CEVE 310/510

PRINCIPLES OF ENVIRONMENTAL
ENGINEERING
Lecture 2:
Mass Balances

MATERIALS BALANCE

Expression of the law of conservation of mass.

Important to assess fate and transport of pollutants

and design treatment reactors

Many approaches to solving these problems

Translating problem statement into correct diagram is key

Many different types of systems

Steady State and Conservative Pollutant

Steady State and Non-Conservative Pollutant

Transient Systems

BASIC CONCEPT

Steady-state implies accumulation = 0

(Time invariant, the concentration remains constant
with time at a given point in the system, typically
requiring constant inputs and outputs, although it
can vary spatially from one point to another)
Steady state equilibrium

Conservative implies decay = 0

(The pollutant may be recalcitrant to biological or
chemical degradation, or it may be in chemical
equilibrium)

STEADY STATE AND CONSERVATIVE POLLUTANT

This is the simplest system

Input = output

The pollutant does not react (conservative)

Concentration does not vary with time (steady-state)

Basic equation of material balance:

Usually given as rates, but could also mean mass.

Mass flow rate =

Q C
(L3/T) (M/L3)

Write equation (input = output) for overall system

and components, then solve

EXAMPLE: PROBLEM 1.7

River with salt serves as water supply. For drinking, salt
500 ppm. To this end, supply is diluted with fresh water.
How much fresh water is needed to dilute Q?
R m3 /s
500 ppm
f Q m3/s
0 ppm
25 m3/s
400 ppm

Q m3/s
Cr ppm
agricultural drainage
5 m3 /s
2,000 mg/L

EXAMPLE (CONTINUED)

To simplify break this into two domains: drainage

confluence and intake points

Write equations for water flows and for salt at confluence:

In Out
Overall flows :
25 m3 / s 5 m3 / s Q m3 / s

25.0 m3/s
400 ppm

Q m3/s
Cr ppm

Q 30 m3 / s
Salt balance :
(25 m3 / s )(400 ppm) (5 m3 / s )(2000 ppm)

5.0 m3/s
2000 ppm

(Q m3 / s )(Cr ppm)
Q 30 m3 / s;
(25)(400) (5)(2000)
Cr
30
Cr 667 ppm

EXAMPLE (CONTINUED)

Solve the other part of the system (intake)

In Out
Flow Balance : Qin Qout
Q fQ R
R 30.0 fQ

R m /s
Cd =500

Material Balance :
3

f Q m /s
Cf =0 ppm
Q = 30 m3/s
Cr =667 ppm

in

Cin Qout Cout

Q Cr fQ C f R Cd
30*667 fQ *0 (30 fQ) *500
20, 000 15, 000 500* fQ
fQ=10 m3 /s and since Q=30 m3 /s.
f = 1/3

STEADY STATE AND

NON-CONSERVATIVE POLLUTANT

What if a substance reacts by chemical, biological

or nuclear processes?

Input = Output does not hold

Now: Input = Output + Decay

Assume decay rate is proportional to concentration

(1st order decay)

dC = -KC
dt
k = reaction rate coefficient (units = 1/time)
The order of the reaction refers to the exponent to which the
independent variable is raised

STEADY STATE AND

NON-CONSERVATIVE POLLUTANT

Integrate:

dC = t -K dt

C C
0
0

For a batch system, the solution is:

C = C 0 e -Kt

Co

t
We will see this exponential form again, and often.

STEADY STATE AND

NON-CONSERVATIVE POLLUTANT

Weareinterestedinthedecayrate(mass/time)
dM/dt=d(CV)/dt=V(dC/dt)=V(KC)

K hasunitsof1/time

C hasunitsofmass/volume

V hasunitsofvolume

Decayrate=KCV(mass/time),assumescompletelymixed,
incompressiblefluid.

Materialbalanceequation:
Inputrate=Outputrate+KCV

Besuretoreadexample1.4inthetext.

EXAMPLE
Lakewithaconstantvolumeof107 m3 isfedbya
cleanstreamataflowof50m3/s.Afactory
dumps5.0m3/sofanonconservativewasteat
100mg/Lintothelake.Thepollutanthasadecay
ratecoefficient(k)of0.25/day.
Findthesteadystateconcentrationofthe
pollutantinthelake.

EXAMPLE (CONTINUED)

Solution: Start by drawing a diagram

Qf = 5 m3/s
Cf = 100 mg/L
Qs = 50 m3/s
Cs = 0 mg/L

V =10 m

Qout
Cout

K = 0.25 /day

Assume that the lake has a constant volume

Thus, for water balance

Outflow = Inflow

EXAMPLE (CONTINUED)
In Out
Flow Balance : Qin Qout
QS QF Qout

Qf = 5 m3 /s
Cf = 100 mg/L

V =107 m3

Qout
Cout

C = Cout

Qout 5 50 55 m / s
3

Qs = 50 m3 /s
Cs = 0 mg/L

K = 0.25 /day

Material Balance :

Q C Q C
Q C

C
in

in

out

in

out

out

KCoutV

in

Since lake is completely mixed,

C (in the lake) = Cout

Qout KV

5*100 50*0
55 (0.25 / 3600 / 24) *107
Cout 5.96 mg / L

Note: K was converted from day-1 to second-1.

TRANSIENT SYSTEMS
Consider the following:

A lake with initially 0 concentration of the pollutant,

A pollutant is introduced (source rate = S, mass/time).

How is the concentration changing with time?

(A transient phenomenon - not steady state)

TRANSIENT SYSTEMS

This is called a step function response.

Eventually system reaches a steady state concentration,

C when accumulation (dC/dt) = 0

Accumulation rate = Input rate - Output rate - Decay rate

VdC = S - QC - KCV
dt
0 = S - QC - KCV

S
C() =
Q + KV

TRANSIENT SYSTEMS

Concentration as a function of time (before steady

state is reached) is given by the solution to:

QC
S
dC
=
- KC
V
V
dt

Look for solution with the form:

C0 - C

TRANSIENT SYSTEMS

dC S Q KV C
dt V V
dC Q KV S Q KV C
V Q KV V
dt
dC C S (Q KV )

V
dt Q KV

but

S
C(see previous slide)
Q KV

dC (C C ) (Q KV )

V
dt

(*)

TRANSIENT SYSTEMS
To integrate, we change variables:
Let y = (C C ) so

dy dC (C C ) (Q KV ) from (*)

V
dt
dt

dy
Q

Thus, K y
V
dt

K t
V

y y0e

C(t) [C(0) C ( )]e (K Q /V )t C ()

Valid for transient, completely mixed systems with
pollutants following first-order (exponential) decay

TRANSIENT SYSTEMS
What is the general behavior of this equation?

At time = 0

C(t) [C(0) C ( )]e ( K Q /V )t C ()

Exponential term goes to 1

C = C0

At time =

C(t) [C(0) C ( )]e ( K Q /V )t C ()

Exponential term goes to 0

C = C

TRANSIENT SYSTEMS
General Shape of this equation:

EXAMPLE: 1.8

Bar with volume of 500 m3

Fresh air enters at a rate of 1000 m3/hr

Bar is clean when it opens at 5 pm

Formaldehyde emitted at 140 mg/hr after 5pm

K = 0.40 /hr

What is the concentration at 6 pm? (t = 1h)

EXAMPLE (CONTINUED)

Governing equation:

C(t)[C(0)C()]e(K Q/V )t C()

Given:

Q = 1000 m3/h

V = 500 m3

S = 140 mg/hr

K = 0.40 /hr

C0 = 0 mg/m3

EXAMPLE (CONTINUED)

Find C, Steady State with Decay

S
C
Q KV
140.0mg / hr

3
3
1000.0 m / hr 0.40 / hr 500 m
0.117 mg / m3
This represents the maximum concentration that would be reached

EXAMPLE (CONTINUED)

Interested in concentration at 6 PM
(one hour after bar opens)

Use:
C(t)[C(0)C()]e(K Q/V )t C()

C (t ) (0 0.117)e (0.401000.0 / 500.0)t 0.117

C (t ) 0.117(1 e 2.4t )
C (1) 0.117(1 e 2.4(1) )

EXAMPLE (CONTINUED)
What if K = 0?

Recalculate C

S
C ( )
Q KV
140.0mg / hr

1000.0 m3 / hr 0 / hr 500 m3
3

mg / m

EXAMPLE (CONTINUED)

Use:
C(t)[C(0)C()]e(K Q/V )t C()

C (t ) (0 0.140)e

(0 1000.0/500.0) t

C (t ) 0.140(1 e

2.0 t

C (1) 0.140(1 e

2.0(1)

0.121 mg / m3

)
)

0.140

EXAMPLE (CONTINUED)
What if Q = 0?

Recalculate C

S
C ( )
Q KV
140.0mg / hr

0 m3 / hr 0.40 / hr 500 m3
0.70 mg / m3

EXAMPLE (CONTINUED)

Use:
C(t)[C(0)C()]e(K Q/V )t C()

C (t ) (0 0.70)e

(0.40 0/500.0) t

C (t ) 0.70(1 e

.40 t

C (1) 0.70(1 e

.40(1)

0.23 mg / m3

)
)

0.70

ANOTHER EXAMPLE
New factory opens discharging pollutant B at 1m3/s, 42 mg/L.
If K is 0.4/day, what is the concentration after 1 week?
1 m3 /s
42 mg/L
pollutant B

V = 1010 m3
C(7 days) = ?
S = (42 mg/L)(1 m3/s)

5 m3/s
0 mg/L

10

V =10 m

(103 L/m3)(3600*24 s/day)

S = 3.628 109 mg/day
Q = 56 m3/s = 4.838 109 L/day
K = 0.4 /day
C(0) = 0

50 m3 /s
0 mg/L
K = 0.4 /day

??

EXAMPLE (CONTINUED)

First, find C

S
C
Q KV
3.628 109 mg / day

4.838 109 L / day 0.4 / day 1010 L

0.410 mg / L

EXAMPLE (CONTINUED)

Use:
C(t)[C(0)C()]e(K Q/V )t C()

C (t ) (0 0.410)e

(0.4 4.838109 /1010 ) t

C (t ) 0.410(1 e .884t )
C (7) 0.410(1 e .884(7) )
0.409 mg / L after 1 week

0.410

EXAMPLE URBAN AIR POLLUTION

(BOX MODEL)

100 km

Q, C0 = 0

C=?

1 km

P = 10 kg/s

k = 0.2 h-1 = 5.56 x 10-5 s-1

Horizontal wind speed: u = 4 m/s

Q, C

EXAMPLE (CONTINUED)

Note:

Q has units of volume / time = length3 / time

u has units of length / time

A has units of length2

Therefore, Q = u*A = wind speed * cross-sectional area

Q = (4 m/s)(100 x 1 km2) x 1 km / 1000 m = 0.4 km3/s

EXAMPLE (CONTINUED)

Mass balance: Steady state with decay, completely mixed

Accum. Rate = Input Rate Output Rate Decay Rate

0 [QC0 P ] QC KCV
kg
km3
0 [0 10 ] (0.4
) * C (5.56 105 s 1 ) * C * (100 100 1 km3 )
s
s
kg
km3
km3
C 0.556
C
0 10 0.4
s
s
s
kg
km3
C
0 10 0.96
s
s
kg
10
C
10.4 3
0.96
km
g
10.4 3
m

EXAMPLE: 10.13 MASS BALANCE

Corn is used to make alcohol. Input is 800 kg/h
of corn into still, it contains 11.3% alcohol,
83.9% water, and inert materials. Finished
product is 12.6% of feed (by mass) and
contains 73.1% alcohol, 26.2% water, and
0.7% inert.
What is quantity and composition of the
bottoms?

EXAMPLE (CONTINUED)
First, diagram:

Product
(0.126)(800) =

Corn Feed

Condenser

800 kg/h

100.8 kg/h

11.3 % Alcohol

73.17 % Alcohol

83.9 % Water

26.20 % Water

4.8 % Inert

0.7 % Inert

Still
Bottoms
B kg/h
X % Alcohol
Y % Water
Z % Inert

EXAMPLE (CONTINUED)

Rate of Input = Rate of Output

Solution:

Overall Balance:

800 100.8 B
B 699.2 kg / h

Alcohol Balance:

X
(0.113)(800) (0.731)(100.8)
(699.2)
100
90.4 73.685 ( X )(6.992)
X 2.39 %

EXAMPLE (CONTINUED)

Solution (continued)

Water Balance:

(0.839)(800) (0.262)(100.8)
Y 92.22 %

Then:

Z 100 X Y
Z 100 2.39 92.22
Z 5.39 %

Y
(699.2)
100

EXAMPLE (CONTINUED)

Therefore, Bottoms:

699.2 kg/h

2.39 % Alcohol

92.22 % Water

5.39 % Inert