CM 4310, Chemical Process Safety/Environment

Homework #1

Fall 2014
Fri. Nov. 14, 2014

1. Global Carbon Dioxide Mass Balance.

Problem 4 in Chapter 1; parts a and c only.

2. Partitioning of Benzene in Soil

The CAS number of Benzene is 71-43-2, and use the EPI Suite software tool to estimate the
required environmental properties for this problem. Use the experimental values if available
from this software. Assume that 1 gram of benzene is allowed to partition into different
phases of 1 m3 of soil, and assume that the 1 m3 of soil is a closed system. Furthermore,
assume that the soil is comprised of 20% by volume (v) air, 20% (v) water, and 60% (v)
solids. The air phase contains only air plus any Benzene that partitions into it at equilibrium.
Water phase contains only water plus any Benzene partitioned into it at equilibrium (no
suspended sediments for example). Solid phase is comprised of mineral and natural organic
matter, and the latter is represented by fraction organic carbon content of foc = 0.02 kg organic
carbon/kg dry soil. The density of soil on a dry basis is s= 1,500 kg dry soil/m3 soil.
Assume soil temperature = 25C.
a. Calculate the concentration of Benzene in the soil air, soil water, and soil organic
carbon.
b. Calculate the percent of the mass in each of the phases, air, water and organic carbon.

3. Volatilization of a Chemical from a River

The lecture slides contain an example of volatilization loss of a chemical from a river after
discharge of the chemical from the wastewater treatment plant of a chemical factory.
a. Verify the derivation starting from the mass/mole balance equation; [(vW CA,W(in))|x (vW CA,W(out))|x+ x](y z) - KA,W CA,W(out) (x y) = 0 and show that the solution
for the change in chemical concentration with distance (x) down river, using the same
boundary condition as in the lecture slides, is
,
,

b. For a slightly volatile chemical (H = 10-5 atm m3/gmole see Henrys Constant
section of Chapter 5), the value of overall mass transfer coefficient is KA,W =
0.359889 m/day, and other parameters in the solution are the river velocity is vW =
43,200 m/day, river area per unit volume is av = 2.59 m-1, and distance to the inlet to
the municipal water treatment plant is 100 km. Show that CA,W / CA,W(o) = 0.1154.

c. Reaction loss: Add a first-order biodegradation reaction loss term (-kB CA,W) to the
mass balance equation and repeat the derivation in part a. Show that the solution is
,
,

d. For a first-order biodegradation rate constant of kB = 0.231 d-1 for this chemical in the
river, repeat the calculation in part b and compare to the result in part b. Is the
concentration lower at the inlet to the municipal water treatment plant?

Due Mon. Dec. 1, 2014

1. Global Carbon Dioxide Mass Balance (30 pts total)

a) A mass balance for CO2 at the earth's surface is
Accumulation of CO2 in atmosphere = rate of CO2 release from surface rate of CO2 removal by surface
Accumulation of CO2 in atmosphere (metric tons C/yr) = (60+6+1.6) - (60+2+.5+1.8)
= 3.3 metric tons C/yr
44 gCO2 103 kg
9
1.21 1013 kgCO2 / yr
= (3.3 10 metric tons / yr)
12 gC
metric ton

c) Rate of change for CO2 concentration in atmosphere (ppm/yr)

Change in number of moles CO2 from part a =
103 g 1moleCO2
13
(1.21 10 kgCO2 / yr)
2.75 1014 moles CO2 / yr

kg 44 gCO2
Change in mole fraction (ppm) of CO2 =

2.75 1014 molesCO2 / yr

1ppm
1.83ppm / yr

molesCO2
1.5 10 20 moles air

10-6

moles air
This rate of change compares well with the observed rate of change of 0.5%/yr, which
at the current concentration of CO2 is (.005)(360 ppm) = 1.80 ppm/yr.

2. Partitioning of Benzene in Soil (40 points)

The CAS number of Benzene is 71-43-2, and use the EPI Suite software tool to estimate the
needed environmental properties for this problem. Use the experimental values if available
from this software. Assume that 1 gram of bernzene is allowed to partition into different
phases of 1 m3 of soil, and assume that the 1 m3 of soil is a closed system. Furthermore,
assume that the soil is comprised of 20% by volume (v) air, 20% (v) water, and 60% (v)
solids. The air phase contains only air plus any Benzene that partitions into it at equilibrium.
Water phase contains only water plus any Benzene partitioned into it at equilibrium (no
suspended sediments for example). Solid phase is comprised of mineral and natural organic
matter, and the latter is represented by fraction organic carbon content of foc = 0.02 kg organic
carbon/kg dry soil. The density of soil on a dry basis is s= 1,500 kg dry soil/m3 soil.
Assume soil temperature = 25C.
a. Calculate the concentration of Benzene in the soil air, soil water, and soil organic
carbon.
b. Calculate the percent of the mass in each of the phases, air, water and organic carbon.

Benzene Partitioning in Soil

Basis: 1 m soil

VT

VA

0.20 m

VW

0.20 m

VS

0.60 m
kg dry soil solids
1,500
m soil
kg oc
0.02
kg dry soil solids

S
f
Basis:MT

1g Benzene

10 kg Benzene

Mass Balance: all mass terms are in grams Benzene; concentrations are mass concentrations.

MT

MS

CA VA

CW VW

CS f S VT

Equilibrium Partitioning:

Henrys Constant: CA
But

RT

CA MW, CW

CA
CA

HP

HC CW

HP
RT

HP

HP : atm m /mole

CW
MW

CW
5.55

Organic Carbon Partitioning: CS

10

10

m
mole

atm

K CW

log K
K

CW

K :

1.75
56.23

Re-stating the Mass Balance and substituting in for the equilibrium partitioning, we can express
each term in the right hand side in terms of water concentration, CW, the only unknown in the
equation.

MT

HP
RT
HP
RT

CW VA
VA

CW VW

VW

K CW 10
10

K OC f

f S VT

S VT CW

MT

CW

HP
V
RT A

VW

K f

m
L

10

S VT

1g
5.55
8.206

m water
10 atm
mole
0.20 m
10 m atm
298.15K
K mole

0.20 m

56.2

kg oc
L
0.02
10
kg oc
kg

m
L

1500 kg
1m
m

CW = 0.517 g benzene/m3water
MW

CW VW

0.517

g
0.20 m
m water

0.103 g Benzene

MW = 0.103 g Benzene in soil water

CA

HP
C
RT W
0.117

5.55
8.206
g Benzene
m air

m water
g
mole
0.517
10 m atm
m water
298.15K
K mole
10

atm

CA = 0.117 g benzene/m3 air

MA

CA VA

HP
C
V
RT W A

m water
g
mole
0.517
0.20 m air
10 m atm
m water
8.206
298.15K
K mole
2.35 10 g Benzene
5.55

10

atm

MA = 2.35 x 10-2 g Benzene in soil air

CS

MS

CW K OC

g
L water
m water
56.23
0.001
m water
kg oc
L water
g Benzene
0.029
kg oc
0.517

CW K OC VT fOC S

g
L water
m water
56.23
1.0 m soil 0.001
m water
kg oc
L water
kg oc
kg soil solids
0.02
1,500
0.873 g Benzene
kg soil solids
m soil
0.517

.
87.3 % of Benzene is adsorbed to soil organic carbon.
10.3 % of Benzene is dissolved in soil water.
2.35 % of Benzene is in soil air.