Mass Balance

Instructor: Pham Ho My Phuong, PhD

Fall 2013

Material Balance with Chemical Reaction

Reference: Chapters 4.6 to 4.8 of R.M. Felder & W. Rousseau, Elementary Principles of
Chemical Processes, 3rd ed. 2005 (Wiley).

Chapter 4: Fundamentals Material Balance

Instructional Objectives
After completing Lectures 5-7, you should be able to do the
following:
Calculate the stoichiometric quantities of reactants and products given
the chemical reaction.
Define excess reactant, limiting reactant, tie component, fractional
conversion, single pass conversion, overall conversion, extent of
reaction, selectivity, and yield in a reaction.

Chapter 4: Fundamentals Material Balance

Instructional Objectives
Identify the limiting and excess reactants and calculate the percent excess
reactant(s), the percent single pass/overall conversion and yield for a
chemical reaction with the reactants being in nonstoichiometric proportions.

Perform the calculations for single-unit and multiple-unit processes. You

should be able to use (i) molecular species balances, (ii) atomic species
balances, and (iii) extents of reaction method in your calculations.

Instructional Objectives
Define flue gas, stack gas, Orsat analysis, dry basis, wet basis, theoretical
air (oxygen), required air (oxygen), and excess air (oxygen).
Given two of the three factors: entering air (oxygen), excess air (oxygen),
and required air (oxygen), compute the third factor.

Given a combustion reactor and information about the fuel composition,

calculate the feed rate of air from a given percent excess or vice versa.
Given additional information about the conversion of the fuel and the
absence or presence of CO in the product gas, calculate the flow rate and
composition of the product gas.

Definitions and Concepts

Stoichiometric equation
Chemical reaction equation which states the relative number of molecules
or moles of reactants and products that participate in the reaction.
Stoichiometric ratio
Ratio of the stoichiometric coefficients of two molecular species
participating in a chemical reaction.

Definitions and Concepts

Definitions and Concepts

Definitions and Concepts

Definitions and Concepts

Generalised equation form for

where

EXAMPLE 4.6-1 (PG 120)

Acrylonitrile is produced by the reaction of propylene,
ammonia, and oxygen.

The feed contains 10 mole% propylene, 12% ammonia, and

78% air. A fractional conversion of 30% of the limiting reactant

is achieved. Taking 100 mol of feed as a basis,

(i) determine which reactant is limiting,
(ii) the percentage by which each of the other reactants is in
excess,
(iii) and the molar amounts of all product gas constituents

Solution

Basic: 100 mol Feed

Solution

Basic: 100 mol Feed

Solution

Solution

Solution

(iii) Outlet stream

Solution

Multiple Reactions
Reactants can usually combine in more than one way, and the product once
formed may react to yield something less desirable.

The result of these side reactions is an economic lost: less of the desired
product is obtained for a given quantity of raw materials, or a greater quantity
of raw materials must be fed to the reactor to obtain a specified product yield.

Yield and Selectivity

The term yield and selectively are used to describe the degree to which
a desired reaction predominates over competing side reactions.

Extents of reactions for Multiple reactions

The concept of extent of reaction can be extended to multiple reactions, only
now each independent reaction has its own extent.
If a set of reaction takes place in a batch or continuous steady-state reactor
and i,j is the stoichiometric coefficient of substance i in reaction j (negative for
reactants, positive for products), we may then write

EXAMPLE 4.6-3 (PG 124)

Solution
Basis: 100 mol Feed

Let
1 be extent of reaction for R1
2 be extent of reaction for R2

Solution

Solution

Solution

Solution

Total amount in the product stream

Molecular Species Balances

Molecular Species Balances

Atomic Species Balances

Summary of Procedure
For Material Balance Calculations Involving Chemical
Reactions, in addition to the general procedure for mass balance
calculations.

Summary of Procedure cont.

EXAMPLE 4.7-1 (PG 131)

INCOMPLETE COMBUSTION OF METHANE
Methane is burned with air in a continuous steady-state combustion reactor to
yield a mixture of carbon monoxide, carbon dioxide, and water. The reactions
taking place are
CH4 + 3/2 O2 CO + 2H2O
(R1)
CH4 + 2 O2 CO2 + 2H2O
(R2)
The feed to the reactor contains 7.80 mole% CH4, 19.4% O2, and 72.8% N2. The
percentage conversion of methane is 90.0%, and the gas leaving the reactor
contains 8 mol CO2/mol CO. Calculate the molar composition of the product
stream using
(1) molecular species balances,
(2) atomic species balances, and
(3) extents of reaction.

Solution
Basis: 100 mol Feed

Inlet stream:
nN2 = (0.728) (100) = 72.8 mol N2
nCH4 = (0.1) (0.078) (100) = 0.78 mol CH4

Solution
METHOD 2: ATOMIC SPECIES BALANCES

Solution

Product Separation and Recycle

Basic schematic system

Product Separation and Recycle

Basic schematic system

1 5
1

Conversion (cont.)

Illustration 1

Solution

Solution

EXAMPLE 4.7-2 (PG 135)

Dehydrogenation of propane produces propylene in a catalytic

reactor:
C3H8 C3H6 + H2
The process aims to achieve an overall conversion of 95%. The effluent from the
reactor is separated into two streams:
i.
Net product stream containing C3H6 , H2 and 0.555% of the unreacted C3H8
leaving the reactor
ii. Recycle stream to reactor containing 5% of C3H6 in the product stream

EXAMPLE 4.7-2 (PG 135)

Calculate:
1. composition of the final (net) product
2. recycle ratio (mol recycled/ mol fresh feed)
3. single-pass conversion

Solution

1) Basis: 100 mols fresh feed (F = 100 mols C3H8)

Overall conversion of C3H8 = 0.95
mols C3H8 consumed = (0.95) (100) = 95 mol =

Solution

C3H8 C3H6 + H2
System 1: Entire Process nf = ni +
C3H8 balance: nf = 100 + (-1) (95) = 5 mol

C3H6 balance: nf = 0 + (1) (95) = 95 mol

H2 balance: nf = 0 + (1) (95) = 95 mol

Solution

1.) Net Product Composition:

Solution
2.) System 2: Separator
Given relations among separator variables

n6 = 5 = (0.555/100) n3 n3 = 900 mol C3H8

n10 = (0.05) n7 = (0.05) 95 n10 = 4.75 mol C3H6
Solution
C3H8 balance:
IN = OUT
n3 = n6 + n9 n9 = n3 n6 = 900 5 = 895 mol C3H8

Solution
2) Recycle ratio based on total stream:

Solution
3) Single-pass conversion of C3H8?

EXAMPLE OF PROCESS WITH RECYCLE AND PURGE

2C2H4 + O2 2C2H4O

EXAMPLE 4.7-3 (PG 139)

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.

Solution
Basis: 100 mol combined Feed to the reactor

Solution

Solution

Solution

Solution

Solution

Solution

Solution

Solution

Solution

Mass Balance
Instructor: Pham Ho My Phuong, PhD
Summer 2013

Material Balance with Combustion

Reference: Chapters 4.8 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical
Processes, 3rd ed. 2005 (Wiley).

Chapter 4: Fundamentals Material Balance

Combustion
Combustion is the rapid reaction of a fuel with oxygen
Combustion reactions are industrially significant:
Large amounts of heat released
Environmental impact of combustion products
Fuels:
Solid: e.g. coal (carbon, hydrogen, some sulfur, and
various minerals)
Liquid: e.g. fuel oil (heavy hydrocarbons, some sulfur)
Gas: e.g. natural gas (mainly methane) or LPG
(propane
and butane)

Combustion Chemistry
Combustion is basically an oxidation reaction. When a fuel is burned,
C reacts with O2 to form CO or CO2; H forms H2O; S forms SO2.

In Complete combustion CO2 is produced.

Example:

C + O2 CO2
CH4 + 2O2 CO2 + 2H2O
C4H8 + 6O2 4CO2 + 4H2O
CS2 + 3O2 CO2 + 2SO2

Incomplete Combustion

Oxygen/Air Requirement

Oxygen & Nitrogen

Orsat Analysis
Flue or stack gas: All the gases resulting from a
combustion process including the water vapour, sometimes

known as a wet basis.

Orsat analysis or dry basis: All the gases resulting from a
combustion process not including the water vapour. Orsat

analysis refers to a type of gas analysis apparatus in which

the volumes of the respective gases are measured over and
in equilibrium with water. The net result of the analysis is to
eliminate water as a component being measured.

Wet basis versus Dry basis

Composition on a wet basis:

- is used to express component mole fraction of a flue gas that contains water
Composition on a dry basis:
- is used to express component mole fractions of the same gas without water

Example 1

Example 2

Theoretical Air
Although combustion is very rapid, it may not be instantaneous and
complete due to insufficient time or poor mixing.
Usually, air is supplied in excess, i.e. more than needed based on
stoichiometry of complete combustion reaction.
Theoretical Oxygen:
Moles of oxygen needed for combustion of all the fuel fed to reactor,

assuming all C is oxidized to CO2 and all H is oxidized to H2O.

Theoretical Air:
Quantity of air that contains the theoretical oxygen.

Excess Air

NOTES

The theoretical air required to burn a given quantity of the fuel does not
depend on how much it is actually burned, or whether the combustion is
incomplete

2. The percent excess air depends only on the theoretical air and the air
feed, and not on how much O2 is consumed or whether the combustion is
complete or partial.

3. If the fuel contains some O2, then this must be subtracted from the
theoretical oxygen amount used for calculating excess air.

Example 3
100 mols of propane (C3H8) are burned with 3000 mols of air to produce 240
mols CO2 and 60 mols CO.
1. Calculate the percentage excess air
2. Determine the composition of the flue gas on both wet and dry bases

1. Percentage excess air ?

1. Percentage excess air ?

2. Composition of Flue Gas?

2. Composition of Flue Gas (cont.)

2. Composition of Flue Gas (cont.)

2. Composition of Flue Gas (cont.)

Example 4 (EXAMPLE 4.8-3)

Ethane (C2H6) is burned with 50% excess air. The percentage conversion of the ethane
is 90%; of the ethane burned, 25% reacts to form CO and the balance to form CO2.
Calculate the composition of the flue gas and the ratio of water to dry flue gas.

Solution

Solution

Solution

Solution

Example 5 (EXAMPLE 4.8-4)

Solution

Solution

Percentage excess air ?

Example 6

Solution

Solution (cont.)

Solution (cont.)

Solution (cont.)

Solution (cont.)

Solution (cont.)

Solution (cont.)

Percentage excess air ?

Percentage excess air ?

Percentage excess air ?

Percentage excess air ?

Percentage excess air ?

Percentage excess air ?

Percentage excess air ?