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DDT
(dichlorodiphenyl-
trichloroethane

3. Reactors

Cin known, Cout<max. value

Retention time required to meet design
objective?
1

You need to know:

§  Write mass balance for ideal reactors
§  Write mass balance for real reactors
§  Residence-time functions for real reactors
§  Relationship among reaction volume, reaction time and
conversion

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Reactor Kinetics (Chapter 10)

§  Ideal reactor CSTR (continuous stirred tank reactor)
and PFR (plug flow reactor): review of reaction
kinetics and mass balance (Notes)
§  Non-ideal reactor: residence-time distribution and
measurement (Clark book: 10.2-10.4)
§  Residence-time distribution for CSTR and PFR,
tanks in series (Clark book: 10.5; 10.7)
§  Conversion in non-ideal reactors (Notes)
§  Group 3 presents paper on reactor kinetics 3

Review: Reaction Kinetics

Which of the following expression is for
zero order A→B (Q1)
CA kt
A. C A = C A,in − kt ; = 1−
C A,in C A,in
CA
B. C A = C A,in exp(− kt ); = exp(−kt )
C A,in
CA 1
C. =
C Ain 1 + C Ain kt
4

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Review: Reaction Kinetics

Which of the following expression is for
second order 2A→B (Q2)
CA kt
A. C A = C A,in − kt ; = 1−
C A,in C A,in
CA
B. C A = C A,in exp(− kt ); = exp(− kt )
C A,in
CA 1
C. =
C Ain 1 + C Ain kt
5

Main Questions

•  Why do we need to use reactors?

•  What do we need to know about reactors?

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Ideal Reactors
1.  Well-mixed batch reactors with constant volume
2.  Steady state well-mixed flow reactor (CSTR-constant
stirred tank reactor or CMFR-complete mixed flow reactor)
3.  Steady state plug flow reactor (PFR)
Clark’s book: perfect mixing reactor and ideal plug-flow reactor

One stream of A coming into a CSTR reactor to form P

(A→P). The flow rate is Q and the reaction is NOT
reversible and is first order.
Do mass balance (Q3)

1 ⎛ C A0 ⎞
Q
A) tCSTR = ⎜ − 1⎟ Q
k ⎜⎝ C Af ⎟
⎠ CA0 CAf
V C A0 − C Af
B ) tCSTR = =
Q k
C ) None of the above
D) I have no idea
8

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Find retention time tCSTR

0 = QC A0 − QC Af + rAV
Q (C Af − C A0 )
rA = − kC Af = <0
V
Q
C Af 1 1
= V = =
C A0 Q V 1 + ktCSTR
+ k 1+ k
V Q
1 ⎛ C A0 ⎞
tCSTR = ⎜ − 1⎟
k ⎜⎝ C Af ⎟
⎠
10

One stream of A coming into a CSTR reactor to form P

(A→P). The flow rate is Q and the reaction is NOT
reversible and is zero order. Do mass balance and
find retention time.

Q
Q
CA0
CAf

11

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Retention time tCSTR for zero-order reaction

kinetics

0 = QC A0 − QC Af + rAV
Q(C Af − C A0 )
rA = −k = <0
V
V C A0 − C Af
tCSTR = =
Q k

12

Two feed streams, one containing CA0 =22 M of chemical A and the other
containing CB0 = 2 M of chemical B, are to be introduced at equal flow rates Q into
the reactor of volume V of 10L. The reaction is A+2B↔R with k1 is the rate
constant for the forward reaction and k2 is the rate constant for the backward
reaction. The rate equation for this reactor is -rA=-rB/2=k1CACB2-k2CR (M/min) with
k1=1 (1/M2.min) and k2=1 (1/min).
What chemical is the limiting reactant (Q4)?
A.  Chemical A
B.  Chemical B
Q, CB0=2M C.  Neither
Q,CA0=22M 2Q D.  Both
CAf, CBf, CR

14

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Conditions
§  The initial concentrations of A and B are half of the
concentration in each stream after mixing.
§  In the mixed feed stream
CA0=11M and CB0=1 M
§  Because it is an elementary reaction A+2B↔R
§  11 M of A would require 22M of B and we only have 1 M of B
so B is the limiting chemical.

16

Two feed streams, one containing CA0 =22 M of chemical A and the
other containing CB0 = 2 M of chemical B, are to be introduced at
equal flow rates Q into the reactor of volume V of 10L. The reaction is
A+2B↔R with k1 is the rate constant for the forward reaction and k2 is
the rate constant for the backward reaction. The rate equation for
this reactor is -rA=-rB/2=k1CACB2-k2CR (M/min) with k1=1 (1/M2.min) and
k2=1 (1/min). What should be the rate of the limiting chemical so
that its conversion is 80% (Q5)

Q, CB0=2M
Q,CA0=22M 2Q
A.  -0.048 mol/L.min
CAf, CBf, CR B.  -0.0048 mol/L.min
C.  -0.48 mol/L.min
D.  None of the above
17

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80% conversion of B means the final concentration of B

CB , f = 1 − 0.8 = 0.2 M
Final concentration of A C Af = 11 − 0.8 / 2 = 10.6 M
CR = 0.8 / 2 = 0.4 M

rB
− rA = − = C ACB 2 − CR [ mol / L.min ]
2
( ) ( )
− rB = 2 × C ACB 2 − CR = 2 × 10.6 × 0.22 − 0.4 = 0.048
rB = −0.048 [ mol / L.min ]

19

Two feed streams, one containing CA0 =22 M of chemical A and the
other containing CB0 = 2 M of chemical B, are to be introduced at
equal flow rates Q into the reactor of volume V 10L. The reaction is A
+2B↔R with k1 is the rate constant for the forward reaction and k2 is
the rate constant for the backward reaction. The rate equation for
this reactor is -rA=-rB/2=k1CACB2-k2CR (M/min) with k1=1 (1/M2.min) and
k2=1 (1/min).
What should be the flow rate of each stream so that the
conversion of the limiting chemical is 80% (Q6)?

A.  0.3 mol/L.min

Q, CB0=2M B.  0.004 mol/L.min
Q,CA0=22M 2Q C.  0.03 mol/L.min
CAf, CBf, CR
D.  None of the above
20

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0 = 2QCB 0 − 2QCBf + rBV

VrB 10 L × ( −0.048 [ M / min ])
2Q = = = 0.6 L / min
(CBf − CB 0 ) 0.2 − 1.0( M )
Q = 0.3L / min

22

Steady State Plug Flow Reactor

V, A(x)
Q CA0 Q CAf
L

Constant velocity for all elements

Same residence time for all molecules 23

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General mass balance for PFR

0 = QC A0 − QC Af + rAV
= QC A0 − Q (C A0 + dC A ) + rAV

QdC A = rAV
V dC A
=
Q rA
C Af
V dC A
t PFR = = ∫
Q C A 0 rA
rA = − kC A n
25

Steady State Plug Flow Reactor

The following elementary reaction A→B is occurring in a
plug flow reactor with first order kinetics. Find the reactor
volume for a given conversion XA, flow rate Q and reaction
rate constant k (Q7).
Q ⎛ C A0 ⎞
A. V = ln ⎜ ⎟
k ⎜ C Af ⎟
⎝ ⎠
Q
B. V =
k
( C A0 − C Af )
26

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First-order reaction in PFR

C C
1 ⎛ C Af ⎞
Af Af
V dC A dC A
t PFR = = ∫ = ∫ = − ln ⎜ ⎟
Q C A 0 rA CA0
− kC A k C
⎝ A0 ⎠
Q ⎛ C A0 ⎞
V = ln ⎜ ⎟
k ⎜ C Af ⎟
⎝ ⎠

28

If we have zero order reaction in a PFR

(do at home)

29

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Summary of retention times of pollutants in

ideal reactors
Zero-order First-order
CSTR

PFR

30

Let’s compare the retention times for 50%

conversion for PFR and CSTR with the
same first order reaction rate constant k

31

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Retention times in ideal reactors assuming

first-order kinetics
100
Design goal:

retention times [h]

10
XA=1-CA,F/CA,0
tCSTR
1 tPFR

0.1
0 0.5 1
conversion

32

Retention times in ideal reactors assuming

first-order kinetics
100
retention times [h]

Design goal: tCSTR

XA=1-CA,out/CA,in 10
tPFR

1
tCSTR>tPFR
For same Q, VCSTR > VPFR 0.1
0 0.2 0.4 0.6 0.8 1
Conversion XA
33

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CSTR in series

Q; CAout1=CAin,2
Q
Q
CAin
Caout,2

34

Write mass balance equation for CSTR 2.

Assume first-order reaction kinetics (Q8)
C A,out ,2
A. 0=QC Aout1 + QC Aout 2 − VkC Aout 2 and = ktCSTR,2
C A,in
C A,out ,2 ⎛ 1 ⎞
B. 0=QC Aout1 − QC Aout 2 − VkC Aout 2 and =⎜ ⎟
C A,out ,1 ⎝ 1+ ktCSTR,2 ⎠

35

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Write mass balance equation for

CSTR 2 (Q8)

36

Conversion

C Aout ,1 ⎛ 1 ⎞
First reactor =⎜ ⎟
C Ain ⎜ 1 + kt ⎟
⎝ CSTR ,1 ⎠

C Aout ,2 ⎛ 1 ⎞
Second reactor =⎜ ⎟
C Aout ,1 ⎜ 1 + kt ⎟
⎝ CSTR ,2 ⎠

C Aout ,2 ⎛ 1 ⎞⎛ 1 ⎞
X = 1− = 1− ⎜ ⎟⎜ ⎟
C Ain ⎝ 1+ ktCSTR,1 ⎠ ⎝ 1+ ktCSTR,2 ⎠
37

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Mass balance for N number of CSTR

with same size in series (do at home)

What happens if the rate constants

are different in each reactor?

38

Review: What reactor is best in

practice?
•  It depends …
•  High conversion requires larger retention times (V/Q) in
CSTR, so larger reactors and/or fast kinetics
•  Shorter retention times for PFR but …
•  If good mixing is required to decrease toxicity, or if settling
needs to be prevented, then well-mixing will be preferred (or
a combination of PFR and CSTR)

39

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What if the reactors do not follow the

derived equations?

Non-ideal reactors

40

Two feed streams, one containing CA0 =22 M of chemical A and the
other containing CB0 = 2 M of chemical B, are to be introduced at
equal flow rates Q into the reactor of volume V 10L. The reaction is A
+2B↔R with k1 is the rate constant for the forward reaction and k2 is
the rate constant for the backward reaction. The rate equation for
this reactor is -rA=-rB/2=k1CACB2-k2CR (M/min) with k1=1 (1/M2.min) and
k2=1 (1/min).
What should be the flow rate of each stream so that the
conversion of the limiting chemical is 80% (Q6)?
Mass balance for B
ACC = QinCB,in − QoutCB,out +VrB

Q, CB0=2M ACC = 0
Qin = Q (for B)
Q,CA0=22M 2Q Qout = 2Q
CAf, CBf, CR CB,in = 2M (influence)
CB,out = CB,sys = 0.2M (well-mixed, calculated)
0 = Q * 2 − 2Q * 0.2 +VrB 41

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Residence Time Distributions

42

How to determine the Residence Time Density

Distribution?

ti+1

Δmi,i+1 = Q ∫ c(t)dt
ti

MT = ∑ Δmi,i+1 43
i

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Residence Time Density Distribution

ti+1

Δmi,i+1 = Q ∫ c(t)dt
ti

MT = ∑ Δmi,i+1 44
i

Residence Time Density Distribution

Function f(t)
Δmi,i+1 f (t ) ≥ 0
f (t) = ∞
M T Δt
∫ f (t )dt = 1
0

45

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Which of the following is

NOT correct (Q9)
t2

∫
t1
f (t ) dt

A. is an area under the curve between t1 and t2

B.  less than or equal to 1
C. is probability of a tracer molecule entering the reactor will
staying between t1 and t2
D. Residence Time Density Distribution Function f(t) is unitless
46

Mean Residence Time

47

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Cumulative Residence Time Distribution F(t)

t
F (t ) = ∫0
f (t ) dt
49

Which of the
following is NOT
correct (Q10)
A. F(t) is between 0 and 1
B. F(t2)-F(t1) is the fraction of molecules with residence
time between t1 and t2
C. Unit of F(t) is time-1
t2

D. F (t2 ) − F (t1 ) = ∫ f (t )dt = prob[t1 ≤ t ≤ t2 ]

t1 50

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Washout Function W(t)

∞
t
W (t ) = ∫
t
f (t )dt F (t ) = ∫ f (t )dt
0
∞
W (t ) = 1- F (t ) = ∫ f (t )dt
t
52

The washout function of a reactor, W(t), [t is in

minutes] is given by the expression W(t)=exp(-kt)
a) What is the cumulative residence time function, F(t)
(Q11)?

A. F (t ) = exp(−kt )
B. F (t ) = 1 − exp(−kt )

53

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∞
Wash out function W (t ) = 1- F (t ) = ∫ f (t )dt
t

F (t ) = 1 − W (t ) = 1 − exp(−kt )

54

The washout function of a reactor, W(t), [t is in minutes] is given by

the expression W(t)=exp(-kt)
b) What is the residence time density function, f(t) (Q12)?

A. f (t ) = k exp( kt )
B. f (t ) = 1 − k exp( − kt )
C. f (t ) = k exp( − kt )

55

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dW (t ) dF (t ) d [1 − exp( − kt )]
f (t ) = − = = = k exp( − kt )
dt dt dt

∫ k exp(−kt )dt = exp(−kt ) |

∞
0 = −0 + 1 = 1
0

56

Given that the washout function of a reactor, W(t), [t is in

minutes] is given by the expression W(t)=exp(-kt)
c) What is the mean residence time for the reactor (Q13)?
∞
A. t RTD = ∫ k exp(−kt ) × tdt
0
∞
B. t RTD = ∫ k exp(kt ) × tdt
0

57

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f (t ) = k exp(−kt )
∞ ∞
t RTD = ∫
0
f (t ) × tdt = ∫ k exp(−kt ) × tdt
0

58

Example: T10
§  Water treatment regulation may require that for disinfection
90% of the chlorine molecules must spend some minimum
residence time in the reactor
§  Find time t* so that F(t*)=0.1 (10% of the molecules will
spend less than t* in the reactor and 90% will spend at least
t* in the reactor
§  The time t* is called the T10.

59

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Measurement of residence-time distribution

Impulse or Pulse method
Positive step input
Negative step input

Why? Residence time functions are easy to determine

60

Pulse method for tracer injection

Instantaneous injection of tracer molecules

ti+1 ti+1

Q ∫ c(t) dt ∫ c(t) dt
Δmi,i+1 ti ti c(t)
f (t) = = = =
MT ∆ t MT ∆ t ∆ t ⋅ MT / Q MT / Q
61

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Cpulse A total of 1 mol of tracer is injected

0.05 mol /L into a reactor at time zero (i.e. pulse
t, min input). The flow rate is 4L/min. A tracer
0 curve for pulse input is shown.
5
Check the mass balance with the
tracer curve to see whether the results
Integral c(t)dt= M/Q are consistent (Q14).

A.  The mass balance is consistent with the

experimental data
B.  The mass balance is NOT consistent the
experimental data
C.  Cannot say from this dataset 62

Theoretically, the area under the curve = total

mass of tracer divided by the flow rate=1 mol/
4L/min=0.25mol/min/L
From the graph, the area under the curve =
0.05mol/L×5min=0.25molxmin/L

64

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A total of 1 mol of tracer is injected into a reactor at time zero (i.e.

pulse input). The flow rate is 4L/min. A tracer curve for pulse input is
shown below.
If the results are consistent, determine the volume of the reactor.

0.05 mol/L A.  V=4L

Cpulse B.  V=10 L
0 5 C.  None of this
t, min

65

output
C (t ) C (t )
0.2
f (t ) = =
∞

∫ C (t )dt
M /Q f(t)
0
0 5
t, min
0.05
to get f (t ) we divide C (t ) over the area under the curve f (t ) = = 0.2
0.25

∞ 5
t2
= ∫ t × f (t ) dt = ∫ t × 0.2dt = = 0.2 ×
5
t RTD 0
= 0.1× (25 − 0) = 2.5
0 0
2

V = t RTD Q = 2.5 min× 4 L / min = 10 L

66

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Positive Step Tracer Injection

C (t )
F (t ) = f(t) and tRTD?
C0
Consider a reactor of volume V m3 through which Q m3/s of fluid
flows. For this reactor, at time t=0, the fluid of tracer with
concentration C0 is introduced into the reactor. The concentration-
time curve is recorded, i.e. C(t) curve. 68

Determine Cumulative Distribution for CSTR in

a positive step tracer test

69

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Negative Step
Tracer test for CSTR

C(t)
W (t) =
C0

71

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