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Che 416 Lecture notes contd.

TEMPERATURE
EFFECTS
Why need to know?
TR: Reference temperature
and pressure:
It is usually taken as the
standard temperature and
pressure of the enthalpy of
formation.

Temperature effects

Real reactions may generate or absorb large amounts of heataffecting 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
Reference state: 25oC & 1 atm
Data available in reference texts

endothermic Reaction-how muchCalculated


heating isfrom
required
heat of? formation
Exothermic:
generate
heat,
and energy change to bring it from TR
Heat
of Reaction
/mole
A negative
Endothermic: absorb heat, positive to T
H 0: Heat of formation [kJ/mol] is zero

The enthalpy change


when stoichiometric quantities of
reactants
react Completely in a single reaction to
form products at the same temperature
H
the heat of reaction as written in the given
and
pressure.
R is
stoichiometry- energy per mole

t of reaction -the energy per mole of component i =

HR/

moles of i that reacted =(n - n )=


i0

lar rate of reaction of i =(Fi0 Fi )=


rate of heat release/absorption by reaction of
i=

Hr: change in enthalpy from reactants to products

Hproducts Hreactants = Hr(T,P),


Q = Hout - Hin = Hr
Units of Hr are energy per mole; e.g., kJ/mol.
Mole of what?
Consider the reaction:
A + 2B = 3D
Hr (energy per mole)
the energy change is as written in the stoichiometry of the
reaction.Hence
Hr 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 Cp?
What is the heat of reaction at 4000C?
What assumption have you made?

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)

=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:

Control
volume of
reactor

Fi0,Ti0,Ei0, CPi0,Pi0, Hi0

Ws

Outflow stream:
Fi, Ti, Ei, CPi,Pi, Hi

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 ]
+[ rate of work done on system ] (1)

Complete energy analysis is complicated

simplified assumptions often made!

convenient to split the work term into 3 parts:


Wf , the work done by the flowing 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

bstituting for Wf in equation

balance equation 2 may be written in terms of enthalpy


(Hi= Ui+PVi) as follows:

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:
*

o balance equation: second value shouldnt be there

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 w

Rate of work due to change in


volume:

rom 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,
H 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
constant density,

-rA =-[dCA/dt]
= kCACB = kCA2

Because from the stoichiometry of


the reaction, CA= CB

e. for 95% conversion

1/0.01725)x(1/0.05x2.0-1/2.0)=551 min

hat 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 (i.e. No heat transfer) temperature rise


is calculated from the energy balance for the case of no
heat-transfer Q=0

stituting from material balance dNA/dt =-rAVR and


ltplying both sides by dt gives:

egrating both sides of the equation: V

T= HR(NA NA0)/VR CP

CPdT= HRdNA

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

uming all components enter at temperature (T 0)


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 @ higher T
As inerts are increased, the same
conversion is reached at a lower
temperature

ADIABATICOPERATION: T vs. XA
Assumes negligible and
Q=0 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

Foradiabatic operation2

conversion increases for exothermic reactions


The EB (Energy Malance) 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 (Material Balance) to get


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

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

Graphical
640

620

600

580

EB

560

540

520

500

MB

480
0

0.2

0.4

0.6

XA

0.8

1.2

Solution

As inerts are increased, you reach


the same conversion at a lower
temperature

CSTR with heat transfer (non adiabatic):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/ =FA0(1-XA)T/T00(1+AXA)]
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/T0

X1

T1

T1/T0

X2

T2

T2/T0

X3

T3

T3/T0

-rA

[FA0/rA]

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

Hr = iHi0 =cHC0+bHB0-aHA0=-1x74.81+1x[-61.09]-1x216.67
=88.77 kJ/mole

me: CPA=13.39;

CPB=20.04; CPC=26.63 J/mole-K

CP cCpC + bCpB-aCpA

J/mole-K kJ/mole-K

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


since only pure acetone was fed

o 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]

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

[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.