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Chemical Engineering Thermodynamics

CHEMICAL REACTION EQUILIBRIUM




Mohammad Fadil Abdul Wahab

Outcomes for This Chapter


a) To dene 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 eect 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

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

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
1 A1 + 2 A 2 3 A 3 + 4 A 4
1 , 2 are stoic. coefficients of reactant ( - value)
3 , 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

CH4 = 1, O2 = 2
CO2 = 1,

H2O = 2

ReacCon Coordinate ()
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


=
=
=
=
= d
1
2
3
4
i
dni = i d

.....(13.3)

Example
The following reaction consumes 10 mols of methane,

CH 4 + 2O2 CO2 + 2H 2O

d =

dnCH 4

CH 4

10
=
= 10,
1

dnCO2 10
=
=
= 10,
CO2
1

dnO2

O2

20
=
= 10,
2

dnH 2O 20
=
= 10
H 2O
2

Reaction coordinate () 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 (=0)
to a state where = , so
ni

nio

dni = i d

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

=0

Summation over all species,

ni = n = nio + i
= no +

So mole fraction of species i,

yi or xi =

ni
=
n

nio + i
no +

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

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 .

yi =

yCH 4

nio = 2 + 1 + 1 + 4 = 8
= i = 1 + 3 1 1 = 2

nio + i

no =

no +

2
=
8 + 2

y H 2O

1
=
8 + 2

yCO

1+
=
8 + 2

yH 2

4 + 3
=
8 + 2

For MulCple ReacCons


dni = ij d j
j

For species i and reaction j, we integrate from initial


state (=0) to a state where j= j, so

ni nio = ij ( j 0)
j

ni = nio + ij j
j

Summation over all species (i),

ni = n = nio + ij j
i

So mole fraction of species i,

yi or xi

ni
=
=
n

nio + ij j
j

nio + ij j
i

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 + i dni

(11.2)

For system with single chemical reaction,


substitute eqn 13.3,
d(nG) = (nV )dP (nS)dT + i i d
i

Apply the criterion of exactness,


d(nG)
d = i i
i

T , P

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)
d = 0

T , P

Hence,

i i = 0
i

(13.8) This is the criteria of


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 i = dGi = RTd ln fi

(contant T)

Integrate from standard state of pure species i


to a state of species i in a solution (at equilibrium T),

f
i Gio = RT ln io
(contant T)
fi
fi
o
i = Gi + RT ln o
fi
Substitute into the criteria of chem rxn equilibrium (eqn 13.8),
fi
i i = i (G + RT ln f o ) = iG + RT ln f o = 0
i
i
i
i
i
i
o
i

fi

o
i

Rearrange:
fi
o
iGi + RT ln o
i
i
fi

fi
o
= iGi + RT ln o
i fi
i

signifies the product over all species i.

e.g.

Let

ai = a1a2 a3a4 a5 .

i=5

fi
f o
i i

=K

(13.10)

K is known as equilibrium constant.

=0

So,

G
i i + RT ln K = 0
i

ln K =

iGio
i

RT

G o
=
RT

where,

iGio = G o

(13.12)

= 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,
G o =

G
i i
i

o
o
o
= H 2GHo 2 + CO GCO
+ CH 4GCH
+

G
4
H 2O H 2O

= H 2 G of , H 2,298 + CO G of ,CO,298 + CH 4 G of ,CH 4,298 + H 2O G of , H 2O,298


=3(0) + 1(-137169) + (-1)(-50460) + (-1)(-228572)
=141863 Joules/mol CH 4 reacted

G o
ln K =
RT

(13.11b)

G o
K = exp

RT

(13.11a)

for T=T0

K0

G0o
= exp

RT0

(13.21)

Note: Data for standard state is


usually available at T0=298.15K
or 25oC and Po=1 bar

Eect of T on K
To calculate K at T other than the standard state T
of 298K. Lets use van Hoffs eqn,
H o
d ln K =
dT
2
RT

(13.14)

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


integration gives,
K
H o 1 1
ln ' =
'

R T T
K

(13.15)

We could rearrange,

1 1
H
'
K = K exp
'

R T T

Let's use H o = H 0o and T ' = To


H 0o 1 1
H 0o T0
K = K 0 exp
= K 0 exp
1

T
RT0
R T T0
= K 0 K1

where,
H 0o T0
K1 = exp
1

T
RT0

(13.22)

K
H o 1 1
ln ' =
'

R T T
K
Eqn (13.15) 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 as shown
T
in Figure 13.2.

Exothermic reaction, slope positive,


(K decrease with increasing T)
Endothermic reaction, slope negative,
(K increase with increasing T)

(13.15a)

H o

= slope
R

If H 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,
G0o
K 0 = exp

RT

H 0o T0
K1 = exp
1

T
RT0

1
1
( 1)2
)] + BT0
+
A[ln (

K 2 = exp
2
2
1
(

1)
(

+
2)
1
D
(

1)

CT02
+

2 T02 2
where,

T
T0

For heat capacity constant, A = i Ai etc.


i

(13.24)

RelaCon of K to equilibrium
composiCon (yi)
Gas-Phase Reactions.
From definition of K,

fi
K = o
i fi

Let the standard state be the ideal-gas state of


pure species i at Po (= 1 bar).
fi
K = o
i P

i yi P
= o
i P

P
= o
P

(
i

i yi

i =

also

P
K = o
P

(
i

i yi

so

(
i

i yi

P
= o
P

(13.26)

If the mixture is an ideal mixture,

( yii )

P
= o
P

(13.27)

If the mixture is an ideal mixture at low pressure,


it becomes an ideal-gas mixture, so

( yi )

P
= o
P

(13.28)

Remember, we can express yi in terms of ,


For single rxn,
nio + i
yi =
nio + i

For multiple rxns,


yi =

nio + ij j
j

nio + ij j
i

Eect of T and P on Equilibrium


Conversion
Consider an ideal gas reaction,

( yi )

P
= o
P

(13.28)

And eqn 13.15a gives the


relation of K wrt. T,

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

Effect of TEMPERATURE

( yi )

For endothermic rxn, an


increase in T will result in
an increase in K,
therefore an increase in,

( yi )

yc c y d d
| |

| |

y a a yb b

The composition or fraction


of products will be higher.
An increase in e.
Shift of rxn to the right.
Higher equilibrium conversion.

P
= o
P

Effect of TEMPERATURE
For exothermic rxn, an increase
in T will result in a decrease in
K, therefore a decrease in,

( yi )

yc c y d d
| |

| |

y a a yb b

The composition or fraction


of products will be reduced.
A decrease in e.
Shift of rxn to the left.
Lower equilibrium conversion.

( yi )

P
= o
P

Effect of PRESSURE

( yi )

If is negative* value, an
increase in P (at constant T)
causes an increase in,
V V
yc y d

( yi ) = |V | |V |
y a yb
i
c

The composition or fraction


of products will be higher.
An increase in e.
Shift of rxn to the right.
Higher equilibrium conversion.
*reduction in mole number

P
= o
P

Effect of PRESSURE

( yi )

If is positive* value, an
increase in P (at constant T)
will result in a decrease in,

( yi )

yc c y d d
|V |

|V |

y a a yb b

The composition or fraction


of products will be reduced.
A decrease in e.
Shift of rxn to the left.
Lower equilibrium conversion.
*increase in mole number

P
= o
P

RelaCon of K to equilibrium
composiCon (xi)
Liquid-Phase Reactions.
From definition of K,

f
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,
i xi f i
K =
o
f
i

To find

fi
fi

in term of measured variable,

Gi = i (T ) + RT ln f i

(11.31)

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

Gio = i (T ) + RT ln f i o
The difference,

Gi G = RT ln
o
i

fi
fi o

From FPR,

dG = VdP SdT

at constant T

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


P

Vi dP

Gi Gio =

Po

Combine ,
RT ln

fi
fi

Vi dP

Po

For Vi =Viliq constant

RT ln

fi
fi o

= Vi (P P o )

So,

Vi (P P o )
ln o =
RT
fi
fi

Vi (P P o )
=exp

o
RT
fi

fi

Substitute and rearrange,


i

i xi f i
Vi (P P )
K =
= i xiexp

o
RT
f
i
i

i
o

o
o

V
(P

P
)
(P

P
)
i
i
i i
= ( i xi ) exp
=
exp
(

V
)
(

x
)

RT i i i i
RT

i
i
i

So,
(P0 P)

( i xi ) = Kexp RT ( iVi )

i
i
i

(13.31)

The exponent term is usually 1, except for high


pressure system, so,

( i xi ) i = K

(13.32)

For ideal liquid solution,

(xi ) i = K

(13.33) Known as the law of mass action

As shown earlier, xi can be written in term of

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

= / (iniCal mol of steam)

Thank You