CHAPTER 13

Chemical-Reaction Equilibria:
Part 1

Muhammad Tahir
Faculty of Chemical and Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

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 Topic Outcomes
Week Topic Topic Outcomes
14 Chemical Reaction Equilibria It is expected that students are able to:

• Introduction to chemical equilibria • Describe the chemical reaction equilibria

• The reaction coordinate and it’s important in chemical
• Application of equilibrium criteria to chemical engineering.
reactions
• The standard Gibbs-energy change and the • Derive excess Gibbs energy equation to
equilibrium constant evaluate equilibrium constant (K) for a
• Effect of temperature on the Equilibrium given reaction and conditions.
constant
• Evaluation of equilibrium constants • Evaluate the equilibrium constant from
• Relation of equilibrium constants to diagram or Excess Gibbs energy for
composition given reaction and conditions.
o Single reaction
o Multiple reactions • Apply the equilibrium constant to
• Phase rule and Duhem’s theorem for reacting determine equilibrium conversion and to
system calculate reaction mixture equilibrium
compositions.

• Solve the mass balance around the

reactor at the equilibrium state.

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 Scope of Lecture

Introduction

The Reaction Coordinate

Equilibrium Criteria to Chemical Reactions

The Go & the Equilibrium Constant

Effect of Temperature on the Equilibrium Constant

Evaluation of Equilibrium Constants

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Introduction

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 Commercial Chemical-Reaction

Chemical reaction is the heart of chemical processes

Take place in a reactor

A value-added process

o Transform raw materials into products of greater value.

o Economic potential or Gross Profit must be positive. i.e.

Main products have a higher price than the raw
materials (reactants).

Note: Gross Profit is based solely on price of reactants and products, excluding the equipment and operating costs.
Study of Chemical Reaction

Reaction kinetics

o The study of rates of reaction

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

Chemical reaction equilibrium

o Determination of maximum possible conversion in a

chemical reaction.

o This chapter will cover this part.

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Reaction Kinetics v.s Conversion

Both reaction kinetics and equilibrium conversion are function

of T, P and composition.

Example: Exothermic reaction

Treaction  rates of reactions  conversion

So both kinetics and equilibrium conversion must be

considered for optimum reactor design.

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 Objective

To determine the effect of temperature, equilibrium constant,

pressure and initial composition on the EQUILIBRIUM

CONVERSIONS OF THE CHEMICAL REACTIONS.

(Since rates are not likely to be influenced by thermodynamic

treatment…)

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 Irreversible Reactions

Single direction (from reactants to products).

→ i.e. forward reaction only

These reactions highly favor formation of the products.

A+B→C+D

Only an extremely small quantity of limiting reactants (if

any) remains in the system at equilibrium.

Usually 100% conversion is considered.

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 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.

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The Reaction Coordinate

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 Stoichiometric Equation

General chemical reaction

Chemical formula (molecules/ atoms)

v1 A1  v 2 A 2  ...  v 3 A 3  v 4 A 4  ...

Stoichiometric coefficient of Stoichiometric coefficient of

reactants (– value) products (+ value)

E.g.
CH4  2O 2  CO2  2H2O
v CH4  1 v CO2  1 v O2  2 v H2O  2

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 Reaction 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 number (vi)

dn1 dn 2 dn 3 dn 4 dni
     dε dni  v idε
v1 v2 v3 v4 vi

Reaction coordinate (): characterize the extent or degree to which

a reaction has taken place.
→Also known as extent of reaction, progress variable, degree of
advancement, degree of reaction.

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Example 1 (Reaction Coordinate)

The following reaction consumes 10 moles of CH4

CH4  2O2  CO2  2H2O

dn CH4  10 dn O2  20
  10   10
v CH4 1 v O2 2
dni  v idε
dn CO2 10 dnH2O 20
  10   10
v CO2 1 v H2 O 2

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 Single Reaction Stoichiometry

For species i, integrate Summation over all species,

dni  v idε n   ni   ni0  ε v i

i i i
ni ε

 dn   v dε i
ni0 i 0 n  n0  vε

ni  ni0  v i ε  0
So, for mole fraction of species i,
ni  ni0  v iε

n i ni 0  v i ε
At initial state prior to reaction  = 0 yi  xi  
n n0  vε

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Example 2 (Single Reaction)

CH4  H2O  CO  3H2

Initial composition (prior to reaction)

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

Express yi as functions of 

n0   ni0  2  1 1 4  8
n ni  v i ε
yi  i  0
n n0  vε v   v i  1 3  1 1  2

2ε 1 ε 1 ε 4  3ε
y CH4  y H2O  y CO  y H2 
8  2ε 8  2ε 8  2ε 8  2ε

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 Multireaction Stoichiometry

2 or more independent reactions proceed simultaneously

→ vi,j: the stoichiometric number of species i in reaction j

The change of moles of species ni: dni   v i,jdε j

j

Integration

ni  ni0   v i,j ε j  0
j

ni  ni0   v i,jε j
j

Summation over
Mole fraction all species i
ni0   v i,jε j species i  
yi  j
n   ni0   v i,jε j  n0     v i,j ε j
n0   v j ε j i i j j  i 
j

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Example 3 (Multireaction, Example 13.3)

Consider a system in which the following reactions occur:

CH4  H2O  CO  3H2 1

CH4  2H2O  CO2  4H2 2

Where the numbers (1) and (2) indicate the value of j, the reaction index. If
there are present initially 2 mol CH4 and 3 mol H2O, determine
expressions for the yi as functions of 1 and 2.

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 Solution 3

i= CH4 H2O CO CO2 H2

j vj

1 –1 –1 1 0 3 2

2 –1 –2 0 1 4 2

2  ε1  ε 2 ε1
y CH4  y CO 
ni0   v i,jε j 5  2ε1  2ε 2 5  2ε1  2ε 2
j
yi 
n0   v j ε j 3  ε1  2ε 2 ε2
j y H2O  y CO 2 
5  2ε1  2ε 2 5  2ε1  2ε 2

3ε1  4ε 2
y H2 
5  2ε1  2ε 2

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 Tutorial 1

Develop expressions for the mole fractions of reacting species

as functions of the reaction coordinate for a system initially
containing 2 mol NH3 and 5 mol O2 and undergoing the reaction:

4NH3(g) + 5O2(g) → 4NO(g) + 6 H2O(g)

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 Tutorial 2

A system initially containing 2 mol C2H4 and 3 mol O2 undergoes

the reactions:

C2H4(g) + 1/2O2(g) → (CH2)2O(g)

C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O

Develop expressions for the mole fractions of the reacting

species as functions of the reaction coordinates for the two
reactions.

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Equilibrium Criteria to
Chemical Reactions

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 Fundamental Property Relation

From FPR for homogenous system of variable composition,

dnG  nV dP  SdT   μidni Chapter 11

i

For system with single chemical reaction, dni may be replaced by

vid

dnG  nV dP  SdT   v iμidε

i

Apply the criterion of exactness

 dnG 
 dε    v iμi
  T,P i

Note: FPR, fundamental property relation Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Criteria of Chemical Reaction Equilibrium

Using 1st law, 2nd law and FPR, we could show that at equilibrium

dG 
t
0  dnG 
 dε    v iμi
T,P

  T,P i

So at chemical reaction equilibrium,

 dnG 
 dε   0 v μ  0i i
Criteria of Chemical
Reaction Equilibrium
  T,P i

All reversible process occurring at constant T & P proceed in such a

direction as to cause a decrease in the Gibbs energy of the system.

Note: FPR, fundamental property relation Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Gt in Relation to 
 is single variable that characterizes the progress of the reaction.
→ The total Gibbs energy at const. T & P is determines by 

Not in chemical equilibrium,

 any reaction leads to a decrease
in the total Gibbs energy of the
system.
Gt

(dGt)T,P = 0 The condition for equilibrium:

→ The total Gibbs energy is
minimum, Gt = f()
→ Its differential zero

e

Note: Gt, total Gibbs energy Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
The Go & the Equilibrium
Constant

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 Equilibrium Constant, K

Recall,

The fugacity of a species in solution: μi  i T   RTln fˆi

For pure species i in its standard state: Gi  i T  RTln f

o o

Differences between 2 species

fˆi fˆi
μi  G  RTln 

i μi  G  RTln 

i
fi fi

Substitute into the criteria of chemical reaction equilibrium v μ  0

i
i i

v
  fˆi   ˆ 
i
f
i v i  Gi  RTi ln f    0
 i v iGi RTi ln f i   0
 i   i 

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 K and Go
Rearrange So,

v
fˆi 
i
v G i

i RTlnK  0
i i
v G RT
ii 
ln  
fi 
0 i


  v iGi
vi  Go
 fˆi  lnK  i

i v iG RTlni  f    0

i RT RT
 i 

Signifies the product over all   Go    G0o 

K  exp   K 0  exp  
species i. E.g. a i  a1a 2a3a 4a5  RT  T = T0  RT0 
i 5

Let, viGio=Go = Standard Gibbs energy

change of reaction at equilibrium T
v
 fˆi 
i

ln     K Equilibrium
i  fi  constant The data for Gio is available in the
form Go f,i,298 (Table C.4)

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 Example 4

CH4  H2Og  CO  3H2

Calculate Go at 298 K,

Go   v iGi
i

 v H2 GH 2  v COGCO  v CH4 GCH4  v H2OGH 2O

 v H2 Gf,H2 ,298  v COGf, CO,298  v CH4 Gf,CH4 ,298  v H2OGf,H2O,298

 30  1 137169    1 50460    1 228572 

Go  141863J/mo lCH 4 reacted

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Effect of Temperature on
the Equilibrium Constant

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 van Hoff’s Equation
  Go 
The equilibrium constant for the reaction, f(T) K  exp  
 RT 

The standard Gibbs energy change of reaction, f(T) Go   v iGi

i

Other standard property changes of reaction: M   v iMi

o 

dGio /RT  d Gio / RT  

o
H  RT
i
2

dT
i v iH  RT
o
i
dT
2

Chap. 6 (6.39)

dlnK H
 o dGio / RT 
2
van Hoff’s equation H  RT
dT RT 2 dT

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 Effect of T on K

To calculate K at T other than the standard state T of 298K. Let’s

use van Hoff’s equation,

H
dlnK  2
dT
RT

If Ho (standard heat of reaction) could be assumed const.

(independent of T)

K ΔH  1 1 
ln     
K  R  T T 

 ΔH  1 1 
K  Kexp    
 R  T T 

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K as Function of T
Rearrange

ΔH 1  ΔH 1 
lnK      ln K 
R T  R T 

Plot: ln K vs 1/T

Exothermic reaction
→ Slope +ve (K decrease with
increasing T)

Endothermic reaction
→ Slope –ve (K increase with
decreasing T)

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 Effect of T on K

For a chemical species in its standard state

Gio  Hio  TSio v G  v H

i
i

i
i
i

i  T v iSi
i
G  H  TS
Summation T CP
H  H  R 
 
0 dT
T0 R

CP dT T
S  S  R 
 
0
T0 R T
H0  G0
S 
0
T0

T T C T C dT
 
 
G  H 

H0  G0  R 
 
0
 P
dT  RT  P
T0 T0 R T0 R T
Divide by RT Eq. 4.19 Eq. 5.15
 G G G0  H0 H 1 T CP T CP dT
lnK      dT  
RT RT RT0 RT T T0 R T0 R T
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 Factor K
The preceding equation may be reorganized so as to factor K into 3
terms

G G0  H0 H 1 T CP T C dT



RT T T0 R
   dT   P
RT RT0 T0 R T

 Go
lnK 
K  K 0 K1 K 2 RT

  G0   H0  T0   1 T CP T C dT 


K 0  exp   K 1  exp  1  K 2  exp    dT   P

 RT0  RT
 0 T   T T0 R T0 R T 

   τ  1  1
K 2  expA lnτ     BT0
τ  1 1
2
 CT0
2

2 τ  1 τ  2


1 D τ  1 
2


   τ   2 τ 6 τ 2 T0
2
τ 2

τ  T/To
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Evaluation of Equilibrium
Constants

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 Example 5 (Example 13.4)
Calculate the equilibrium constant (K) for the vapor-phase hydration of
ethylene at 145 and at 320°C from data given in App. C (text book).

Solution 5:

First determine values for A, B, C, and D for the reaction:

C2H4(g)  H2O(g)  C2H5OH(g)

The meaning of  is indicated by: A = (C2H5 OH) – (C2H4) – (H2O).

Thus, from the heat-capacity data of Table C. 1:

A = 3.518 –1.424 – 3.470 = –1.376

B = (20.001 – 14.394 – 1.450) x 10-3 = 4.157 x l0-3
C = (–6.002 + 4.392 – 0.000) x 10-6 = –1.610 x 10-6
D = (–0.000 – 0.000 – 0.121) x 105 = –0.121 x 105
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 Solution 5

Values of ΔH°298 and ΔG°298 at 298.15K for the hydration reaction are
found from the heat of formation and Gibbs energy of formation data
of Table C.4:

ΔH°298 = – 235,100 – 52,510 – (– 241,818) = – 45,792 J mol-1

ΔG°298 = –168,490 – 68,460 – (–228,572) = – 8,378 J mol-1

For T = 145 + 273.15 = 418.15 K, values of the integrals,

Eq. 4.19: IDCPH(298.15,418.15;–1.376,4.157E–3,–1.610E–6,–0.121 E+5) = – 23.121

Eq. 5.15: IDCPS(298.15,418.15;–1.376,4.157E–3,–1.610E–6,–0.121 E+5) = – 0.06924

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 Solution 5 (Cont.)
G G0  H0 H 1 T CP T C dT


RT T T0 R
   dT   P
RT RT0 T0 R T

Substitute of values into Eq. (13.18) for a reference temperature =

298.15,

ΔG418  8,378  45,792  45,792  23.121

    0.06924  1.9356
RT 8.314 298.15  8.314 418.15  418.15

For T = 320 + 273.15 = 593.15 K,

Eq. 4.19: IDCPH(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) = 22.632

Eq. 5.15: IDCPS(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) = 0.01731

ΔG593  8,378  45,792  45,792 22.632

    0.01731  5.8286
RT 8.314 298.15  8.314 593.15  593.15

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 Solution 5 (Cont.)
Finally,
At 418.15K: ln K = –1.9356 and K = 1.443 x 10-1
At 593.15K: ln K = –5.8286 and K = 2.942x 10-3

 H0  T0     τ  1 1 τ  12  1 CT 2 τ  12 τ  2   1 D τ  12 

K1  exp  1  K 2  exp A lnτ      BT0 0 
 RT0  T     τ  2 τ 6 τ 2 T02 τ 2 

Application of Eqns. (13.21), (13.22), and (13.24) provides an

alternative solution to this example. By Eq. (13.21),

  G0  8,378
K 0  exp   K 0  exp  29.366
 RT0  8.314 298.15 

ΔH0  45,792
  18.473
RT0 8.314 298.15 

Moreover, with these values, the following results are readily obtained:
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 Solution 5 (Cont.)

T/ K  K0 K1 K2 K

298.15 1 29.366 1 1 29.366

418.15 1.4025 29.366 4.985x10-3 0.9860 1.443x10-1

593.15 1.9894 29.366 1.023x10-4 0.9794 2.942x10-3

Clearly, the influence of K1, is far greater than that of K2.

This is a typical result, and accounts for the fact that the lines on Fig.
13.2 are nearly linear.

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 Tutorial 3

Develop a general equation for the standard Gibbs-energy

change of the reaction G as a function of temperature for the
following reactions:
N2(g) + 3H2(g) → 2NH3(g)

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 C6H5OH + 11H2O 6CO2 + 14H2

100

80

Conversion,Yield and
60 C6H5OH conversion

Selectivity %
H2 yield
H2 selectivity
CO2 selectivity
40 CO selectivity
CH4 selectivity

20

0
100 300 500 700 900 1100

Temperature (0C)

Catalyst T(0C) S/C Phenol conversion % H2 yield % Ref

Exp TDA Exp TDA
Ni-MgO/Al2O3 700 27.3:1 95 100 80 87 [41]
Ni-La/Al2O3 750 27.3:1 100 100 82 85.7 [42]
Rh /MgCeZrLaO 730 80:1 95 100 90 94.9 [43]
Rh /CeZrLaO 450 67:1 80 100 80 80 [44]
 CHAPTER 13
Chemical-Reaction Equilibria:
Part 2

Muhammad Tahir
Faculty of Chemical and Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Scope of Lecture

Relation of Equilibrium Constants to Composition

Equilibrium Conversions for Single Reactions

Phase Rule & Duhem’s Theorem for Reacting Systems

Multireaction Equilibria

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 Relation of Equilibrium
Constants to Composition

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Gas Phase Reactions

From definition of K,
vi
 fˆi 
K     
i  fi 

Let the standard state be the ideal-gas state of pure species i at Po (=1
bar)  f˚i = P˚
v i v

v v
 vi
 fˆi   ˆi y iP 
 
i i
 P  v

 ˆ y 
P
vi
K                ˆi y i K   
vi

i P  i  P P  i i
 i P  i

• Calculation of ̂i
o Using methods of Sec. 11.6 & 11.7 e.g. Eq. 11.61 v

 ˆ y 
iteration vi P
i i    K
i P 

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Gas Phase Reactions (Cont.)

If the equiibrium mixture in an ideal Remember, we can express yi

mixture, in terms of 
Evaluate form generalized
ˆi  i correlation
v Single ni0  εv i
P yi 

 ii
y  v i
   K reaction n i0  ε v i
i P 

If the equilibrium mixture in an ideal ni0   v ijε

Multiple yi  j
mixture at low P ideal-gas mixture reaction  n   v ε
i
i0
i j
ij j

v
P
 y 
vi
i    K
i P 

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 Effect of T & P on Equilibrium Conversion

Consider an ideal gas reaction, And the relation of K wrt. T

v
P ΔH 1  ΔH 1 
 y 
vi
   K lnK      ln K 
i
i
P  R T  R T 

Effect of temperature

If endothermic reaction The composition or fraction of

T  K product will be higher

An increase in e
y cv c y dv d
 y 
vi
 o Shift of reaction to the right
i va vb
i y y a b
o Higher equilibrium conversion

Note: wrt., with relation to Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Effect of Temperature (Cont.)

If exothermic reaction

T  K

y cv c y dv d
 y 
vi
i  v v
i y a a yb b

The composition or fraction of product will be reduced

An decrease in e
o Shift of reaction to the left
o Lower equilibrium conversion

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 Effect of Pressure

If total stoichiometric number v (≡ivi) is negative value,

P (at constant T)

y cv c y dv d
 y 
vi
i  v v
i y a a yb b

The composition or fraction of product will be higher

An increase in e
o Shift of reaction to the right
o Higher equilibrium conversion
→ Reduction in mole number
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 Effect of Pressure (Cont.)

If total stoichiometric number v (≡ivi) is positive value,

P (at constant T)

y cv c y dv d
 y 
vi
i  v v
i y a a yb b

The composition or fraction of product will be reduced

An decrease in e
o Shift of reaction to the left
o Lower equilibrium conversion
→ Increase in mole number
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Liquid Phase Reactions

From definition of K,
vi
 fˆi 
K     
i  fi 

Let the standard state be the pure liquid of species i at system

temperature and 1 bar.

 i x i f i  fˆi Equation 11.90

vi
Substitute
  i x i fi 
K     
i  fi 
fi
Need to determine  in term of measured variable
fi

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Liquid Phase Reactions (Cont.)

Recall for pure liquid at T & P, From FPR,

Gi  i T  RTln fi dG  VdP  SdT

Apply at T and standard state Integrate at constant T for pure

pressure of P = 1 bar liquid i from P to P

G  i T   RTln fi
P P
  f
i Gi  G   VidP

i RTln i   VidP
P
f i P

The difference, For Vi = Viliq  constant

fi
Gi  Gi  RTln
 Vi P  P  
fi
fi  RTln 
fi

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Liquid Phase Reactions (Cont.)

So,
fi  Vi P  P
 exp 
  

fi   RT 

Substitute and rearrange

 
vi vi
 x f    Vi P  P 
K    i i i      i x iexp   

i  fi  i   RT 

   i x i 

 v i Vi P  P   exp  P  P  v V   x 


 RT  
vi vi
exp   i i i i
i  RT   i  i


 P  P  v V 
  i x i  
vi
 K exp   i i
i  RT i 

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Liquid Phase Reactions (Cont.)

The exponent term is usually 1, except for high pressure

system

  x 
vi
i i K
i

Determine using Wilson equation

(Eqn. 12.19) or UNIFAC method

For the equilibrium mixture is an ideal liquid solution

 x 
vi
i  K Known as the law of mass action
i

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

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Equilibrium Conversions
for Single Reactions

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 Single-Phase Reactions

Suppose a single reaction occurs in a homogenous system and

suppose the equilibrium conversion is known.

Calculation of the phase composition is straightforward if the phase is

assumed an

 Ideal gas  Ideal solution

v
P P
v

 y 
vi
   K
 y  
vi
i    K
i P  i
i i
P 
or

 ix v i
K
i

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 Example 6 (Example 13.5)

The water-gas-shift reaction,

CO(g) + H2O(g) → CO2(g) + H2(g)

is carried out under the different sets of conditions described below. Calculate the
fraction of steam reacted in each case. Assume the mixture behaves as an ideal
gas.

(a) The reactants consist of 1 mol of H2O vapor and 1 mol of CO. The temperature
is 1,100 K and the pressure is 1 bar.
(b) Same as (a) except that 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. Other conditions are the
same as in (a).
(e) The reactants are 1 mol of H2O and 2 mol of CO. Other conditions are the
same as in (a).
(f) The initial mixture consists of 1 mol of H2O, 1 mol of CO, and 1 mol of CO2.
Other conditions are the same as in (a).
(g) Same as (a) except that the temperature is 1,650 K.

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 Solution 6
a) For the given reaction at 1,100 K

104/T = 104/1100 = 9.05

Fig. 13.2
 ln K = 0 or K = 1

v = vi = 1+1–1–1 = 0

ln K
Since the reaction mixture is an ideal gas, eqn. 13.28

P
v y H2 y CO2
 y 
vi
   K K 1
i
i
P  y CO y H2O

ni 0  v i ε
By eqn. 13.5  yi 
n0  vε 1/T  104/K-1

1 ε e 1 ε e ε ε ε 2e
y CO  y H2 O  y CO2  e y H2  e 1
2 2 2 2 1 ε e 2

e = 0.5  fraction of steam that reacts = 0.5

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 Solution 6 (Cont.)
=0
b) P = 10 bar P
v

 y 
vi
i    K
i P 

Since v = 0 , P increase, no effect on the ideal-gas reaction

 εe is still 0.5.

c) 2 mol of N2 is included in the reactants

N2 does not take part in the reaction  serves only as a diluent.

It does increase the initial number of moles no from 2 to 4.
 Mole fractions are all reduced by a factor of 2.

y H2 y CO2 Unchanged and reduces to the same expression as

K 1
y CO y H2O before. Therefore, εe is again 0.5

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Solution 6 (Cont.)

d) Reactants are 2 mol of H2O and 1 mol of CO

In this case the mole fractions at equilibrium,

1 ε e 2  εe εe εe
y CO  y H2 O  y CO2  y H2 
3 3 3 3

y H2 y CO2 ε 2e
K 1 1
y CO y H2O 1 ε e 2  ε e 

εe = 0.667

The fraction of steam that reacts is then 0.667/2 = 0.333

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Solution 6 (Cont.)
e) Reactants are 1 mol of H2O and 2 mol of CO

Expressions for yCO and yH2O are interchanged,

 Equilibrium equation the same as in (d).

Therefore εe = 0.667, and the fraction of steam that reacts is 0.667.

f) Initial mixture consists of 1 mol of H2O, 1 mol of CO, & 1 mol of CO2

In this case
CO2 = product
y H2 y CO2 ε e 1 ε e 
K 1 1
y CO y H2O 1 εe  2

εe = 0.333

The fraction of steam reacted is 0.333.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Solution 6 (Cont.)

f) T = 1,650 K

At 1,650 K, 104/T = 6.06, ln K = –1.15 or K = 0.316.

ln K
y H2 y CO2 ε 2e
K  0.316
y CO y H2O 1 ε e 

εe = 0.36

1/T  104/K-1

The reaction is exothermic, and conversion decreases with

increasing temperature.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Example 7 (Example 13.6)

Estimate the maximum conversion of ethylene to ethanol by vapor-

phase hydration at 250°C and 35 bars for an initial steam-to-ethylene ratio
of 5.

Solution 7:

C2H4(g)  H2O(g)  C2H5OH(g)

The calculation of K  same as Example 5 (13.4) (T = 250°C =

523.15 K):

K = 10.02 x 10-3

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Solution 7 (Cont.)
v

 y ˆ 
vi P
The appropriate equilibrium expression i i    K
i P 

Requires evaluation of the fugacity coefficients

P  1 
May be accomplished with ln ˆk   Bkk   y i y l  ik   il 
calculations involve iteration RT  2 i l 

ASSUMPTION
The reaction mixture is an
ideal solution  reduce to

v
P
 y  
vi
i i    K
i P 
Requires fugacity coefficients of the
pure gases of the reacting mixture

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 Solution 7 (Cont.)

Since v   v i  1 this equation, becomes:

i

y EtOHEtOH P

    10.02 10 3
y C2H4 C2H4 y H2OH2O  P 


PHIB(TR,PR,OMEGA) = i

 Pr 0
i  exp  B  ωB1  Eqn. 11.65
 Tr 
0.172 0 0.422
B1  0.139  B  0.083  Eqn. 3.61 & 3.62
Tr4.2 Tr1.6

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 Solution 7 (Cont.)

The results of these calculations

App. B

Tc / K Pc / bar ωi Tri Pri B0 B1 i

C2H4 282.3 50.40 0.087 1.853 0.694 -0.074 0.126 0.977

H2O 647.1 220.55 0.345 0.808 0.159 -0.511 -0.281 0.887

EtOH 513.9 61.48 0.645 1.018 0.569 -0.327 -0.021 0.827

y EtOH C2H4 H2O  P 

y C2H4 y H2O
 
   10.02  10
EtOH  P 
3


y EtOH

0.977 0.887  35  10.02  10 3  0.367
 
y C 2H 4 y H2 O 0.827 
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 Solution 7 (Cont.)
ni ni 0  v i ε
By yi  
n n0  vε

1 ε e 5  εe εe
y C 2H 4  y H2 O  y EtOH 
6  εe 6  εe 6  εe

Substitute

ε e 6  ε e 
 0.367 2
ε e  6.000ε e  1.342  0
5  ε e 1 ε e 

Using quadratic equation for the smaller root  εe = 0.233.

 larger root is greater than unity  it does not represent a
physically possible result.
 The maximum conversion =23.3%.

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 Tutorial 4

The following reaction reaches equilibrium at 500 C and 2 bar.

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

If the system initially contain 5 mol HCl for each mole of oxygen,
what is the composition of the system at equilibrium? Assume
ideal gases.

Examples: 13.7, 13.8, 13.9

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Phase Rule & Duhem’s
Theorem

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 Phase Rule

Previous: Non-reacting system

F  2 N

This is phase rule for reacting systems (modified)

No. of chemical species

F  2    N r

No. of phases No. of independent chemical reactions

at equilibrium within the system

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 Special Constraints

To determine the no. of independent chemical reactions,

1. Write chemical equations for the formation  from
constituent elements.
2. Combine these equations  eliminate elements

Special constraints  modified

F  2    N r  s

Special constraints

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 Example 8

Determine the number of degree of freedom F for each of the following

systems.

a) A system of two miscible nonreacting species which exists as an

azeotrope in vapor/liquid equilibrium

b) A system prepared by partially decomposing CaCO3 into an

evacuated space.

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

space.

d) A system consisting of the gases CO, CO2, H2, H2O and CH4 in
chemical equilibrium.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Solution 8

a) 2 miscible nonreacting species, exist as azeotrope

If no azeotrope
 2220  2
F  2   N r

Azeotrope exist  special constraints

F  2    N r s
 2  1 2  1 1  1

One phase

Just 1 phase-rule variable  T, P or x1(=y1)

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 Solution 8 (Cont.)

b) Partially decomposing CaCO3 c) Partially decomposing NH4Cl into

into an evacuated space an evacuated space

Single chemical reaction Chemical reaction

CaCO 3 s   CaOs   CO 2 g NH4Cls   NH3 g  HClg

F  2    N r s F  2    N r s
 2  3  3  1 0  1  2  2  3  1 1  1

No special constraint is imposed Special constraint is imposed by

by the decomposition of CaCO3 the decomposition of NH4Cl

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 Solution 8 (Cont.)
d) CO, CO2, H2, H2O & CH4 in CO2  H2  CO  H2O
chemical equilibrium
CH4  2H2O  CO2  4H2
5 species, single gas phase

C  1/2O 2  CO
C  O 2  CO 2 F  2    N r s
H2  1/2O 2  H2O  2  1 5  2  0  4
C  2H2  CH4
No special constraint
Eliminate

CO  1/2O 2  CO2 Special constraint through material

balance
CH4  O2  2H2  CO2  Reduce the DOF of 2
(Duhem’s theorem)
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Multireaction Equilibria

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 Multireaction Equilibria
Equilibrium state in a reacting system depends on 2 or more
independent chemical reactions
 Equilibrium conversion can be found by direct extension of the
methods developed for single reactions.
v i,j
 fˆi 
i  f    Kj
 i 

For gas phase reaction : j is the reaction index

v i,j
 fˆi 
i  P   Kj
 

For the equilibrium mixture is an ideal-gas,

v j
P
 y 
v i,j
i    Kj
i P 

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 Example 9 (Example 13.12)

A feedstock of pure n-butane is cracked at 750 K and 1.2 bar to produce

olefins. Only two reactions have favorable equilibrium conversions at
these conditions:

C 4H10  C 2H4  C 2H6 I

C 4H10  C3H6  CH4 II

If these reactions reach equilibrium, what is product composition?

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 Solution 9

Use same method as Example 5 to determine K

KI  3.856 KII  268.4

Equation relating the product composition to the reaction

coordinates (basis = 1 mol of n-butane feed)

1  εI  εII εI
y C 4H10  y C 2H4  y C 2H6 
1  εI  εII 1  εI  εII

εII
y C 3H6  y CH4 
1  εI  εII

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 Solution 9 (Cont.)

Equilibrium relations,

1
y C2H4 y C2H6 P 
1
y C3H6 y CH4 P 
    KI     K II
y C 4H10 P  y C 4H10 P 

Combine
1 1
εI2 P  εII2 P 
    KI     K II
1 εI  εII 1 εI  εII   P  1 εI  εII 1 εI  εII   P 

Divide

1/2
K 
εII  εI     II 
 KI 
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 Solution 9 (Cont.)

Reduction εII  8.343  0.1068   0.8914


εI  

K I P /P  
1/2

2 
 1  K IP 
/P 
  1  The product-gas composition

1/2
 268.4  y C4H10  0.0010
    8.343
 3.856 
y C 2H4  y C 2H6  0.0534
Substitute

 3.856 1/1.2  
1/2
y C3H6  y CH4  0.4461
εI   2 
 1  .856 1/1.2 9.343  
εI  0.1068

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Tutorial 5

Consider ther reactions,

1/2N2 (g) + 1/2O2(g) → NO (g)

1/2N2 (g) + O2(g) → NO2 (g)

If the reactions come to equilibrium after combustion in an internal-

combustion engine at 2000 K and 200 bar, estimate the mole fractions
on NO and NO2 present for mole fractions of nitrogen and oxygen in the
combustion products of 0.70 and 0.05.

Example 13.14

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Homework

13.11, 13.12, 13.13, 13.14, 13.15,

Chapter 13 :
13.16, 13.17, 13.18, 13.19, 13.20

Dateline :

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia