Chemical Reaction Engineering

Lecture 2: Review of Undergraduate Material

Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Ethylene production by thermal cracking of ethane
!  The thermal cracking of ethane is carried out in
multitubular reactor. Typical production capacity
of each tube is 10000 Tons per annum.

!  Reactor specifications:
"  Feed to the reactor: ethane + steam (?)
"  Inlet pressure - 2.99 atm; temperature - 680°C
"  Tube length 95 m, ethylene conversion – 60%

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Cracking of ethane to ethylene
C
H
26!C
H
24+
H2

Mole
balances
Batch/
Rate of CSTR/
reaction PFR

Stoichiometry
conversion
molar flows
Conversion
Volume
Production rate
CSTR +PFR
Reactor Design
Topic 1: Basic concepts

!  Representation of reaction
!  Extent of reaction and conversion
!  Thermodynamics and chemical reactions
"  Heat of reaction
"  Condition of equilibrium

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Representation of chemical reaction – single reaction

!  Considera single chemical reaction in N species

A1, A2,…., AN

!  General representation:
N

"! A j j =0
j =1

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Representation of chemical reaction – multiple reactions

!  Consider R chemical reactions in N species A1,

A2,…., AN

!  General representation:
N

"! ij A j = 0, i = 1,!2,!.........,!R
j =1

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Representation of chemical reaction – independent reactions

!  Stoichiometric matrix

" !11 … !1N %

$ '
!=$ ! " ! '
$# ! R1 # ! RN '&
!  Number of independent reaction
R!=!rank!! "#! $%

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Progress of chemical reaction – single reaction

!  Considera reaction ! !jAj = 0 taking place in a

closed system
nj0 = number of moles of species j present initially
nj = number of moles of species j at any time t

!  Molar extent of reaction - "

nj " nj0
!=
#j

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Molar extent of reaction nj " nj0
!=
!  Properties of " #j
"  defined for the reaction
n j " n j 0 nk " nk 0
!= =
#j #k
#k
$!!nk = nk 0 +
#j
(nj " nj0 )
"  Extensive property in moles

"  Always positive

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Conversion of species

!  Conversion X
nj0 ! nj
X=
nj0

!  Stoichiometrically limiting species k

# nj0 &
min!! % ! (
$ " j '

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Cracking of ethane to ethylene
C
H
26!C
H
24+
H2

Molar flow at Molar flow at

entry exit
Ethane, F10 Ethane, F1
Ethylene, F2 …
Stoichiometric tables – Flow reactor
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

Species Entry Change Exit from the reactor

(mol/ (mol/ (mol/min)
min) min)
A1 F1O -(F10X) F1=F10- F10X
Aj j=2,3, 4 FjO - #j/#1 Fj=Fj0- #j/#1 F10X
(F10X)
I (inerts) FI0 ----- FI= FI0

Total FT0 FT=FT0-(!#j/#1)F10X

FT=FT0+ ! F10X
Concentrations in terms of conversion
P v = Z FT RT !
# % P0 ( % Z ( % T ( % FT (
" v = v0 ' * ' * ' * ' *
P0 v0 = Z0 FT 0 RT0 #
$ & P ) & Z 0 ) & T0 ) & FT0 )

FT = FT 0 + + F10 X
FT F10
= 1+ + X = 1 + + y10 X = 1 + , X
FT 0 FT 0

% P0 ( % Z ( % T (
(
v = v0 ' * ' * ' * 1 + , X
& P ) & Z0 ) & T0 )
)
Concentrations in terms of conversion

FA0
CA0 =
v0
FA FA0 "FA0X
CA = =
v v
# 1" X $# P $# Z0 $#T0 $
CA =CA0 % &% &% &% &
'1 +! X (' P0 (' Z ('T0 (
# )B "b/ aX $# P $# Z0 $#T0 $
CB =CA0 % &% &% &% &
' 1 +! X (' P0 (' Z ('T0 (
Summary – Stoichiometry of reaction
!  Keywords & concepts
"  Stoichiometric coefficients
"  Multiple reactions
"  Set of independent reactions
"  Extent of reaction
"  Conversion
"  Stoichiometric tables

Indian Institute of Science

Chemical Reaction Engineering
Lecture 3: Review of Undergraduate Material

Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Ethylene production by thermal cracking of ethane
!  The thermal cracking of ethane is carried out in
multitubular reactor. Typical production capacity
of each tube is 10000 Tons per annum.

!  Reactor specifications:
"  Feed to the reactor: ethane + steam (?)
"  Inlet pressure - 2.99 atm; temperature - 680°C
"  Tube length 95 m, ethylene conversion – 60%

Indian Institute of Science

Thermodynamic considerations
!  Equilibrium conversion

!  Working conditions of the reactor

!  Heat effects in a chemical reaction

Why thermodynamics
A! B
A(B
# 15000 & # 25000 &
"% "%
!15
000" $ T (' $ T ('
#
6 & T %
$ r = 2.6 ! 106 e C A " 3.9 ! 1033 e CB
r=2 )0e
.61 '
C
A

2.0 2.0 CA
1.8 1.8 X
CB
1.6 1.6
CA
CA (mol/dm ), X

CA (mol/dm ), X
1.4 X 1.4
CB
1.2 1.2
3

3
1.0 1.0
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 1 2 3 4 5
time (h) time (h)
Effect of temperature
A! B A! B
T = 320 T = 330

2.0 CA
2.0 CA
1.8 X 1.8 X
CB CB
1.6 1.6
CA (mol/dm ), X

CA (mol/dm ), X
1.4 1.4
1.2 1.2
3

3
1.0 1.0
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 1 2 3 4 5
time (h) time (h)
Chemical Equilibrium
!  Consider a reaction ! !jAj = 0 taking place at
constant temperature T and pressure P. The
system will spontaneously change in the direction
of increasing entropy, reaching equilibrium when
entropy can not increase further.
!  Free energy and Gibb s equations
N
dG = Vdp ! SdT + " µ j dn j ,
j =1

$ #G '
Chemical!Potential! µ j = & )
% #n j ( T , P,nk

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Chemical Equilibrium
N
Gibb's!Equation dG = Vdp ! SdT + " µ j dn j
j =1

Progress!of !reaction n j = n j 0 + ! j" !!or!!dn j = ! j d" !

N
!!!!!dG = Vdp " SdT + % # j µ j d$
j =1
!  Equilibrium condition
!!
# !G & N

%$ (' = * ) j µ j = 0
!" T , P j =1

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Chemical potential
y = composition!,!
!  Perfect gas mixture
T = temperature,!
P = pressure
( ) ( )
Py j
µ j T , P, y = µ j 0 T , P , y + RT ln
r r
superscript !r!=!reference
Pr
P r = 1!atm
!  Non-ideal gas mixture y r = pure! j
f j = fugacity

( ) ( )
fj
µ j T , P, y = µ j 0 T , P , y + RT ln
r r

f jr

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Chemical potential
!  Solution

( )
µ j (T , P, x ) = µ j 0 T , P r , x r + RT ln ! j x j

x = composition!,!
T = temperature,!
P = pressure
superscript !r!=!reference
! = activity!coefficient

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Free energy change
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

µ j = µ j0 + RT ln a j ( )
( )
N

"! µ j j
= " ! j µ j0 + RT " ! j ln a j
j =1 j j

$ #j '
!G = !G + RT ln & " a j )
0

% j (
!G = !G + RT ln K a
0
Equilibrium condition
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

$ #j '
!G = !G + RT ln & " a j ) = 0
0

% j (
!G = !G 0 + RT ln K a = 0
$ #j ' $ *!G '
0
K a = & " a j ) = exp & )
% j ( % RT (
 Equilibrium constant
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0
# "j & # )*G 0
&
K a = % ! a j ( = exp % (
$ j ' $ RT '
# "j & #
( ) &
"j
Pressure K P = % ! Pj ( = % ! Py j ('
$ i ' $ i
# "j &
Fugacity Kf = %! fj (
$ i '
# "j &
Concentration KC = % ! C j (
$ i '
Equilibrium extent of reaction
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

# "j & Nj
K P = % ! Pj ( Pj = y j P = P
$ j ' NT
N j = N j0 + " j)

+ % (
"j
.
- ' N j0 + " j# * 0
KP = - ! 'P N + # " * 0=F #( )
- j ' T0 $ j* 0
, & j ) /
Extent of reaction and operating conditions
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0
+ % (
"j
.
- N j0 + " j# * 0
K P (T ) = - !
- j
'
'P N + # " *
$ j* 0
(
0 = F # , P, N j0 )
' T0
, & j ) /

d
dY
!" ln K P (T ) #$ =
d !
dY "( #
F % , P, N j0 =
$ )&F &F d%
+
&Y &% dY
Extent of reaction and operating conditions
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0
d!
=C
F ! ( )
dY F' ! ( )
"H
Temperature C = "H = heat of reaction
RT 2
%$ j

Pressure C=#
j

P
%$ j
= change in no. of moles
j

Inerts C=?
Equilibrium conversion - Exothermic reaction

1.0
Isothermal

0.8

0.6 Adiabatic
Xeq

0.4

0.2

0.0
300 320 340 360 380 400
T

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Equilibrium conversion - Endothermic reaction
1.0

0.8

0.6 Adiabatic
Isothermal
Xeq

0.4

0.2

0.0
300 320 340 360 380 400
T

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Equilibrium extent of reaction
N

"! ij
Aj = 0, i = 1, 2, ...., R
j =1

# " ij &
K Pi = % ! Pj (
$ j '
R
N j = N j0 + * " ij) i
i =1
Heat of reaction
!1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

!H R = # " j h j
j
T
h j (T ) = h + $
0
j
C Pj dT
298

!H R = # " j h + # " j $
T
0
j
C Pj dT
298
j j

!H R = !H + # " j $
T
0
R
C Pj dT
298
j
Summary
!  Free energy
!  Chemical potential
!  Condition of Equilibrium
!  Equilibrium constant
!  Equilibrium extent of reaction
!  Operating conditions

Indian Institute of Science

Chemical Reaction Engineering
Lecture 4: Review of Undergraduate Material

Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Chemical Kinetics: Basic concepts

!  Kinetics of irreversible and reversible reactions

"  Power law kinetics
"  Law of mass action kinetics
!  Rate of simple reactions

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Science
Classification of reactions
!  Based on mechanism of the reaction
"  Elementary and nonelementary reactions

Example: chlorination of nitric oxide to give nitrosyl chloride

2NO + Cl2 ! 2NOCl

Classification of reactions
!  Based on the direction of the reaction
"  Irreversible and reversible reactions

cyclopropane ! propylene

trans " butylene ! cis " butylene

Classification of reactions
!  Based on number of phases present in the system
"  Homogenous and heterogeneous reactions

C2 H 6 (g) ! C2 H 4 (g) + H 2 (g)

CO2 (g) + NaOH (l) ! NaHCO3 (l)

Rate of chemical reaction – single reaction

!  Consider a reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system
!  Rate of reaction - r

1 d! nj " nj0
r= !=
V dt #j
1 dn j
rj =
V dt

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Science
Reaction rate

!  Considera reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system

r = r(T , P, y1 , y 2 ...yN !1 )
= r(T , P,C1 ,C 2 ...C N !1 )
= r(T ,C1 ,C 2 ...C N !1 ,C N )

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Science
Reaction rate – power law kinetics

!  Considera reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system
N
r = kC C .....C = k! C
q1 q2 qN qj
1 2 N j
j =1

qj is the order of the reaction wrt species Aj

q = ! qj is the overall order !

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Science
Reaction rate – law of mass action kinetics

!  Considera reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system
N
r = k! C
qj
j
j =1

qj =
1
2
(
"j #"j )
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 Effect of temperature on rate
k
40

35 ! E"
#$ %
30

25
k=Ae &RT'
k (s )

20
-1

15
k
10

5
10
0
300 400 500
1
T (K)
(400, 0.85605)

k (s )
-1
0.1

0.01 (310, 0.00359)

1E-3 (300, 0.0016)

300 400 500
T (K)
Activation energy ! E "
#$ %
k = Ae & RT '

E
lnk = ln A#
RT ln (k)

ln (k)
-2

-4

-6

0.0020 0.0025 0.0030 0.0035

-1
1/T (K )
Reaction rate – reversible reaction

!  Consider a reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system
N N
r = kf !C " kb ! C
qj q'j
j j
j =1 j =1

qj =
1
2
(
#j "#j )
qj =
' 1
2
(
#j +#j )
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Variation of reaction rate with progress of reaction

!  Consider a reaction ! !jAj = 0 taking place in a

closed, isothermal, constant pressure system
N N
r = rf ! rb = k f (T )" C ! kb (T )" C
qj q'j
j j
j =1 j =1

C j = C j 0 + #$ j
r(# ,T ) = rf (# ,T ) ! rb (# ,T )

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Rate contours – endothermic reaction
100

0.9 90

0.8 80

0.7 70

0.6 60
Extent

0.5 50

0.4 40

0.3 30

0.2 20

0.1 10

0
700 750 800 850 900 950 1000
Temperature

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Rate contours – exothermic reaction
500

0.9 450

0.8 400

0.7 350

0.6 300
Extent

0.5 250

0.4 200

0.3 150

0.2 100

0.1 50

0
450 500 550 600 650 700
Temperature K

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Summary
!  Rate of reaction
!  Power law kinetics
!  Law of mass action kinetics
!  Exothermic and endothermic reactions

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