MATERIAL BALANCE CALCULATIONS

1. Elements and components

2. Nomenclature
3. Mass or mols?
4. Defining a stream, the unknowns
5. The essence of the problem
6. Which equations to use
Component balances
Element balances
Total mass balance
7. Dependent equations
8. Independent equations
9. Solution strategies
10. Electronic spreadsheets
1. Elements and components

The streams entering and leaving a system have one or more

COMPONENTS. A component may have one or more elements.

STREAM COMPONENT ELEMENT

FUEL CH4, methane C,H
AIR O2, “oxygen” O
N2, “nitrogen” N
COMBUSTION GASES CO2, carbon dioxide C,O
(or, FLUE GAS) H2O, water vapour H,O
O2, “oxygen” O
N2, “nitrogen” N

A component with a single element is not necessarily represented

with just the symbol of that element: the representation of the
component includes the form in which the element appears, e.g. N2
or O2 (molecules) in the air. When we talk about “oxygen” in the
air, we are referring to oxygen molecules in air, not the element
oxygen in the periodic table! Likewise, we qualify the H2O in the
combustion gas as “water vapour” since “water” is typically used
for the liquid state of water and “ice” for the solid state, even
though they all have the same molecular formula and without
knowing the state we would say H2O is “water”.
2. Nomenclature

With numerous streams in a system, numerous components in a stream

and two different ways of quantifying components, it pays to
adopt a nomenclature when analyzing material balance problems.

e.g.
m(i,j) : quantity of component j in stream i

F(i) : total quantity of stream i

x(i,j) : fraction of component j in stream i

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We need to make sure we specify whether these symbols will
represent mol or mass quantities.

Other nomenclatures can be used as long as they are clearly

stated. The above nomenclature requires that we assign specific
numbers to streams and components and is convenient for
manipulations with a computer program. For hand calculations it
may be more effective to work with short and meaningful names as
in the previous examples.

3. Mass or mols?

Quantities and fractions can be either molar or mass. We should

make this choice by looking at the information available on the
particular stream and we should do this before we do anything
else.

In the absence of any piece of information on the stream we can

use the established convention of:

molar quantities for gases

mass for liquids and solids

4. Defining a stream, the unknowns

If we have n components, the above nomenclature identifies 2n+1

pieces of information for their mixture (n quantities, n
fractions, 1 total quantity). Of course they are not all
independent; we have:
F(i) = m(i,1)+ m(i,2)+ m(i,3)+ ..... + m(i,n) 1 equation

m(i,j) = F(i) * x(i,j) n equations

so that there are only n independent pieces of information.

The first equation above ("the whole is equal to the sum of its
parts") can be expressed alternately as:

1 = x(i,1) + x(i,2) + ..... + x(i,n)

Which n pieces of information should we use to define the stream

with n components?

If we know any of the fractions or the total quantity then our

algebra will most likely involve these and we should use:

n-1 fractions plus the total quantity

Otherwise it is simpler to use n quantities directly (for the n

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components).

There will be the occasional case where a mixture of quantities

and fractions is used. The important thing to remember is that we
can only have n pieces of independent information for a mixture of
n components.
5. The essence of the problem

Of the n pieces of information for a stream some may be known,

some unknown. When all the streams associated with a system are
considered, we may have unknowns in some or all of the streams.

By writing material balances we obtain algebraic equations which

can be solved for the unknowns.
6. Which equations to use

Should we write material balances for the components, the elements

making up the components, total material or some combination of
these? Some general guidelines can be formulated to help with
analyzing specific cases.

COMPONENT BALANCES

Since the streams are defined in terms of their components it is

reasonable to expect that component balances should be the most
direct way of solving for the unknowns. However, the very essence
of the systems we are interested in (chemical reactions) is also
the reason that component balances are not always the most useful.

For a component taking part in a chemical reaction in the system,

the material balance at steady state is of the form:
INPUT + GENERATION = OUTPUT
or,
INPUT - CONSUMPTION = OUTPUT

The INPUT and OUTPUT are made up of terms which are used to define
the streams.

The GENERATION or CONSUMPTION terms on the other hand pertain to

processes inside the system. Unless we have independent
information about the reactions in the system (conversion or
yield) they become additional unknowns and the component balance
is no longer useful for solving the unknowns in the INPUT and
OUTPUT terms.

ELEMENT BALANCES

When writing element balances we must consider all the forms in

which the element occurs in the streams. Although the element may
change form, there is no generation or consumption so that element

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balances at steady state have the simple form:

INPUT = OUTPUT

A component balance also has this simple form if the component

does not take part in any chemical reactions (an inert).

TOTAL MASS BALANCE

If we consider the mass of all material entering and leaving, we

can write one equation at steady state for the whole system:

INPUT = OUTPUT

Since all the components in all the streams are involved, this
equation will have the maximum number of unknowns in the system.
It is therefore not an immediately useful one to solve any
particular unknown. On the other hand, it is one of the most
convenient for checking the final solution.

If molar units have been used throughout the solution we will need
to do some legwork to use this equation; it has to be written in
mass units as the total number of mols entering and leaving need
not be equal (due to chemical reaction).
7. Dependent equations

Material balances give us:

- one equation for each element in the system

- one equation for each component in the system

- one equation for total mass.

All of these equations are not independent however; some are

identical, some are multiples of others, and some can be derived
from others by algebraic manipulations that are not immediately
obvious.

Clearly, the total mass balance can be expressed as the sum of all
the component balances written in mass units.

In a less obvious way we should expect that since components are

made up of elements, the information contained in all the
component balances cannot be independent of the information in all
the element balances.
8. Independent equations

Since elements are the smallest building block we have identified,

the material balance for each element should give an independent
equation. It can be easily demonstrated that this is not always

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true. In the following system:

┌────> 25 wt.% NaCl in H2O sol'n

│
█████████
NaCl >────█████████───< 23 wt.% NaCl in H2O sol'n
█████████

The Na and Cl balances for this system are not independent. If

molar units are used they are numerically identical! If mass
units are used the ratio between corresponding terms of the
balances is the ratio of the atomic weights of Na and Cl.
Likewise the H and O balances are not independent. For this system
we have only two independent material balances: NaCl and H2O. Since
there is no chemical reaction, these components are in effect
behaving like “elements”.

──────────────────────────────────────────────────────────────────
The number of elements involved in a system gives the maximum
number of independent material balances that can be written. The
actual number may be less if some elements behave proportionately
in the system.
─────────────────────────────────────────────────────────────────
9. Solution strategies

To solve for N unknowns we need N independent equations which we

can hopefully find among the element, component and total mass
balances that we can write for the various systems that we can
define.

Mathematically, the ideal situation would be to have N equations

each of which have a single unknown. We can then solve these
equations, one at a time. However, we often face two or more
equations involving two or more unknowns.

The next best situation is to have "two unknown - two equation"

groups. Three unknowns appearing in each of three equations is
still a few minutes' job but anything over 4 unknowns appearing in
each of 4 equations becomes very boring and prone to error if
tackled without a computer.
10. Electronic Spreadsheets

Probably the single most useful computer tool for material balance
problems is the electronic spreadsheet. Electronic spreadsheets
were first developed for use by accountants who had to keep track
of money going through their many categories. They are thus ideal
tools for keeping track of material going through systems in
different forms.

The following example shows an electronic spreadsheet set up to

complete the material balance calculations for the combustion of

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1 mol of CH4 with excess air. The problem has been formulated as
follows:

Given: % excess air

Calculate: The flue gas composition on a dry basis

The quantities of oxygen and nitrogen going in are readily

calculated from the definition of excess air and the composition
of air. The material balances for CH4, O2, N2, and H2O give the
quantities going out. The composition by mol% can then be
calculated from the molar quantities of the components.

B C D E F G H I
1 Material Balance for CH4 combustion with excess air
2
3
4 COMBUSTION
5 GASES
6
7
FUEL
8
9 CH4
10 CH4 + 2O2 CO2 + 2H2O
11
12
13 AIR
14 0.21 O2
15 0.79 N2
16
17
18 BASIS : 1 mole of CH4 IN
19 Excess air : 20 %
20
21 IN, moles OUT, moles Flue gas composition, dry basis
22 CH4 1.00 0.00
23 O2 2.40 0.40 3.84 %
24 N2 9.03 9.03 86.58 %
25 CO2 0.00 1.00 9.59 %
26 Total (dry) 12.43 10.43 100 %
27 H2O 0.00 2.00
28 Total 12.43 12.43

Thus, by changing the number in the “% excess air cell”, all other
numbers can be updated by the electronic spreadsheet.

What if the problem is formulated as follows:

Given: % O2 in flue gas

Calculate: quantity of air an the % excess air

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We have two options:
1) Design a new spreadsheet to do the required calculations
2) Use the existing spreadsheet by trying different values of
the % excess air, until the calculated % O2 in flue gas
matches the given value.

The second option is obviously easier. In fact there are

functions in electronic spreadsheets that automate the process.

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