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CHEMICAL ENGINEERING

THERMODYNAMICS (ECH3108)
CHAPTER 6: CHEMICAL REACTION
EQUILIBRIUM

Learning outcomes
Determine equilibrium composition for a system with a
single chemical reaction given the reaction stoichiometry,
temperature and pressue.
Use thermochemical data to determine the equilibrium
constant for a chemical reaction at any given temperature.

THERMODYNAMICS VS KINETICS

Equilibrium Analysis
The goal of applying equilibrium analysis to
chemical reactions is to determine the extent to
which products are favoured given specified
elemental composition, temperature, and pressure.
Chemical reaction equilibria tell us nothing about
how fast a reaction will proceed.
Reaction kinetics tells us how fast a reaction will
proceed.
The calculations here do not account for rates of
product formation. They are valid only at
equilibrium, where the reactions are
thermodynamically controlled.

Chemical reaction & Gibbs energy


H 2 Cl2 2HCl

A1 A2 2A3

Figure 9.3, p. 568

If we can calculate the total Gibbs energy


of the system whose initial state is
described above for all extents of reaction;
we can then determine at which extent of
reaction the Gibbs energy is the smallest.
This minimum in Gibbs energy will
represent the equilibrium conversion.

Extent of reaction
Extent of reaction, , is the measurement of
how far a reaction has proceeded. We
designate one species (typically the limiting
reactant), upon which to base the extent of
reaction and then write the other species in
relation to the species we have chosen.
where ranges from 0 (no reaction) to 1
mole (complete reaction) ???

Equilibrium for a single reaction


Stoichiometric coefficients, vi.
vreactants <0, vproducts > 0, vinerts = 0.

A1 A2 2A3
H 2 Cl2 2HCl

Example: A1 = H2, A2 = Cl2, A3 = HCl


v1 = -1, v2 = -1, v3 = 2

ni ni0 vi
nv

vapour

ni n0 v

where

ni ni0 vi
yi 0
nv n v

n0

ni0

and

vapour

ni ni0 vi
xi 0
nl n v

v
i

vapour

Example: extent of reaction


Initially 1 mole of H2, 1 mole of Cl2
At 1 bar total pressure

H 2 Cl2 2HCl

Example: extent of reaction


5 moles of H2, 2 moles of CO2 and 1.5 moles of CH3OH
vapour are combined in a closed system methanol
synthesis reactor at 500 K and 1 Mpa. Develop
expressions for the mole fractions of the species in
terms of the extent of reaction.

2 H 2 CO CH 3OH

Example: extent of reaction


Fuel cells provide an attractive energy source. They
require an H2 feed stream to operate. Consider a fuel
cell based on the conversion of methanol to form
hydrogen. T= 60 C and low pressure, with a feed of
twice as much water as methanol. Extent of reaction is
0.87. What is the mole fraction of H2?

H 2O CH 3OH CO2 3H 2

Criterion for chemical equilibrium


The change in Gibbs energy

dG i vi d

The system comes to chemical equilibrium at the extent of


reaction for which the Gibbs energy is a minimum (see Figure
9.3, Koresky):
dG
0 i vi
d

Equilibrium constant for a gasphase reaction


And defining chemical potential in terms of fugacities, followed by
integration and rearranging, we arrive at

vi

0
v
g
ii

0
f
g
ln i0
rxn
fi
RT
RT

Equilibrium constant, K
0
grxn
ln K
RT

f i 1 bar

vi

fi K
f 0
i

Calculation of K from Gibbs Energy of Formation

0
grxn,298
g1 g2
0
grxn
vi gi0 vi g0f

Gibbs energy of formation at a temperature


different from 25 C is calculated by using heat
of reaction.

Temperature dependence of K
0
dln K hrxn

dT
RT 2

(i) h

0
rxn = Constant

(ii)

0
= Function of T
hrxn

0
hrxn
vi hi0 vi h0f
0
1
ln K T
hrxn
1

K 298
R T 298

K for a gas phase reaction


Rigorous, where the fugacity coefficient depends on the
concentration of all the species in the mixture

i
K fi [bar] yi i P[bar]

(Lewis fugacity rule), where the fugacity coefficient of species I in the


mixture can be approximated by the pure species fugacity
coefficient, which is therefore independent of concentration.

K yi
Ideal gas
K

vi

i i P v
v

y P
vi

(Ideal gas)

Heat of Reaction
reactions h

exothermi < 0
c

Decreases as
temperature increase

Endother
mic

Increases as
temperature increase

0
rxn

>0

Example: Equilibrium Constant


Calculate the equilibrium constant for the reaction of
(a)at 298 K
(b)At 60 C for constant heat of reaction, and heat of
reaction dependence of temperature.
(c)Is this reaction edothermic or exothermic?

H 2O CH 3OH CO2 3H 2

Multiple Reactions
Koretsky, 2nd edition, pp. 599 612
To set-up a multiple reaction equilibria problem, we must
pick
R different independent chemical reactions to describe the
system. A set of reactions is deemed independent if you
cannot construct any one of the given reactions by a linear
combination of the others.
Each equilibrium constant be found independently, using
the approach described earlier.
The results we obtain is a set of coupled nonlinear
algebraic equations that we must then solve for the
extents of reaction.
Once all the extents of reaction are determined, the
equilibrium composition can be found.

Exercise
Koretsky, 2nd edition.
Q 9.6
Q 9.19
Q 9.20
Q 9.25