Chapter 13

Chemical Reaction Equilibrium

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CONTENT
CHEMICAL-REACTION EQUILIBRIA
13.1 The Reaction Coordinate
13.2 Application of Equilibrium Criteria to Chemical Reactions
13.3 The Standard Gibbs-Energy Change and the Equilibrium Constant
13.4 Effect of Temperature on the Equilibrium Constant
13.5 Evaluation of Equilibrium Constants
13.6 Relation of Equilibrium Constants to Composition
13.7 Equilibrium Conversions for Single Reactions
13.8 Phase Rule and Duhem’s Theorem for Reacting Systems

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13.6 RELATION OF EQUILIBRIUM CONSTANTS TO
COMPOSITION
Gas-Phase Reactions
The standard state for a gas is the ideal-gas state of the pure gas at the
standard-state pressure P° of 1 bar.

The fugacity of an ideal gas is:

Thus for gas-phase reactions:

(13.10) (13.25)

Recall: (11.48) (13.26)

If the assumption that the equilibrium mixture is an ideal solution:

( ) (13.27)
Example 13.6

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For pressures sufficiently low or temperatures sufficiently high, the equilibrium
mixtures essentially as an ideal gas.

(13.28)
Example 13.5

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Liquid-Phase Reactions
For a reaction occurring in the liquid phase:

(13.10)
The usual standard state for liquids is the pure liquid i at the temperature
of the system & at 1 bar, for which the fugacity 𝑓𝑖𝑜 :

The activity coefficient,

(13.2)

where fi is the fugacity of pure liquid i at the T & P the equilibrium mixture.

Thus:
(13.29)

and

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Vi changes little with pressure for liquids (and solids), so assume constant.

(13.30)

Using Eqs. (13.29) & (13.30), we can now write Eq. (13.10) as:

(13.31)

Except for high pressures, the exponential term is close to unity & may be
omitted.

(13.32)

and the only problem is determination of the activity coefficients.

If the equilibrium mixture is an ideal solution, then 𝛾𝑖 is unity, & Eq. (14.32) becomes:

(13.33)

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For species known to be present in high concentration, the equation
is usually nearly correct.

For species at low concentration in aqueous solution, a different procedure has

been widely adopted, because in this case the equality of
is usually far from correct.

The method is based on the use of a fictitious or hypothetical standard state

for the solute, taken as the state

Henry's Law Standard State

(13.34)

Valid for a species whose concentration approaches zero.

moles of solute
where mi  molality 
kg solvent

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The dashed line drawn tangent to the curve at
the origin represents Henry’s law, & it is valid
in the case shown to a molality < 1.

The standard-state fugacity is

Hence, for any species at a concentration

low enough for Henry’s law to hold,

Figure 13.3: Schematic illustration of an

alternative standard state for dilute aqueous
solutions.
(13.35)

The advantage of this standard state is that it provides a very simple relation
between fugacity & concentration for cases in which Henry’s law is at least
approximately valid.

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14.7 EQUILIBRIUM CONVERSIONS FOR SINGLE
REACTIONS
Suppose a single reaction occurs in a homogeneous system, & suppose the
equilibrium constant is known.

The calculation of the phase composition at equilibrium is straightforward if

the phase is assumed to be in the ideal-gas state [Eq. (13.28)] or if it
can be treated as an ideal solution [Eq. (13.27) or (13.33)].

Single-Phase Reactions
The following examples illustrate the application of equations developed in the
preceding sections.

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Example 13.5

Initial moles

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Example 13.5

Solution:
(13.2),

(13.28)

(13.5),

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Solution cont.:

Figure 13.2: Equilibrium constants as a function of

temperature.

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Example 13.5

Solution:

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Example 13.5

Solution:

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Example 13.5

Solution:

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Example 13.5

Solution:

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Example 13.5

Solution:

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Example 13.5

Solution:
(13.2)

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Solution cont.:

Figure 13.2: Equilibrium constants as a function of

temperature.

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Example 13.6 Not ideal gas!

Solution:
13.4

(13.26)

Need to evaluate of the fugacity coefficients of the species present in the

equilibrium mixture.
(11.61)

The calculations involve iteration because the fugacity coefficients are functions
of composition. For purposes of illustration, we assume here that the reaction
mixture can be treated as an ideal solution, which eliminates the need for
iteration.
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Solution cont.:
With the assumption of ideal solution behavior, Eq. (13.26) reduces to Eq.
(13.27), which requires fugacity coefficients of the pure gases of the reacting
mixture at the equilibrium T & P.

(13.26) Ideal (13.27)

solution

Eqn (13.27) becomes:

Computations based on Eq. (11.65) in conjunction with Eqs. (3.61) & (3.62)
provide values represented by:

(11.65)

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Solution cont.:

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Solution cont.:
(13.5)

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Example 13.7

Solution:

(13.11b)

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Solution cont.:
(13.2)

Figure 13.2: Equilibrium constants as a

function of temperature.

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Solution cont.:

(13.28)

(13.5)

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Example 13.8

Solution:

(13.11b),

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Solution cont.:
(13.15) is ade-

Eq.13.15

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Example 13.9

Solution:

Moles fed of excess reactant =

Moles required * [1+Excess Ratio]

Every 21 moles of O2 in Air are

accompanied by 79 moles of N2
(13.4)

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Solution cont.:

(3.7)

𝑴𝑪𝑷𝑯 𝑻𝟎 , 𝑻, 𝑨, 𝑩, 𝑪, 𝑫
𝑻
𝑫
=න 𝑨 + 𝑩 𝑻 + 𝑪 𝑻𝟐 + 𝒅𝑻
𝑻𝟎 𝑻𝟐

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Solution cont.:

(13.28)

(13.18)

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Example 13.10 Page 511-514

For knowledge

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 Reference
Smith J.M., Van Ness H.C., & Abbott M. M., Introduction to
Chemical Engineering Thermodynamics, 7th Edition, McGraw
Hill, New York, 2001.

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