1

Residence Time Distribution for

Chemical Reactors

2
General Characteristics
The two major uses of the residence time distribution to characterize nonideal reactors
are
1. To diagnose problems of reactors in operation
2. To predict conversion or effluent concentrations in eisting!available reactors when
a new reaction is used in the reactor.
"ot all molecules are spending
the same time in the reactor.
Three concepts were used to describe
nonideal reactors# the distribution of
residence times in the s$stem% the
&ualit$ of miing and the model used
to describe the s$stem.
3
Residence'Time Distribution (RTD)
*unction
+The time the atoms have spent in the reactor is called the residence time
of the atoms in the reactor.
+,n an$ reactor% the distribution of residence times can significantl$ affect
its performance.
+The residence'time distribution (RTD) of a reactor is a characteristic of
the miing that occurs in the chemical reactor.
+"ot all RTDs are uni&ue to a particular reactor t$pe- mar.edl$ different
reactors can displa$ identical RTDs.
+The RTD ehibited b$ a given reactor t$pe $ields distinctive clues to the
t$pe of miing occurring within it and is one of the most informative
characterizations of the reactor.
4
/easurement of the RTD
+The RTD is determined eperimentall$ b$ injecting an inert chemical% molecule%
or atom% called a tracer% into the reactor at some time t01 and then measuring
the tracer concentration% C% in the effluent stream as a function of time.
+,n addition to being a nonreactive species that is easil$ detectable% the tracer
should have ph$sical properties similar to those of the reacting miture and be
completel$ soluble in the miture.
+,t also should not adsorb on the walls or other surfaces in the reactor. The latter
re&uirements are needed so that the tracer2s behavior will honestl$ reflect that
of the material flowing through the reactor.
+Colored and radioactive materials along with inert gases are the most common
t$pes of tracers.
5
3ulse ,nput 4periment
,n a pulse input% an amount of tracer "
1
is suddenl$ injected in one shot
into the feedstream entering the reactor in as short a time as possible.
*irst% we choose an increment of time t
sufficientl$ small that the concentration of
tracer% C(t)% eiting between time t and t5t
is essentiall$ the same. The amount of tracer
material% "% leaving the reactor between
time t and t5t is then
6e shall anal$ze the injection of a tracer
pulse for a single'input and single'output
s$stem in which onl$ flow carries the
tracer material across s$stem
boundaries.
t v ) t ( C N
t
N
v ) t ( C
N
N
0 0

" is the amount of material eiting the reactor

that has spent an amount of time between t and
t5t in the reactor.
v is the effluent volumetric flow rate representing the fraction of material
that have a residence time in the
reactor between time t and t5t
6
0
N
v ) t ( C
) t ( E
*or pulse injection we define
t ) t ( E
N
N
0

residence'time distribution function

describing in a &uantitative manner
how much time different fluid elements

have spent in the reactor
The &uantit$ 4(t)dt is the fraction of fluid eiting the reactor that has spent between
time t and t5dt inside the reactor.
vdt ) t ( C dN
vdt ) t ( C N
0
0

dt ) t ( C
) t ( C
) t ( E
0

dt ) t ( E
and t n t mes betwee for ti
ctor in the rea s resided that ha
he reactor leaving t f material Fraction o
2
1
t
t
2 1

1
1
1
]
1

1 dt ) t ( E
0

7
4ample 17'1
8 sample of the tracer h$tane at 721 9 was injected as pulse to a reactor% and the effluent
concentration was measured as a function of time% resulting in the data shown in Table 417'1.1.
The measurement represent the eact concentrations at the times listed and not average values
between the various sampling tests.
(a) Construct figures showing C(t) and 4(t) as functions of time.
(b) Determine both the fraction of material leaving the reactor that has spent between 7 and :
min in the reactor and the fraction of material leaving the reactor that has spent between
;.;< and =.2< min in the reactor% and
(c) determine the fraction of material leaving the reactor that has spent 7 min or less in the
reactor.
8
>olution
(a)
dt ) t ( C dt ) t ( C dt ) t ( C
14
10
10
0 0

+

3
14
10
3
10
0
m min/ g 6 2 ! 0 ) 6 0 ( 4 " 1 #
3
2
dt ) t ( C
m min/ g 4 4$
)! " 1 ( 1 ) 2 2 ( 4 ) 0 3 ( 2 ) 4 ( 4
) 6 ( 2 ) % ( 4 ) 10 ( 2
) % ( 4 ) " ( 2 ) 1 ( 4 ) 0 ( 1 #
3
1
dt ) t ( C
+ +

+ + + +
+ + +
+ + +

3
14
10
10
0 0
m min/ g 0 "0 6 2 4 4$
dt ) t ( C dt ) t ( C dt ) t ( C
+
+

9
vdt ) t ( C
) t ( C
) t ( E
0

3
0
m min/ g 0 "0 dt ) t ( C

(b)
"1 0 ! 12 0 ) 16 0 ( 3 ) 2 0 ( 3 16 0 )# 1 (
%
3
dt ) t ( E
6
3
+ + +

6e find that <1? of material leaving the reactor spends

between 7 and : min in the reactor.
03 0 min ) $" $ 2" % min)( 06 0 ( t E dt ) t ( E
average
2" %
$" $

6e find that 7? of material leaving the reactor spends

between ;.;< and =.2< min in the reactor.
10
(c)
area01.21
6e see that 21? of the material has spent
7 min or less in the reactor.
6e see that =1? of the material has spent 7 min or more in the reactor.
11
+The principal difficulties with the pulse techni&ue lie in the problems connected
with obtaining a reasonable pulse at a reactor2s entrance.
+The injection must ta.e place over a period which is ver$ short compared with
residence times in various segments of the reactor or reactor s$stem% and there must
be a negligible amount of dispersion between the point of injection and the entrance
to the reactor s$stem.
+There are problems when the concentration'time curve has a long tail because the
anal$sis can be subject to large inaccuracies. This problem principall$ affects the
denominator of the right'hand side of the following e&uation
,t is desirable to etrapolate the tail and anal$ticall$ continue the calculation.
+The tail of the curve ma$ sometimes be approimated as an eponential deca$. The
inaccuracies introduced b$ this assumption are ver$ li.e to be much less than those
resulting from either truncation or numerical impression in this region.
dt ) t ( C
) t ( C
) t ( E
0

12
>tep Tracer 4periment
The output concentration from a vessel is related to the input concentration
b$ the convolution integral#
& dt ) & t ( E ) & t t ( C ) t ( C
t
0
in o't


pulse input
step input

'

<

0 t t tan cons ) C (
0t 0
) t ( C
0
in
constant volumetric rate
& dt ) & t ( E C ) t ( C
t
0
0 o't

) t ( F & dt ) & t ( E
C
) t ( C
t
0
ste(
0
o't

1
]
1

cumulative distribution
ste(
0
o't
C
) t ( C
dt
d
) t ( E
1
]
1

13
+The positive step is usuall$ easier to carr$ out eperimentall$ than the
pulse test% and it has the additional advantage that the total amount of
tracer in the feed over the period of the test does not have to be .nown
as it does in the pulse test.
+@ne possible drawbac. in this techni&ue is that it is sometimes difficult
to maintain a constant tracer concentration in the feed.
+@btaining the RTD from this test also involves differentiation of the
data and presents an additional and probable more serious drawbac.
to the techni&ue% because differentiation of data can% on occasion% lead
to large errors.
+8 third problem lies with the large amount of tracer re&uired for this
test. ,f the tracer is ver$ epensive% a pulse test is almost alwa$s used to
minimize the cost.
14
Characteristics of the RTD
>ometimes 4(t) is called the eit'age distribution function. ,f we regard the AageB of
an atom as the time it has resided in the reaction environment% then 4(t) concerns the
age distribution of the effluent stream. ,t is the most used of the distribution function
connected with reactor anal$sis because it characterizes the length of time various
atoms spend at reaction conditions.
,ntegral
Relationships
) t ( F
t than time for less
ctor een in rea that has b
nt of effl'e Fraction
dt ) t ( E
t
0

1
1
1
]
1

) t ( F 1
me t er than ti for long
ctor een in rea that has b
nt of effl'e Fraction
dt ) t ( E
t

1
1
1
]
1

cumulative distribution function

6e can calculate *(t) at various
times t from the area under the
curve of an 4(t) versus t plot.
15
+The * curve is another function that has been defined as the normalized
response to a particular input.
+8lternativel$% the following e&uation has been used as a definition of
*(t)% and it has been stated that as a result it can be obtained as the
response to a positive'step tracer test.
+>ometimes the * curve is used in the same manner as the RTD in the
modeling of chemical reactors.
dt ) t ( E ) t ( F
t
0

16
/ean Residence Time
dt ) t ( tE
dt ) t ( E
dt ) t ( tE
t
0
0
0
m

6e have a reactor completel$ filled with maize molecules. 8t time t01 we start blue
molecules to replace the maize molecules that currentl$ fill the reactor. ,nitiall$% the
reactor volume C is e&ual to the volume occupied b$ the maize molecules. "ow% in a
times dt% the volume of molecules that will leave the reactor is (vdt). The fraction of
these molecules that have been in the reactor a time t or greater is D1'*(t)E. Fecause
onl$ the maize molecules have been in the reactor a time t or greater% the volume of
maize molecules% dC% leaving the reactor in a time dt is
)! t ( F 1 )# vdt ( d) )! t ( F 1 )# vdt ( d) dt )! t ( F 1 # v )
0

volumetric flow
is constant

0
dt )! t ( F 1 # v )

+ +

1
0
1
0
0
tdF 0 tdF )! t ( F 1 # t
v
)
dt ) t ( E dF
m
0
t dt ) t ( tE

v
)

*or li&uid reactions% no change in
volumetric flow rate.
*or gas reactions% no pressure drop%
isothermal operation% and no change
in the total number of moles (01). ) * 1 /( t
m
+
17
@ther /oments of the RTD
dt ) t ( E ) t t (
0
2
m
2

Cariance or s&uare of the standard deviation is defined as
The magnitude of this moment is an indication of
the AspreadB of the distribution- the greater the
value of this moment is% the greater a distribution2s
spread will be.
>.ewness is defined as
dt ) t ( E ) t t (
1
s
0
3
m
2 / 3
3

The magnitude of this moment measures the

etent that a distribution is s.ewed in one
direction or another in reference of the
mean.
18
4ample 17'2
Calculate the residence time and the variance for the reactor characterized in 4ample 17'1
b$ the RTD obtained from a pulse input at 721 9.
>olution
min 1" " "$3 0 "% 4
! 0 ) 14 0 ( 4 3 0 #
)! 3 0 ( 1 ) 40 0 ( 4 ) 4% 0 ( 2 ) "6 0 ( 4 ) $2 0 ( 2
) % 0 ( 4 ) % 0 ( 2 ) 4% 0 ( 4 ) 2 0 ( 2 ) 02 0 ( 4 ) 0 ( 1 #
dt ) t ( tE dt ) t ( tE dt ) t ( tE t
3
2
3
1
14
10
10
0 0
m
+
+ + +
+ + + + +
+ + + + +
+

19
2
0
2
m
2
min 11 6
dt ) t ( E ) t t (

2
m
0
2
2
m
2
m
0
2
0
2
m
0
m
0
2
0
2
m
2
t dt ) t ( E t
t t 2 dt ) t ( E t
dt ) t ( E t dt ) t ( tE t 2 dt ) t ( E t
dt ) t ( E ) t t (

+
+

2
2
3
2
3
1
14
10
2
10
0
2
0
2
min $1 32
min ! 0 ) $3 1 ( 4 0 3 # ! 0 3 ) "6 3 ( 4
) %4 3 ( 2 ) +2 3 ( 4 ) 32 4 ( 2 ) 0 4 ( 4
) 2 3 ( 2 ) 44 1 ( 4 ) 4 0 ( 2 ) 02 0 ( 4 0 #
dt ) t ( E t dt ) t ( E t dt ) t ( E t

+ + + + +
+ + + +
+ + + +
+

2 2 2
m
0
2 2
min 1+ 6 ) 1" " ( $1 32 t dt ) t ( E t

20
"ormalized RTD *unction%
4()
,f the parameter is defined as

t
a dimensionless function 4() can be defined as
The &uantit$ represents the number of reactor
volumes of fluid based on entrance conditions that
have flowed through the reaction in time t.
The purpose of creating this normalized distribution is that the flow
performance inside reactors of different sizes can be compared
directl$.
+,f the normalized function 4() is used% all perfectl$ mied C>TRs
have numericall$ the same RTD.
+,f the simple function 4(t) is used% numerical values of 4(t) can differ
substantiall$ for different C>TRs.

/ t
e
1
) t ( E

e ) t ( E ) ( E
1 d ) ( E
0

) t ( E ) ( E
21
,nternal'8ge Distribution% ,()
+,() is the fraction of material inside the reactor that has been inside
the
reactor for a period of time between and 5.
+4() is the fraction of material leaving the reactor that has spent for a
time between and 5 in the reactor.

) ( F 1
) ( ,

d
)! ( , # d
) ( E
dt
) t ( dF
) t ( E
*or a C>TR%

/
e
1
) ( ,
22
RTD in ,deal Reactors
RTD in Fatch and 3lug'*low Reactors
8ll the atoms leaving such reactors have spent precisel$ the same amount of time
within the reactors.
The distribution function in such a case is a spi.e of infinite height and zero
width%
whose area is e&ual to 1- the spi.e occurs at t0C!v0% or 01.
) t ( ) t ( E

'

0 0
) ( g d- ) - ( ) - ( g 1 d- ) - (
0 when -
0 when - 0
) - (



dt ) t ( t dt ) t ( tE t
0 0
m
0 dt ) t ( ) t ( dt ) t ( E ) t t (
0
2
0
2
m
2



dt ) t ( dt ) t ( E ) t ( F
t
0
t
0


8ll material spends eactl$ a time
in the reactor% there is no varianceG
23
>ingle'C>TR RTD
8 material balance on an inert tracer that has been injected as a pulse at time
t01 into a C>TR $ields for tH1
dt
dC
) vC 0
on .cc'm'lati /'t ,n

Fecause the reactor is perfectl$ mied% C in this
e&uation is the concentration of the tracer either
in the effluent or within the reactor.
0 at t C C
0

/ t
0
e C ) t ( C

/ t
/ t
0
0
/ t
0
0
e
dt e C
e C
dt ) t ( C
) t ( C
) t ( E
) t ( E ) ( E

t

e ) ( E

e 1 d ) ( E ) ( F
0

dt e
t
dt ) t ( tE t
0
/ t
0
m
2
0
- 2 2
0
/ t
2
2
d- e ) 1 - ( dt e
) t (

24
Iaminar *low Reactor
(I*R)
*or laminar flow in a tubular reactor% the
velocit$ profile is parabolic% with the fluid in
the center of the tube spending the shorter
time in the reactor. 8 schematic diagram of
the fluid movement after a time t is shown in
*igure 17'=. The figure at the left shows
how far down the reactor each concentric
fluid
element has traveled after a time t.
1
1
]
1

,
_

1
1
]
1

,
_

1
1
]
1

,
_

2
2
0
2
avg
2
ma-
0
r
1
0
v 2
0
r
1 1 2
0
r
1 1 1
J
ma
is the centerline velocit$
J
avg
is the average velocit$ through
the tube.
J
avg
is the volumetric flow rate
divided b$ the cross'sectional area.
! ) 0 / r ( 1 # 2 ! ) 0 / r ( 1 # 2
1
v
2 0
) r ( 1
2
) r ( t
2 2
0
2

The time of passage of an element of fluid at a radius r is
25
The volumetric flow rate of fluid out between r and r5dr% dv% is
rdr 2 ) r ( 1 dv
The fraction of total fluid passing between r and r5dr% dv!v
1
% is
0 0
v
rdr 2 ) r ( 1
v
dv

) r ( 1
2
) r ( t

,
_

0 0
v
rdr 2
t
2
v
dv
! ) 0 / r ( 1 # 2
) r ( t
2

rdr
0
t 4
rdr
! ) 0 / r ( 1 #
2 /
0
4
! ) 0 / r ( 1 # 2
rdr 2
0
dt
2
2
2
2 2 2 2 2

'

dt
t 4
0
rdr
2
2

dt ) t ( E dt
t 2
dt
t 4
0
v
2
t
2
v
rdr 2
t
2
v
dv
3
2
2
2
0 0 0

,
_

,
_

2 / t
t 2
2 /t 0
) t ( E
3
2

'

<

2 v 2
)
0
0
1 2
2
1
2
t
0
2
2
avg ma-
min

,
_

26
2
2
t
2 /
3
2
t
2 /
3
2
t
2 /
t
0
t
1 dt
t
1
2
dt
t 2
dt ) t ( E 0 dt ) t ( E ) t ( F

dt
t
1
2
dt ) t ( tE t
2 /
2
2
0
m

" 0
2
1
" 0 0
) ( E
3

'

<

,
_

+


2
2 / 1
3
0
4
1
1 d
2
1
0 d ) ( E ) ( F

" 0
4
1
1
" 0 0
) ( F
2

'

,
_

<

27
Diagnostics and Troubleshooting
General Comments
*igure 17'11(a) and (b) correspond to nearl$
ideal 3*Rs and C>TRs% respectivel$.
*igure 17'11(d) shows that a principal pea.
occurs at a time smaller than the space time
(0C!v
1
) (i.e. earl$ eit of fluid) and also that
some fluid eits at a time greater than space'
time . This curve could be representative of
the RTD for a pac.ed'bed reactor with
channeling and dead zones shown in *igure
17'11(c).
*igure 17'11(f) shows the RTD for the
nonideal C>TR in *igure 17'11(e)% which has
dead zones and b$passing. The dead zone
serves to reduce the effective reactor volume%
so the active reactor volume is smaller than
epected.
28
>imple Diagnostics and Troubleshooting Jsing the RTD for ,deal Reactors
C>TR

/ t
0
e C ) t ( C

/ t
e
) t ( E


/ t
e 1 ) t ( F
0
v
)

3erfect @peration (3)
,f is large% there will be a slow deca$ of the output transient% C(t)% and
4(t) for a pulse input.
,f is small% there will be rapid deca$ of the transient% C(t)% and 4(t) for a
pulse input.
29
F$passing (F3)
b 34 0
v v v +
0 34
v v <
>
34
v
1
is the total volumetric flow rate
v
>F
is the volumetric flow rate entering the s$stem volume
v
b
is the volumetric flow rate b$passing the reactor
The space time%
>F
% will be greater than that if there
were no b$passing. Fecause
>F
is greater than there
will be a slower deca$ of the transients C(t) and 4(t)
than of perfect operation.
34
/ t
0
2
34
0
b
e
)v
v
) 0 t (
v
v
) t ( E

+
Kaving an initial jump e&ual
to the fraction b$'passed.
30
Dead Colume (DC)
35 5
) ) ) + ) )
35
< <
35
C is the total volume
C
D
is the dead volume
C
>D
is the s$stem volume
The transients C(t) and 4(t) will deca$ more rapidl$ than that for perfect
operation because there is a smaller s$stem volume.
31
>ummar$
32
3*R
0
v
)

>
34 0 34
v v <
3erfect @peration (3)
F$passing (F3)
Dead Colume (DC)
) )
35
< <
35
33
>ummar$
34
3*R!C>TR >eries RTD
The reacting miture ma$ follow a somewhat tortuous path
either before entering or after leaving the perfectl$ mied
zone'or even both. This tortuous path ma$ be modeled as a
plug'flow reactor. Thus this t$pe of tan. reactor ma$ be
modeled as a C>TR in series with a plug'flow reactor% and
the 3*R ma$ either precede or follow the C>TR.

t
e
t 0
) t ( E
(
s
/ ) t (
(
s 6

'

<

s
is the residence time in the C>TR

p
is the residence time in the 3*R
The output will be dela$ed b$ a time
p
at the outlet of the plug'flow section
3*R5C>TR
t
e
t 0
) t ( E
(
s
/ ) t (
(
s 6

'

<

,f the pulse of tracer is introduced into
the entrance of the plug'flow section%
then the same pulse will appear at the
entrance of the perfectl$ mied section

p
seconds later.
35
4ample 17'7
Consider a second'order being carried out in a real C>TR that can be modeled as two
different reactor s$stems# ,n the first s$stem an ideal C>TR is followed b$ an ideal 3*R-
in the second s$stem the 3*R precedes the C>TR. Iet
s
and
p
each e&ual 1 min% let the
reaction rate constant e&ual 1.1 m
7
!.molmin% and let the initial concentration of li&uid
reactant% C
81
% e&ual 1 .mol!m
7
. *ind the conversion in each s$stem.
>olution
8 mole balance on the C>TR section gives
) 7C ) C C ( v
2
.i .i 0 . 0

0 C C 7C
0 . .i
2
.i s
+
7 2
1 7C 4 1
C
s
0 . s
.i

3
.i
m / 7mol 61% 0
2
1 4 1
C
+

8 mole balance on the 3*R section gives

2
. .
(
. .
0
.
7C r
d
dC
d)
dC
v
d)
dF

7
C
1
C
1
(
.i .

1
61% 0
1
C
1
.

3
.
m / 7mol 3%2 0 C
8 % 61 61% 0
1
3%2 0 1
*

36
7
C
1
C
1
(
0 . .i

1
1
1
C
1
.

3
.
m / 7mol " 0 C
0 C C 7C
.i .
2
. s
+
3
s
.i s
.
m / 7mol 366 0
1
1 2 1
7 2
1 7C 4 1
C
+

The conclusions from this eample are of etreme importance in reactor anal$sis#
+The RTD is not a complete description of structure for a particular reactor or s$stem
of reactors.
+The RTD is uni&ue for a particular reactor% however% the reactor or reaction s$stem is
not uni&ue for a particular RTD.
+,n addition to the RTD% an ade&uate model of the nonideal reactor flow pattern and
.nowledge of the &ualit$ of miing or Adegree of segregationB are both re&uired to
characterize a reactor properl$.
37
Reactor /odeling Jsing the RTD
RTD
/odel
9inetic Data
4it Concentration
4it Conversion
RTD tells us how long the various fluid elements have been in the reactor% but it
does not tell us an$thing about the echange of matter between the fluid elements
(i.e.% the miing).
) * 1 ( 7
dt
d*

The conversion is independent of concentration
*or reactions other than first order% the degree of
miing of molecules must be .nown in addition to
how long each molecule spends in the reactor.
38
+/acromiing produces a distribution of residence times without specif$ing how
molecules of different ages encounter one another in the reactor.
+/icromiing describes how molecules of different ages encounter one another in
the reactor.
+Complete segregation# all molecules of the same age group remain together as the$ travel
through the reactor and are not mied with an$ other age until the$ eit the reactor.
+Complete micromiing# molecules of different age groups are completel$ mied at the
molecular level as soon as the$ enter the reactor.
*or a given sate of macromiing (i.e.% a given RTD)% these two etremes
of micromiing will give the upper and lower limits on conversion in a
nonideal reactor.
*or reaction orders greater than one or less than zero% the segregation
model will predict the highest conversion.
*or reaction orders between zero and one% the maimum miedness
model will predict the highest conversion.
39
8 fluid in which the globules of a given age do not mi
with other globules is called a macrofluid. 8 macrofluid
could be visualized as noncoalescent globules where all
the molecules in a given globule have the same age.
8 fluid in which molecules are not constrained
to remain in the globule and are free to move
ever$where is called a microfluid.
late miing + complete segregation
earl$ miing + maimum miedness
40
Lero'3arameter /odels
>egregation /odel
,n the segregated flow model we visualize the flow
though the reactor to consist of a continuous series
of globules (*igure 17'22).
,f fluid elements of different ages do not mi together at all% the elements remain
segregated from each other% and the fluid is termed completel$ segregated.
These globules retain their identit$- that is% the$ do not interchange
material with other globules in the fluid during their period of residence
in the reaction environment% i.e.% the$ remain segregated.
,n addition% each globule spends a different amount of time in the reactor.
6hat we are doing is lumping all the molecules that have eactl$ the same
residence time in the reactor into the same globules.
41
Fecause the fluid flows down the reactor in plug flow% each eit stream corresponds
to a specific residence time in the reactor.
Fatches of molecules are removed from the reactor at different locations along the
reactor in such a manner as to duplicate the RTD function% 4(t).
The molecules removed near the entrance to the
reactor correspond to those molecules having
short residence times in the reactor.
This effluent would correspond to the molecules
that channel rapidl$ through the reactor.
The farther the molecules travel along the reactor
before being removed% the longer their residence
time.
The points at which the various groups or batches
of molecules are removed correspond to the RTD
function for the reactor.
42
Fecause there is no molecular interchange between globules% each acts essentiall$
as its own batch reactor. The reaction time in an$ one of these tin$ batch reactors
is e&ual to the time that the particular globules spends in the reaction
environment.
1
1
1
1
1
1
]
1

1
1
1
1
]
1

1
1
1
1
1
1
]
1

+
r reacto
dt in the and t
een t s(end betw
s that of glob'le
on fracti
e reactor in th
e t ding a tim after s(en
es n a glob'l achieved i
sion conver
actor in the re
dt t time t and
etween s(ending b
lob'les of those g
rsion mean conve
dt ) t ( E ) t ( * * d
) t ( E ) t ( *
dt
* d

0
dt ) t ( E ) t ( * *
,f we have the RTD% the reaction rate epression% then for a segregated flow
situation (i.e.% model)% we have sufficient information to calculate the
conversion.
43
Consider a first'order reaction
(rod'ct .
7

) r
dt
dN
.
.

) * 1 ( N N
0 . .

) * 1 ( 7N 7N ) 7C ) r
dt
d*
N
0 . . . . 0 .

) * 1 ( 7
dt
d*

7t
e 1 ) t ( *

0
dt ) t ( E ) t ( * *

0
7t
0 0
7t
dt ) t ( E e dt ) t ( E dt ) t ( E ) e 1 ( *

0
7t
dt ) t ( E e 1 *
44
4ample 17'M
Derive the e&uation of a first'order reaction using the segregation model when the RTD is
e&uivalent to (a) an ideal 3*R% (b) an ideal C>TR% and (c) a laminar flow reactor. Compare
these conversions with those obtained from the design e&uation.

0
7t
dt ) t ( E e 1 *
>olution
(a) 3*R
) t ( ) t ( E
5a 7
0
7t
e 1 e 1 dt ) t ( e 1 *

) * 1 ( 7
d
d*

5a 7
e 1 e 1 *


(b) C>TR

0
7t
dt ) t ( E e 1 *
5a 1
5a
7 1
7

e
1
/ 1 7
1
1 dt
e
1 *
0
t ) 7 / 1 (
0
t ) 7 / 1 (
+

+
+

) r * F
. 0 .

/ t
e
1
) t ( E
) ) * 1 ( 7C * C v
0 . 0 . 0

7 1
7
*
+

45
(c) laminar flow reactor

2 / t
t 2
2 /t 0
) t ( E
3
2

'

<

" 0
2
1
" 0 0
) ( E
3

'

<

0
7t
dt ) t ( E e 1 *

0
7
d ) ( E e 1 *

" 0
3
7
d
2
e
1 *

d
e
) 7 " 0 ( e ) 7 " 0 1 ( 1 *
" 0
7
2 7 " 0
5a e ) 5a 4 (
4 5a e ) 5a 4 (

5a 2" 0 e ) 5a 2" 0 1 (
1
1
7 2" 0 e ) 7 2" 0 1 (
1
1 *
5a " 0
5a " 0
5a " 0 7 " 0
a((ro-
+ +
+ +

+ +

+ +

46
*or large values of Dam.ohler number then% there is
complete conversion along the streamlines off the center
streamline so that the conversion is determined along
the pipe ais such that
7
e 4
1 d e 4 1 *
7 " 0
" 0
7

" 0
3
7
d
2
e
1 *
" 0
7 e arg l
47
+6e have just shown for a first'order reaction that whether $ou
assume complete micromiing or complete segregation in a C>TR% the
same conversion results.
+This phenomenon occurs because the rate of change of conversion for
a first'order does not depend on the concentration of the reacting
molecules- it does not matter what .ind of molecule is net to it or
colliding with it.
+The etent of micromiing does not affect a first'order reaction% so the
segregation flow model can be used to calculate the conversion.
+@nl$ the RTD is necessar$ to calculate the conversion for a first'order
reaction in an$ t$pe of reactor.
+9nowledge of neither the degree of micromiing nor the reactor flow
pattern is necessar$.
48
4ample 17'<
Calculate the mean conversion in the reactor we have characterized b$ RTD measurements in
4amples 17'1 and 17'2 for a first'order% li&uid'phase% irreversible reaction in a completel$
segregated fluid#
8products
The specific reaction rate is 1.1 min
'1
at 721 9.

0
dt ) t ( E ) t ( * *
>olution
Fecause each globule acts as a batch
reactor of constant volume% we use the
batch reactor design e&uation to arrive
at the e&uation giving conversion as a
function of time#
t 1 0 7t
e 1 e 1 ) t ( *


49
3%" 0
! 0 ) 00%4 0 ( 4 01%+6 0 # ! 01%+6 0 ) 0261 0 ( 4
) 0331 0 ( 2 ) 0402 0 ( 4 ) 0"41 0 ( 2 ) 062+ 0 ( 4
) 066 0 ( 2 ) 0414 0 ( 4 ) 01% 0 ( 2 ) 001+ 0 ( 4 0 #
dt ) t ( E ) t ( * dt ) t ( E ) t ( * dt ) t ( E ) t ( * *
3
2
3
1
14
10
10
0 0

+ + + + +
+ + + +
+ + + +
+

8s discussed previousl$% because the reaction is first order% the calculated conversion would be
valid for a reactor with complete miing% complete segregation% or an$ degree of miing between
the two. 8lthough earl$ miing or late miing does not affect a first'order reaction% micromiing
or complete segregation can modif$ the results of a second'order s$stem significantl$.
50
4ample 17':
The li&uid'phase reaction between c$tidine and acetic anh$dride
85FC5D
is carried out isothermall$ in an inert solution of "'meth$l'2'p$rrolidine ("/3) with
"/3
02=.N.
The reaction follows an elementar$ rate law. The feed is e&ual molar in 8 and F with C
81
01.;<
mol!dm
7
% a volumetric flow rate of 1.1 dm
7
!s and a reactor volume of 111 dm
7
. Calculate the
conversion in (a) a 3*R% (b) a batch reactor% and (c) a laminar flow reactor.
8dditional information
mol / 7cal 44 0 9 : + 2%
F
F
-ing for 9eat of mi
mol / 7cal " 10 9 : mol / 7cal 3 13 E
C "0 s at mol / dm 10 +3 4 7
mi-
0 .
N;6
N;6
r-
3 3




51
>olution
The reaction will be carried out isothermall$ at <1C. The space time is
s 1000
s / dm 1 0
dm 100
v
)
3
0

(a) 3*R
0 .
.
F
r
d)
d*

4 . .
C 7C r
. 4
0 . .
C C
) * 1 ( C C

0 . 0
2 2
0 .
C v
) * 1 ( 7C
d)
d*

0 for ) 0 *
v / )
0


2
2
0 .
0 .
5a 1
5a
7C 1
7C
*
+

$ 3 ) dm / mol $" 0 )( mol s / dm 10 + 4 )( s 1000 ( 7C 5a

3 3 3
0 . 2


$%$ 0
$ 3 1
$ 3
5a 1
5a
*
2
2

+

52
(b) Fatch Reactor
0 .
.
C
r
dt
d*

4 . .
C 7C r
. 4
0 . .
C C
) * 1 ( C C

2
0 .
) * 1 ( 7C
dt
d*

0 for t 0 *
t 7C 1
t 7C
*
0 .
0 .
+

$ 3 ) dm / mol $" 0 )( mol s / dm 10 + 4 )( s 1000 ( t7C

3 3 3
0 .


$%$ 0
$ 3 1
$ 3
*
+

batch reaction time is the same

time as the space time
53
(c) Iaminar *low Reactor
t 7C 1
t 7C
*
0 .
0 .
+

) t ( E ) t ( *
dt
* d


2 / t
t 2
2 /t 0
) t ( E
3
2

'

<

$41 0 *
1
]
1

,
_

,
_

5a
2
1 ln
2
5a
1 5a *
eact solution
$ 3 5a
$42 0 *
54
/aimum /iedness /odel
6e return again to the plug'flow reactor with side
entrances% onl$ this time the fluid enters the reactor
along its length (*igure 17'2M).
8s soon as the fluid enters the reactor% it is completel$
mied radiall$ (but not longitudinall$) with the other
fluid alread$ in the reactor.
The entering fluid is fed into the reactor through the
side entrances in such a manner that the RTD of the
plug'flow reactor with side entrances is identical to
the RTD of the real reactor.
The globules at the far left of *igure 17'2M correspond to the molecules that spend
a long time in the reactor while those at the far right correspond to the molecules
that channel through the reactor.
,n the reactor with side entrances% miing occurs at the earliest possible moment
consistent with the RTD.
The effect of miing occurs as earl$ as possible throughout the reactor% and this
situation is termed the condition of maimum miedness.
55
,n a reactor with side entrances% let be the time it ta.es for the fluid
to move from a particular point to the end of the reactor. ,n other
words% is the life epectanc$ of the fluid in the reactor at that point.
/oving down the reactor from left to
right% decreases and becomes zero at the
eit. 8t the left end of the reactor%
approaches infinit$ or the maimum
residence time if
it is other than infinite.
4() is the fraction of the total that has life
epectanc$ between and 5.
v
1
4() is the volumetric rate of fluid entering through
the sides of volume C.
+
+
) ( E v v v
0
) ( E v
d
dv
0

is the volumetric flow rate at

C
5
is the volumetric flow rate at 5
0
56
)! ( F 1 # v d ) ( E v v
0 0

at v v
at 0 v
Consider a mole balance on substance 8 between and 5
0
n b< reactio
=eneration
at
/'t
de thro'gh si
,n
at
,n

1
]
1

+
1
]
1

1
]
1

+
1
]
1

+
The volume of fluid with a life
epectanc$ between and 5
is
)! ( F 1 # v )
0
The rate of generation of substance
8 in this volume is
)! ( F 1 # v r ) r
0 . .
0 )! ( F 1 # v r C )! ( F 1 # v ) ( E C v C )! ( F 1 # v
0 . . 0 0 . 0 . 0
+ +
+
0 )! ( F 1 # r
d
)> ( C )! ( F 1 ?# d
) ( E C
.
.
0 .
+

+
0

0
< v dividing b
57
0 )! ( F 1 # r ) ( E C
d
dC
)! ( F 1 # ) ( E C
. .
.
0 .
+

+
) ( F 1
) ( E
) C C ( r
d
dC
0 . . .
.

d
) ( dF
) ( E
) * 1 ( C C
0 . .

) ( F 1
) ( E
* C r
d
d*
C
0 . . 0 .

*
) ( F 1
) ( E
C
r
d
d*
0 .
.

The boundar$ condition is

at 0 *
at C C
0 . .
To obtain a solution% the e&uation is integrated bac.wards numericall$% starting
a ver$ large value of and ending with the final conversion at 01.
*or a given RTD and reaction orders greater than one% the maimum miedness
model gives the lower bound on conversion.
58
4ample 17';
The li&uid'phase% second order dimerization
2
. .
7C 4 r . 2
*or which .01.11 dm
7
!molmin is carried out at a reaction temperature of 721 9. The feed is pure
8 with C
81
0= mol!dm
7
. The reactor is nonideal and perhaps could be modeled as two C>TRs with
interchange. The reactor volume is 1111 dm
7
% and the feed rate for our dimerization is going to be
2< dm
7
!min. 6e have run a tracer test on this reactor% and the results are given in columns 1 and
2 of Table 417';.1. 6e wish to .now the bounds on the conversion for different
possible degrees of micromiing for the RTD of this reactor. 6hat are these boundsO
Tracer test on tan. reactor# "
1
0111 g% v02< dm
7
!min
59
t 7C 1
t 7C
*
0 .
0 .
+

0
dt ) t ( E ) t ( * *
>olution
Conversion if fluid is completel$ segregated.
The batch reactor e&uation for a second'order reaction of this t$pe is
The conversion for a completel$ segregated fluid in a reactor is
The calculation for this integration are
carried out in Table 417';.2. The numerical
integration uses the simple trapezoid rule.
The conversion for this s$stem if the fluid
were complete segregated is 1.:1 or :1?.
60
Conversion for maimum miedness.
*
) ( F 1
) ( E
C
r
d
d*
0 .
.

) * 1 ( 7C r
2
0 . .

i
i
i
0 .
2
i
2
0 . 1 i i
*
) ( F 1
) ( E
C
) * 1 ( 7C * *

1
]
1

2
i 0 . i
i
i
i 1 i
) * 1 ( 7C *
) ( F 1
) ( E
* *
2 ! ) 0 1 )( % )( 01 0 ( ) 0 )( 0$" 0 )#( 2" ( 0
)) 200 ( * 1 ( 7C ) 200 ( *
) 200 ( F 1
) 200 ( E
) 2" ( ) 200 ( * ) 1$" ( *
2
2
0 .

1
]
1

The conversion for a condition of maimum miedness
in this reactor is 1.<: or <:?.
There is little difference in the conversion for the two conditions
of complete segregation (:1?) and maimum miedness (<:?).
6ith bounds this narrow% there ma$ not be much point in
modeling the reactor to improve the predictabilit$ of
conversion.
C>TR<=?
3*R;:?
61
The intensit$ function% (t) can be thought of as the probabilit$ of a particle
escaping the s$stem between a time t and (t5dt) provided the particle is still in the
s$stem.
()d is the fraction of fluid in the vessel with age that will leave
between and 5d.
*
) ( F 1
) ( E
C
r
d
d*
0 .
.

1
1
1
1
1
1
]
1

1
1
1
]
1

1
1
1
1
]
1

+
d and time
between will leave
that age
d with the fl'i
n of fractio
time
at remaining
fl'id vol'me of
d and
mes between ti
ing fl'id leav
vol'me of
! d ) ( )!# ( ), # d ) ( E v
0

) ( F 1
) ( E
d
)! ( , ln# d
) ( ,
) ( E
) (

) ( * ) (
C
) ( r
d
) ( d*
0 .
.
+

m in s<stme molec'les ges of all iance of a var

@ s int (o @ n fl'id ges betwee iance of a var
A
P01complete segregation
P01maimum miedness
Degree of segregation% P

d
)! ( , # d
) ( E
62
Comparing >egregation and /aimum /iedness 3redictions
mm seg
2
.
.
2
seg mm
2
.
.
2
mm seg
2
.
.
2
* then * 0
C
) r (
,f
* then * 0
C
) r (
,f
* then * 0
C
) r (
,f

> <

> >

seg mm
2
.
.
2
seg mm
2
.
.
2
mm seg
2
.
.
2
mm seg
2
.
.
2
* and * 0
C
) r (
then : 1 or 0 ,f n
* and * 0
C
) r (
then : 1 n 0 ,f
* and * 0
C
) r (
then : 0 ,f n
* and * 0
C
) r (
then : 1 ,f n

> <

< <
> >

<
> >

>
2 n
.
2
.
.
2
1 n
.
.
.
n
. .
7C ) 1 n ( n
C
) r (
n7C
C
) r (
7C r

63
Jsing >oftware 3ac.ages
>egregation /odel
0 .
.
C
r
dt
d*
) t ( E ) t ( *
dt
* d

at t B *
) * ( f r
t a t a a ) t ( E
.
2
2 1 0

+ + +
/5E solver
/aimum /iedness /odel
*
) ( F 1
) ( E
C
r
d
d*
0 .
.

C D
D C


*
) C D ( F 1
) C D ( E
C
r
dC
d*
0 .
.

D at C B *
) * ( f r
t b t b b ) t ( F
t a t a a ) t ( E
.
2
2 1 0
2
2 1 0

+ + +
+ + +
/5E solver
"ote that the maimum value of *(t) is set at 1.NNN.
64
There are three cautions one must be aware of when fitting 4(t) to a pol$nomial.
*irst% $ou use one pol$nomial 4
1
(t) as 4(t) increases with time to the top of the
curve shown in *igure 17'2;. 8 second pol$nomial 4
2
(t) is used from the top as
4(t) decreases with time.
>econd% one should be certain that the pol$nomial used for 4
2
(t) does not become
negative when etrapolated to long times. ,f it does% then constraints must be
placed on the fit using ,* statements in the fitting program.
*inall$% one should chec. that the area under the 4(t) curve is virtuall$ one and
that the cumulative distribution *(t) at long times is never greater than 1.
65
4ample 17'=
Jse an @D4 solver to determine the conversion predicted b$ the maimum miedness model
for the 4(t) curve given in 4ample 17';.
>olution
02% 0 10 6"$ % 10 3"3 1 10 1%0 1 10 44$ 4 ) ( E
$0
4 2 " 3 $ 4 10
1
+ +
<

01" 0 10 40$ 2 10 361% 1 10 640 2 ) ( E
$0
4 2 6 3 +
2
+ +
>

66
C 200
200 C


*
) C 200 ( F 1
) C 200 ( E
C
r
dC
d*
0 .
.

200 at C "63 0 *
) ( E
d
dF

*01.NNN at 0211
67
RTD and /ultiple Reactions
>egregation /odel

0
4 4
0
. .
dt ) t ( E ) t ( C C
dt ) t ( E ) t ( C C

E
1 i
i4 4
4
E
1 i
i. .
.
r r
dt
dC
r r
dt
dC
) t ( E ) t ( C
dt
C d
) t ( E ) t ( C
dt
C d
4
4
.
.


B C
B C
4
.

RTD
/aimum /iedness /odel
) ( F 1
) ( E
) C C ( r
d
dC
) ( F 1
) ( E
) C C ( r
d
dC
0 4 4 i4
4
0 . . i.
.

RTD
at t
B C
B C
4
.

0 at
68
4ample 17'=
Consider the following set of li&uid'phase reactions#
E 5 4
5 .
C 4 .
3
2
1
7
7
7
+

+
which are occurring in two different reactors with the same mean residence time t
m
01.2: min.
Kowever% the RTD is ver$ different for each of the reactors% as can be seen in *igures 417'N.1
and 417'N.2.
(a) *it a pol$nomial to the RTDs.
(b) Determine the product distribution (e.g.% >
C!D
% >
D!4
) for
1. The segregation model
2. The maimum miedness model
8dditional information
.
1
0.
2
0.
7
01 in appropriate units at 7<1 9
69
>olution
>egregation /odel
5 4 3 E 3 E
E
5 4 3 . 2 5 3 5 2 5
5
4 . 1 C 1 C
C
5 4 3 4 . 1 4 3 4 1 4
4
. 2 4 . 1 . 2 . 1 .
.
C C 7 r r
dt
dC
C C 7 C 7 r r r
dt
dC
C C 7 r r
dt
dC
C C 7 C C 7 r r r
dt
dC
C 7 C C 7 r r r
dt
dC

+

+
+
) t ( E ) t ( C
dt
C d
i
i

0 at t 0 C C C : 1 C C
E 5 C 4 .

42 2 at t
70
/aimum /iedness /odel
) ( F 1
) ( E
) C C ( C C 7
d
dC
) ( F 1
) ( E
) C C ( C C 7 C 7
d
dC
) ( F 1
) ( E
) C C ( C C 7
d
dC
) ( F 1
) ( E
) C C ( C C 7 C C 7
d
dC
) ( F 1
) ( E
) C C ( C 7 C C 7
d
dC
0 E E 5 4 3
E
0 5 5 5 4 3 . 2
5
0 C C 4 . 1
C
0 4 4 5 4 3 4 . 1
4
0 . . . 2 4 . 1
.

+ +

+ +

+ +

C 6 6 C
6 C 0 at
71
Closure
+8fter completing this section the student will use the tracer concentration
time data to calculate the eternal age distribution function 4(t)% the
cumulative distribution function *(t)% the mean residence time% t
m
% and the
variance%
2
.
+The student will be able to s.etch 4(t) for ideal reactors% and b$ comparing
4(t) from eperiment with 4(t) for ideal reactors (3*R% 3FR% C>TR%
laminar flow reactor) the student will be able to diagnose problems in real
reactors.
+The student will also be able to couple RTD data with reaction .inetics to
predict the conversion and eit concentrations using the segregation and
the
maimum miedness models without using an$ adjustable parameters.
+F$ anal$zing the second derivate of the reaction rate with respect to
concentration% the student will be able to determine whether the
segregation
model or maimum miedness model will give the greater conversion.