Chemical Reaction Engineering II

2. Reaction Equilibria

Y.H.Yap

May 2017
1. Introduction Todays Topics

Reaction Heterogeneous
Introduction
Equilibria Reactions

External Internal Diffusion Design of

Diffusion Limited Limited Multiphase
Reactions Reactions Reactor
Catalyst Non-elementary
Resistance
Deactivation and Reaction
Analysis
Regeneration mechanisms
 1. Introduction Fundamentals of Chemical Engineering

Fundamentals
IN Process OUT

For fluid:

Domain How much How fast Driving force Device Quality

Distribution,
Mass Mass Unit
Mass Concentration Purity,
balance transfer operation
selectivity
Furnace, Heat
Thermo- Heat
Energy Temperature heat efficiency,
dynamics transfer
exchanger % Heat loss
Pressure
Momentum Fluid Pipes,
Momentum Pressure drop, flow
balance dynamics pumps
rate
1. Introduction

Why study Chemical Reaction Equilibria

To determine ____________to which products are
favored given specified elemental composition,
temperature and pressure, i.e. the farthest a
reaction can possibly go.
If thermodynamics tells us a given reaction will
not proceed to a significant degree, we do not
consider it further
Only when thermodynamics tells us the reaction is
possible do we need to consider the kinetics
1. Introduction Definition

What is Chemical Reaction Equilibria

A state in which both reactants and products are
present in concentrations which have no further
tendency to change with time
Consider
A+BS+T

The equilibrium constant is defined as:

s t
k+ [ S ] [T ]
Kc = =
k- [ A]a [ B] b
1. Introduction Definition

What is Chemical Reaction Equilibria

At constant T & P, chemical equilibrium is attained
when Gibbs free energy of the system is at its
minimum.
RT ln K P G
1. Introduction Example

Kinetic vs. thermodynamically controlled:

Diamond Graphite
is a spontaneous (thermodynamically favorable) process
at room temperature and pressure. Despite this, this
process has an extremely slow rate and take place over
the course of million years
Kinetically controlled

Ammonia synthesis
is spontaneous (thermodynamically favorable) but
kinetically controlled at low temperature
Thermodynamically controlled at high temperature
1. Introduction Example Butadiene - HBr

Difference between kinetically controlled

reaction and thermodynamically controlled
reaction
At T = - 80oC: kinetic controlled
Yield

3-bromo-1-butane (80%)
Butadiene + HBr
1-bromo-2-butane (20%)

Even though 1-bromo-2-butane is more favorable

thermodynamically, the kinetic is too slow
1. Introduction Example Butadiene - HBr

Difference between kinetically controlled

reaction and thermodynamically controlled
reaction
At T = 40oC: thermodynamically controlled
Yield

3-bromo-1-butane (20%)
Butadiene + HBr
1-bromo-2-butane (80%)

Thermodynamic analysis is only valid for

thermodynamically controlled reaction
 2. Thermodynamic analysis Ammonia synthesis

Industrial operating condition:

N2 + 3H2 2NH3, R = - 45.8 kJ/mol

Temperature: 400 500 oC

Pressure: 150 250 bar
Conversion: 15% per pass
Through recycling and reaction engineering,
conversion can be increased to 97%

There must be a reason why industrial

operation is run at such severe condition
 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

Consider reaction temperature of 500oC and ideal
gas conditions
What is the maximum possible conversion?
Thermochemical data (at 298K and 1 bar):

Species i hf0 (kJ/mol) gf0 (kJ/mol) Ai Bi Di

NH3 2 -46.11 -16.45 3.578 3.020 x 10-3 -0.186 x 105

N2 -1 0 0 3.280 0.593 x 10-3 0.040 x 105

H2 -3 0 0 3.249 0.422 x 10-3 0.083 x 105

vi( )i -2 -92.22 -32.90 -5.871 4.180 x 10-3 -0.661 x 105

Enthalpy energy Gibbs energy Parameters for

of formation of formation heat capacity
 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

Express number of moles in terms of extent of
reaction
Species Moles outlet Mole fraction
N2

H2

NH3

Total

Note the difference between extent of reaction

and conversion
 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

Equilibrium constant can be written as the
product of partial pressure:

2


= = 3
2
2 32

2 2
4 2 2
2 2 4 2 2 2
= 3 = 3
1
1 3 3 1 3 3
4 2 4 2
 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

Equilibrium constant can be calculated from
thermochemical data
773
0 0

,773 = ,298 + + + + 2 + 3
2


298

Employing Vant Hoff equation:

0
ln
=
2
0

d ln = 2
3

 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

Substitute 2 into 3 and integrate both sides
0
,298 2
+ 298 + 298 1 1
ln = 2
298 3
298
+ 298 + (298)4
3 298 4

2
+ ln + 298 + 2982
298 2 6

1 1 3
+ 2 2 + 2983
2 298 12

C and E terms are cancelled because parameters are

not provided in thermochemical data
 2. Thermodynamic analysis Ammonia synthesis 1 bar

Production of ammonia at 1 bar

K298 can be calculated with Gibbs energy
0
32,900
298 = exp = exp = 5.81 105
8.314 298.2

Substitute thermochemical data and T = 773 K

= 1.51 105

Plugging this into 1 and P = 1 bar

=
Almost negligible extent of reaction !! which is why you never get any
ammonia at such condition. Lower T will lead to higher equilibrium
conversion. However, low T means reaction is too slow. Since v is negative,
increase in pressure will increase conversion. We will examine operating
pressure of 300 bar.
 2. Thermodynamic analysis Ammonia synthesis 300 bar

Production of ammonia at 300 bar

Now consider P = 300 bar and T = 500oC

2 2
4 2 2
2 2 4 2 2 2
= 3 = 3
1 3 3 1 3 3
4 2 4 2

= 1.51 105
=

Operating at higher temperature dramatically increased the extent of reaction.

However, we assumed gas is ideal. If Lewis fugacity rule is employed to account
for gas phase non-ideality, the extent of reaction is 0.33 (details see reference),
which is still substantially higher than P = 1 bar.
 2. Thermodynamic analysis Conclusion

We can see that:

Thermodynamics (reaction equilibria) will tell us
how much (extent of reaction) a reaction can
possibly go given specified elemental composition,
temperature and pressure
However, kinetics will tell us how fast a reaction
will proceed. The right type of catalysts can speed
up the reaction, with desirable selectivity
 2. Thermodynamic analysis Conclusion

A catalyst:
o affects the rate of a reaction but the process
unchanged (does not affect the equilibrium), and it
itself remain unconsumed
o they may be inhibited, deactivated or destroyed by
secondary processes
o usually changes a reaction rate by promoting a
different molecular path/mechanism for the reaction
o can affect both the yield and the selectivity
 Reference

Koretsky, 2004, Engineering and Chemical

Thermodynamics, 1st edition.
Chapter 9

Next Lecture

Heterogeneous Reactions