Modelling Fundamentals

Dr. Prateek Sharma

Associate Professor
Department of Natural Resources, TERI University,
10, Institutional Area, Vasant Kunj, New Delhi-110 070
Email: prateeks@teri.res.in
Web site: www.teriuniversity.ac.in
Brief outline of the lecture

 Introduction
 Prerequisites
 Fundamental and derived quantities
 Intensive and extensive properties
 Units and Dimensions
 Concepts of
 System
 Boundary
 Control volume
 Boundary conditions

 Principles of conservation of
 Mass (The material balance approach)
Introduction

When you can measure what you are speaking about, and
express it in numbers, you know something about it; but when
you cannot measure it, when you cannot express it in numbers,
your knowledge is of a meagre and unsatisfactory kind; it may
be the beginning of knowledge, but you have scarcely, in your
thoughts, advanced to the stage of science.

- William Thomson,
Lord Kelvin (1891)
Introduction (contd.)

 Every physical problem has key quantitative aspects.

 For example, it is NOT ENOUGH simply to know that there is pollution

somewhere, for unfortunately, there is pollution almost everywhere.
One needs to know HOW SERIOUS the problem is, if it is getting better
or worse, and HOW MUCH it might be IMPROVED by implementing
various remedial actions.
 These are all quantitative questions for which one would expect
quantitative methods to be useful.

 Therefore, by trying to make precise quantitative statements about

various “problems” (environment included), one will actually develop a
MORE PRECISE and REFINED understanding of the underlying
problems themselves.
Introduction (contd.)

 Modelling is a quantitative science. To describe any physical phenomenon,

measurement of different physical quantities is essential in order to understand
the enormity, “smallness” or the extent of the physical phenomenon/process of
study. This would help us to “control/manage” the phenomenon more efficiently.

 Measurements of any physical quantity involves comparison with a certain

basic, arbitrarily chosen, internationally accepted reference standard called unit.
 The result of a measurement of a physical quantity is expressed by a number (or numerical
measure) accompanied by its unit.

 Although the number of physical quantities that we measure is very large, we

need only limited number of units for expressing all the physical quantities, since
they are interrelated with one another.

 The basic physical quantities that are independent of each other and whose
units of measurement are prescribed by International System of Units (SI) are
known as fundamental or basic quantities.

 All other physical quantities that can be derived from the fundamental quantities
are known as derived quantities.
Fundamental quantities

Fundamental quantity SI unit

Length metre (m)
Mass kilogram (kg)
Time second (s)
Electric current ampere (A)
Thermodynamic temperature kelvin (K)
Amount of substance mole (mol)
Luminous intensity candela (cd)
Fundamental and derived quantities

 The fundamental quantities are described symbols such as (M)

for mass, (L) for length, (T) for time () for temperature.
 The symbols are known as the dimensions of the respective
quantities.
 The dimensions are a code for telling us how the numerical
value of a quantity changes when basic units of measurement
are subjected to prescribed changes.
 Illustration
displacement
velocity time
Force  mass  acceleration  mass   mass 
time time
L
M T  M L T 2
T
which is written as 
M L T 2
Extensive and intensive properties

 The amount of any physical quantity in a physical system is

formally referred to as an extensive property.
 Examples
 Mass, volume, heat, force, etc

 Extensive properties are additive in nature. That is one can simply

add two masses in a container to get the total mass contained in a
container. Thus, mt = m1 + m2

 A quantity that is normalized to a measure of system size is

referred to as an intensive property.
 Examples
 Temperature, density, pressure, concentration, etc
 Intensive properties are not additive in nature. They represent the
“strength” rather than the “quantity” of a physical quantity.
Properties relevant to environmental problems

 Mass and Concentration

 Mass is the amount of a pollutant discharged in a given medium
(physical system – air, water, soil)
 Concentration is the amount of pollutant discharged in a (divided by)
unit volume of the medium.
 Concentration in liquid medium
 Expressed usually in terms of mass of substance (pollutant) per unit
volume of mixture.
 Concentration in gaseous medium
 Expressed usually in terms of volume of gaseous pollutant per unit
volume of air mixture.
 Concentration in liquid and gaseous medium

In liquid medium

Most often the units are mg or g of substance per litre (L) of mixture. At times they
may be expressed in g/m3.
Alternatively,
Concentrations in liquids are expressed as mass of substance per mass of mixture,
With the most common units being parts per million (ppm), or parts per billion (ppb).

1 mg/L = 1 g/m3 = 1 ppm (by weight)

1 g/L = 1 mg/m3 = 1 ppb (by weight

Note
In unusual circumstances, the concentration of liquid wastes my be so high
that the specific gravity of the mixture is affected, in which case a correction
factor may be required:

mg/L = ppm (by weight)  specific gravity of mixture

Contd…

In gaseous medium

For most air pollution work, it is customary to express pollutant concentrations

in volumetric terms.
1 volume of gaseous pollu tan t
For example  1 ppm (by volume)  1 ppmv
10 6 volumes of air

At times, concentrations are expressed as mass per unit volume, such as 1 g/m3
or mg/m3. The relationship between ppmv and mg/m3 depends on the pressure,
temperature, and molecular weight of the pollutant. The ideal gas law helps us to
establish that relationship:

PV = nRT
Where
P = absolute pressure (atm)
V = volume (m3)
n = mass (mol)
R = ideal gas constant = 0.082056 L.atm.K-1.mol-1
T = absolute temperature (K)
Contd…

The mass is expressed as moles of gas.

One mole of any gas has Avogadro’s number of molecules in it

= 6.02  1023 molecules/mol
And has a mass equal to its molecular weight.

K = C + 273

1 atm = 101.325 kPa

1 kPa = 1 bar;
100 Pa = 1 millibar, which is the unit of pressure often used in
meteorology.
Illustration
Find the volume that 1 mol of an ideal gas would occupy at standard temperature
and pressure (STP) conditions of 1 atm and 0C temperature. Repeat the
calculations for 1 atm and 25C.
nRT 1 mol  0.082056 L  atm  K 1  mol 1  273.15 K
V    22.414L
P 1 atm
Solution
For 25 oC
PV = nRT nRT 1 mol  0.082056 L  atm  K 1  mol 1  298.15 K
V    24.465L
P 1 atm

Thus, 1 mol of an ideal gas at 0C and 1 atm occupies a volume of 22.414 L
i.e. 22.414 10-3 m3.
ppm  mol wt
1 mg / m 3  ; (at 0 oC and 1 atm)
Conversion formula 22.414
ppm  mol wt
1 mg / m 3  ; (at 25 oC and 1 atm)
24.465

In general
ppm  mol wt 273.15 K P (atm)
1 mg / m 3   
24.465 T (K ) 1 atm
 Illustration

Express 9.0 ppm CO concentration as

(i) percent by volume; and
(ii) in mg/m3 at 1 atm and 25C

Solution
9.0
(i) Percent CO % CO   100  0.0009%
1 10 6

(ii) In mg/m3

Mol wt of CO = 28

ppm  mol wt
1 mg / m 
3
; (at 25 oC and 1 atm)
24.465
Thus, x ppm will be equal to
x ppm  mol wt 9 ppm  mol wt
 mg / m 3 ; Thus, 9 ppm   10.3 mg / m 3
24.465 24.465
System and Boundary

A “system” can be thought of as a collection of one or more related

objects, where an “object” can be a physical entity with specific attributes
or characteristics.

The system is isolated from its surroundings by the “boundary”, which

can be physical or imaginary.

The objects within a system may or may not interact with each other and
may or may not interact with objects in the surroundings, outside the
boundary.

A system is characterized by the fact that the modeler can define its
boundaries, its attributes, and its interactions with the surroundings to the
extent that the resulting model can satisfy the modelling objectives.
System and Boundary (contd.)

•The largest possible system of all is the universe.

•One can, depending on the modelling goals, isolate a part of the universe
such as a continent, or a country, or a city, or the city’s wastewater
treatment plant, and define that as a system for modelling purposes.

•The “entity” to be studied is considered within the system “boundaries”

and its interaction with the surroundings.

•The boundaries may be fixed or deformable. It may be in motion or at rest

with respect to a chosen co-ordinate system.

•A system diagram shows the system’s boundary and significant

interactions between the system and its surroundings.
Open and closed systems

A system is called a closed system when it does not interact with

the surroundings. In closed systems neither mass nor energy will
cross the boundary.

If the system interacts with the surroundings, it is called an open

system. In open system mass and energy can cross the
boundary.

When mass does not cross the boundary (but energy does), an
open system is referred to as a non-flow system. If mass crosses
the boundary, it is called a flow system.
Control volume and boundary conditions

A control volume is an open-system which has its boundary

fixed with respect to a fixed co-ordinate system.

The CV is thus, an arbitrary volume fixed in space and bounded by

a closed surface which is known as the control surface. The
physical “entity” may enter and leave the control volume by
crossing the bounding surface (the control surface) enabling
transfer of mass, momentum and energy.

The “values” of the physical “entity” under study and the flow
characteristics at the boundaries of the hypothetical or the real
surface define the boundary conditions.
Material balance – Law of conservation of
matter
“Everything has to go somewhere”
Objective: To track the materials from one place to another

Steps

 Identify the region (space) where the material is to be tracked or estimated.

 Define the boundary conditions.
 Identify the “entry” and “exit” points of the material (material flow).
 Identify possible ways of material “loss” and “gain” (material accumulation)
 Write the net material balance for the control volume

Boundary

Accumulation
Inputs Outputs
Decay
 Material balance (contd.)

A material that enters the CV has three possible fates:

•Some of it may leave the CV unchanged
•Some of it may accumulate within the boundary
•Some of it may be converted to some other substance
This can be represented as the material balance for the CV as
(Input rate) = (Output rate) + (Decay rate) + (Accumulation rate)
Depending on the conditions of the physical system and
the nature of the material, above equation can be mathematically simplified.
Steady-state (or equilibrium conditions)
- prevail when nothing changes with time;
- thus, material amount in a given CV does not change with time;
- i.e., the accumulation rate = 0.
Conservative substance
- when a substance is conserved within the CV;
- thus, there is no radioactive decay, bacterial decomposition, or chemical
reaction (transformation)
- i.e., the decay rate = 0.
Mathematical simplifications
(assumptions for system analysis)

 Steady-state (time invariant) conservative systems

 mathematically least rigorous
 involves simple algebraic equation (addition/subtraction)

 Steady-state (time invariant) non-conservative systems

 additional relationship of material transformation with time and space needs to be
incorporated in the material balance, making it slightly more mathematically complex
with inclusion of calculus, though independent of time.

 Unsteady-state (time variant) conservative systems

 additional expression of material accumulation/loss as a function of time needs to be
incorporated in the material balance, making it slightly more mathematically complex
with inclusion of calculus and dependence of the material in the region on time.

 Unsteady-state (time variant) non-conservative systems

 in addition to relationship of material transformation with time and space, expression of
material accumulation/loss as a function of time needs to be incorporated in the material
balance, making it mathematically most rigorous.
Steady-state conservative systems

Consider the following system that can be

Decay rate = 0
- A lake;
Accumulation rate = 0
- A section of free-flowing; or
- The mass of air above a city

Stream
Flow rate = Qs Mixture
Concentration = Cs Flow rate = Qm
Concentration = Cm
Wastes

Flow rate = Qw
Concentration = Cw
0 0

(Input rate) = (Output rate) + (Decay rate) + (Accumulation rate)

 (Input rate) = (Output rate)

Steady-state conservative systems

Illustrative example – two polluted streams

Problem definition: A stream flowing at 10.0 m3/s has a tributary feeding into it
with a flow 5.0 m3/s. The steam’s concentration of chlorides upstream of the
junction is 20.0 mg/L and the tributary chloride concentration is 40.0 mg/L.
Treating chlorides as a conservative substance, and assuming complete mixing
of the two streams, (this assumption makes chloride concentration
independent of space at the mixing point), find the downstream chloride
concentration.

System characterization
Control region
Cm = ?
Control volume Qm = ?

Cs = 20.0 mg/L
Qs = 10.0 m3/s

Cw = 40.0 mg/L
Qw = 5.0 m3/s
Contd…

Mass balance for the CV

(Input rate) = (Output rate)

Inputs (rate)
- CsQs
- CwQw

Outputs (rate)
- CmQm
 CsQs + CwQw = CmQm

CsQs + CwQw
Thus, = CsQs + CwQw =
Cm Qm + Qw
Qm

20.0 10.0  40.0  5.0 mg L  m

3

 Cm  s  26.67 mg / L
10.0  5.0 m s
3
Steady-state systems with non-conservative
substances (pollutants)
Many contaminants undergo chemical, biological, or nuclear reactions at rate
sufficient to necessitate them as non-conservative substances.

If we continue to assume that steady-state conditions prevail so that the

accumulation rate is zero, but now treat the pollutants as non-conservative,
then the mass balance for such a system becomes 0

(Input rate) = (Output rate) + (Decay rate) + (Accumulation rate)

Thus, (Input rate) = (Output rate) + (Decay rate)

The decay of non-conservative substances is frequently modeled

as a first-order reaction; that is, it is assumed that the rate of loss of the substance
is proportional to the amount of the substance that is present.
 dC
 C
dt
dC
or   KC (1)
dt
Where K is a reaction rate coefficient with dimension of (time-1),the negative sign
implies a loss of substance with time, and C is the pollutant concentration.
To solve equation (1), we can rearrange the terms and integrate
C t

  K dt
dC
C dt  0
0

which yields
 C 
log e ( C )  log e ( C 0 )  log e     Kt
 C0 
Solving for C , we get
C  C 0 e  Kt (2)
where C0 is the initial concentration at t = 0
Equation (2) indicates the rate of change of concentration of the substance.
If we assume that the substance is uniformly distributed throughout a constant
volume V, then the total amount of the substance is CV. The total rate of decay
of the amount of a non-conservative substance is thus

d ( CV ) dC
V
dt dt
So, using equation (1) we can write for a non-conservative substance:

dC dC
  KC ; or V   KVC
dt dt

Thus, decay rate = KCV (3)

The mass balance equation for steady-state non-conservative substance becomes

Input rate = Output rate + KCV (4)

Important note
Implicit in equation (4) is the assumption that the concentration C is
uniform throughout the volume V. This complete mixing assumption is
common in the analysis of chemical tanks, called reactors, and in such
cases the idealization is referred to as a continuously (or completely)
stirred tank reactor (CSTR) model, which is also used to simulate
water quality in case of pond or lake (in the natural physical system).

In other contexts, such as modelling air pollution, the assumption is

referred to as complete mix box model.
 Steady-state non-conservative systems

Illustrative example 1 – A polluted lake

Problem definition
Consider a 10.0 106 m3 lake fed by a polluted stream having a flow rate of
5.0 m3/s and pollution concentration equal to 10.0 mg/L. There is also a sewage
outfall that discharges 0.5 m3/s of wastewater having a pollutant concentration
of 100 mg/L. The stream and sewage wastes have a reaction rate coefficient
of 0.20/day. Assuming the pollution is completely mixed in the lake, and assuming
no evaporation or other water losses or gains, find the steady-state concentration.

Outfall Qw = 0.5 m3/s

Qs = 5.0 m3/s Cw = 100.0 mg/L
Cs = 10.0 mg/L
Lake Outgoing stream
Incoming
stream V = 10.0  106 m3
K = 0.20/day Qm = ?
Cm = ? Cm = ?
Assuming that complete and instantaneous mixing occurs in the lake.

The concentration in the lake C is the same as the concentration of the mix
leaving the lake (= Cm) and is thus, independent of space variables x, y and z.

Thus, the mass balance can be written as

Input rate = output rate + KCV

Input rate = QsCs + QwCw

= (5.0 m3/s 10.0 mg/L + 0.5 m3/s 100.0 mg/L) 1000 L/m3

Output rate = QmCm

= (5.0 + 0.5) m3/s  C mg/L  1000 L/m3
= 5.5  103 C mg/s

Decay rate = KCV

0.20 / d  C mg / L  10 .0  10 6 m 3  10 L / m 3
KCV   23 .1  10 3 C mg / s
24 hr / d  3600 s / hr
  1.0 105 = 5.5 103C + 23.1 103C
= 28.6 103C

110 3
C   3.5 mg / L
28.6 10 3

Note
Idealized models involving non-conservative pollutants in completely mixed,
steady-state systems are used to analyze a variety of commonly encountered
water pollution problems particularly involving lakes and ponds.
Steady-state non-conservative systems

Illustrative example 2 – A smoky bar

Problem definition
A bar with volume 500 m3 has 50 smokers in it, each smoking two cigarettes
per hour. An individual cigarette emits, among other things, about 1.4 mg of
formaldehyde (HCHO). Formaldehyde converts to carbon dioxide with a reaction
rate coefficient K 0.40/hr. Fresh air enters the bar at the rate of 1000 m3/hr, and
stale air leaves at the same rate. Assuming complete mixing, estimate the
steady-state concentration of HCHO in the air. At 25 C and 1 atm of pressure,
how does the result compare with the threshold for eye irritation of about 0.05 ppm?
CV

Fresh air Indoor concentration C V = 500 m3

Stale air
1000 m3/hr
1000 m3/hr
C=0 K = 0.40/hr
Cm = ?
140 mg/hr
For CSTR, the mass balance equation for non-conservative pollutant

Input rate = Output rate + KCV

0
Input rate = Cf  Qf + 50 smokers  2 cigs/hr  1.4 mg of HCHO/cig
= 140 mg/hr

Note
Since complete mixing is assumed (CSTR), the concentration of HCHO
C in the bar is the same as the concentration in the air leaving the bar, so

Output rate = 1000 m3/s  C mg/m3

= 1000 mg/hr

Decay rate = KCV

= 0.40/hr + C mg/m3 + 500 m3
= 200 C mg/hr

Thus, 140 = 1000C + 200C;  C = 140/1200 = 0.117 mg/m3

HCHO C at 25 C and 1 atm Mol. Wt. of HCHO = 30

C (mg / m 3 )  24.465 0.117(mg / m 3 )  24.465

   0.095 ppm
mol. wt. 30