COLLEGE OF

Engineering

DEPARTMENT OF
Civil and Environmental
Engineering

• CENG241
Environmental Engineering and Science
• Hamdan Hamdan
• [email protected]

• Lecture 2: Mass Balance

APPLICATIONS

• Hydrologic Balance
• “Rational Method” for Predicting
Runoff
• Volume of Retention Ponds &
Reservoirs
• Reactor Design
• Water Treatment
• Wastewater Treatment
• Air Pollution Control
• Oxygen Balance in Streams & Rivers
• Waste Audits in Hazardous Waste
APPLICATIONS

1. Hydrologic Balance
APPLICATIONS

2.“Rational Method” for

Predicting Runoff
APPLICATIONS

3. Volume of Retention Ponds

& Reservoirs
APPLICATIONS

• 4. Reactor Design
• Water Treatment
• Wastewater Treatment
• Air Pollution Control
APPLICATIONS

• 5. Oxygen Balance in
Streams & Rivers
APPLICATIONS

• 6. Waste Audits in Hazardous

Waste
 • Analogous to Balancing Checkbook
• Balance = Deposit - Withdrawal
Concept • or
• Deposit - Withdrawal - Balance = 0
 • A series of actions or steps taken in order to achieve a particular
end
• Ex: A chemical process: a method of changing one or more
chemicals or chemical compounds → chemical reactions
process • Types of diagrams (help in understanding mass balances)
• Block Diagram
• Flow Diagram
• P&ID Diagram
Block Diagram

• A simple diagram that

• “shows at a glance” the
process
• Most used for MB solving; it
shows
• Flows
• Units of operations
• Some additional important
data and information
 • Recommended for
Flow diagram • “General” information
P&ID Diagram

• Pipe and Instrumentation Diagram

• The “formal language” for a
diagram
 Unit Operation

• Basics Process Step in process engineering

• Unit operations involve: Physical

changes or chemical transformations
• Ex: Separation, settling, evaporation,
filtration, other reactions, even heat
exchange

• Environmental systems

• Processes can add or remove material

• Ex:
• Lake and pollutants
• Water and wastewater treatment
processes
 Process variable

• A process variable, value or parameter

• Is the current status of a process
under control

• Example:
• Temperature of a furnace
• Concentration of pollutant in a lake

• Typical P.V.
• Pressure
• Volume
• Temperature
• Concentration (Ex. Of a pollutant in a
water body)
• Flow
• Etc.
 Flow: mass, moles,
volume…
• Flow: how much quantity of something is
flowing over time:

• Mass flow (kg/s) = mass flow per unit

time
• Mole flow (mol/s) = mole flow per unit
time
• Volume flow (m3/s) = Volume flow per
unit time
• Flow (Q) = amount (Ex. Volume)/time
• Q=V/t
 System State
• Steady State

• Typical for continuous

processes

• Transient state
• Also known as
unsteady/non-steady state
• Typical for batch and semi-
batch processes
• When any of the variables
change with time
• Ex: 10 L of mixture is fed into
a pot; after 5 hours, the
volume left is 2 L
 Classification of
Processes

• Batch Process
• Process is being fed once,
then time lapses, then the
process products are
removed

• Continuous process:
• Inputs and outputs
flow/react continuously
throughout the duration
of the process

• Semi-Batch
• Combination of bath and
continuous processes
 Types of systems

• Open systems
• Inlet/outlet of materials to system
• Closed system
• No inlet/outlet of materials
• Isolated system
• No inlet/outlet of materials
• No inlet/outlet of energy to the systems
Mass balance
principle

• Mass can neither be

created nor destroyed

• Can only be
transformed
 The mass balance
equation
• General Mass Balance Equation
• Inlet – outlet + production – consumption = accumulation

• Mass balance of a certain component within a system

• Inlet(i) – outlet (i) + production (i) – consumption (i) = accumulation (i)
 The mass balance
equation
• Types of mass balances
• Differential
• Integral

• Differential mass balances

• A differential mass balance is used to generate differential equations that can provide an effective
tool for modelling and understanding the target system.
• Used usually to address velocities
• usually solved in two steps:
• first, a set of governing differential equations must be obtained,
• then these equations must be solved

• Integral Mass Balances

• Occur between 2 instances
• Used for quantities rather than velocities
• Typical for batch processes
 • No accumulation (no differential equations!!)
Steady State MB
• Inlet – outlet + production – consumption = 0
 • No inlet/outlet; closed system
Batch MB • Production, consumption and accumulation
• in – out + P – C = Accumulation
Diagram Flow
Construction

• Look for information

• Organize and draw

• Unit operation blocks or “box”

• Flows are arrows

• No matter size/direction of
arrows
• In the end: MB must balance
out between input and
output
• Simplest example is a
balanced chemical equation
 • No reaction in the system
• Production=0
Non-reactive • Consumption=0
systems • It is a steady state
• Hence accumulation=0
IN ENVIRONMENTAL SYSTEMS
Accumulation of mass = Input of mass – Output of mass
 • A. Draw a flowchart to show Inputs,
Outputs, and Accumulation
PROBLEM
• B. Mark system boundaries (Similar to Free
SOLVING Body Diagrams)
APPROACH • C. Example: Mark boundaries around
watershed as shown in next slide
 Mass Balance Concept Example

River
Lake River

Stream

Groundwater

Mass balance for water in the lake in this system can be simplified to:
Mass Out (Evaporation)

Mass in or Water in (river) Mass out or Water Out (river+ stream)

Lake

Mass in/Out or Water in /out (seepage to

and from Groundwater)
 D. Identify inputs,
outputs and
accumulations

QP QE QT

Qout
Qin

Storage QIout
QIin
(Qs) QR
E. Convert Concentrations and
Flow Rates to Mass Units

• Example Calculation of Mass

• a. Flow
• Mass = (Flow) (Density) (Time)
• 1 m3/d = ? kg
• Mass = (1m3/d) (1000 kg/m3) (1d) = 1,000
kg

• b. Compounds in Water
• Mass = (Concentration) (Volume)
• 1 mg/L in 1 m3 = ? Mg
• Mass = (1 mg/L) (1 m3) (1,000 L/m3) =
1,000mg
F. Write Mass Balance 1. Inputs
Equation to Account 2. Outputs
for:
3. Accumulations
D. Verify That System “Closes” or
Balances
Input of mass – Accumulation of Mass – Output of Mass = 0
A simple example
• Mr. and Mrs. Green have no children.
• In an average week they purchase and bring into their
house approximately 50 kg of consumer goods (food,
magazines, newspapers, appliances, furniture, and
associated packaging).
• Of this amount, 50 percent is consumed as food.
• Half of the food is used for biological maintenance and
ultimately released as CO2; the remainder is discharged
to the sewer system.
• The Greens recycle approximately 25 percent of the
solid waste that is generated.
• Approximately 1 kg accumulates in the house.
• Estimate the amount of solid waste they place at the
curb each week.
Solution
• Begin by drawing a
mass balance
diagram and labeling
the known and
unknown inputs and
outputs.
Time as a Factor
Rate • “Rate” Means “Change With Respect to Time” so,
Concept • Rate of Accumulation of mass = Rate of Input of mass – Rate of Output of mass
 In Calculus

dM d(In) d(Out)
= −
dT dT dT
Steady state
• condition called steady state.
• system has rate of input and rate of output
constant and equal
• and hence the rate of accumulation is zero:
(i.e., dM/dt 0)

• solving mass-balance problems

• convenient to assume steady-state conditions
have been achieved

• steady state does not imply equilibrium

• water running into and out of a pond at the
same rate is not at equilibrium, otherwise it
would not be flowing.
• if there is no accumulation in the pond, then
the system is at steady state.
 Mixing status of
systems

• If a system is completely mixed

• we may assume that output
from system (concentration,
temperature, etc.) is same as
contents within system
boundary.

• we frequently make use of

assumption of complete mixing
to solve mass-balance problems
• very difficult to achieve in
real systems
 Plug-Flow systems

• In terms of fluid flow

• each drop of fluid along the direction
of flow remains unique and, if no
reactions take place, contains the
same concentration of material or
physical property that it had when it
entered the plug-flow system.
• Mixing may or may not occur in the
radial direction.
• Same as completely mixed systems
• ideal plug-flow systems don’t happen
very often in the real world
 • Same as above but often requires selection of
“convenient” time interval
Problem Solving
Approach • Examples of Convenient Time intervals
• m3 / d →convenient →1 day
• L / s →convenient →1 s
Example
• Truly Clearwater 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 Truly 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
Mass Balance With
Transformations
• Examples
• 1. Softening Water
• a. Input → Ca(HCO3)2
• b. Reaction → CaCO3
• 2. Change of O2 in Stream
• a. Input → O2
• b. Microorganisms Use O2→CO2

• IN THESE INSTANCES
• THE PREVIOUS EXPRESSION SHOWS ONLY THAT
Ca(HCO3)2 OR O2 “DISAPPEARED”!
 MASS BALANCE
WITH
TRANSFORMATION
• Rate of accumulation of mass =
Rate of input of mass
- Rate of output of mass
+ Rate of transformation of mass
•Time Dependent
Reactions are
called “Kinetic
Reactions”
•“Stoichiometric Reactions” are those that have achieved equilibrium.

•Transformation rate is described by the “Reaction Rate” ‘r’

•Reaction rate r is function of Temperature, Pressure, Reacting components or

Products, etc.
 Including reactions

• Accumulation rate=
• input rate - output rate + transformation rate

• Time-dependent reactions
• are called kinetic reactions.

• rate of transformation
• or reaction rate: (r)
Including reactions
• In many environmental problems, for example: oxidation of organic compounds by
microorganisms and radioactive decay
• reaction rate, r, may be assumed to be directly proportional to the amount of
material remaining, that is the value of n=1.
• This is known as a first-order reaction.

• first-order reactions
• rate of loss of the substance is proportional to the amount of substance present at
any given time, t.

• Degradation of environmental pollutants in nature

• usually follows first-order decay
First-order • The minus sign before reaction rate, k,
kinetics • indicates the disappearance of a substance or
chemical species
derivation
First-Order kinetics in environmental
systems
 Example: MB with
decay
• A well-mixed sewage lagoon (a shallow pond) is receiving
430 m3/d of sewage out of a sewer pipe.

• The lagoon has a surface area of 10 ha (hectares) and a

depth of 1.0 m.

• The pollutant concentration in the raw sewage discharging

into the lagoon is 180 mg/L.

• The organic matter in the sewage degrades biologically

(decays) in the lagoon according to first-order kinetics.

• The reaction rate constant (decay coefficient) is 0.70/d.

• Assuming no other water losses or gains (evaporation,

seepage, or rainfall) and that the lagoon is completely
mixed, find the steady-state concentration of the pollutant
in the lagoon effluent.
Solution
Plug-Flow with
Reaction.
• As noted in Figure 2-1, in plug-flow systems
• “plug” element of fluid does not mix with the fluid ahead or behind it.
• However, a reaction can take place in system (Ex. car tank in the example)
• even at steady state
• contents within the element can change with time as the plug moves downstream.
• The control volume for the mass balance is the plug or differential element of fluid.
• The mass balance for this moving plug may be written as:
Example
• A wastewater treatment plant must disinfect its effluent
before discharging the wastewater to a near-by stream.

• The wastewater contains 4.5x105 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 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 0.23/mm.
 Reactors
• Reactors
• The tanks in which
physical, chemical, and
biochemical reactions occur, for example, in water softening and wastewater treatment

• reactors are classified based on

• flow characteristics
• their mixing conditions

• Batch reactors: fill-and-draw type

• materials are added to the tank (Figure 2-2a) → Materials mixed for sufficient time to allow
the reaction to occur (Figure 2-2b) → Content then drained (Figure 2-2c).
• reactor is well-mixed and contents are uniform at any instant in time
• composition within tank changes with time as reaction
proceeds

• A batch reaction is unsteady

• Because there is no flow into or out of a batch reactor
 CSTR
• Flow reactors have a continuous type of operation:
• material flows into, through, and out of the reactor at all times.

• Flow reactors may be further classified by mixing conditions.

• completely mixed flow reactor (CMFR): also called a continuous-
flow stirred tank reactor (CSTR): ideally are uniform throughout
the tank.
• composition of effluent is same as composition in tank.

• If the mass input rate into the tank remains constant

• composition of the effluent remains constant.
• mass balance for a CMFR is described by Equation 2-16: Hence
similar approach to environmental systems
 Plug-flow
reactors
• In plug-flow reactors (PFR)
• fluid particles pass through the tank in sequence
• Those that enter first leave first

• In ideal case, it is assumed that no mixing occurs in the lateral

direction.
• Although composition varies along the length of the
tank, if flow conditions remain steady, the composition
of the effluent remains constant.
• A schematic diagram of a plug-flow reactor is shown in
Figure 2-4.

• The mass balance for a PFR is described by Equation 2-18

• time element (dt) is the time spent in the PFR as
described by Equation 2-23 (can be converted to
distance along the reactor)

• In ideal reactors
• average time in the reactor (detention time or retention
time or, for liquid systems, hydraulic detention time or
hydraulic retention time) is defined as (2-27)
 Batch Reactor
• Laboratory experiments are often conducted in batch reactors
• because they are inexpensive and easy to build.

• Industries that generate small quantities of wastewater (less

than 150 m3/d)
• use batch reactors because they are easy to operate and
provide an opportunity to check the wastewater for
regulatory compliance before discharging it.

• Because there is no influent to or effluent from a batch

reactor
• introduction of a conservative substance into the reactor
either as a step increase or a pulse results in an
instantaneous increase in concentration of the
conservative substance in the reactor.

• The concentration plot is shown in Figure 2-6.

• Because there is no influent or effluent, for a
nonconservative substance that decays as a first-order
reaction, the mass balance is described by Equation 2-26.
Integration yields Eq 2-28
Example
• A contaminated soil is to be excavated
and treated in a completely mixed
aerated lagoon at a Superfund site.
• 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
percent reduction in the original
concentration.
 CMFR
• A batch reactor is used for small volumetric flow rates.

• When water flow rates are greater than 150 m3/d, a CMFR
may be selected for chemical mixing.

• Examples of this application include equalization reactors

to adjust the pH, precipitation reactors to remove metals,
and mixing tanks (called rapid mix or flash mix tanks) for
water treatment.

• Because municipal wastewater flow rates vary over the

course of a day, a CMFR (called an equalization basin)
may be placed at the treatment plant influent point to
level out the flow and concentration changes.

• Some natural systems such as a lake or the mixing of two

streams or the air in a room or over a city may be
modeled as a CMFR as an approximation of the real
mixing that is taking place.
Example
• Before entering an underground utility vault to
do repairs, a work crew analyzed the gas in the
vault and found that it contained 29 mg/m3 of
hydrogen sulfide.
• Because the allowable exposure level is 14
mg/m3 the work crew began ventilating the vault
with a blower.
• If the volume of the vault is 160 m3 and the flow
rate of contaminant-free air is 10 m3/min, how
long will it take to lower the hydrogen sulfide
level to a level that will allow the work crew to
enter?
• Assume the manhole behaves as a CMFR and
that hydrogen sulfide is nonreactive in the time
period considered.
Solution
Other
applications
of material
balances
Additional
considerations
and solved
examples
Long-term persistence of
dangerous components
• Example: toxic chemicals, hazardous wastes, etc.
• Best described by first order decay for most
components.
Example:
Persistence of toxic
chemicals

• Determine the time required

for the concentration of
toluene and Dieldrin spilled in a
shallow leachate treatment
pond to be reduced to one-half
of their original values.
• Assume that the first-order
decay rates for toluene and
Dieldrin are 0.0665/hr and
2.665x10-5/hr, respectively.
 Why would knowing half-life be important?

• Example:
• Agricultural chemicals that
reside for long times in the
agricultural waste products
• solid waste containing traces
of radioactivity is in the form of
syringes, needles, cotton ...
• Certain pollutants in landfills
• Etc.
• Note (figure):
• Each half-life passing results in
loss of half the remaining
amount
• Complete loss of compound
requires a significantly long
time to achieve (infinity)
 1. Draw the inputs and the
outputs
Representative example of 2. Write the proper
corresponding terms for
environmental MB problems inputs and outputs
3. Solve

Very
important
example
Questions