Material and Energy Balance

In an environmental system, the law of conservation of mass and law of conservation of energy shall
hold good.
These laws tell that within any environmental system, we should be able to account for the flow of
energy and materials into, and out of, that system.

Materials Balance
Everything has to go somewhere.
The law of conservation of mass says that when chemical reactions take place, matter is neither created
nor destroyed. Although in nuclear reactions, matter is converted to energy.
Using the law of conservation of mass, we shall be able to quantitatively track pollutants as they
disperse in the environment.
The first step in a mass balance analysis is to define a particular region in space that is to be analysed.
This is called the control volume.
Example of a control volume: simple chemical mixing tank, a coal fired power plant, a lake, stretch of a
stream, or the globe itself.
By picturing an imaginary boundary around the control volume, we can quantify the flow of materials
across the boundary as well as the accumulation and reaction of materials within the region.
A substance that enters the control volume has four possible fates. Some of it may leave the region
unchanged, some of it may accumulate within the boundary, and some of it may be converted to some
other substance.
The conversion and production process are lumped into a single category termed reactions.
Accumulation rate = input rate output rate + reaction rate.

Fig. 1. Material balance diagram

1

(1)

The reaction rate may be positive or negative. The reaction rate is positive if generation of substance is
faster than its decay. It is negative if decay is faster than its generation.
Likewise the accumulation rate may be positive or negative.
The reaction term does not imply a violation of the law of conservation of mass. Atoms are conserved.
But there is no constraint on the chemical compounds. The atmos may change chemically from one
substance to another.
Eq (1) can be simplified. The most common simplification results when steady state or equilibrium
conditions can be assumed.
Equilibrium means that there is no accumulation of mass with time; Accumulation rate is zero.
A second simplification can be done by conserving the mass within the control volume. There is no
reaction occurring, no radioactive decay, bacterial decomposition, or chemical decay, or generation. For
such conservative substances the reaction rate is zero.
Examples of conservative substances are: TDS, heavy metals in soils, CO2 in air etc.
Radioactive gases, decomposing organic wastes in a lake are examples of non-conservative substances.
For non-conservative substances when the reaction rate is very small they can be ignored thus
simplifying the mas balance analysis.

Steady-state conservative systems

Stream Cs, Qs

Accumulation=0
Reaction=0

Cm, Qm

Mixture

Q = Flow rate
C = Concentration of pollutants

Waste Cw, Qw

Fig.2. steady state conservative system

The simplest system for steady state for a conservative substance is when input rate is equal to the
output rate.
Input rate = output rate (2)
Consider the steady state conservative system shown in Fig. 2. The system contained within the
boundary could be a lake, a section of a free flowing stream, or the mass of air above a city.
2

One input to the system is a stream (of water, say) with a flow rate Qs (m3/s) and pollutant
concentration Cs.
The other input is a waste stream with a flow rate Qw and pollutant concentration Cw.
The output is a mixture with flow rate Qm and pollutant concentration Cm.
Since the pollutants are conservative and we assume steady state conditions, we can write
CsQs + CwQw = CmQm

Batch system with non-conservative pollutants

Simplest system with a non-conservative pollutant is a batch system or batch reactor.
There is no contaminant flow into or out of a batch system. Yet the contaminants in the system undergo
chemical, biological, or nuclear reactions fast enough and they are treated as non-conservative
substances.
A batch reactor assumes that its contents are homogeneously distributed and is referred to as
completely mixed batch reactor (CMBR).
The bacterial concentration in a closed water storage tank may be considered a non-conservative
pollutant in a batch reactor. The bacterial population will change even if no water is fed or withdrawn
from the tank.
Similarly, the concentration of carbon dioxide in a poorly ventilated room modeled as a nonconservative batch system because the concentration of CO2 increases as people in the room breathe.

Fig. 3. completely mixed batch reactor

For a batch reactor, Accumulation rate = reaction rate
Reaction rate is the sum of the rates of decay (which is negative), rates of generation (which is positive).
Most nuclear, chemical, and bio-chemical reactions rates can be approximated as either a zero-, first- or
second- order reactions rates.
Zero-order reaction
In a zero-order reaction the rate of reaction, r(C), of the substance is not dependent on the amounts of
the substance present and can be expressed as
r(c) = k (generation)
r(C ) = -k (for decay)
where k is the reaction rate constant (k has a unit of mass/(volume.time)).
The rate of evaporation of water from a bucket is zero order reaction because the rate of loss of water is
not dependent on the amount of water present in the bucket but is only dependent on the surface area
of the water and its temperature.

For a batch reactor with zero order reaction rate, we can write V

= -Vk.

Integrating between time t= 0 to time t=t, 0 = 0

C 0 =
Finally we get the expression for a zero order reaction:

C = 0

This expression can be shown graphically as shown in figure below.

200
Decay

Concentration

150

100

50

-k

Production

0
0

20

40

60

80

100

Time

Figure 1. Zero-order reaction rate in a batch system

First order reaction
For most of the non-conservative pollutants the decay is a first order reaction. In such cases, the rate of
the reaction r(C ) is dependent on the amount of pollutant present.
r(c) = kC (generation)

or r(C ) = -kC (for decay)

dC/dt = -kC
where k is again the reaction rate constant. Here k has a unit of per time (t-1). Radioactive decay of
radon gas follows the first order reaction. The mass that decays in a given time is directly proportional to
the mass that is present at that time.
This equation can be integrated by separation of variables and then integrated between time t= 0 to t=t
to give the relationship as:
=
That is assuming a first-order reaction, the concentration of a substance decays exponentially. The first
order decay and growth for a batch reactor is shown in Figure 2.

Concentration

250
200
150
Decay

Growth

100
50

Time

Figure 2. Growth and decay for a first order reaction in a batch reactor.

Units of measurement
In the study of environmental engg, we encounter extremely large as well as small quantities.
Liquids
Concentrations of substances dissolved in water are usually expressed in mass or number of unit volume
of mixture. Units in mg, g or moles per liter of mixture.
Also concentrations in liquids are expressed as mass of substance per mass of mixture (ppm, ppb).
1 ppm (by weight) = 1 g/m3 = 1 mg/L
1 ppb = 1 mg/m3 = 1 g/L
In unusual case, the concentration of liquid wastes may be so high that the specific gravity of the
mixture is affected. In such case the units can be converted as below:
mg/L = ppm (by weight) x specific gravity of mixture

Example 1: The fluoride concentration in drinking water is increased to help prevent tooth decay by
adding sodium fluoride. However excessive fluoride may cause mottling of the teeth. The maximum
dose of fluoride allowed is 0.053 mM/L (milli mole per litre). If sodium fluoride is purchased in 25 kg
bags, how many gallons of water would a bag treat?
Solution:
Molar weight of NaF = 23 + 19 = 42 gm ( Na-23; F-19)
Number of moles of fluoride in 25 Kg = 25 x1000/42 = 595.24 moles
One gallon of water = 3.785 L
Maximum dose of fluoride = 0.053 mM/L
Volume of water that one 25 kg bag could treat = 595.24 *1000 (mM) / 0.053 (mM/L) = 11.23 x 10^6 L
= 11.23 x 10^6 /3.785 = 2.97 x 10^6 Gallons
Gases

1 ppm (by volume) = 1 ppmv = (1 volume of gaseous pollutants) / (106 volumes of air)
Mass per unit volume = mg/m3 and g/m3
The relationship between ppmv and mg/m3 depends on the pressure, temperature and molecular
weight of the pollutant.
The ideal gas law gives us the relationship between mass and volume
PV = n RT
R = ideal gas constant = 0.082056 L.atm./(K.mol)
mg/m3 = ppmv x mol.wt/ 22.414 ( at 0 0C and 1 atm)
mg/m3 = ppmv x mol.wt/ 24.465 ( at 250C and 1 atm)
Example 2: The CO concentration in a mine air sample is 9 ppmv. Express the concentration in volume
percentage as well as in mg/m3 at 1 atm and 25 deg C.
Solution:
% CO = 9 ppm =

9.0
1106

x 100 = 0.0009%

mg/m3 = 9 x 28/24.465 = 10.3 mg/m3

Steady state system with non-conservative pollutants
For a steady state system, accumulation rate = 0.
The mass balance equation will be: 0 = Input rate output rate + reaction rate
(1)
Output rate = Input rate + reaction rate
The batch reactor cant describe a steady state system for non-conservative substance because now
there is input and output.
A continuously stirred tank reactor (CSTR) may be suitable to analyse such a system.
Example: a) water in a pond with inlet and outlet
b) air in a well-ventilated room
In a CSTR the concentration C in the tank is uniform everywhere.
The reaction rate can be either generation or decay. The reaction rate can be approximated by a
zero-, first-, or second- order reactions.
If the tank volume = V
Concentration of pollutant = C
Reaction rate
Reaction type
Zero order
First order
2nd order

Reaction rate
Vk
VkC
VkC2

For a CSTR with 2nd order reaction rate for a non-conservative pollutant
Output rate = Input rate kVC2 (for decay)

Example:

10