6 Volatilization

6.1. What is the difference between vapor pressure and Henry’s law constant? What is an
application of each?

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6.2. For each of the following compounds, estimate the Henry’s law constant from its water
solubility and vapor pressure using the temperatures-dependent values listed in Appendices
B and J. Compare the estimated values to the tabulated values.
a. TCE f. Acrylonitrile
b. Benzene g. 2,3,7,8-TCDD
c. 2,4,6-Trichlorophenol h. Carbon tetrachloride
d. Dieldrin i. Malathion
e. Aroclor 1248
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6.3. A pit-pond-lagoon system at 20 ˚C contains 48 mg/L methanol, a volatile organic compound
with a vapor pressure of 97.6 mm Hg. Would you expect a high methanol volatilization rate
from the lagoon? Provide a conceptual basis for your answer using the Henry’s law
constant, vapor pressure, and water solubility of methanol.

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6.4. In a property transfer site assessment, a records search confirmed that the insecticide
dieldrin dissolved in acetone was disposed of on a low-permeability soil 10 years ago.
Would you expect either of the chemicals to be present 10 years later based on their
volatilities?

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6.5. Air stripping—the process of dropping water down a packed tower with a countercurrent
of air blown in from the bottom—is the most commonly used design for the removal of
volatile organics from groundwater after it is pumped to the surface (called pump-and-treat
remediation). Based on the concepts that you have learned in Chapter 6, which of the
following would you expect to be effectively and economically treated using air stripping?
a. Pentachlorophenol
b. TCE

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 c. PCE
d. Vinyl chloride
e. MEK
f. Chloroform
g. Dieldrin
h. BTEX
Justify your answer based on the chemical properties that control volatilization.

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6.6. A small storage cabinet 2 m × 2 m × 3 m high (6.6 ft × 6.6 ft × 9.8 ft) contains an open 208-
L (55-gal) drum of aqueous TCE at a concentration of 120 mg/L. The cabinet has been
closed for over 2 months, so equilibrium conditions have been established. What is the TCE
concentration in the water and vapor phases at this time? Assume that the temperature is 25
˚C.

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6.7. A 208-L (55-gal) drum 0.4 m (1.3 ft) in diameter containing PCE is open in a small drum
storage area 5 m × 5 m × 2.5 m high (16.4 ft × 16.4 ft × 8.2 ft). The temperature is 25 ˚C
and the atmospheric pressure is 1 atm. Ventilation in the structure provides four changes of
air per hour. Determine (a) the volatilization rate of PCE from the drum, and (b) the steady-
state PCE concentration in ppm in the structure. Assume k = 0.2.

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6.8. A waste receptacle 3 m long × 1.5 m wide × 20 cm deep (9.8 ft × 4.9 ft × 0.66 ft) in a
building that houses a metal parts cleaning operation contains a layer of TCA 8 cm (0.26 ft)
deep. The temperature is 25 ˚C and the atmospheric pressure is 1 atm. The ventilation rate
in the building is 200 L/h. Determine the TCA volatilization rate from the waste receptacle.
Assume k = 0.4.

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6.9. Repeat problem 6.8 with (a) pentane and (b) dodecane as the compounds in the waste
receptacle.

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6.10. A large spill of PCE occurred in a storage building 10 m × 8 m × 6 m high (32.8 ft × 26.2
ft × 19.7 ft), resulting in a PCE depth of 0.1 m (0.33 ft) (release from the building was
protected by a containment berm). The temperature in the building is 25 ˚C. If k = 0.3 and
the ventilation system provides 15 changes of air per hour, determine the steady-state
concentration in the building.

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6.11. A pesticide truck spills 54 kg (120 lb) of 80% DDT on a dirt road over 85 m2 (914 ft2). The
average depth for the DDT is 4 cm (1.6 in). The bulk density of the soil is 1800 kg/m3. How
long will it take for the DDT to volatilize to a level of 0.01 ppm in the soil? Assume
negligible effects of temperature differences at which water solubility and vapor pressure
are reported.

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6.12. Two hundred kilograms (440 lb) of 4,6-dinitro-o-cresol (DNOC) have been spilled on an
asphalt surface and held there at an average depth of 2 cm (0.8 in). The surface area of the
spill is 100 m2 (1080 ft2), and the bulk density of the asphalt is 2100 kg/m3. If volatilization
is the only significant chemodynamic pathway, how long will it be until the DNOC level
drops to 10 ppm? Assume negligible effects of temperature differences at which water
solubility and vapor pressure are reported.

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6.13. One hundred kilograms (220 lb) of 60% solution of nirvanum, an experimental new
insecticide, is spilled over a 28,000 m2 (301,000 ft2) area of hardpan soil in a layer 79 mm
thick. The log Koc for nirvanum = 2.7, the vapor pressure = 2.3 × 10−5 mm Hg, the water
solubility = 12 mg/L, and the soil bulk density = 2600 kg/m3. Estimate the time required for
the nirvanum soil concentration to drop to 1 mg/kg by volatilization.

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6.14. A pesticide truck spills 55 kg (121 lb) of 80% endrin on a dirt road over 85 m2 (914 ft2).
The average spill depth is 4 cm (1.6 in.). The bulk density of the soil is 1800 kg/m3. How
long will it take for the endrin to volatilize to a level of 1 ppb in the soil? Assume negligible
effects of temperature differences at which water solubility and vapor pressure are reported.

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6.15. Determine the half-life of hexachlorobenzene by volatilization if the contamination is on
the soil surface. Assume negligible temperature effects.

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6.16. One hundred cubic meters (131 yd3) of gasoline-contaminated soil have been laid out on a
concrete pad at a depth of 0.5 m (1.64 ft). As environmental facilities manager at the
petrochemical facility where the waste has been placed, you have been approached by state
regulatory personnel to control volatile gasoline emissions. Based on the physical
properties, are the concerns of the regulators justified? List a possible measure that could
be used to control the emissions.

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6.17. The concentration of PCE in a soil with infinitely deep contamination is 1270 ppm.
Determine the volatilization flux over 1 week using the Hamaker equation if the soil bulk
density = 1800 kg/m3 and D = 0.142 cm2/sec.

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6.18. Soil under a dried-up hazardous waste disposal pit contains DDT at an average soil
concentration of 3,800 ppm. Using the soil-air D for ethylene dibromide and ethanol to
estimate the soil-air D for DDT, estimate the time required for the DDT to drop to 0.01 ppm
in the soil. Assume the depth of contamination is 10 m (32.8 ft), the surface area = 100 m 2
(1080 ft2), and ρB = 1600 kg/m3. Ignore the wick effect.

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6.19. A soil disposal area is characterized by deep (semi-infinite) contamination of anthracene
with a mean concentration of 240 mg/kg. If the bulk density of the soil is 1700 kg/m 3,
determine the flux of anthracene out of the soil over a time period of 10 days. Ignore the
wick effect.

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6.20. Repeat Problem 6.19 accounting for the wick effect. The loss of water vapor from the soil
over the 10-day period is 8.2 g/cm2 and the loss of liquid water is 1.1 g/cm2. Assume that
10% of the anthracene is present in the soil water.

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6.21. A soil (ρB = 1700 kg/m3) is deeply contaminated with 800 mg/kg anthracene. Estimate the
volatilization flux at 1-day intervals up to 10 days using the Hamaker equation.

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6.22. A hazardous waste landfill is contaminated with 1,1,2,2-tetrachloroethane. Assume that the
relative humidity = 48%, the temperature = 20 ˚C, and the thickness of the stagnant
boundary layer = 0.5 cm. Estimate the flux of the 1,1,2,2-tetrachloroethane out of the soil.

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6.23. A 208-L (55-gal) drum of toluene has ruptured and contaminated a section of soil 5 m (16.4
ft) in diameter and 1.5 m (4.9 ft) deep. Estimate the time required for the toluene to volatilize
if the relative humidity = 26%, the temperature = 14 ˚C, and the thickness of the stagnant
boundary layer = 0.5 cm.

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6.24. A soil disposal pit (ρB = 1700 kg/m3) is contaminated with benzene at an average
concentration of 285 mg/kg. The temperature = 22 ˚C, the relative humidity = 70%, and the
thickness of the stagnant boundary layer = 0.8 cm. Estimate and compare the flux of
benzene over 1 day from the soil using both the Hartley and Hamaker equations.

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6.25. Estimate the flux of carbon tetrachloride from a soil based on total water loss if the carbon
tetrachloride concentration in the soil water is 0.0084%. The flux of water vapor is 0.048
g/cm2day, and the flux of liquid water is 0.013 g/cm2day.

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6.26. Estimate the flux of chloroform from a soil based on total water loss if the flux of water
vapor is 0.0095 g/cm2-day. Assume that the flux of liquid water is negligible.

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