W

W
K

? ???

WK

WK

K
K
K
K

--

W
EFEbatchF

E JFKcontinuous

FK

E
K

(Batch)W J
--

E JF
K

K
K

(Continuous)W J

E3 JF(Semibatch)

--

Reactant
A
+
Products

(Semibatch)W J
W

F(Continuous Stirred Tank Reactor, CSTRF

E JFE

(Steady-state) (CSTR)
KK

KK

--

W J

(Plug Flow Reactor, PFR)

KKE JF

K
K

K
KE JF

--

(Plug Flow Reactor, PFR)W J

W J
W

(Bubble
Column Reactor).
--

(Fixed Bed Reactor)(Two-Phase Slurry Reactor)

(Three-FK

K JKPhase Slurry Reactor

(A)

(B)

(B) K(A) W J
(Fluidized bed Reactor)

--

K J

Cracked
products

Combustion
gases

Spent
Catalyst

Air
Regenerated
Catalyst

Hydrocarbon
Feed

(Fluidized Bed)W J

E JF

--

W J

JF

K(

W J

E JF

K
--

W J
K(CO) J

KW J
--

Chemical Kinetics

K
K

K



Excel

--

(Scale-up)

FK
E

(Plug Flow K

Reactor, PFR)

(Rate law) K
(Reactor Design)

Homogenous Reaction
K
Heterogeneous Reaction
K
Irreversible Reaction
KE A B F

--

Reversible Reaction

(Equilibrium)
KE A B F

Rate of Homogenous Reaction

1 dn i
r =
i
Vi dt

(2 1)

KVn i

WCi

ni

ci =
V

( 2 2)
W

ri =

ri =

d(

ni

V
dt
dc i

(2 3)
(2 4)

dt

--

W
aA + bB

cC + dD

(2 5)

stoichiometric coefficientsb, a

d, c

DC
WK

1 d nA
1 d nB 1 d nC 1 d nD
=
=
=
d dt
a dt
b dt
c dt
r
-r
r
-r
A = B= C= D

d
b
c
a
-

( 2 6)
( 2 7)

Chemical Conversion EF
K

tnAnAoA

WA

X A (t) =

n Ao - n A
n Ao

100

(2 8)

KE50 %FK J2-1

(Catalyst)A

KB

2 JKE2 JF
--

45%t125%

2 JK

5%

2J 1

--

2 J 2

WEF

( 2 9)

- rA c A c B

A:
KB
K :+
WE JF ( )

- rA = k A c A c B

(2 10)

(Specific reaction rate)kA

--

Arhenius equation
W
k (T) = A e

RT

( 2 11)

EK

KE JFAE
k

W(ln)EF

ln k = ln A -

E
RT

(2 12)

(T/1)(y)(ln kF
K(ln A)(y)

E
(x)
R

EFTk
Tk

Reaction Order

WK

(Reaction mechanism)
(Reaction mechanism)K
--

K
K

K
W

H2 + I2 2 HI

(2-13)

K
W

NaOH +CH3Br CH3OH +NaBr

(2-14)

W
2NO +2H2 N2 + 2H2O

(2-15)

W
2NO +H2 N2 +H2 O2

(2-16)

H2O +H2 2H2O

(2-17)

E JF
E JF

(mechanism)K

K
K

--

K


A P

(2-18)

dc

A = k (c ) 0 = k
A
dt

(2 - 19)

WE JF

cA
t
d c A = k dt
cAo
0

(2 20)

[c A c A0 ]= kt

(2 - 21)

[cA0 cA ]= kt

(2 - 22)

E JFKtAcAAcAo
(x) (y)(cA FA

--

cA

cAo
t

mol /m3 sSIk -k
KcAoK(y)

A P

(-23)

dc

A =kc
A
dt

(2 24)

cA
ln
c

= kt

A cAo

(2 - 25)

ln c Ao - ln c A = kt

(2 - 26)

c Ao
ln
= kt

cA

(2 - 27)

--

WE JF

ln (c Ao/c A)

t

kk
Ks-1SI

K

W
2A P

(2 - 28)

aA + bB P

(2 - 29)
AE JF

dc

A = k c2
A
dt

cA

c Ao

(2 30)

d cA t
= k dt
2
cA
0

(2 31)
--

c Ao

1
c = k t
A c

(2 - 32)

1
1

=kt

c A c Ao

(2 - 33)

t(y)1/cA

W1/cAo(y)k(x)

1/cA

1/cAo
t

B A

WBA

aA

+ bB P

(2 - 34)

d cA
= k cA cB
dt

(2 35)
W

b = a(cAo = cBo)BA K
--

cA = cB
KE JFE JF
Kb acAo cBo K
W

d cA
= k cA cB
dt

(2 36)

cAcB

AKnBoBnAoA

WE JFKnBB nAt

b
n
=
n

(
) (n A n A )
B
B
a
0

(2 37 )

b
c
=
c

(
) (c A c A )
B
B
a
0

(2 38)

WE JFcB

cA

c Ao

t
d cA
= k d t
b
b
c A (c Bo c Ao + c A ) 0
a
a

(2 39)

1

b
c Bo - c Ao
a

cB
ln
cA

c Bo

= k t
ln

c Ao
--

(2 - 40)

K
EF
K

Method of Half Life

t1/2

K
K

nA
-

(2 - 41)

d cA
= k c nA
dt
cA

c Ao

(2 42)

d cA t
= k d t
n
cA
0

(2 43)

1 1
1

t
=

n -1
n -1

k(n - 1) c A c Ao
--

(2 44)

n 1

c
1
Ao

t = k c n -1 (n - 1) c - 1

A
Ao

(2 45)

cA =1/2 cAot = t1/2

t1

2 n -1 - 1 1
=
k (n - 1) c nAo-1

(2 46)

2 n -1 - 1
+ (1 - n) ln c Ao
ln t 1 = ln
(n - 1)k
2

(2 - 47)

(y)E JF

1-n(x)

Kk(y)Kn

n=1
W

c Ao
ln
=kt

cA

(2 - 48)
cA =1/2cAot = t1/2

ln

c Ao
= k t1
1
2
c Ao
2

(2 49)

ln 2
= t1

k
2

(2 50)
--

c Ao
= t1

2k
2

(2 51)
W

l
= t1

k c Ao
2

(2 52)

K
K

K .
K .
K .

--

- -

Homogeneous Reactors

- -

EF EFW

KEF

Reactor design and laboratory rate data

FEF

KEBatch
FEPFR

(Feed flow rate)K

J J(Product flow rate)

K

EF EFW

EOptimization techniqueF
K

EStorage tank F

KECyclicalF

EReactor controlF

K
(Fluctuations)(Strategy)

K(Semi-computerized )
(Manual)
Direct-

EClosed-loopFEdigital)

- -

K
K

(Iterative)
K

WK

(Bench-scale laboratory reactor) K

EF(Diffusion)
KK

K(Pilot plantF K
K K

K (SO2)
K

K (SO3)
SO3

(Pilot-plant)

K
- -

(Diffusion)
K

KK

(Prediction methods)

Mass and Energy Balances

(Single-reaction system)K
(Limiting reactant)
(Limiting

KKreactant)

(Conversion)
K(Stoichiometry)

Multiple-reaction systems)F
K

- -

K(X)

(Successive reactions) (Simultaneous reactions)

J
K(CSTR)

C 6 H 6 + Cl 2

C 6 H 5 Cl

HCl

C 6 H 5 Cl + Cl 2

C 6 H 4 Cl 2

HCl

C 6 H 3 Cl 3

HCl

C 6 H 4 Cl 2 + Cl 2

K(NB0)

XDXMK

KXT

(Limiting reactant)

NTNDNMNBK

xD =

2N D
N CL

(3 1)

- -

x =
T

3N T
N Cl

(3 2)

W
N B = 1 ( N M + N D + N T ) = 1 ( xM +

1
1
x D + xT ) N Cl
2
3

(3 3)

(3-(3-1)(NB0)/V[B0]

K2)
W

[M ] =

(NB )NM
0

= [ B0 ] N Cl xM

(3 4)

1
[ D] = [ B0 ] N Cl xD
2
1
[T ] = [ B0 ]N Cl xT
3

(3 5)

(3 6)

[ B] =

( N B0 ) N B
V

= [1 ( xM +

1
1
xD + xT ) N Cl2 ][ B0 ]
2
3

(3 7)

W
N Cl 2

= N M + 2 N D + 3 NT
- -

(3 7)

K

WC J J J

N Cl 2 = X m N Cl 2 + X D N Cl 2 + X T N Cl 2

(3 8)

XM

+ X D + X T =1

(3 - 9)

E JF

E250OC200OCF

1
C 2 H 4 (g) + O 4 (g) C 2 H 4 O(g)
2

C2 H 4 ( g ) + 3O2 ( g ) 2CO2 ( g ) + 2 H 2 O( g )
WX2X1

X1 =

NC H O
2

or N C H O = X 1

1
N CO
2
or N CO = 2 X 2
X2 =
1
2

W
2X 2

= H 2O

1 X 1 X 2 = C2 H 4
N2 = O.79(air)

- -

1
O
=
o
.
21
(
air
)

(
X1 + 3X 2 )
2
2
1
X 1
2
W
1 + air

C2 H 4O =
CO2 =
H 2O =

X1
1+ A

1
X4
2

2X 2
1 + air

1
X4
2

2X 2

1
X4
2
1 X1 X 2
C2 H 4 =
1
1 + air X 4
2
1 + air

0.79air
1
1 + air X 4
2
1
0.21air ( X 4 + 3 X 2 )
2
O2 =
1
1 + air X 4
2

N2 =

X1 KX1HX2

KX1LX2

{} J{}
} = {} J

E JF{

- -

K
r t K

rKr

E JF
K

Mass Balance

V E JFE JF

KE JF

K
XF

WE JF(Bulk flow)
F (1 X )t
X + K
K F (1 X X )
K
K r rVt

K V
r
K

- -

KE)

EF
V K

W t

} J{ }
} = { } H{

E JF{

(Internal

(Kinetic energy)(Potential energy)energy)

KE F
E JFK

E JFE JF
K

K(Diffusion )EMixing)

E JFE JFK

- -

The Ideal Stirred-tank Reactor

(Steady-(CSTR)

(Batch reactor)state flow reactor)

KE F(Semi-batch reactor)
K

EF

K
K

Steady-State Flow
K E JF

E JF

K t ELimiting reactant)

K

XFF

XP

K F (1 X P )t F (1 X F )t

CSTRW J

- -

ErP

K rEVt

WE JF

F (1 X F ) t F (1 X E )t rEVt = 0

V XE XF
=
F
rE
XE

K rE FXF

K XE

KKK

rE
E JF KV

EF(Base state)K

(Enthalpy)K

KHEHFEF

Ft H E t Ft H F t Ft

F1 ( H F H E )t + UAh (Ts TE )t = 0
- -

F1 ( H F H E ) + UAh (Ts TE ) = 0

(Overall-heat-transfer coefficient)UTs
H KAh(Effective area)

K HEr H
T , r , H HF JHE

K TETF

W ( X E X F )H / M Cp(TE-TF)

H e H F = eP (TE TF ) + ( X E X F ) + ( X E X F )

HF
MF1

(Limiting reactant)M
E JFE JFK

F1 (TF Te )eP F ( X E X F )

+ UAh (Ts TE ) = 0
M

E JFXE JXF

F1 (TF TE )eP rEV

+ UAh (Ts TE ) = 0
M

E JFE JFE JF
(Homogeneous reactors)
- -

Batch Operation (Non steady-State) EF

K

t
W mX t
rVt = mX
K

t 0 t E JF

V
dx
=
r

E JF
dt
m
Fr
KXE
E JF

m X dX
X dX
= X
1 = m X
E JF
rv mt
r

KtX2X1
Kmt

rK
K

K
2

- -

E JFEF

K
K H / M )rVt

T t
WE JF nt Cv T
UAh (Ts T )t =

rVt + mt c e
M

E JFT

E JF

Semi-batch Operation

K(CSTR)

KEF

- -

(Hexamethylenetetramine)
EF
K(Exothermic reaction)

E
F
K

EF
The Ideal Tubular-flow Reactor (Plug-flow Reactor, PFR)
(PFR)

KE J F

K EF

J J
K

KE JFE JFV

K V

Partial differential FE JFE JF

Kequations)

- -

PFR

W J

KEF
(Plug-flow

Kreactor)
K

KK

- -

Heterogeneous Reactions

K
K
K

--

Types of Heterogeneous Reactions

K
K

(Cracking)W

F(Dehydrogenation)(Reforming)

(Isomerization)E

KKKK(Desulfurization)
K
EF

KE F

(Transient)
K(Steady-state)

WNaClNa2SO4

2NaCl(s) + SO3(g) + H 2 O(g) Na 2SO4(s) + 2HCl(g)

K

(Bubble

column)

F(Co-current)(Countercurrent)
(Spray

column
--

CO2KE
K(Amine Solution)

K J

AlCl3(s) (Alkylation)
K

K(Sludge)
K

(Hydrogenation)

K

(CSTR)

K
(Fixed Bed Reactors)

(Volatility)

--

Design Of Heterogeneous Catalytic Reactors

K

K

K
FIXED BED REACTORS
Construction and Operation

K
K

FE
KEExothermic

reaction

K
--

KW J

K
K

(Hot

SpotFK
K

}(Intercooler)

K J

--

()

()

EFW J
EF

--

W
J
J
H J

KE JF

F
E

(Equilibrium

KConversion)

WK

K J

--

K400-500oC

J
W

K EF
K EF

(Regeneration)

J K

(Shut

down) J

K
K

K
0.91 m
--

3 m
3

Monolith Catalyst Beds

(Airfoil)
K J

K W J

--

(NOx)
(Pt)(CO) (HC)

K(Pd)(Rh)
J
J

K
Auto Thermal Reactors
F
Water-Shift

reaction)W

ECO+H2OH2+CO2
K

KEF

(Recycle)E JF

KE JF

(Auto Thermal)

K
J
K





--

KW J

FLUIDIZE BED BEACTORS

K
--

K J(Bubbling

Regime)

K J
(Dense

Phase)

KE

KE JF

KW J


--

KW J

Operating Characteristics

K
103F

K
JKE

EF(Regenerator)
KEF

K J

(Hot

KSpot)
K
--

KE

(Cyclone

Separators)

K
(Gas

Oil)

(Molecular
KSieve

KW J

--

SLURRY REACTORS
E JF

W
J
J
K J

xe

Qg.Cg.f
Xf

W J

K
K

--

KK

J
J
KEF JK

W J

--

Catalysis

K


K

--

EThermodynamicF
K

K K

K
--

K
K

(Active centers) K

K
K

(Equilibrium conversion) K

(Forward reaction)
K(Reverse reaction)

K(Selectivity) K

K
(Chain reaction)
K

(Auto catalytic reaction) K

K

K
Activity
K
Selectivity
K

--

Poisoning
K

W

K(Active ingredient) Ka

(Support) Kb
K

(Inhibitors) Kc
K

K
K

(Promoters) Kd
K

Heterogeneous Catalysis

K
K

W(A B)

--

KA(External Diffusion) K
KA(Internal Diffusion) K

(Adsorption) K
K(Chemisorption)(Physisorption)

K (Surface reaction) K
K(Desorption) K
KB K

KB K
Homogeneous Catalysis
K
KK

K(PdCl2)

EF

--

(Precipitation) K

Impregnation K

K
K

Fusion K

EFusionF
EFe3O4F

EK2OFEAl2O3F

KECaOF

WK
--

K
K

K
K

K
K

J J

--

(1)

k (h-1)

0.5

1.1

2.2

4.0

.0

T(oC)

30

40

50

60

70

LE

K
W5
1/Tln k

1/T ln k

L E
--

WindowsExcel

B 303enterA1+273

303

B1

--

C11/T

--

ln (E1FEDk
k

--

CEInsertColumn

--

--

FE

XY(scatter)

--

Next

Add Trendline chart

--

linearAdd trendline

Woptions

--

--

OK

grid lines

--

ln L6529.4-E/R

X E=54.29 kJ/molR = 0.008314 kJ/mol K20.927

L = 3.191011
Excel

--

--

--

--

--

1. Scott, H., Fogler,O., Elements of Chemical Reaction Engineering,

International edition, Prentice Hall Inc., USA, 1999
2. Smith, J.M., Chemical Reaction Engineering, International edition, McGraw-Hill,
USA, 1981

- -

.....................................................................................................................
...........................................................................................................
...........................................................................................................
............................................................Chemical Kinetics
............................................. Method of Half Life
........................................................ Homogeneous Reactors
................................................. Heterogeneous Reactions
................................................................................................ Catalysis
.........................................................................................................
............................................................................................................
.....................................................................................................
..................................................................................................................