Chapter 3

Material & Energy

Balance
Eskedar T. (AAiT-CED)
Materials and Energy
Balances
Tools for quantitative understanding of the
behavior of environmental systems.
For accounting of the flow of energy and
materials into and out of the environmental
systems.
Materials and Energy
Balances
Material Balance Energy Balance

Pollutant Energy
modeling
production, transport, and fate
 Unifying Theories
onservation of Matter

The law of conservation of matter states that

(without nuclear reaction) matter can neither
be created nor destroyed.
We ought to be able to account for the
matter at any point in time.
The mathematical representation of this
accounting system is called a materials
balance or mass balance.
 Unifying Theories
onservation of Energy

The law of conservation of energy states that

energy cannot be created or destroyed.
Meaning that we should be able to account
for the energy at any point in time.
The mathematical representation of this
accounting system we use to trace energy is
called an energy balance.
Material Balances
The
simplest form of a materials balance or
mass balance

Accumulation = input output

input
Accumulation output
Environmental System
(Natural or Device)
The control volume
Control Volume

Consumer Food to
goods Accumulation people

Solid
Waster
Examples of Control
Volume
Time as a factor

Mass rate of accumulation =

Mass rate of input Mass rate of output
Example 3.1
Selam is filling her bathtub but she forgot to put
the plug in. if the volume of water for a bath is
0.350 m3 and the tap is flowing at 1.32 L/min
and the drain is running at 0.32 L/min, how long
will it take to fill the tub to bath level? Assuming
Selam shuts off the water when the tub is full
and does not flood the house, how much water
will be wasted? Assume the density of water is
1,000 kg/m3
 Solution

Vaccumulation
Qin = 1.32 L/min Qout = 0.32 L/min

We must convert volumes to masses.

Mass = (volume)(density)
Volume = (flow rate)(time) = (Q)(t)
Solution
From mass balance we have
Accumulation = mass in mass out
(Vacc)() = (Qin)()(t) - (Qin)()(t)
Vacc = (Qin)(t) (Qin)(t)
Vacc = 1.32t 0.32t
350L = (1.00 L/min)(t)
t= 350 min or 5.833 hr
The amount of wasted water is
Waste water = (0.32)(350) = 112 L
 Efficiency
Mass
Mass flow rate = (concentration)(flow rate)
time
dM
Mass balance cinQin coutQout
dt
dM dt Cin Qin Cout Qout
Efficiency of a system
Cin Qin Cin Qin

mass in mass out

OR mass in
 Example
The air pollution control equipment on a municipal waste
incinerator includes a fabric filter particle collector (known as a
baghouse). The baghouse contains 424 cloth bags arranged in
parallel, that is 1/424 of the flow goes through each bag. The gas
flow rate into and out of the baghouse is 47 m 3/s, and the
concentration of particles entering the baghouse is 15 g/m 3. In
normal operation the baghouse particulate discharge meets the
regulatory limit of 24 mg/m3.
Calculate the fraction of particulate matter removed and the efficiency
of particulate removal when all 424 bags are in place and the
emissions comply with the regulatory requirements. Estimate the
mass emission rate when one of the bags is missing and recalculate
the efficiency of the baghouse. Assume the efficiency for each
individual bag is the same as the overall efficiency for the baghouse.
 Solution
Cout = 24 mg/m3
Qout = 47 m3/s
Baghouse
Cin = 15 g/m3
Accumulation =
Qin = 47 m3/s particle
removal

Hopper
 Contd

= (15,000mg/m3)(47m3/s)-(24mg/m3)(47m3/s)=703,872 mg/s
The fraction of particulates removed is

The efficiency of the baghouse is

=
=99.84%
 Contd
Cin = 15 g/m3 Cemission= ?
QBypass =(1/424)( 47 m3/s) Qemission= 47 m3/s

Bypass

Baghouse Cout= ?
Qout= (423/424)47 m3/s
Cin = 15 g/m3
Qin =( )( 47 m3/s)

=?
Control Volume
Contd

A control volume around the baghouse alone reduces the number of
unknowns to two:
Because we know the efficiency and the influent mass flow rate, we can
solve the mass balance equation for the mass flow rate out of the filter.
Cin Qin Cout Qout

Cin Qin

Solving for CoutQout

CoutQout =(1- )CinQin= (1-0.9984)(15,000mg/m3)(47m3/s)()
=1,125mg/s
 Contd
Effluent

Bypass
=
CinQin from bypass +CinQin from baghouse-CemissionQemission

Because there is no accumulation in the junction

=0 and the mass balance equation
From baghouse
CoutQout=CinQin from bypass +CinQin from baghouse
= ( 15,000mg/m3
)(47m 3
/s)(1/424)+1,125=2788 mg/s
The concentration in the effluent is
= = 59 mg/m3

The overall efficiency of the baghouse with missing bag is

== 99.61%
Exercise
A storm sewer is carrying snow melt
containing 1.200 g/L of sodium chloride into a
small stream. The stream has a naturally
occurring sodium chloride concentration of 20
mg/L. If the storm sewer flow rate is 2.00
L/min and the stream flow rate is 2.0 m3/s,
what is the concentration of salt in the stream
after the discharge point? Assume that the
sewer flow and the storm flow are completely
mixed, that the salt is a conservative
substance (it does not react) and that the
Reaction Order and Reactors
kinetic reactions : reactions that
are time dependent.
Reaction kinetics: the study of
the effects of temperature,
pressure, and concentration on the
rate of a chemical reaction.
Rate of reaction
The rate of reaction, ri, the rate of formation
or disappearance of a substance.
+r, r=-KCn
Homogenous reactions. single phase
reactions
Heterogeneous reactions : multiphase
reactions (between phases surface)
 Rate of reaction
ri = kf1(T,P);f2([A],[B], )

Rate constant
Concentration of reactant
Assuming that the pressure and temperature are constant
aA + bB cC

Rate of reaction rA = - k[A][b] = k[C]

 Order of reaction
Rate of reaction rA = - k[A][b] = k[C]
order of reaction = + ,
the order with respect to reactant A is , to B is , and to product C is
.
rA = -k zero-order reaction
rA = -k[A] first-order reaction
rA = -k[A2] second-order reaction
rA = -k[A][B] second-order reaction
Order of reaction
Types of Reactors
batch reactors and flow
reactors.
fill-and-draw
material flows into, through,
and out of the reactor
Unsteady state
Flow reactors
IDEAL REACTORS REAL REACTOR
Steady-state conservative system
Conserved system: where no chemical or
biological reaction takes place and no
radioactive decay occurs for the substance in
the mass balance.
Steady-state:
Input rate = Output rate Accumulation =0
Steady-state conservative system

Decay rate = 0
Accumulation rate = 0
Qs
Stream
Qm
Cs Mixture
Cm
Qw
Wastes Q = flow rate
Cw C = concentration

CsQs + QwCw = QmCm

Including reactions
For
non-conservative substances
Accumulation rate = input rate output
rare transformation rate
 Simple completely mixed systems
With first-order reactions
Total mass of substance = concentration x volume
when V is a constant, the mass rate of decay of the
substance is

first-order reactions can be described by r = -kC=dC/dt,

 Example
A well-mixed sewage lagoon is receiving 430 m 3/d of
sewage out of a sewer pipe. The lagoon has a
surface area of 10 ha and a depth of 1.0m. The
pollutant concentration in the raw sewage
discharging into the lagoon is 180 mg/L. The organic
matter in the sewage degrades biologically in the
lagoon according to first-order kinetics. The reaction
rate constant is 0.70 d-1. Assuming no other water
losses or gains and that the lagoon is completely
mixed, find the steady-state concentration of the
pollutant in the lagoon effluent.
 Solution
Decay

Cin = 180 mg/L Sewage Cef = ?

Qin = 430 m3/d Lagoon Qef = 430 m3/d

Control volume

Accumulation=input rate output rate decay rate

Assuming steady-state condition, accumulation = 0
input rate = output rate + decay rate
CinQin = CeffQeff + (K)(Clagoon)(V)
Ceff=1.10mg/ L
 Batch reactors

d (in ) d (out )
dM/dt = ? 0
dt dt
dM
kCV
dt
dM dC dC
V kC C Co e kt
dt dt dt
 Plug-flow reactors

Mass balance for each plug element

dM d (in ) d (out ) d (C )
V
dt dt dt dt
No mass exchange occurs across the plug
boundaries, d(in) and d(out) = 0

dM dC dC kt
V kC Cout Cin e
dt dt dt
 Plug-flow reactors
k
Cin Cout e Residence time

L=length
The residence time for each plug:
( L) ( A) V

(u ) ( A) Q
Cout ( L) V
ln k k k
Cin (u ) Q
Example
A wastewater treatment plant must disinfect its
effluent before discharging the wastewater to a near-by
stream. The wastewater contains 4.5 x 105 fecal
coliform colony-forming units (CFU) per liter. The
maximum permissible fecal coliform concentration that
may be discharged is 2,000 fecal coliform CFU/L. It is
proposed that a pipe carrying the wastewater be used
for disinfection process. Determine the length of the
pipe required if the linear velocity of the wastewater in
the pipe is 0.75 m/s. Assume that the pipe behaves as
a steady-state plug-flow system and that the reaction
rate constant for destruction of the fecal coliforms is
-1
 Solution

Cin=4.5x105 CFU/L Cout=2,000 CFU/L

U=0.75 m/s U=0.75 m/s

Using the steady-state solution on the mass-balance equation, we obtain

Cout L
ln K
Cin u
2000CFU / L 1 L
ln 23 min
4.5 x105 CFU / L (0.75m / s )(60 s / min)

Solving for the length of pipe, we have

ln(4.44x10-3)=-0.23min-1
L=1,060m
 Example
A contaminated soil is to be excavated and treated
in a completely mixed aerated lagoon. To
determine the time it will take to treat the
contaminated soil, a laboratory completely mixed
batch reactor is used to gather the following data.
Assuming a first-order reaction, estimate the rate
constant, k, and determine the time to achieve 99
% reduction in the original concentration.
Time (d) Waste Concentration (mg/L)
1 280
16 132
 Solution
Using the 1st and 16th day, the time interval t=
16-1 = 15 d
Ct 132mg / L k (15d )
e kt e
Co 280mg / L
Solving for k, we have k = 0.0501 d-1
To achieve 99 % reduction the concentration at
Time t must be 1 0.99 of the original concentration
Ct
0.01 e 0.05( t ) t = 92 days
Co
 Step function response
Concentration, Cin

0 0 0
Time Time Time
Step increase Step decrease pulse/spike increase
 Batch reactor
Concentration, Cin

0 1/k 1/k
Time Time Time
Decay Formation
Ct kt
e
Co
 CMFR Conservative
C1 C1
Concentration, Cin

Concentration, Cin
-0.37C0 + 0.63C1

C0
C0

0 0 t=
Time Time
Influent concentration Effluent concentration
Concentration, Cin

Concentration, Cin
C0
C0

0.37C0
 CMFR Conservative
Forbalanced flow (Qin = Qout) and no
reaction, the mass balance becomes
dM
cinQin coutQout
dt
Where M = CV. The solution is
t t
Ct C0 exp C1 1 exp

Where = V/Q
 CMFR Conservative
Flushing
of nonreactive contaminant from a
CMFR by a contaminant-free fluid
Which means Cin = 0 and the mass balance
becomes
dM
coutQout
dt
Where M = CV. The initial concentration is C0=M/V
t
For time t 0 we obtain Ct C0 exp

Exercise
Before entering an underground utility vault to do
repairs, a work crew analyzed the gas in the vault
and found that it contained 29mg/m 3 of H2S.
Because the allowable exposure level is 14 mg/m 3
the work crew began ventilating the vault with a
blower. If the volume of the vault is 160 m 3 and
the flow rate of contaminant-free air is 10 m 3/min,
how long will it take to lower the H2S level to that
will allow the work crew to enter? Assume the
manhole behaves as CMFR and that H 2S is
nonreactive in the time period considered.
 CMFR NonConservative
For
balanced flow (Qin = Qout) and first-order
reaction the mass balance becomes
dM
CinQin CoutQout kCoutV
dt
Where M = CV. By dividing with Q and V we have

dC 1
Cin Cout kCout
dt
 CMFR NonConservative
For stead-state conditions dC/dt=0
Co Co
Cout Cout
1 k OR 1 k
Decay Formation
Co Co
Concentration, Cin

Concentration, Ceff
0 0
Time Time
 CMFR NonConservative
A step decrease in influent concentration
(Cin=O)
for non-steady-state
dM conditions with first-
order decay 0 CoutQout kCoutV
dt
Where M = CV. By dividing with Q and V we have

dC 1 Co
k Cout Cout Co exp t
dt 1 k
 CMFR NonConservative
Concentration, Cin

Concentration, Cin
C0
C0

0
0
Time
Time
Effluent concentration
Influent concentration
Example
A chemical degrades in a flow-balanced, steady-state
CMFR according to first-order reaction kinetics. The
upstream concentration of the chemical is 10 mg/L and the
downstream concentration is 2 mg/L. Water is being treated
at a rate of 29 m3/min. The volume of the tank is 590 m3.
What is the rate of decay? What is the rate constant?
 Solution
For a first-order reaction, the rate of decay, r =-
kC, thus we have to solve for kC from
dM
CinQin CoutQout kCoutV
dt
For steady-state, dM/dt = 0 and for balanced
flow, Qin = Qout
CinQin CoutQout (10mg / L 2mg / L)( 29m 3 / min)
r kC
V 580m 3
r=kC=0.4
Solution
For a first-order reaction in a CMFR
Co
Cout
1 k
The mean hydraulic detention time is
V 580m 3
3
20 min
Q 29m / min
Solving for the rate constant we get
(Co / Cout ) 1 (10mg / L / 2mg / L) 1 1
k 0.20 min
20 min
Mini Project

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Last Date of Submission: June , 2011