Unit 2.

Quantifying Reaction Progress

Introduction
This unit completes the review of chemical reaction stoichiometry. Unit 1 provided a
definition of what constitutes a chemical reaction and focused upon the stoichiometry of
chemical reactions. This unit examines how stoichiometry is used in expressing how far a
reaction has progressed from a given starting condition. The information presented in this unit is
often first encountered in an introductory chemistry course or in an introductory chemical
engineering course on material and energy balances.
The unit begins by comparing intensive and extensive variables. The extent of reaction is
then defined explicitly for a single reaction system and implicitly for systems involving multiple
reactions. Conversion, another variable used to quantify reaction progress, is next considered and
a few different ways of defining it are presented. Selectivities and yields are then identified as
variables that can be used to describe progress in systems where two or more reactions occur.
Finally, the construction of mole tables is described.
The ability to distinguish between intensive and extensive variables will be important in
later units because this aspect of the variables determines whether or not one can choose a basis
in their calculations. Clearly, reaction progress (how far a reaction has gone) is intimately related
to both kinetics and reaction engineering. As a consequence, the concepts that are reviewed in
this unit will be encountered continually throughout the remainder of the TExT.

Information
Reaction progress variables give some measure of how much reaction has taken place
relative to a specified starting condition. When more than one reaction takes place
simultaneously, relative reaction progress variables can also be defined to specify how much of
one reaction has taken place relative to another reaction. Over time, many different variables
have been used to characterize reaction progress. Reaction progress variables can be classified as
extensive variables or intensive variables. An extensive variable is one which is dependent upon
or imposes a value on the size (or extent) of the system. For example, the number of moles is
clearly an extensive variable. An intensive variable, not surprisingly, is independent of the size of
the system under consideration. Mole fractions are examples of intensive variables.

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The extent of reaction is a common extensive reaction progress variable. In a situation

where there is only one reaction, j, taking place, the extent of that reaction, ξj, is defined by
equation (2.1), wherein n is the number of moles of species i, νi,j is the stoichiometric coefficient
i

of species i in reaction j, and a superscripted 0 denotes the starting number of moles. The extent,
as defined here, has units of moles. Equation (2.2) gives the corresponding definition that is used
for flow systems. The molar flow rate of species i is denoted as ni in equation (2.2) with a

superscript 0 denoting the inlet value. In equation (2.2) the extent of reaction, ξ , has units of
moles per time. (Note, a convention used throughout this TExT is that a dot over the symbol for
a quantity indicates a flow rate while the absence of a dot indicates an amount. Thus, as seen
here, ni denotes the moles of i while ni denotes the molar flow rate of i.)

(n − n )
i
0
i
ξj =
j
(2.1)
ν i, j

( n − n )
i
0
i
ξ j =
j
(2.2)
ν i, j

When more than one reaction is taking place simultaneously, the extent of reaction must be
defined differently. Before doing so, the set of reactions must be reduced to a mathematically
independent set by eliminating any reactions that are linear combinations of other reactions. For
a given group of reactions, there can be several different sets of mathematically independent
reactions. Any one of the mathematically independent sets can be used for the purpose of
defining the extent of reaction. The supplemental information at the end of Section I.A of the
TExT describes how to identify a mathematically independent set of reactions or equations.
Once a mathematically independent set of reactions has been identified, the extent of
reaction can be implicitly defined using equation (2.3). Note that in equation (2.3), the subscript j
is limited to include only a mathematically independent subset of the reactions that are taking
place. Again, for flow systems, an equivalent definition can be used where the moles are
replaced with molar flow rates and the extent has units of moles per time.

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N independent reactions

ni = ni0 + ∑ ν i, jξ j (2.3)
j =1

Two important attributes of the extent of reaction must be recognized. The first is that it
uses the stoichiometric coefficient in its definition. Stoichiometric coefficients are not unique.
For example, a reaction could be written as 2 A ⇄ B or as A ⇄ ½ B. The reaction is the same in
both cases, but the stoichiometric coefficients are different. Consequently, the value computed
for the extent of reaction will depend upon which set of stoichiometric coefficients is used.
Hence it is critical that in the course of any one analysis (i. e. while solving any one problem)
only one consistent set of stoichiometric coefficients be used throughout the entire analysis. The
second point to recognize is that once a set of stoichiometric coefficients has been selected, the
extent of reaction j can be computed using the moles of any species i that appears in reaction j.
The critical point here is that no matter which species i is used, the value of the extent, ξj, will be
the same.
The fractional conversion (or the equivalent percent conversion) is probably the most
common intensive reaction progress variable. The fractional conversion is only defined for
reactants, and for a single reaction it is preferable (though not universally practiced) to define it
in terms of the limiting reactant. If one starts with different amounts of each of the reactants, the
limiting reactant is the one that will first become completely consumed. A quick way to identify
the limiting reactant is to divide the starting amount of each reactant by the absolute value of its
stoichiometric coefficient. The reactant for which this quotient has the smallest value is the
limiting reactant. Equation (2.4) defines the fractional conversion of species k, fk, for a batch
system while equation (2.5) defines it for a flow system.

nk0 − nk
fk = (2.4)
nk0

nk0 − nk
fk = (2.5)
nk0

Notice that the fractional conversion is dimensionless. In the case of a single irreversible
reaction, the fractional conversion of the limiting reactant will lie between 0 and 1, while the
fractional conversions of the other reactants will lie between 0 and a number less than or equal to

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1. That is, the maximum value of the fractional conversion of a reactant other than the limiting
reactant may be less than one. In the case of a single reversible reaction, even the fractional
conversion of the limiting reagent will have a maximum value less than 1. For a single reversible
reaction, the fraction of equilibrium conversion, gk, defined in equation (2.6) is sometimes used.
The fraction of equilibrium conversion is just the actual conversion divided by the conversion if
the system had gone to equilibrium. The principle advantage of the fraction of equilibrium
conversion is that it must have a value between 0 and 1. Equation (2.6) gives the definition in
terms of a batch system, a corresponding definition applies for flow systems wherein the number
of moles in each instance is replaced with the corresponding molar flow rate.

nk0 − nk
fk nk0 nk0 − nk
gk = = = (2.6)
(f )
k equilibrium
( )
nk0 − nk
equilibrium
( )
nk0 − nk
equilibrium
0
n k

When multiple reactions take place, there are several reaction progress variables that can be
used to characterize how far one reaction has gone relative to another reaction. Unfortunately,
some of these reaction progress variables for multiple reaction systems have acquired more than
one definition over the years. Therefore whenever a value of a reaction progress variable is
given, it is wise to ask how that variable was defined if there is any possibility of ambiguity.
Generally the term selectivity refers to the ratio of the amount of one product or group of
products to the amount of a second product or group of products. Similarly, the term yield
generally refers to the ratio of the amount of one product or group of products relative to the
amount of one particular reactant. With yields, a further source of confusion is that the amount of
reactant can be either the amount consumed or the starting amount. Both selectivities and yields
can be expressed using either moles or mass. Once again, whenever there is any possibility of
ambiguity of the meaning of selectivity or yield, it is wise to ask for the definition being used.
A mole table can be very useful when performing calculations involving reacting systems.
It shows how the amounts of the different species are related to each other through the
stoichiometry of the reactions taking place. There are three columns in a mole table. The first
column contains species present in the system, the second column contains the initial number of
moles of each species and the third column contains the number of moles of each species after

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some arbitrary extent of reaction has taken place, making use of the definition of extent of
reaction above. A mole table usually contains one row for each species present in the system plus
one row for the total moles. If one is analyzing a flow system, a corresponding table can be
constructed using the molar flow rates in place of the moles. The general structure for a mole
table is given below:

Number of Moles after

Species Initial Number of Moles
Reaction
N independent reactions

i n 0
i
n +
0
i ∑ ν i, jξ j
j =1

  
N independent reactions
= ∑ ni0 +∑ ∑
0
Total Moles ntotal 0
ntotal ν i, jξ j
i
i j =1

© 2009, Carl Lund, all rights reserved. Part I, Section A, Unit 2 p. 5