Problem 2

A student uses a reactor to mimic the environment for a class demonstration. The sealed 1 L
rector contains 500 ml of water, 200 ml of soil (1 % of organic carbon, density = 2.1 g/cm 3)
and 300 ml air. The temperature of the reactor is 25 0
C. After adding 100 µg of
trichloroethylene (TCE) to the reactor, the student incubates the reactor until equilibrium is
achieved between all three phases. The Henry’s law constant for TCE is 10.7 (L . atm)/mol at
25 0C, and TCE has a log Kow of 2.42. Assuming that no chemical or biological degradation of
TCE occurs during the incubation, what is the aqueous phase concentration of TCE at
equilibrium? What is the mass of TCE in the aqueous, air and soil phases after equilibrium is
attained?

Solution
1. Mass balance equation:
mtot (TCE, after addition to the reactor) = mw + ma + ms
mw – mass of TCE in water
ma – mass of TCE in air
ms – mass of TCE in soil
100 µg = (Vw Cw) + (Va Ca) + (Ms Cs); (Ms is mass of soil)

2. Ms =Vsoil × density = 200 ml × 2.1 g/cm3 = 420 g

3. Concentration of the chemical in air:

' 107( L∗atm)/mol
KH
H= = L∗atm = 0.44
RT 0.082 . ×298 K
K∗mol
C air
H=
Cw
C air =0.44 C w

4. Concentration of the chemical in soil:

Cs
K sw =
Cw
To find a relation between Cs and Cw, we need to find Ksw

1
Ksw = Koc × foc
log Koc= 0.903 log Kow + 0.094 = 0.903 × 2.42 + 0.094 = 2.28
Ksw = Koc × foc = 10 2.28 × 0.01 = 1.9 L/kg
Cs = 1.9 × Cw

5. Substitute into the mass balance equation all concentrations in terms of Cw:
100 µg = (500 ml × Cw) + (300 ml × 0.44 × Cw) + (420 g × 1.9L/kg × Cw)
Cw = 0.07 mg/L

6. The total mass of TCE:

a) In water:
0.07 mg/L in 1 L;
In 500 ml 2 times less  35µg
b) In air:
Ca = 0.44 × Cw = 0.44 × 0.07 mg/L = 0.0308 mg/L
In 300 ml 3.33 times less  9.25 µg
c) In soil:
Cs = 1.9 L/kg × 0.07 mg/L = 0.133 mg/kg
In 420 g 2.38 times less  0.056 mg

2
Problem 3
The log Henry’s const measured at 25 °C for trichloroethylene is 1.03 (L*atm)/mol
tetrachloroethylene is 1.44 (L*atm)/mol
1.2-dimethylbenzene is 0.71 (L*atm)/mol
Parathion is -3.42 (L*atm)/mol
a) What are the dimensionless Henry’s law const for each chemical?
b) Rank the chemicals in order of ease of transfer from water to air.

Solution
K 'H ' L−atm
1. H= K H=
RT mol

L−atm
101.03
mol
2. H TCE= = 0.44
L−atm
0.082 ×298 K
K∗mol
L−atm
1.44
10
mol
H PCE= = 1.1
L−atm
0.082 ×298 K
K∗mol
L−atm
100.71
mol
H DMB= = 0.21
L−atm
0.082 × 298 K
K∗mol
L−atm
−3.42
10
mol
H Parathion= = 1.6 × 10-5
L−atm
0.082 × 298 K
K∗mol

C air
3. H=
Cw
1.1 0.44 0.21 1.6 × 10-5
PCE > TCE > DMB > Parathion
Easy pass from water to air difficult pass from water to air

3
Problem 4
Suppose the gas above the soda in a bottle of soft drink is pure carbon dioxide at a pressure of
2 atm. Find the pH of the soft drink at 25 °C. It is known that Henry’s law constant for
carbon dioxide is 0.033 mol/L-atm.

Solution
1. Henry’s law: P= KH’CW
KH’= P/ CW
KH’’=1/ KH’
KH’’=0.033 mol/L-atm
CW=P/ KH’=P × KH’’ = 2 atm × 0.033 mol/L-atm = 0.066 mol/L

2. ICF table for carbonic acid (CO2 +H2O)

1st dissociation step
H2CO3 ↔ H + + HCO3-
ICF Table 1
H2CO3 H+ HCO3-
I 0.066 0 0

C -x +x +x

F 0.066-x x x

Ka= ¿ ¿= 10 -6.35 = 4.47 × 10-7

4
 x2
4.47 × 10 =
-7
0.066−x
x = 1.7 × 10-4
pH = - log [H+]= -log [1.7 × 10-4] = 3.77

3. 2d dissociation step of carbonic acid

HCO3- ↔ H + + CO32-
ICF Table 2
HCO3- H+ CO32-
I 1.7 × 10-4 1.7 × 10-4 0

C -x +x +x

F (1.7 × 10-4 - x) (1.7 × 10-4 + x) x

Ka = 10 -10.33= ¿ ¿
( 1.7 ×10−4 + x ) ×(x )
4.68 × 10 =
-11
−4
(1.7 × 10 −x)
x = 4.68 x 10-11
pH(final) = (1.7 × 10-4 + 4.68 x 10-11 ) = 3.77