TEMPERATURE EFFECTS-

Part B 2018/2019 Session

Non-isothermal reactions
 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
•Data available in reference texts
TR: Reference temperature and pressure:
It is usually taken as the standard temperature and
pressure of the enthalpy of formation.
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 K?

What is ΔCp?

What is the heat of reaction at 4000C? 10

 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
15
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 ]

19
• 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 =

Substitute for Wf in Energy equation on previous slide

• then ,neglecting boundary work
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

24
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

43
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

EB

MB
 CSTR with heat transfer:two
methods-non adiabatic
• 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(equil. Const.)
• 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;

note: for reactant species
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: slide 128
•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.