CHEMICAL REACTION

EQUILIBRIA

Smith et al. Chapter 13

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MOODLEYK6@UKZN.AC.ZA

INTRODUCTION
o There are two factors that decide if a chemical reaction is significant
1. The chemical composition of the reactants and products
2. The rate at which the reaction occurs

o In this section we study the thermodynamic relationship between the

temperature
and pressure at which a reaction occurs with the resulting
composition at equilibrium.
oThe equilibrium composition is a result of the maximum conversion being
achieved for a particular reaction at a fixed T and P.
oThe speed (rate) at which this reaction is achieved is not studied here.
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WHAT IS EQUILIBRIUM?
o A system at a constant T, P with phases in chemical equilibrium is
said to be in thermodynamic equilibrium.
Can only occur if any
reaction present is also in
equilibrium

WHAT IS A PHASE?
o A phase is a region of space that is distinct in boundary, and has
uniform composition.
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OUTLINE
1. We develop mass balance equations that describe the composition profile as a reaction
proceeds, (13.1) (single and multiple reactions) using a parameter (Xi)/ (Epsilon)- the extent
of reaction. This parameter can also be related to the total Gibbs energy of the system.
(13.2)
2. We then use the Gibbs energy changes of the system to rigorously formulate the energy
balances of the reaction, (13.3-13.5). The reaction temperature is factored in here.
3. In 13.6 we see the relationship between the mass and energy balance at equilibrium, and
how we can use the mass balance to solve for the reaction temperature or vice versa.
4. We then go through calculation procedures for the above mentioned calculations for single
reactions in either gas, liquid systems (homogeneous) or gas-liquid systems
(heterogeneous), 13.7.
5. In Section 13.9 we look at procedures to solve systems involving multiple reactions. This
also includes a procedure for the global minimization of the total Gibbs energy (Gt) of a
system- a sure-fire way to solve ALL G-optimization problems.
6. Section 13.8 was covered in MEB and will not be covered here. You are encouraged to read
through it on your own. 13.10 will not be covered.
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13.1 THE REACTION

COORDINATE
oWe provide here the rigorous thermodynamic development of the
method. You will soon realise you have been doing this all along.
(13.1)
o For a reaction, the change in the number of moles of a component
A1 is directly proportional to the change in the number of moles of A3.
As A1 depletes, A3 increases. The proportionality constant is
oEqually the change in the number of moles of a component A1 is
directly proportional to the change in the number of moles of A2. As
A1 depletes, A2 depletes. The proportionality constant is
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13.1 THE REACTION

COORDINATE
So the depletion of A1 :

And the depletion of A2:

And the growth of A3:
Now remember that is positive for products and negative for
reactants
So is a and is a
As we said earlier, each proportional change is equal, therefore:

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13.1 THE REACTION

COORDINATE

Now if we want to rather examine a differential change in the number of

moles we can say
(13.2) or for every component i in the reaction (13.3)
Now if we integrate from the start of the reaction (where no reaction has
occurred, =0 ) to some arbitrary point where :

We get or

(13.4)
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EXERCISE 1: 3 MINUTES
o If the mole fraction, is given by definition as:
Determine a general expression for , in terms of , , and

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EASILY:

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13.1 THE REACTION

COORDINATE

Now for multiple reactions we must consider an additional step:

reaction 1
reaction 2
Then the change in the number of moles of component i is due to both reactions:
+
So = +
Or more generally , where i, refers to the component number and j refers to the
number of reaction equations.
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HOMEWORK 1
o If the mole fraction, is given by definition as:

Determine a general expression for , in terms of , , and

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13.2 APPLICATION OF
EQUILIBRIUM CRITERIA TO
CHEMICAL
REACTIONS

o Like all real closed systems, a

spontaneously reacting system at
constant T and P will proceed in such
a way to attain the lowest total Gibbs
energy state. This occurs at a
minimum H and a maximum S. This is
a consequence of the 3 laws of
thermodynamics.

o At equilibrium , P, yi, is constant and

therefore, Gt must be a minimum.
oThis occurs at the equilibrium extent
or for equilibrium.
oIf Gt is a minimum, or turning point,
then any differential changes in the
total Gibbs energy must be zero.

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WHAT DOES THIS MEAN?

o We are therefore presented with two options for solving the point, at which minimum Gt occurs at constant T and P.
o We can either

1. minimize Gt directly
2. or we can set

o Option 1 is the more rigorous calculation, and guarantees a solution (if it exists)
o Option 2 is a shortcut method, that employs the use of equilibrium constants. It is sometimes called the K method. This method can almost
always be used for single reactions but sometimes fails in multi-reaction systems.

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13.3 THE STANDARD GIBBS-ENERGY

CHANGE AND THE
EQUILIBRIUM CONSTANT
1. Start with the fundamental
property relation (11.2).
2. If we assume that chemical
equilibrium is only due to
changes from reacting species
then we can replacewith some
relation to
3. T, P are fixed so and we get
(13.8)

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13.3 THE STANDARD GIBBS-ENERGY

CHANGE AND THE
EQUILIBRIUM CONSTANT
Now work on eliminating the
4.
chemical potential given by
(11.42)
(which
is
immeasurable).
5. Since we know (11.30) and
we can define a standard state
at a particular temperature and
pressure then we get:
6. Now subtract this
(11.42) and we get (13.9)
7. Eliminating
(13.8)

from

in equation
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13.3 THE STANDARD GIBBS-ENERGY

CHANGE AND THE
EQUILIBRIUM CONSTANT
8. Now simplify

9. We define K to represent:
Where:
10. For a reacting system by
definition:
11. Hence
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13.3 THE STANDARD GIBBS-ENERGY

CHANGE AND THE
EQUILIBRIUM CONSTANT
12. All property relations apply
to standard property changes of
reaction. Hence the standard
enthalpy change of reaction can
be related to the standard Gibbs
energy change of reaction:

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13.4 EFFECT OF
TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
o Despite being called the equilibrium constant, K, is in fact strongly influenced by temperature.
o We can calculate this temperature dependence by finding the derivative of lnK with respect to T.
o Hence

(13.14)

o A check confirms that for a reaction that is exothermic (product has less enthalpy than reactant), and that an increase in T will cause a reduction
in K.
o And that if then an increase in T will cause an increase in K.

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13.4 EFFECT OF
TEMPERATURE ON THE
EQUILIBRIUM CONSTANT

o Equation 13.14 can be integrated

easily if the standard enthalpy change
of reaction is assumed to not vary with
T.

o If it IS dependent on T however, we
must use a more rigorous method to
integrate the preceding equation for K.
oWe start with the G axiom
standard changes of reaction:
oThen apply our rule
change of reaction

for

for

property

oSimplifying

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13.4 EFFECT OF
TEMPERATURE ON THE
EQUILIBRIUM
CONSTANT
oWork on , which was covered
previously (4.18)
o And if we use the property
change of reaction tool we can
get from (13.17)
oCombine and simplify (13.18)

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13.4 EFFECT OF
TEMPERATURE ON THE
EQUILIBRIUM
CONSTANT
ln(K )
ln(K
)
ln(K )

ln(K)

Now if we multiply by -1and take logarithms we get

o So
o And

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13.4 EFFECT OF
TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
o And K2 which accounts for the
two integrals, is (13.24):

Where
o From the log rules we can
therefore say (13.20):

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HOMEWORK 2
1. From the Cp integral equations provided in your text, show by
rigorous calculation that equation (13.24) is valid.
2. If

determine the equation for K2

3. Compare with friends

4. Perform example 13.5 from the textbook. Ensure you follow all
the calculations and obtain the solutions given. DO NOT USE
EXCEL.
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13.6 RELATION OF
EQUILIBRIUM CONSTANTS
TO COMPOSITION

oGas phase reactions (homogenous)

oLiquid phase reactions (homogenous)

oMixture of gas and liquid (heterogeneous)

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ELIMINATING
FUGACITY
IN
SOLUTION ()

We defined the relationship between

the fugacity in solution, standard
fugacity and K in Section 13.3
(13.10)

If we choose a reference state as the

ideal gas state, then the component
fugacity if equal to the pressure at
that reference temperature. We get
this reference pressure from the
same table we acquire standard
property changes of reaction. (13.25)
Now what we do is use the
relationships between fugacity in
solution (), fugacity coefficient in
solution (), and composition (yi or xi )
to eliminate fugacity in solution

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SUMMARY OF
REPLACEMENTS
Condition

Gas Phase
Partial residual Gibbs
energy

Partial excess Gibbs

energy

Where by definition:

Where by definition:

Real
Ideal solution
Ideal Gas

Liquid phase

N/A

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WHAT ARE THE EQUILIBRIUM

EQUATIONS FOR EACH TYPE
OF REACTION?
Condition

Gas Phase

Liquid phase

Partial residual Gibbs

energy

Partial excess Gibbs

energy

Where by definition:

Where by definition:

Real

Ideal solution
Ideal Gas

N/A

Complete this table for Homework 3

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ELIMINATING FOR LIQUIDS

Integrate 6.10 at constant T from stand pressure to system pressure

(6.10)

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