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Ideal Reactors for a Single Reaction

Homogeneous reactions will be considered.

Batch Reactor

dXA
-rA=CA0 (constant volume)
dt

CA0 dXA
-rA= (volume varies)
1+dyAoXA dt
from these equations, given conversion vs. time (or some equivalent thereof) we can get
the rate law. Alternatively, the reactor can be designed (volume of reactor, time of
running for a given conversion) can be found given rate law.

Flow Reactors

Space-time and Space-velocity

t is space-time, the time required to process one reactor volume of feed at specified conditions, s is the space-
velocity, number of reactor volumes of feed at specified conditions that can be treated in unit time.

Example, space-time of 2 s means one reactor volume can be processed by given reactor in 2 s.

t and s are defined in terms of the feed stream:

CA0V V
t= =
v0 Note that residence time, which for the case of flow reactors is the average amount of time
v0
spent by molecule inside the reactor is
V
t=
v . The two are equivalent only for constant density systems since in other cases the inlet and outlet
volumetric flow rate are different (expansion factor). A

Space-time is a design variable and its definition arises naturally out of the material balance for CSTRs and
PFRs. It is based on inlet flow and concentration conditions. It is important to note the conditions at which
space-time is defined.

CSTR:

FA0-FA=(-rA)V or
CA0XA
t= assuming the initial feed stream has unconverted A. If the feed is partially converted,
(-rA)
CA0(XA-XA0)
t=
(-rA)exit For constant density,

t = CA0-CA

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(-rA) Thus given any three of V,FA0,XA,(-rA) the other one can be easily calculated. Note that the
reaction rate is relatively easily obtained in this case as compared to Batch reactor data (no need
for differentiation here). Graphically, we can represent these equations as:

Simplifications for first and second order reactions:

1. First order reaction

-rA=kCA so

CA0XA XA(1+dyAoXA)
t= =
kCA k(1-XA)
XA
kt = for constant density systems
1-XA
2. Second order reaction 2A- > Prodts

CA0XA XA(1+dyAoXA)2
t= =
kCA2 k(1-XA)2
XA
kCA0t = for constant density systems
(1-XA)2
The dimensionless group formed from k,t,CA0 is called the Damkohler number. Its
numerical value depends only on conversion for the case of isothermal CSTRs:

Reaction Type Da Variable Density Constant Density

First order kt XA(1+dyAoXA) XA

(1-XA) 1-XA

Second order, 2A- > Prodts kCA0t XA(1+dyAoXA)2 XA

(1-XA)2 (1-XA)2

Second order, A+B- > Prodts, CB0=MCA0 kCA0t XA(1+dyAoXA)2 XA

(1-XA)(M-XA) (1-XA)(M-XA)

nth order reaction -rA=kCAn kCA0n-1t XA(1+dyAoXA)n XA

(1-XA)n (1-XA)n

Damkohler number is extremely useful in design and scale-up of reactors.

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Example Problems

Ex. 5.20 Levenspiel.

CSTR, A- > R, aqueous solution of 100 mmol A/liter is fed to a 1 liter reactor. Outlet concentrations of A versus
flow rates are measured. Determine rate equation. Assume the reactant alone determines the rate.

v, l/min 1 6 24
CA, mmol/l 4 20 50
CA0-CA 96 80 50

-rA=v0(CA0-CA)/V, mmol/l/min 96 480 1200

Examining the data above, we see that the rate law is

-rA=24(min-1)CA

Note that in this case 'aqueous solution' gives us the hint that we are dealing with constant density system. Also,
in case the data did not look so perfect as above, we could have used graphical methods we know in order to
evaluate the reaction order and rate constant.

Ex. 5.4 L:

Plan to replace present CSTR with one having double the volume. For same aqueous feed (10 mol A/l) and same
feed rate find the new conversion. The reaction kinetics is given by : A- > R;-rA=kCA1.5 and the present
conversion is 70%.

2CA0v0XA1 CA0v0XA2
= since feed concentration and volumetric flow rate are unchanged.
kCA01.5(1-XA1) 1.5 kCA01.5(1-XA2)1.5

2XA1 XA2
1.5
=8.52=
(1-XA1) (1-XA2)1.5 Solving this non-linear equation, we get the new conversion to be 79.4%.

3. The kinetics of a 'simple isothermal homogeneous fluid reaction A + ... -> products' has been measured in a
CSTR by changing the residence time. (Separation method: the concentrations of the other components are kept
constant). The data is: CA,0 = 1 (mol/l)

tau (sec) 0.1 0.5 2 12 90

C(mol/l) 0.92 0.73 0.5 0.25 0.1

Calculate: conversion of A, reaction rate r(A), reaction order concerning A, and rate constant.

Answer: The reaction is of second order and has a rate constant of 1 (l/mol sec)

Plug Flow Reactor:

-rA=FA0 dXA
or since FA0 is constant,
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dV
XAf dXA
t = CA0
0 (-rA)

For constant density systems:

C
Af dCA
t=-
C (-rA)
A0

Simplifications for known rate law:

1. Zeroth Order: kt = CA0XA

2. First Order Irreversible: kt = -(1+dyAo)ln(1-XA)-dyAoXA

constant density: kt = -ln(1-XA)

Note that the equation describing the space-time for PFR is identical in form to the equation describing time in
batch reactor in case of constant density systems.

Example problems:

1. Derive the expression for a Damkohler number for PFR for first order reversible reaction A rR with
CR0/CA0=M and -rA=k1CA-k2CR and equilibrium conversion of XAe.

At equilbrium,

1-XAe M+rXAe
k1CA0( )=k2CA0( ) or
1+dyAoXAe 1+dyAoXAe

1-XAe
k2=k1( )
M+rXAe
XA (1+dyAoXA)dXA
t = CA0
0 k1CA0(1-XA)-k2CA0(M+rXA)

M+rXAe XA (1+dyAoXA)dXA
t=
k1 0 (1-XA)(M+rXAe)-(M+rXA)(1-XAe)

M+rXAe XA (1+dyAoXA)dXA
k1t =
M+r 0 XAe-XA

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M+rXAe XAe
k1t = (1+dyAoXA)ln( )-dyAoXA
M+r XAe-XA

Note that to solve PFR problems, integration is required, much like batch reactor systems.
E.g. 5.3 Levenspiel:

Elementary liquid phase reaction A+2B R with rate equation

-rA=-rB/2=[(12.5l2/mol2/min)CACB2-(1.5min-1)CR]mol/l/min

is to take place in a 6 l steady-state mixed flow reactor. Two feed streams, one containing 2.8 mol A/l and the
other containing 1.6 mol B/l are to be introduced at equation volumetric flow rates into the reactor. 75%
conversion of the limiting reactant is desired. What should be the flow rate of each stream? Assume constant
density.

Solution:

When the feed streams are mixed, volume is 2 liters. The number of moles of A and B are 2.8 and 1.6 moles
respectively. Therefore

CA0=1.4mol/l

CB0=0.8mol/l

CR0=0

The limiting reactant in this case has to be B, based on the initial concentrations and the stoichiometric
coefficients.

CB=0.8mol/l(1-0.75)=0.2mol/l

CA=1.4-0.75*0.8/2=1.1mol/l

CR=0.3mol/l

Therefore,

-rA=0.1mol/l/min

-rB=2(-rA)=0.2mol/l/min

v0=(-rB)V/(CB0-CB)=2l/min

2. P4.3 Fogler: Zeroth order reaction A- > 3B, gas-phase, isothermal. Initial concentration of A is 2 mol/l, there
are 40% inerts in the feed. Specific rate constant is 0.1 mol/l/min and activation energy is 40kJ/mol. Final
conversion required is 80%. in case of flow reactors, the volumetric flow rate to be used is 2 l/min. Calculate

(a) Time required in a constant volume batch reactor:

t=CA0XA/k=16min

(b) Time required in a constant pressure batch reactor

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1 dNA
- =k and NA=NA0(1-XA) and V=V0(1+(3-1)*0.6XA)=V0(1+1.2XA)
V dt
So,

CA0 XA dXA CA0

t= = ln(1+1.2XA)=11.2min
k 0 (1+1.2XA) 1.2k

(c) Volume required of a CSTR

V=FA0XA/k=v0CA0XA/k=32l

(d) Volume required of a PFR

v0CA0 X
V= 0 AdXA=32l
k
Flow Reactors in Series:

Often, more than one reactor is used to perform the reaction. The merits and demerits of this can be analysed
fairly easily for simple reactions.

Consider two CSTRs in series. Inlet molar flow rate into the first reactor is FA0, the conversion out of the first
reactor is X1 and this is the feed into the second reactor. The exit flow rate and conversion are FAe and Xe
respectively. If the rate equation is known (or if a graph of 1/-ra vs. Xa is given), we can calculate the volumes
of the two CSTRs through our material balance equations:

1
V1=FA0( )X
-rA1 1
FA1-FAe+rAeV2=0 but FA1=FA0(1-X1) and FAe=FA0(1-Xe) therefore,

1
V2=FA0( )(Xe-X1)
-rAe Thus, knowing the rate of the reaction at conversions corresponding to X1 and Xe, the
volume of the reactors can be found. If we were to use one single CSTR for converting to Xe,with
everythingelse the same, the volume of this reactor would be

1
V=FA0( )X
-rAe e
We can see that V V1+V2. This is easy to figure out graphically. Note that the depending on
whether reaction is positive or negative order in the reactant, and depending the intermediate conversion
required, the sum of the volumes of two CSTRs in series could be less than or more than volume of one reactor
achieving all the conversion.

Similarly for PFRs in series,

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dXA
V1=FA00X1 ;
(-rA)
dXA
V2=FA0X1Xe
(-rA) but in this case volume of a single reactor to achieve this conversion

dXA
V=FA00XAe =V1+V2
(-rA) and this fact is independent of the order of the reaction.

Other situations, such as CSTR followed by PFR and so on can be analysed in a similar manner through the use
of proper material balance equations.

Example problems.

1. n-Tanks In Series Model:

Consider a first order reaction in a series of n CSTRs of same volume. Develop a relationship between final
conversion and Damkohler number

C0X1 X1
t1= = or
-r1 k(1-X1)

kt1
X1= and
1+kt1
C0
C1=
1+kt1 Mole balance on reactor 2:

F1-F2=v0(C1-C2)=(-r2V2) or

C1-C2
t2= or
kC2
C1 C0
C2= =
1+kt2 (1+kt1)(1+kt2) Extending to n-reactors, we get

C0
Cn=
(1+kt1)(1+kt2)...(1+ktn) If all reactors are of same size and have same volumetric flow rate,

C0
Cn=
(1+kt)n

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Or, exit conversion,

1
X=1-
(1+kt)n

Plotting X vs. Da, we find that when Da> >1, 90% conversion is achieved in 2-3 reactors.

Reactors in Parallel:

For reactors in parallel, V/FA0 is equal for each parallel stream, assuming no mixing occurs before the final
outlet. Two CSTRs in parallel:

V1=FA01XA/(-rA); V2=FA02XA/(-rA) so the total volume of the two reactors is V=FA0XA/(-rA). Clearly, this is
the volume we would have required of a SINGLE CSTR to get to the same conversion.

Recall that the same result was obtained for PFRs in series. Thus, for CSTRs in parallel and PFRs in series, we
can analyse by replacing the reactor network with one large reactor. Looking at this from the other angle, if we
replace two CSTRs in series with a large CSTR of volume equal to the sum of volumes of the two CSTRs, then
the conversion obtained will be different. Likewise for two PFRs in parallel.

File translated from TEX by TTH, version 3.11.

On 24 Jan 2003, 11:41.

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