Lect-1
Lect-1
1
Chemical kinetics enables us (as a
chemical engineer) to, for instances,
• predict the rate at which chemical
substances react (consumed or
generated)
• control the rate of any given reaction
• choose suitable chemical reactions
to produce desirable chemical
products
• select an appropriate catalyst to
enhance the rate of a specific
reaction
2
Chemical reaction engineering (CRE)
is concerned with the design and/or
analysis of the performance of chemical
reactors
A chemical reactor is a device in which
a chemical reaction takes place
The design of chemical reactors
includes determining
• type
• size
• configuration
• operating conditions
• cost
of chemical reactors
3
Note that chemical reactors do not have
to be in the form of, e.g., tank, vessel, tube,
they can also be, for instances,
• human organs, such as stomach,
lung, heart, muscle, at which
chemical reactions take place
Reactions in Stomach
(from www.wikipedia.org)
4
Reactions in Lungs
(from www.wikipedia.org)
6
• a garbage basin, in which an
anaerobic digestion occurs (turn
organic materials to CH4 and/or H2S)
(from www.ecofriend.org)
7
Chemical engineers employ the
kinetic information (from chemists),
such as rate of reaction, dependence of
reaction rate on various factors (e.g.,
concentrations of reactants, temperature),
to determine, e.g., reactor size, flow
pattern, thermal configuration
9
To answer the 1st question, you need to
learn “thermodynamics”
Let’s consider the following chemical
reaction:
C2H4 + H2O U C2H5OH
in which equilibrium constant ( K ) at
145 oC is 6.8 × 10 −2
Thermodynamics
From General Chemistry or Physical
Chemistry or Chemical Thermodynamics,
we have learned that the “equilibrium
constant” equation can be written as
follows
K =
[ C2H5OH]
(1.1)
[CH4 ] [H2O]
11
Thus, the concentration of C2H5OH at
equilibrium can be calculated as follows
6.8 × 10 −2
=
[ x]
(1.2)
[1 − x ][5 − x ]
Solving Eq. 1.2 for x yields
x 0.243
13
dN A
r1.3 = −rA = − (1.4)
dt
dN C
or r1.3 = +rC = + (1.5)
dt
(Note: N i = number (#) of moles of species i)
14
• Rate of the consumption of A per
volume (V ) of a system
1 ⎛ dN A ⎞
r1.3 =− ⎜ ⎟ (1.6)
V ⎝ dt ⎠
• Rate of generation of C per mass of
catalyst (Wcat )
1 ⎛ dN C ⎞
r1.3 =+ ⎜ ⎟ (1.7)
Wcat ⎝ dt ⎠
17
Design Equations for Ideal Reactors
CA1
CB1 CA2
CC1 CB2
uniformly CC2
mixed
18
Ideal continuous reactors
Ideal continuously stirred tank
reactor (CSTR)
• The reactor is well-mixed or
perfectly mixed – thus, the exit
stream from the reactor has the
same composition as the fluid
within the reactor
Hence, CSTR may be called “mixed
reactor” and “back-mixed reactor”
19
CA1
CB1
CC1
Feed
Product
perfectly
CA2
mixed
CB2
CC2
20
Ideal plug flow reactor (PFR)
• The flow in the reactor is in order –
no overtaking and/or mixing with
other elements ahead or behind
• No back-mixing
Feed Product
21
Design Equations for Ideal Batch
Reactors
22
The above expression can be written in
an equation form as follows
dN i
Fio − Fi − Gi = − (1.13)
dt
where
Fio = Molar flow rate of species i
23
For batch reactors, since there are no
streams flowing in and out (i.e. Fio = 0 &
24
Re-arranging Eq. 1.16 gives
−dN i
dt = (1.17)
−rV
i
where
N io = initial # of moles of species i
25
Substituting Eq. 1.20 into Eq. 1.18:
Ni
−dN i
t= ∫
N io
−rV
i
(1.18)
gives
Ni
−d ⎡⎣N io (1 − x i ) ⎤⎦
t= ∫
N io
−rV
i
(1.21)
26
Re-arranging Eq. 1.18:
Ni
−dN i
t= ∫
N io
−rV
i
(1.18)
gives
⎛ Ni ⎞ ⎛ Ni ⎞
Ni −d ⎜ ⎟ Ni d ⎜ ⎟
V
⎝ ⎠ =t =− V
⎝ ⎠
t= ∫
N io
−ri ∫N −ri
i o
Ci
dCi
t =−∫ (1.23)
Cio
−ri
27
Example The data for a constant-V Rxn:
P Æ Q in a batch reactor are presented in
the following Table
⎡ ( mol / L ) ⎤
CP [mol/L] -rP ⎢ ⎥
⎣ s ⎦
0.1 0.10
0.3 0.50
0.5 0.55
0.7 0.10
0.8 0.06
1.0 0.05
1.3 0.045
2.0 0.042
28
Since the volume of this system (V ) is
constant, and the data are presented in the
form of the concentration of P (C P ) , Eq.
1.23:
CP
dC P
t=−∫ (1.23)
CPo
−rP
29
Re-arranging Eq. 1.24 for species P
results in
C Po − C P
xP = (1.25)
C Po
30
The numerical value of the integration:
CP
dC P or, in fact, the amount of time required
− ∫
C Po
−rP
25.0
20.0
1/-rP [s/(mol/L)]
15.0
10.0
5.0
0.0
0.0 0.5 1.0 1.5 2.0 2.5
CP [mol/L]
31
The area under the curve (between
C Po = 1.2 mol/L and C P = 0.30 mol/L ) is found
32
Design Equations for Ideal CSTRs
33
In addition to space/residence time (τ ) ,
there is another technical term for a
continuous reactor, which is “space
velocity ( s ) ”
34
In other words, the residence time
required for this reaction is
1
τ =
s
1
=
4 h−1
τ = 0.25 h = 15 min
Let
V = volume of a reactor
v o = volumetric flow rate of
a substance flowing into
the reactor
36
Combining Eq. 1.16 with Eq. 1.28 and
re-arranging results in
Fio − Fi − Gi = 0
Fio − Fi − rV
i =0
−rV
i = Fi − Fio (1.29)
sign
38
Re-arranging Eq. 1.33 results in
N io x i
τ =
−rV
i
⎛ N io ⎞
⎜ V ⎟ xi
τ =⎝ ⎠
−ri
Cio x i
τ = (1.34)
−ri
39
Substituting Eq. 1.27 into Eq. 1.35 and
re-arranging yields
⎛V ⎞
⎜v ⎟ x
⎝ o⎠= i
Cio −ri
V xi
= (1.36)
v oCio −ri
The dimensions of
L3
• v o , a volumetric flow rate, is or
t
volume
time
• Cio , an initial concentration of
N # of moles
species i, is 3 or
L volume
40
Hence, the dimension of the term v oCio
is
L3 N N # of moles
× 3 = ≡
t L t time
41
Re-arranging Eq. 1.24
Ci = Cio (1 − x i ) (1.24)
yields
Ci = Cio − Cio x i
42
It is important to note that −ri is rate of
Rxn. at the exit point of a CSTR
This is because, for an ideal CSTR, the
composition inside the reactor is identical
to that at the exit of the reactor; since the
rate of reaction at the exit can be
measured easier than that in the reactor,
the rate of Rxn. is, thus, evaluated at the
exit point (instead of being evaluated at
any point inside the reactor)
43
Example The reaction rate data at various
concentration of A of the liquid-phase
Rxn.: A Æ C is shown in the following
Table
CA ⎡ kmol ⎤ 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
⎢⎣ m3 ⎥⎦
−rA
0.50 0.70 0.85 0.92 0.95 0.93 0.88 0.80 0.70 0.60
⎡ kmol ⎤
⎢⎣ m3 ⋅ h ⎥⎦
kmol/h
44
Since this is a liquid-phase Rxn., it is
safe to assumed that this Rxn. is of
constant volume
45
It is given that
• C Ao = 1.0 kmol/m3
• x A = 0.80
46
From the given data, the final
concentration of A is 0.2 kmol/m3, which
is corresponded to the reaction rate of 0.50
kmol/(m3-h)
τ = 1.6 h
47
CA -rA 1/-rA
0.2 0.50 2.000
0.4 0.70 1.429
0.6 0.85 1.176
0.8 0.92 1.087
1.0 0.95 1.053
1.2 0.93 1.075
1.4 0.88 1.136
1.6 0.80 1.250
1.8 0.70 1.429
2.0 0.60 1.667
2.50
2.00
1/-rA [h/(kmol/m )]
3
1.50
1.00
0.50
0.00
0.0 0.4 0.8 1.2 1.6 2.0 2.4
3
CA [kmol/m ]
48
The residence time is the area of the
1
rectangular with the height of and the
−rA
width of C Ao − C A
In this Example,
1 m3 ⋅ h
• =2
−rA kmol
kmol
• C Ao − C A = 1 − 0.2 = 0.8
m3
which results in the area (or residence
time) of
m3 ⋅ h kmol
2 × 0.8 3
= 1.6 h
kmol m
49
It is given that FAo = 2 kmol/h
as follows
FAo × τ
V =
C Ao
⎛ 2 kmol ⎞ × 1.6 h
⎜ ⎟ ( )
h ⎠
=⎝
⎛1.0 kmol ⎞
⎜ 3 ⎟
⎝ m ⎠
V = 3.2 m3
50
Design Equations for PFRs
51
dN i
At steady state, = 0 , and Eq. 1.16,
dt
−Gi = −rV
i (1.16)
can be written for a change in a small
volume (dV ) as
−Gi = −ri dV (1.43)
52
−ri dV = dFi (1.45)
53
For the case that species i is a reactant,
dFi is of negative (–) sign
54
xi f
V dx i
Fio
= ∫
0
−ri
(1.50)
Ci
d (Cio x i )
or τ = ∫
Cio
−ri
(1.53)
55
Combining Eq. 1.53 with Eq. 1.39
Cio x i = Cio − Ci (1.39)
yields
Ci
d (Cio − Ci )
τ = ∫
Cio
−ri
(1.54)
56
Eqs. 1.51 & 1.55
xi f
V τ dx i
=
Fio Cio
= ∫
0
−ri
(1.51)
Ci
dCi
τ =−∫ (1.55)
Cio
−ri
57
Example Redo the Example on Page 44
for a PFR
58
2.50
2.00
1/-rA [h/(kmol/m )]
3
1.50
1.00
0.50
0.00
0.0 0.4 0.8 1.2 1.6 2.0 2.4
3
CA [kmol/m ]
59
The volume of a PFR can, thus, be
calculated, using Eq. 1.38:
V τ
= (1.38)
Fio Cio
as follows
τ
V = Fio
Cio
= ( 2 kmol/h )
(1.04 h )
(1.0 kmol/m ) 3
V = 2.08 m3
60