Summary for Material Balance calculations

Every chemical process analysis involves writing and solving material balances to account for
all process species in feed and product streams. The procedure is to draw and label a flowchart,
perform a degree-of-freedom analysis to verify that enough equations can be written to solve
for all unknown process variables and write and solve the equations.
• The general balance equation is:
input + generation - output - consumption = accumulation
A differential balance applies to an instant of time and each term is a rate (mass/time or
moles/time). An integral balance applies to a time interval and each term is an amount
(mass or moles). Balances may be applied to total mass, individual species, or energy.
• For a differential balance on a continuous process (material flows in and out throughout the
process) at steady-state (no process variables change with time), the accumulation term in
the balance (the rate of buildup or depletion of the balanced species) equals zero.
For an integral balance on a batch process (no material flows in or out during the process),
the input and output terms equal zero and accumulation = initial input - final output. In both
cases, the balance simplifies to:
input + generation = output + consumption
If the balance is on total mass or on a nonreactive species, the equation simplifies further
to:
input = output
• A process stream on a flowchart is completely labeled if values or variable names are
assigned to one of the following sets of stream variables: (a) total mass flow rate or total
mass and component mass fractions; (b) mass flow rates or masses of each stream
component; (c) total molar flow rate or total moles and component mole fractions; and (d)
molar flow rates or moles of each stream component. If a total amount or flow rate or one
or more component fractions are known for a stream, use (a) or (c) to incorporate the known
values into the labeling. If neither the total nor any fractions are known, using (b) or (d)
(component amounts or flow rates) often leads to easier algebra. Volumetric quantities
should be labeled only if they are either given or requested in the problem statement. A
flowchart is completely labeled if every stream is completely labeled.

• A basis of calculation for a process is an amount or flow rate of one of the process streams.
If two or more stream flow rates or amounts are given in the problem statement, they
constitute the basis of calculation. If one is given, it may be assumed as a basis, but it may
also be convenient to assume another basis and then scale the flowchart to the specified
value. If no flow rates or amounts are given, assume one as a basis, preferably an amount
of a stream with known composition.

• To perform a degree-of-freedom analysis on a single-unit nonreactive process, count

unknown variables on the flowchart, then subtract independent relations among them. The
difference, which equals the number of degrees of freedom for the process, must equal zero
 for a unique solution of the problem to be determinable. Relations include material balances
(as many as there are independent species in the feed and product streams), process
specifications, density relations between labeled masses and volumes, and physical
constraints (e.g., the sum of the component mass or mole fractions of a stream must add up
to 1).

• To perform a degree-of-freedom analysis on a multiple-unit process, perform separate

analyses on the overall process, each process unit, each stream mixing or stream splitting
point, and, if necessary, on combinations of process units. When you find a system with
zero degrees of freedom, assume that you can solve for the unknown variables in the feed
and output streams for that system; then, considering those variables as known, try to find
another system with zero degrees of freedom. This procedure helps you to find an efficient
solution procedure before you undertake time-consuming calculations.

• Once you have written the system equations for a process, you may solve them using an
equation-solving computer program. Put all the equations as a single system of linear
equations and solve them simultaneously using the computer to find all the unknowns.

• Recycle is a common feature of chemical processes. Its most common use is to send unused
raw materials emerging from a process unit back to the unit. Overall system balances are
usually (but not always) convenient starting points for analyzing a process with recycle. A
purge stream is withdrawn from a process when a species enters in the process feed and is
completely recycled. If this species were not removed in the purge, it would keep
accumulating in the process system and eventually lead to shutdown.

• The limiting reactant in a reactive process is the one that would be completely consumed
if the reaction proceeded to completion. All other reactants must either be fed in
stoichiometric proportion to the limiting reactant (the feed rates are in the ratio of the
stoichiometric coefficients) or in excess of the limiting reactant (in greater than
stoichiometric proportion to it).

• The theoretical requirement for an excess reactant is the amount required to react
completely with the limiting reactant. The percentage excess of the reactant is:

amount fed − amount theoretically required

%excess = × 100%
amount theoretically required

• The percentage excess depends only on the feed rates of the excess and limiting reactants
and on their stoichiometric coefficients; it does not depend on how much actually reacts or
on anything else that happens in the reactor.

• The fractional conversion of a reactant is the ratio of amount reacted to amount fed. The
fractional conversions of different reactants are generally different unless the reactants are
fed in stoichiometric proportion.
• The extent of reaction, ξ is a species-independent dimensionless quantity that satisfies the
equation:
𝑛𝑖 = 𝑛𝑖0 + 𝜈𝑖 ξi
where 𝑛𝑖0 is the number of moles of species 𝑖 in the feed to the reactor, 𝑛𝑖 is the number of
moles of species 𝑖 in the stream leaving the reactor, and 𝜈𝑖 is the stoichiometric coefficient
of species 𝑖 (negative for reactants, positive for products, and zero for nonreactive species).
If you know the inlet and outlet amounts or flow rates of any reactive species, you can
determine ξ by applying this equation to that species. You may then substitute the calculated
value into the equations for the other species in the stream leaving the reactor to determine
the amounts or flow rates of those species.

• You may analyze reactive processes using (a) molecular species balances (the only method
used for nonreactive processes), (b) atomic species balances, or (c) extents of reaction.
Molecular species balances on reactive processes are often cumbersome: they must include
generation and consumption terms for each species, and one degree of freedom must be
added for each independent reaction. Atomic species balances have the simple form
input = output and are usually more straightforward than either of the other two methods.
Extents of reaction are particularly convenient for reaction equilibrium calculations and for
computer programs.

• The terms yield and selectivity are used to describe the degree to which a desired reaction
predominates over competing side reactions.

moles of desired product formed

𝐘𝐢𝐞𝐥𝐝 =
moles that would have been formed if there were no side
reactions and the limiting reactant had reacted completely

moles of desired product formed

𝐒𝐞𝐥𝐞𝐜𝐭𝐢𝐯𝐢𝐭𝐲 =
moles of undesired product formed

• Two definitions of reactant conversion are used in the analysis of chemical reactors with
product separation and recycle of unconsumed reactants:

reactant input to process − reactant output from process

𝐎𝐯𝐞𝐫𝐚𝐥𝐥 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 =
reactant input to process

reactant input to reactor − reactant output from reactor

𝐒𝐢𝐧𝐠𝐥𝐞 𝐏𝐚𝐬𝐬 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 =
reactant input to reactor

• Combustion is a rapid reaction between a fuel and oxygen. The carbon in the fuel is
oxidized to CO2 (complete combustion) or CO (partial combustion) and the hydrogen in
the fuel is oxidized to water. Other species in the fuel like sulfur and nitrogen may be
 partially or completely converted to their oxides. Combustion reactions are carried out
commercially either to generate heat or to consume waste products.

• The following terms are commonly used to describe the quantities of fuel and air fed to a
reactor.
Theoretical Oxygen: The moles (batch) or molar flow rate (continuous) of O2 needed for
complete combustion of all the fuel fed to the reactor, assuming that all carbon in the fuel
is oxidized to CO2, all the hydrogen is oxidized to H2O, and all the sulfur is converted to
SO2.
Theoretical Air: The quantity of air that contains the theoretical oxygen.
Excess Air: The amount by which the air fed to the reactor exceeds the theoretical air.

(moles air)fed − (moles air)theoretical

Percent Excess Air = × 100%
(moles air)theoretical

• If you know the fuel feed rate and the stoichiometric equation(s) for complete combustion
of the fuel, you can calculate the theoretical O2 and air feed rates. If in addition you know
the actual feed rate of air, you can calculate the percent excess air. It is also easy to calculate
the air feed rate from the theoretical air and a given value of the percentage excess: if 50%
excess air is supplied, for example, then:
(moles air)fed = 1.5 × (moles air)theoretical

• The term composition on a wet basis is commonly used to denote the component mole
fractions of a gas that contains water, and composition on a dry basis signifies the
component mole fractions of the same gas without the water. For example, a gas that
contains 33.3 mole% CO2, 33.3% N2, and 33.3% H2O (wet basis) contains 50% CO2 and
50% N2 on a dry basis.