (4 + 25)
(𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑇𝑇𝑇𝑇𝑇𝑇)𝑚𝑚𝑚𝑚𝑚𝑚 = = = 27.62
𝐶𝐶𝑖𝑖 4 25
∑ +
(𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑇𝑇𝑇𝑇𝑇𝑇)𝑖𝑖 5 100

Total concentration = 4+25 = 29 > 27.62

Value has been exceeded.

3
 CHE61403 – Safety in Process Plant Design
Tutorial 2
Lecturer : Eunice Phang S.W.
4. The TLV-TWA for a substance is 150ppm, TLV-STEL at 160ppm and TLV-C at 250ppm. A
worker begins a work shift at 8 AM and completes the shift at 5PM. A one-hour lunch break is
included between 12noon and 1PM, when it can be assumed that no exposure to the chemical
occurs. The data were taken in the work area at the time indicated. Has the worker exceeded the
TLV specification?

Solution:
1. Add in 8:00am time slot, assuming the concentration remained same with the first reading
2. Add 12:00 and 1:00pm in the time slot

Time Time Concentration

Concentration
Time exposed exposed, Average, CT
(ppm)
(min) T (hr) C (ppm)
8:00am 110
8:10am 110 10 0.167 110.0 18.333
9:05am 130 55 0.917 120.0 110.000
10:07am 143 62 1.033 136.5 141.050
11:20am 162 73 1.217 152.5 185.542
12:00pm 146.62 40 0.667 154.3 102.872
12:12pm 142 12 0.200 no exposure 0
1:00pm 153.08 48 0.800 no exposure 0
1:17pm 157 17 0.283 155.0 43.917
2:03pm 159 46 0.767 158.0 121.133
3:13pm 165 70 1.167 162.0 189.000
4:01pm 153 48 0.800 159.0 127.200
5:00pm 130 59 0.983 141.5 139.142
Total = 1178.189
Interpolation

∑ 𝐶𝐶𝑖𝑖 𝑇𝑇𝑖𝑖 1178.189

Given TLV-TWA calculation = = = 147.27
8 8

Finding: Given TLV-TWA for a substance is 150ppm, TLV-STEL at 160ppm and TLV-C at 250ppm
• TLV-TWA of the area is 162.78, which exceeded the limit. Hence, the operator is overexposed
according to TWA level

4
 CHE61403 – Safety in Process Plant Design
Tutorial 2
Lecturer : Eunice Phang S.W.
• TLV-STEL standard is 15 minutes maximum exposure, however, the operator is expose to more
than 160ppm at 3:13pm for more than 1 hour. This is non-compliance. Operator is again over
exposed according to STEL level
• TLV-C given at 250ppm, no recording level exceeded this limit.
• Since both TWA and STEL level is exceeded, action needed to be taken to lower the concentration
in the work area. At the same time, operators are required to wear appropriate PPE while working in
the area.