CHEMICAL REACTION

ENGINEERING II

CHE 416
 CHEMICAL KINETICS AND REACTOR
DESIGN:
• Motivation for understanding chemical kinetics and
reaction design:
• This is what makes us chemical engineers – the
reactor is the central feature of most chemical
processes.
• Even if separation costs dominate, the reactor often
determines the separation costs.
• Chemical reactions are ubiquitous in nature and
industry.
 COURSE OUTLINE:CHE416
• IDEAL REACTORS
• ASSUMPTIONS (IDEAL VS. REAL)
• MATERIAL BALANCE / PERFORMANCE OR
DESIGN EQUATIONS
• COMPARISON OF IDEAL REACTORS
• NONISOTHERMAL OPERATION
• ENERGY BALANCE EQUATION
• APPLICATION TO DESIGN
 OUTLINE:CHE416 CONTD.
• REAL VERSUS IDEAL REACTORS
• SOURCE OF DEVIATIONS
• RESIDENCE TIME DSTRIBUTION
• RTD FUNCTIONS
• CONVERSIONS-1ST ORDER RXNS
• REACTOR MODELS
REQUIREMENTS FOR PASSING THIS
COURSE
•ATTENTION IN CLASS

•RE-READ NOTES

•PRACTICE SOLVING QUESTIONS YOURSELF

•ASK QUESTIONS TO BE SURE YOU

UNDERSTAND
Some useful texts
1. Chemical reaction engineering by
Levenspiel O.
2. Elements of Chemical reaction engineering
by Fogler S.
3. Chemical reactor analysis and design by
Froment and Bishoff
4. Fundamentals of chemical reaction
engineering by Holland, C.D. and Anthony,
R.G.
 WHY IDEAL REACTORS?
• Represent distinct extremes of mixing
(100% in BR and CSTR; 0% in axial
direction for PFR)
1. Ideal reactors simpler to analyse [well
defined flow pattern of fluid in reactors]
2. More complex real reactors can be
examined in terms of ideal reactors
3. For new designs ideal reactors help
determine type of mixing that leads to
better results
 WHY IDEAL REACTORS? Contd.
• much to gain from a study of ideal reactors.
• estimate the size of the required reactor syst.
• INSIGHT into:
• the operation of the real reactors
• Effect of parameters on results
• most important factors to control
• Hence powerful models for chemical reaction
systems
 WHAT ARE IDEAL REACTOR MODELS
• Based on assumptions about mixing
patterns within REACTORS
• One of the assumptions represent the
best way of contacting the reactants
• Easy to treat mathematically
• Insights obtained are significant for real
reactors-type of mixing, important design
parameters, better control
 Ideal reactor types:
1.Batch Reactor (BR) 100%
mixing

2.Continuously(operated)
Stirred Tank Reactor (CSTR)

3.Plug Flow Reactor (PFR)

 Batch Reactor (BR)
• operates in a discontinuous way(wrt
time)
• reactants and any other substances
(catalyst, solvent etc.) are loaded into the
reactor at beginning
• Contents subjected to perfect mixing
(and left to react) for a certain period.
• The resultant mixture is then discharged.
Batch reactor: homogenous reaction
mixture
 Batch Reactor (BR)2
• operates in unsteady mode with respect
to time at any position
• Composition at any point in reactor
changes continuously w.r.t time
• 1st order reaction: CA=CA0e-kt
• operates in steady mode w.r.t space. No
variation from point to point because of
perfect mixing at any point in time
 CHANGES IN A Batch Reactor
• reactants are consumed and products
formed with reaction
• -the composition of mixture changes
continuously[reactants decrease and
products increase)
• at any given time there is no variation in
composition at different points in the
reactor because of perfect mixing inside
the reactor
CA VS t,
 CA VS t,p Fig
• 1
Q2
The gas-phase reaction
A  B+C
is carried out isothermally in a 20-dm3 constant-volume batch reactor. Twenty moles of pure A is initially placed in the reactor. The reactor is
well mixed
(a) If the reaction is first order with a specific rate constant of 0.865 min-1
calculate the time necessary to reduce the number of moles of A in the reactor to 0.2 mol.
(Ans.: t = 5.3 min)
(b) If the reaction is second order with a specific rate constant of 2 dm3/ mol.min, calculate the time necessary to consume 19.0 mol of A.
(c) If the temperature is 127"C, what is the initial total pressure?
What is the final total pressure assuming the reaction goes to completion?
Q3 Repeat Q2 assuming the reaction is in a constant-pressure batch reactor
Q4
The irreversible gas-phase nonelementary reaction
A+2B - - - -> C
is to be carried out isothermally in a constant-pressure batch reaction. The feed is at a temperature of 2270C, a pressure of 1013 kPa,
and its composition is 33.3% A and 66.7% B. Laboratory data taken under identical conditions are as follows:
-rA(mol/dm3.s)x103 0.0l 0.005 0.002 0.001

-xA 0.0 0.2 0.4 0.6

Calculate :8
•The volume of the reaction mixture at xA=0
•The time required to attain 60% conversion
•The volume of the reaction mixture at xA=0.60
 Advantages/Disadvantages of BR
• is simple,
• needs little supporting equipments,
• high flexibility-high conversions
through high reaction time as
desired
• ideal for small-scale experiments
(kinetics studies).
 Advantages/Disadvantages of BR2
• single unit may be used for the
manufacture of relatively small
amounts of different material
(drugs, dyes, cosmetic articles)
• not a dedicated unit
• Disadvantages -idle periods (for
loading, unloading, cleaning, heating
etc).
• Labour cost
 Design equation of BR
• Obtained from the law of conservation
of matter.
• Written for any component in the system
[ reactant, product, inert]
• Usually in terms of limiting reactant ,A
• Control volume is the whole volume of
reactor because of uniform conditions
within it
• element of volume= Control volume
 Control volume/element of volume
• Reactions occur in a localized region of space
• Control volume or element of volume is
• any region of space that has a finite volume
with boundaries that clearly separate the
region from the rest of the universe.
• real or abstract , macro sized
• Chosen according to the dictates of the
analysis that we are undertaking
 Law of conservation of mass

• a
 Balance after t>0
• Rate in=0 no inflow after charging
• Rate out=0 no outflow after charging
• Rate of disappearance by reaction=V(-rA)
• V(-rA)= vol x [mol/vol-time]=mol/time

• Rate of accumulation=dNA/dt

• t=reaction time
• V= volume of the reaction mixture
Substituting in equation:
0 -0 - V(-rA) = -NA0dXA/dt
Integrating between from t=0, XA=0
X Ae
t X Ae
dX A

dX A
 dt  N  t  NA0
0
A0
0
V(  rA ) 0
V(  rA )
For constant volume reaction mixture
X Ae
dX A
t  CA 0  0
( rA )

•equation gives time required for a desired level of conversion

•Integral evaluated by methods discussed
 Evaluating the integral
 d CA
X Ae CA CA 0
dX A d CA
t  CA 0 
0
(  rA )
 CA 0 
CA 0
 
(  rA )CA 0 C A (  rA )
CA  CA 0 (1  xA )
 d C A  C A 0 d xA
 d C A / C A 0  d xA
 Reaction time, t, is the performance
measure for a Batch Reactor
• Integral =area under the curve of 1/(-rA )
vs. XA.
• It may be evaluated:
1.Analytically
2.Graphically
3.Numerically( minimum of 5 points
considered sufficient)
f(x)
Graphical

1
2
3

a=0 x=(a+b)/2 b=XAe

 NUMERICAL integration : Simpson’s
1/3 rule
• Divide area into even number of equal–size
strips of width h
• Area=(h/3)x[ENDS + 4 x ODDS + 2 x EVENS]
For 4 equal size strips
• Area=(h/3) x [(f0 + f4) +4(f1 + f3)+2f2 ]
• h=(b-a)/4
• Applicable for even number of strips
• Limitations exist for this calculation
 Variable volume reaction mixture-constant
pressure reactor for gas phase reaction

Substituting in the batch reactor design equation

t
 CONTINUOUS STIRRED TANK REACTOR
(CSTR)
• feed mixture continuously enters and the outlet
mixture is continuously withdrawn. Hence
• ‘Continuous’ refers to the inflow and outflow of
materials. Hence Continuous flow stirred tank reactor is
a better name CFSTR
• CSTR also misses the essence of the idealization
completely
• ideality arises from assumption that the reactor is
perfectly mixed and hence homogeneous. Hence:
• Continuous perfectly mixed reactor(=CPMR) is an even
better name
• used alone or as part of a battery of CSTRs
 CSTR: Homogeneous reaction
mixture, constant inflow & outflow
Steady inflow

Steady outflow
 CSTR contd2.
• mixing so perfect that concentration and
temperature are spatially uniform within
whole of reactor and
• correspond to those of the exit stream;
• operates in a steady mode w.r.t. time
–at all times, Ci is same at any point
• operates in a steady mode w.r.t. Space
–Ci is same at all points at any t
Design equation: CSTR
element of volume= whole reactor. Why?- whole
reactor forms a homogeneous mixture
• Rate in=FA0
• Rate out=FAe
• Rate of disappearance by reaction = V(-rA)
• Rate of accumulation = 0 (steady state)
• FA0 - FAe- V(-rA)=0
 CSTR contd.
•reactants continuously fed into the reactor
•products continuously drawn from reactor
• *
•Also called vat,
•backmix reactor,
•Mixed-flow reactor
•100% back mixing reactor
 Term In Square Brackets
=area of the rectangle: 1/(-rAe) By XAe
• Rearranging to obtain the space time,

CA0/-rAe

CA0/-rA

xA xAe
VCSTR=[FA0/(-rA)] x XAe
 Space time and space velocity
• τ = time required to process one reactor volume of feed
measured at specified conditions, usually feed conditions
• τ = V/vo = (reactor volume)/(volumetric feed rate
• =space time
• Space velocity=1/space time
• But feed and reaction mixture may be in different phases.
• gas hourly Space velocity=GHSV=
• = [volume of gaseous feed per hour]=/[volume of reactor]
• liquid hourly Space velocity=LHSV=
• =[volume of liquid feed per hour]/[volume of reactor]
• feed may enter as a liquid but react as a vapour -important
to state conditions
 APPLICATION OF CSTR.
For continuous production
• WHEN INTENSE MIXING IS REQUIRED
• CAN BE USED ALONE OR AS part OF BATTERY of
CSTRs
• EASY TO MAINTAIN GOOD TEMPERATURE
CONTROL-perfect mixing
• CONVERSION OF REACTANT PER VOLUME IS
LOWEST OF THE FLOW REACTORS- large volume is
required
• USED FOR MOST LIQUID PHASE REACTIONS
Plug/Piston/ slug flow reactor [PFR]
Continuous Tubular Reactors (CTRs).
Plug flow Tubular Reactors (PFTR)

• FLUID flows orderly through the reactor

• No element of fluid mixes with or Overtakes
any other element ahead or Behind.
• There may Be Lateral Mixing,
• No diffusion along the flow path
• (0% of backmixing).
 Plug flow Tubular Reactors (PFTR)
• CONTINUOUS OPERATION
• reactants continuously fed into the reactor
• products continuously drawn from reactor
• operates in a steady mode wrt. time
• [at all times, Ci is same at a given point]
• Spatial variation in composition and
temperature from entrance to exit of
reactor
 PFR or PFTR or CTRs
• Variation in composition and temperature
along the length of reactor
• The PFR model works well for many fluids:
liquids, gases, and slurries.
• turbulent flow and axial diffusion cause a
degree of mixing in the axial direction in real
reactors
• PFR model is appropriate when these effects
are sufficiently small that they can be
ignored.
Design equation2
 DESIGN EQUATION: PFR
• element of volume is a section of tube of
volume ∆V, small enough for the rate of
reaction within it to be considered uniform.
• Rate in (moles / time) =FA
• Rate out (moles / time) = FA + ∆ FA
• Rate of disappearance by reaction = ∆ V(-rA)
• Rate of accumulation =0 (steady state)
• Substituting in balance equation
FA-(FA+∆FA)-(-rA)∆V=0. Simplifying yields
• -∆FA=(-rA)∆V
• ∆FA/∆V=-(-rA)=rA
• As ∆V→0, equation becomes
• dFA/dV =(rA) or dV= dFA/(rA)
• Differentiating FA = FA0(1- XA ) w.r.t V,
• dV =FA0 [dXA/(-rA)]
From : FA= FA0(1- XA)

Separating variables

and integrating to give volume of reactor

Space time
 Applications of PFR
• Large-scale reactions
• Homogeneous or heterogeneous reactions
• Continuous production
• Most gas phase reactions
• Relatively Easy to maintain(no moving parts)
• Highest conversion per volume
• Difficult to control temperature within the
reactor, hence hot spots for exothermic rxns
• As one long tube or as a tube bank
Actual residence time and space time
• THE actual time a fluid element resides in the
reactor will be equal to the space time only
if:
1. There is no change in the number of moles
during the reaction
2. There is no change in temperature along the
reactor
3. There is no change in pressure
Because: υ= vo(1+XAεA) [T /T0][P 0 /P]
 Actual residence time: PFR
If the time to traverse an element of volume of
reactor dV at constant and pressure, is dtr
• then
• From differential form of the design equation

• Substituting for dV from above,

•

• tr=Actual residence time of fluid in reactor,

 Actual residence time: PFR contd.
Summing up over the whole length of the reactor- by integrating

Q
The vapor-phase cracking of acetone to ketene and methane: CH3OCH3 → CH2O+ CH4
is first-order with respect to acetone and the specific reaction rate can be expressed by:
k=exp(34.34-34222/T) ; where k is in reciprocal seconds and T is in Kelvin.
In this design, it is desired to feed 2.5 g mol/min of acetone to a tubular reactor that is operated isothermally.
The feed of pure acetone enters at 1000 K and a pressure of 162 kPa. Assuming the same constant pressure
and temperature throughout the reactor, determine for 40% conversion of the acetone
a) the space time ,
b) space velocity and
c) the actual residence time
d) Explain any difference between the space tie and the actual residence time
 PFR VS CSTR
• In a PFR, each and every molecule spends the same
amount of time in the reactor
• that period is equal to the residence time
• the concentration in each parcel of fluid entering the
reactor drops by the same amount.
• In contrast, in a CSTR there is no single amount of time
that each small parcel of fluid spends in the reactor.
• perfect mixing: some parcels may spend a long time
mixing around inside the CSTR
• others may, by chance, reach the exit in a relatively
short time. Since all these parcels are mixed together
to result in a single outlet concentration, an average
value of residence concentration results
 Some comments about the ideal reactors
• Comparison can be made from the Levenspiel plots
• For the plots shown VCSTR > VPFR Why?
Comparison: CSTR vs. PFR
CSTR IN SERIES VS. SINGLE CSTR
V SINGLE CSTR >V TWO CSTR in series

Why?

FA0
1/-rA2

XA2
FA2
1/-rA1
V1 XA1
V2
FA1
PFR IN SERIES VS. SINGLE PFR
V SINGLE PFR =V TWO PFR in series
Order of Sequencing Reactors in series
•Performance depends on intermediate conversion
• As the number of equal-size CSTR in series is
increased
• the performance approaches that of a single PFR
of the same total volume
cost of using several smaller reactors, which will be
greater than the cost of a single larger reactor.

Hence: there may be some economic trade-offs

between reactor size and cost.
TEMPERATURE EFFECTS

Why need to know?

 Temperature effects
• Real reactions may generate or absorb large amounts of heat-
affecting T of reaction mixture
• Affects rate
• rate of heat addition/removal to maintain desired reaction
temperature ?
• Reaction Temperature-what should it be?
• Advantageous to operate exothermic reactors
nonisothermally
• Higher temperatures lead to higher reaction rates and smaller
reactors
• If temperature too high equilibrium can limit conversion
• High temperatures can lead to hot spots and reactor failure
• endothermic Reaction-how much heating is required ?
 Heat of Reaction /mole A

Exothermic: generate heat, negative

Endothermic: absorb heat, positive

•Calculated from heat of formation and energy change to

bring it from TR to T
•Hi0: Heat of formation [kJ/mol] is zero for elements
substances.

•Reference state: 25oC & 1 atm

T•Data
R: Reference
availabletemperature
in referenceand pressure:
texts
It is usually taken as the standard temperature and
Heat of Reaction:
The enthalpy change
when stoichiometric quantities of reactants
react Completely in a single reaction to form products at
the same temperature and pressure.
ΔHR is the heat of reaction as written in the given stoichiometry-
energy per mole

Heat of reaction -the energy per mole of component i = ΔHR/υi

moles of i that reacted =(ni0 - ni )=ξ

molar rate of reaction of i =(Fi0 – Fi )=
rate of heat release/absorption by reaction of i =
ΔHr: change in enthalpy from reactants to
products
• ΣHproducts – ΣHreactants = ΔHr(T,P),
• ΔQ = Σ Hout - Σ Hin = ΔHr
• Units of ΔHr are energy per mole; e.g., kJ/mol.
• Mole of what?
• Consider the reaction:
• A + 2B = 3D ΔHr (energy per mole)
• the energy change is as written in the stoichiometry of the
reaction.Hence
• ΔHr is energy per mole of A
• = energy per 2 moles of B
• = energy per 3 moles of D
• enthalpy difference between the products and the reactants
depends on the nature of the bonds broken and formed.
•Energy is required to break bonds
•energy is released when bonds are formed.
•internal energy of the system, Usystem , and
•enthalpy of the system, Hsystem, increase as reactants move to transition
state -absorb energy to break bonds
•energy is released during the bond formation, hence internal energy of
the system, Usystem , and the enthalpy of the system, Hsystem, decrease as
the transition complex moves to products
When (Enthalpy)products < (Enthalpy)reactants then more energy is released
by product from bond formation than is absorbed when reactant break
bonds. The reaction is therefore exothermic.
 RAPID REVIEW

• Heat capacity:
Energy/mole-K

• average Heat capacity between T1 and T2 is

• Enthalpy of i at T

• Enthalpy of formation at TR=

• Enthalpy change (Tio –T) for no phase change):

 Heat of Reaction /mole A:
• Heat of Reaction /mole A at temperature,T
• *

• Heat of Reaction /mole A at reference tempereature,TR

• Heat of Reaction /mole A at TR

*
Assuming mean specific heat for components of the reaction mixture
Heats of Reaction

There are inerts I present in the system.

What is the heat of reaction at 298 C?

What is ΔCp?

What is the heat of reaction at 4000C?

 NONISOTHERMAL REACTOR:
RATIONALE

• LET US CALCULATE THE VOLUME OF A PLUG

FLOW REACTOR NECESSARY TO ACHIEVE 70%
CONVERSION.
• THE CHEMICAL REACTION IS EXOTHERMIC AND
THE REACTOR IS OPERATED ADIABATICALLY.
• AS A RESULT, THE TEMPERATURE WILL
INCREASE WITH CONVERSION DOWN THE
LENGTH OF THE REACTOR.
NONISOTHERMAL REACTOR: RATIONALE
Van't Hoff equation:KP=f(T)

δ=d+c-b-a

For the special case of:

Integrating the Van't Hoff Equation gives
If reaction first order and reversible
 Analysis of Nonisothermal Reactors
The energy balance is an accounting of rate of:
• heat flow into the reactor with reactants
• heat flow out of the reactor with products
• heat generated/absorbed by reaction
• heat added/removed from reactor
• work done by stirrers and friction
 ENERGY BALANCE
Q

Inflow stream: Fi0,Ti0,Ei0,

Control volume
CPi0,Pi0, Hi0 Outflow stream: Fi,
of reactor
Ti, Ei, CPi,Pi, Hi

Ws
The statement of conservation of energy for
this system takes the form:
( rate of energy accumulation in system )

=[rate of energy entering system by inflow of

materials]

-[rate of energy leaving system by outflow of

materials]

+[ rate of heat added to system ]

• Complete energy analysis is complicated

• simplifying assumptions often made!

• convenient to split the work term into 3 parts:

• Wf , the work done by the flow streams while moving
material into and out of the reactor,
• Ws, the shaft work being done by stirrers, compressors,
etc., and
• Wb, the work done when moving the system boundary.
*

• total energy may be regarded as composed of many

forms:
• total energy arise from the internal, kinetic and
potential energies.
• kinetic and potential energies and boundary work
negligible.
• If flow work= Wf =

• then ,neglecting boundary work

Substituting for Wf in equation
balance equation 2 may be written in terms of enthalpy
(Hi= Ui+PVi) as follows:

In terms of molar flow rate and enthalpies:

Inflow

Outflow

Balance applies to all components entering and

leaving the system
Flow rate in terms of FA0 and conversions XA:

• *
 Into balance equation:

Expanding
Using mean specific heat and expanding
• *

NOTE: the different terms one has to consider before evaluation

•Inlet temperatures of different inputs, Tio
•Reference temperature, TR
•Reaction temperature, T
 Energy Equation for Batch
Reactor
Neglecting kinetic energy, potential energy and shaft work

Rate of work due to change in volume:

From Definition for enthalpy:
Calculate the temperature change for 95 % conversion of A
Q.2 The exothermic elementary liquid-phase reaction
A +B - C -rA = kCACB
is carried out in a batch reactor with a cooling coil to keep the reactor isothermal
at 27C. The reactor is initially charged with equal concentrations of A and B at 2.0
mol/L and no C

1. How long does it take to reach 95% conversion?

2. What is the total amount of heat (kcal) that must be removed by the cooling coil
when this conversion is reached?
3. What is the maximum rate at which heat must be removed by the cooling coil
(kcal/min) and at what time does this maximum occur?
4. What is the adiabatic temperature rise for this reactor and what is its
significance?

Rate constant, k =0.01725 L/mol-min, at 270C

Heat of reaction, ΔH R =-10 k cal/mol A, at 270C
Partial molar heat capacities:
CPA =CPB =20 cal/mol-K, CPC =40 cal/mol-K
Reactor volume: VR =1200 L
 Solution to Q.2

1. Assuming -rA =-[dCA/dt]

constant density,
= kCACB = kCA2

Because from the stoichiometry of the

reaction, CA= CB

i.e. for 95% conversion

t=(1/0.01725)x(1/0.05x2.0-1/2.0)=551 min
2. What is the total amount of heat that must be removed?

Energy balance equation for the batch reactor with heat

transfer but isothermal conditions now becomes

in equation yields

* note the difference between the total heat transfer

and the rate of heat transfer
Integrating both sides of equation:

3.maximum rate at which heat must be removed by the cooling coil

(kcal/min) and at what time does this maximum occur?
Maximum cooling rate occurs when CA is maximum: CA= CA0 at t=0

4. The adiabatic temperature rise is calculated from the energy

balance for the case of no heat-transfer Q=0

Substituting from material balance dNA/dt =-rAVR and

multplying both sides by dt gives:

Integrating both sides of the equation: VR ρCPdT= ΔHRdNA

Δ T= ΔHR(NA –NA0)/VR ρCP

 Application to Flow Reactors in Steady State

• At steady state

•negligible shaft work,

• For negligible shaft work and adiabatic

operation: =0; and
-
ADIABATIC OPERATION: =0

• Hence

Assuming all components enter at temperature (T0)

And adding to numerator:

 Effects of inerts on T and X

•Slope is positive for exothermic reactions

•Slope increases with increase of inerts in feed
•As inerts are increased, the same conversion is
reached at a lower temperature
•Slope is negative for endothermic reactions
I

ADIABATICOPERATION: T vs. XA Q=0

Assumes negligible and exothermic reaction

Increasing slope

•Temperature increases with conversion for exothermic

reactions
•Temperature decreases with conversion for endothermic
reactions
•increasing inerts will increase and hence decrease
slope
 For adiabatic operation2
• *

•conversion increases for exothermic reactions

• The EB gives the relation between XA and
temperature at any point in the reactor
CSTR: For adiabatic IRREVERSIBLE
reaction
• If T or XA is known; to calculate V
• EB is used to calculate XA or T

• Substitute into MB to required volume:

• V=FA0 XA /(- rA)
• Remember(- rA)is a function of temperature
• Hence temperature is required to evaluate it
Q1
What temperature must the reactor be operated at to achieve
80% conversion in a CSTR?
Q2.
What is the heat duty of the heat exchanger inside the reactor?
What is the heat duty of the heat exchanger placed outside the
reactor if reactor effluent must be at 250C before storage
Approximate the heat capacity of the reaction mixture with that of
water.
CSTR: For adiabatic IRREVERSIBLE
reaction1
• If V is known: to calculate T or XA
• EB is used to calculate T as a function of XA

• MB is used to calculate T as a function of XA

• MB and EB solved simultaneously:
• -graphically
• numerically
 Graphical
630

620

610

600

590
EB
T

580

570

560

550

540
MB
530
0 0.2 0.4 0.6 0.8 1 1.2

XA
• Solution
•

As inerts are increased, you reach the same

conversion at a lower temperature
 CSTR with heat transfer:two methods
• Cooling coils
• Jackets
• Material balance unchanged, Neglecting volume of
coils
• EB: Neglecting Ws
• for high flow rate of coolant/heating fluid
• inlet temperature = outlet temperature
 CSTR with heat transfer2
substituting for yields

simplifying yields

This EB equation is solved simultaneously with the MB

Equation for T, XA and volume
PFR: For adiabatic IRREVERSIBLE reaction1
• negligible shaft work done on or by the fluid in a
PFR
• No Heat transfer- adiabatic reaction
• Hence temperature changes along the length of the
reactor
• conversion changes along the length of the reactor
• The EB is used to calculate the relation between XA
and temperature along the length of the reactor
 Algorithm Adiabatic Reactions:1
• Choose(initial) XA
• Calculate T from Adiabatic Energy Balance:

• Calculate k (Arrhenius equation)

• Calculate KC or Kp (Van't Hoff equation)-for
Reversible Reactions
• Calculate CA , CB e.g.
• [CA=FA/ υ =FA0(1-XA)T/T0υ0(1+εAXA)]
• Calculate -rA
 Algorithm Adiabatic Reactions:2
• Increment X and then repeat calculations.
• Plot FA0 /(-rA) vs. XA or
• use some numerical technique to find V
• Plot for an exothermic, adiabatic reaction
 Algorithm Adiabatic Reactions:3
XA T T/T0 k K -rA [FA0/-rA]

0
X1 T1 T1/T0

X2 T2 T2/T0

X3 T3 T3/T0
Q1:The vapour-phase cracking of acetone to ketene and methane:

is first-order with respect to acetone and the specific reaction rate

can be expressed by
where k is in s-1
and T is in Kelvin. In this design, it is desired to feed 8000 kg of
acetone per hour to a tubular reactor. The reactor consists of a bank
of 1000 tubes (o.D. = 26.6 mm). We will consider two cases:
(a) the reactor is operated adiabatically;
(b) The reactor is surrounded by a heat exchanger where the heat-
transfer coefficient is
and the ambient temperature is 1150 K.

(c)What is the arrangement of the tubes?

The inlet temperature and pressure are the same for both cases at 1035 K and 162
kPa, respectively

Solution:
Step1: XA=0

Step2:At XA=0, T = T0 = 1400K; TR=298K

DHr = SniDHi0 =cHC0+bHB0-aHA0=-1x74.81+1x[-61.09]-1x-216.67
=88.77 kJ/mole
Assume: CPA=13.39; CPB=20.04; CPC=26.63 J/mole-K

D CP  cCpC + bCpB-aCpA
26.63+20.0413.39
33.28J/mole-K 0.03328 kJ/mole-K

=1 X CPA =13.39=13.39 J/mole-K =0.0139 kJ/mole-K;

since only pure acetone was fed

Into energy balance equation yields;

T=1400-XA[88.77+0.03328 x( 1400-298)]/[0.01339+0.03328XA]

=1400-125.44XA/[0.01339+0.03328XA]

k=exp(34.34-34222/T); CA0=PA0/RT=162/8.309 X 1400=0.0139 mol/L

εA =[2-1]/1=1; CA=CA0 [1-XA]/(1+XA)
Two differential equations have two unknowns and can be
solved simultaneously
•total energy may be regarded as composed of many forms:
•total energy arise from the internal, kinetic and potential
energies.
•only these forms of energy considered here.