Chemical Engineering Thermodynamics

CHEMICAL  REACTION  EQUILIBRIUM    

                                   

Mohammad Fadil Abdul Wahab

 Outcomes  for  This  Chapter  

a)  To  define  what  is  extend  of  reacCon  and  relate  it  to  the  
mole  fracCon  (composiCon)  
b)  To  derive  the  equilibrium  criteria  for  chemical  reacCon  
c)  Use  b)  to  derive  equilibrium  constant  (K)  and  able  to  
calculate  K  
d)  To  relate  K  to  fugacity  and  mole  fracCon  and  able  to  
calculate  the  equilibrium  conversion  for  gas  phase  
reacCon  
e)  Analyze  the  effect  of  T  and  P  on  K  and  equilibrium  
composiCon  endothermic  and  exothermic  reacCons  
 Commercial  Chemical-­‐ReacCon  
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-­‐ReacCon  
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.
 ReacCon  KineCcs  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  ReacCons  
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  ReacCons  
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  EquaCon  
ν 1 A1 + ν 2 A 2 → ν 3 A 3 + ν 4 A 4

ν1 ,ν 2 are stoic. coefficients of reactant ( - value)

ν 3 ,ν 4 are stoic. coefficients of product ( + value)
A1 , A 2 , A 3 , A 4 are molecules or atoms

Example,
CH 4 + 2O2 → CO2 + 2H 2O
ν CH4 = −1, ν O2 = −2
ν CO2 = 1, ν H2O = 2
 ReacCon  Coordinate  (ε)  
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

= = = = = dε
ν1 ν2 ν3 ν4 νi

dni = ν i d ε .....(13.3)
 Example  
The following reaction consumes 10 mols of methane,

CH 4 + 2O2 → CO2 + 2H 2O

dnCH 4 −10 dnO2 −20

dε = = = 10, = = 10,
ν CH 4 −1 ν O2 −2

dnCO2 10 dnH 2O 20
= = = 10, = = 10
ν CO2 1 ν H 2O 2
Reaction coordinate (ε) characterizes the extent
or degree to which a reaction has taken place.

Also known as,

the extent of reaction (as used in Felder and Rousseau),

progress variable,
degree of advancement,
degree of reaction.
 For  Single  ReacCon  
For species i, integrate eqn 13.3 from initial state (ε=0)
to a state where ε = ε , so
ni ε

∫ dni = ∫ ν i d ε
nio 0

ni − nio = ν i (ε − 0)
ni = nio + ν iε
Note: At initial state prior to reaction, ε=0

Summation over all species,

∑ ni = n = ∑ nio + ε ∑ ν i
= no + νε
So mole fraction of species i,

ni nio + ν iε
yi or xi = =
n no + νε

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

Example  
CH 4 +H 2O → CO +3H 2

Initial composition (prior to rxn):

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

Express yi as functions of ε.

nio + ν iε no =∑ nio = 2 + 1 + 1 + 4 = 8
yi =
no + νε ν = ∑νi = 1 + 3 − 1 − 1 = 2

2−ε 1− ε 1+ ε 4 + 3ε
yCH 4 = y H 2O = yCO = yH 2 =
8 + 2ε 8 + 2ε 8 + 2ε 8 + 2ε
 For  MulCple  ReacCons  
dni = ∑ ν ij d ε j
j

For species i and reaction j, we integrate from initial

state (ε=0) to a state where εj= εj, so

ni − nio = ∑ ν ij (ε j − 0)
j

ni = nio + ∑ ν ij ε j
j

Summation over all species (i),

∑ ni = n = ∑ nio + ∑ ∑ ν ijε j
i i i j
 So mole fraction of species i,

nio + ∑ ν ij ε j
ni j
yi or xi = =
n ∑ nio + ∑ ∑ ν ijε j
i i j

Example of multiple rxns, Main reaction,

C2 H 6 → C2 H 4 + H 2

Side reactions,

C2 H 6 + H 2 → 2CH 4

C2 H 4 + C2 H 6 → C3 H 6 + CH 4
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  
From FPR for homogenous system of variable composition,
d(nG) = (nV )dP − (nS)dT + ∑ µi dni (11.2)
i

For system with single chemical reaction,

substitute eqn 13.3,

d(nG) = (nV )dP − (nS)dT + ∑ ν i µi d ε

i

Apply the criterion of exactness,

⎡ d(nG) ⎤
⎢ d ε ⎥ = ∑ ν i µi
⎣ ⎦T , P i
Using 1st law, 2nd Law and FPR, we could show that at
equilibrium (see chapter 14 and next slide),

(dnG)T , P = 0 (14.68)

So, at chemical rxn equilibrium,

⎡ d(nG) ⎤
⎢ dε ⎥ = 0
⎣ ⎦T , P
Hence,

∑ ν i µi = 0 (13.8) This is the criteria of

i Chemical Rxn Equilibrium
All irreversible process occurring at constant T & P proceed in
such a direction as to cause a decrease in the Gibbs energy
of the system.
As derived previously (eqn 11.8, 11.46),

d µi = dGi = RTd ln fˆi (contant T)

Integrate from standard state of pure species i

to a state of species i in a solution (at equilibrium T),
fˆ
µi − Gio = RT ln io (contant T)
fi
fˆi
µi = Gi + RT ln o
o

fi

Substitute into the criteria of chem rxn equilibrium (eqn 13.8),

νi
fˆi ⎛ fˆi ⎞
∑ ν i µi = ∑ ν i (G + RT ln f o ) = ∑ ν iG + RT ∑ ln ⎜ f o ⎟ = 0
i
o
i
o

i i i i i ⎝ i ⎠
Rearrange:
νi νi
⎛ fˆi ⎞ ⎛ fˆi ⎞
∑ ν iGi + RT ∑ ln ⎜ o ⎟
o
= ∑ ν iGi + RT ln ∏ ⎜ o ⎟
o
=0
i i ⎝ fi ⎠ i i ⎝ fi ⎠

∏ signifies the product over all species i.

i

e.g. Π ai = a1a2 a3a4 a5 .

i=5

νi
⎛ fˆi ⎞
Let ∏⎜ f o ⎟ =K (13.10)
i ⎝ i ⎠

K is known as equilibrium constant.

So,
∑ i i + RT ln K = 0
ν G o

− ∑ ν iGio
−ΔG o
ln K = i
=
RT RT

where,
∑ ν iGio = ΔG o (13.12)
i

= The Std Gibbs Energy Change of Rxn at equi T

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

See Table C.4 pg 686

 EXAMPLE
CH 4 +H 2O(g) → CO +3H 2

Calculate ∆Go at 298K,

ΔG o = ∑ i i
ν G o

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

= ν H 2 ΔG of , H 2,298 +ν CO ΔG of ,CO,298 + ν CH 4 ΔG of ,CH 4,298 + ν H 2O ΔG of , H 2O,298

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

=141863 Joules/mol CH 4 reacted #

 −ΔG o
ln K = (13.11b)
RT

⎛ −ΔG o ⎞
K = exp ⎜ ⎟ (13.11a)
⎝ RT ⎠

for T=T0

⎛ − ΔG0o ⎞
K0 = exp ⎜ ⎟ (13.21)
⎝ RT0 ⎠

Note: Data for standard state is

usually available at T0=298.15K
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,

ΔH o
d ln K = 2
dT (13.14)
RT

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

integration gives,

K ΔH o ⎛ 1 1 ⎞
ln ' = − ⎜ − '⎟ (13.15)
K R ⎝T T ⎠
We could rearrange,
⎡ ΔH o
⎛ 1 1 ⎞⎤
K = K exp ⎢ −
'
⎜ − '⎟⎥
⎣ R ⎝T T ⎠⎦

Let's use ΔH o = ΔH 0o and T ' = To

⎡ ΔH 0o ⎛ 1 1 ⎞ ⎤ ⎡ ΔH 0o ⎛ T0 ⎞ ⎤
K = K 0 exp ⎢ − ⎜ − ⎟ ⎥ = K 0 exp ⎢ ⎜ 1− ⎟ ⎥
⎢⎣ R ⎝ T T0 ⎠ ⎥⎦ ⎢⎣ RT0 ⎝ T ⎠ ⎥⎦

= K 0 K1

where,
⎛ ΔH 0o ⎛ T0 ⎞ ⎞
K1 = exp ⎜ ⎜ 1− ⎟⎟ (13.22)
⎝ RT0 ⎝ T ⎠⎠
 K ΔH o ⎛ 1 1 ⎞
ln ' = − ⎜ − '⎟
K R ⎝T T ⎠
Eqn (13.15) can also be written as,

ΔH o 1 ⎛ ΔH o 1 ⎞
ln K = − +⎜ '
+ ln K '⎟ (13.15a)
R T ⎝ R T ⎠
1
Plot of ln K vs is a straightline as shown
T
in Figure 13.2. ΔH o
− = slope
R

Exothermic reaction, slope positive,

(K decrease with increasing T)

Endothermic reaction, slope negative,

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

K = K 0 K1 K 2 Note: Data for standard state is

usually available at T0=298.15K
or 25oC and Po=1 bar
where,
⎛ −ΔG0o ⎞ ⎛ ΔH 0o ⎛ T0 ⎞ ⎞
K 0 = exp ⎜ ⎟ K1 = exp ⎜ ⎜ 1− ⎟⎟
⎝ RT0 ⎠ ⎝ RT0 ⎝ T ⎠⎠

⎧ τ −1 1 (τ − 1)2 ⎫
⎪ ΔA[ln τ − ( )] + ΔBT0 + ⎪
⎪ τ 2 τ ⎪
K 2 = exp ⎨ 2 ⎬ (13.24)
⎪ 1 (τ − 1) 2
(τ + 2) 1 ΔD (τ − 1) ⎪
ΔCT02 +
⎪⎩ 6 τ 2 T02 τ 2 ⎪⎭
T
where, τ= For heat capacity constant, ΔA = ∑ ν i Ai etc.
T0 i
 RelaCon  of  K  to  equilibrium  
composiCon  (yi)  
Gas-Phase Reactions.
νi
From definition of K, ⎛ fˆi ⎞
K = ∏⎜ o ⎟
i ⎝ fi ⎠

Let the standard state be the ideal-gas state of

pure species i at Po (= 1 bar).

⎛ fˆi ⎞
νi
⎛ φ̂i yi P ⎞
νi ∑ νi
⎛ P⎞
∏ (φ̂i yi )
νi
K = ∏⎜ o ⎟ = ∏⎜ o ⎟ = ⎜ o⎟
i ⎝ P ⎠ i ⎝ P ⎠ ⎝P ⎠ i
also ∑νi = ν
ν
⎛ P⎞
∏ (φ̂i yi )
νi
K = ⎜ o⎟
⎝P ⎠ i

so

−ν
⎛ P⎞
∏ (φ̂i yi )
νi
= ⎜ o⎟ K (13.26)
i ⎝P ⎠
If the mixture is an ideal mixture,

−ν
⎛ P⎞
∏ ( yiφi )
νi
= ⎜ o⎟ K (13.27)
i ⎝P ⎠

If the mixture is an ideal mixture at low pressure,

it becomes an ideal-gas mixture, so

−ν
⎛ P⎞
∏ ( yi )
νi
= ⎜ o⎟ K (13.28)
i ⎝P ⎠
Remember, we can express yi in terms of ε ,

For single rxn,

nio + εν i
yi =
∑ nio + ε ∑ ν i

For multiple rxns,

nio + ∑ ν ij ε j
j
yi =
∑ nio + ∑ ∑ ν ijε j
i i j
 Effect  of  T  and  P  on  Equilibrium  
Conversion  
Consider an ideal gas reaction,
−ν
⎛ P⎞
∏ ( yi )
νi
= ⎜ o⎟ K (13.28)
i ⎝P ⎠

And eqn 13.15a gives the

relation of K wrt. T,
ΔH o 1 ⎛ ΔH o 1 ⎞
ln K = − +⎜ '
+ ln K '⎟
R T ⎝ R T ⎠
Effect of TEMPERATURE ⎛ P⎞
−ν

∏ ( yi )
νi
= ⎜ o⎟ K
i ⎝P ⎠
For endothermic rxn, an
increase in T will result in
an increase in K,
therefore an increase in,
ν ν
yc c y d d
∏ ( yi )
νi
= |ν | |ν |
i y a a yb b

The composition or fraction

of products will be higher.

An increase in εe.

Shift of rxn to the right.

Higher equilibrium conversion.

Effect of TEMPERATURE ⎛ P⎞
−ν

∏ ( yi )
νi
= ⎜ o⎟ K
i ⎝P ⎠
For exothermic rxn, an increase
in T will result in a decrease in
K, therefore a decrease in,
ν ν
yc c y d d
∏ ( yi )
νi
= |ν | |ν |
i y a a yb b

The composition or fraction

of products will be reduced.

A decrease in εe.

Shift of rxn to the left.

Lower equilibrium conversion.

 −ν
Effect of PRESSURE ⎛ P⎞
∏ ( yi )
νi
= ⎜ o⎟ K
i ⎝P ⎠

If ν is negative* value, an
increase in P (at constant T)
causes an increase in,
V V
yc y d
∏ ( yi ) = |V | |V |
c d
ν
i

i y a yb
a b

The composition or fraction

of products will be higher.

An increase in εe.

Shift of rxn to the right.

Higher equilibrium conversion.

*reduction in mole number

 −ν
Effect of PRESSURE ⎛ P⎞
∏ ( yi )
νi
= ⎜ o⎟ K
i ⎝P ⎠

If ν is positive* value, an
increase in P (at constant T)
will result in a decrease in,
V V
yc c y d d
∏ ( yi )
νi
= |V | |V |
i y a a yb b

The composition or fraction

of products will be reduced.

A decrease in εe.
Shift of rxn to the left.

Lower equilibrium conversion.

*increase in mole number
 RelaCon  of  K  to  equilibrium  
composiCon  (xi)  
Liquid-Phase Reactions.
νi
From definition of K, ⎛ fˆ ⎞
K = ∏ ⎜ io ⎟
i ⎝ fi ⎠

Let the std state be the pure liquid of

species i at the system temperature and 1 bar.
Substitute eqn 11.90,
νi
⎛ γ i xi f i ⎞
K = ∏⎜ o ⎟
i ⎝ f i ⎠
 fi
To find o in term of measured variable,
fi

Gi = Γ i (T ) + RT ln f i (11.31)

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

Gio = Γ i (T ) + RT ln f i o

The difference,

fi
Gi − G = RT ln
i
o

fi o
From FPR, dG = VdP − SdT at constant T

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

P
Gi − Gio = ∫ Vi dP
Po

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

For Vi =Viliq ≈ constant

fi
RT ln = Vi (P − P o )
fi o
So, fiVi (P − P o ) fi ⎛ Vi (P − P o ) ⎞
ln o = o
=exp ⎜ ⎟
fi RT fi ⎝ RT ⎠
Substitute and rearrange,
νi νi
⎛ γ i xi f i ⎞ ⎛ ⎛ Vi (P − P ) ⎞ ⎞
o
K = ∏⎜ o⎟
= ∏ ⎜ γ i xiexp ⎜ ⎟⎟
i ⎝ f i ⎠ i ⎝ ⎝ RT ⎠⎠

⎛ ν V (P − P o
) ⎞ ⎛ (P − P o
) ⎞
= ∏ (γ i xi ) exp ⎜ ⎜ RT ∑ i i ⎟ ∏ i i
νi νi
i i
⎟ = exp (ν V ) (γ x )
i ⎝ RT ⎠ ⎝ i ⎠ i
So,

⎛ (P0 − P) ⎞
∏ (γ i xi ) = Kexp ⎜ RT ∑ (ν iVi )⎟
νi
(13.31)
i ⎝ i ⎠
The exponent term is usually 1, except for high
pressure system, so,

∏ (γ i xi ) i = K
ν
(13.32)
i

For ideal liquid solution,

∏ (xi ) i = K
ν
(13.33) Known as the law of mass action
i

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

 Exercise  
•  Calculate  K  in  Example  13.5a  and  for  
equilibrium  reacCon,  determine  the  fracConal  
conversion  of  steam.  

•  FracConal  conversion  of  steam  

     =  ε  /  (iniCal  mol  of  steam)    
Thank  You