Chemical Reaction

Equilibrium

ECH3120 Chemical Engineering

Thermodynamics
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 Outcomes for This Chapter

1. To define what is extend of reaction and relate it to the

mole fraction (composition)
2. To derive the equilibrium criteria for chemical
reaction
3. Use 2) to derive equilibrium constant (K) and able
to calculate K
4. To relate K to fugacity and mole fraction and able to
calculate the equilibrium conversion for gas phase
reaction
5. Analyze the effect of T and P on K and equilibrium
composition endothermic and exothermic reactions
 Commercial Chemical-‐Reaction
1. Chemical reaction is the heart of chemical processes.

2. Take place in a reactor.

3. A value-added process.
• Transform raw materials into products of greater value.

Economic potential or Gross Profit must be positive.

i.e. Main products have a higher price than the raw materials

(reactants).

Gross Profit is based solely on price of reactants and products ,

excluding the equipment and operating costs.
 Study of Chemical-‐Reaction
1. Reaction Kinetics

The study of rates of reaction

i.e. How fast is the reaction?
You will learn this in your Chemical Reaction Engineering
class.

2. Chemical Reaction Equilibrium

Determination of maximum possible conversion

in a chemical reaction.
This chapter will cover this part.
 Reaction Kinetics vs Conversion
1. Both reaction kinetics and equilibrium conversion are
function of T, P and composition

2. Example: Exothermic reaction,

• An increase in reaction T will increase in rates of reaction

but decreases the conversion.

3. So both kinetics and equilibrium conversion must be

considered for optimum reactor design.
 Note:

Overall Conversion

reactant input to process - reactant output from process

= x100
reactant input to process

Single-Pass Conversion

reactant input to reactor - reactant output from reactor

= x100
reactant input to reactor
 Irreversible Reactions
Single direction (from reactants to products).
i.e. forward reaction only.

These reactions highly favor formation of the products.

L + R P + S

Only an extremely small quantity of limiting

reactants (if any) remains in the system at equilibrium.

Usually 100% single-pass conversion (of limiting reactant) is

considered.
 Reversible Reactions

Forward and reverse reactions.

• Eventually equilibrium is reached where rate of forward

reaction is equal to rate of reverse reaction
A +B C + D

• Appreciable quantities of all reactants and products

species can coexist at equilibrium.

• Hence the extent of reaction (also conversion) is

limited by the chemical equilibrium.
Stoichiometric Equation
 Extent of reaction(ξ)
For a reaction, the changes in the number of moles (ni) of the
species present in the reaction chamber are in direct
proportion to the stoichiometric numbers (vi).

dn1 dn2 dn3 dn4 dni

= = = = = dξ
v1 v2 v3 v4 vi

dni = viξ Eqn 1

 Example
The following reaction consumes 10 mols of methane,

CH4 + 2O2 → CO2 + 2H 2 O

dnCH 4 −10 dnO2 −20

dξ = = = 10, = = 10,
νCH 4 −1 νO 2 −2

dnCO2 10 dnH 2O 20
= = = 10, = = 10
νCO 2 1 ν H 2O 2
 Extent of Reaction

Extent of reaction(ξ) characterizes the extent or

degree to which a reaction has taken place.

Also known as,

 Reaction coordinates,
 progress variable,
 degree of advancement ,
 degree of reaction.
 For Single Reaction
For species i, integrate Eqn 1 from initial state (ξ=0) to a
state where ξ = ξ , so
ni ε

∫ dni = ∫ ν i d ξ
nio 0

• ni − nio = νi (ξ − 0)
• ni = nio + νiξ
• Note: At initial state prior to reaction, ξ= 0
• Summation over all species,

• ∑n = n = ∑n
i io + ξ ∑νi
• = no + νξ
 + νiξ

So mole fraction of species i,

ni nio + νiξ
yi or xi = =
n no + νξ

.......... mole fraction of species i is a function of ξ

 Example
CH4 +H2O → CO +3H2

Initial composition (prior to rxn):

2 mol CH4, 1 mol H2O, 1 mol CO and 4 mol H2.

Express yi as functions of ξ.

nio + νiξ no = ∑ nio = 2 + 1 + 1 + 4 = 8

yi =
no + νξ ν = ∑ν i = 1 + 3 − 1 − 1 = 2

2−ξ 1− ξ 1+ ξ 4 + 3ξ
yCH 4 = y H 2O = yCO = yH 2 =
8 + 2ξ 8 + 2ξ 8 + 2ξ 8 + 2ξ
 For Multiple Reactions
dni = ∑ ν ij d ξ j
j

For species i and reaction j, we integrate from initial

state (ξ=0) to a state where ξj= ξj, so

ni − nio = ∑νij (ξ j − 0)
j

ni = nio + ∑νijξ j
j

Summation over all species (i),

∑ ni = n = ∑ nio + ∑∑νijξ j
i i i j
So mole fraction of species i,
nio + ∑νijξ j
ni j
yi or xi = =
n ∑ nio + ∑∑ ν ijξ j
i i j

Example of Main reaction,

multiple rxns,
C2 H6 → C2 H4 + H2

Side reactions,
C2 H6 + H2 → 2CH4
C2 H4 + C2 H6 → C3 H6 + CH4
 Also for multiple reactions,

Yield

moles of desired product formed

=
moles that would have been formed if there were no side reactions and
the limiting reactant had reacted completely

Selectivity

moles of desired product formed

=
moles of undesired product formed
 Criteria of Chem Rxn Equilibrium
For homogenous system of variable composition,

d(nG) = (nV )dP − (nS )dT + ∑ µi dni (Eqn 2)

i

For system with single chemical reaction, substitute eqn 1,

d(nG) = (nV )dP − (nS )dT + ∑νi µidξ

i

Apply the criterion of exactness,

 d (nG ) 
 d ξ  = Σi vi µi
 T , P
The system comes to chemical equilibrium at the extent of
reaction for which the Gibbs energy is a minimum. Applying this
criterion gives:

(dnG)T , P = 0

So, at chemical rxn equilibrium,

Hence,
∑νi µi = 0 This is the criteria of
i Chemical Rxn Equilibrium
• The minimum Gibbs
Free Energy balances
the entropy gained
through diversifying
the material present
with the energy gained
by changing the bond
energies.
• We note that the
minimum free energy
as a function of ξ is
found where dG/dξ =0.
Using the standard state, the change chemical potential is written as:

dµ = dG = RTd ln fˆ (contant T)
i i i

Integrate from standard state of pure species i

to a state of species i in a solution (at equilibrium T),
f iˆ
µi − G = RT ln
i
o
(contant T)
fi o

fˆi
µi = G + RT ln o
i
o

fi

Substitute into the criteria of chem rxn equilibrium,

fˆ  fˆ  νi
∑ νi µi = ∑ ν i (Gio + RT ln f io ) = ∑ ν iGio + RT ∑ ln  f io  = 0
i i i i i  i 
Rearrange:
 fˆ  νi  fˆ  νi
∑ ν iGio + RT ∑ ln  io  = ∑ ν iGio + RT ln ∏  io  = 0
i i  fi  i i  fi 

∏ signifies the product over all species i.

i

e.g. Π ai = a1a2 a3a4 a5 .

i =5

ν
 fˆ  i
Let ∏  io  = K
i  fi 

K is known as equilibrium constant.

So,
∑ ν iGio + RT ln K = 0
i

− ∑ ν iGio
−∆ G o
ln K = i
=
RT RT

where,
∑ ν iGio = ∆Go
i

= The Std Gibbs Energy Change of Rxn at equi. T

The data for Gio is available in the form of ∆Gof,i,298

 Example

CH4 + H 2 O(g) → CO + 3H2

Calculate ∆Go at 298K,

∆Go = ∑ ν iGio
i

= ν H 2GoH 2 +ν CO GCO
o
+ ν CH 4GCH
o
4
+ ν G o
H 2O H 2O

= ν H 2 ∆Gof , H 2,298 +ν CO ∆Gof ,CO,298 + ν CH 4 ∆G f ,CH 4,298 + ν H 2O ∆Gof , H 2O,298

o

=3(0) + 1(-137169) + (-1)(-50460) + (-1)(-228572)

=141863 Joules/mol CH4 reacted #

 −∆G 0
ln K =
RT
 −∆G 0 
K = exp  
 RT 

for T=T0

 −∆G 0  Note: Data for standard state is

K 0 = exp   usually available at T0=298.15K
 RT0  or 25oC and Po=1 bar
 Effect of T on K
To calculate K at T other than the standard state T of 298K.
Let’s use van Hoff’s eqn,

If ∆H o (std heat of rxn) could be assumed CONSTANT,

integration gives,

K −∆H 0  1 1 
ln '
=  − '
K R T T 
We could rearrange,
 ∆H o  1 1  
K = K exp −
'
− '

 R T T  

Let's use ∆H o = ∆H0 and T = To

o '

K = K0 exp − ∆H o0  1 − 1   = K0 exp  ∆H0o  1 − T0  

 R  T T0    RT0  T  

= K0 K1

where,
 ∆H0o  T0  
K1 = exp  1 − T 
 RT0
 This eqn can also be written as,

∆H o 1 +  ∆H o 1 
ln K = −  + ln K '
R T  R T '


1
Plot of ln K vs is a straightline
T
− ∆H o
= slope
R

Exothermic reaction, slope positive,

(K decrease with increasing T)

Endothermic reaction, slope negative,

(K increase with increasing T)
 If ∆H o could not be assumed constant,

K = K0 K1 K2 Note: Data for standard state is

usually available at T0=298.15K
or 25oC and Po=1 bar
where,
 −∆G o   ∆H0o  T0  
K 0 = exp K1 = exp  1− T 
0

 RT0   RT0

 τ − 1)] + 1 ∆BT (τ − 1)2 

∆
 A[lnτ − ( 0 + 
 τ 2 τ 
K 2 = exp  2
 1 ( τ − 1) 2
( τ + 2) 1 ∆D ( τ − 1) 
∆CT02 +
 6 τ 2 T02
τ 2


T
where, τ= For heat capacity constant, ∆A = ∑ν i Ai etc.
T0 i
 Relation of K to equilibrium composition (yi)
Gas-Phase Reactions.
vi
 fˆ 
From definition of K, K = Π 0 
i  f 
 i 

Let the standard state be the ideal-gas state of pure species i

at Po (= 1 bar).

v
 fˆ 
i vi Σvi
 ϕi yi P   P 
K=
Π 0  = Π 0  =   Π (ϕi yi )
  0
p   p  p  i
i i
also ∑νi = ν
v
 P 
=K  0  Π (ϕi yi )vi
p  i

So,
−v
 P 
Π (ϕi yi ) =
vi
 0 K
i
p 
If the mixture is an ideal mixture,
−v
 P 
Π (ϕi yi ) =
vi
 0  K
i
p 

If the mixture is an ideal mixture at low pressure, it becomes an

ideal-gas mixture, so

−v
vi  P 
Π ( yi ) =
 0 K
i
p 
Remember, we can express yi in terms of ξ,

For single rxn,

nio + ξνi
yi =
∑ nio + ξ ∑ν i

For multiple rxns,

nio + ∑νijξ j
j
yi =
∑ nio + ∑∑ν ijξ j
i i j
Effect of T and P on Equilibrium Conversion
Consider an ideal gas reaction,
−v
vi  P 
Π ( yi ) =
 0 K
i
p 

This below equation gives the relation of K wrt. T,

 Effect of Temperature
−v
For endothermic rxn, an increase in T vi  P 
Π ( yi ) =  0 K
will result in an increase in K, i
p 
therefore an increase in,
vc vd
vi y c yd
Π ( yi ) = va vb
i
ya yb

The composition or fraction of products will be higher.

• An increase in ξe.
• Shift of rxn to the right.

• Higher equilibrium conversion.

 Effect of Temperature
−v
For exothermic rxn, an increase in T vi  P 
Π ( yi ) =  0 K
will result in an decrease in K, i
p 
therefore an increase in,
vc vd
vi y c yd
Π ( yi ) = va vb
i
ya yb

The composition or fraction of products will be reduce.

• An decrease in ξe.
• Shift of rxn to the left.

• Lower equilibrium conversion.

 Effect of PRESSURE
If ν is negative* value, an −v
 P 
increase in P (at constant T) vi
Π ( yi ) =  0 K
causes an increase in,
i
p 

vc vd
viy y
Π ( yi ) = c
va
d
vb
i
y y a b

The composition or fraction of products will be higher.

• An increase in ξe.
• Shift of rxn to the right.

• Higher equilibrium conversion.

• *reduction in mole number

 Effect of PRESSURE
If ν is positive* value, an −v
 P 
increase in P (at constant T) vi
Π ( yi ) =  0 K
causes an increase in,
i
p 

vc vd
viy y
Π ( yi ) = c
va
d
vb
i
y y a b

The composition or fraction of products will be reduce.

• An decrease in ξe.
• Shift of rxn to the left.

• Lower equilibrium conversion.

• *increase in mole number

 Example 3

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 Solution

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 E-1

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Since P = 1 bar, equation (E-3) becomes

E-4

ξ ξ ξ ξ

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 ζ≅ξ

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 Relation of K to equilibrium composition (xi)
Liquid-Phase Reactions.
ν
 fˆ  i
From definition of K, K = ∏  io 
i  fi 

Let the std state be the pure liquid of

species i at the system temperature and 1 bar.

vi
 γ i xi fi 
K = Π 0 
i
 fi 
 fi
To find fi o
in term of measured variable,

Gi = Γ i (T ) + RT ln fi

Apply at T and std state pressure of P=1 bar,

Gio = Γ (T ) + RT ln f o
i i

The difference,

fi
Gi − Gio = RT ln
fi o
From FPR, dG = VdP − SdT at constant T

Integrate at constant T for pure liquid i from Po to P,

P
Gi − Gio = ∫ Vi dP
Po

Combine ,
fi P
RT ln o =
fi
∫ Vi dP
Po

For V =Vliq ≈ constant

i i

fi
RT ln = V ( P − P o
)
fi o i
So, f i Vi (P − Po ) fi  Vi ( P − Po ) 
ln o = =exp 
fi RT fi o
 RT 
Substitute and rearrange,
νi νi
 γ i xi f i    Vi ( P − Po )  
K = ∏  = ∏  γ i xiexp  
i  fi o  i   RT 

 ν V ( P − Po )   ( P − Po ) 
= ∏(γ i xi ) exp
νi i i
RT
 = exp  RT ∑ ( ν i i ∏
V )
 i
( γ x
i i
) νi

i   i

So,

 ( P0 − P) 
∏(γ i xi ) = Kexp  RT ∑(ν iVi ) 
νi

i i
The exponent term is usually 1, except for high pressure
system, so,

Π (γ i xi ) =
vi
K
i

For ideal liquid solution,

vi Known as the law of mass

Π ( xi ) =
K action
i

As shown earlier, xi can be written in term of ξ

 Discussion
Consider the production of ammonia from the catalytic reaction
of a stoichiometric feed of nitrogen and hydrogen. As we saw,
when the reaction temperature is 500°C and the reactor
pressure is 1 bar, the conversion is very low. We wish to change
the reactor conditions to increase conversion. Would you pick T
or P? Which way would you change?

N2 + 3H2 ⇔ 2NH3

Hint:

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