Mass and Energy Transfer
Materials Balance
Lecture 2
Mass and Energy Transfer
• Everything has to go somewhere is a simple way to express one of the
most fundamental engineering principles.
• More precisely, the law of conservation of mass says that when
chemical reactions take place, the matter is neither created nor
destroyed (though in nuclear reactions, mass can be converted to
energy).
• What this concept allows us to do is track materials, for example,
pollutants, from one place to another with mass balance equations.
This is one of the most widely used tools in analyzing pollutants in the
environment.
Mass and Energy Transfer
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 (e.g.,
entering may be oxidized to within
the region). There is also the
possibility that more substance
may be produced (e.g., may be
produced by cigarette smoking
within the control
volume of a room).
Mass and Energy Transfer
• The reaction rate may be positive if the generation of the substance is faster than its decay, or negative if it is
decaying faster than it is being produced.
• The accumulation rate may be positive or negative. The reaction term in (12) does not imply a violation of
the law of conservation of mass.
• Each term in (12) quantifies a mass rate of change (e.g., mg/s, lb/hr) and not a mass.
• It is a mass rate balance rather than a mass balance,
• The equation denotes that the rate of mass accumulation is equal to the difference between the rate the
mass enters and leaves plus the net rate that the mass reacts within the defined control volume.
Simplification: Steady State (equilibrium)
conditions
• The most common simplification results when steady state or equilibrium
conditions can be assumed.
• Equilibrium simply means that there is no accumulation of mass with time;
the system has had its inputs held constant for a long enough time that any
transients have had a chance to die out.
• Pollutant concentrations are constant. Hence the accumulation rate term
in (12) is set equal to zero, and problems can usually be solved using just
simple algebra.
Simplification: No Reaction Rates
• When a substance is conserved within the region in question, meaning there is no reaction
occurring—no radioactive decay, bacterial decomposition, or chemical decay or generation.
• For such conservative substances, the reaction rate in (12) is 0. Examples of substances that are
typically modeled as conservative include:
• total dissolved solids in a body of water,
• heavy metals in soils,
• and carbon dioxide in air.
• Radioactive radon gas in a home or decomposing organic wastes in a lake are examples of non-
conservative substances.
• Often problems involving non-conservative substances can be simplified when the reaction rate is
small enough to be ignored.
Steady-state conservative system
Example 4. Two Polluted Streams
Solution
Batch Systems with Non-conservative Pollutants
• Batch System by definition is the simplest system with a non-
conservative pollutant
• No contaminant flow into or out of a batch system
• Yet the contaminants in the system undergo chemical, biological, or
nuclear reactions fast enough that they must be treated as non-
conservative substances
• Completely mixed batch reactor (CMBR) or a batch system (reactor)
assumes that its contents are homogeneously distributed
Batch Systems with Non-conservative Pollutants
• The bacterial concentration in a closed water storage tank may be
considered a non-conservative pollutant in a batch reactor because it
will change with time even though no water is fed into or withdrawn
from the tank.
• Similarly, the concentration of carbon dioxide in a poorly ventilated
room can be modeled as a non-conservative batch system because
the concentration of carbon dioxide increases as people in the room
breathe
Batch Systems with Non-conservative Pollutants
• For a batch reactor, (12) simplifies to:
• Reaction rate is the sum of the rates of decay, which are negative, and
the rates of generation, which are positive
• Most nuclear, chemical, and biochemical reaction rates can be
approximated as either zero-, first-, or second-order reaction rates.
Batch Systems with Non-conservative Pollutants
• In a zero-order reaction, the rate of reaction, r(C) , of the substance is
not dependent on the amount of the substance present and can be
expressed as
• where k is a reaction rate coefficient, which has the units of
• Using (15) and (16), the mass balance for the zero-order reaction of a
substance in a batch reactor is
Batch Systems with Non-conservative Pollutants
• To solve the differential equation, the variables are separated and
integrated as
Where C0 is the initial concentration
Batch Systems with Non-conservative Pollutants
Batch Systems with Non-conservative Pollutants
• The first-order reaction rate is
Where k is still a reaction rate constant
• Although decay and generation rates may be any order, the most
commonly encountered reaction rate for generation is zero-order,
whereas for decay it is first order
• Using (15) and (19), the mass balance for a pollutant undergoing first-
order decay in a batch reactor is
Batch Systems with Non-conservative Pollutants
• Using (15) and (19), the mass balance for a pollutant undergoing first-
order decay in a batch reactor is
• When solved for concentration, it yields
Batch Systems with Non-conservative Pollutants
Batch Systems with Non-conservative Pollutants
• Although not nearly as common as first-order processes, sometimes a substance
will decay or be generated by a second-order process
k is a reaction rate constant with units of
The differential equation for the second order decay of a non-conservative
substance in a batch reactor
which can be integrated and then solved for the concentration to yield
Batch Systems with Non-conservative Pollutants
Steady-State Systems with Non-conservative Pollutants
• If we assume that steady-state conditions prevail and treat the
pollutants as non-conservative, then (12) becomes
• The batch reactor, which has just been discussed, can’t describe a
steady-state system with a non-conservative substance because now
there is input and output.
• Such a system is variously termed a continuously stirred tank reactor
(CSTR), a perfectly mixed flow reactor, and a complete mix box model.
Steady-State Systems with Non-conservative Pollutants
• In summary we can write the reaction rate expressions for a non-conservative
substance:
• For example, to model a CSTR containing a substance that is decaying with a
second-order rate, the mass balance involving a non-conservative pollutant in a
steady-state, CSTR system:
Example 5- a Polluted Lake
Solution
• Assuming that complete and instantaneous mixing occurs in the
lake—it acts as a CSTR—implies that the concentration in the lake, C,
is the same as the concentration of the mix leaving the lake, Cm
• The units (day-1) of the reaction rate constant indicate this is a first-
order reaction. Using (23) and (26)
Step Function Response
• Quite often, we will be interested in how the concentration will change with time
when there is a sudden change in the amount of pollution entering the system.
This is known as the step function response of the system.
• In Figure 10, the environmental system to be modeled has been drawn as if it
were a box of volume V that has flow rate Q in and out of the box.
• Let us assume the contents of the box are at all times completely mixed
continuously stirred tank reactor (a CSTR model) so that the pollutant
concentration C in the box is the same as the concentration leaving the box.
Step Function Response
We’ll also assume there are both production
and decay components of the reaction rate
and designate the decay coefficient 𝑘𝑘𝑑𝑑 and
the generation coefficient 𝑘𝑘𝑔𝑔
However, as is most common, the decay will
be first-order, so 𝑘𝑘𝑑𝑑 ’s units are 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 −1 ,
whereas the generation is zero-order, so
𝑘𝑘𝑔𝑔 ’s units are (𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 . 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 −1 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 −1 )
Step Function Response
Step Function Response
Problems
Problems