Chemical Reaction Engineering -II

Spring 2023

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
Tue, 21/03/23

Heat of reaction from Thermodynamics

𝑎𝐴 → 𝑟𝑅 + 𝑠𝑆

The heat liberated or adsorbed during reaction at temperature T2 depends on the nature of the reacting system, the
amount of material reacting, and the temperature and pressure of the reacting system, and is calculated from the heat
of reaction ∆𝐻𝑟

Heat of Reaction and Temperature

The first task is to evaluate the heat of reaction at temperature T2 knowing the heat of reaction at temperature T1.
Following law of conservation of energy can be used:

(heat absorbed during = (heat added to + (heat absorbed + (heat added to products
reaction at temperature T2) reactants to change during reaction to bring them back to
their temperature from at temperature T2 from T1)
T2 to T1) T 1)

In terms of enthalpies of reactants and products this becomes

∆𝐻𝑟2 = − 𝐻2 − 𝐻1 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 + ∆𝐻𝑟1 + (𝐻2 − 𝐻1 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Where, subscripts 1 and 2 refer to quantities measured at temperatures T1 and T2 respectively. 2

In terms of specific heats
𝑇2
∆𝐻𝑟2 = ∆𝐻𝑟1 + න ∇𝐶𝑝 𝑑𝑇
𝑇1
Where,
∇𝐶𝑝 = 𝑟𝐶𝑝𝑅 + 𝑠𝐶𝑝𝑆 − 𝑎𝐶𝑝𝐴

And, 𝐶𝑝 is function of temperature

Equilibrium Conversion
𝐾2 1 𝑇2 ∆𝐻𝑟
𝑙𝑛 = න 𝑑𝑇
𝐾1 𝑅 𝑇1 𝑇 2
Following conclusions can be drawn from thermodynamics:

1. The thermodynamics equilibrium constant is unaffected by the pressure

of the system, by the presence or absence of inerts, or by the kinetics
of the reaction, but is affected by the temperature of the system.

2. Though the thermodynamic equilibrium constant is unaffected by

pressure or inerts, the equilibrium concentration of materials and
equilibrium conversion of reactants can be influenced by these
3
variables.
3. K>> 1 indicates that practically complete conversion may be possible and that the reaction can be considered as irreversible.
K<< 1 indicates that reaction will not proceed to any appreciable extent.

4. For an increase in temperature, equilibrium conversion rises for endothermic reactions and drops for exothermic reactions.

5. For an increase in pressure in gas reactions, conversion rises when the number of moles decreases with reaction; conversion
drops when the number of moles increases with reaction.

6. A decrease in inerts for all reactions acts in the way that an increase in pressure acts for gas reactions.

4
Q.1

(a) Between 0°C and 100°C determine the equilibrium conversion for the elementary aqueous reaction

°
𝐽 °
𝐽
𝐴↔𝑅 ∆𝐺298𝐾 = −14 130 ; ∆𝐻298𝐾 = −75 300
𝑚𝑜𝑙 𝑚𝑜𝑙

𝐶𝑝𝐴 = 𝐶𝑝𝑅 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Present the results in the form of a plot of temperature versus conversion.

(b) What restrictions should be placed on the reactor operating isothermally if we are to obtain a conversion of
75% or higher?

5
Wed, 22/03/23

General graphical design procedure

Figure shows different ways of representing the relationship of temperature, composition, and rate for a single homogeneous
reaction.

For a given feed (fixed CA0, CB0,…) and using conversion of key component as a measure of the composition and extent of
reaction, the 𝑋𝐴 𝑣𝑒𝑟𝑠𝑢𝑠 𝑇 plot has the general shape as shown in below figure.

General shape of the temperature-conversion plot for different reaction types

6
The above plot can be prepared either form a thermodynamically consistent rate expression for the reaction (the rate must be
zero at equilibrium) or by interpolating from a given set of kinetic data in conjunction with thermodynamic information on the
equilibrium.

The size of reactor required for a given duty and for a given temperature progression is found as follows:

1. Draw the reaction path on the 𝑋𝐴 𝑣𝑒𝑟𝑠𝑢𝑠 𝑇 plot. This is the operating line for the operation.

2. Find the rates at various 𝑋𝐴 along this path.

1
3. Plot the −𝑟 𝑣𝑒𝑟𝑠𝑢𝑠 𝑋𝐴 curve for this path.
𝐴

𝑉
4. Find the area under this curve. This gives 𝐹
𝐴0

Finding the reactor size for different types of flow

and for a feed temperature T1.
7
Mon, 27/03/23

Energy Balance for MFR

Inlet Outlet
ν, ρ, 𝐶𝑝 , 𝑇0 , 𝑋 = 0 ν, ρ, 𝐶𝑝 , 𝑇, 𝑋 = 𝑋𝐴

Energy balance:

Input = Output + Reaction + Heat removed by external means

νρ𝐶𝑝 𝑇0 = νρ𝐶𝑝 𝑇 + −𝑟𝐴 𝑉 ∆𝐻𝑟 + 𝑄

νρ𝐶𝑝 𝑇0 = νρ𝐶𝑝 𝑇 + ν𝐶𝐴0 𝑋𝐴 ∆𝐻𝑟 + 𝑄

For adiabatic, Q = 0
νρ𝐶𝑝 (𝑇0 − 𝑇) = ν𝐶𝐴0 𝑋𝐴 ∆𝐻𝑟

ρ𝐶𝑝 (𝑇0 − 𝑇) = 𝐶𝐴0 𝑋𝐴 ∆𝐻𝑟

∆𝐻𝑟 𝐶𝐴0
∆𝐻𝑟 𝐶𝐴0 β=
(𝑇0 − 𝑇) = 𝑋𝐴 ρ𝐶𝑝
ρ𝐶𝑝
∆𝐻𝑟 can be positive or negative
(𝑇0 − 𝑇) = β𝑋𝐴
8
 Inlet Outlet
ν, ρ, 𝐶𝑝 , 𝑇0 , 𝑋 = 0 𝑇 ν, ρ, 𝐶𝑝 , 𝑇, 𝑋 = 𝑋𝐴

𝑇𝐶
For non-adiabatic reactions,

𝑄 = 𝑈𝐴 (𝑇 − 𝑇𝐶 )

Exothermic, obtained from energy balance

With slope β

𝑇0
Further, the –rA and XA values can be obtained to compute volume required.
9
Q. 2
With the system of Q.1 and starting with an R-free solution, kinetic experiments in a batch reactor give 58.1% conversion
in 1 min at 65°C, 60% conversion in 10 min at 25°C. Assuming reversible first-order kinetics, find the rate expression for
this reaction and prepare the conversion-temperature chart with reaction rate as parameter.

10
Tue, 28/03/23

Optimum Temperature Progression

Operating lines for minimum reactor size

𝑉
Optimum temperature progression is defined to be that progress which minimizes 𝐹 for a given conversion of reactant.
𝐴0

This optimum may be an isothermal or it may be a changing temperature; in time for a batch reactor, along the length
of PFR or from stage to stage for a series of MFR.

It is important to know this progress because it is the ideal which we try to approach with a real system. It also allows us
to estimate how far any real system departs from this ideal.

The optimum temperature progression in any type of reactor: at any composition, it will always be at the temperature
where the rate is maximum. The locus of maximum rates is found by examining the 𝑟(𝑇, 𝐶) curves.
11
Note:

1. For irreversible reactions, the rate always increases with temperature at any composition, so the highest rate occurs at the
the highest allowable temperature. This temperature is set by the materials of construction or by the possible increasing
importance of side reactions.

2. For endothermic reactions, a rise in temperature increases both the equilibrium conversion and the rate of reaction. Thus,
as with irreversible reactions, the highest allowable temperature should be used.

3. For exothermic reversible reactions the situation is different, for here two opposing factors are working when the temp. is
raised- the rate of forward reaction speeds up but the maximum attainable conversion decreases.

Therefore, in general, a reversible exothermic reaction starts at a high temperature which decreases as conversion rises.

12
Heat effects
If the reaction is exothermic and if heat transfer is unable to remove all of the liberated hear, then the temperature of the
reacting fluid will rise as conversion rises.

Whereas, for endothermic reactions, the fluid cools as conversion rises.

Adiabatic Operations

Adiabatic operations with large enough heat effect to cause a rise in temperature (exothermic) or drop in temperature
(endothermic) in the reacting fluid

𝐶𝑝′ , 𝐶𝑝" = 𝑀𝑒𝑎𝑛 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑓𝑒𝑒𝑑 𝑠𝑡𝑟𝑒𝑎𝑚 𝑎𝑛𝑑 𝑜𝑓 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒𝑙𝑦 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑠𝑡𝑟𝑒𝑎𝑚 𝑝𝑒𝑟
mole of entering reactant A
𝐻′, 𝐻" = 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑓𝑒𝑒𝑑 𝑠𝑡𝑟𝑒𝑎𝑚 𝑎𝑛𝑑 𝑜𝑓 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒𝑙𝑦 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑠𝑡𝑟𝑒𝑎𝑚 𝑝𝑒𝑟
mole of entering reactant A
∆𝐻𝑟𝑖 = 𝐻𝑒𝑎𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑝𝑒𝑟 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝐴, 𝑎𝑛𝑑 𝑎𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇𝑖
13
With T1 as the reference temperature on which enthalpies and heats of reaction are based we have

Enthalpy of entering feed:

𝐻1′ = 𝐶𝑝′ 𝑇1 − 𝑇1 = 0 𝐽/𝑚𝑜𝑙𝐴

Enthalpy of leaving stream:

𝐻2" 𝑋𝐴 + 𝐻2′ (1 − 𝑋𝐴 ) = 𝐶𝑝" 𝑇2 − 𝑇1 𝑋𝐴 + 𝐶𝑝′ (𝑇2 − 𝑇1 )(1 − 𝑋𝐴 ) 𝐽/𝑚𝑜𝑙𝐴

Energy absorbed by reaction:

∆𝐻𝑟1 𝑋𝐴 𝐽/𝑚𝑜𝑙𝐴

Replacing these quantitates in the energy balance,

input= output + accumulation + disappearance by reaction

We obtain at steady state
0 = 𝐶𝑝" 𝑇2 − 𝑇1 𝑋𝐴 + 𝐶𝑝′ 𝑇2 − 𝑇1 1 − 𝑋𝐴 + ∆𝐻𝑟1 𝑋𝐴

By rearranging,
𝐶𝑝′ 𝑇2 − 𝑇1 𝐶𝑝′ ∆𝑇
𝑋𝐴 = =
−∆𝐻𝑟1 − (𝐶𝑝" − 𝐶𝑝′ ) 𝑇2 − 𝑇1 −∆𝐻𝑟1 − 𝐶𝑝" − 𝐶𝑝′ ∆𝑇 14
 𝐶𝑝′ ∆𝑇 ℎ𝑒𝑎𝑡 𝑛𝑒𝑒𝑑𝑒𝑑 𝑡𝑜 𝑟𝑎𝑖𝑠𝑒 𝑓𝑒𝑒𝑑 𝑠𝑡𝑟𝑒𝑎𝑚 𝑡𝑜 𝑇2
𝑋𝐴 = =
−∆𝐻𝑟2 ℎ𝑒𝑎𝑡 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑏𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑎𝑡 𝑇2
Which for complete conversion becomes
−∆𝐻𝑟2 = 𝐶𝑝′ ∆𝑇 for 𝑋𝐴 = 1
The heat released by reaction just balances the heat necessary to raise the reactants from T1 to T2.

Graphical representation of energy balance equation for adiabatic operation. These are adiabatic operating lines.

The resulting lines are straight for all practical purposes since the variation of the denominator term of these
equations is relatively small. When, 𝐶𝑝" − 𝐶𝑝′ = 0, the heat of reaction is independent of temperature:

𝐶𝑝 ∆𝑇
𝑋𝐴 =
−∆𝐻𝑟 15
Wed, 29/03/23
Best adiabatic operations

A single PFR are found by shifting the operating line

(changing the inlet temperature) to where the rates
have the highest mean value.

For endothermic operations, it starts at the highest allowable temperature.

For exothermic reactions, it straddles the locus of maximum rates. A few trials will locate the best inlet temperature, that
𝑉
minimizes 𝐹 . Note, for mixed flow, the reactor should operate on the locus of maximum rates.
𝐴0

Best reactor type

𝑉
is the one which minimizes 𝐹 , and found directly from 𝑋𝐴 𝑣𝑒𝑟𝑠𝑢𝑠 𝑇 graph. If the rate progressively decreases with
𝐴0
conversion, then use PFR. For instance, endothermic reactions and close to isothermal exothermic reactions.

For exothermic reactions that have a large temperature rise during reaction, the rate rises from a very low value to a maximum
at some intermediate 𝑋𝐴 , then falls. This behaviour is characteristic of autocatalytic reactions, thus recycle operations are best.
Note:
𝐶𝑝
1. For small −∆𝐻 (𝑝𝑢𝑟𝑒 𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) mixed flow is best
𝑟
𝐶𝑝
2. For large −∆𝐻 (𝑔𝑎𝑠 𝑤𝑖𝑡ℎ 𝑚𝑢𝑐ℎ 𝑖𝑛𝑒𝑟𝑡𝑠, 𝑜𝑟 𝑙𝑖𝑞𝑢𝑖𝑑 𝑠𝑦𝑠𝑡𝑒𝑚𝑠) plug flow is best. 16
𝑟
Finding reactor size for adiabatic operations of PFR and MFR.

17
18
Non-adiabatic Operations
Let Q be the total heat added to a reactor per mole of entering reactant A, and let this heat also include the losses to the
Surroundings. The energy balance about the system, is then modified to

Q = 𝐶𝑝" 𝑇2 − 𝑇1 𝑋𝐴 + 𝐶𝑝′ 𝑇2 − 𝑇1 1 − 𝑋𝐴 + ∆𝐻𝑟1 𝑋𝐴

𝑇2
Which on rearrangement and with ∆𝐻𝑟2 = ∆𝐻𝑟1 + න ∇𝐶𝑝 𝑑𝑇
𝑇1
Gives,

𝑛𝑒𝑡 ℎ𝑒𝑎𝑡 𝑠𝑡𝑖𝑙𝑙 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑓𝑡𝑒𝑟 ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑡𝑜 𝑟𝑎𝑖𝑠𝑒

𝐶𝑝′ ∆𝑇
−𝑄 𝑓𝑒𝑒𝑑 𝑡𝑜 𝑇2
𝑋𝐴 = =
−∆𝐻𝑟2 ℎ𝑒𝑎𝑡 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑏𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑎𝑡 𝑇2

And for, 𝐶𝑝" = 𝐶𝑝′

𝐶𝑝 ∆𝑇 − 𝑄
𝑋𝐴 =
−∆𝐻𝑟
With heat input proportional to ∆𝑇 = 𝑇2 − 𝑇1
The energy balance line rotates about 𝑇1 . Other modes of heat addition or removal yield corresponding shifts in the
energy balance line. 19
 Sketch of the energy balance equation showing the shift in adiabatic line caused by heat exchange with surroundings.

Ways to remove heat:

1. Heat exchange with incoming fluid
2. Multistage operations with inter-stage cooling between adiabatic sections

20
 For a given feed temperature T1 the intersection of the energy balance line with the S-shaped material balance line for
the operating τ gives the conditions within the reactor.

Three types of solutions to the energy and material balances for exothermic irreversible reactions.

1. The energy balance line T1A represents the situation where insufficient heat is liberated by reaction to raise the
temperature to a high enough level for the reaction to be self-sustaining. Hence, conversion is negligible.

2. At the other extreme, if we have more than enough heat liberated, the fluid will be hot and conversion essentially complete.
(shown by T1B).

3. Finally, line T1C indicates an intermediate solution which has three solutions to the material and energy balance equations,
points M’, M”, M”’.

21
Point M” is an unstable state because with a small rise in temperature the heat produced (with the rapidly rising material
balance curve) is greater than the heat consumed by the reacting mixture (energy balance curve). The excess heat
produced will make the temperature rise until M” is reached.

If the temperature drops slightly below M” it will continue to drop until M’ is reached. Thus, we look upon M” as the
ignition point. If the mixture can be raised above this temperature, then the reaction will be self-sustaining.

Solution of energy and material balances for reversible exothermic reaction. 22

Mon, 03/04/23

Q. 3
Using the optimal temperature progression in a PFR for the reaction of Q. 1 and Q.2,
(a) Calculate the space time and volume needed for 80% conversion of a feed of FA0= 1000mol/min, where
CA0 = 4mol/l
(b) Plot the temperature and conversion profile along the length of the reactor.

Let the maximum allowable operating temperature be 95°C.

23
24
Q. 4

𝑚𝑜𝑙
A concentrated aqueous A-solution of the previous question 𝐶𝐴0 = 4 𝑙
, 𝐹𝐴0 = 1000𝑚𝑜𝑙/𝑚𝑖𝑛 is to be 80%
converted in a mixed flow reactor.

(a) What is the size of reactor needed?

(b) What is the heat duty if feed enters at 25 °C and product is to be withdrawn at this temperature?

Note that
𝑐𝑎𝑙 1𝑘𝑔 1 𝑙𝑖𝑡𝑒𝑟 𝑐𝑎𝑙
𝐶𝑝𝐴 = 1000 ∙ ∙ = 250
𝑘𝑔 ∙ 𝐾 1 𝑙𝑖𝑡𝑒𝑟 4 𝑚𝑜𝑙 𝐴 𝑚𝑜𝑙 𝐴 ∙ 𝐾

25