CHEMICAL-REACTION

EQUILIBRIA

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 Chemical reaction

Both the rate and equilibrium conversion

of a chemical reaction depend on the
temperature, pressure, and composition
of reactants.
Although reaction rates are not susceptible
to thermodynamic treatment, equilibrium
conversions are.
The purpose of this lecture is to determine
the effect of temperature, pressure, and
initial composition on the equilibrium
conversions of chemical reactions.
 REACTION COORDINATE

Chemical reaction

|1|A1 + |2|A2 + .. |3|A3 + |4|A4 + .

|1| = stoichiometric coefficient (+ve) product; (-)ve reactant
A1 = chemical formula

CH4 + H2O CO + 3H2

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 Final number of moles, ni
ni = nio + i reaction coordinate

n = ni = nio + i

n = no +
n = ni; no = nio; = i

ni nio + i
yi = =
n no +
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For a system in which the following reaction occurs, CH 4 + H 2O CO + 3H 2
assume there are present initially 2 mol CH4, 1 mol H2O, 1 mol CO and 4 mol H2.
Determine expressions for the mole fractions yi as functions of .
 Exercise 1

Develop expressions for the mole fractions of reacting

species as functions of the reaction coordinate.
Assume there are present initially the raw materials
with the number of moles according to the
stoichiometric numbers.

1. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

2. 2H2S(g) + 3O2 (g) 2H2O(g) + 2SO2 (g)

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 Multireaction Stiochiometry
Let j = reaction number For reaction j,
j = reaction coordinate for j = i , j
reaction j i
Then, final number of moles of Then
species i,
n = no + j j
ni = nio + i , j j j
j
Summing over all species,
nio + i , j j
n = nio + i , j j yi =
j

i i j no + j j
j

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Consider a system in which the following reactions occur,
CH 4 + H 2O CO + 3H 2 CH 4 + 2H 2O CO2 + 4H 2
if there are present initially 2 mol CH4 and 3 mol H2O, determine expressions for the
yi as functions of 1 and 2 .
 Exercise 2

Develop expressions for the mole fractions of reacting

species as functions of the reaction coordinate for the
two reactions. Assume there are present initially 3 moles
of C2H4 and 2 moles of O2.

C2H4(g) + 1/2O2 (g) [(CH2) 2)O(g)

C2H4 (g) + 3O2 (g) 2CO2 (g) + 2H2O(g)

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 Application of Equilibrium Criteria to
Chemical Reactions
Equilibrium and Stability
Qsys 1. System and surroundings
Wsurr are always in thermal and
mechanical equilibrium.
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2. Heat exchange and
expansion work are
accomplished reversibly.
2

dQsurr dQ
1 A, B, C dSsurr = =
Tsurr T

Closed system at nonequilibrium

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 2nd Law requires Combine the two
dS t + dSsurr 0 dU t + PdV t TdS t
dU t + PdV t TdS t 0
t
dQ TdS
At constant St and Vt
1st Law provides
(dU )
t
S t ,V t 0
dU t = dQ + dW = dQ PdV t
t
dQ = dU + PdV At constant Ut and Vt
(dS )
t
U t ,V t 0
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 For a process to occur at constant T and P
dUTt ,P + d (PV t )T ,P d (TS t )T ,P 0
d (U t + PV t TS t ) 0
From Gibbs energy :

G t = H t TS t = U t + PV t TS t

Therefore
(dG t )T ,P 0

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 If all real irreversible processes occurring at
constant T,P results in a decrease in Gibbs
Free Energy
The equilibrium state of a closed system is that
state for which the total Gibbs energy is a
minimum with respect to all possible changes at
the given T and P.

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 Standard Gibbs-Energy Change and The
Equilibrium Constant
Fundamental relation for single-phase systems:
d (nG ) = (nV )dP (nS )dT + i dn i
i

d (nG ) = (nV )dP (nS )dT + i i d

i

Because nG is a state function, at constant T,P

(nG ) (G t )
i i i = =
T ,P T ,P
At the equilibrium state:
i i =0
i
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 Recall the definition of
fugacity ^
G o
RT ln fi = 0
^ i i i
+
f io
i = i (T ) + RT ln f i

Gio = i (T ) + RT ln fi o ^ i

G o
RT n fi =0
i i
+i i f io
The difference between
the two equations:
^
^ i iGio
fi ln (f i / fi o ) i =
o
i G = RT ln o
i
i RT
fi
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 In exponential term
^
(f i / fi o ) i = K
i

The definition of K
G o
K exp
RT

G o
ln K =
RT
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Effect of Temperature on the Equilibrium Constant

The dependence of Go on T:

d ( G o / RT ) H o
=
dT RT 2

d ln K H o
=
dT RT 2

K H o 1 1
ln =
K' R T T '

See Figure 13.2

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Ln K vs 1/T
Effect of Temperature on the Equilibrium Constant

Standard Gibbs Energy

G o = H o TS o

o o
T CPo
H = H + R
0 dT
To R

o
T C P dT
S o = S0o + R
To R T

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Effect of Temperature on the Equilibrium Constant

Estimating standard Gibbs energy:

G o G0o H0o H0o 1 T CPo o

T C dT
P
= + + dT R
RT RT0 RT T To R To R T

Equilibrium constant:
G o
ln K =
RT

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Relation of Equilibrium Constants to Composition

Gas-Phase Reactions For mixture at equilibrium

SS for a gas is the ideal-gas behaves as an ideal solution
state of the pure gas fo =

Po. Thus for gas phase P
reactions: ( y i i ) i = o K
i P
^
i

fi
o = K For pressure sufficiently low or
i P
temperature sufficiently high,
equilibrium mixture behaves as
^ ^
Fugacity is defined as: f i = i y i P an ideal gas i = 1

^
P P
( y i i ) i = o K ( y i ) i = o K
i P i P
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 Exercise 3

The following reaction reaches equilibrium at 500oC and

2 bar:

4HCl(g) + O2(g) 2H2O(g) + 2Cl2(g)

If the system initially contains 5 mol HCl for each mole of

oxygen, what is the composition of the system at
equilibrium? Assume ideal gases.

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 Conclusion
d ln K H o
From dT
=
RT 2
the effect of T on K is determined by the sign of
Ho. When Ho is (+)ve, T K and vice-versa.

Equation

P
( y i ) = o K
i
i P
shows that K at constant P results in ( y i ) ; implies shift of
i
i
reaction to the right and e and vice-versa.

If is (-)ve, an increase in P at constant T causes ( y i ) ;

i
i
implies shift of reaction to the right and e and vice-versa.

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 Liquid-Phase Reactions
=1
o
( P P)
( xi i ) = K exp
i
( iVi )
i
RT i

( xi i ) i = K
i
i could be determined by Wilson equation or
UNIFAC method
If equilibrium mixture is an ideal solution, i = 1
( xi ) i = K
i

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 EQUILIBRIUM CONVERSIONS FOR SINGLE
REACTIONS

Water-gas-shift reaction:

CO(g) + H2O(g) CO2 (g) + H2 (g)

Assuming the mixture behaves as an ideal gas, calculate

the fraction of steam reacted for the following cases:

(a) The reactants consist of 1 mol of H2O vapor and 1

mol of CO. The temperature is 1100K and pressure is 1
bar

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b) Same as (a) except the pressure is 10 bar
c) Same as (a) except that 2 mol of N2 is included in the
reactants
d) The reactants are 2 mol of H2O and 1 mol of CO
e) The reactants are 1 mol of H2O and 2 mol of CO
f) The initial mixture consists of 1 mol of H2O, 1 mol of
CO and 1 mol of CO2.
g) Same as (a) except the temperature is 1650K

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 Exercise 4

Estimate the maximum conversion of ethylene to ethanol

by vapor-phase hydration at 250oC and 35 bars for an
initial steam-to-ethylene ratio of 5

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 Exercise 5

Acetic acid is esterified in the liquid phase with ethanol at

100oC and atmospheric pressure to produce ethyl
acetate and water according to the reaction:

CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)

If initially there is one mole each of acetic acid and

ethanol, estimate the mole fraction of ethyl acetate in the
reacting mixture at equilibrium.

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 REACTIONS IN HETEROGENEOUS
SYSTEMS
Consider the reaction ^
(f i / fi o ) i = K
i

A(g) + B(l) C(aq) ^

f c / f oc mc
^ ^
= ^
=K
Equilibirium constant is (f B / f Bo)(f A / f Ao) ( B xB )(f A / P o )
based on mixed standard
states*
C as solute in an ideal 1-
molal aqueous solution
B as pure liquid at 1 bar
C as pure ideal gas at 1
bar
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PHASE RULE AND DUHEMS THEOREM
FOR REACTING SYSTEMS
For non-reacting systems
Variables No. of
variables
T, P 2

Mol fractions N-1

Phases
Degrees of freedom
Total 2 + (N-1)

Equations No. of relations F = 2 + (N-1) ( 1)N

Equilibrium ( - 1)N F=2+N
relation
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PHASE RULE AND DUHEMS THEOREM
FOR REACTING SYSTEMS
For reacting systems
Variables No. of variables
Degrees of freedom
T, P 2

Mol fractions N-1

F = 2 + (N-1) ( 1)N - r
Phases F=2+Nr

Total 2 + (N-1)
When there is special
Equations No. of relations constraint, s is the number
of equations:
Equilibrium ( - 1)N
relation
F=2+Nr-s
Independent r
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chemical reactions
 Determining F and r for reacting systems

Determine F for each of the following systems:

(a) A system of two miscible non-reacting species which
exist as an azeotrope in VLE

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(b) A system prepared by partially decomposing CaCO3
into an evacuated space:

CaCO3(s) CaO(s) + CO2(g)

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c) A system prepared by partially decomposing NH4Cl into
an evacuated space.

NH4Cl NH3(g) + HCl(g)

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 MULTIREACTION EQUILIBRIA

When the equilibrium state in a reacting system depend on two or

more independent chemical reactions:
^
i,j

fi
o = Kj
i f
i ^
i,j

For a gas phase reaction: f i
= Kj
i
o
P

If the equilibrium mixture is an ideal gas:
j
i,j P
( y i ) = o Kj
i P

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 Exercise

The feed gas to a methanol synthesis reactor is

composed of 75 mol% H2, 15 mol% CO, 5 mol% CO2
and 5 mol% N2. The system come to equilibrium at 550K
and 100 bar with respect to the reactions:

2H2 (g) + CO(g) CH3OH(g)

H2 (g) + CO2 (g) CO(g) + H2O(g)

Assuming ideal gases, determine the composition of the

equilibrium mixture

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