LECTURE 4

FUNDAMENTALS OF
MATERIAL BALANCE
The objectives of this lecture are to:
❑ Application of ideal gas law, Avogadro’s Law, Dalton’s Law
❑ Ability to draw and fully label a flowchart, choose a basis for calculation, perform
degree of freedom analysis
❑ Define and articulate fractional conversion, degrees of freedom, percent excess
reactant, dry basis composition, theoretical air and percent excess air in a
combustion reaction
❑ Introduce material balances with chemical reactions
❑ Given the combustion reactor and information on fuel composition, calculate the
feed rate of air from a given percent excess air and vice versa
Avogadro's Law

Volume occupied by 1 mole of any ideal gas is the same

under like conditions of temperature and pressure.
Under normal conditions of pressure (1atm ) and
temperature (0 °C) the volume of one g mole of any
ideal gas is equal to 22.4 L

➢ 1 atm, 0°C, 1 g. mole =22.4 liters; 1 kg. mole = 22.4

m3
Daltons Law
The total pressure of a mixture of gases is the
sum of the partial pressures of the constituents

Ideal Gas Law

R
pv = RT pV = nRT pV = mRT R=
M

p = absolute pressure R = 8.314 kJ/kmol  K

T = absolute temperature =0.08206L.atm/(mol.K)
v = specific volume = 1.986 Btu/lbmol  R
Conversion from a composition by Mass to a Molar Composition

A mixture of gases has the following composition by mass:

O2 16%
CO 4.0%
CO2 17%
N2 63%
What is the molar composition?
Practice

40 kg moles of CO2, 4 kg. moles of water vapor and 200 kg.

moles of N2 and 10 kg. moles of oxygen flow from a stack at
150 °C every minute.

What is the volumetric flow rate in m3/h?

What is the partial pressure of water vapor in the flue gas in atm.
MATERIAL BALANCES WITHOUT
CHEMICAL REACTIONS
Basis of calculation

A basis of calculation is an amount (mass or moles) or flow rate

(mass or molar) of one stream or stream component in a
process.

The first step in balancing a process is to choose a basis of

calculation; all unknown variables are then determined to be
consistent with this basis.
 Flowcharts

Flowcharts help in organizing information in a way that is convenient for the

subsequent calculations.
The best way to do this is to draw a flowchart of the process, using boxes
or other symbols to represent process units
(reactors, mixers, separation units, etc.) and lines with arrows to
represent input and outputs.
Flowchart of a combustion condensation process

Example – Draw the flow chart;

A gas fired boiler burns 1,000 kg./h natural gas with

21,000 kg./h of air. The fuel and air enter at 25 C
and 1 atm. Pressure. The flue gas leaves at 150 C.
Flowchart of an Air Humidification and
Oxygenation Process

Example:
An experiment on the growth rate of certain organisms requires
environment of humid air enriched in oxygen. Three input streams are fed
into an evaporation chamber to produce an output stream with the
desired composition.
A. Liquid water, fed at a rate of 20.0 cm3/min
B. Air (21 mole % O2, the balance N2)
C. Pure oxygen, with a molar flow rate one-fifth of the molar flow rate of
stream B
The output gas is analyzed and is found to contain 1.5 mole % water. Draw
and label a flowchart of the process, and calculate all unknown stream
variables.
Analysis of Degrees of Freedom

A drier takes in wet biomass with 20.1% water and

reduces the water content to 8.6%.You want to
determine the kg of water removed per kg of biomass
that enters the drier.
MATERIAL BALANCES WITH
CHEMICAL REACTIONS
Stoichiometry

Stoichiometric calculations deal with weights of materials

and quantities of energy entering and leaving chemical
reactions

Stoichiometry is the theory of the proportions in which

chemical species combine with one another. The
stoichiometric equation of a chemical reaction is a
statement of the relative number of molecules or moles of
reactants and products that participate in the reaction.

For Example:
2 SO2+ O2 ----→2 SO3
Stoichiometric Ratio

The Stoichiometric ratio of two molecular species participating in a

reaction is the ratio of their stoichiometric coefficients in the
balanced reaction equation.
This ratio can be used as a conversion factor to calculate the amount
of a particular reactant (or product) that was consumed (or
produced), given a quantity of another reactant of product that
participated in the reaction.
A tank of propane with a mass of 16 kg is bought at a store. The empty
tank weighs 6.2 kg. The propane is completely burnt to CO2 and H2O.
What would be the molecular weight of the flue gas and the partial
pressure of H2O ?
Example of Stoichiometry

A limestone analyses gives CaCO3 94.52%, MgCO3 4.16%

and SiO2 1.32%.
a) Calculate how many kgs of calcium oxide could be
obtained from a ton of limestone
b) How many kgs of carbon dioxide are given off per kg of
the limestone?
 Limiting and Excess Reactants, Fractional
Conversion, and Extent of Reaction

• Two reactants, A and B, are said to be present in Stoichiometric

proportion if the ratio (moles A present)/(mole B present) equals the
stoichiometric ratio obtained from the balanced reaction equation.
• The reactant that would run out if a reaction proceeded to completion
is called the Limiting reactant and the other reactants are termed
excess reactants.
• 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 =
𝑎𝑚𝑜𝑢𝑛𝑡 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙𝑙𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑
Fractional excess of a reactant

Suppose (nA)stoich is the Stoichiometric requirement of A, or the

amount needed to react completely with the limiting reactant.
Then (nA)feed–(nA) Stoich is the amount by which the A in the feed
exceeds the amount needed to react completely if the reaction goes to
completion.
The fractional excess of the reactant is the ratio of the excess to the
stoichiometric requirements:

(𝑛𝐴)𝑓𝑒𝑒𝑑 − (𝑛𝐴)𝑠𝑡𝑜𝑖𝑐ℎ
𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑓 𝐴 =
(𝑛𝐴)𝑠𝑡𝑜𝑖𝑐ℎ
Fractional Conversion

Chemical reactions do not take place instantaneously, and indeed often

proceed rather slowly. In such cases, it is not practical to design the
reactor for complete conversion of the limiting reactant; instead, the
reactor effluent emerges with some of the limiting reactant still
present and is then usually subjected to a separation process to
remove the unconverted reactant from the product. The separated
reactant is then recycled to the reactor inlet. The Fractional
Conversion of a reactant is the ratio

𝑚𝑜𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑓=
𝑚𝑜𝑙𝑒𝑠 𝑓𝑒𝑑
Balancing Reaction Equation for a
Biological Reaction

The primary energy source for cells is the aerobic catabolism

(oxidation of glucose (C6H12O6, a sugar). The overall oxidation
of glucose produces CO2 and H2O by the following reaction:

C6H12O6 + a O2----→b CO2+ c H2O

Determine the values of a, b and c that balance this chemical

reaction equation
 Combustion Stoichiometry

Deals with the proportion in which the reactants react and the
products form

CH4 + 2 O2 → CO2 + 2H2O

 m m  m
Cn H m +  n +  ( O2 + 3.76 N 2 ) → nCO2 + H 2O + 3.76  n +  N 2
 4 2  4

• For every mole of fuel CnHm burned 4.76(n+m/4) mol of air are
required and n moles of CO2 is generated and m/2 moles of water is
produced

• A total 4.76 (n+m/4)+m/4 mol of products are produced

• This is important for material balances and flow rate calculations

 Example

Determine the stoichiometry, fuel/air mass ratio and

product gas composition for combustion of octane

C8H18 + 12.5 (O2 +3.76 N2) ----> 8 CO2 + 9 H2O + (3.76 *12.5) N2

1 mol of fuel needs 59.5 mol of air Total moles of combustion

products = 8 + 9 + 47= 64 moles yCO2 = 8/64= 12.5% ; yH2O =
9/64 = 14.0% yN2 = 47/64= 73.4%
Equivalence Ratio

The equivalence ratio, is defined as the Fuel/Air ratio

normalized to the stoichiometric Fuel/Air ratio

𝑚𝑓
ൗ𝑚𝑎 Φ>1 Fuel rich conditions
Φ= 𝑚
𝑓
ൗ𝑚𝑎 𝑠𝑡𝑜𝑖𝑐ℎ Φ<1 Fuel lean conditions

Percent Excess Air

1−Φ
%𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = x100%
Φ
Combustion Products Calculation

• Calculate the products of combustion from a coal burning in 20%

excess air.
The coal has the following properties:
C=78.3%; O=6.5%; H=5.3%; N=1.4%; S=1.2%; Ash=6.2%
• Redo the problem with 25% excess air
Typical Excess Air Levels

Fuel/Combustion Excess Air %

Method
PC 15-40
Stoker Combustion 15-50
Fuel Oil 5-20
Natural Gas 5-10
Wood 20-25
STOKER COMBUSTION

Under Feed Stoker Travel Grate Stoker

Pulverized Combustion Fluidized Bed Combustion
Theoretical Air Required for Solid Fuels

8
  C + 8H + S − O
Total Air Required =  3
0.231
100   8  
=    C + 8H + S − O 
23.14   3  

Where C,H,S and O are % by weight in solid fuels and the air
requirement would be for 100 units (kg, lbm or grams)
Flue gas wet and dry basis

• Similar to as determined vs dry basis for coal analysis

➢ Eliminate water vapor and recalculate gas composition for dry basis

• Orsat analysis (an old wet chemical technique for stack gas analysis)
yields gas composition on a dry basis
Excess Air

Fuels other than gasoline are being eyed for motor vehicles because they
generate lower levels of pollutants than does gasoline. Compressed
propane is one such proposed fuel.

Suppose that in a test 20kg of C3H8 is burned with 400kg of air to

produce 44kg CO2 and 12kg CO.
What was the percent excess air?
Application to Electrochemical Engineering

A Fuel Cell is an open system into which fuel and air are fed, and out of
which comes electricity and waste products.
Look at the sketch of a fuel cell in which a continuous flow of methane
(CH4) and air (O2 plus N2) produce electricity plus CO2 and H2O.
Special membranes and catalysts are needed to promote the reaction of
CH4.
Based on the sketch in the next slide, calculate the composition of the
products in P. Find the excess air
Fuel cell contd
Combustion of a Hydrocarbon
Fuel
A hydrocarbon gas is burned with air. The dry-basis gas composition is
1.5 mole% of CO, 6.0% CO2, 8.2% O2, and 84.3% N2. There is no
atomic oxygen in the fuel. Calculate the ratio of hydrogen to carbon in
the fuel gas and speculate on what might the fuel be. Then calculate the
percent excess air fed to the reactor.