Material and Energy Balance

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, µg 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 µg/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) / (10 6 volumes of air)
Mass per unit volume = mg/m3 and µg/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 25 0C 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/m 3 at 1 atm and 25 deg C.

Solution:
9.0
% CO = 9 ppm = x 100 = 0.0009%
1 X 106
mg/m3 = 9 x 28/24.465 = 10.3 mg/m3

Materials Balance
In an environmental system, the law of conservation of mass and law of conservation of energy shall
hold good.

 Conservation of material
 Conservation of energy

The law of conservation of mass tells that within any environmental system (control volume), we should
be able to account for the flow of materials into, and out of, that system.

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 this law, 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: A class room, atmosphere over a city, 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 (eg. CO converted to CO 2).
 More substances may be produced within the control volume.
The conversion and production process are lumped into a single category termed reactions.
Accumulation rate = input rate – output rate + reaction rate. (1)

Fig. 1. Material balance diagram

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 atoms 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. Conservative substances do not react.

Examples of conservative substances are: TDS in a body of water, heavy metals in soils, CO 2 in air etc.
Examples of non-conservative substances are: radioactive gases, decomposing organic wastes in a lake.
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 Cm, Qm
Reaction=0 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.

One input to the system is a stream (of water, say) with a flow rate Qs (m 3/s) and pollutant
concentration Cs.

The other input is a waste stream with a flow rate Q w and pollutant concentration Cw.

The output is a mixture with flow rate Q m and pollutant concentration Cm.

Since the pollutants are conservative and we assume steady state conditions, we can write

CsQs + CwQw = CmQm (3)

EXAMPLE: Two Polluted Streams

A stream flowing at 10.0 m3/s has a tributary feeding into it with a flow of 5.0 m3/s. The stream's
concentration of chloride upstream of the junction is 20.0 mg/L, and the tributary chloride
concentration is 40.0 mg/L. Treating chloride as a conservative substance and assuming
complete mixing of the two streams, find the downstream chloride concentration.

Figure 3. Sketch of system, variables, and quantities for a stream and tributary mixing example. (Taken
from Master’s Book)

Solution: The first step in solving a mass balance problem is to sketch the problem, identify the "region"
or control volume that we want to analyze, and label the variables as has been done in Figure 3.

Next the mass balance equation (Equation 1 ) is written and simplified to match the problem's
conditions

The Equation 1 is then written for this problem as:

0 = CSQS + CwQw + CmQm

The next step is to rearrange the expression to solve for C m, the chloride concentration downstream of
the junction.

We know that Qm = QS + Qw.

Cm = (Cs Qs + CwQw)/Qm = (Cs Qs + CwQw)/ (Qs + Qw)

The final step is to substitute the appropriate values for the known quantities into the expression, which
brings us to a question of units.
Units of C are in mg/L, and that of Q are m 3/s. Taking the product of concentrations and flow rates yields
mixed units of mg/L. m3/s, which we could simplify by applying the conversion factor of 1 m 3 = 1000 L.
The downstream concentration of chloride is thus

Cm = ((20.0 x 10.0 + 40.0 x 5.0) mg/L • m3/s)/((10.0 + .5.0) m3/s ) = 26.7 mg/L

This stream mixing problem is relatively simple. The same approach will be followed even for complex
systems.
The approach step wise includes drawing the system, labeling the variables and parameters, writing and
simplifying the mass balance equation, and then solving it for the variable of interest.

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 non-
conservative batch system because the concentration of CO 2 increases as people in the room breathe.
 Fig. 4. 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.