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. specifications:

! Reactor
" " "

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

Indian Institute of Science

Cracking of ethane to ethylene

C H ! C H + H 2 6 2 4 2
Mole balances Batch/ CSTR/ PFR
Stoichiometry conversion molar flows

Rate of reaction

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

Indian Institute of Science

Representation of chemical reaction single reaction

! Consider

a single chemical reaction in N species A1, A2,., AN

! General

representation:

"! A
j =1 j
Indian Institute of Science

=0

Representation of chemical reaction multiple reactions

! Consider

A2,., AN
! General
N

R chemical reactions in N species A1,

representation:
ij

"!
j =1

A j = 0,

i = 1,! 2,!.........,! R

Indian Institute of Science

Representation of chemical reaction independent reactions

! Stoichiometric

matrix

" !11 !1N $ !=$ ! " ! $ # ! R1 # ! RN

! Number

% ' ' ' &

of independent reaction

$ R ! = ! rank !! " ! # %
Indian Institute of Science

Progress of chemical reaction single reaction

! Consider

a 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 - "

!=
Indian Institute of Science

nj " nj0

#j

Molar extent of reaction

! Properties
"

!=

nj " nj0

of "

#j

defined for the reaction n j " n j 0 nk " nk 0 != = #j #k

#k $!! nk = nk 0 + nj " nj0 #j

"

Extensive property in moles Always positive

Indian Institute of Science

"

Conversion of species
! Conversion

X
X= nj0 ! nj nj0

! Stoichiometrically

limiting species k
# nj0 & min!! % ! ( " $ j '

Indian Institute of Science

Cracking of ethane to ethylene

C H ! C H + H 2 6 2 4 2
Molar flow at entry Ethane, F10 Molar flow at exit Ethane, F1 Ethylene, F2

Stoichiometric tables Flow reactor !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

Species Entry (mol/ min) Change (mol/ min) -(F10X) - #j/#1 (F10X) ----Exit from the reactor (mol/min) F1=F10- F10X Fj=Fj0- #j/#1 F10X FI= FI0 FT=FT0-(!#j/#1)F10X FT=FT0+ ! F10X

A1 F1O Aj j=2,3, 4 FjO I (inerts) Total FI0 FT0

Concentrations in terms of conversion

P v = Z FT RT P0 v0 = Z0 FT 0 RT0 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 ) ! % P0 ( % Z ( % T ( % FT ( # " v = v0 ' * ' * ' * ' * P Z T F & ) & ) & ) & # 0 0 T0 ) $

Concentrations in terms of conversion

F A0 C = A0 v0 F F A0 "F A0 X A C = A= v v $ # 1" X $# P $# Z0 $#T 0 C A =C A0 % &% &% &% & 1 + ! X ' (' P 0 (' Z ('T 0( # $ 0 $#T $ #) 0 B "b/ aX $ P # Z C B =C A0 % &% &% &% & 1 + ! X ' (' P 0 (' Z ('T 0(

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. specifications:

! Reactor
" " "

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

Indian Institute of Science

Thermodynamic considerations
! Equilibrium ! Working ! Heat

conversion

conditions of the reactor

effects in a chemical reaction

Why thermodynamics
A ( B r = 2 . 61 ) 0 e
2.0 1.8 1.6

A! B
1 5 0 0 0 ! " # $ 6 & T % '

C A

r = 2.6 ! 106 e

# 15000 & "% $ T ( '

C A " 3.9 ! 1033 e

# 25000 & "% $ T ( '

CB

2.0 1.8 1.6

CA X CB

CA (mol/dm ), X

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 1 2 3 4

CA (mol/dm ), X

CA X CB

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

time (h)

time (h)

Effect of temperature
A! B T = 320
2.0 1.8 1.6 2.0 1.8 1.6

A! B T = 330

CA X CB

CA X CB

CA (mol/dm ), X

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 1 2 3 4 5

CA (mol/dm ), X

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 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
dG = Vdp ! SdT + " j dn j ,
j =1 N

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

Indian Institute of Science

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

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

!! !!! dG = Vdp " SdT + % # j j d$
! Equilibrium
N j =1

condition
!!
N # !G & = *) j j = 0 % ( $ !" ' T , P j =1

Indian Institute of Science

Chemical potential
! Perfect

gas mixture

y = composition !,! T = temperature,! P = pressure superscript ! r ! = ! reference P r = 1! atm y r = pure! j f j = fugacity

j T , P, y = j 0 T , P , y + RT ln
r r

Py j Pr

! Non-ideal

gas mixture

j T , P, y = j 0 T , P , y + RT ln
r r

fj f jr

Indian Institute of Science

Chemical potential
! Solution

j (T , P, x ) = j 0 T , P r , x r + RT ln ! j x j
x = composition !,! T = temperature,! P = pressure superscript ! r ! = ! reference

! = activity ! coefficient

Indian Institute of Science

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

j = j 0 + RT ln a j

( )
j

"!
j =1 j

= " ! j j 0 + RT " ! j ln a j
j

( )

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

!G = !G 0 + RT ln K a = 0
0 $ *!G ' $ #j ' K a = & " a j ) = exp & ) % j ( % RT (

Equilibrium constant !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0
0 # & )* G # & "j K a = % ! a j ( = exp % ( $ j ' RT $ '

Pressure Fugacity Concentration

"j & # # K P = % ! Pj ( = % ! Py j $ i ' $ i "j & # Kf = %! fj ( $ i ' "j & # KC = % ! C j ( $ i '

( )

"j

& ( '

Equilibrium extent of reaction !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

# "j & K P = % ! Pj ( $ j ' N j = N j 0 + " j) Pj = y j P = Nj NT P

+ KP = - ! - j ,

% ( N j 0 + " j# * ' 'P N + # " * $ j* T0 ' j & )

"j

. 0 0=F # 0 /

( )

Extent of reaction and operating conditions !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

+ K P (T ) = - ! - j , % ( N j 0 + " j# * ' 'P N + # " * $ j* T0 ' j & )
"j

. 0 0 = F # , P, N j 0 0 /

d d ! &F &F d% # ! ln K P (T ) # = F % , P, N j 0 = + " $ " $ dY dY &Y &% dY

Extent of reaction and operating conditions !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0

F ! d! =C dY F' !

( ) ( )
"H = heat of reaction
j

"H Temperature C = RT 2 Pressure Inerts C=# C=?

j

%$
P

%$
j

= change in no. of moles

Equilibrium conversion - Exothermic reaction

1.0
Isothermal

0.8 0.6
Xeq
Adiabatic

0.4 0.2 0.0 300 320 340 360 380 400

T

Indian Institute of Science

Equilibrium conversion - Endothermic reaction

1.0 0.8 0.6
Xeq
Adiabatic Isothermal

0.4 0.2 0.0 300 320 340 360 380 400

T

Indian Institute of Science

Equilibrium extent of reaction

"!
j =1

ij

Aj = 0,

i = 1, 2, ...., R

K Pi

# " ij & = % ! Pj ( $ j '

R i =1

N j = N j 0 + * " ij) i

Heat of reaction !1 A1 + ! 2 A2 + ! 3 A3 + ! 4 A4 = 0
!H R = # " j h j
j

h j (T ) = h + $
0 j j

298

C Pj dT
T j 298

!H R = # " j h + # " j $
0 j

C Pj dT

!H R = !H + # " j $
0 R j

298

C Pj dT

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

Indian Institute of Science

Classification of reactions
! Based
"

on mechanism of the reaction

Elementary and nonelementary reactions

Example: chlorination of nitric oxide to give nitrosyl chloride

2 NO + Cl2 ! 2 NOCl

Classification of reactions
! Based
"

on the direction of the reaction

cyclopropane ! propylene trans " butylene ! cis " butylene

Irreversible and reversible reactions

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! r= V dt 1 dn j rj = V dt

!=

nj " nj0

#j

Indian Institute of Science

Reaction rate
! Consider

a 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 )

Indian Institute of Science

Reaction rate power law kinetics

! Consider

a reaction ! !jAj = 0 taking place in a closed, isothermal, constant pressure system

r = kC C .....C
q1 1 q2 2

qN N

= k! C
j =1

qj j

qj is the order of the reaction wrt species Aj q = ! qj is the overall order !

Indian Institute of Science

Reaction rate law of mass action kinetics

! Consider

a reaction ! !jAj = 0 taking place in a closed, isothermal, constant pressure system

r = k! C
j =1

qj j

1 qj = "j #"j 2
Indian Institute of Science

Effect of temperature on rate

k

40 35 30 25

k = A e

! E" # $ % R T & '

k (s )

20 15 10 5 0 300 400 500

10 1
k

-1

k (s )

T (K)

0.1 0.01 1E-3 300

(400, 0.85605) (310, 0.00359) (300, 0.0016)

400 500

-1

T (K)

Activation energy

k = Ae

! E " #$ % T' &R

E lnk = ln A# R T
2 0

ln (k)

ln (k)

-2 -4 -6 0.0020 0.0025 0.0030

-1

0.0035

1/T (K )

Reaction rate reversible reaction

! Consider

a reaction ! !jAj = 0 taking place in a closed, isothermal, constant pressure system

r = kf !C
j =1

qj j

" kb ! C
j =1

q'j j

1 qj = #j "#j 2 1 ' qj = #j +#j 2

Indian Institute of Science

( (

) )

Variation of reaction rate with progress of reaction

! Consider

a reaction ! !jAj = 0 taking place in a closed, isothermal, constant pressure system

N qj j

r = rf ! rb = k f (T )" C
j =1

! kb (T )" C
j =1

q'j j

C j = C j 0 + #$ j r (# , T ) = rf (# , T ) ! rb (# , T )
Indian Institute of Science

Rate contours endothermic reaction

100 0.9 90

0.8

80

0.7

70 60

0.6

Extent

0.5

50

0.4

40 30

0.3

0.2

20

0.1

10

700

750

800

850

900

950

1000

Temperature

Indian Institute of Science

Rate contours exothermic reaction

500 0.9 450

0.8

400

0.7

350 300

0.6

Extent

0.5

250

0.4

200 150

0.3

0.2

100

0.1

50

450

500

550

600

650

700

Temperature K

Indian Institute of Science

Summary
! Rate

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

Indian Institute of Science