CE20023 - REACTION

ENGINEERING 2
• Basic reactor designs: batch, CSTR, plug flow.
• Application of stoichiometric tables; chemical
equilibrium.
• Definition of reaction rate; elementary reactions; and
temperature dependence.
• Mass and energy balances appropriate to each reactor.
• Ideal batch reactor; constant volume, variable volume,
variable temperature and pressure.
• Expansion factor: irreversible and reversible reactions.
• Performance comparison between batch, CSTR and plug
flow.
 CE20023 - REACTION
ENGINEERING 2

• Optimisation: multiple reaction; parallel; series;

series-parallel; selectivity and yield; optimum
temperature; isothermal, adiabatic and non-
adiabatic modes of operation; multiple reactions
temperature effects, heterogeneous kinetics.
 Reactions
Catalytic

Non-catalytic
 Reactors
Continuous Flow

CSTR Tubular
Batch
 The processes occurring in a
reactor
• REACTION SO2 + 1/2O2 SO3

SO2
• MASS TRANSFER
V2O5
catalyst
• ENERGY TRANSFER
Exothermic

• MOMENTUM TRANSFER
Pressure drop
Heterogeneous catalytic reaction -
simplified steps
A B (1) External diffusion

(2) Internal diffusion

(3) Adsorption/Desorption
(4) A B Reaction
A typical silica-alumina cracking catalyst has:
- specific pore volume of 0.6 cm3g-1
- pore radius of 4 nm
- specific surface area of 300 m2g-1
 Rate data
Tb
Cb

Tp
Cp

Intrinsic kinetics

Data obtained under conditions when the rate is not controlled

by external or internal mass transfer:
Cb = Cp
also Tb = Tp
 Global rate data
Tb
Cb

Tp
Cp

The measured rate is associated with bulk concentrations

and temperatures.

•Simplifies modelling
•Care needs to be taken with scale-up
•Often used in industry
 Example of variables
Reactor: Feed:
•size/geometry •composition
•temperature •temperature
•pressure •flowrate
•degree of mixing
•energy transfer
•residence time Modes of operation
•Isothermal or Non-
isothermal
•Adiabatic or Non-adiabatic
•Complete mixing
•Plug flow
•Non-ideal flow
 REACTION RATE
aA  bB  cC  dD
Homogeneous
rA, is the number of moles of A reacting per unit time per unit volume.

1 dN j dC j (N/V = C + if j is a product
rj    at const. vol.) - if j is a reactant
V dt dt
For the heterogeneous case the rate will depend on:
- the mass of catalyst/solid
- surface area
- the reactor volume etc.
 ELEMENTARY REACTIONS
The rate equation corresponds to stoichiometric equation:
A B  P rA = k CA CB
or for
Reaction is 3rd
2 A  3B  P rA = k CA2 CB3 order with respect
to species B
Reaction is 2nd order with
respect to species A
But the overall order is 2 + 3 = 5
aA  bB  cC  dD The rate of change of a species is

1 dN A

1 dN B 1 dN C 1 dN D
 
related by the stoichiometry
a dt b dt c dt d dt
The molar extent of reaction, for a batch reactor is:
N A  N A0 N B  N B 0 N C  N C 0 N D  N D 0
    
a b c d
 ELEMENTARY REVERSIBLE REACTIONS
k1
A 2R
k2

Gas phase

rf = k1 pA Forward reaction Units, e.g.

rr  k 2 p R2 Reverse reaction mol m-3 s-1

At equilibrium
rf = rr
pR2e k1
k1 p Ae  k 2 p 2
Re Also Kp  
p Ae k2
 Batch Reaction Kinetics Equations
Rate expressions discussed below refer to the situation where the
reactants are added to a vessel at time t = 0, and then nothing more is
added to, or taken from, the vessel until it is examined at a later time t.

A
Zeroth order reaction  B
dC C = concentration of reactant
Rate equation: r   k (units: mol/m3)
dt k = rate constant (mol/m3.s)
r = rate (mol/m3.s, ALWAYS)
What has happened after time t has elapsed? - integrate rate eq.
Ct t
 dC    k .dt   Ct  C0   kt  Ct  C0  kt
C0 0
 Batch Reaction Kinetics Equations #2
First order reaction A
 B
dC C = concentration of reactant
Rate equation:   k .C (units: mol/m3)
dt k = rate constant (s-1)
Integrate: Ct
dC t
    k .dt   ln C  Ct
C0
  kt  Ct  C0 .e  kt
C C 0
0

Second order reaction A A

 B
dC C = concentration of reactant
Rate equation:   k .C 2 (units: mol/m3)
dt k = rate constant (m3/mol. s)
Ct t C
dC   1 t 1 1
Integrate:  2    k .dt      kt    kt
C0 C 0  C  C0 C0 Ct
 REACTOR DESIGN
MATERIAL BALANCE

MOMENTUM
ENERGY BALANCE
BALANCE
ARE LINKED

e.g.
- As T increases reaction rate increases
- For gases, as T increases, volumetric flow increases
and P increases
 We start by writing an equation for an element of
volume

If the composition is uniform, then the

whole of the reactor is the volume element

If composition in the reactor

varies, then we consider a
differential element of volume
and integrate across the reactor
 MATERIAL BALANCE
Master Equation and its application to Batch Kinetics:

IN + MADE = OUT + ACCUMULATION

=0 add kinetics =0
 dC 
Nothing is x volume of Nothing is  V . 
added during reactor removed during  dt 
reaction e.g. 1st order reaction
reaction
 V .  k .C  Leads to: V.
dC
 k .C .V
dt
...as before
(Units of each term are mol/s (or molecules/s)
V = volume of reactor (m3))
 MATERIAL BALANCE
Let species A
be a reactant Element of
volume
FA0 FA
e.g.
FA0 = 100 mol s-1 NA = no. of moles
of A within
dN A volume
FA0  FA  G A 
dt element
input outpu = CA.V or CA.dV
accumulation term
t
rate of disappearance
by chemical reaction
GA = rA V
= - rate of appearance
N.B. beware definition of terms or
and note where they appear GA = rA dV
in the equations to determine signs
 a) IDEAL BATCH - CONSTANT VOLUME
dN A
FA 0  FA  G A 
dt
=0 =0 = rA V

 dN A  d  N A 0 1  X A   dX A
rAV     N A0
dt dt dt
t XA
N A0 dX A
  dt  
0
V 0
rA
XA XA
N A0 dX A dX A
t 
V 0
rA
 C A0 
0
rA

or CA
dC A
t 
C A0
rA
 APPLICATION - Ideal Batch Reactor
(constant V and T)
XA CA
dX A dC A
t  C A0 
0
rA
 
C A0
rA

A to products
CA
rA  kC A  kt   ln   ln 1  X A 
C A0

2A to products
1 1 1  XA 
rA  kC A  kt 
2
   
C A C A0 C A0  1  X A 
 CSTR Reactor for Liquid Phase Reaction
Reactor operates at
outlet conditions.
Reactant supply in:
Reactor is well-
Liquid flow rate = v m3/s
mixed, hence
Concentration = C0 mol/m3
concentration of
reactant throughout
is = C

Remaining reactant out:

Volume of reactor = V m3 Liquid flow rate = v m3/s
Concentration = C mol/m3

Reactor operates at steady-state - variables do not change with t

 Material Balance for CSTR
Master Equation:

IN + MADE = OUT + ACCUMULATION

=0
add kinetics = v.C at steady-state
= v.C0 x volume of
(no change with t)
reactor
i.e. no build up
e.g. 1st order
of material within
reaction
the reactor
 V .  k .C 
Leads to:
C0
v.C0    k .C .V   v.C  v.C0   v  kV  C  C 
 kV 
1  
 v 
 CSTR
dN A
FA0  FA  G A   rAV  FA0  FA
dt
= rA V
=0
 FA0  FA0 1  X A   FA0 X A

Since
FA0 = v0 CA0 Case for constant volume V,
concentration CA0 of inlet stream
v0
 rA  C A0 X A C A  C A 0 1  X A 
V
V C A0 X A subst. for  C A0 X A
   
v0 rA rA

 C A  C A0  rA τ
Most reactions in a CSTR are in the
liquid phase
 CSTR
A B rA  kC A  C A  C A0  kC A

2A  B rA  kC 2
A

 1  1  4kC A0
 C A  C A0  kC  2
A  CA 
2k
Second order, reversible reaction in a CSTR with constant volume
k1
A+B C+D Feed: CA0, CB0, CC0 = 0, CD0 = 0
k2
From: C A0  C A C B 0  C B CC  CC 0 C D  C D 0
    
a b c d

 C A 0  C A  C B 0  C B  CC  C D
 CSTR
rA  rf  rr  k1C AC B  k 2CC C D
Mass balance
C A  C A0  rA
C A  C A0    k1C AC B  k 2CC C D 

Substitute
CB = CA - CA0 + CB0
CC = CD = CA0 - CA


 C A  C A0   k1C A  C A  C A0  C B 0   k 2  C A0  C A 
2

Solve for CA
 PLUG FLOW REACTOR
Since the composition within the reactor varies -
we take a balance over a differential element of volume
V

FA0 FA(y) FA(y+y) Faf

XA0 = 0 XAf
v0
y y+y
dN A
FA ( y )  FA  y  y   G A 
dt =0 Concentration at
rA V = rA A y point y is constant
across reactor
 FA  y  y   FA  y   cross-section
    rA A
 y 
The basic limiting process of calculus states that for any quantity
FA, which is a smooth continuous function of y

FA 2  FA1 FA dFA

lim
y 2  y1 y2  y1
 lim
y 0 y

dy

Taking the limit as y tends to 0

dFA
  rA A
dy
Usually we have V rather than y as the independent variable:

Since dV = A dy
dFA
  rA
dV
 Liquid State Reaction in a PFR

Reactant supply in: Remaining reactant out:

Liquid flow rate = v m3/s Liquid flow rate = v m3/s
Concentration = CA0 mol/m3 Concentration = CA mol/m3

FA  v.C A  v.C A0 1  X A  mol / s

dFA dX A X A dX
 rA  v.C A0  rA  V  v.C A0  A
dV dV X rA
A0
 CSTR vs. PLUG FLOW
Isothermal
CSTR vC A0 X A
V
rA
General form
of rate curve
1/rA

XA
PLUG FLOW
XA
dX A
V  vC A0 
0
rA
 CSTR VS Plug Flow
•A combination of PFRs giving a particular final conversion have the
 same volume as a single PFR which gives the same total conversion.
•A series of CSTRs can be useful to reduce the overall volume:
V1 V2 1/rA

0 X Ai XAf V2
V1

X Ai XAf XA
Other rate expressions 1/r
Rate low at low
•rA=kCAn - as n increases, PFR
conversion due
 more favourable to
•zero order reactions are low CB
 reactor independent
•autocatalytic reactions VCSTR VPFR
 A B rA=kCACB X
XIN XCSTR XOUT
 Ideal batch - variable volume
dN A dN A
FA0  FA  G A   rAV  
dt dt
=0 =0
= rAV
This two-term expression
1 d  C AV  1  dC A dV  can be avoided if we use
rA     V  CA
V dt V  dt dt  fractional conversion and
expansion factor
c d a b
aA  bB  cC  dD N T  N T 0  N A0      X A
a a a a
NT N
 1  A0  A X A  1   A X A
NT 0 NT 0
Expansion factor
For constant P and T
Volume
Thus:
V
 1   A X A varies linearly C  N A  N A0 1  X A   N A0 1  X A   C A0 1  X A 
V0 V0 1   A X A  1   A X A 
A
with conversion V V
From
1 dN A
rA  
V dt
N A0 d 1  X A 

V dt
N A0 d 1  X A 

V0 1   A X A  dt

C A0 dX A
 rA  Constant T & P
1   A X A dt
 IDEAL BATCH
V, P & T varying
From PV = zNTRT get P0V0 = z0 NT0RT0

V  z T P0  NT V  z T P0 
      1   A X A  (1)
V0  z0 T0 P  N T 0 V0  z0 T0 P 

Since
N A N A0 1  X A   z0T0 P 
CA     (Subst. for V from (1))
V V0 1   A X A   zTP0 

Then
1 dN A  z0T0 P  C A0 dX A
rA    
V dt  zTP 0  1   A X A  dt

Can be solved provided we know how P and T are varying

with time
 Comparison of CSTR vs. Plug Flow for
nth order reactions
100
n=2
A  products
 n V
C A0 v  n=1 rA  kC An
CSTR

 n V 10
C A0 v  n=0.5
PFR

1
0.01 0.1 1.0
(1-XA)
Comments
(1) n +ve VCSTR > VPFR
(2) n=0 VCSTR = VPFR
(3) low XA flow type influence is small
(4) read Levenspiel 2nd edition p. 124-127 and make
 OPTIMIZATION
-REACTOR DESIGN FOR MULTIPLE
REACTIONS
• They can be considered to be a combination of parallel and
series reactions.
• Easier to deal with concentration rather than conversion.
• Eliminate time variable by dividing one rate by the other.
• The two requirements are:
– minimum reactor size
– maximum of desired products
may run counter to each other - then perform an economic
analysis
• In general product distribution controls.
• We will ignore expansion effects.
• We consider isothermal reactions
 REACTIONS IN PARALLEL
k1
B Desired product
A
C (Isothermal, Irreversible)
k2

dC B dCC (2)
rB   k1C A (1) rC   k 2C A
dt dt
Dividing (2) by (1)
rC dCC k 2  
  CA Ratio to be small
rB dC B k1
k1, k2,  are all constant. CA is the only variable.
• To keep CA
– Low - Use: CSTR, maintain high XA, increase
inerts in the feed, decrease pressure in a gas
phase system.
– High - Use: Batch/Plug Flow, maintain low XA
– If:  is -ve high CA  is +ve
low CA  - product distribution fixed -
reactor volume important
• OTHER WAYS TO CHANGE PRODUCT
DISTRIBUTION
– Change temperature and hence k2/k1 may vary (see later)
– Use a catalyst
 1st Order, Irreversible, Parallel, Constant
Volume
1 dN A dC
t=0 Rate rA    A
V dt dt
CA = CA0 equations
dC A
CB = CB0
k1 B rA    k1C A  k 2C A
A dt
CC = CC0 k2
C
dCB
rB   k1C A
dt
dCC
rC   k 2C A
dt
Integrating rate equations using initial conditions:
  k1  k 2  t
C A  C A0 e
 CB 0 
C B  C A0  
k1

1  e  k1  k 2  t  
 C A0 k1  k 2 
 CC 0 
CC  C A 0  
k2

1  e  k1  k 2  t  
 C A0 k1  k 2 
 1.0

Cj /CA0
B
C
A

For plug flow reactor, replace t with 

e.g.
  k1  k 2 
C A  C A0e
 CSTR
CA0 C A  C A0   k1  k 2 C A
CB0
CC0
k1 B C B  C B 0  k1C A
CA
A C
CB CC  CC 0  k 2C A
k2 CC

Thus:
C A0 k1C A0
CA  CB  CB0 
1   k1  k 2  1   k1  k 2 

k 2C A0
C C  CC 0 
1   k1  k 2 
For two competing reactions forming:
D Desired product
A
U Unwanted product

Selectivity Yield
(A is reactant)
rD rD
Sr  GENERAL Yr 
rU rA
FD FD
SF  FLOW YF 
FU FA0  FA
ND ND
SN  BATCH YN 
NU N A0  N A
Space time

V
 (mean residence time)
v0

Space velocity
 vo  STP

V

GHSV Gas Hourly Space Velocity, h-1

v0 at STP

LHSV Liquid Hourly Space Velocity, h-1

v0 at some reference temperature
 Temperature and Energy Effects in Chemical
Reactors
• Equilibrium yield
Affected by
• Rate of reaction temperature
• Product distribution (multiple)
• Reactions are generally accompanied by
heat effects
– How will they change the temperature ?
• Economic considerations
– Identify optimum
• Reactor stability
– operating point
(1) Effect of temperature on equilibrium
Endothermic
d ln K H  1.0

dT RT 2 XA
VAN’T HOFF Exothermic
Exothermic (Ho<0): T rises, K decreases
Endothermic (Ho>0): T rises, K increases T
If H = const. (not really)
o  K 2   H   1 1
 ln
K   
T  

 1 R  2 T1 

(2) Effect of temperature on rate

ARRHENIUS k0
E
k  k0 exp 
 RT  k
Note:
Van’t Hoff is thermodynamic and
thus always true. Arrhenius is an
approximate model T
(3) Choice of operating temperature
Endothermic: High T maximises the rate and the eqm. conversion
- thus choose as high a T as possible
Exothermic: High T maximises the rate, but
Low T maximises the eqm. conversion
- compromise between kinetics and thermodynamics

(4) Effect of T on actual conversion

(a) Irreversible reaction assymptote just less than 1
- any reactor type 1
(batch, CSTR, PFR etc.) higher
- arbitrary kinetics 
XA exhaustion
“S- shaped curve” of reactants
Note: assymptote not XA = 1 in lower
general, as rate finite at T = infinity 
thus XA<1, but can be treated
dominated by Arrhenius T
as such.
(b) Reversible reaction
Endothermic
1

XA equilibrium
conversion
lower 

T
Exothermic
i.e. get a maximum 1
in XA vs. T (for a equilibrium
lower
given )
XA 

T
 (5) Temperature Effects in Isothermal
Reactors
Definition
Isothermal: enthalpy removed from (or added to) the reactor by cooling
(or heating) so that T=const. within the reactor and equals the feed
temperature.

(a) Irreversible Reactions

Use usual design equations with Arrhenius dependence in rate constant

(b) Reversible Reactions Volumetric

- illustrate with a CSTR flowrate, v
V
CA0
k1
CB0 v
A B Liquid phase
CA
k-1
CB
 Reversible Reaction
V C A0 X A
CSTR design equation  
v   rA 
  rA   k1C A  k1CB  k1C A0 1  X A   k1  CB 0  C A0 X A 
Combine:   C A0 X A
k1C A0 1  X A   k 1  C B 0  C A0 X A 
If let CB0 = 0 then: XA

k1 1  X A   k 1 X A
In practice, we may have one rate constant (e.g. k1) and eqm. const. K
Assume and ideal mixture, thus: K 
CB

k1
CA eqm
k 1
Hence:   XA
i.e. we have XA as a func. of
  X A 
k1 1  X A    (T,) or (T,XA)
  K 
 Non-isothermal CSTR
v
CA0 A B irreversible
T0 - Heat transfer coefficient h
- Area A
T - Temperature TC
V v
CA - Kinetics: (-rA)= kCA
- Enthalpy change of reaction =
Cooling water H
h, A, TC - Assume: CpA = CpB = const.
Mass balance: V C A0 X A C A0  C A
  
v   rA    rA 
Subst. kinetics V C A0  C A C A0
   CA 
v k1C A kV
1
v
 C A0
Insert Arrhenius CA 
expression:
  
k0 exp  E
RT
 
V  Rate of reaction
per unit volume
1  
 v 
Energy balance:
Heat generated (exothermic) - Qg   kC A V   H 

Arrhenius - Heat evolved per

mole reactant
 Qg  k0 exp  E / RT  C AVH
 vC A0 H
Substitute for CA from above and rearrange: Qg 
v
Thus in the limit - 1 exp E / RT 
 vC A0 H Vk0
T  0, Qg  0 T  , Q g 
v
1
Vk0
Heat removed -
Qr  vC p  T  T0   hA T  TC    vC p  hAT   vC pT0  hATC 
AT STEADY STATE: Qr = Qg
 Qr 1 2 3 Cases 1, 3 - single steady
Qg, Qr Qg states
Case 2 - “multiple
steady states”

Case 2 has three possibilities

T - which steady state do we
actually get ?
Stability of steady states
Definition: a steady state is stable if, when subjected to a perturbation,
it returns to the steady state.
Q Steady state a
Qg, c r
Qg - If Ta increases to Ta + T
Qr Qr > Qg thus T reduces
b - If Ta decreases to Ta - T
Qr < Qg thus T increases
a
System acts to eliminate the perturbation
Ta Tb - thus steady state a is stable.
Tc T
 Steady state b
- If Tb increases to Tb + T
Qr < Qg T increases further until steady state c is reached
- If Tb decreases to Tb - T
Qr > Qg thus T decreases further to Ta

Steady state c
as per case a, i.e. stable
Implications for operability Start up temperature, Ts
Qr, If Ts>Ti, Qg>Qr and the reactor goes to the
Qr
upper steady state (high T implies high
Qg Qg
conversion). This is usually the desired
steady-state.
This may not be desired due to:-
high T encourages side reactions, or the
material of the reactor may not stand high
T, or the rate may become dangerously high.
Ti T
If Ts < Ti, Qg < Qr and the reactor goes to the lower steady-state (low conversion).

May need to pre-heat reactants at start-up even if reaction is exothermic.

Example 1.1: Operation of a CSTR with Heat Effects
A first order reaction is to be carried out in a CSTR. The conversion is
required to be at least 75 % and the reactor temperature must not
exceed
340 K. In order to facilitate start-up, the reactor should have only one
steady state.

Data
V = 10 m3 Three feed temperatures are to be
C0 = 5 kmol m-3 considered: T0=290 K, 300 K and
v = 10-2 m3s-1 310 K.
H = -2x107 J kmol-1
k = 1013exp(-12000/T) s-1
 = 850 kg m-3
Cp = 2200 J kg-1
(1) Can this reactor be operated adiabatically ?
Fig. 1 shows the Qr and Qg curves for adiabatic operation. The steady-
state temperatures are read from the graph. (in practice the heat
generation and heat removal equations would be solved numerically.)
The conversion, X, is calculated from the heat generation equation.
In this case:
Qg = C0X.v.(-H) = X.106 J/s

Figure 1
The results are as follows:
T0 = 290 K: one steady state, T = 291 K, X = 0.01 (too low)
T0 = 300 K: lower steady state, T = 303 K, X = 0.06 (too
low)
upper steady state, T = 349 K, X = 0.92 (too
hot)
T0 = 310 K: one steady state, T = 362 K, X = 0.98 (too hot)
Adiabatic operation does not meet the temperature and conversion
constraints.
(2) A cooling coil is added. Can the requirements be satisfied now ?

Data
hA = 9x103 J s-1 K-1
Tc = 310 K

Fig. 2 shows the Qr and Qg curves with the reactor with the cooling coil
for Tc = 310 K.

With the cooling coil in operation, a single steady state at T = 339 K,

X = 0.82 is obtained, which satisfies the requirements.
 6. Adiabatic PFR
PFR design equation
T0 T XA
V C A0 dX A dX A
Molar
nA
   V  n A0    rA 
nB v  rA 0
flowrate
s Can’t integrate because rA = f(XA, T)
nA0, nB0
Energy balances
Steady state: Input - Output + Generated = 0
Assume Cp= const., i.e. Cp is not a function of T
n A0   
C p A  nB 0C pB T0  n AC p A  nB C pB T   n A0  n A   H   0

T 
 n C A0 pA  nB 0C pB T0  
n A0 X A   H 
n C A pA  nB C p B  n AC p A  n B C p B

When XA = 1, (T-T0) is often called the “ADIABATIC

TEMPERATURE RISE”, tad.
If “capacity flowrate” is constant: (i.e. CpA = CpB in this case)
n A0   H  n   H 
Tad   A0
 n A 0 C p A  nB 0 C p B   n A 0  nB 0  C p
From above we have T = f(XA), and reaction rate is rA = f(XA, T).
Hence now have rA = f(XA only) and we can integrate the PFR
design equation.
Example 1.2: Design of an Adiabatic PFR

The first order gas phase reaction A B is to be carried out in an

adiabatic PFR. Calculate the size of reactor required for a conversion
of 30 %. The feed is 100 mol/s of pure A at 700 K and 2 bar.

Data
Forward rate constant k1 = 4.6x105exp(-12500/T) s-1
Reverse rate constant k2 = 7.7x106exp(-15000/T) s-1
H = -20000 J mol-1
Cp = 40 J mol-1 K-1 for both species
Solution X
PFR design equation: 1
V  n A0  dX
0
r
Assume ideal gas conditions (OK because low P and high T):
X X
1 1
V  n A0  dX  n A0  dX
 p   p    nA   nB   p A 0
0 k1  A   k 2  B  0
k1    k 2  
 RT   RT    n A0   n A0  RT
Introduce definition of conversion: n A0 R
X
T
V 
p A0 0 k1 1  X   k 2 X
dX

k1 and k2 are given as functions of T in the Arrhenius expressions

above. Before V can be evaluated, T must be found as a function of
X by an energy balance: X   H   C p  T  T0 

Substituting for T0, H and Cp:

T = 700 + 500X
The integrand of the expression for V is now known as a function of X.
The equation is integrated numerically giving the results shown in the
handout figure. Note that the maximum conversion is restricted by
chemical equilibrium; under these conditions, the maximum conversion
is 47 %. The volume required for a conversion of 30 % is 37.9 m3.

Isothermal and adiabatic operations are extremes. How about controlling

the temperature profile so that the reaction is neither isothermal nor
adiabatic ?...

7. Optimal Temperature Profile XA

From section 4(b) Decreasing 
Exothermic Reaction Constant 
Desired (residence
Possible design strategy XA *
time)
(1) Choose XA
(2) Choose T so that  is minimised
for this XA (* on diagram).
T T
BUT WE CAN DO BETTER !
   rA   k1C A  k2CB
k1
A B Exothermic
k2
Better Design Strategy (-rA) Initial rate depends
on kinetics
- Start with high T at low XA
and progressively reduce T as 30 oC
XA increases. 20 oC
- At any XA, operate at T that 10 oC
gives the highest rate, called:
OPTIMAL TEMPERATURE
PROGRESSION XA
(-rA) Maximum Max. conversion
reaction rate depends on eqm.
N.B. Initial rate is determined
T decreasing
by max. allowable T.
Practically - metal mpt
- undesired side
XA reactions
Practical Schemes
(1) PFR with heat removal rate varying along the reactor
(2) e.g. PFRs or CSTRs with inter-coolers

30 oC 20 oC 10 oC

(3) “Cold Shot Cooling”

 Design calculations for optimal T progression
We want max. rate at each XA:  rA  X A , T  
  0
 T XA
Example 1.3 Optimal Temperature Progression

The first-order gas phase reaction A B is to be carried out in a

PFR. Calculate the size of the reactor required for a conversion of 50
%,
if the temperature profile is optimal. The feed is 1 mol/s of A and
1 mol/s of B at 2 bar. The reactor may not operate at more than 800 K.

Data
Forward rate constant k1 = 4.6x105exp(-12500/T) s-1
Reverse rate constant k2 = 7.7x106exp(-15000/T) s-1
H = -20000 J/mol
Cp = 40 J/mol K for both species.
 Solution X
1
PFR design equation: V  n A0  dX
0
r

Assume ideal gas under these conditions (OK because low P and high T)
X X
1 1
V  n A0  dX  n A0  dX
 p   p    nA   nB   p A 0
0 k1  A   k 2  B  0
k1    k 2  
 RT   RT    n A0   n A0  RT

Introduce definition of conversion: For optimal

n A0 R
X
T & temperature dr
V 
p A0 0 k1 1  X A   k 2 1  X A 
dX progression:
dT
0

Differentiation of the rate law and rearrangement gives:

2500
T The expression for V can now be evaluated
 20.091  X A  
ln   to give the value required for any conversion
 1  X A 
with optimal temperature progression.
 Thermal Runaway in Closed Systems
1. Useful references: Coulson and Richardson series,
Denbigh and Turner, “Chemical Reactor Theory”

2. Definitions and Examples

Thermal runaway is the sudden inflammation of a uniformly heated

mass (as opposed to that caused by a spark etc. which is localised)
e.g. peroxides, haystacks (spontaneous combustion)

3. Aims
- To see how little self-heating can lead to thermal runaway.
- To explore heat balance equations and to lay foundations for
understanding other instabilities.
- To introduce useful dimensionless variables and parameters.
 Dimensionless Temperature
Reaction rate constants often have an Arrhenius temperature
dependence:
dk E
k  k0 exp  E / RT    2
.k
dT RT

Thus the group RT2/E is a natural yardstick of temperature:

T  Ta

 RT 2 
 
 E 
 
where Ta is the ambient temperature, and T is the temperature
in a reactor, say.
 Stationary States and “Criticality” (ignition)
Assumptions:-
- ignition has a thermal origin
- neglect:- (i) reactant consumption
(ii) T as a function of position, thus assume a
mean temperature

Thermal diagram
Volume, V
Surface Area, A
Temperature: inside, T
A outside, Ta
Reactant concentration, C=C0
T, V, C
Reaction rate constant, k
Heat transfer coefficient, h
Qr, Qg T
Qr, Super-critical
Qg Qg
Qg (Runaway)
B
Qr
C
Qr
A Sub-critical
C

Ta T Ta T time

No stationary state Stationary states:

A - stable
B - unstable
C - critical point
For all stationary states (including C): Qr = Qg
Thus: hA(T - Ta) = V(-H)kC0

dQr dQg E - defines the

At point C:   hA  V (  H )C0 2
k critical point,
dT dT RT
and thus TC
 Thus: T - Ta = RT2/E at T = TC (the critical temperature)

Solve the quadratic:

RTC2
 TC  Ta  0 ..to find TC
E
Main result
RTC2 ~ typically = 10-15 K, i.e. a small difference,
TC  Ta 
E hence very little consumption is needed (~2 %),
so our initial assumption of negligible reactant
consumption is reasonable.
From the definition of , this equation also implies that:
C = 1 for ignition.

A single dimensionless group encapsulates the criterion for criticality.

8. Temperature Effects With Multiple Reactions
Product Distribution

(a) Parallel reactions Assume reactions are of the same

order
(1) R desired We want: k1 large
A k2 small
(2) S unwanted
k = k0exp(-E/RT)
If E1>E2, (1) increases with T more rapidly than (2) - Use high T
If E1<E2, (2) increases with T more rapidly than (1) - Use low T

(b) Series Reactions

(1) (2)
If E1>E2 use high T A R S
If E1<E2 use low T desired
(c) Mixed reaction scheme (i.e. series and parallel elements)
(1) (3) (i) E1>E2>E3 - use high T
A R S
(2) desired (ii) E1>E2, E1<E3
T
Want high T to Want low T to
maximise R minimise S

- Use falling temperature

T

(iii) E1<E2 and E3 - use low temperature

(iv) E1<E2, E1>E3, use rising T (opposite of (ii))

 The Rate-Limiting Step
It would be wrong to assume that the rate of reaction is always the
rate-limiting step. Mass transfer may control.

Consider A Z where rZ = kCA on the surface of a catalyst.

Assume a steady-state, the rate of mass transfer equals the rate of reaction,
thus the rate per unit area is given by:
pAbulk p Ai
Solid

r  k g p bulk
A  p i
A 
 kC A  k / i
pA
r r i
Now  p bulk
A  p i
A and /
 p A
kg k
 1 1 
Gas film  r   /   p bulk
A  r  k // bulk
pA
 k g k 
1 1 1
where //
  /
k kg k
So, in general, the rate of reaction is a function of both kinetics and
mass transfer. May have a fast reaction rate or slow mass transfer,
then MASS TRANSFER controls the reaction.

How do you find this out ? - estimate kg from correlations

- find the temperature dependence of
the reaction

In general: k// = k0exp(-E/RT) At low T,

high E
Ln k//
For diffusion/mass transfer:
E ~ 30-50 kJ mol-1 At high T,
low E
For reactions:
E > 100 kJ mol-1 Solid line shows observed rate

1/T
Lowest rate controls and so is observed as k //
 General Energy Balances
(1) (2)
T0 T
Fi0 Fi
Hi0 Hi
Q
Ws

n n  dE 
Q  Ws   Fi 0 H i 0   Fi H i   
i 1 i 1  dt  sys
Rate of heat
flow TO system Rate of accumulation
from surroundings Rate of work of energy within the
done BY the system system
ON the surroundings
Change in Heat Work Energy of Energy
energy of = added to - done by +
mass
-
of mass
system system system on entering leaving
surroundings system system
For steady state:
0 = Q - W + (QvE)1 + (QvE)2

where Q is in Watts,  is the mass density, Qv is the volumetric

flowrate, and E is the specific energy.

E = U + u2/2 + gZ

where U is the internal energy, u2/2 is the kinetic energy and gZ is the
potential energy.
In a reacting system the kinetic energy and potential energy are relatively
small, thus E~U.
U consists of:
•Sensible energy
–translational
–rotational Affected by T
–vibrational
•Latent energy - change of phase
•Chemical bonds - chemical reaction
Viscous and
W= Flow Shaft
+ frictional + = (Wf )1 - (Wf )2
work work
work
If we consider viscous/frictional work and shaft work terms to be small,
for a fluid entering the system:
(Wf )1 = (-PAu)1 = (-PAQv/A)1 = (-PQv)1
Wf is a negative quantity because the fluid does work on the system.
(u is velocity, A is area of flow)
Q + (PQv)1 -(PQv)2 + (QvU)1 - (QvU)2 = 0

We now introduce enthalpy, H = U + P/thus:

Q + [Qv(U+P/)]1 - [Qv(U+P/)]2 = Q + [QvH]1 - [QvH]2 = 0

Let then Q - mTH = 0

If Q = 0, then H = 0 and enthalpy of the inlet stream is equal to the

outlet stream.

At steady-state, under adiabatic conditions, and neglecting work done

n n
by the system:  Fi 0 H i 0   Fi H i  0 where Fi is the molar flowrate
i 1 i 1
and Hi is molar enthalpy
T
Reminder: Hi  H i ( TR )   C pi dT
TR
 In a chemical reacting system this results in:
Tout
 Fi 0  C pi dT  ( Rate )H R ,Tout  0
inlet Tin

For this adiabatic system, the heat released by the chemical reaction
must be used to raise the temperature of the product stream.

Simplification

FA0  i C pi  T  T0    FA0 X A H R  TR   Ĉ p  T  TR  
Assume
i = Fio/FA0 Mean value …assume
= HR(T) or...
for feed T
T  C p dT
 C pi dT Ĉ p 
TR
0
T0 T  TR
C pi 
T  T0
  
FT C p Tout  Tin   FA ,0 X AH R ,Tref

FT   Fi 0 Mean value H R ,Tout  H R ,Tref

for feed

b c d
Note that for the general reaction: A B  C  D
a a a
d c b
C p  C p D  C pC  C p B  C p A
a a a

In general Cp is a function of temperature which is generally

correlated (e.g. Perry) in a form: 2
C pi   i   iT   iT
T
If used in  C p dT where Cpi is evaluated at the mean
this form Ĉ p 
TR

then T  TR temperature between T and TR