Material Balance

Dr. Chetan M. Patel

Associate Professor
Chemical Engineering Department
Sardar Vallabhbhai National Institute of Technology-Surat
Material Balance:
A balance on a conserved quantity (Total mass, mass of particular species, energy, momentum)
in a system may be written in the following general equation form:

Input + generation - output - Consumption = Accumulation

(enters through system (generate within system) (leaves through (consumed within system) (buildup within system)
boundaries) system boundaries)

This is general balance equation may be written for any material that enters or leaves any
System.

It can be applied to the total mass of the material or to any molecular or atomic species
involved in the process.

The accumulation term for steady-state continuous process is zero, and we can write Eqn. as follow for
Reactive system

Input + generation = output + Consumption

For physical process, since there is no chemical reaction, the generation and consumption
terms will become zero.

The balance equation then for non reactive steady-state process will be simply reduced to

Input = output
Differential Balances: indicate what is happening in a system at an instant in time.
Each term of the balance equation is a rate. This is the type of balance usually applied to a continuous process.

Integral Balances : describe what happens between two instants of time. Each term of equation is an amount of the
balanced quantity. This type of balance is usually applied to a batch process.

Differential balances applied to continuous steady-state systems and

Integral balances applied to batch systems between their initial and final states.

Balances on Continuous Steady-State Processes

Input + generation = output + Consumption

Integral Balances on Batch Processes

Initial input + generation = Final output + Consumption

 Procedure for Material Balance Calculations

In material balance problems, you will usually be given a description of a process, the values
of several process variables, and a list of quantities to be determined.

Follow the steps summarized below to perform material balance calculations:

1. Draw and label the process flow chart / block diagram. Identify all the input and output
Streams. Write the values of known streams and assign symbols to unknown stream variables
(i.e. label the streams).

2. Select a basis of calculation. This is usually the given stream amounts or flow rates, if not
given then assume an amount of a stream with known composition.

3. Scale up or scale down using scale factor after solving for the given basis.

3. Write material balance equations. It is possible to write as many independent

material balance equations as the number of species present in the input and
output streams of the system. Write balances that involve the fewest unknown variables.

4. Identify tie components/inert species to write balance equations, which are easy to solve.

5. Solve the equations derived in above steps for the unknown quantities to be determined.
Choice of basis for calculations:

The correct choice of the basis for a calculation is very essential to make calculations correct and simpler.

The selection depends on judgment gained by the experience, However, some rules will help as
given below:

1. Time: choose the time basis in which results are to be presented, e.g. kg/s, g/s etc.
2. For batch process, use one batch as basis.
3. Choose as the mass basis for the stream flow for which most information is available.
4. It is often easy to work with mols, rather than mass or weight.
5. Use volume basis, if the compositions are given by volume for gases, as volume fraction is equivalent
to mol fraction upto moderate pressures.
Stoichiometry, Limiting and Excess Reactants

Theory of proportions in which chemical compounds react is called stoichiometry.

A statement of the relative number of moles or molecules reacting to produce products

is given by a chemical equation known as stoichiometric equation. For example, ammonia
synthesis given in following equation:

N2 + 3H2 2NH3

Ratio of stoichiometric coefficients of two species is known as stoichiometric ratio.

The chemical compound which is present in less than its stoichiometric amount, will disappear
first. This reactant is the limiting reactant.

all the others are excess reactants.

Fractional and percentage excess: In industrial reactions the components are hardly fed to the
reactor in stoichiometric amounts. A excess reactants may be supplied to promote the reaction or to
ensure complete reaction of reactants, which is difficult to proceed to completion due to kinetics and
thermodynamic limitations.

Fractional and percentage excess formulas

n = number of moles fed; ns = number of moles corresponding to stoichiometric amount

Example : If 1 gmole of C7H16 and 12 gmole CO2 of are mixed to conduct following reaction. Find limiting
reactant.

C7H16 + 11O2 7CO2 + 8H2O

Ratio in feed Ratio in reaction

Thus, Heptane (C7H16) is limiting reactant and oxygen is excess reactant

Fractional and percent Conversion, Degree of completion of reaction

Degree of completion of reaction is measured in the same way as fractional Conversion.

Example:
If 100 mol/s of a reactant A is fed and the fractional conversion of A is 0.9

The mol/s of A reacted= (100)(0.9) = 90 mol/s of A has reacted

and (100)(1 – 0.9) = 20 moles/s of A remains unreacted.

 Extent of reaction
When a reaction is not complete, remaining amount in the reactor will be given by

Above equation is valid even for molar flow rate

Example : The feed to a continuous reactor consists of 100 mol/s of nitrogen, 300 mol/s of hydrogen, and 1 mol/s of
argon (an inert gas). It is possible to write following equations for the reactor outlet flow rates using above equation

all in moles/s
If the exit flow rate of any component or the fractional conversion of nitrogen or hydrogen is known, one can calculate
extent of reaction and then the other unknown outlet flow rates. Thus, for a fractional hydrogen conversion of 0.6,
Conversion of H2 = moles of H2 reacted/ moles of H2 charged

Moles H2 reacted =0.6 x 300 = 180 moles/s

H2 Balance gives,
H2 in input – H2 reacted = H2 in output

H2 in output = = 120 moles/s

= 60 moles/s 40 moles/s 120 moles/s
Extent of reaction and conversion relationship:

term, , is amount of species i reacted

Hence by definition term, , represents fractional conversion f

Thus, Extent of reaction and conversion are related by following equation:

When we have multiple reactions, the remaining amount or flow rate will be given by
 Multiple Reactions, Yield and Selectivity
Yield is a measure of the performance of a reactor or plant

In a chemical process, our objective is to produce a certain desired product.

But often there may be several unwanted or undesirable side reactions, which will produce
undesirable by products.

Therefore, maximization of the production of a desired product in the process is essential.

Two quantities, yield and selectivity, are used for this purpose and they are defined as follows:

Reactor Yield vs. Plant yield

Stoichiometric factor = Stoichiometric amount of
reactant Required per mole of product formed
Problem
Consider the pair of reactions:
Suppose 100 mol of A is fed to a batch reactor and the final product contains 10 mol of A, 160
mol of B, and 10 mol of C. Calculate The fractional conversion of A, The percentage yield of B, The selectivity of
B relative to C, The extents of the first and second reactions

Using the definitions,

Moles of desired product formed if there were no side reactions and the limiting reactant reacts completely
= 100 moles of A x ( 2 moles of B formed/ 1 mole of a reacted)
= 200 moles
Yield = 160/200 = 80 %

Selectivity = 160/10 = 16

Using equation for extent of reaction for multiple reactions

 Atomic and Molecular Balances

In a chemical process, molecules are either generated (produced) or consumed. Therefore,

one should take into account the amounts (moles) generated, consumed, fed and remaining in
molecular balances.

Atoms can neither be created (produced) nor destroyed (consumed) according to conservation
principle,

Therefore, in atomic balances there is no generation or consumption terms.

input = output.
 Recycle and Purge

Single Pass and Overall Conversion

Example: Consider following problem represented in the flow chart

Degree-of-Freedom Analysis:

Use a properly drawn and labeled flowchart to determine whether enough information is available to
solve a given problem. The procedure for determining so is known as degree-of-freedom analysis.

Draw and completely label flowchart to perform a degree-of-freedom analysis.

Count the unknown variables and count the independent equations relating them.

Degrees of freedom of process (ndf) is determined by subtracting the second number from the first.

1. If ndf = 0, Number of Unknowns and same number of independent equations are available,
enough information is available and problem can be solved.
2. If ndf > 0, More unknowns than independent equations .Problem is underspecified
and additional information is needed to solve problem.
3. If ndf < 0, More independent equations than unknowns. Problem is overspecified
with redundant and inconsistent relations and problem cannot be solved.

Sources of equations relating unknown variables include the following:

(1) Material Balance equations
(2) Energy Balance equations
(3) Process specifications
(4) Physical properties and laws
(5) Physical Constraints
Problem:
Methanol is produced in the reaction of carbon dioxide and hydrogen:

CO2 + 3H2 CH3OH + H2O

The fresh feed to the process contains hydrogen, carbon dioxide, and 0.400 mole% inerts (I). The reactor effluent
passes to a condenser that removes essentially all of the methanol and water formed and none of the reactants or
inerts. The latter substances are recycled to the reactor. To avoid buildup of the inerts in the system, a purge stream
is withdrawn from the recycle. The feed to the (not the fresh feed to the process) contains 28.0 mole% CO2,70.0
mole% H2 , and 2.00 mole% inerts. The single-pass conversion of hydrogen is 60.0%. Calculate the molar flow rates
and molar compositions of the fresh feed, the total feed to the reactor, the recycle stream, and the purge stream
for a methanol production rate of 155 kmol CH3OH.

Mixed feed to reactor is convenient to be taken as a basis for calculation

Basis: 100 mols of mixed feed to the reactor

The flow sheet was schematically shown in the next slide with all the information.

All the streams were identified, numbered with available information. Also, unknown flow rates and
composition of streams are labeled with appropriates notations.

To identify best point to start calculations Degrees-of-freedom analysis will be applied (Refer procedure given
in the reference book)

Reactor was found to be the best starting point.

60% Single-Pass H2 Conversion

n2 = H2 in reactor outlet is = H2 unreacted.

H2 reacted/consumed = 0.6*70 = 42 mol

H2 balance over reactor

H2 in - H2 consumed = H2 out

n2 = H2 out = 70-42 = 28 mols

CO2 balance over reactor: CO2 in - CO2 consumed = CO2 out
CO2 Consumed from reaction = 42/3 = 14 mol
CO2 out = n1 = 28-14 =14 mol

CH3OH balance over reactor: CH3OH out = CH3OH produced

CH3OH out = n3 = 14 mol
Similarly ,
H2O out = n4 = 14 mol

Balance over condenser:

Overall Balance: input = output

n1 + n 2 + n 3 + n 4 + 2 = n3 + n 4 + n 5
n5 = 44 mol

CO2 balance over condenser: input = output

n1 = n5 X5,c
X5,c = 0.3182

H2 balance over condenser: input = output

n2 = n5 X5,H
X5,H = 0.6364
X5,I = 1-X5,C -X5,H = 0.04545
Balance over Fresh Feed–Recycle Mixing Point:

Overall Balance: input = output

n0 + nR = 100
n5 = 44 mol

I balance over Mixing point: I in = I out

n0 (0.004) + nR (0.04545) = 100 (0.002)

solving above two equations for n0 and nR

n0 = 61.4 mol, nR = 38.6 mol

CO2 balance over Mixing point: input = output

n0 X0,c + nR X5,c = 28
X0,c =0.256
X0,H = 1- X0,I - X0,c = 0.74

Balance over Recycle–Purge Splitting Point:

Overall Balance: input = output
n P + n R = n5
nP = 5.4 mol
For the basis of 100 mol mixed feed to the reactor, the production rate of methanol is 14 mol CH3OH.

Thus, to produce methanol with rate of 155 kmol CH3OH/h, multiply all molar flow rate (all individual
and total flow rates) by the scale factor calculated as follows:

Scale factor = (155 kmol CH3OH/h)/(14 mol CH3OH)

= (11.1 kmol/h) per mol
References:

1. Felder R. M. & Rousseau R.W., “Elementary principles of chemical processes”, 3rd Ed., John Wiley & Sons, Inc.,
New York, 2000.
2. Himmelblau D.M., “Basics Principles and Calculations in Chemical Engineering” 6th Ed., Prentice-Hall India,1996.