1
1
In-Out+Production=Accumulation
Thermodynamics
Suppose ZZZ
A + B YZZ
k1
X
Z 2C
k −1
− ΔG RT
Ke = e
ΔG = ΔG °f , products − ΔG °f ,reactants
Kc =
[ B ][C ] has units. You need to use standard states, such as 1M, to make it
[ A]
dimensionless.
Enzyme Catalysis
without enzyme
with enzyme
Energy
P
Reaction Progress
Figure 1. Energy diagram for a reaction with and without enzyme.
Cite as: William Green, Jr., and K. Dane Wittrup, course materials for 10.37 Chemical and Biological
Reaction Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of
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E + S U ES
ES → E + P
Pseudo steady state approximation:
d [ ES ]
=0
dt
[ ES ] = f (other species)
Cell Growth
# cells
N=
volume
N = N0e μ t
Monod kinetics:
μmax [ S ]
μ=
KS + [S ]
ΔA
YA =
B
ΔB
Rate Constants
k (T ) = Ae − Ea RT
CSTRs
FA0 X A
V=
−rA
Incorporates changing
volumetric flow rate
If the reaction is 1st order and it consists of liquids with constant density:
XA
τ=
k (1 − X A )
V volume
τ= =
ν0 volumetric flow rate
τk
XA =
1+ τ k
Da = τ k =Damköhler number: ratio of kinetic effect to volumetric effect or
ratio of reaction rate to dilution rate
2nd order reaction:
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XA
τ=
kC A0 (1 − X A )
2
Da = τ kC A0
1 + 2 Da − 1 + 4 Da
XA =
2 Da
Cˆ A =
1
1 + Da
( ˆ
1 − e− (1+ Da )t )
Tanks in series: 1st order reaction
C A,0
C A, n =
(1+ Da )
n
If A( g ) → 2 B( g )
Use ν 0 ρ0 = νρ (conservation of mass)
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Pm ⎛ m ⎞
Introduce ideal gas law ρ=
⎜ nRT = Pν = P = FT RT ⎟
FT RT ⎝ ρ ⎠
FT = FT 0 (1 + ε X )
Reactor volume:
positive order
VCSTR reactions
FAo
− rA
VPFR (area under curve)
XA
Figure 2. Levenspiel plot for a CSTR and a PFR for positive order reactions.
Selectivity
CSTR
φinst
Φ overall ΔC A
C Af C A0 CA
Figure 3. Fractional yield versus concentration. Overall yield times concentration
difference shown for a CSTR.
CSTR
A ⎯⎯ k1
→ P ⎯⎯ k2
→C
A ⎯⎯ k3
→U
( k1 [ A] + k3 [ A])V = FA0 − [ A]ν
Non-ideal reactors
Residence time distribution E(t)
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δ (t ) ⎯⎯⎯
reactor
→ C (t )
E(t) must have a pulse trace
∞
C (t )
E (t ) = ∞ ∫ E (t ) = 1
∫ C (t )dt
0
0
∞
tm = ∫ tE (t )dt
0
Mean residence time, tm, for an:
Ideal CSTR: τ
Ideal PFR: τ
∞
σ 2 = ∫ ( t − tm ) E (t )dt
2
0
Variance, σ2, for an:
Ideal CSTR: τ2
⎛ ⎛ V ⎞⎞
Ideal PFR: 0 ⎜ E (t ) = δ ⎜ t − ⎟⎟
⎝ ⎝ ν ⎠⎠
∞
∫ f (t )δ (t − t )dt = f (t )
0
0 0 Åproperty of a dirac delta function
e−t τ
For a CSTR, E (t ) =
τ
Example 1
z
L
FA0 FA, FB, FC
A ⎯⎯ r1
→ B ⎯⎯
r2
→C
r1 = k1C A r2 = k2CB
moles of B produced FB ( L)
YB = =
moles of A in FA0
Mole balance on B
1 dFB
= rB = r1 − r2 = k1C A − k2CB
Axs dz
FB = CBν 0
FA0 = C A0ν 0
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ν 0 dCB
= k1C A − k2CB
Axs dz
ν 0 dC A
= −k1C A
Axs dz
dC A −k1 Axs
= dz
CA ν0
−k A
ln C A = 1 xs z + φ
ν0
Initial condition at z=0 gives:
ln C A0 = 0 + φ
⎡ −k A ⎤
C A = C A0 exp ⎢ 1 xs z ⎥
⎣ ν0 ⎦
dCB k2 Axs kA ⎡ −k A ⎤
+ CB = 1 xs C A0 exp ⎢ 1 xs z⎥
dz ν0 ν0 ⎣ ν0 ⎦
Axs
z [ = ] time, call it τ
ν0
This is the time it takes for something to flow to the end of the reactor (of length z).
ν0 G
= V velocity
Axs
dCB
+ k2CB = k1C A0 e− k1τ
dτ
kτ
Integrating factor: e 2
d
⎡⎣CB ek2τ ⎤⎦ = k1C A0 e( k2 − k1 )τ
dτ
kC
CB ek1τ = 1 A0 e( 2 1 ) + φ
k −k τ
k2 − k1
Initial condition: z=0, CB=0 B
kC
0 = 1 A0 + φ
k2 − k1
kC
CB (τ ) = 1 A0 ⎡⎣e− k1τ − e− k2τ ⎤⎦
k2 − k1
1 dFC
= + r2
Axs dz
1 dFA
= −r1
Axs dz
1 dFB
= r1 − r2
Axs dz
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1 ⎡ dFA dFB dFC ⎤
+ + =0
Axs ⎢⎣ dz dz dz ⎥⎦
FA0 = FA + FB + FC
FC = FA0 − FA + FB
find
A
B C
τ∗ τ
Figure 5. Graphs of flow rates of A, B, and C as a function of residence time.
dCB k1C A0
dτ
=
k2 − k1
( )
−k1e− k1τ * + k2 e− k2τ * = 0
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τ *ν 0
L= = length of reactor
Axs
Example 2
If A → 2 B (Assume negligible pressure drop)
r = kC A
z
L
FA0
dFA
= −rA = − kC A
dV
ν0 ↔ν
PV = nRT
( Ftotal = n , ν = V )
RT
ν = Ftotal −1
= Ftotal Ctotal
P
Ftotal = FA + FB
FA = C Aν = y A Ftotal
dFA FA P
= − ky ACtotal = − k
dV FA + FB RT
dFB FA P
= +2ky ACtotal = +2k
dV FA + FB RT
If P or T changes, you need other equations.
No reaction:
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Technology. Downloaded on [DD Month YYYY].
dN
= N 0δ (t ) −ν C
dt
N
= N 0δ (t ) −ν
V
dN ν
+ N = N 0δ (t )
dt V
⎛ν ⎞
Integrating factor: exp ⎜ t⎟
⎝V ⎠
d ⎛ ⎛ν ⎞⎞ ⎛ν ⎞
⎜ N exp ⎜ t ⎟ ⎟ = exp ⎜ t ⎟ N 0δ (t )
dt ⎝ ⎝V ⎠⎠ ⎝V ⎠
⎛ν ⎞ ⎛ν ⎞
N exp ⎜ t ⎟ = N 0 ⋅ exp ⎜ 0 ⎟ = N 0 + φ
⎝V ⎠ ⎝V ⎠
Initial condition: t=0, N=N0 Æ φ=0
⎛ ν ⎞
N = N 0 exp ⎜ − t ⎟
⎝ V ⎠
ν 1
=
V τ
⎛ −t ⎞
C = C0 exp ⎜ ⎟
⎝τ ⎠
C
E (t ) = ∞
0
∫ Cdt
∞ ∞ ∞
dt = C0 ⎡ −τ e ⎤ = C ⎡ −τ ( 0 − 1) ⎤ = C τ
−t −t
∫ Cdt = ∫ C0e
0 0
τ
⎣⎢
τ
⎦⎥ 0 0 ⎣ ⎦ 0
−t −t
Ce τ e τ
E (t ) = 0 =
C0τ τ
Long-chain approximation
ZZZ
E + S YZZ1
X
Z ES ⎯⎯
k k2
→P+ E
k −1
tRNA ⎯⎯
→E k3
E ⎯⎯
k4
→ Deactivate
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Technology. Downloaded on [DD Month YYYY].
ES ⎯⎯ k5
→ destruction
k3 [tRNA] = k4 [ E ] + k5 [ ES ]
Suppose there is a production term
C ⎯⎯
k6
→E
Add another term
k6 [C ] + k3 [tRNA] = k4 [ E ] + k5 [ ES ]
dX F
= A0 , − rA = kC A
Adz −rA
This is a single differential equation in terms of X. Use for PFR with gas flow.
ρ0ν 0 = ρν
C A0 (1 − X ) T0 P
CA =
1+ ε X P0T
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Technology. Downloaded on [DD Month YYYY].