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Title: Chemical Reaction Engineering

Course Codes: CENG3003, BENG3008

Value: ½ Unit

Lecturers: Prof. A Gavriilidis

Dr N. Szita

Aims: Development of the structure necessary for solving

chemical reaction engineering problems. Ultimate goal is
the design of chemical reactors.

Coursework: 4 sets

Assessment: Written examination (80%)

Coursework (20%)

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SYNOPSIS

Introduction: Brief survey of the scope of the subject together with a

review of some of its foundations.

Mole Balances: Definition of reaction rate. The general mole balance. The
batch, plug flow and continuous stirred reactors. Industrial reactors.

Conversion and Reactor Sizing: Definition of conversion. Design

equations for batch and flow systems. Reactors in series. Space velocity
and space time.

Rate Laws and Stoichiometry: Concepts of reaction rate, reaction order,

elementary reaction and molecularity. Stoichiometric table. Reactions
with phase change.

Isothermal Reactor Design: Design structure for isothermal batch, plug

flow and continuous stirred reactors. Design of multiple reactor systems.
Pressure drop in reactors. Reversible reactions.

Catalysis and Catalytic Reactors: Catalyst definition and properties. Steps

in catalytic reactions. Synthesising rate laws. Guidelines for design of
reactors for gas-solid reactions. Heterogeneous data analysis for reactor
design.

Nonisothermal Reactor Design: The energy balance. Algorithms for

nonisothermal plug flow and continuous stirred reactor design.
Equilibrium conversion. Steady state multiplicity.

Multiple Reactions: Conditions for maximising yield and selectivity in

parallel and series reactions.

Biochemical Reaction Engineering: Characteristics of enzyme catalysed

reactions. Biocatalyst selection and production. Use of immobilised
biocatalysts. Use of organic reaction media. Reactor selection and
operation.

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TEXTS

Recommended:

“Elements of Chemical Reaction Engineering”

H.S. Fogler
Prentice-Hall, 4th Ed., 2006

Other good texts:

“Chemical Reaction Engineering”

O. Levenspiel
Wiley International, 3rd Ed., 1999

“Chemical Reactor Analysis and Design”

G.F. Froment and K. B. Bischoff
Wiley International, 2nd Ed., 1990

“Chemical Engineering Kinetics”

J.M. Smith
McGraw-Hill, 3rd Ed., 1981

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INTRODUCTION

Raw Materials

Physical purification,
Treatment heating,
Steps mixing, etc.
Typical
Chemical
Process
Chemical
Recycle Treatment
Steps

Physical distillation,
Treatment extraction,
Steps filtration, etc.

Products

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Knowledge and information from:

− Thermodynamics
− Chemical Kinetics
− Fluid Mechanics
− Heat/Mass Transfer
− Economics

Chemical Reactor Design

distinguishes the chemical engineer from other engineers

Most common industrial reactors

BR: Batch Reactor

CSTR: Continuous-Stirred Tank Reactor

PFR: Plug-Flow Reactor

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CONTINUOUS STIRRED TANK REACTORS

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PLUG FLOW REACTORS

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1. MOLE BALANCES
1.1 Definition of the Rate of Reaction, -rA

Chemical Species: Chemical Compound or element with a given identity

(determined by kind, number and configuration of atoms).

Chemical Reaction: One or more chemical species have lost their

chemical identity.

Types of Reactions

Decompostition:

CH(CH3)2

C3H6

cumene benzene propylene

Combination: N2 + 3H2 2NH3

Izomerization:

CH3 CH3

CH2 = C – CH2CH3 CH3C = CHCH3

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Classification of Reactions

Homogeneous: reaction takes place in one phase alone

Heterogeneous: requires the presence of at least two phases

Catalytic: requires the presence of a catalyst

Noncatalytic: does not require a catalyst

Noncatalytic Catalytic

Most gas-phase Most liquid-phase

reactions reactions
Homogeneous

Burning gas flame Enzyme reactions

Burning of coal NH3 synthesis

Heterogeneous

Reduction of iron ore to

Cracking of crude oil
iron

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A products

Reaction rate, -rA is defined as the number of moles of A reacting

(disappearing) per unit volume (mol/m3 – s).

dCA
Note: rA = is NOT a definition for chemical reaction rate.
dt

Rate law: function of T, C must be determined experimentally

e.g.
− rA = kC A , − rA = kC A2
k1C A
− rA =
1 + k 2C A

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1.2 The General Mole Balance Equation

moles
dN j
Fjo + Gj − Fj =
dt
↓ ↓ ↓ ↓
In Generation Out Accumulation

moles moles moles moles

time time time time

system volume

Fjo Gj Fj

If variables (C, T) uniform throughout system volume ⇒

Gj = rj ⋅ V
↓
moles moles
= ⋅ volume
time time ⋅ volume

If variables (C, T) NOT uniform in the system volume:

∆V1

r j1
rj2 ∆V2 V

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∆G j1 = r j1 ⋅ ∆V1 (subvolume ∆V1)

M M
G j = ∑ ∆ G ji = ∑ r ji ∆ Vi (M subvolumes = total system volume)
i =1 i =1

By taking limits: M ∞, ∆V 0

V
G j = ∫ r j dV

dN i
F jo − F j + G j =
dt

v
dN j
F jo − F j + ∫ rj dV = dt

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1.3 Batch Reactors

no in flow, no out flow, perfectly mixed

⇓ ⇓ ⇓
Fjo = 0 Fj = 0 Gj = rj V

Mole balance becomes:

dN j
= rj V Design equation for BR
dt

– Constant Volume BR

Pressure gauge

NA
CA = ⇒
V
dN A
= rA V
dt
d (C A ⋅V ) dC A
= rA V ⇒ V = rA ⋅ V
dt dt
dC A
= rA
dt

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– Constant Pressure BR
- Movable piston
NA
CA = ⇒
V
dN A
= rA V
dt
d (C A ⋅ V )
= rA V ⇒
dt
dC A dV
V⋅ + CA = rA ⋅ V
dt dt
dC A C A dV
+ = rA
dt V dt
dC A d ln V
+ CA = rA
dt dt

1.41 Continuous-Stirred Tank Reactor

steady-state, perfectly mixed

⇓ ⇓
dN j
=0 Gj = r j V
dt

Recall mole balance:

dN j
Fjo – Fj + Gj =
dt

F jo − F j
V = Design equation for CSTR
− rj

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Reactants

well-mixed
conditions the same everywhere
conditions in the exit ≡
conditions in the tank.

Products

Relationship between molar and volumetric flow rates:

Fj = Cj·υ

moles = moles • volume

time volume time

1.42 Tubular Reactor

Flow field is modeled by plug flow, i.e. no radial variation of C, T.

Therefore reactor is: plug-flow reactor (PFR).

Concentration (⇒ rj also) varies along the axial direction.

Divide reactor into subvolumes ∆V.

Conditions (C, T) uniform in each ∆V.

∆y

Fjo Fj, exit

y y + ∆y

Fj(y) ∆V Fj (y + ∆y)

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dN j
steady-state ⇒ =0
dt

Mole balance for subvolume ∆V:

F j ( y ) − F j ( y + ∆y ) + r j ∆V = 0 ⇒

∆V = A ⋅ ∆y

 F j ( y + ∆y ) − F j ( y ) 
−  = − A rj
 ∆ y 

Take limit as ∆y → 0

dF j
− = − A rj
dy

Divide by –1, substitute Ady = dV

dF j
= rj Design equation for PFR
dV

Note that for a reactor in which the cross-section A varies along the
reactor, the design equation remains the same.

Example 1-3

A→B

CA, exit = 0.1⋅CAO

υO = 10 dm3/min
-rA = kCA
k = 0.23 min-1
VPFR = ?

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dFA
= rA
dV
d (C A ⋅ υ O ) dC
= υO = rA
dV dV
dC A
υO = − kC A
dV

υO  dC A 
−   = dV
k  A 
C

Integration limits:

V =0 C A = C AO

V = V PFR C A = C A, exit

υO dC A
∫ ∫
C A, V PFR
− =
exit
dV
k C AO CA 0

υO C AO
V PFR = ln
k C A , exit

10 dm 3 / min C AO
V PFR = ⋅ ln = 100 dm 3
0 .23 / min 0 .1 ⋅ C AO

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BR CSTR PFR

Production Rate Small High High

Capital Cost Small High High

Labour Cost High Small Small

Scale of Operation Small Large Large

Reactant Conversion High Small High

Temperature Control Easy Easy Difficult

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2. CONVERSION AND REACTOR SIZING

2.1 Definition of Conversion

aA + bB → cC + dD

Basis of calculation: Limiting reactant, A . Arrange reaction on a “per

mole of A” basis.

b c d
A+ B→ C + D
a a a

moles of A reacted
Conversion, XA: XA =
moles of A fed

N AO - N A
Batch Systems: XA =
N AO

FAO - FA
Flow Systems: XA =
FAO

2.2 Design Equations

2.21 Batch Systems

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N AO − N A
X A = ⇒
N AO

N A = N AO − N AO ⋅ X A ⇒

dN A dX A
= 0 − N AO ⇒
dt dt
dN A
recall : = rA ⋅ V
dt
dX A
N AO = − rA ⋅ V
dt

design equation for BR (differential form)

If reactor volume is not constant then:

t XA
dX A
V = f (t ): ∫ Vdt = N AO ∫ −r
0 0 A

XA
dX A
V = f ( X A ): t = N AO ∫−r
0 A ⋅V

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2.2.2 Flow Systems

FAO − FA
XA = ⇒
FAO

FA = FAO − FAO ⋅ X A ⇒

FAO − FA = FAO ⋅ X A ⇒

Recall: FAO − FA = − rA ⋅ V ← CSTR

FAO ⋅ X A = − rA ⋅ V ⇒

FAO ⋅ X A
V = Design equation for
(− rA ) exit CSTR

FA = FAO − FAO ⋅ X A
⇒
dFA
Recall: = rA ← PFR
dV
dX A Design equation
FAO ⋅ = − rA
dV for PFR

XA
dX A
⇒ V = FAO ∫0 − rA

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2.3 Applications of the Design Equation

− rA = f (C A ) ⇒ − rA = f ( X A )

C A = f (X A )

− rA = kC AO (1 − X A )

1 1 1
= ⋅
− rA kC AO (1 − X A )

1
−
rA

XA

0 0.2 0.4 0.6 0.8 1.0

1
X A ≈ 0 → − rA : large → : small
− rA

1
X A ≈ 1 → − rA ≈ 0 → ≈∞
− rA

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Example 2-1 (refer to previous figure)

1  dm 3 s 
−  
rA  g mol 

FA0 = 20 mol/s
XA = 0.8 30
VCSTR = ?

20

10

F A0 ⋅ X A XA
V =
− rA
0 0.2 0.4 0.6 0.8 1.0
 1 
V = F A0 ⋅   ⋅ X A
−
 Ar

V  1 
=   ⋅ 0.8
FA0  − rA 

1
From figure : X A = 0.8 → = 27.5
− rA

dm 3 ⋅ s
= (27.5) ⋅ (0.8) = 22
V
F A0 mol

V
or = area of shaded rectangle
F A0

mol dm 3 ⋅ s
V = 20 ⋅ 22
s mol

VCSTR = 440 dm 3 = 440 litres

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Design Equation for PFR

dX A
FA 0 = − rA
dV

Integrate and rearrange

XA
dX A
V = FA0 ∫ − rA
1  dm s 3 0
−  
r
The  g mol
A integral  the
is

30

20

0.8
10 dX A
I= ∫0 − rA
XA

0 0.2 0.4 0.6 0.8 1.0

From figure we can evaluate graphically

dm 3 ⋅ s
0 .8
dX A
∫
0 − rA
= 10
mol

mol dm 3 ⋅ s
V = 20 ⋅ 10
s mol

V PFR = 200 dm 3

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Example 2-2 (refer to previous figure)

Compare VPFR with VCSTR for

XA = 0.6
FA0 = 5 mol/s

1  dm 3 s  CSTR
−  
rA  g mol 
30
PFR

20

10
XA

0 0.2 0.4 0.6 0.8 1.0

 1 
VCSTR = FA0 ⋅   ⋅ X A
−
 Ar

5 mol 16 dm 3 ⋅ s
= ⋅ ⋅ 0.6
s mol

VCSTR = 48 dm 3
⇒ VPFR < VCSTR
0.6
dX A
V PFR = FA0 ⋅ ∫0 − rA
5 mol 5.1 dm 3 ⋅ s
= ⋅
s mol

V PFR = 25.5 dm 3 (always true for iso-T, first order rxns)

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2.4 Reactors in Series

Consider the system:

XA = 0 XAI
V1V1
FA0 FA1
XA2 XA3
V2 V3
FA2 FA3

Define conversion

total number of A reacted up to point 2

X A2 =
moles of A fed to first reactor

valid when: - no sidestreams withdrawn

- feed enters only the first reactor

FA 0 − FA 2
X A2 = ⇒ FA 2 = FA 0 − FA 0 X A 2
FA 0

Mole balance for species A, for second reactor (CSTR)

in – out + generation = 0
FA1 – FA2 + rA2V2 = 0

( FA 0 − FAO X A1 ) − (FA0 − FA0 X A 2 ) + rA2V2 = 0

FA0 ( X A 2 − X A1 )
V2 =
− rA2
evaluated at XA2

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Example 2 – 3

Gas mixture of 50% A, 50% inerts

PO = 10atm
TO = 149ºC
R = 0.082 dm3.atm/mol.K
υO = 6 dm3/s (at 149oC)
CAO = ?
FAO = ?

PAO y ⋅P
C AO = = AO O
RTO RTO

yAO = 0.5 (mole fraction of A)

TO = 149ºC = 422 K

C AO =
(0.5) ⋅ (10 atm )
 dm 3 ⋅ atm 
 0.082  (422.2 K )
 mol ⋅ K 
mol
C AO = 0.144
dm 3
 mol   dm 3 
FAO = C AO ⋅ υ O =  0.144  6.0
3  

 dm   s 
mol
FAO = 0.867
s

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Laboratory data for examples 2 – 3 through 2 – 6

Isothermal, gaseous decomposition A 3B

T = 49ºC
P = 10atm
yAO = 0.5 (rest inerts)

 mol 
XA -rA  3 
 dm s 
(1 / − rA )
0 0.0053 189

0.1 0.0052 192

0.2 0.0050 200

0.3 0.0045 222

0.4 0.0040 250

0.5 0.0033 303

0.6 0.0025 400

0.7 0.0018 556

0.8 0.00125 800

0.85 0.0010 1000

υO = 6.0 dm3/s

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FAO

XA1 = 0.4

FAe
XA2 = 0.8

 1 
V1 = FAO   X A1
 − rA1 

FAO ( X A 2 − X A1 )
V2 =
− rA 2

Example 2 – 4

XA1 = 0.4
XA2 = 0.8 (i.e. FAe = 0.2·FAO)
VCSTR1 = ? VCSTR2 = ?
FAO = 0.867mol/s

1
−
rA

dm 3 ⋅ s 800
g mol

CSTR2
CSTR1
400

XA

0 0.2 0.4 0.6 0.8 1.0

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1 dm 3 ⋅ s
X = 0 .4 → = 250
− r A1
A1
mol

 1 
V 1 = F AO   X = (0 . 867 )(250 )(0 . 4 )
 − r A1
A1


V 1 = 86 . 7 dm 3

1 dm 3 ⋅ s
X = 0 .8 → = 800
− rA 2
A2
mol

 1 
V 2 = F AO   ( X − X )=
−
A2 A1
 r A 

 mol   dm 3 ⋅ s 
=  0 . 867 
  800  (0 . 8 − 0 . 4 )
 s  mol 

V 2 = 277 . 4 dm 3

V T = V 1 + V 2 = 364 dm 3

same conversion (80%) in one CSTR

 1 
V = FAO   X = (0 . 867 )(800 )(0 . 8 )
−
A
 r A 

V = 555 dm 3

V 1 CSTR > V 2 CSTR 's (iso − T, 1st order )

However for PFRs V 1 PFR = V 2 PFRs because
X2 X1 X2
dX dX dX
∫
0
− rA
≡ ∫
0
− rA
+ ∫−r
X1 A

FAO XA1 = 0.4

FAe
XA2 = 0.8
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Example 2 – 5

XA1 = 0.4
XA2 = 0.8
VPFR1 = ? VPFR2 = ?
FAO = 0.867 mol/s

1
−
rA

dm 3 ⋅ s 800
g mol

PFR1 PFR2
CSTR1
400

XA

0 0.2 0.4 0.6 0.8 1.0

Evaluate integrals numerically

Simpson’s three point rule:
∆x
∫ f ( x ) dx = [ f (x0 ) + 4 f (x1 ) + f (x2 )]
X2

X0 3
First reactor: X0 = 0, X1 = 0.2, X2 = 0.4, ∆X = 0.2

dX ∆X  1 1 1 
V1 = FAO ⋅ ∫
0.4
= FAO ⋅  + 4 + 
0 − rA 3  − rA (0 ) − rA (0.2 ) − rA (0.4 ) 

 mol   0.2  dm 3 ⋅ s
V1 =  0.867   [189 + 4 ⋅ (200 ) + 250]
 s  3  mol

V1 = 71.6 dm 3

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Second reactor: X0 = 0.4, X1 = 0.6, X2 = 0.8, ∆X = 0.2

∆X  1 1 1 
V2 = FAO ⋅  + 4 + 
3  − rA (0.4 ) − rA (0.6 ) − rA (0.8) 

 mol   0.2  dm 3 ⋅ s
V2 =  0.867   [250 + 4 ⋅ (400 ) + 800]
 s  3  mol

V2 = 153 dm 3

VT = V1 + V2 = 225 dm 3

Scheme A:

FAO X1

X2 = 0.8

Scheme B:

FAO

X1
X2 = 0.8

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Example 2 – 6

X1 = 0.5
X2 = 0.8
V1 = ? V2 = ?
mol
FAO = 0.867
s

1
− CSTR
rA
PFR
dm 3 ⋅ s 800 800
mol

400 400

X X

0 0.4 0.8 0 0.4 0.8

Scheme A Scheme B

Scheme A

 ∆X 
 3 [ f ( X 0 ) + 4 f ( X 1 ) + f ( X 2 )]
dX
∫
0.5
V1 = F AO = F AO
0 − rA  

∆X  1 4 1 
= F AO ⋅  + + 
3  − rA (0) − rA (0.25) − rA (0.5) 

= 0.867 ⋅
0.25
[189 + 4 ⋅ (211) + 303]
3

V1 = 96.5 dm 3 (PFR)

X 2 − X1
V 2 = F AO = 0.867 ⋅ (0.8 − 0.5) ⋅ 800
− rA2

V 2 = 208 dm 3 (CSTR)

VTOTAL = V1 + V 2 = 305 dm 3 2-15

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Scheme B

= 0.867 ⋅ (0.5) ⋅ 303 = 131.4 dm 3

X1
V1 = FAO
− rA1

= 0.867 ⋅ (151) = 130.9 dm 3

dX
V2 = FAO ∫
0.8

0.5 − r
A

VTOTAL = 262 dm 3

Which scheme gives the smaller VTOTAL depends on X1.

For certain T, P, CAO, we need only – rA = f (XA) and FAO to size reactors.

2.5 Some Further Definitions

V
Space time, τ τ ≡
υo

Space time is the time necessary to process one reactor volume of fluid
based on entrance conditions.

reactor

20 m 20 m
X dX
V = F AO ∫ o − rA

X dX
Divide by τ = C AO ∫
o − rA

(υ o )STP 1
Space velocity, SV SV ≡ =
V τ
υ o not necessarily at reactor entrance conditions.

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When volumetric flowrate remains constant along a PFR, i.e. υ = υ o

FAO − FA C AO υ O − C A υ C AO − C A
X = = =
FAO C AO υ O C AO

X = 0 → C A = C AO

X = X → CA = CA

Differentiate the equation for X

dC A
dX = −
C AO
C AO C AO
dC A dC A
Design equation for PFR
⇒ V = υo ∫
CA
− rA
⇒τ = ∫
CA
− rA

dX
∫
X
V = FAO valid only if υ = υ o
0 − rA

1
− C AO
dC A
τ = area = ∫ − rA
rA

 dm 3 ⋅ s  C A1
 
 mol 

mol
CA dm 3

CA1 CAO

2-17

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DESIGN EQUATIONS

Differential Form Algebraic Form Integral Form

x
dX
t = N AO ∫ and
dX − rAV
BR
N AO = − rAV o

dt t x

∫V (t )dt = N AO ∫
dX
o o
− rA

FAO ( X OUT − X IN )
CSTR V=
(− rA )OUT

XOUT
dX dX
PFR FAO
dV
= − rA V = FAO ∫
XIN
− rA

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3. RATE LAWS & STOICHIOMETRY

3.1 Basic Definitions

Homogeneous/Heterogeneous
Catalytic/Noncatalytic
Reversible/Irreversible
p p
XA <1 XA = 1 for t = f

3.1.1 The Reaction Rate Constant

Kinetic Expression or Rate Law

-rA = k(T)˜ fn (CA, CB, …)

p
reaction rate constant

Arrhenius Equation: kT A ˜ e  E / RT

A { preexponential factor
E { activation energy, J/mol
R { gas constant, = 8.314 J/mol K
T { absolute temperature, K

Activation energy is determined experimentally from experiments at

different temperatures

E§1·
ln k ln A 
¨ ¸ (3-3)
R ©T ¹
p p p p
y = a – b˜ x

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Example 3 – 1

AoB+C

first-order
E=?

k(s-1) 0.00043 0.00103 0.00180 0.00355

T(K) 313 319 323 333
1000/T(K-1) 3.2 3.14 3.10 3.05

Convert equation (3-3) to log base 10

E §1·
log k log A  ¨ ¸
2.3 ˜ R © T ¹

1
Plot k vs. u 10 3 K 1 on semilog paper
T

0.01
3.04 3.06 3.08 3.1 3.12 3.14 3.16 3.18 3.2 3.22
k (s -1)

0.001

0.0001
3 -1
1/T x 10 (K )

3-2

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For two different points

E §1·
log k1 log A  ¨¨ ¸¸
2.3 ˜ R © T1 ¹

E § 1 ·
log k 2 log A  ¨¨ ¸¸
2.3 ˜ R © T2 ¹

Substracting yields

k2 E § 1 1·
log ¨¨  ¸¸
k1 2.3 ˜ R © T2 T1 ¹

2.3 ˜ R ˜ log k 2 / k1
E 
1 / T2  1 / T1

Use the decade method (i.e. k1/k2 = 10)

k1 = 0.005 o 1/T1 = 0.00303

k2 = 0.0005 o 1/T2 = 0.00319
log (k2/k1) = -1

J
2.3 ˜ 8.314
2.3 ˜ R mol.K
E
1 / T2  1 / T1 1
0.00319  0.00303
K
kJ
E 120
mol

The larger the E, the more temperature-sensitive is the reaction rate.

3-3

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3.1.2 The Reaction Order

fn(cj) o determined from experiments

 rA k ˜ C DA ˜ CBE
D: order with respect to A
E: order with respect to B
D + E: overall order

D,E,D + E do not have to be integers.

CO + Cl2 o COCl2

 rCO k C CO C Cl3 /22

2N 2 O o
Pt
2N 2  O 2

k C N 2O
 rN 2O
1  k cC O 2

C O 2 : small o “apparent” 1st order (N2O)

C O 2 : large o “apparent” 1st order (N2O)
-1st order (O2)

Units of k

zero order: -rA = k

[k] = mol/dm3˜s

First order: -rA = kCA

[k] = s-1

Second order: -rA = kCA2

[k] = dm3/mol˜s

3-4

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3.1.3 Elementary Reactions and Molecularity

Elementary reaction is one in which the reaction order of each species is

identical with the stoichiometric coefficient of that species for the reaction
as written.

H2 + I2 o 2HI
-rH2 = kCH2·CI2 elementary

CO + Cl2 o COCl2 non elementary

-rCO = kCCO·CCl23/2

Molecularity is the number of atoms, ions or molecules involved

(colliding) in the rate-limiting step of the reaction.

NaOH + CH3Br o CH3OH + NaBr

elementary reaction Ÿ

-rMB = kCNaOHCCH3Br

Example 3 – 2

NaOH + C(CH3)3Br o C(CH3)3OH + NaBr

reaction order = ?

rate law determined from experiments

-rTBB = kCTBB

3.1.4 Reversible Reactions

k1
2C6H6 C12H10 + H2
k2

reversible and elementary

-rB = k1CB2 – k2CD·CH2

§ C D ˜ C H2 ·
 rB k1 ¨¨ C B2  ¸
¸
© KC ¹
k1
KC = concentration equilibrium constant
k2
(true only for elementary reactions)

3-5

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Thermodynamic Relationships

b c d
A B C  D (gas-phase)
a a a

Pressure equilibrium constant

PCc / a ˜ PDd / a
KP
PA ˜ PBb / a

Pi = partial pressure of species i, in atm

Concentration equilibrium constant

CCc / a ˜ C Dd / a
KC
C A ˜ C Bb / a

For ideal gases

KP = KC (RT)G
c d b
G   1
a a a

KP is a function only of temperature, Van’t Hoff’s equation:

d ln K P 'H run T
dT RT 2

d ln K P 'H r$un TR  'C P T  TR

dT RT 2
If 'CP = 0, we can integrate to obtain

K p2 'H r$un TR § 1 1·
ln ¨¨  ¸¸
K p1 R © T1 T2 ¹

3-6

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From Van’t Hoff’s equation

'Hrun – ve (exoth.) Tn KP p
'Hrun + ve (endoth.) Tn KP n

Kp Kp

T T

Exothermic reaction Endothermic reaction

Equilibrium constant (in terms of activities)

D Cc / a ˜ D Dd / a
K
D A ˜ D Bb / a

 RT ˜ ln>K T @ 'Gr$un T

c $ d $ b
'Gr$un Gc  G D  G B$  G A$
a a a
Example C – 1
H2O + CO CO2 + H2

T = 1000K
P = 10atm
yH2O = yCO = 0.5 initially
Xe = ?
'Gr$un = – 730 cal/mol at 1000K & 10 atm
 RT ˜ ln K 'Gr$un T

cal cal
 1.987 ˜ 1000 K ˜ ln K  730 Ÿ
mol ˜ K mol
K 1.44

3-7

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D CO 2 ˜ D H 2
K
D CO ˜ D H2O

fi fugacity
Di
fi$ standard state

Ideal gases: fi= Pi fi0 = 1 atm

PCO 2 ˜ PH 2
K
PCO ˜ PH 2O

Using ideal gas law: Pi = Ci˜ RT

CCO 2 ˜ C H 2
K
CCO ˜ C H 2O

Since volume of reaction mixture doesn’t change as reaction proceeds.

C CO,e C CO,O ˜ 1  X e
C H2O,e C H2O,O ˜ 1  X e C CO,O ˜ 1  X e
C CO2 ,e C CO,O ˜ X e from stoichiometry:
C H 2 ,e C CO,O ˜ X e CO2 produced = CO reacted
2
Xe
K 1.44 Ÿ
1  Xe
2

Xe 0.55

3-8

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3.1.5 Nonelementary Reactions

H2 + Br2 2HBr

Proceeds by a free-radical mechanism

1
Br2 2Br ˜
2
3
Br ˜  H 2 HBr  H ˜
4

H ˜  Br2 
o
5
HBr  Br ˜

2Br ˜ Br2

c
k1 ˜ C H 2 ˜ C Br
1/ 2

rHBr
c
k 2  C HBr /C Br2

There is no correspondence between stoichiometry and rate law.

CH3CHO CH4 + CO

 rCH 3CHO k ˜ C 3/2

CH 3CHO

3.2 Present Status of Our Approach to Reactor Sizing and Design

Reactor Design Equation

+
– rA = f(Cj)
+ o -rA = g(X)
Cj = hj(X)

3-9

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3.3 Stoichiometric Table

Use the stoichiometric table to relate the concentrations of different

species to each other.

The stoichiometric table presents the relationships between reacting

molecules for a single reaction.

aA + bB cC + dD

Divide by the stoichiometric coefficient of A

b c d
A Bo C  D
a a a
rate of formation of C =

c
rate of disappeara nce of A
a
c c
rC  rA  rA
a a
Similarly

c
rC rD
d
Generally

 rA  rB rC rD
a b c d

3-10

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3.3.1 Batch Systems

b c d
A + B o C + D
a a a

Initially: NAO NBO NCO NDO

b c d
Change: -NAOX  N AO X N AO X N AO X
a a a

Remain: NA NB NC ND

NA = NAO - NAO ·X
b
NB = NBO  N AO X
a
c
NC = NCO + N AO X
a
d
ND = NDO + N AO X
a

§d c b ·
NT = NTO + ¨    1 ¸ ·NAO · X
©a a a ¹

NT = NTO + G ·NAO · X

d c b
G   1
a a a

G represents the change in the total number of moles per mole of A

reacted.

3-11

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STOICHIOMETRIC TABLE

Species Initially (mol) Change (mol) Remaining (mol)

A NAO -NAO X NA N AO  N AO ˜ X

b b
B NBO  N AO X NB N BO  N AO ˜ X
a a

c c
C NCO N AO X NC N CO  N AO ˜ X
a a

d d
D NDO N AO X ND N DO  N AO ˜X
a a

I
NIO NI = NIO
(inerts)

§ d c b ·
NTO NT N TO  ¨    1¸ N AO ˜X
© a a a ¹

Calculate concentrations by

Ni
Ci
V

3-12

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NA N AO 1  X
CA
V V

NB N BO  b / a N AO ˜ X
CB
V V

Define:

N io C io y io
Ti
N AO C AO y AO
N BO N CO N DO
TB , TC ,TD
N AO N AO N AO

N AO >T B  b / a ˜ X @
CB
V

NC N CO  c / a N AO ˜ X
CC
V V

N AO >T c  c / a X @
CC
V

N D N DO  d / a N AO ˜ X
CD
V V

N AO >T D  d / a ˜ X @
CD
V

We need now V(X) to obtain Cj = hj(X)

3-13

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3.3.2 Constant-Volume Reaction Systems

In constant-volume or constant-density systems the reacting system

undergoes no change in volume as the reaction progresses.

Gas-phase

 When the reactor is a sealed vessel

 When G = 0 (and P,T constant)
e.g. CO + H2O CO2 + H2

Liquid-phase

 Most reactions taking place in solution (except polymerizations)

For a constant-volume system:

V = VO

Therefore

N AO 1  X
CA C AO 1  X
VO

N AO > T B  b / a X @ § b ·
CB C AO ¨T B  X ¸
VO © a ¹

§ c ·
CC C AO ¨T C  X ¸
© a ¹

§ d ·
CD C AO ¨T D  X ¸
© a ¹

3-14

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Example 3 – 3

3A + B o 3C + D

is a liquid-phase reaction.
Set up a stoichiometric table.

1 1
A B o C  D
3 3

C BO C CO C DO
V V0 , T B , TC , TD
C AO C AO C AO

NA NA N AO 1  X
CA C AO 1  X
V VO VO

Species Initially Change Remaining Conentration

A NAO -NAOX NAO(1-X) CAO(1-X)

1 § X· § X·
B NBO  N AO X N AO ¨T B  ¸ C AO ¨T B  ¸
3 © 3¹ © 3¹

C NCO NAOX NAO(TC+X) CAO(TC+X)

1 § X· § X·
D NDO N AO X N AO ¨T D  ¸ C AO ¨T D  ¸
3 © 3¹ © 3¹

Inert NIO  NIO CIO

NTO 0 NT=NTo

3-15

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Example 3 – 4

For previous example and

CAO = 10 mol/liter CCO = CDO = 0

CBO = 2 mol/liter
CD = ?
CB = ?
XA = 20%, 90%

CCO C DO
TC 0 TD 0
C AO C AO

a) XA = 20%

§X· mol § 0.2 · mol

CD C AO ¨ ¸ 10 ¨ ¸ 0.67
©3¹ lt © 3 ¹ lt

§ X· mol § 2 0.2 · mol

CB C AO ¨T B  ¸ 10 ¨  ¸ 1.33
© 3¹ lt © 10 3 ¹ lt

b) XA = 90%

§X· mol § 0.9 · mol

CD C AO ¨ ¸ 10 ¨ ¸ 3
©3¹ lt © 3 ¹ lt

§ 2 0.9 · mol
CB 10 ˜ ¨  ¸ 1
© 10 3 ¹ lt

Negative concentration!
XA = 90% impossible
B is the limiting reactant

3-16

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3.3.3 Flow Systems

Batch system: Nj, Njo

Flow system: Fj, Fjo

FA
Recall: CA =
X

FA F Ao
CA 1 X
X X
FB F BO  b / a F AO ˜ X
CB
X X
FC FCO  c / a F AO ˜ X
CC
X X
FD F DO  d / a F AO ˜ X
CD
X X

For liquids o no volume change

X = Xo

F AO
CA 1 X C AO 1  X
XO

§ b ·
CB C AO ¨ T B  X ¸ etc.
© a ¹

F BO C BO ˜ X O C BO y BO
TB
F AO C AO ˜ X o C AO y AO

3-17

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STOICHIOMETRIC TABLE

Feed rate to Change in

Effluent Rate from Reactor
Species Reactor Reactor
(mol/time)
(mol/time) (mol/time)

A FAO -FAO X FA F AO 1  X

b § b ·
B FBO = TBFAO  F AO X FB F AO ¨ T B  X ¸
a © a ¹

c § c ·
C FCO = TCFAO F AO X FC F AO ¨ T C  X ¸
a © a ¹

d § d ·
D FDO = TDFAO F AO X FD F AO ¨ T D  X ¸
a © a ¹

I FIO = TIFAO – FI F AO ˜ T I

§ d c b ·
FT F TO  ¨    1 ¸ F AO ˜ X
FTO © a a a ¹

FT F TO  G F AO X

3-18

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3.3.4 Volume Change with Reaction

N2 + 3H2 2NH3

Batch System (const P): V changes

Flow System : X changes

Relate V (or X) to X through an equation of state:

PV ZN T RT (3-30)
atm
2 K
1.1 mol
atm.lt
mol.K
Z = compressibility factor

For t = 0: POVO=ZO ˜ NTO ˜ R ˜ TO (3-31)

(3-30) y (3-31) Ÿ
§ P ·§ T ·§ Z ·§ N T ·
V V O ¨ O ¸ ¨¨ ¸¸ ¨¨ ¸¸ ¨¨ ¸¸ (3-32)
© P ¹ © O ¹ © O ¹ © N TO
T Z ¹

For a Batch system:

From stoichiometric table:

NT = NTO + GNAO ˜ X

NT N AO
1 ˜G ˜ X 1  G ˜ y AO X
N TO N TO
yAO: mole fraction of A at t=0

If all of the species in stoichiometric equation are in the gas phase, then

d c b
G   1
a a a

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when reaction is
Define H completed

change in total number of moles

H
total number of moles fed to reactor

§d c b ·§ N ·
¨    1 ¸ ¨¨ AO ¸¸ y AO ˜ G
©a a a ¹ © N TO ¹
H y AO ˜ G

Equation (3-32) becomes

§ P · § T ·¸ §¨ Z ·¸
V V O ¨ O ¸ ¨¨ ¸¨ Z ¸ 1  HX
© P ¹© O ¹© O ¹
T

We will only consider cases where Z=ZO

§ P · § T ·¸
V V O ¨ O ¸ ¨¨ ¸ 1  HX
© P ¹© O ¹
T

b c d
So for a variable-volume BR and A  B o C  D
a a a
NA N AO 1  X TO P
CA ˜ ˜
V VO 1  HX T PO
§ 1  X · TO P
CA C AO ¨ ¸ ˜
© 1  H X ¹ T PO
NB N AO T B  b / a ˜ X T P
CB ˜ O ˜
V VO 1  HX T PO
ª T  b / a ˜ X º TO P
CB C AO « B » ˜
¬ 1  HX ¼ T PO

3-20

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For a Flow system:

FT P
CT (3 – 40)
X ZRT
At reactor entrance

F TO PO
C TO (3 – 41)
XO Z O RT O

(3 – 40) y (3 – 41) and assuming Z = ZO Ÿ

§ F · § PO · § T ·
X X o ¨¨ T ¸¸ ¨ ¸ ¨¨ ¸¸
© F TO ¹© P ¹© O ¹
T

From stoichiometric table

FT FTO  F AO G X

F TO  F AO G X § PO · § T ·
X XO ¨ ¸ ¨¨ ¸¸
F TO © P ¹© TO ¹

§ P ·§ T ·
X X O 1  y AO ˜ G ˜ X ¨ O ¸ ¨¨ ¸¸
© P ¹© TO ¹

§ P ·§ T ·
X X O 1  H X ¨ O ¸ ¨¨ ¸¸
© P ¹© TO ¹

3-21

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b c d
So for a flow system and A  B o C  D
a a a
FA F AO 1  X TO P
CA ˜ ˜
X X O 1  HX T PO

§ 1  X · TO P
CA C AO ¨ ¸˜ ˜
© 1  HX ¹ T PO

FB F AO >T B  b / a ˜ X @ ˜ TO P
CB ˜
X X O 1  HX T PO

ª T  b / a ˜ X º TO P
CB C AO « B ˜
» T ˜
¬ 1  HX ¼ PO

FC F AO >T C  c / a ˜ X @ ˜ TO P
CC ˜
X X O 1  HX T PO

ªT  c / a ˜ X º TO P
CC C AO « C ˜
» T ˜
¬ 1  HX ¼ PO

FD F AO >T D  d / a ˜ X @ ˜ TO P
CD ˜
X X O 1  HX T PO

ª T  d / a ˜ X º TO P
CD C AO « D ˜
» T ˜
¬ 1  HX ¼ PO

Note that the Cj = hj(X) expressions are identical to the

ones of a variable-density Batch system.

3-22

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Example 3-6

2SO2 + O2 o 2SO3
A B C

Flow reactor
Feed: 28% SO2, 72% air
PO = 1485 K Pa const.
TO = 227qC
Assume: -rA = kCA ˜ CB (k = 200lt/mol.s)
Develop the –rA = g(X) relationship
A + ½B o C

STOICHIOMETRIC TABLE

Species Initially Change Remaining

A FAO FAO X FA F AO 1  X

F AO X § X ·
B FBO = TB ˜ FAO  FB F AO ¨ T B  ¸
2 © 2 ¹

C 0 +FAO X FC F AO X

I FIO = TIFAO – FI F IO T I ˜ F AO

F AO X
FTO FT F TO 
2

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F BO
TB
F AO
FAO = 0.28 ˜ FTO
FBO = 0.72 ˜ 0.21 ˜ FTO

0 . 72 ˜ 0 . 21
TB 0 . 54
0 . 28
F IO 0 . 72 ˜ 0 . 79
TI 2 . 03
F AO 0 . 28
FA F AO 1  X
CA
X X
PO T
X XO 1  HX ˜
P TO
P PO , T TO
X X O 1  HX
F AO 1  X § 1 X ·
CA C AO ¨ ¸
X O 1  HX © 1  HX ¹
P
C AO y AO ˜ C TO y AO ˜ O
RT O
1485 K Pa
0 . 28
K Pa ˜ dm 3
8 . 314 u 500 K
mol ˜ K
mol
0 .1
dm 3

3-24

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§ 1·
H y AO ˜ G 0.28 ˜ ¨ 1 - 1 - ¸  0 . 14
© 2¹

§ 1 X · mol
CA 0 .1 ˜ ¨ ¸
© 1  0 . 14 ˜ X ¹ dm
3

§ 1 · § 1 ·
F AO ¨ T B  X ¸ ¨T B  X ¸
CB
FB © 2 ¹
C AO © 2 ¹
X X O 1  HX 1  HX

§ 0 . 54  0 . 5 ˜ X · mol
0 .1 ˜ ¨ ¸
© 1  0 . 14 ˜ X ¹ dm
3

 rA kC A ˜CB

dm 3 § 1 X · mol § 0 . 54  0 . 5 X · mol
200 ˜ 0 .1 ˜ ¨ ¸ ˜ 0 . 1 ˜ ¨ ¸
mol ˜ s © 1  0 . 14 ˜ X ¹ dm
3
© 1  0 . 14 X ¹ dm
3

2 1  X 0 . 54  0 . 5 X
 rA
1  0 . 14 ˜ X
2

0 . 5 1  0 . 14 ˜ X
2
1
 rA 1  X 0 . 54  0 . 5 ˜ X

1
 rA

3-25

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3.4 Reactions with Phase Change

V = VO(1 + yAO ˜ G ˜ X)

Expansion/Contraction of gas-phase volume

So G o change of moles in the gas-phase.

Gas phase reaction in which condensation occurs:

C2H6(g) + 2Br2 (g) o C2H4Br2(g,l) + 2HBr(g)

Chemical Vapor Deposition (microelectronics)

GaCl2(g) + ½As2(g) + H2(g) o GaAs(s) + 2HCl(g)

PX is vapor pressure of D at temperature T

Mole fraction of D at which condensation begins:

PX
y D ,e
PT

Example 3-7

Consider the isothermal reaction

A(g) + 2B(g) o C(g) + D (g,l)
-rA = kCA ˜ CB
Feed: yAO = 0.33 yBO = 0.67 (stoichiometric amounts of A and B)
TO = 300K (const.)
PO = 101.3 K Pa (const.)
PX = 16 K Pa
XC = ? (where condensation begins)
rA = g(X)?

3-26

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STOICHIOMETRIC TABLE

Species Initial Change Remaining Remaining

(before cond.) (after cond.)

A FAO  FAOX FAO(1 – X) FAO(1 – X)

B FBO = 2FAO – 2FAOX FAO(2 – 2X) FAO(2 – 2X)

C  FAOX FAOX FAOX

D  FAOX FAOX FD = yD,e ˜ FT

FT = yD,e ˜ FT +
FTO = 3FAO FT = FAO(3 – X)
3FAO – 2FAOX

Solving for FT
FT = 2FAO (1.5 – X)/(1 – yD,e)

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FD F AO ˜ X C XC
y D ,e
FT F AO 3  X C 3 X C

PX , D 16
y D ,e 0 . 158
PT 101 . 3

XC
0 . 158 Ÿ X 0 . 41
3 X
C
C

For X < XC

C AO 1  X
C
1  HX
A

H y AO ˜ G 0 . 33 ˜ 1  1  2  1  0 . 33

§ 1 X ·
C C ¨ ¸
© 1  0 . 33 ˜ X ¹
A AO

§ 2  2˜X ·
CB C ¨ ¸
© 1  0 . 33 ˜ X ¹
AO

P PO
CT C TO
ZRT Z O RT O

 rA kC A ˜CB

1 X
2
 rA
2
2 kC
1  0 . 33 ˜ X
AO 2
(3 – 7.8)

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For X > XC

PD = PX
FT
FT = CT ˜ X Ÿ X = XO
FTO = CTO ˜ Xo FTO

2 F AO 1.5  X
1 y D , e X O 1 .5  X
X XO
3FAO 1  y D , e ˜ 1 .5
FA FAO 1  X 1  y D,e 1  X
CA 1.5C AO
X X o ˜ 1. 5  X 1. 5  X
1.5 1 y D , e

FB FAO 2  2 X 1  y D,e 1  X
CB 3C AO
X X o ˜ 1. 5  X 1 .5  X
1.5 1 y D , e

 rA kC AC B
2
2 2 1 X
 rA 4.5kC AO 1  y D,e
2
1. 5  X

equation 3 – 7.8
1
 rA
equation 3 – 7.14

X
XC

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4. ISOTHERMAL REACTOR DESIGN

4.2 Scale-Up of Liquid-Phase Batch Reactor Data to Reactor Design

4.2.1 Batch Operation

Liquid-phase reaction  V = VO

1  dN A 
mole balance:    rA
V  dt 

rate law:  rA  kC A2

stoichiometry: (V = VO)

NA NA
CA  
V VO

1  dN A  d N A / VO  dC A
  
VO  dt  dt dt

combine rate law and mole balance:

dC A
  kC A2
dt
dC A
  kdt
C A2
integrate: (T = const)

1 C dC A t
 C 2
  dt
A

k CA 0 AO

1 1 1 
    t
k  C A C AO 

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The above time, t is only the reaction time.

Total cycle time, tt is

tt = tf + te + tc + t

Where: tf = time to fill reactor

te = time to empty reactor
tc = time to clean reactor

For a typical batch polymerization

t = 5-60 h

tf + th + te + tc = 3-6 h

time to heat reaction mixture

Example 4-1
C2H4O + H2O   C2H4(OH)2
H 2SO 4

A + B C

Reaction takes place isothermally at 55C in BR

Reaction is first order in C2H4O.

500 ml 500 ml
H2O 2M of C2H4O in H2O
so, H2O in excess

Time (min) CC (mol/lt)

0.0 0.000
0.5 0.145
1.0 0.270
1.5 0.376
2.0 0.467
3.0 0.610
4.0 0.715
6.0 0.848
10.0 0.957

Find reaction rate constant.

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1 dN A
mole balance:  rA
V dt

rate law:  rA  kC A
stoichiometry: Liquid-phase  V=VO

NA NA
CA  
V VO

1  dN A  d  N A / VO  dC A
  
VO  dt  dt dt
combine rate law and mole balance:

dC A
  kC A
dt
dC A
  kdt
CA
integrate:

C dC A t
   
A
kdt
C AO CA 0

C AO
ln  kt
CA

C A  C AO  e  kt

Our data give CC = f(t)

Use stoichiometric table to relate CC to CA.

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Species Initial Change Remaining Concentration

A NAO – NAO  X NA = NAO(1 – X) CA = CAO(1 – X)

CB = CAO (B – X)
B BNAO – NAO  X NB = NAO(B – X)
CB  CAOB = CBO

CC = CAO  X
C 0 NAO  X NC = FAO  X
= CAO - CA

CC = CAO – CA = CAO – CAO  e-kt

C AO  CC
 e kt
C AO

C AO  CC
ln  kt
C AO

C AO  1.0 mol/lt

C AO  CC
plot ln vs. t
C AO

C AO  C C
t (min)
C AO
0.0 1.000
0.5 0.855
1.0 0.730
1.5 0.624
2.0 0.533
3.0 0.390
4.0 0.285
6.0 0.152
10.0 0.043
t (min)

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t (min)
1
0 2 4 6 8 10 12

C AO  C C
C AO

0.1

0.01

Decade method: (CAO – CC)/CAO = 0.6 t = 1.55 min

(CAO – CC)/CAO = 0.06 t = 8.95 min

ln 10 2.3
k   0.311 min -1
t 2  t1 8.95  1.55

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4.2.2 Design of CSTRs

Design equation for CSTR

FAO  X
V
 rA exit
No volume change

 C CA 
V   O  AO 
  r A 
V C CA
  AO
O  rA

Take a first-order reaction

 rA  kC A

Combine rate law and design equation

C AO  C A C
  C A  AO
kC A 1  k

C AO  C A
X  V  const 
C AO

C AO
C AO 
X  1  k
C AO

k
X 
1  k

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Da =  k= Damköhler number (1st order reaction)

[ k CAO = Damköhler number (2nd order reaction)
Damköhler number gives an estimate of degree of conversion
V k
Da  ↑ X↑
O

CSTRs in Series
CA1
CA0
X1

CA2
X2

Liquid-phase, 1st order reaction

Mole balance for reactor 1

F A0  F A1  o  C A0  C A1 
V1  
 rA1 k1C A1

C A0  C A1    1 k1C A1
C A0
C A1 
1   1 k1

Mole balance for reactor 2

F A1  F A2  0 C A1  C A2 
V2  
 rA 2 k 2 C A2

C A1  C A2   2 k 2 C A 2

C A1
C A2 
1 2 k2

C A0
C A2 
1   2 k 2 1   1 k1 

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If we have n CSTRs in series of equal size  1     ...... n    operating

at the same temperature k1  k   ......k n  k 
C A0
C An 
1  k n
Overall conversion after nth reactor

C A0  C An C
X   1  An
C A0 C A0

1
X  1
1  k n
CSTRs in Parallel

FA0 FA0i

i
Xi

FA0n

Equal-sized reactors
Feed is distributed equally
All operate at the same temperature

So,  X 1  X   ......X n  X 
 rA1  rA   ......  rA n  rA 

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Volume of each reactor

V
Vi 
n

Flowrate for each reactor

FA0
FA0i 
n

Design equation for i-th CSTR

 X 
Vi  FA0i  i 
  rAi 

V FA 0  X i 
  
n n   rAi 

F A 0 X i FA 0 X
V 
 rAi  rA

Conversion achieved in the i-th reactor is identical to what would be

achieved if the reactant were fed in one stream to one large reactor of
volume V.

A 2nd order Reaction in a CSTR

Liquid-phase reaction.
Combine design equation and the rate law

FA0  X
V
kC A2

Constant density:    0

F A 0  F A C A 0  0  C A 
X 
F A0 C A 0  0

C A  C A0 1  X 

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F A0  X  0  C A0  X
V 
kC A 0 1  X  kC A 0 1  X 
2 2 2 2

 Da1  X   X  0
X

2

kC A0 1  X 
2

Da  kC A0  leads to X > 1

Da  X 2  2 Da  1  X  Da  0

2 Da  1

2 Da  12  4 Da 2
X
2 Da

2 Da  1  4 Da  1
X
2 Da

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Example 4 – 2

C2H4O + H2O  4  C2H4 (OH)2

2 H SO

A + B C

Need to produce 2  108 lb/year of C.

Feed: 1lbmol/ft3 A in B equal volume flowrates
+ 0.9 wt% H2SO4 in B

X = 80% VCSTR = ?
Two 800 gal. CSTRs in Series: X = ?
Two 800 gal. CSTRs in Parallel: X = ?

-rA = (0.311 min-1)CA

Liquid-phase reaction

lb 1 yr 1 day 1h 1 lbmol
FC  2  10 8    
yr 365 days 24 hr 60 min 62 lb

FC = 6.137 lbmol/min

FC = FA0  X FA0
10 20
FC 6.137 (CA0)1
lbmol
FA 0    7.67
X 0 .8 min

FA 0  X
Design Equation: V 
 rA
Rate Law: -rA = kCA FA0

Stoichiometry: ( = 0) 0
CA = CA0(1 – X) CA0

FA 0  X
V 
kC A0 1  X 
Combining:
0  X
V   E 4  2 .4 
k 1  X 

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FA0 7.67 lbmol/min ft 3

10    7.67
C A0 1 1 lbmol/ft 3 min

 10   20

ft 3
 0   10   20  15.34
min

ft 3
15.34  0 .8
 E 4  2 .4   V  min
 1  0.8
1
0.311
min
7.482 gal
V  197.3 ft 3   1480 gal
1ft 3

2 CSTRs in parallel

k
X
1  k

V  1ft 3  1
   800 gal   
0 / 2  7.48 gal  7.67 ft 3 / min

  13.94 min

Da  k  13.94 min  0.311 min -1  4.34

4.34
X  0.81
1  4.34

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2 CSTRs in series
 1k
X1 
1   1k

V1  1ft 3  1
    800 gal   
 01  7.48 gal  15.34 ft 3 / min

   6.97 min

Da     k  6.97 min  0.311 min -1  2.167

2.167
X1   0.684
3.167

Calculate the conversion exiting the 2nd reactor

V1  V 2  V
 1  2 
 01   02   0

Combine mole balance with rate law

F X  X 1 
V  A0 2
 rA 2

C A0   0   X 2  X 1 
V
kC A0 1  X 2 

0  X 2  X1 
V   
k  1  X 2 

X 1  k 0.684  2.167
X2    0.90
1  k 1  2.167

Alternatively
1 1
X 2  1  1  0.90
1  k  2
1  2.167 2
So, 2 CSTRs in series better than 2 CSTRs in parallel.

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4.3 Tubular Reactors

Plug flow: no radial gradients in temperature, velocity or concentration

X
dX
Design equation: V  FA 0 
0
 rA

Rate Law: (2nd order reaction)

 rA  kC A2

Stoichiometry: (gas phase reaction, T = const, P = const)

 1 X 
C A  C A0  
 1  X 

X
1
V  FA0  dX
Combining: kCA0 1 X 
2 2

0
1X  2

1  X 
2
FA 0 X

kC A 0 0 1  X 
V 2 2
dX

I 

X1  X 
2
dX
0
1  X 2
X 1 X X
 dX  2  dX
0
1  X  2 0
1  X  2

A B
X2
  1  X 
2
2
dX

d 1  X 
X 1 X 1
A dX   
0
1  X 2 0
1  X 2

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1 1 11 X
 X
 1
1 X 1 X 1 X
0

X
A
1 X

X X X X 11
B  dX   dX
0 1  X  0 1  X 
2 2

X 1 X X 1
 2dX   dX
0 1  X  0 1  X 
2

X
d 1  X   A
1
 
0 1 X

 ln1  X  X0  A

 ln1  X   ln1 
X
1 X
B  ln1  X  
X
1 X
X2
C X
0 dX
1  X 2
X X 2  2X  2X 11
  dX
0 1  X 2
X 1  X 2  2 X  1
  dX
0 1  X 2

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X  dX
X X X
1
C   1  dX  2   dX
0 0 1  X  2
0 1  X  2

 X  2 B  A

 X  2  ln1  X  
2X X

1 X 1 X

C  X  2  ln1  X  
X
1 X

I  A  2  B   2  C

 2  ln1  X   2   X   2  2 2  ln1  X    2
X X X

1 X 1 X 1 X

 2 1     ln1  X     X 
X
1 X
1  2     

I  2      ln1 - X    
X
1    X
2

1 X

  1   2 X 
2     ln1  X    X 

V 0 
kC A0  1  X 

Divide by reactor cross-sectional area AC

0  1  X 
2

2     ln1  X    X 

L 
kC A0 AC  1 X 

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 = -0.5

 = 0.0

= 1.0

Highest conversion for  = – 0.5 i.e. decrease in the total number of moles
(reactant spends more time in the reactor).

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Example 4 – 4
C2H6  C2H4 + H2
A B +C
Need to produce 300 million lb/year of B
Reaction is irreversible and elementary
X = 80%
T = 1100 K (const)
P = 6 atm (const)
k = 0.072s-1 at 1000K
E = 82 kcal/mol
VPFR = ?

lb 1 year 1 day 1 hr 1 lbmol

FB  300  106    
year 365 days 24 h 3600s 28 lb

lbmol
FB  0.34
s
FB  FA0  X

FB 0.34 lbmol
FA0    0.425
X 0.8 s

dX
PFR Design Equation: FA0  rA
dV

X
dX
V  FA0 
0
 rA

Rate law:  rA  kC A

Stoichiometry: (gas-phase, T = const, P = const)

   0 1  X 

FA FA0 1  X 
CA  
  0 1  X 

 1 X 
C A  C A0  
 1  X 

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Combining:

X
dX
V  FA0 
0
kC A0 1  X  / 1  X 

1  X
X
F
V  A0  dX
kC A0 0 1  X

T  const

1  X
X
I dX
0
1  X
X X
1 X
 dX    dX
0
1  X 
1  X
X X
d 1  X 
1 1
A  dX   
B
A
0
1  X 0
1  X

  ln1  X  X0   ln1  X   ln 1
A   ln1  X 
X 11
X X
X
B dX   dX
0
1  X 0
1  X
1 X
X X
1
  dX   dX
0 1  X 0 1  X
X
   dX  A
0

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B   X  ln1  X 

I  A  B

  ln1  X     X  ln1  X 

I  1    ln1  X   X

V
FA0
 1    ln1  X   X 
kC A0

Parameter evaluation

y A0  P0
C A0  y A0  CT 0 
R  T0
1x6 atm

0.73 ft  atm/lbmol  R  1980 R
3

lbmol
C A0  0.00415
ft 3
  y A0    1  1  1  1  1

We need to calculate k at 1100K

E

k T1   A  e RT1

E

k T2   A  e RT2

Divide

E 1 1
k T2    
R  T1 T2 
e
k T1 

E 1 1 
  
R  T1 T2 
k T2   k T1   e

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82000 cal/mol  1 1 1
  
k 1100K   k 1000K   e 1.987 cal/mol.K  1000 1100  K

k 1100K   0.072s 1  42.6

k 1100K   3.07 s 1

0.425 lbmol
V s
 1  1 ln1  0.8  1  0.8
3.07 s  0.00415 lbmol
1
ft 3

V  80.7ft 3

If we use pipes of 2-in. schedule 80 (cross-sectional area is 0.0205 ft2) of

40 ft length, we will need
80.7 ft 3
n  98.4
 
0.0205 ft 2  40 ft 
about 100 pipes.

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4.4 Pressure Drop in Reactors

In gas-phase reactions: ci  PTOT. Therefore pressure changes have to be

taken into account.

4.4.1 Pressure Drop and the Rate Law

dX 
Mole balance: FA0  rA
dW
(differential form) catalyst weight


Rate law:  rA  kC A

C A  C A0
1  X   P  TO
Stoichiometry:
1  X  PO T
P
Need to find as a function of W or V.
PO

Ergun equation for packed beds:

dP G 1    1501     
   1.75G     O 
dL g c D p  3  Dp  

P = pressure, lb/ft2
 = void fraction
gc = 32.174 lbmft/s2lbf (conversion factor) depends on units
Dp = particle diameter, ft
 = gas viscosity, lbm/fth
L = reactor length, ft
u = superficial velocity (based on empty pipe), ft/h
 = gas density, lb/ft3
G =   u = superficial mass velocity g/cm2s or lbm/ft2h
G1    1501    
o    1.75G 
 o g c 3 D p  Dp 
O =  at reactor entrance

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At steady-state, the mass flow rate at any point down the reactor, m is
constant.
m  m o

 o o    

Po T 
   o 1  X   
P  To 

 T  1   P 
           
 T  1  X   P 

So the Ergun equation becomes

 TP 
   o  o 1  X  4  30
dP
dL  To P 

We want to substitute L in terms of catalyst weight, W.

W  1     AC  L  C 4  24
[Weight of catalyst] = [volume of solids]  [density of solid catalyst]

dW  1     AC   C  dL

Po
dP

a T
1  X 
dW 2 To P / Po  (4-32)

2 o
a
AC   C  1   Po
Where

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If  = 0 (or X<<1) and isothermal operation (T=TO) equation (4-30)

becomes:
dP P
  o o
dL P
P L

 PdP   
Po
o Po   dL
O

P 2 Po2
    o  Po  L
2 2
2
P 2 L
   1  o
 Po  Po

1
P  2 o  L  2
 1  
Po  Po 

or in terms of catalyst weight (using equation (4 – 24)):

 1  aW  2
P 1
(4 – 35)
Po

Combining rate law and mole balance:

dX kC AO 1  X  P
FAO   
dW 1  X  PO (iso – T)

dX k (1  X ) P
   (4 – 21)
dW  O (1  X ) PO

In general we have to solve (4 – 21) and (4 – 32) simultaneously using

numerical techniques. When  = 0, we substitute (4 – 35) in (4 – 21) so we
have to solve only one differential equation

k 1  X 
 1  aW  2
dX 1
 
dW o 1  X 

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Note that this equation is still an approximation, i.e. we have assumed that
X  1 in the Ergun equation but not in the rate law.

X
 o 1  X  W

 k 1  X    
1
 dX  1  aW 2 dW
o o

o   2  3 
Integrating gives: 1    ln
1
 X 
 3a 1  1  aW  2

k  1 X 

1  1  3a o / 2k 1     ln1 / 1  X   X 

2
3
Solving for W: W 
a

4.5 Reversible Reactions

k1
N2 + O2 2NO
k –1
Assume reaction is elementary

 rN 2  k1C N 2  C O 2  k 1C NO
2

k1
KC 
 C NO  2
k1
 k1  C N 2 C o 2 
 K C 

Equilibrium conversion, Xe can be calculated by setting  rN  0 and 2

substituting Ci in terms of X (use stoichiometric table). see § 3.1.4

Example C – 1

Example 4 – 9

N2 + O2 2NO
A + B 2C
Xe = 0.02
VBR = 0.4 dm3
KC = 0.01
P = 20 atm
T = 2700 K
Initially 77% N2, 15% O2, 8% inerts
80% of equilibrium is reached in 151 s
k1 = ?

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C AO 
y AO  Po

0.77   20 atm 
R  TO  atm  dm 3 
 0.082 2700 K 
 mol  K 
C AO  6.96  10  2 mol/dm3

For 80% of equilibrium conversion X = 0.8 Xe = 0.016

dX
Design Equation: N AO  rA  V
dt

N AO dX
V  VO    rA
VO dt

dX
C AO  rA
dt

X dX
Integrate: t  C AO O
 rA
 C 2 
 r A  k1  C A  C B  C 
Rate law:  K C 

Stoichiometry: gas phase,  = 0, V = Vo

C A  C AO 1  X 

C B  C AO  B  X 

CC  2C AO  X

Combining:

X
1 dX
t 
k1C AO 0 1  X  B  X   4X 2 / KC

y B ,O 0.15
B    0.195
y A,O 0.77

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Solving for k1 and substituting for CAO, B, t and Ke gives

0.016
1 dX
k1 
15110 s 0.0696 mol/dm 
6 3
  0.195  1.195  X  399  X 2
0

dm 3 0.016
k1  9.51  10  f  X dX
4
mol  s 0

XO = 0 f(X0) = 5.128
X1 = 0.008 f(X1) = 6.25
X2 = 0.016 f(X2) = 13.56

Simpson’s rule: (h = 0.008)

X2
 f  X dX 
h
 f  X 0   4 f  X 1   f  X 2 
X0 3

 0.008 
k1  9.51  10 4   5.128  4  6.25  13.56
 3 

k1  1.11  10 4 dm 3 /mol  s

4.6.2 Semibatch Reactors

FAO

A+B=C

Mole balance on species A

dN A
FAO  0  rA  V t  
dt
d C A  V  VdC A dV
 o C AO  rAV   CA
dt dt dt (4 – 53)

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V=V(t) because reactor is being filled. Can be calculated from an overall

mass balance
d  V 
o  0  0 
dt
in out generation accumulation
for a constant density system, o = 

d  V  dV
  O   O O (4 – 55)
dt dt
V t
 dV   O  dt
VO 0

V  VO   O  t (4 – 56)

Substitute (4 – 55) in (4 – 53)

dC A
OC AO  rAV  V  O C A
dt
O C AO  C A   rAV  V
dC A
dt

(4  56)   O     O  t  d  dt

Divide mole balance by O, and substitute for dt

dC A
C AO  C A  rA     (4 – 57)
d

Apparent First-Order Reaction

When B is in excess:  rA  k C A C B  k C BO C A

 rA  kC A

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dC A
C AO  C A  kC A  
d
dC A 1  k C
 C A  A0
d  
This is a first order linear differential equation of the form
dy
 Py  Q
dx

By multiplying through with the integrating factor:

IF  e 
Pdx

e  dy  P  y  e   dx  Q  e 
Pdx Pdx Pdx
 dx

 
d e  Pdx  y  Q  e 
Pdx
 dx

Integrating, the solution is

y  e   Q  e
Pdx Pdx
dx  constant

1k d
  d     kd
IF  e e  e ln   e k    ek
Therefore the solution is

C AO
C A    ek      ek  d  const.


1
C A    ek  C AO   ek  const
k

Calculate const by using the initial condition: C A  C Ai when  o

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1
C Ai  O  e O k  C AO   e O k  const 
k
 C 
const  e O k  C Ai o  AO 
 k 

So
C AO k  O k  C 
C A   ek   e  e  C Ai o  AO 
k  k 
C AO    C 
CA   e o k k   o    C Ai  AO 
k     ok 

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Example 4 – 10

CNBr + CH3NH2  CH3Br + NCNH2

A + B  C + D

irreversible, elementary, liquid-phase reaction carried out in a semibatch

reactor. Initially only A in the reactor. Express XA as a function of time.

FBO

VO, CAO

Mole balance on species A

dN A
 rA  V t 
dt
N A  N AO 1  X 

dX
N Ao   rA  V
dt

dX  rA  V

dt N AO

Rate law:  rA  kC A  C B

Stoichiometry:

initially change (mol) remaining

A NAO – NAOX N A  N AO 1  X 
B NBi FBO  t  N AO X N B  N Bi  FBO  t  N AO  X

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N A N AO 1  X 
CA  
V VO   o  t

N B N Bi  FBO  t  N AO  X
CB   (NBi = 0)
V VO   o  t

Combining: dX VO   O  t  N AO 1  X  FBO  t  N AO  X 

 k 
dt N AO VO   O  t  VO   O  t 
dX k 1  X FBo  t  N AO  X 
 F X , t  
dt VO   O  t

Numerical techniques (see Appendix A.6) Euler’s one step method.

 f X , Y 
dY
dX
Choose a small enough X (i.e. such that f(X,Y) does not change
significantly)

– Calculate Y as a function of X

dY Y1  Y0
  f  X 0 , Y0 
dX X
Y1  Y0  X  f  X 0 , Y0 

X 1  X

Y2  Y1  X  f  X 1 , Y1 

X 2  2  X

Yi 1  Yi  X  f  X i , Yi 

X i 1  i  1  X

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The accuracy of this technique is not always good, especially when steep
gradients (i.e. large dY/dX) exist.

Runge-Kutta method

dY
 f X , Y 
dX

Yi 1  Yi 
X
6
  
k1  2  2 k 2  2  2 k 3  k 4   
where

k1  f  X i , Yi 

 X X 
k2  f  X i  , Yi  k1 
 2 2 

 X  1 1  1  
k3  f X i  , Yi    X  k1  1  X  k 2 
 2  2 2  2 

 X  1  
k 4  f  X i  X , Yi  k 2  1  X  k 3 
 2  2 

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